Patent Application
20230365812
The present invention relates to a kit of parts comprising a surface-treated calcium carbonate-containing filler material and a peroxide agent for improving the mechanical properties of a polymer mixture comprising at least one polyethylene polymer and at least one polypropylene polymer, a filled polymer mixture comprising a surface-treated calcium carbonate-containing filler material, a peroxide agent, at least one polyethylene polymer and at least one polypropylene polymer, a process for the preparation of a filled polymer composition, a filled polymer composition obtained thereby or obtainable by reacting the filled polymer mixture, the use of a surface-treated calcium carbonate-containing filler material and a peroxide reagent for reacting a polymer composition comprising at least one polyethylene polymer and at least one polypropylene polymer, as well as an article comprising the filled polymer mixture or the filled polymer composition.
Polyolefins, such as polyethylene and polypropylene, are ubiquitously used in a variety of applications, including packaging (in the form of plastic bags, films, containers, bottles, food packagings, microwavable containers, trays etc.), building and construction, automotive, electrical and electronic, agricultural, household, leisure and sports applications. In 2019, the European plastic converters demanded nearly 10 Mt of polypropylene, nearly 9 Mt of LDPE and LLDPE, and about 6 Mt of HDPE and MDPE. As many plastic products have a lifespan of less than one year, a huge amount of plastic waste is generated. In 2018, 29.1 Mt of post-consumer plastic waste were collected in the EU, whereof 32.5% were recycled, 42.6% were energetically recovered and 24.9% ended up on landfills. It has been estimated that worldwide, as of 2018, about 6300 Mt plastic waste had been generated. Thereof, only 9% were recycled and 12% were energetically recovered. 79% ended up on landfills. In view of steadily increasing awareness on environmental pollution and restrictions on plastic waste trade and landfill accumulation, there is a need to significantly increase the rates of plastic recycling. According to an EU Action Plan, circular economy is promoted to achieve “zero waste” and to recycle 100% of plastic waste by 2040.
Still, the recycling of plastics remains a challenging task, since plastic waste typically is a mixture of a variety of polymers. A common approach for their separation is sorting by gravimetry. However, different polyolefins have almost the same density (about 0.9 g/cm3) or may form part of multilayer films, such that they cannot be separated gravimetrically. Thus, the polymer mixture obtained thereby comprises mixtures of polyethylene polymers and polypropylene polymers, and optionally further small amounts of other polymers. As polyethylene and polypropylene are immiscible, the reprocessing of the so-obtained polymer mixture yields articles having poor mechanical properties. Therefore, the mechanical properties, such as the impact strength, of the so-obtained polymer composition have to be improved prior to re-use, for example, by improving the compatibility between polyethylene and polypropylene.
In the art, several approaches of compatibilizing polyethylene and polypropylene polymers have been suggested and include the use of compatibilizing or coupling agents, peroxide reagents and combinations thereof.
U.S. Pat. US9969868 B2 discloses methods and compositions related to recycling polymer waste, the composition comprising at least one polymer, a functional filler, and preferably a peroxide-containing additive. Applications US20170261131 A1, US20180186971 A1, US201190291301 A1 relate to polymer compositions comprising at least two polyethylene polymers, for example, recycled polymer compositions, a compatibilizer (or functional filler) and optionally a peroxide-containing additive. US20190153204 A1 relates to a resin composition comprising polypropylene, optionally polyethylene and a compatibilizer, wherein the polymers may be recycled polymers. In each of the aforementioned documents, the functional filler or compatibilizer comprises an inorganic particulate material and a coating comprising a first compound including a terminating propanoic group or ethylenic group with one or two adjacent carbonyl groups.
U.S. Pat. US4873116 discloses a method of preparing mixtures of incompatible hydrocarbon polymers using a compatibilizing system, comprising a mineral filler and reinforcement additives.
In view of the foregoing, there is still a need in the art for further and improved methods of improving the mechanical properties of and/or compatibilizing mixtures of polyethylene and polypropylene, in particular, mixtures of polyethylene and polypropylene derived from waste polymers. More precisely, there is a need for filler materials, which are capable of improving the mechanical properties of a polymer composition comprising mixtures of polyethylene and polypropylene, e.g., derived from waste polymers.
Accordingly, it is an objective of the present invention to provide a kit of parts comprising a filler and a peroxide for use in a polymer composition comprising at least one polyethylene polymer and at least one polypropylene polymer, wherein the mechanical properties of said polymer composition are improved. Preferably, the kit of parts can be easily handled and can be used for improving the mechanical properties of and/or for compatibilizing a wide range of polymer compositions comprising at least one polyethylene polymer and at least one polypropylene polymer, such as those polymer compositions, which are derived from waste polymers.
These and other objectives of the present invention can be solved by the inventive kit of parts, the inventive filled polymer mixture, the inventive process for the production thereof, the inventive polymer composition, the use of a surface-treated calcium carbonate-containing filler material and a peroxide agent in a polymer composition, and the inventive article comprising the inventive filled polymer mixture or the inventive filled polymer composition.
According to one aspect of the present invention, a kit of parts for improving the mechanical properties of a polymer mixture comprising at least one polyethylene polymer and at least one polypropylene polymer is provided. The kit of parts comprises
The inventors surprisingly found that the surface-treated calcium carbonate-containing filler material, in combination with the peroxide agent, greatly improves the mechanical properties of the mixture of the at least one polyethylene polymer and the at least one polypropylene polymer. The mechanical properties, for example, the impact strength, can be improved, compared to the same composition not comprising any filler material or a calcium-carbonate containing filler material of the prior art, or not comprising the peroxide agent. The inventive filler material is particularly efficient due to the interplay of the use of a calcium carbonate-containing filler material having a comparatively low particle size, i.e., having a weight median particle size (d50) value in the range from 0.03 µm to 4.0 µm and a top cut (d98) value of 30 µm or less, the specific surface-treatment layer deposited thereon, and the peroxide agent. Without wishing to be bound by any theory, it is believed that the hydrophobic surface-treatment layer interacts with both the polyethylene phase and the polypropylene phase of the filled polymer composition, such that the inventive filler can be positioned at the interface of both phases. Subsequently, the peroxide agent, upon exposure of the mixture to heat, can initiate a chemical reaction between the surface-treatment layer and the polymeric matrix, leading to the formation of strong bonds at the interfaces that further improve the mechanical properties.
A second aspect of the present invention relates to a filled polymer mixture comprising
According to a third aspect of the present invention, a process for the production of a filled polymer composition is provided. The process comprises the steps of
The present inventors found that the inventive filler material and the peroxide agent may be mixed with at least one polyethylene polymer and at least one polypropylene polymer or with a polymer mixture comprising polyethylene and polypropylene, which may be derived, e.g., from waste polymers, in a compounding step, for example, an extrusion step. The compounding allows for an intricate mixing of the respective materials, such that the interfacial area of the different phases, whereon the inventive filler material is positioned, can be maximized. At the compounding temperature, the peroxide agent can initiate a chemical reaction between the surface-treatment layer and the polymeric matrix, leading to the formation of strong bonds that further improve the mechanical properties.
A third aspect of the present invention relates to a filled polymer composition obtainable by reacting the inventive filled polymer mixture or obtainable by the inventive process.
A fourth aspect of the present invention relates to the use of a surface-treated calcium carbonate-containing filler material and a peroxide reagent for reacting a polymer mixture comprising at least one polyethylene polymer and at least one polypropylene polymer,
wherein the surface-treated calcium carbonate-containing filler material comprises a calcium carbonate-containing filler material having
A fifth aspect of the present invention relates to an article comprising the inventive filled polymer mixture or the filled polymer composition.
A sixth aspect of the present invention relates to a surface-treated calcium carbonate-containing filler material,
Advantageous embodiments of the present invention can be found in the corresponding dependent claims.
According to one embodiment of any one of the aspects of the present invention, the calcium carbonate-containing filler material has
According to another embodiment of any one of the aspects of the present invention, the surface-treatment layer comprises
According to still another embodiment of any one of the aspects of the present invention, the surface-treatment layer further comprises at least one saturated surface-treatment agent selected from the group consisting of
According to yet another embodiment of any one of the aspects of the present invention, the surface-treatment layer is present on the calcium carbonate-containing filler material in an amount of from 0.1 to 6 wt.-%, preferably from 0.3 to 5 wt.-%, more preferably from 0.4 to 4 wt.-%, and most preferably from 0.5 to 3 wt.-%, based on the total amount of the surface-treated calcium carbonate-containing filler material.
In one embodiment of any one of the aspects of the present invention, the surface-treated calcium carbonate-containing filler material has
In another embodiment of any one of the aspects of the present invention, the surface-treatment layer comprises the peroxide agent, preferably wherein the peroxide agent is present on the calcium carbonate-containing filler material in an amount from 0.01 to 0.5 wt.-%, preferably from 0.02 to 0.3 wt.-%, more preferably from 0.03 to 0.2 wt.-%, and most preferably from 0.04 to 0.15 wt.-%, based on the total amount of the surface-treated calcium carbonate-containing filler material.
In yet another embodiment of any one of the aspects of the present invention, the surface-treated calcium carbonate-containing filler material is comprised in a treated masterbatch in an amount from 50 to 85 wt.-%, preferably 60 to 85 wt.-%, more preferably 65 to 80 wt.-%, based on the total amount of the masterbatch, wherein the treated masterbatch comprises at least one polyethylene polymer and/or at least one polypropylene polymer, and wherein the peroxide agent is present on the surface of the treated masterbatch in an amount from 0.01 to 0.5 wt.-%, preferably from 0.02 to 0.3 wt.-%, more preferably from 0.03 to 0.2 wt.-%, and most preferably from 0.04 to 0.15 wt.-%, based on the total amount of the surface-treated calcium carbonate-containing filler material.
In still another embodiment of any one of the aspects of the present invention,
According to one embodiment of any of the aspects of the present invention, the filled polymer mixture or filled polymer composition further comprises at least one additive selected from the group consisting of further fillers, preferably selected from the group consisting of talc, mica, kaolin, bentonite or mixtures thereof, UV-absorbers, light stabilizers, processing stabilizers, antioxidants, heat stabilizers, nucleating agents, metal deactivators, impact modifiers, plasticizers, lubricants, rheology modifiers, processing aids, pigments, dyes, optical brighteners, antimicrobials, antistatic agents, slip agents, anti-block agents, coupling agents, dispersants, compatibilizers, oxygen scavengers, acid scavengers, markers, antifogging agents, surface modifiers, flame retardants, blowing agents, smoke suppressors, or mixtures of the foregoing additives, and/or further comprising at least one further polymer preferably selected from the group comprising polystyrene, polyesters, preferably polyethylene terephthalate, polylactic acid, polyhydroxybutyrate and polyethylene-2,5-furandicarboxylate, polyvinyl chloride, polybutadiene, polyacrylonitrile, polymethylmethacrylate, polyamides, polyurethanes, and mixtures thereof.
In one embodiment of the inventive process, step a) of providing the surface-treated calcium carbonate-containing filler material comprises the sub-steps of
In one embodiment of any of the aspects of the present invention, the impact strength of the polymer composition is increased, preferably by at least 10%, more preferably by at least 20%, determined by ISO 179-1eA:2010-11, compared to the same polymer composition not comprising the peroxide agent or compared to the same polymer composition comprising the same calcium carbonate-containing filler material lacking a surface-treatment layer or compared to the same polymer composition not comprising the surface-treated calcium carbonate-containing filler material.
It should be understood that for the purposes of the present invention, the following terms have the following meanings.
The term “surface-treated calcium carbonate-containing filler material” in the meaning of the present invention refers to a material, which has been contacted with a surface-treatment agent such as to obtain a coating layer on at least a part of the surface of the calcium carbonate-containing filler material, wherein the calcium carbonate-containing filler material comprises at least 50 wt.-%, preferably at least 80 wt.-% calcium carbonate, based on the total dry weight of the surface-treated calcium carbonate-containing filler material.
The term “ground natural calcium carbonate” (GNCC) as used herein refers to a particulate material obtained from natural calcium carbonate-containing minerals, such as chalk, limestone, marble or dolomite, or from organic sources, such as eggshells or seashells, which has been processed in a wet and/or dry comminution step, such as crushing and/or grinding, and optionally has been subjected to further steps such as screening and/or fractionation, for example, by a cyclone or a classifier.
A “precipitated calcium carbonate” (PCC) in the present meaning is a synthesized material, obtained by precipitation following a reaction of carbon dioxide and calcium hydroxide (hydrated lime) in an aqueous environment. Alternatively, precipitated calcium carbonate can also be obtained by reacting calcium and carbonate salts, for example calcium chloride and sodium carbonate, in an aqueous environment. PCC may have a vateritic, calcitic or aragonitic crystalline form. PCCs are described, for example, in EP2447213 A1, EP2524898 A1, EP2371766 A1, EP2840065 A1, or WO2013142473 A1.
The “particle size” of the calcium carbonate-containing materials herein is described by its weight distribution of particle sizes dx. Therein, the value dx represents the diameter relative to which x% by weight of the particles have diameters less than dx. This means that, for example, the d20 value is the particle size at which 20 wt.-% of all particles are smaller than that particle size. The d50 value is thus the weight median particle size, i.e. 50 wt.-% of all particles are smaller than that particle size and the d98 value, referred to as top cut, is the particle size at which 98 wt.-% of all particles are smaller than that particle size. The weight median particle size d50 and top cut d98 are measured by the sedimentation method, which is an analysis of sedimentation behaviour in a gravimetric field. The measurement is made with a Sedigraph™ 5100 of Micromeritics Instrument Corporation, USA. The method and the instrument are known to the skilled person and are commonly used to determine particle size distributions.
Throughout the present document, the term “specific surface area” (in m2/g), which is used to define calcium carbonate or other materials, refers to the specific surface area as determined by using the BET method (using nitrogen as adsorbing gas), as measured according to ISO 9277:2010.
For the purposes of the present application, the “volatile onset temperature” is defined as the temperature at which volatiles - including volatiles introduced as a result of common mineral filler preparation steps including grinding, with or without grinding aid agents, beneficiation, with or without flotation aid or other agents, and other pre-treatment agents not expressly listed above, detected according to the thermogravimetric analysis described hereafter - begin to evolve, as observed on a thermogravimetric (TGA) curve, plotting the mass of remaining sample (y-axis) as a function of temperature (x-axis), the preparation and interpretation of such a curve being defined hereafter. TGA analytical methods provide information regarding losses of mass and volatile onset temperatures with great accuracy, and is common knowledge; it is, for example, described in “Principles of Instrumental analysis”, fifth edition, Skoog, Holler, Nieman, 1998 (first edition 1992) in Chapter 31 pages 798 to 800, and in many other commonly known reference works. The thermogravimetric analysis (TGA) may be performed using a Mettler Toledo TGA/DSC3+ 851 based on a sample of 250 ± 50 mg in a 900 µL crucible and scanning temperatures from 25 to 280° C. or 25 to 400° C. at a rate of 20° C./minute under an air flow of 80 ml/min. The skilled man will be able to determine the “volatile onset temperature” by analysis of the TGA curve as follows: the first derivative of the TGA curve is obtained and the inflection points thereon between 150 and 280° C. or 25 to 400° C. are identified. Of the inflection points having a tangential slope value of greater than 45 ° relative to a horizontal line, the one having the lowest associated temperature above 200° C. is identified. The temperature value associated with this lowest temperature inflection point of the first derivative curve is the “volatile onset temperature”. The total weight of the surface treatment agent on the accessible surface area of the filler can be determined by thermogravimetric analysis by mass loss between 105° C. to 400° C.
For the purposes of the present application, the “total volatiles” associated with mineral fillers and evolved over a temperature range of 25 to 280° C. or 25 to 400° C. is characterised according to% mass loss of the mineral filler sample over a temperature range as read on a thermogravimetric (TGA) curve. The “total volatiles” evolved on the TGA curve can be determined using Star® SW 9.01 software. Using this software, the curve is first normalised relative to the original sample weight in order to obtain mass losses in% values relative to the original sample. Thereafter, the temperature range of 25 to 280° C. or 25 to 400° C. is selected and the step horizontal (in German: “Stufe horizontal”) option selected in order to obtain the% mass loss over the selected temperature range.
Unless indicated otherwise, the “residual total moisture content” of a material refers to the percentage of moisture (i.e. water) which may be desorbed from a sample upon heating to 220° C. The “residual total moisture content” is determined according to the Coulometric Karl Fischer measurement method, wherein the filler material is heated to 220° C., and the water content released as vapor and isolated using a stream of nitrogen gas (at 100 ml/min) is determined in a Coulometric Karl Fischer unit (e.g. Mettler-Toledo coulometric KF Titrator C30, combined with Mettler-Toledo oven DO 0337).
The term “moisture pick-up susceptibility” in the meaning of the present invention refers to the amount of moisture adsorbed on the surface of the powder material or surface-treated filler material product and can be determined in mg moisture/g of the dry powder material or surface-treated filler material product after exposure to an atmosphere of 10 and 85% of relative humidity, respectively, for 2.5 hours at a temperature of +23° C. (± 2° C.).
The term “(total) dry weight of the calcium carbonate-containing filler material” is understood to describe a filler material having less than 0.3% by weight of water relative to the filler material weight. The% water (equal to residual total moisture content) is determined as described herein.
As used herein, the term “polymer” generally includes homopolymers and co-polymers such as, for example, block, graft, random and alternating copolymers, as well as blends and modifications thereof. The polymer can be an amorphous polymer, a crystalline polymer, or a semi-crystalline polymer, i.e. a polymer comprising crystalline and amorphous fractions. The degree of crystallinity is specified in percent and can be determined by differential scanning calorimetry (DSC). An amorphous polymer may be characterized by its glass transition temperature and a crystalline polymer may be characterized by its melting point. A semi-crystalline polymer may be characterized by its glass transition temperature and/or its melting point.
For the purposes of the present invention, a “polyethylene polymer” is understood to relate to a polymer, which is derived from at least 50 mol-%, preferably at least 75 mol-%, more preferably at least 90 mol-% polyethylene monomers, based on the total amount of monomers in the polymer. Likewise, a “polypropylene polymer” is understood to designate a polymer, which is derived from at least 50 mol-%, preferably at least 75 mol-%, more preferably at least 90 mol-% polypropylene monomers, based on the total amount of monomers in the polymer.
The expression “isotactic polymer” refers to a polymer, wherein more than 95%, preferably more than 97% of all substituents are located on the same side of the macromolecular backbone.
The term “melt flow rate” (MFR) as used herein refers to the mass of the polymer, given in g/10 min, which is discharged through a defined die under specified temperature and pressure conditions. For polyethylene polymers, the MFR is commonly measured under a load of 2.16 kg at 190° C., according to EN ISO 1133:2011. For polypropylene polymers, the MFR is commonly measured under a load of 2.16 kg at 230° C., according to EN ISO 1133:2011. The MFR is a measure of the viscosity of the polymer, which is mainly influenced by the molecular weight of the polymer, but also by the degree of branching or the polydispersity.
The expression “polydispersity index” (Mw / Mn) as used herein is a measure of the molecular mass distribution and refers to the ratio of the weight-average molar mass and the number-average molar mass of the polymers as determined by gel permeation chromatography (GPC), e.g., according to EN ISO 16014-1:2019.
The term “masterbatch” refers to a composition having a concentration of the surface-treated calcium carbonate-containing filler material that is higher than the concentration of the final filled polymer composition. That is to say, the masterbatch is further diluted, e.g., during step c3) and/or step d) of the process of the present invention, such as to obtain the final filled polymer composition.
For the purposes of the present invention, the term “waste polymers” is understood to refer to polymers originating from plastic waste, i.e., waste comprising or consisting essentially of polymers that have been disposed of, e.g., after having exceeded their service life. In one embodiment, the plastic waste is post-consumer plastic waste. For the purposes of the present invention, the term “post-consumer plastic waste” refers to plastic waste generated by consumers. In another embodiment, the plastic waste is post-industrial plastic waste. For the purposes of the present invention, the term “post-industrial plastic waste” refers to plastic waste generated in the industry or during the manufacture of polymeric articles.
The term “waste polymers” is understood to include “primary plastics”, i.e., plastics that are in their original form when collected, and “secondary plastics”, i.e., plastics that have resulted from the partial degradation of primary plastics.
Plastic waste typically is a mixture of several types of polymeric materials, including, but not limited to polyolefins, such as polyethylene (PE) and polypropylene (PP), polyesters, such as polyethylene terephthalate (PET) and polylactic acid (PLA), polyvinyl chloride (PVC), polystyrene (PS), polyurethanes (PUR), polycarbonates (PC), polyamides (PA), polyimides (PI), and/or polyether ether ketone (PEEK). Furthermore, plastic waste may contain further additives, such as pigments, dyes, antioxidants, flame retardants or fillers, and contaminants. Common contaminants include residues of packaged goods, dirt and/or grease.
Where an indefinite or definite article is used when referring to a singular noun, e.g., “a”, “an” or “the”, this includes a plural of that noun unless anything else is specifically stated.
Where the term “comprising” is used in the present description and claims, it does not exclude other elements. For the purposes of the present invention, the term “consisting of” is considered to be a preferred embodiment of the term “comprising”. If hereinafter a group is defined to comprise at least a certain number of embodiments, this is also to be understood to disclose a group, which preferably consists only of these embodiments.
Whenever the terms “including” or “having” are used, these terms are meant to be equivalent to “comprising” as defined hereinabove.
Terms like “obtainable” or “definable” and “obtained” or “defined” are used interchangeably. This, for example, means that, unless the context clearly dictates otherwise, the term “obtained” does not mean to indicate that, for example, an embodiment must be obtained by, for example, the sequence of steps following the term “obtained” though such a limited understanding is always included by the terms “obtained” or “defined” as a preferred embodiment.
According to one embodiment of the present invention a kit of parts for improving the mechanical properties of a polymer mixture comprising at least one polyethylene polymer and at least one polypropylene polymer is provided. The kit of parts comprises
When in the following reference is made to embodiments or technical details of the inventive kit of parts, it is to be understood that these embodiments or technical details also refer to the inventive filled polymer mixture, the inventive process, the inventive polymer composition, the inventive use and the inventive article.
The inventive kit of parts, the inventive filled polymer mixture, the inventive filled polymer composition, the inventive process, the inventive use and the inventive article make use of a surface-treated calcium carbonate-containing filler material. The surface-treated calcium carbonate-containing filler material comprises
The surface-treated calcium carbonate-containing filler material is formed by contacting the calcium carbonate-containing filler material and the at least one surface-treatment agent.
The calcium carbonate-containing filler material in the meaning of the present invention refers to a material preferably selected from the group consisting of ground natural calcium carbonate (GNCC), precipitated calcium carbonate (PCC) and mixtures thereof, having
Preferably, the calcium carbonate-containing filler material is a GNCC.
According to one embodiment of the present invention, the amount of calcium carbonate in the calcium carbonate-containing filler material is at least 80 wt.-%, e.g. at least 95 wt.-%, preferably between 97 and 100 wt.-%, more preferably between 98.5 and most preferably 99.95 wt.-%, based on the total dry weight of the calcium carbonate-containing filler material.
The calcium carbonate-containing filler material is in the form of a particulate material, and has a particle size distribution as required for the filled polymer composition of the present invention. Thus, the calcium carbonate-containing filler material has a weight median particle size d50 from 0.03 µm to 4.0 µm, preferably from 0.05 µm to 3 µm, more preferably from 0.1 to 2.5 µm, and most preferably from 0.2 to 2.0 µm.
The present inventors found that the particle size of the surface-treated calcium carbonate-containing filler material is important for obtaining the desired improvement of the mechanical properties of the filled polymer composition. Therefore, the particle size of the calcium carbonate-containing filler material is selected accordingly. The weight median particle size should not exceed 4 µm, since the larger particles may induce large voids acting as initiation sites for fracturing. However, the weight median particle size at the same time should not be below 0.03 µm, since the very fine particles tend to form larger aggregates, which cannot be easily deaggregated, e.g., during a surface-treatment step.
Additionally, the calcium carbonate-containing filler material has a top cut (d98) of 30 µm or less, preferably 20 µm or less, more preferably 10 µm or less, and most preferably 7.5 µm or less. It is understood that the top cut of the material is selected such that the particles can be evenly distributed in the filled polymer mixture and the filled polymer composition.
Additionally or alternatively, the calcium carbonate-containing filler material may have a BET specific surface area of from 0.5 to 120 m2/g, preferably from 1 to 50 m2/g, more preferably from 2 to 35 m2/g, and most preferably from 2.5 to 15 m2/g, as measured by the BET method according to ISO 9277:2010.
Additionally or alternatively, the calcium carbonate-containing filler material may have a residual total moisture content of at most 0.3 wt.-%, for example from 0.001 wt.-% to 0.3 wt.-%, preferably of at most 0.2 wt.-%, for example from 0.002 wt.-% to 0.2 wt.-%, more preferably of at most 0.15 wt.-%, for example from 0.0025 wt.-% to 0.15 wt.-%, based on the total dry weight of the calcium carbonate-containing filler material.
According to one embodiment of the present invention, the calcium carbonate-containing filler material has a weight median particle size d50 from 0.03 µm to 4.0 µm and/or a top cut (d98) of 30 µm or less and/or a specific surface area (BET) of from 0.5 to 120 m2/g, as measured by the BET method.
In one embodiment of the present invention, the calcium carbonate-containing filler material is preferably a ground natural calcium carbonate having a median particle size diameter d50 value from 0.03 µm to 4.0 µm, preferably from 0.05 µm to 3 µm, more preferably from 0.1 to 2.5 µm, and most preferably from 0.2 to 2.0 µm. In this case, the calcium carbonate-containing filler material may exhibit a BET specific surface area of from 0.5 to 120 m2/g, preferably of from 1 to 50 m2/g, more preferably of from 2 to 35 m2/g and most preferably of from 2.5 to 15 m2/g, measured by the BET method.
For example, the calcium carbonate-containing filler material may have a median particle size diameter d50 value from 0.1 µm to 2.5 µm, a top cut (d98) of 10 µm or less, more preferably of 7.5 µm or less, and optionally a BET specific surface area of from 1 to 50 m2/g, preferably of from 2 to 35 m2/g, measured by the BET method.
It is preferred that the calcium carbonate-containing filler material is a dry ground material, a material being wet ground and dried or a mixture of the foregoing materials. In general, the grinding step can be carried out with any conventional grinding device, for example, under conditions such that refinement predominantly results from impacts with a secondary body, i.e., in one or more of a ball mill, a rod mill, a vibrating mill, a roll crusher, a centrifugal impact mill, a vertical bead mill an attrition mill, a pin mill, a hammer mill, a pulveriser, a shredder, a de-clumper, a knife cutter, or other such equipment known to the skilled man.
In case the calcium carbonate-containing filler material is a wet ground calcium carbonate-containing filler material, the grinding step may be performed under conditions such that autogenous grinding takes place and/or by horizontal ball milling, and/or other such processes known to the skilled man. It is to be noted that the same grinding methods can be used for dry grinding the calcium carbonate-containing filler material. The wet processed ground calcium carbonate-containing filler material thus obtained may be washed and dewatered by well-known processes, e.g. by flocculation, filtration or forced evaporation prior to drying. The subsequent step of drying may be carried out in a single step such as spray drying, or in at least two steps, e.g. by applying a first heating step to the calcium carbonate-containing filler material in order to reduce the associated moisture content to a level which is not greater than about 0.5 wt.-%, based on the total dry weight of the calcium carbonate-containing filler material. The residual total moisture content of the filler material can be measured by the Karl Fischer coulometric titration method, desorbing the moisture in an oven at 195° C. and passing it continuously into the KF coulometer (Mettler Toledo coulometric KF Titrator C30, combined with Mettler oven DO 0337) using dry N2 at 100 ml/min, e.g. for 10 min. The residual total moisture content may be further reduced by applying a second heating step to the calcium carbonate-containing filler material. In case said drying is carried out by more than one drying steps, the first step may be carried out by heating in a hot current of air, while the second and further drying steps are preferably carried out by an indirect heating in which the atmosphere in the corresponding vessel comprises a surface treatment agent. It is also common that the calcium carbonate-containing filler material is subjected to a beneficiation step (such as a flotation, bleaching or magnetic separation step) to remove impurities.
In one embodiment of the present invention, the calcium carbonate-containing filler material comprises a dry ground calcium carbonate-containing filler material. In another preferred embodiment, the calcium carbonate-containing filler material is a material being wet ground, and subsequently dried.
According to the present invention, the calcium carbonate-containing filler material may have a residual moisture content of at most 0.3 wt.-%, for example from 0.001 to 0.3 wt.-%, based on the total dry weight of the calcium carbonate-containing filler material. Depending on the calcium carbonate-containing filler material, the calcium carbonate-containing filler material may have a residual total moisture content of at most 0.2 wt.-%, for example from 0.002 to 0.2 wt.-%, preferably from 0.01 to 0.2 wt.-% and most preferably from 0.02 to 0.15 wt.-%, based on the total dry weight of the calcium carbonate-containing filler material.
For example, in case a wet ground and spray dried marble is used as calcium carbonate-containing filler material, the residual total moisture content of the calcium carbonate-containing filler material is preferably from 0.01 to 0.3 wt.-%, more preferably from 0.02 to 0.2 wt.-%, and most preferably from 0.04 to 0.15 wt.-%, based on the total dry weight of the calcium carbonate-containing filler material. If a PCC is used as calcium carbonate-containing filler material, the residual total moisture content of the calcium carbonate-containing filler material is preferably in the range from 0.01 to 0.2 wt.-%, more preferably from 0.05 to 0.17 wt.-%, and most preferably from 0.05 to 0.15 wt.-%, based on the total dry weight of the calcium carbonate-containing filler material.
As a non-limiting example, the calcium carbonate-containing filler material may be obtained by a process as described in WO2016110459 A1 or the references cited therein.
According to one embodiment of the present invention, the precipitated calcium carbonate is precipitated calcium carbonate, preferably comprising aragonitic, vateritic or calcitic mineralogical crystal forms or mixtures thereof.
In a preferred embodiment of the present invention, the calcium carbonate-containing filler material comprises a precipitated calcium carbonate having a median particle size diameter d50 value from 0.03 µm to 4.0 µm, preferably from 0.05 µm to 3 µm, more preferably from 0.1 to 2.5 µm, and most preferably from 0.2 to 2.0 µm. In this case, the precipitated calcium carbonate may exhibit a BET specific surface area of from 0.5 to 120 m2/g, preferably of from 1 to 50 m2/g, more preferably of from 2 to 35 m2/g and most preferably of from 2.5 to 15 m2/g, measured by the BET method. For example, the precipitated calcium carbonate may have a median particle size diameter d50 value from 0.2 µm to 2.0 µm, a top cut (d98) of 20 µm or less, more preferably of 10 µm or less, and optionally a BET specific surface area of from 1 to 50 m2/g, preferably of from 2 to 35 m2/g, measured by the BET method.
According to the present invention, the surface-treated calcium carbonate-containing filler material comprises a surface-treatment layer on at least a part of the surface of said calcium carbonate-containing filler material, wherein the surface-treatment layer comprises at least one mono-or di-substituted succinic anhydride comprising at least one unsaturated carbon moiety and/or a salt thereof and/or acid thereof and/or salty reaction products thereof.
The wording “comprising at least one unsaturated carbon moiety” should be understood in that the respective compound may comprise one unsaturated carbon moiety. However, the respective compound may also comprise more than one unsaturated carbon moiety.
For the purposes of the present invention, an “unsaturated carbon moiety” refers to a double or triple bond, for example a carbon-carbon double bond, a carbon-carbon triple bond or a carbon-heteroatom multiple bond. Preferably, the unsaturated carbon moiety is a carbon-carbon double bond. It is appreciated that the unsaturated carbon moiety should be able to react with the peroxide agent, i.e., does not form part of an aromatic system.
The term “succinic anhydride containing compound” refers to a compound containing succinic anhydride. The term “succinic anhydride”, also called dihydro-2,5-furandione, succinic acid anhydride or succinyl oxide, has the molecular formula C4H4O3 and is the acid anhydride of succinic acid.
The term “mono-substituted” succinic anhydride containing compound in the meaning of the present invention refers to a succinic anhydride wherein a hydrogen atom is substituted by another substituent.
The term “di-substituted” succinic anhydride containing compound in the meaning of the present invention refers to a succinic anhydride wherein two hydrogen atoms are substituted by another substituent.
The term “succinic acid containing compound” refers to a compound containing succinic acid. The term “succinic acid” has the molecular formula C4H6O4.
The term “mono-substituted” succinic acid in the meaning of the present invention refers to a succinic acid wherein a hydrogen atom is substituted by another substituent.
The term “di-substituted” succinic acid containing compound in the meaning of the present invention refers to a succinic acid wherein two hydrogen atoms are substituted by another substituent.
The term “succinic acid salt” refers to a compound containing succinic acid, wherein the active acid groups are partially or completely neutralized. The term “partially neutralized” succinic acid salt containing compound refers to a degree of neutralization of the active acid groups in the range from 40 and 95 mol-%, preferably from 50 to 95 mol-%, more preferably from 60 to 95 mol-% and most preferably from 70 to 95 mol-%. The term “completely neutralized” succinic acid salt containing compound refers to a degree of neutralization of the active acid groups of > 95 mol-%, preferably of > 99 mol-%, more preferably of > 99.8 mol-% and most preferably of 100 mol-%. Preferably, the active acid groups are partially or completely neutralized.
The succinic acid salt containing compound comprising at least one unsaturated carbon moiety is preferably a compound selected from the group consisting of sodium, potassium, calcium, magnesium, lithium, strontium, primary amine, secondary amine, tertiary amine and/or ammonium salts thereof, whereby the amine salts are linear or cyclic. It is appreciated that one or both acid groups can be in the salt form, preferably both acid groups are in the salt form.
The term “mono-substituted” succinic acid salt in the meaning of the present invention refers to a succinic acid salt wherein a hydrogen atom is substituted by another substituent.
The term “salty reaction products” in the meaning of the present invention refers to products obtained by contacting the calcium carbonate-containing filler material with a surface-treatment composition, i.e., a composition comprising at least one mono- or di-substituted succinic anhydride comprising at least one unsaturated carbon moiety and/or a salt thereof and/or acid thereof. Said salty reaction products may be formed between e.g. the succinic anhydride and reactive molecules or moieties located at the surface of the calcium carbonate-containing filler material.
In a preferred embodiment, the surface-treatment layer is present on the calcium carbonate-containing filler material in an amount of from 0.1 to 6 wt.-%, preferably from 0.3 to 5 wt.-%, more preferably from 0.4 to 4 wt.-%, and most preferably from 0.5 to 3 wt.-%, based on the total amount of the surface-treated calcium carbonate-containing filler material.
In another preferred embodiment, the surface-treatment layer is present on the calcium carbonate-containing filler material in an amount of from 0.25 to 5 mg/m2, preferably 0.5 to 4.5 mg/m2 and most preferably from 1 to 4 mg/m2, based on the surface area of the calcium carbonate-containing filler material as determined by the BET method.
The present inventors found that the surface-treatment layer renders the calcium carbonate-containing filler more hydrophobic, thus improving its miscibility and dispersibility within the polymeric matrix. Furthermore, without wishing to be bound to any theory, it is believed that the hydrophobic surface-treatment layer interacts with both the polyethylene phase and the polypropylene phase. Furthermore, the at least one unsaturated carbon moiety may constitute reaction sites for the peroxide agent, which facilitate the chemical reaction between the filler material and the polymer phase.
Thus, in a preferred embodiment, the surface-treatment layer comprises
Preferably, the surface-treatment layer comprises the at least one mono- or di-substituted succinic anhydride comprising at least one unsaturated carbon moiety and having a total amount of carbon atoms from C2 to C30 in the substituent and/or an acid and/or salt thereof in an amount from 0.1 to 6 wt.-%, preferably from 0.3 to 5 wt.-%, more preferably from 0.4 to 4 wt.-% and most preferably from 0.5 to 2.5 wt.-%, based on the total amount of the surface-treated calcium carbonate-containing filler material.
Preferably, the surface-treatment layer comprises the grafted polymer comprising at least one succinic anhydride group obtained by grafting maleic anhydride onto a homo- or copolymer comprising butadiene units and optionally styrene units in an amount from 0.1 to 3 wt.-%, preferably from 0.15 to 2 wt.-%, more preferably from 0.2 to 1.5 wt.-%, and most preferably from 0.25 to 1.2 wt.-%, based on the total amount of the surface-treated calcium carbonate-containing filler material.
In still another preferred embodiment, the surface-treatment layer further comprises at least one saturated surface-treatment agent selected from the group consisting of
The term “carboxylic acid and/or salts thereof” refers to carboxylic acids, carboxylic acid salts and their mixtures. The term “carboxylic acid” in the sense of the present invention is understood to refer to a “monocarboxylic acid”, i.e. the carboxylic acid is characterized in that a single carboxyl group is present.
The terms “alkyl” and “aliphatic” in the meaning of the present invention refers to a linear or branched, saturated organic compound composed of carbon and hydrogen. For example, “alkyl carboxylic acids” are composed of linear or branched, saturated hydrocarbon chains containing a pendant carboxylic acid group.
A linear group is understood to be a group, wherein each carbon atom has a direct bond to 1 or 2 other carbon atoms. A branched group is understood to be a group, wherein at least one carbon atom has a direct bond to 3 or 4 other carbon atoms. A saturated group is understood to be a group, which does not contain a carbon-carbon multiple bond, i.e., a carbon-carbon double bond or a carbon-carbon triple bond. A cyclic group is understood to be a group, wherein at least three carbon atoms are linked together in a way such as to form a ring. An acyclic group is understood to be a group, wherein no ring is present.
The term “alkenyl” in the meaning of the present invention refers to a linear or branched, unsaturated organic compound composed of carbon and hydrogen. Said organic compound further contains at least one double bond in the substituent, preferably one double bond. It is appreciated that the term “alkenyl” in the meaning of the present invention includes the cis and trans isomers.
In still another embodiment, the surface-treatment layer comprises
In the following, the surface-treatment agents will be described more in detail.
According to one embodiment, the surface-treatment agent comprises at least one mono- or di-substituted succinic anhydride comprising at least one unsaturated carbon moiety and having a total amount of carbon atoms from C2 to C30 in the substituent and/or an acid and/or salt thereof.
In another embodiment of the present invention, the mono-substituted succinic anhydride compound comprising at least one unsaturated carbon moiety is at least one linear or branched alkenyl mono-substituted succinic anhydride compound comprising unsaturated carbon moieties. For example, the at least one alkenyl mono-substituted succinic anhydride is selected from the group comprising ethenylsuccinic anhydride, propenylsuccinic anhydride, butenylsuccinic anhydride, triisobutenyl succinic anhydride, pentenylsuccinic anhydride, hexenylsuccinic anhydride, heptenylsuccinic anhydride, octenylsuccinic anhydride, nonenylsuccinic anhydride, decenyl succinic anhydride, dodecenyl succinic anhydride, hexadecenyl succinic anhydride, octadecenyl succinic anhydride, and mixtures thereof.
Accordingly, it is appreciated that e.g. the term “hexadecenyl succinic anhydride” comprises linear and branched hexadecenyl succinic anhydride(s). One specific example of linear hexadecenyl succinic anhydride(s) is n-hexadecenyl succinic anhydride such as 14-hexadecenyl succinic anhydride, 13-hexadecenyl succinic anhydride, 12-hexadecenyl succinic anhydride, 11-hexadecenyl succinic anhydride, 10-hexadecenyl succinic anhydride, 9-hexadecenyl succinic anhydride, 8-hexadecenyl succinic anhydride, 7-hexadecenyl succinic anhydride, 6-hexadecenyl succinic anhydride, 5-hexadecenyl succinic anhydride, 4-hexadecenyl succinic anhydride, 3-hexadecenyl succinic anhydride and/or 2-hexadecenyl succinic anhydride. Specific examples of branched hexadecenyl succinic anhydride(s) are 14-methyl-9-pentadecenyl succinic anhydride, 14-methyl-2-pentadecenyl succinic anhydride, 1-hexyl-2-decenyl succinic anhydride and/or iso-hexadecenyl succinic anhydride.
Furthermore, it is appreciated that e.g. the term “octadecenyl succinic anhydride” comprises linear and branched octadecenyl succinic anhydride(s). One specific example of linear octadecenyl succinic anhydride(s) is n-octadecenyl succinic anhydride such as 16-octadecenyl succinic anhydride, 15-octadecenyl succinic anhydride, 14-octadecenyl succinic anhydride, 13-octadecenyl succinic anhydride, 12-octadecenyl succinic anhydride, 11-octadecenyl succinic anhydride, 10-octadecenyl succinic anhydride, 9-octadecenyl succinic anhydride, 8-octadecenyl succinic anhydride, 7-octadecenyl succinic anhydride, 6-octadecenyl succinic anhydride, 5-octadecenyl succinic anhydride, 4-octadecenyl succinic anhydride, 3-octadecenyl succinic anhydride and/or 2-octadecenyl succinic anhydride. Specific examples of branched octadecenyl succinic anhydride(s) are 16-methyl-9-heptadecenyl succinic anhydride, 16-methyl-7-heptadecenyl succinic anhydride, 1-octyl-2-decenyl succinic anhydride and/or iso-octadecenyl succinic anhydride.
In one embodiment of the present invention, the at least one alkenyl mono-substituted succinic anhydride is selected from the group comprising hexenylsuccinic anhydride, octenylsuccinic anhydride, hexadecenyl succinic anhydride, octadecenyl succinic anhydride, and mixtures thereof.
In one embodiment of the present invention, the mono-substituted succinic anhydride compound comprising at least one unsaturated carbon moiety is one alkenyl mono-substituted succinic anhydride. For example, the one alkenyl mono-substituted succinic anhydride is hexenylsuccinic anhydride. Alternatively, the one alkenyl mono-substituted succinic anhydride is octenylsuccinic anhydride. Alternatively, the one alkenyl mono-substituted succinic anhydride is hexadecenyl succinic anhydride. For example, the one alkenyl mono-substituted succinic anhydride is linear hexadecenyl succinic anhydride such as n-hexadecenyl succinic anhydride or branched hexadecenyl succinic anhydride such as 1-hexyl-2-decenyl succinic anhydride. Alternatively, the one alkenyl mono-substituted succinic anhydride is octadecenyl succinic anhydride. For example, the one alkyl mono-substituted succinic anhydride is linear octadecenyl succinic anhydride such as n-octadecenyl succinic anhydride or branched octadecenyl succinic anhydride such iso-octadecenyl succinic anhydride, or 1-octyl-2-decenyl succinic anhydride.
In one embodiment of the present invention, the one alkenyl mono-substituted succinic anhydride is linear octadecenyl succinic anhydride such as n-octadecenyl succinic anhydride. In another embodiment of the present invention, the one alkenyl mono-substituted succinic anhydride is linear octenylsuccinic anhydride such as n-octenylsuccinic anhydride.
In one embodiment of the present invention, the mono-substituted succinic anhydride compound comprising at least one unsaturated carbon moiety is a mixture of two or more kinds of alkenyl mono-substituted succinic anhydrides. For example, the mono-substituted succinic anhydride compound comprising at least one unsaturated carbon moiety is a mixture of two or three kinds of alkenyl mono-substituted succinic anhydrides.
If the mono-substituted succinic anhydride compound comprising at least one unsaturated carbon moiety is a mixture of two or more kinds of alkenyl mono-substituted succinic anhydrides, one alkenyl mono-substituted succinic anhydride is linear or branched octadecenyl succinic anhydride, while each further alkenyl mono-substituted succinic anhydride is selected from ethenylsuccinic anhydride, propenylsuccinic anhydride, butenylsuccinic anhydride, pentenylsuccinic anhydride, hexenylsuccinic anhydride, heptenylsuccinic anhydride, nonenylsuccinic anhydride, hexadecenyl succinic anhydride and mixtures thereof. For example, the mono-substituted succinic anhydride compound comprising at least one unsaturated carbon moiety is a mixture of two or more kinds of alkenyl mono-substituted succinic anhydrides, wherein one alkenyl mono-substituted succinic anhydride is linear octadecenyl succinic anhydride and each further alkenyl mono-substituted succinic anhydride is selected from ethenylsuccinic anhydride, propenylsuccinic anhydride, butenylsuccinic anhydride, pentenylsuccinic anhydride, hexenylsuccinic anhydride, heptenylsuccinic anhydride, nonenylsuccinic anhydride, hexadecenyl succinic anhydride and mixtures thereof. Alternatively, the mono-substituted succinic anhydride compound comprising at least one unsaturated carbon moiety is a mixture of two or more kinds of alkenyl mono-substituted succinic anhydrides, wherein one alkenyl mono-substituted succinic anhydride is branched octadecenyl succinic anhydride and each further alkenyl mono-substituted succinic anhydride is selected from ethenylsuccinic anhydride, propenylsuccinic anhydride, butenylsuccinic anhydride, pentenylsuccinic anhydride, hexenylsuccinic anhydride, heptenylsuccinic anhydride, nonenylsuccinic anhydride, hexadecenyl succinic anhydride and mixtures thereof.
For example, the mono-substituted succinic anhydride compound comprising at least one unsaturated carbon moiety is a mixture of two or more kinds of alkenyl mono-substituted succinic anhydrides comprising one or more hexadecenyl succinic anhydride, like linear or branched hexadecenyl succinic anhydride(s), and one or more octadecenyl succinic anhydride, like linear or branched octadecenyl succinic anhydride(s).
In one embodiment of the present invention, the mono-substituted succinic anhydride compound comprising at least one unsaturated carbon moiety is a mixture of two or more kinds of alkenyl mono-substituted succinic anhydrides comprising linear hexadecenyl succinic anhydride(s) and linear octadecenyl succinic anhydride(s). Alternatively, the mono-substituted succinic anhydride compound comprising at least one unsaturated carbon moiety is a mixture of two or more kinds of alkenyl mono-substituted succinic anhydrides comprising branched hexadecenyl succinic anhydride(s) and branched octadecenyl succinic anhydride(s). For example, the one or more hexadecenyl succinic anhydride is linear hexadecenyl succinic anhydride like n-hexadecenyl succinic anhydride and/or branched hexadecenyl succinic anhydride like 1-hexyl-2-decenyl succinic anhydride. Additionally or alternatively, the one or more octadecenyl succinic anhydride is linear octadecenyl succinic anhydride like n-octadecenyl succinic anhydride and/or branched octadecenyl succinic anhydride like iso-octadecenyl succinic anhydride and/or 1-octyl-2-decenyl succinic anhydride.
If the mono-substituted succinic anhydride compound comprising at least one unsaturated carbon moiety is a mixture of two or more kinds of alkenyl mono-substituted succinic anhydrides, it is appreciated that one alkenyl mono-substituted succinic anhydride is present in an amount of from 20 to 60 wt.-% and preferably of from 30 to 50 wt.-%, based on the total weight of the mono-substituted succinic anhydride provided.
For example, if the mono-substituted succinic anhydride compound comprising at least one unsaturated carbon moiety is a mixture of two or more kinds of alkenyl mono-substituted succinic anhydrides comprising one or more hexadecenyl succinic anhydride(s), like linear or branched hexadecenyl succinic anhydride(s), and one or more octadecenyl succinic anhydride(s), like linear or branched hexadecenyl succinic anhydride(s), it is preferred that the one or more octadecenyl succinic anhydride(s) is present in an amount of from 20 to 60 wt.-% and preferably of from 30 to 50 wt.-%, based on the total weight of the mono-substituted succinic anhydride.
It is also appreciated that the mono-substituted succinic anhydride compound comprising at least one unsaturated carbon moiety may be a mixture of alkyl mono-substituted succinic anhydrides and alkenyl mono-substituted succinic anhydrides.
In a preferred embodiment, the at least one mono- or di-substituted succinic anhydride comprising at least one unsaturated carbon moiety and having a total amount of carbon atoms from C2 to C30 in the substituent and/or an acid and/or salt thereof does not comprise a terminal double bond. Thus, the at least one mono- or di-substituted succinic anhydride comprising at least one unsaturated carbon moiety and having a total amount of carbon atoms from C2 to C30 in the substituent and/or an acid and/or salt thereof comprises an internal double bond. For the purposes of the present invention, a “terminal double bond” is understood to be a moiety of the formula H2C=CR1R2, wherein R1 is an organyl group and R2 is H or an organyl group. An “internal double bond” is understood to be a moiety of the formula R1C(H)=CR2R3, wherein R1 is an organyl group, R3 is an organyl group and R2 is H or an organyl group.
In another embodiment, the surface-treatment agent may be a mono-substituted succinic acid compound comprising at least one unsaturated carbon moiety or a mono-substituted succinic acid salt compound comprising at least one unsaturated carbon moiety, wherein the mono-substituted succinic acid compound comprising at least one unsaturated carbon moiety or the mono-substituted succinic acid salt compound comprising at least one unsaturated carbon moiety is derived from the mono-substituted succinic anhydride compound comprising at least one unsaturated carbon moiety as described hereinabove.
In yet another embodiment, the surface-treatment agent is a grafted polymer comprising at least one succinic anhydride group obtained by grafting maleic anhydride onto a homo- or copolymer comprising butadiene units and optionally styrene units and/or an acid and/or salt thereof, preferably a grafted polymer comprising at least one succinic anhydride group obtained by grafting maleic anhydride onto a homopolymer comprising butadiene units and/or an acid and/or salt thereof.
The grafted polymer preferably has
The term “grafted polymer” means that a succinic anhydride is obtained by reaction of a polymer comprising a carbon-carbon double bond with the double bond of maleic anhydride. Thus, the term “grafted polymer comprising at least one succinic anhydride group obtained by grafting maleic anhydride onto a homo- or copolymer comprising butadiene units and optionally styrene units” refers to a polybutadiene homopolymer and a polybutadiene-styrene copolymer each bearing succinic anhydride moieties formed from the reaction of a carbon-carbon double bond with the double bond of maleic anhydride, respectively.
The term “anhydride equivalent weight” refers to the number average molecular weight Mn measured by gel permeation chromatography divided by the number of anhydride groups per chain.
For example, the grafted polymer may have a number average molecular weight Mn measured by gel permeation chromatography from 1000 to 20000 g/mol, preferably from 1400 to 15000 g/mol, more preferably from 2000 to 10000 g/mol, an acid number in the range from 20 to 200 meq KOH per g of grafted polymer, preferably 30 to 150 meq KOH / g, measured according to ASTM D974-14, and a molar amount of 1,2-vinyl groups in the range from 10 to 60 mol-%, preferably 15 to 40 mol-%. In another embodiment, the grafted polymer may have a number average molecular weight Mn measured by gel permeation chromatography from 2000 to 5000 g/mol, an acid number in the range from 30 to 100 meq KOH / g, measured according to ASTM D974-14, and a molar amount of 1,2-vinyl groups in the range from 15 to 40 mol-%.
In one embodiment of the present invention, the salt of the grafted polymer may be selected from the group comprising sodium salts, potassium salts, calcium salts, magnesium salts, lithium salts, strontium salts, primary amine salts, secondary amine salts, tertiary amine salts and/or ammonium salts thereof, and preferably is selected from the group consisting of sodium salts, potassium salts, calcium salts and/or magnesium salts thereof.
In a preferred embodiment of the present invention, the surface-treatment agent is a salt of a grafted polymer comprising at least one succinic anhydride group obtained by grafting maleic anhydride onto a homopolymer comprising butadiene units selected from the group consisting of sodium, potassium, calcium, magnesium, lithium, strontium, primary amine, secondary amine, tertiary amine and/or ammonium salts thereof, preferably selected from the group consisting of sodium, potassium, calcium and/or magnesium salts thereof. More preferably, the salt of the grafted polymer comprising at least one succinic anhydride group obtained by grafting maleic anhydride onto a homopolymer comprising butadiene units has a number average molecular weight Mn measured by gel permeation chromatography from 1000 to 20000 g/mol, preferably from 1400 to 15000 g/mol, more preferably from 2000 to 10000 g/mol, an acid number in the range from 20 to 200 meq KOH per g of the grafted polymer, preferably 30 to 150 meq KOH / g, measured according to ASTM D974-14, and a molar amount of 1,2-vinyl groups in the range from 10 to 60 mol-%, preferably 15 to 40 mol-%.
The salt of the grafted polymer may be obtained by hydrolysis and partial or full neutralization from the corresponding anhydride, e.g., by treatment of the grafted polymer comprising at least one succinic anhydride group obtained by grafting maleic anhydride onto a homo- or copolymer comprising butadiene units and optionally styrene units and/or acid thereof with a base, preferably sodium hydroxide or an aqueous solution of sodium hydroxide.
Thus, it is to be understood that the acid or salt of the grafted polymer comprising at least one succinic anhydride group obtained by grafting maleic anhydride onto a homopolymer comprising butadiene units is preferably derivable by hydrolysis from a grafted polymer comprising at least one succinic anhydride group obtained by grafting maleic anhydride onto a homopolymer comprising butadiene units having
The surface-treatment composition may comprise, preferably consist of a grafted polymer comprising at least one succinic anhydride group obtained by grafting maleic anhydride onto a homo-or copolymer comprising butadiene units and optionally styrene units and/or an acid and/or salt thereof, preferably a grafted polymer comprising at least one succinic anhydride group obtained by grafting maleic anhydride onto a homopolymer comprising butadiene units and/or an acid and/or salt thereof. Thus, the surface-treatment layer of the porous filler may be formed by contacting the filler material with said surface-treatment composition in an amount from 0.1 to 3 wt.-%, preferably from 0.15 to 2 wt.-%, more preferably from 0.2 to 1.5 wt.-%, and most preferably from 0.25 to 1.2 wt.-%, based on the total amount of the surface-treated calcium carbonate-containing filler material.
For example, the surface-treatment layer on at least a part of the surface of the calcium carbonate-containing filler material may be formed by contacting the calcium carbonate-containing filler material with the grafted polymer comprising at least one succinic anhydride group obtained by grafting maleic anhydride onto a homopolymer comprising butadiene units, or the grafted polymer comprising at least one succinic anhydride group obtained by grafting maleic anhydride onto a homopolymer comprising butadiene units having a number average molecular weight Mn measured by gel permeation chromatography from 1000 to 20000 g/mol, preferably from 1400 to 15000 g/mol, more preferably from 2000 to 10000 g/mol, an acid number in the range from 20 to 200 meq KOH per g of grafted polymer, preferably 30 to 150 meq KOH / g, measured according to ASTM D974-14, and/or a molar amount of 1,2-vinyl groups in the range from 10 to 60 mol-%, preferably 15 to 40 mol-%, in an amount from 0.1 to 3 wt.-%, preferably from 0.15 to 2 wt.-%, more preferably from 0.2 to 1.5 wt.-%, and most preferably from 0.2 to 1.2 wt.-%, based on the total amount of the surface-treated calcium carbonate-containing filler material.
According to one embodiment of the present invention, the surface-treatment layer further comprises a saturated surface-treatment agent, which is a phosphoric acid ester blend of one or more phosphoric acid mono-ester and/or salts thereof and/or one or more phosphoric acid di-ester and/or salts thereof and/or salty reaction products thereof.
For example, said blend comprises phosphoric acid in an amount of ≤ 8 mol.-%, preferably of ≤ 6 mol.-%, and more preferably of ≤ 4 mol.-%, like from 0.1 to 4 mol.-%, based on the molar sum of the compounds in the blend.
The term “phosphoric acid mono-ester” in the meaning of the present invention refers to an o-phosphoric acid molecule mono-esterified with one alcohol molecule selected from unsaturated, branched or linear, aliphatic or aromatic alcohols having a total amount of carbon atoms from C6 to C30, preferably from C8 to C22, more preferably from C8 to C20 and most preferably from C8 to C18 in the alcohol substituent.
The term “phosphoric acid di-ester” in the meaning of the present invention refers to an o-phosphoric acid molecule di-esterified with two alcohol molecules selected from the same or different, unsaturated, branched or linear, aliphatic or aromatic alcohols having a total amount of carbon atoms from C6 to C30, preferably from C8 to C22, more preferably from C8 to C20 and most preferably from C8 to C18 in the alcohol substituent.
In one embodiment of the present invention, the one or more phosphoric acid mono-ester consists of an o-phosphoric acid molecule esterified with one alcohol selected from saturated, branched or linear, aliphatic or aromatic alcohols having a total amount of carbon atoms from C6 to C30 in the alcohol substituent. For example, the one or more phosphoric acid mono-ester consists of an o-phosphoric acid molecule esterified with one alcohol selected from saturated, branched or linear, aliphatic or aromatic alcohols having a total amount of carbon atoms from C8 to C22, more preferably from C8 to C20 and most preferably from C8 to C18 in the alcohol substituent.
Alkyl esters of phosphoric acid are well known in the industry especially as surfactants, lubricants and antistatic agents (Die Tenside; Kosswig und Stache, Carl Hanser Verlag München, 1993).
The synthesis of alkyl esters of phosphoric acid by different methods and the surface treatment of minerals with alkyl esters of phosphoric acid are well known by the skilled man, e.g. from Pesticide Formulations and Application Systems: 17th Volume; Collins HM, Hall FR, Hopkinson M, STP1268; Published: 1996, US3897519 A, US4921990 A, US4350645 A, US6710199 B2, US4126650 A, US5554781 A, EP1092000 B1 and WO2008/023076 A1.
In one embodiment of the present invention, the one or more phosphoric acid mono-ester consists of an o-phosphoric acid molecule esterified with one alcohol selected from saturated and linear and aliphatic alcohols having a total amount of carbon atoms from C6 to C30, preferably from C8 to C22, more preferably from C8 to C20 and most preferably from C8 to C18 in the alcohol substituent. Alternatively, the one or more phosphoric acid mono-ester consists of an o-phosphoric acid molecule esterified with one alcohol selected from saturated and branched and aliphatic alcohols having a total amount of carbon atoms from C6 to C30, preferably from C8 to C22, more preferably from C8 to C20 and most preferably from C8 to C18 in the alcohol substituent.
In one embodiment of the present invention, the one or more phosphoric acid mono-ester is selected from the group comprising hexyl phosphoric acid mono-ester, heptyl phosphoric acid mono-ester, octyl phosphoric acid mono-ester, 2-ethylhexyl phosphoric acid mono-ester, nonyl phosphoric acid mono-ester, decyl phosphoric acid mono-ester, undecyl phosphoric acid mono-ester, dodecyl phosphoric acid mono-ester, tetradecyl phosphoric acid mono-ester, hexadecyl phosphoric acid mono-ester, heptylnonyl phosphoric acid mono-ester, octadecyl phosphoric acid mono-ester, 2-octyl-1-decylphosphoric acid mono-ester, 2-octyl-1-dodecylphosphoric acid mono-ester and mixtures thereof.
For example, the one or more phosphoric acid mono-ester is selected from the group comprising 2-ethylhexyl phosphoric acid mono-ester, hexadecyl phosphoric acid mono-ester, heptylnonyl phosphoric acid mono-ester, octadecyl phosphoric acid mono-ester, 2-octyl-1-decylphosphoric acid mono-ester, 2-octyl-1-dodecylphosphoric acid mono-ester and mixtures thereof. In one embodiment of the present invention, the one or more phosphoric acid mono-ester is 2-octyl-1-dodecylphosphoric acid mono-ester.
It is appreciated that the expression “one or more” phosphoric acid di-ester means that one or more kinds of phosphoric acid di-ester may be present in the treatment layer of the surface-treated material product and/or the phosphoric acid ester blend.
Accordingly, it should be noted that the one or more phosphoric acid di-ester may be one kind of phosphoric acid di-ester. Alternatively, the one or more phosphoric acid di-ester may be a mixture of two or more kinds of phosphoric acid di-ester. For example, the one or more phosphoric acid di-ester may be a mixture of two or three kinds of phosphoric acid di-ester, like two kinds of phosphoric acid di-ester.
In one embodiment of the present invention, the one or more phosphoric acid di-ester consists of an o-phosphoric acid molecule esterified with two alcohols selected from saturated, branched or linear, aliphatic or aromatic alcohols having a total amount of carbon atoms from C6 to C30 in the alcohol substituent. For example, the one or more phosphoric acid di-ester consists of an o-phosphoric acid molecule esterified with two fatty alcohols selected from saturated, branched or linear, aliphatic or aromatic alcohols having a total amount of carbon atoms from C8 to C22, more preferably from C8 to C20 and most preferably from C8 to C18 in the alcohol substituent.
It is appreciated that the two alcohols used for esterifying the phosphoric acid may be independently selected from the same or different saturated, branched or linear, aliphatic or aromatic alcohols having a total amount of carbon atoms from C6 to C30 in the alcohol substituent. In other words, the one or more phosphoric acid di-ester may comprise two substituents being derived from the same alcohols or the phosphoric acid di-ester molecule may comprise two substituents being derived from different alcohols.
In one embodiment of the present invention, the one or more phosphoric acid di-ester consists of an o-phosphoric acid molecule esterified with two alcohols selected from the same or different, saturated and linear or branched and aliphatic alcohols having a total amount of carbon atoms from C6 to C30 in the alcohol substituent. For example, the one or more phosphoric acid di-ester consists of an o-phosphoric acid molecule esterified with two alcohols selected from the same or different, saturated and linear or branched and aliphatic alcohols having a total amount of carbon atoms from C8 to C22, more preferably from C8 to C20 and most preferably from C8 to C18 in the alcohol substituent.
In one embodiment of the present invention, the one or more phosphoric acid di-ester consists of an o-phosphoric acid molecule esterified with two alcohols selected from the same or different, saturated and linear and aliphatic alcohols having a total amount of carbon atoms from C6 to C30, preferably from C8 to C22, more preferably from C8 to C20 and most preferably from C8 to C18 in the alcohol substituent. Alternatively, the one or more phosphoric acid di-ester consists of an o-phosphoric acid molecule esterified with two alcohols selected from the same or different, saturated and branched and aliphatic alcohols having a total amount of carbon atoms from C6 to C30, preferably from C8 to C22, more preferably from C8 to C20 and most preferably from C8 to C18 in the alcohol substituent.
In one embodiment of the present invention, the one or more phosphoric acid di-ester is selected from the group comprising hexyl phosphoric acid di-ester, heptyl phosphoric acid di-ester, octyl phosphoric acid di-ester, 2-ethylhexyl phosphoric acid di-ester, nonyl phosphoric acid di-ester, decyl phosphoric acid di-ester, undecyl phosphoric acid di-ester, dodecyl phosphoric acid di-ester, tetradecyl phosphoric acid di-ester, hexadecyl phosphoric acid di-ester, heptylnonyl phosphoric acid di-ester, octadecyl phosphoric acid di-ester, 2-octyl-1-decylphosphoric acid di-ester, 2-octyl-1-dodecylphosphoric acid di-ester and mixtures thereof.
For example, the one or more phosphoric acid di-ester is selected from the group comprising 2-ethylhexyl phosphoric acid di-ester, hexadecyl phosphoric acid di-ester, heptylnonyl phosphoric acid di-ester, octadecyl phosphoric acid di-ester, 2-octyl-1-decylphosphoric acid di-ester, 2-octyl-1-dodecylphosphoric acid di-ester and mixtures thereof. In one embodiment of the present invention, the one or more phosphoric acid di-ester is 2-octyl-1-dodecylphosphoric acid di-ester.
In one embodiment of the present invention, the one or more phosphoric acid mono-ester is selected from the group comprising 2-ethylhexyl phosphoric acid mono-ester, hexadecyl phosphoric acid mono-ester, heptylnonyl phosphoric acid mono-ester, octadecyl phosphoric acid mono-ester, 2-octyl-1-decylphosphoric acid mono-ester, 2-octyl-1-dodecylphosphoric acid mono-ester and mixtures thereof and the one or more phosphoric acid di-ester is selected from the group comprising 2-ethylhexyl phosphoric acid di-ester, hexadecyl phosphoric acid di-ester, heptylnonyl phosphoric acid di-ester, octadecyl phosphoric acid di-ester, 2-octyl-1-decylphosphoric acid di-ester, 2-octyl-1-dodecylphosphoric acid di-ester and mixtures thereof.
Additionally or alternatively, the surface treatment agent is a salt of a phosphoric acid ester. In one embodiment, the salt of a phosphoric acid ester may further comprise minor amounts of a salt of phosphoric acid.
The term “salt of phosphoric acid ester” refers to a phosphoric acid ester, wherein the active acid group(s) is/are partially or completely neutralized. The term “partially neutralized” phosphoric acid esters refers to a degree of neutralization of the active acid group(s) in the range from 40 and 95 mol-%, preferably from 50 to 95 mol-%, more preferably from 60 to 95 mol-% and most preferably from 70 to 95 mol-%. The term “completely neutralized” phosphoric acid esters refers to a degree of neutralization of the active acid group(s) of > 95 mol-%, preferably of > 99 mol-%, more preferably of > 99.8 mol-% and most preferably of 100 mol-%. Preferably, the active acid group(s) is/are partially or completely neutralized.
The salt of phosphoric acid ester is preferably a compound selected from the group consisting of sodium, potassium, calcium, magnesium, lithium, strontium, primary amine, secondary amine, tertiary amine and/or ammonium salts thereof, whereby the amine salts are linear or cyclic.
According to another embodiment of the present invention, the surface-treatment layer further comprises a saturated surface-treatment agent, which is at least one saturated aliphatic linear or branched carboxylic acid and/or salts thereof, preferably at least one aliphatic carboxylic acid having a total amount of carbon atoms from C4 to C24 and/or a salt thereof, more preferably at least one aliphatic carboxylic acid having a total amount of carbon atoms from C12 to C20 and/or a salt thereof, most preferably at least one aliphatic carboxylic acid having a total amount of carbon atoms from C16 to C18 and/or a salt thereof and/or salty reaction products thereof.
The aliphatic carboxylic acid in the meaning of the present invention may be selected from one or more linear chain, branched chain, saturated, and/or alicyclic carboxylic acids. The aliphatic carboxylic acid is a monocarboxylic acid, i.e. the aliphatic carboxylic acid is characterized in that a single carboxyl group is present. Said carboxyl group is placed at the end of the carbon skeleton.
In one embodiment of the present invention, the aliphatic linear or branched carboxylic acid and/or salt thereof is selected from saturated unbranched carboxylic acids, preferably selected from the group of carboxylic acids consisting of pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, nonadecanoic acid, arachidic acid, heneicosylic acid, behenic acid, tricosylic acid, lignoceric acid, their salts, their anhydrides and mixtures thereof.
In another embodiment of the present invention, the aliphatic linear or branched carboxylic acid and/or salt thereof is selected from the group consisting of octanoic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid and mixtures thereof. Preferably, the aliphatic carboxylic acid is selected from the group consisting of myristic acid, palmitic acid, stearic acid, their salts, their anhydrides and mixtures thereof.
Preferably, the aliphatic carboxylic acid and/or a salt or anhydride thereof is stearic acid and/or a stearic acid salt or stearic anhydride.
According to another embodiment of the present invention, the surface-treatment layer further comprises a saturated surface-treatment agent, which is at least one mono-substituted succinic anhydride consisting of succinic anhydride mono-substituted with a group selected from a linear, branched, aliphatic and cyclic group having a total amount of carbon atoms from C2 to C30 in the substituent and/or salts thereof and/or salty reaction products thereof.
Accordingly, it should be noted that the at least one mono-substituted succinic anhydride may be one kind of mono-substituted succinic anhydride. Alternatively, the at least one mono-substituted succinic anhydride may be a mixture of two or more kinds of mono-substituted succinic anhydride. For example, the at least one mono-substituted succinic anhydride may be a mixture of two or three kinds of mono-substituted succinic anhydride, like two kinds of mono-substituted succinic anhydride.
In one embodiment of the present invention, the at least one mono-substituted succinic anhydride is one kind of mono-substituted succinic anhydride.
It is appreciated that the at least one mono-substituted succinic anhydride represents a surface treatment agent and consists of succinic anhydride mono-substituted with a group selected from any linear, branched, aliphatic, and cyclic group having a total amount of carbon atoms from C2 to C30 in the substituent.
In one embodiment of the present invention, the at least one mono-substituted succinic anhydride consists of succinic anhydride mono-substituted with a group selected from a linear, branched, aliphatic, and cyclic group having a total amount of carbon atoms from C3 to C20 in the substituent. For example, the at least one mono-substituted succinic anhydride consists of succinic anhydride mono-substituted with a group selected from a linear, branched, aliphatic, and cyclic group having a total amount of carbon atoms from C4 to C18 in the substituent.
In one embodiment of the present invention, the at least one mono-substituted succinic anhydride consists of succinic anhydride mono-substituted with one group being a linear and aliphatic group having a total amount of carbon atoms from C2 to C30, preferably from C3 to C20 and most preferably from C4 to C18 in the substituent. Additionally or alternatively, the at least one mono-substituted succinic anhydride consists of succinic anhydride mono-substituted with one group being a branched and aliphatic group having a total amount of carbon atoms from C2 to C30, preferably from C3 to C20 and most preferably from C4 to C18 in the substituent.
Thus, it is preferred that the at least one mono-substituted succinic anhydride consists of succinic anhydride mono-substituted with one group being a linear or branched, alkyl group having a total amount of carbon atoms from C2 to C30, preferably from C3 to C20 and most preferably from C4 to C18 in the substituent.
For example, the at least one mono-substituted succinic anhydride consists of succinic anhydride mono-substituted with one group being a linear alkyl group having a total amount of carbon atoms from C2 to C30, preferably from C3 to C20 and most preferably from C4 to C18 in the substituent. Additionally or alternatively, the at least one mono-substituted succinic anhydride consists of succinic anhydride mono-substituted with one group being a branched alkyl group having a total amount of carbon atoms from C2 to C30, preferably from C3 to C20 and most preferably from C4 to C18 in the substituent.
In one embodiment of the present invention, the at least one mono-substituted succinic anhydride is at least one linear or branched alkyl mono-substituted succinic anhydride. For example, the at least one alkyl mono-substituted succinic anhydride is selected from the group comprising ethylsuccinic anhydride, propylsuccinic anhydride, butylsuccinic anhydride, triisobutyl succinic anhydride, pentylsuccinic anhydride, hexylsuccinic anhydride, heptylsuccinic anhydride, octylsuccinic anhydride, nonylsuccinic anhydride, decyl succinic anhydride, dodecyl succinic anhydride, hexadecanyl succinic anhydride, octadecanyl succinic anhydride, and mixtures thereof.
Accordingly, it is appreciated that, e.g., the term “butylsuccinic anhydride” comprises linear and branched butylsuccinic anhydride(s). One specific example of linear butylsuccinic anhydride(s) is n-butylsuccinic anhydride. Specific examples of branched butylsuccinic anhydride(s) are iso-butylsuccinic anhydride, sec-butylsuccinic anhydride and/or tert-butylsuccinic anhydride.
Furthermore, it is appreciated that, e.g., the term “hexadecanyl succinic anhydride” comprises linear and branched hexadecanyl succinic anhydride(s).
In one embodiment of the present invention, the at least one alkyl mono-substituted succinic anhydride is selected from the group comprising butylsuccinic anhydride, hexylsuccinic anhydride, heptylsuccinic anhydride, octylsuccinic anhydride, hexadecanyl succinic anhydride, octadecanyl succinic anhydride, and mixtures thereof.
In one embodiment of the present invention, the at least one mono-substituted succinic anhydride is one kind of alkyl mono-substituted succinic anhydride. For example, the one alkyl mono-substituted succinic anhydride is butylsuccinic anhydride. Alternatively, the one alkyl mono-substituted succinic anhydride is hexylsuccinic anhydride. Alternatively, the one alkyl mono-substituted succinic anhydride is heptylsuccinic anhydride or octylsuccinic anhydride. Alternatively, the one alkyl mono-substituted succinic anhydride is hexadecanyl succinic anhydride. For example, the one alkyl mono-substituted succinic anhydride is linear hexadecanyl succinic anhydride such as n-hexadecanyl succinic anhydride or branched hexadecanyl succinic anhydride such as 1-hexyl-2-decanyl succinic anhydride. Alternatively, the one alkyl mono-substituted succinic anhydride is octadecanyl succinic anhydride. For example, the one alkyl mono-substituted succinic anhydride is linear octadecanyl succinic anhydride such as n-octadecanyl succinic anhydride or branched octadecanyl succinic anhydride such as iso-octadecanyl succinic anhydride or 1-octyl-2-decanyl succinic anhydride.
In one embodiment of the present invention, the one alkyl mono-substituted succinic anhydride is butylsuccinic anhydride such as n-butylsuccinic anhydride.
In one embodiment of the present invention, the at least one mono-substituted succinic anhydride is a mixture of two or more kinds of alkyl mono-substituted succinic anhydrides. For example, the at least one mono-substituted succinic anhydride is a mixture of two or three kinds of alkyl mono-substituted succinic anhydrides.
According to another embodiment of the present invention, the surface-treatment layer further comprises a saturated surface-treatment agent, which is at least one polydialkylsiloxane and/or reaction products thereof.
Preferred polydialkylsiloxanes are described e.g. in US20040097616 A1. Most preferred are polydialkylsiloxanes selected from the group consisting of polydimethylsiloxane, preferably dimethicone, polydiethylsiloxane and polymethylphenylsiloxane and/or mixtures thereof.
For example, the at least one polydialkylsiloxane is preferably a polydimethylsiloxane (PDMS).
According to yet another embodiment of the present invention, the surface-treatment layer further comprises a saturated surface-treatment agent, which is at least one trialkoxysilane and/or reaction products thereof. A trialkyoxysilane is represented by the formula R5-Si(OR4)3. Therein, the substituent R5 represents any kind of saturated substituent, i.e., any branched, linear or cyclic alkane moiety having a total amount of carbon atoms from C1 to C30, such as a methyl, ethyl, propyl, allyl, butyl, butenyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, phenyl or benzyl group moiety, which optionally comprises a further substituent. The further substituent may be selected from the group consisting of a hydroxyl group, an alkoxy group, an acyloxy group, an acryloxy group, a methacryloxy group, an ethacryloxy group, a carboxyl group, an epoxy group, an anhydride group, an ester group, an aldehyde group, an amino group, an ureido group, an azide group, a halogen group, a phosphonate group, a phosphine group, a sulfur-containing group, an isocyanate group or masked isocyanate group, a phenyl group, a benzyl group, and a benzoyl group, and preferably is selected from the group consisting of an amino group and a sulfur-containing group. Preferably, the trialkoxysilane is substituted with a group R5 selected from a linear, branched, aliphatic and cyclic group having a total amount of carbon atoms from C4 to C18 in the substituent, such as butyl, butenyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, or octadecyl.
OR4 is a hydrolyzable group, wherein substituent R4 represents any saturated or unsaturated, branched, linear, cyclic or aromatic moiety from having a total amount of carbon atoms from C1 to C30, such as a methyl, ethyl, propyl, allyl, butyl, butenyl, phenyl or benzyl group. According to a preferred embodiment, R4 is a linear alkyl group having a total amount of carbon atoms from C1 to C15, preferably from C1 to C8 and most preferably from C1 to C2. According to an exemplified embodiment of the present invention the hydrolysable alkoxy group is a methoxy or an ethoxy group. Thus, specific or preferred examples of the trialkoxysilane include methyltriethoxysilane, methyltrimethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, dodecyltriethoxysilane, dodecyltrimethoxysilane, n-octadecyltriethoxysilane, n-octadecyltrimethoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane, benzyltriethoxysilane, benzyltrimethoxysilane, aminoethyltriethoxysilane, aminomethyltriethoxysilane, aminopropyltriethoxysilane, aminopropyltrimethoxysilane, N-(aminoethyl)aminopropyltriethoxysilane, and N-(aminoethyl)aminopropyltrimethoxysilane.
In a preferred embodiment, the surface-treatment layer comprises at least one mono- or di-substituted succinic anhydride comprising at least one unsaturated carbon moiety and having a total amount of carbon atoms from C2 to C30, preferably from C4 to C24, and more preferably from C8 to C20 in the substituent and/or an acid or salt thereof and/or salty reaction products thereof as described hereinabove, and more preferably wherein the at least one mono- or di-substituted succinic anhydride does not comprise a terminal double bond.
In another particularly preferred embodiment, the surface-treatment layer comprises a grafted polymer comprising at least one succinic anhydride group obtained by grafting maleic anhydride onto a homo- or copolymer comprising butadiene units and optionally styrene units and/or an acid and/or salt thereof as described hereinabove; and at least one saturated aliphatic linear or branched carboxylic acid and/or salts thereof, preferably at least one aliphatic carboxylic acid having a total amount of carbon atoms from C4 to C24 and/or a salt thereof, more preferably at least one aliphatic carboxylic acid having a total amount of carbon atoms from C12 to C20 and/or a salt thereof, most preferably at least one aliphatic carboxylic acid having a total amount of carbon atoms from C16 to C18 and/or a salt thereof.
Exemplarily, the surface-treatment layer comprises a grafted polymer comprising at least one succinic anhydride group obtained by grafting maleic anhydride onto a homopolymer comprising butadiene units having a number average molecular weight Mn measured by gel permeation chromatography from 1000 to 20000 g/mol, preferably from 1400 to 15000 g/mol, more preferably from 2000 to 10000 g/mol, an acid number in the range from 20 to 200 meq KOH per g of grafted polymer, preferably 30 to 150 meq KOH / g, measured according to ASTM D974-14, and/or a molar amount of 1,2-vinyl groups in the range from 10 to 60 mol-%, preferably 15 to 40 mol-%, and at least one aliphatic carboxylic acid having a total amount of carbon atoms from C12 to C20 and/or a salt thereof, preferably at least one aliphatic carboxylic acid having a total amount of carbon atoms from C16 to C18 and/or a salt thereof, for example the at least one aliphatic carboxylic acid is stearic acid.
It is appreciated that the surface-treatment layer on at least a part of the calcium carbonate-containing filler material is formed by contacting the calcium carbonate-containing filler material with the surface-treatment agent as described hereinabove. Preferably, the calcium carbonate-containing filler material is contacted with the surface-treatment agent or the surface-treatment composition in an amount from 0.1 to 6 wt.-%, preferably from 0.3 to 5 wt.-%, more preferably from 0.4 to 4 wt.-%, and most preferably from 0.5 to 3 wt.-%, based on the total amount of the surface-treated calcium carbonate-containing filler material. That is, a chemical reaction may take place between the calcium carbonate-containing filler material and the surface treatment agent. In other words, the surface-treatment layer may comprise the surface treatment agent and/or salty reaction products thereof.
The term “salty reaction products” of the surface-treatment agent refers to products obtained by contacting the filler material with the surface-treatment agent or the surface-treatment composition comprising the surface-treatment agent. Said reaction products are formed between at least a part of the applied surface-treatment agent and reactive molecules located at the surface of the calcium carbonate-containing filler material.
For example, if the surface-treatment layer is formed by contacting the calcium carbonate-containing filler material with the mono- or di-substituted succinic anhydride containing compounds comprising at least one unsaturated carbon moiety, the surface-treatment layer may further comprise a salt formed from the reaction of the mono- or di-substituted succinic anhydride containing compounds comprising at least one unsaturated carbon moiety with the calcium carbonate-containing filler material. Likewise, if the surface-treatment layer is formed by further contacting the calcium carbonate-containing filler material with stearic acid, the surface-treatment layer may further comprise a salt formed from the reaction of stearic acid with the calcium carbonate-containing filler material. Analogous reactions may take place when using alternative surface treatment agents according to the present invention.
According to one embodiment the salty reaction product(s) of the mono- or di-substituted succinic anhydride containing compounds comprising at least one unsaturated carbon moiety are one or more calcium and/or magnesium salts thereof.
According to one embodiment the salty reaction product(s) of the mono- or di-substituted succinic anhydride containing compounds comprising at least one unsaturated carbon moiety formed on at least a part of the surface of the calcium carbonate-comprising filler material are one or more calcium salts and/or one or more magnesium salts thereof.
According to one embodiment the molar ratio of the mono- or di-substituted succinic anhydride containing compounds comprising at least one unsaturated carbon moiety to the salty reaction product(s) thereof is from 99.9:0.1 to 0.1:99.9, preferably from 70:30 to 90:10.
According to one embodiment of the present invention, the calcium carbonate-containing filler material comprises, and preferably consists of, a calcium carbonate-containing filler material and a treatment layer comprising mono- or di-substituted succinic anhydride containing compounds comprising at least one unsaturated carbon moiety and/or salty reaction products thereof. The surface-treatment layer is formed on at least a part of the surface, preferably on the whole surface, of said filler material.
In one embodiment of the present invention, the surface-treatment layer formed on the surface of the calcium carbonate-containing filler material comprises the at least one mono- or di-substituted succinic anhydride comprising at least one unsaturated carbon moiety and/or a salt thereof and/or acid thereof and/or salty reaction products thereof obtained from contacting the calcium carbonate-containing filler material with the at least one mono- or di-substituted succinic anhydride comprising at least one unsaturated carbon moiety and/or a salt thereof and/or acid thereof. For example, the treatment layer formed on the surface of the calcium carbonate-containing filler material comprises a grafted polymer comprising at least one succinic anhydride group obtained by grafting maleic anhydride onto a homo- or copolymer comprising butadiene units and optionally styrene units and/or an acid and/or salt thereof and/or salty reaction products thereof obtained from contacting the calcium carbonate-containing filler material with the grafted polymer comprising at least one succinic anhydride group obtained by grafting maleic anhydride onto a homo- or copolymer comprising butadiene units and optionally styrene units.
Methods for preparing the surface-treated calcium-carbonate containing filler material treated with at least one phosphoric acid ester blend and suitable compounds for coating are described e.g. in EP 2 770 017 A1, which is thus incorporated herewith by reference.
Methods for preparing the surface-treated calcium carbonate-containing filler material treated with at least one mono-substituted succinic anhydride consisting of succinic anhydride mono-substituted with a group selected from a linear, branched, aliphatic and cyclic group having a total amount of carbon atoms from C2 to C30 in the substituent and suitable compounds for coating are described e.g. in WO 2016/023937 A1, which is thus incorporated herewith by reference.
If the surface-treatment layer is formed by contacting the calcium carbonate-containing filler material with a surface-treatment composition comprising two or more surface-treatment agents, it is to be understood that the two or more surface-treatment agents may be provided as a mixture prior to contacting the calcium carbonate-containing filler material with the surface-treatment composition. Alternatively, the calcium carbonate-containing filler material may be contacted with the first surface-treatment agent, and the second surface-treatment agent is added subsequently, that is, a surface-treatment composition is formed upon contacting the mixture of the calcium carbonate-containing filler material and the first surface-treatment agent with the second surface-treatment agent.
In one embodiment of the present invention, the surface treatment is carried out in the wet state, i.e. the surface treatment is carried out in the presence of an aqueous solvent, preferably water.
Thus, the filler material may be provided in form of an aqueous suspension having a solids content in the range from 5 to 80 wt.-%, based on the total weight of the aqueous suspension. According to a preferred embodiment, the solids content of the aqueous suspension is in the range from 10 to 70 wt.-%, more preferably in the range from 15 to 60 wt.-% and most preferably in the range from 15 to 40 wt.-%, based on the total weight of the aqueous suspension.
The term “aqueous” suspension refers to a system, wherein the liquid phase comprises, preferably consists of, water. However, said term does not exclude that the liquid phase of the aqueous suspension comprises minor amounts of at least one water-miscible organic solvent selected from the group comprising methanol, ethanol, acetone, acetonitrile, tetrahydrofuran and mixtures thereof. If the aqueous suspension comprises at least one water-miscible organic solvent, the liquid phase of the aqueous suspension comprises the at least one water-miscible organic solvent in an amount of from 0.1 to 40.0 wt.-% preferably from 0.1 to 30.0 wt.-%, more preferably from 0.1 to 20.0 wt.-% and most preferably from 0.1 to 10.0 wt.-%, based on the total weight of the liquid phase of the aqueous suspension. For example, the liquid phase of the aqueous suspension consists of water. Suitable wet surface-treatment processes are known to the skilled person, and taught, e.g., in EP 3 192 837 A1.
The surface-treated calcium carbonate-containing filler material according to the present invention has excellent surface characteristics. The surface-treated calcium carbonate-containing filler material preferably has
The “hydrophilicity” of a mineral filler product is evaluated at +23° C. by determining the minimum water to ethanol ratio in a volume/volume based water/ethanol-mixture needed for the settling of the majority of said mineral filler product, where said mineral filler product is deposited on the surface of said water/ethanol-mixture by passage through a house hold tea sieve. The volume/volume base is related to the volumes of both separate liquids before blending them together and does not take into account the volume contraction of the blend. The evaluation at +23° C. refers to a temperature of +23° C. ± 1° C.
An 8:2 volumetric ratio of a water/ethanol-mixture has typically a surface tension of 41 mN/m and a 6:4 volumetric ratio of a water/ethanol-mixture has typically a surface tension of 26 mN/m measured at +23° C. as described in the “Handbook of Chemistry and Physics”, 84th edition, David R. Lide, 2003 (first edition 1913).
The “moisture pickup susceptibility” of a material refers to the amount of moisture adsorbed on the surface of said material within a certain time upon exposure to a defined humid atmosphere and is expressed in mg/g. The “normalized moisture pickup susceptibility” of a material refers to the amount of moisture adsorbed on the surface of said material within a certain time upon exposure to a defined humid atmosphere and is expressed in mg/m2.
The moisture pick up susceptibility (in mg/g) is determined by exposure of a sample to an atmosphere of 10 and 85% relative humidity, respectively, for 2.5 hours at a temperature of 23° C. (± 2° C.). For this purpose, the sample is first kept at an atmosphere of 10% relative humidity for 2.5 hours, then the atmosphere is changed to 85% relative humidity at which the sample is kept for another 2.5 hours. The weight increase between 10 and 85% relative humidity is then used to calculate the moisture pick-up in mg moisture/g of sample. The moisture pick up susceptibility in mg/g divided by the specific surface area in m2/g (BET method) corresponds to the “normalized moisture pick up susceptibility” expressed in mg/m2 of sample.
In another preferred embodiment of the present invention, the surface-treated calcium carbonate-containing filler material may have a high volatile onset temperature, for example ≥ 250° C., preferably of ≥ 260° C., and most preferably of ≥ 270° C., and a high thermal stability, e.g. up to temperatures of 250° C., 270° C., or 290° C. Additionally or alternatively, the surface-treated calcium carbonate-containing filler material may have total volatiles between 25° C. and 400° C. of less than 6.3%, and preferably of less than 6.2% by mass, e.g., of from 0.14 to 6.2% by mass, preferably from 0.4 to 5.2% by mass, more preferably from 0.5 to 4.1% by mass.
The term “volatile onset temperature” in the meaning of the present document refers to the temperature at which volatiles - including volatiles introduced or formed during a preparation process such as grinding agents (unless indicated otherwise) - begin to evolve as observed by thermogravimetric analysis (TGA).
In the present invention, thermogravimetric analysis (TGA) is performed using a Mettler Toledo TGA/DSC3+ based on a sample size of 250 ± 50 mg in a 900 µL crucible and scanning temperatures from 25 to 400° C. at a rate of 20° C./minute under an air flow of 80 ml/min.
The skilled man will be able to determine the “volatile onset temperature” by analysis of the TGA curve as follows: the first derivative of the TGA curve is obtained and the inflection points thereon between 150 and 400° C. are identified. Of the inflection points having a tangential slope value of greater than 45° relative to a horizontal line, the one having the lowest associated temperature above 200° C. is identified. The temperature value associated with this lowest temperature inflection point of the first derivative curve is the “volatile onset temperature”.
For the purpose of the present application, the “total volatiles” associated with mineral fillers and evolved over a temperature range of 25 to 400° C. is characterized according to% mass loss of the mineral filler sample over a temperature range as read on a thermogravimetric (TGA) curve.
TGA analytical methods provide information regarding losses of mass and volatile onset temperatures with great accuracy, and is common knowledge; it is, for example, described in “Principles of Instrumental analysis”, fifth edition, Skoog, Holler, Nieman, 1998 (first edition 1992) in Chapter 31 pages 798 to 800, and in many other commonly known reference works. In the present invention, thermogravimetric analysis (TGA) is performed using a Mettler Toledo TGA/DSC3+ based on a sample of 250 ± 50 mg in a 900 µL crucible and scanning temperatures from 25 to 400° C. at a rate of 20° C./minute under an air flow of 80 ml/min.
It is to be understood that the particle size or properties of the calcium carbonate-containing filler material is not altered or only slightly altered by the surface-treatment. Thus, in a preferred embodiment, the surface-treated calcium carbonate-containing filler material has a weight median particle size d50 from 0.03 µm to 4.0 µm, preferably from 0.05 µm to 3 µm, more preferably from 0.1 to 2.5 µm and most preferably from 0.2 to 2.0 µm. Accordingly, the surface-treated calcium carbonate-containing filler material has a top cut (d98) of 30 µm or less, preferably 20 µm or less more preferably 10 µm or less, and most preferably 7.5 µm or less.
Furthermore, the surface-treated calcium carbonate-containing filler material may have a BET specific surface area of from 0.5 and 120 m2/g, preferably from 1 to 50 m2/g, more preferably from 2 to 35 m2/g, and most preferably from 2.5 to 15 m2/g, as measured by the BET method according to ISO 9277:2010.
According to one embodiment of the present invention, the surface-treated calcium carbonate-containing filler material has a weight median particle size d50 from 0.03 µm to 4.0 µm and/or a top cut (d98) of 30 µm or less and/or a specific surface area (BET) of from 0.5 to 120 m2/g, as measured by the BET method.
For example, the surface-treated calcium carbonate-containing filler material may have a median particle size diameter d50 value from 0.1 µm to 2.5 µm, preferably from 0.2 µm to 2.0 µm, a top cut (d98) of 10 µm or less, more preferably of 7.5 µm or less, and optionally a BET specific surface area of from 1 to 50 m2/g, preferably of from 2 to 35 m2/g, measured by the BET method.
The inventive kit of parts, the inventive filled polymer mixture, the inventive process, the inventive filled polymer composition, the inventive use and the inventive article make use of a peroxide agent.
For the purposes of the present invention, a “peroxide agent” is a compound comprising a peroxide group, i.e., an O—O group. Preferably, the peroxide agent is an organic peroxide, i.e., a compound of the formula R1—O—O—R2, wherein R1 is an organyl group and R2 is H or an organyl group.
An “organyl group” in the meaning of the present invention is any organic substituent group, regardless of functional type, having one free valence at a carbon atom, e.g. CH3CH2—, ClCH2—, CH3C(═O)—, 4-pyridylmethyl- (see IUPAC Gold Book, https://doi.org/10.1351/goldbook.O04329).
The peroxide agent can be selected from a very wide range, including peresters, perketals, hydroperoxides, peroxydicarbonates, diacyl peroxides and ketone peroxides. Examples of such peroxides include t-butyl peroctanoate, perbenzoate, methyl ethyl ketone peroxide, cyclohexanone peroxide, acetyl acetone peroxide, dibenzoyl peroxide, bis(4-t-butyl-cyclohexyl) peroxydicarbonate, dicumyl peroxide, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 2,5-bis-(t-butylperoxy)-2,5-dimethylhexane, 2,5-bis-(t-butylperoxy)-2,5-dimethylhexyne, or α,α′-bis(tert-butylperoxy)diisopropylbenzene, diisopropyl peroxydicarbonate, 1,1-bis(tert-hexylperoxy)-3,5,5-trimethylcyclohexane, 2,5-dimethylhexane-2,5-dihydroperoxide, di-tert-butyl peroxide, tert-butylcumyl peroxide, 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane, 2,5-dimethyl-2,5-bis(tert-butylperoxy)-3-hexine, tert-butyl peroxybenzoate, 2,5-dimethyl-2,5-bis(benzoylperoxy)hexane, tert-butyl peroxymaleate or tert-hexylperoxyisopropyl monocarbonate and the like. If desired, a mixture of two or more peroxides can be used.
Without wishing to be bound by any theory, it is believed that the peroxide reagent, once the mixture is heated above a certain temperature, e.g., above the decomposition temperature of the peroxide agent or to a temperature as required for extrusion, may undergo a chemical reaction with the polymers of the filled polymer mixture and/or the surface-treatment layer of the surface-treated calcium carbonate-containing filler material at the interface of said filler material with the at least one polyethylene polymer and/or the at least one polypropylene polymer, thus leading to the formation of a crosslinked material, i.e., the filled polymer composition. Thus, the filled polymer composition may comprise a reaction product of the peroxide reagent, e.g., with the at least one polyethylene polymer and/or the at least one polypropylene polymer and/or the surface-treatment layer of the surface-treated calcium carbonate-containing filler material.
The inventive filled polymer mixture, the inventive filled polymer composition, the inventive process, the inventive use and the inventive article make use of at least one polyethylene polymer.
For example, the at least one polyethylene polymer is a homopolymer and/or copolymer of polyethylene. The at least one polyethylene polymer may be a homopolymer of polyethylene.
The expression homopolymer of polyethylene used in the present invention relates to polyethylene comprising a polyethylene that consists substantially, i.e. of more than 99.7 wt.-%, still more preferably of at least 99.8 wt.-%, based on the total weight of the polyethylene, of ethylene units. For example, only ethylene units in the homopolymer of polyethylene are detectable.
For example, the polyethylene polymer may be selected from the group comprising homopolymers and/or copolymers of polyethylene like high-density polyethylene (HDPE), medium-density polyethylene (MDPE), low-density polyethylene (LDPE), very low-density polyethylene (VLDPE), linear low-density polyethylene (LLDPE), and mixtures thereof.
In case the at least one polymeric resin of the polymer composition comprises a copolymer of polyethylene, it is appreciated that the polyethylene contains units derivable from ethylene as major components. Accordingly, the copolymer of polyethylene comprises at least 55 wt.-% units derivable from ethylene, more preferably at least 60 wt.-% of units derived from ethylene, based on the total weight of the polyethylene. For example, the copolymer of polyethylene comprises 60 to 99.5 wt.-%, more preferably 90 to 99 wt.-%, units derivable from ethylene, based on the total weight of the polyethylene. The comonomers present in such copolymer of polyethylene are C3 to C10 α-olefins, preferably 1-butene, 1-hexene and 1-octene, the latter being especially preferred.
Furthermore, it is appreciated that the at least one polyethylene polymer may be selected from polyethylene polymers having a broad spectrum of melt flow rate. In general, it is preferred that the at least one polyethylene polymer has a melt flow rate MFR (190° C., 2.16 kg) of from 0.1 to 3 000 g/10 min, more preferably of from 0.2 to 2500 g/10 min. For example, the at least one polyethylene polymer has a melt flow rate MFR (190° C., 2.16 kg) of from 0.3 to 2000 g/10 min, preferably from 0.3 to 1600 g/10 min, more preferably from 1 to 100 g/10 min and most preferably from 1 to 50 g/10 min.
The at least one polyethylene polymer may have a rather low melt flow rate. Accordingly, it is preferred that the at least one polyethylene polymer has a melt flow rate MFR (190° C., 2.16 kg) of from 0.5 to 50 g/10 min, more preferably of from 0.7 to 45 g/10 min. For example, the at least one polyethylene polymer has a melt flow rate MFR (190° C., 2.16 kg) of from 0.9 to 40 g/10 min, preferably from 0.9 to 30 g/10 min.
In one embodiment of the present invention, the at least one polyethylene polymer is a virgin polymer, that is, the polyethylene polymer is produced directly from the petrochemical feed-stock.
In a preferred embodiment of the present invention, the at least one polyethylene polymer is derived from waste polymers. In view thereof, the at least one polyethylene polymer being “derived from” waste polymers is understood in that the polyethylene polymer is obtained by a purification process. The purification process may include at least one of, preferably at least two of the steps of pre-sorting, grinding, cleaning and sorting, in any order, preferably in the order set out herein.
In one embodiment, the process for obtaining the polyethylene polymer comprises a pre-sorting step. During pre-sorting, separate and discrete pieces of different polymeric materials may be identified, e.g., by Fourier-transform infrared spectroscopy (FTIR), near-infrared spectroscopy, optical color recognition, X-ray detection, laser sorting and/or electrostatic detection, and subsequently mechanically separated, e.g., by selective collection and/or automated or manual sorting.
In one embodiment, the process for obtaining the polyethylene polymer comprises a grinding step. During the grinding step, the size of the waste plastic is reduced in order to facilitate the subsequent separation, cleaning and re-processing steps. The grinding step may be performed inter alia by shredding, crushing or milling. Preferably, the average particle size of the ground waste plastic is in the range from 0.2 to 10 mm.
In one embodiment, the process for obtaining the polyethylene polymer comprises a cleaning step. During cleaning, the waste plastic, which is optionally ground, may be washed with a liquid preferably selected from the group consisting of water, optionally comprising at least one detergent and/or a soap, and/or organic solvents, such as alcohols, ketones and aliphatic hydrocarbons. Preferably, the organic solvent does not dissolve the polymers within the waste plastic.
In one embodiment, the process for obtaining the polyethylene polymer comprises a sorting step. The sorting step may be selected from gravimetrical sorting and/or sorting by dissolution/reprecipitation.
For the purposes of the present invention, the term “gravimetrical sorting”, also termed “sink-float density separation” or “density separation” refers to a method for separating different types of polymers based on their respective density. During gravimetrical sorting, the waste plastic, which is preferably ground and optionally cleaned, may be dispersed in a solvent having a defined density and sorted in a gravity separator, a sorting cyclone or a sorting centrifuge. Thereby, the plastic waste fractions are separated according to their density, i.e., the plastic waste fraction having a density below the density of the solvent floats to the top, and the plastic waste having a density above the density of the solvent sinks to the bottom. The so-obtained plastic waste fractions may be subject to another gravimetrical sorting step using a solvent having a different density. Suitable solvents include water, alcohols, and salt solutions.
Alternatively, in the “dissolution/reprecipitation” process, the waste plastic, which is preferably ground and optionally cleaned, may be dissolved in a solvent, such as xylene, toluene, dichloromethane, benzyl alcohol or a mixture thereof. Subsequently, a non-solvent, such as n-hexane or methanol, is added to selectively precipitate the different polymeric materials. The process may be repeated one or more times.
Preferably, the process for obtaining the polyethylene polymer comprises a drying step. Drying may take place using any suitable drying equipment and can, for example, include thermal drying and/or drying at reduced pressure using equipment such as an evaporator, a flash drier, an oven, a spray drier (such as a spray drier sold by Niro and/or Nara), and/or drying in a vacuum chamber.
In view of the foregoing, it is to be understood that, in case the at least one polyethylene polymer is derived from waste plastic, the at least one polyethylene polymer may comprise further polymers and/or additives and/or contaminants, depending on the composition of the waste plastic. Therefore, the present invention is not limited to certain types or compositions of polyethylene polymers. In particular, the polyethylene polymer may be selected from the group consisting of HDPE, MDPE, LDPE, VLDPE, LLDPE, and mixtures thereof, may comprise further polymers, such as PP, PET, PVC, PLA, PA and/or PS, and/or may comprise further additives.
The expression “at least one” polyethylene polymer means that one or more kinds of polyethylene polymer may be present in the inventive filled polymer composition. Accordingly, it is appreciated that the at least one polyethylene polymer may be a mixture of two or more kinds of polyethylene polymers, e.g., a mixture of LDPE and/or LLDPE with MDPE and/or HDPE.
The inventive filled polymer mixture, the inventive filled polymer composition, the inventive process, the inventive use and the inventive article make use of at least one polypropylene polymer. The polypropylene polymer may be a homopolymer and/or copolymer of polypropylene. The expression homopolymer of polypropylene as used throughout the instant invention relates to a polypropylene that consists substantially, i.e. of more than 99 wt.-%, still more preferably of at least 99.5 wt.-%, like of at least 99.8 wt.-%, based on the total weight of the polypropylene, of propylene units. In a preferred embodiment only propylene units are detectable in the homopolymer of polypropylene. The homopolymer of polypropylene may be an isotactic polypropylene homopolymer.
In case the at least one polymeric resin of the polymer composition comprises a copolymer of polypropylene, the polypropylene preferably contains units derivable from propylene as major components. The copolymer of polypropylene preferably comprises, preferably consists of, units derived from propylene and C2 and/or at least one C4 to C10 α-olefin. In one embodiment of the present invention, the copolymer of polypropylene comprises, preferably consists of, units derived from propylene and at least one α-olefin selected from the group consisting of ethylene, 1-butene, 1-pentene, 1-hexene and 1-octene. For example, the copolymer of polypropylene comprises, preferably consists of, units derived from propylene and ethylene. In one embodiment of the present invention, the units derivable from propylene constitutes the main part of the polypropylene, i.e. at least 60 wt.-%, preferably of at least 70 wt.-%, more preferably of at least 80 wt.-%, still more preferably of from 60 to 99 wt.-%, yet more preferably of from 70 to 99 wt.-% and most preferably of from 80 to 99 wt.-%, based on the total weight of the polypropylene. The amount of units derived from C2 and/or at least one C4 to C10 α-olefin in the copolymer of polypropylene, is in the range of 1 to 40 wt.-%, more preferably in the range of 1 to 30 wt.-% and most preferably in the range of 1 to 20 wt.-%, based on the total weight of the copolymer of polypropylene.
If the copolymer of polypropylene comprises only units derivable from propylene and ethylene, the amount of ethylene is preferably in the range of 1 to 20 wt.-%, preferably in the range of 1 to 15 wt.-% and most preferably in the range of 1 to 10 wt.-%, based on the total weight of the copolymer of polypropylene. Accordingly, the amount of propylene is preferably in the range of 80 to 99 wt.-%, preferably in the range of 85 to 99 wt.-% and most preferably in the range of 90 to 99 wt.-%, based on the total weight of the copolymer of polypropylene.
Furthermore, it is appreciated that the at least one polypropylene polymer may be selected from polypropylene polymers having a broad spectrum of melt flow rate. In general, it is preferred that the at least one polypropylene polymer has a melt flow rate MFR (230° C., 2.16 kg) of from 0.1 to 3 000 g/10 min, more preferably of from 0.2 to 2500 g/10 min. For example, the at least one polypropylene polymer has a melt flow rate MFR (230° C., 2.16 kg) of from 0.3 to 2000 g/10 min, preferably from 0.3 to 1600 g/10 min, more preferably from 1 to 100 g/ 10 min, most preferably from 1 to 50 g/10 min.
In one embodiment of the present invention, the at least one polypropylene polymer is a virgin polymer, that is, the polypropylene polymer is produced directly from the petrochemical feed-stock.
In a preferred embodiment of the present invention, the at least one polypropylene polymer is derived from waste polymers. The at least one polypropylene polymer being “derived from” waste polymers is understood in that the polypropylene polymer is obtained by a purification process. Suitable purification processes are described hereinabove within context of the at least one polyethylene polymer.
In view of the foregoing, it is to be understood that, in case the at least one polypropylene polymer is derived from waste plastic, the at least one polypropylene polymer may comprise further polymers and/or additives and/or contaminants, depending on the composition of the waste plastic. Therefore, the present invention is not limited to certain types or compositions of polypropylene polymers. In particular, the polypropylene polymer may be selected from the group consisting of expandable polypropylene (EPP), high-impact polypropylene (HIPP), and mixtures thereof, may comprise further polymers, such as PE, PET, PVC, PLA, PA and/or PS, and/or may comprise further additives.
The expression “at least one” polypropylene polymer means that one or more kinds of polypropylene polymer may be present in the inventive filled polymer composition. Accordingly, it is appreciated that the at least one polypropylene polymer may be a mixture of two or more kinds of polypropylene polymers.
In a first aspect of the present invention, a kit of parts for improving the mechanical properties of a polymer mixture comprising at least one polyethylene polymer and at least one polypropylene polymer is provided. The kit of parts comprises
It is appreciated that the at least one polyethylene polymer, the at least one polypropylene polymer, the surface-treated calcium carbonate-containing filler material, the calcium carbonate-containing filler material and the surface-treatment layer have been described in detail hereinabove.
In a preferred embodiment of the present invention, the surface-treatment layer comprises the peroxide agent. That is, the peroxide agent is dispersed or dissolved in the surface-treatment layer. The peroxide agent may be dissolved or dispersed into the surface-treatment layer by a process as described hereinbelow. Preferably, the peroxide agent is present on the calcium carbonate-containing filler material in an amount from 0.01 to 0.5 wt.-%, preferably from 0.02 to 0.3 wt.-%, more preferably from 0.03 to 0.2 wt.-%, and most preferably from 0.04 to 0.15 wt.-%, based on the total amount of the surface-treated calcium carbonate-containing filler material.
The inventors surprisingly found that the peroxide agent can be uniformly dispersed in the surface-treatment layer. Consequently, when the peroxide-loaded surface-treated calcium carbonate-containing filler material is uniformly dispersed in the polyethylene polymer and the polypropylene polymer, the peroxide agent is already present at the interface of the polymeric phase and the surface-treatment layer of the surface-treated calcium carbonate-containing filler material. Thus, the handling and dosing of the components of the kit of parts is greatly improved.
In other words, a preferred embodiment of the present invention relates to a surface-treated calcium carbonate-containing filler material,
In another preferred embodiment, the surface-treated calcium carbonate-containing filler material is comprised in a treated masterbatch in an amount from 50 to 85 wt.-%, preferably 60 to 85 wt.-%, more preferably 65 to 80 wt.-%, based on the total amount of the treated masterbatch, wherein the treated masterbatch comprises at least one polyethylene polymer and/or at least one polypropylene polymer, and wherein the peroxide agent is present on the surface of the treated masterbatch preferably in an amount from 0.01 to 0.5 wt.-%, more preferably from 0.02 to 0.3 wt.-%, even more preferably from 0.03 to 0.2 wt.-%, and most preferably from 0.04 to 0.15 wt.-%, based on the total amount of the surface-treated calcium carbonate-containing filler material.
Typically, a masterbatch may be obtained as a material having a defined shape, such as pellets, spheres, pearls, beads, prills, flakes, chips or slugs, or a non-defined shape, such as, for example, crumbles. The inventors found that the peroxide agent can be dispersed onto such masterbatch material having a defined or non-defined shape, e.g., by a process as described hereinbelow. The treated masterbatch material having a defined or non-defined shape, e.g., the masterbatch pellets, comprises the peroxide agent on the surface of the treated masterbatch, i.e., the peroxide agent is dispersed in or dissolved in the outer layer of the masterbatch material (i.e., on the surface thereof), by being soaked into the masterbatch. Thereby, the handling and dosing of the components of the kit of parts is greatly improved.
Preferably, the at least one polyethylene polymer and/or at least one polypropylene polymer comprised in the treated masterbatch is derived from virgin polymers.
In other words, a preferred embodiment of the present invention relates to a treated masterbatch, wherein the treated masterbatch comprises
The treated masterbatch may be obtained by a process involving the steps of
Process steps a), b), c), c1) and c2) are described in detail hereinbelow.
In a second aspect of the present invention, a filled polymer mixture is provided. The filled polymer mixture comprises
The at least one polyethylene polymer, the at least one polypropylene polymer, the surface-treated calcium carbonate-containing filler material, the calcium carbonate-containing filler material, the surface-treatment layer and the peroxide agent have been described in detail hereinabove.
It is to be understood that the term “filled polymer mixture” relates to an unreacted mixture of the at least one polyethylene polymer, the at least one polypropylene polymer, the surface-treated calcium carbonate-containing filler material and the peroxide agent, Conversely, the term “filled polymer composition” relates to a reaction product, which may be obtained by reacting the filled polymer mixture, e.g., by heating it to a certain temperature, for example above the decomposition temperature of the peroxide agent or by a process as described hereinbelow. Thus, when in the following reference is made to specific technical details of the “filled polymer mixture”, it is to be understood that these details are also applicable to the “filled polymer composition”. However, it is to be understood that the filled polymer composition comprises reaction products of the peroxide agent with the surface-treatment layer of the surface-treated calcium carbonate-containing filler material and/or the polyethylene polymer and/or the polypropylene polymer.
In a preferred embodiment of the present invention, the at least one polyethylene polymer and the at least one polypropylene polymer are at least partially derived from waste polymers. Thus, the filled polymer mixture may comprise a mixture of virgin and recycled polymers. For example, the filled polymer mixture may comprise at least one polyethylene polymer being derived from waste polymers and at least one polypropylene polymer being derived from waste polymers in a combined amount of at least 20 wt.-%, preferably at least 50 wt.-%, more preferably at least 70 wt.-%, still more preferably at least 85 wt.-%, and most preferably at least 95 wt.-%, based on the total amount of polymer in the filled polymer mixture. In other words, the filled polymer mixture may comprise a total amount of polymer being derived from waste polymers of at least 20 wt.-%, preferably at least 50 wt.-%, more preferably at least 70 wt.-%, still more preferably at least 85 wt.-%, and most preferably at least 95 wt.-%, based on the total amount of polymer in the filled polymer mixture.
In a preferred embodiment of the present invention, the filled polymer mixture comprises a polymer mixture comprising the at least one polyethylene polymer and the at least one polypropylene polymer. Preferably, the polymer mixture is derived from waste polymers comprising the at least one polyethylene polymer and the at least one polypropylene polymer. The polymer mixture being “derived from” waste polymers is understood in that the polymer mixture is obtained by a purification process. Suitable purification processes are described hereinabove within context of the at least one polyethylene polymer. It is to be stressed that the separation of polyethylene polymers and polypropylene polymers in such process may be incomplete, such that the polymer mixture indeed is a mixture of the at least one polyethylene polymer and the at least one polypropylene polymer. Furthermore, the polymer mixture may comprise further polymers, e.g., polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), but also degradable polyesters, such as polylactic acid (polylactide, PLA) and polyethylene-2,5-furandicarboxylate, polyvinyl chloride, polyvinylidene chloride (PVDC), polyvinylidene fluoride (PVDF) and polytetrafluoroethylene (PTFE), polybutadiene, polyacrylonitrile, polymethylmethacrylate, polyamides, polyurethanes, and mixtures thereof.
In one embodiment of the present invention, the at least one polypropylene polymer is present in the inventive filled polymer mixture in an amount from 0.5 to 99 wt.-%, preferably from 1 to 70 wt.-%, more preferably from 1 wt.-% to 50 wt.-%, still more preferably from 1 to 30 wt.-%, even more preferably from 2 to 30 wt.-% and most preferably from 5 to 30 wt.-%, based on the total weight of the polymer in the filled polymer mixture. Additionally or alternatively, the at least one polyethylene polymer is present in the inventive filled polymer mixture in an amount from 1.0 to 99.5 wt.-%, preferably from 30 to 99 wt.-%, more preferably from 50 wt.-% to 99 wt.-%, still more preferably from 70 to 99 wt.-%, even more preferably from 70 to 98 wt.-%, and most preferably from 70 to 95 wt.-%, based on the total weight of the polymer in the filled polymer mixture. In the case that the at least one polyethylene polymer and the at least one polypropylene polymer are at least partially derived from waste polymers, it is to be understood that the amounts of the at least one polyethylene polymer and the at least one polypropylene polymer are determined at least partially by the source and/or mixture of the waste polymer. In view thereof, it is appreciated that the invention is not limited to specific amounts of polyethylene polymer and polypropylene polymer.
As an illustrative example, the filled polymer mixture may comprise a polymer mixture being derived from waste polymers, which comprises, e.g., from 50 to 99 wt.-%, preferably from 70 to 99 wt.-%, more preferably from 70 to 98 wt.-%, and most preferably from 70 to 95 wt.-%, based on the total weight of the polymer mixture, of at least one polyethylene polymer and, e.g., from 1 to 50 wt.-%, preferably from 1 to 30 wt.-%, more preferably from 2 to 30 wt.-%, and most preferably from 5 to 30 wt.-%, based on the total weight of the polymer mixture, of at least one polypropylene polymer. The polymer mixture being derived from waste polymers may be present in an amount of at least 20 wt.-%, preferably at least 50 wt.-%, more preferably at least 70 wt.-%, still more preferably at least 85 wt.-%, and most preferably at least 95 wt.-%, based on the total amount of polymer in the filled polymer mixture. Additionally, the filled polymer mixture may comprise at least one further polyethylene polymer being a virgin polymer and/or at least one further polypropylene polymer being a virgin polymer, e.g., such that the polymer mixture and the at least one further polyethylene polymer being a virgin polymer and/or at least one further polypropylene polymer being a virgin polymer add up to 100 wt.-%, based on the total amount of polymer in the filled polymer mixture.
Thus, in a preferred embodiment of the present invention, the filled polymer mixture comprises a total amount of polymer being derived from waste polymers of at least 20 wt.-%, preferably at least 50 wt.-%, more preferably at least 70 wt.-%, still more preferably at least 85 wt.-%, and most preferably at least 95 wt.-%, based on the total amount of polymer in the filled polymer mixture.
Preferably, the inventive filled polymer mixture comprises the at least one polyethylene polymer and the at least one polypropylene polymer in a combined amount of at least 50 wt.-%, preferably at least 80 wt.-%, more preferably at least 95 wt.-%, and most preferably at least 98 wt.-%, based on the total weight of the polymer in the filled polymer mixture.
In one embodiment of the present invention, the surface-treated calcium carbonate-containing filler material is present in the inventive filled polymer mixture in an amount from 2 wt.-% to 70 wt.-%, preferably from 5 wt.-% to 60 wt.-%, more preferably 7 wt.-% to 40 wt.-%, based on the total weight of the filled polymer mixture.
The inventive filled polymer mixture may comprise at least one further polymer. The at least one further polymer may be selected from the group comprising polystyrene, polyesters, such as polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), but also degradable polyesters, such as polylactic acid (polylactide, PLA) and polyethylene-2,5-furandicarboxylate, polyvinyl chloride, polyvinylidene chloride (PVDC), polyvinylidene fluoride (PVDF) and polytetrafluoroethylene (PTFE), polybutadiene, polyacrylonitrile, polymethylmethacrylate, polyamides, polyurethanes, and mixtures thereof.
Preferably, the at least one further polymer is selected from the group comprising polystyrene, polyesters, preferably polyethylene terephthalate, polylactic acid, polyhydroxybutyrate and polyethylene-2,5-furandicarboxylate, polyvinyl chloride, polybutadiene, polyacrylonitrile, polymethylmethacrylate, polyamides, polyurethanes, and mixtures thereof.
The at least one further polymer may be present in the inventive filled polymer mixture in an amount of at most 50 wt.-%, preferably at most 30 wt.-%, more preferably at most 15 wt.-%, and most preferably at most 5 wt.-%, based on the total amount of the polymer in the filled polymer mixture.
In a preferred embodiment of the present invention, the at least one further polymer is derived from waste polymers. For example, the at least one further polymer is contained in the polymer mixture being derived from waste polymers as described hereinabove. In other words, said polymer mixture may be contaminated by the at least one further polymer, e.g., due to an incomplete purification process. In said embodiment, it is preferred that the inventive filled polymer mixture comprises the at least one further polymer in an amount of at most 5 wt.-%, preferably at most 2 wt.-%, based on the total amount of polymer in the filled polymer mixture.
Additionally or alternatively, the inventive filled polymer mixture may further comprise at least one additive selected from the group consisting of further fillers, preferably selected from the group consisting of talc, mica, kaolin, bentonite or mixtures thereof, UV-absorbers, light stabilizers, processing stabilizers, antioxidants, heat stabilizers, nucleating agents, metal deactivators, impact modifiers, plasticizers, lubricants, rheology modifiers, processing aids, pigments, dyes, optical brighteners, antimicrobials, antistatic agents, slip agents, anti-block agents, coupling agents, dispersants, compatibilizers, oxygen scavengers, acid scavengers, markers, antifogging agents, surface modifiers, flame retardants, blowing agents, smoke suppressors, or mixtures of the foregoing additives. The at least one additive may be present in an amount of up to 30 wt.-%, preferably up to 5 wt.-%, more preferably up to 2 wt.-%, based on the total weight of the filled polymer mixture. The total amount of additives may be up to 35 wt.-%, preferably up to 5 wt.-%, more preferably up to 2 wt.-%, based on the total weight of the filled polymer mixture.
The at least one additive may be added to the inventive filled polymer mixture on purpose and/or may be present due to the at least one polyethylene polymer and/or the at least one polypropylene polymer being derived from waste polymers.
According to one embodiment, the polymer mixture comprises a further filler. The further filler may be selected from the group comprising carbon black, silica, ground natural calcium carbonate, precipitated calcium carbonate, nanofillers, graphite, clay, talc, diatomaceous earth, barium sulfate, titanium dioxide, wollastonite, and mixtures thereof. Preferably, the further filler is selected from the group consisting of talc, mica, kaolin, bentonite or mixtures thereof. The further filler may be present in the inventive filled polymer mixture in an amount of at most 30 wt.-%, more preferably at most 15 wt.-%, and most preferably at most 5 wt.-%, based on the total amount of the filled polymer mixture.
It is to be understood that the further filler can be distinguished from the surface-treated calcium carbonate-containing filler material, e.g., by its chemical composition and/or by its particle size. In other words, if the at least one further filler is selected from ground natural calcium carbonate or precipitated calcium carbonate, said further filler has a weight median particle size (d50) value of more than 4.0 µm and/or a top cut (d98) value of more than 30 µm and/or does not comprise a surface-treatment layer as defined hereinabove.
The filled polymer mixture preferably comprises the peroxide agent in an amount from 0.01 to 0.5 wt.-%, preferably from 0.02 to 0.3 wt.-%, more preferably from 0.03 to 0.2 wt.-%, and most preferably from 0.04 to 0.15 wt.-%, based on the total amount of the surface-treated calcium carbonate-containing filler material.
In an exemplary embodiment of the present invention, the filled polymer mixture comprises
In another exemplary embodiment of the present invention, the filled polymer mixture comprises
More preferably, the filled polymer mixture comprises
In a third aspect of the present invention, a process for the production of a filled polymer composition is provided. The process comprises the steps of
According to step a) of the inventive process, a surface-treated calcium carbonate-containing filler material and a peroxide agent are provided. The surface-treated calcium carbonate-containing filler material comprises a calcium carbonate-containing filler material having
It is appreciated that the surface-treated calcium carbonate-containing filler material, the calcium carbonate-containing filler material, the at least one surface-treatment agent and/or salty reaction products thereof and the peroxide agent are defined hereinabove.
In a preferred embodiment of the present invention, step a) of providing the surface-treated calcium carbonate-containing filler material comprises the sub-steps of
It is preferred that in step a1) the calcium carbonate-containing filler material is provided in dry form. Heating step a4) may be performed by any means known to the skilled person. The optionally present at least one saturated surface-treatment agent as defined hereinabove and/or the peroxide agent of step a3) may also be heated prior to contacting step a5). It should be noted that the at least one saturated surface-treatment agent may be heated to a temperature in the range from the melting point of the at least one saturated surface-treatment agent to less than 200° C., preferably less than 120° C., for example, by admixing the saturated surface-treatment agent with the mono- or di-substituted succinic anhydride and/or a salt thereof and/or acid thereof prior to step a4). If a peroxide agent is provided, it is appreciated that said peroxide agent throughout process steps a3) to a5) is at most heated to a temperature slightly below the decomposition temperature of the peroxide agent, e.g., 90° C., preferably 70° C. While the peroxide agent may be admixed with the saturated surface-treatment agent and the mono- or di-substituted succinic anhydride and/or a salt thereof and/or acid thereof prior to step a4), provided that heating step a4) is performed at most at a temperature slightly below the decomposition temperature of the peroxide agent, e.g., 90° C., preferably 70° C., it is preferred that the peroxide agent is added separately during step a5), for example, after the molten mono- or di-substituted succinic anhydride and/or a salt thereof and/or acid thereof of step a4) and optionally the at least one saturated surface-treatment agent of step a3) have been contacted with the calcium carbonate-containing filler material and the temperature is reduced to a temperature of at most slightly below the decomposition temperature of the peroxide agent, e.g., 90° C., preferably 70° C.
It is preferred that steps a4) and a5) are carried out simultaneously, preferably in the same vessel. In said embodiment, heating step a4) may be performed by adding the mono- or di-substituted succinic anhydride and/or a salt thereof and/or acid thereof of step a2) to the calcium carbonate-containing filler material of step a1), which has been pre-heated to a temperature in the range from the melting point of the at least one surface-treatment agent to less than 200° C., preferably less than 120° C. In this embodiment, the optionally present at least one saturated surface-treatment agent of step a3) is also heated to a temperature in the range from the melting point of the at least one surface-treatment agent to less than 200° C., preferably less than 120° C., by contacting with the pre-heated calcium carbonate-containing filler material. The optionally present peroxide agent may be added to the pre-heated calcium carbonate-containing filler material, provided that its temperature does not exceed the decomposition temperature of the peroxide agent, e.g., 90° C., preferably 70° C. Step a5) is carried out under mixing. It is appreciated that the mixing can be carried out by any method or in any vessel known to the skilled person resulting in a homogeneous composition. For example, step a5) is carried out in a high speed mixer or pin mill.
Alternatively, the surface-treated calcium carbonate-containing filler material is obtained in a wet surface-treatment step. Suitable wet surface-treatment processes are known to the skilled person, and taught, e.g., in EP3192837 A1.
According to step b) of the inventive process, at least one polyethylene polymer and at least one polypropylene polymer and/or a polymer mixture comprising polyethylene and polypropylene is provided. It is appreciated that the at least one polyethylene polymer and the at least one polypropylene polymer are as defined hereinabove.
It is to be understood that the at least one polyethylene polymer and the at least one polypropylene polymer may be provided separately and/or in the form of a polymer mixture. Preferably, the at least one polyethylene polymer, the at least one polypropylene polymer and/or the polymer mixture are derived from waste polymers.
In a preferred embodiment of the present invention, in step b) a polymer mixture is provided, which is derived from waste polymers comprising polyethylene and polypropylene. The polymer mixture being “derived from” waste polymers is understood in that the polymer mixture is obtained by a purification process. In this embodiment, step b) of providing the polymer mixture may comprise at least one of, preferably at least two of the sub-steps of b1) pre-sorting the waste plastic, b2) grinding the waste plastic, b3) cleaning the waste plastic and b4) sorting the waste plastic, in any order, preferably in the order set out herein.
According to pre-sorting step b1), separate and discrete pieces of different polymeric materials may be identified, e.g., by Fourier-transform infrared spectroscopy (FTIR), near-infrared spectroscopy, optical color recognition, X-ray detection, laser sorting and/or electrostatic detection, and subsequently mechanically separated, e.g., by selective collection and/or automated or manual sorting.
According to grinding step b2), the size of the waste plastic is reduced in order to facilitate the subsequent separation, cleaning and re-processing steps. The grinding step may be performed inter alia by shredding, crushing or milling. Preferably, the average particle size of the ground waste plastic is in the range from 0.2 to 10 mm.
According to cleaning step b3), the waste plastic, which is optionally ground, may be washed with a liquid preferably selected from the group consisting of water, optionally comprising at least one detergent and/or a soap, and/or organic solvents, such as alcohols, ketones and aliphatic hydrocarbons. Preferably, the organic solvent does not dissolve the polymers within the waste plastic.
According to sorting step b4), the polymer mixture preferably undergoes a step selected from gravimetrical sorting and/or sorting by dissolution/reprecipitation.
Preferably, the process for providing the polymer mixture comprises the sub-step of b5) drying the polymer mixture obtained after one of, or more of steps b1) to b4). Drying may take place using any suitable drying equipment known to the skilled person.
It is to be stressed that the separation of polyethylene polymers and polypropylene polymers in such process may be incomplete, such that the polymer mixture indeed is a mixture of polyethylene and polypropylene. Furthermore, the polymer mixture may comprise further polymers, e.g., polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), but also degradable polyesters, such as polylactic acid (polylactide, PLA) and polyethylene-2,5-furandicarboxylate, polyvinyl chloride, polyvinylidene chloride (PVDC), polyvinylidene fluoride (PVDF) and polytetrafluoroethylene (PTFE), polybutadiene, polyacrylonitrile, polymethylmethacrylate, polyamides, polyurethanes, and mixtures thereof.
Preferably, process steps b1) to b5) are performed such that the polymer mixture comprises the further polymers in an amount of at most 5 wt.-%, preferably at most 2 wt.-%, based on the total amount of polymer in the filled polymer composition.
In a preferred embodiment of the inventive process, in step b) a polymer mixture comprising polyethylene and polypropylene is provided, wherein the polymer mixture is derived from waste polymers.
In another preferred embodiment of the inventive process, in step b) a polymer mixture comprising polyethylene and polypropylene is provided, wherein the polymer mixture is derived from waste polymers, and additionally at least one polyethylene polymer and/or at least one polypropylene polymer is provided, wherein the at least one polyethylene polymer and the at least one polypropylene polymer are derived from virgin polymers.
According to step c) of the inventive process, the polyethylene polymer and the polypropylene polymer and/or the polymer mixture of step b), and the surface-treated calcium carbonate-containing filler material and the peroxide agent of step a) are mixed, in any order, to obtain a mixture.
Mixing step c) may be performed by any means known to the skilled person, including, but not limited to, blending, extruding, kneading, and high-speed mixing.
According to step d) of the inventive process, the mixture of step c) is compounded to obtain a filled polymer composition, wherein the filled polymer composition comprises the surface-treated calcium carbonate-containing filler material in an amount from 2 wt.-% to 85 wt.-%, based on the total weight of the filled polymer composition.
In a preferred embodiment of the present invention, mixing step c) and compounding step d) are performed simultaneously. Preferably, the surface-treated calcium carbonate-containing filler material of step c) is admixed after mixing the polyethylene polymer and the polypropylene polymer and/or the polymer mixture of step b), more preferably wherein the mixture of the polyethylene polymer and the polypropylene polymer and/or the polymer mixture of step b) is at least partially in the molten state. Thus, it is appreciated that the mixing step c) may take place during compounding step d).
Mixing step c) and/or compounding step d) may be done with a suitable extruder, preferably by a twin screw extruder (co- or counter-rotating) or by any other suitable continuous compounding equipment, e.g. a continuous co-kneader (Buss), a continuous mixer (Farrel Pomini), a ring extruder (Extricom) or the like. The continuous polymer mass from extrusion may be either pelletized by (hot cut) die face pelletizing with underwater pelletizing, eccentric pelletizing and water ring pelletizing or by (cold cut) strand pelletizing with underwater and conventional strand pelletizing to form the extruded polymer mass into pellets.
Optionally, mixing step c) and/or compounding step d) may also be performed with a discontinuous or batch process using an internal (batch) mixer, e.g. a Banburry mixer (HF Mixing Group) or a Brabender mixer (Brabender) or the like.
During mixing step c) and/or compounding step d), at least one further polymer may be added. The at least one further polymer may be selected from the group comprising polystyrene, polyesters, such as polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), but also degradable polyesters, such as polylactic acid (polylactide, PLA) and polyethylene-2,5-furandicarboxylate, polyvinyl chloride, polyvinylidene chloride (PVDC), polyvinylidene fluoride (PVDF) and polytetrafluoroethylene (PTFE), polybutadiene, polyacrylonitrile, polymethylmethacrylate, polyamides, polyurethanes, and mixtures thereof. Preferably, the at least one further polymer is selected from the group comprising polystyrene, polyesters, preferably polyethylene terephthalate, polylactic acid, polyhydroxybutyrate and polyethylene-2,5-furandicarboxylate, polyvinyl chloride, polybutadiene, polyacrylonitrile, polymethylmethacrylate, polyamides, polyurethanes, and mixtures thereof. The at least one further polymer may be added in an amount of at most 50 wt.-%, preferably at most 30 wt.-%, more preferably at most 15 wt.-%, and most preferably at most 5 wt.-%, based on the total amount of the polymer in the filled polymer composition.
Additionally or alternatively, during mixing step c) and/or compounding step d), at least one additive may be added. The additive is selected from the group consisting of further fillers, preferably selected from the group consisting of talc, mica, kaolin, bentonite or mixtures thereof, UV-absorbers, light stabilizers, processing stabilizers, antioxidants, heat stabilizers, nucleating agents, metal deactivators, impact modifiers, plasticizers, lubricants, rheology modifiers, processing aids, pigments, dyes, optical brighteners, antimicrobials, antistatic agents, slip agents, anti-block agents, coupling agents, dispersants, compatibilizers, oxygen scavengers, acid scavengers, markers, antifogging agents, surface modifiers, flame retardants, blowing agents, smoke suppressors, or mixtures of the foregoing additives. The at least one additive may be added in an amount of up to 30 wt.-%, preferably up to 5 wt.-%, more preferably up to 2 wt.-%, based on the total weight of the filled polymer composition. The total amount of additives added may be up to 35 wt.-%, preferably up to 5 wt.-%, more preferably up to 2 wt.-%, based on the total weight of the filled polymer composition.
According to one embodiment, a further filler is added. The further filler may be selected from the group comprising carbon black, silica, ground natural calcium carbonate, precipitated calcium carbonate, nanofillers, graphite, clay, talc, diatomaceous earth, barium sulfate, titanium dioxide, wollastonite, and mixtures thereof. Preferably, the further filler is selected from the group consisting of talc, mica, kaolin, bentonite or mixtures thereof. The further filler may added in an amount of at most 30 wt.-%, more preferably at most 15 wt.-%, and most preferably at most 5 wt.-%, based on the total amount of the filled polymer composition.
It is to be understood that the further filler can be distinguished from the surface-treated calcium carbonate-containing filler material, e.g., by its chemical composition and/or by its particle size. Thus, it is to be understood that, if the at least one further filler is selected from ground natural calcium carbonate or precipitated calcium carbonate, said further filler has a weight median particle size (d50) value of more than 4.0 µm and a top cut (d98) value of more than 30 µm and/or does not comprise a surface-treatment layer as defined hereinabove.
It is appreciated that in compounding step d), a filled polymer composition is obtained. The filled polymer composition comprises the surface-treated calcium carbonate-containing filler material in an amount from 2 wt.-% to 85 wt.-%, based on the total weight of the filled polymer composition. It is to be understood that the amounts of the at least one polyethylene polymer, the at least one polypropylene polymer and/or the polymer mixture comprising polyethylene and polypropylene, the surface-treated calcium carbonate-containing filler material and optionally the at least one further polymer and/or the at least one additive and/or the peroxide agent, if present, are provided and/or added during mixing step c) and/or compounding step d) such that the so-obtained filled polymer composition comprises the surface-treated calcium carbonate-containing filler material in the required amounts.
If in step b) a polymer mixture comprising polyethylene and polypropylene and being derived from waste polymers is provided, it is appreciated that said polymer mixture may comprise further polymers and further additives. Furthermore, if said polymer mixture is derived from waste polymers comprising the inventive filler, as would be the case, if the inventive filled polymer composition as described hereinabove were to be disposed of and would form part of said waste polymers, the polymer mixture provided in step b) already contains certain amounts of the inventive filler. Consequently, the amounts of polyethylene, polypropylene, further polymers, further additives and the surface-treated calcium carbonate-containing filler material, which may already be present in the polymer mixture have to be taken into account when performing the inventive process.
The skilled person knows how to determine the composition of the polymer mixture by routine methods, such as determination of the ash content, Fourier-transform infrared spectroscopy (FTIR), near-infrared spectroscopy, X-ray detection, laser sorting, nuclear magnetic resonance and/or electrostatic detection methods. If the polymer mixture is derived from post-industrial waste polymers, the composition may be well-known from the manufacturer of said post-industrial waste polymers.
Consequently, the inventive process is performed such that the filled polymer composition obtained in step d) comprises the surface-treated calcium carbonate-containing filler material in an amount from 2 wt.-% to 85 wt.-%, preferably from 2 wt.-% to 70 wt.-%, more preferably from 5 wt.-% to 60 wt.%, most preferably 7 wt.-% to 40 wt.-%, based on the total weight of the filled polymer composition. Preferably, the inventive process is performed such that the filled polymer composition obtained in step d) comprises the peroxide agent and/or reaction products thereof in an amount from 0.01 to 0.5 wt.-%, preferably from 0.02 to 0.3 wt.-%, more preferably from 0.03 to 0.2 wt.-%, and most preferably from 0.04 to 0.15 wt.-%, based on the total amount of the surface-treated calcium carbonate-containing filler material.
Additionally or alternatively, the filled polymer composition obtained in step d) comprises the at least one polypropylene polymer in an amount from 0.5 to 99 wt.-%, preferably from 1 to 70 wt.-%, more preferably from 1 wt.-% to 50 wt.-%, still more preferably from 1 to 30 wt.-%, even more preferably from 2 to 30 wt.-% and most preferably from 5 to 30 wt.-%, based on the total weight of the polymer in the filled polymer composition. Additionally or alternatively, the filled polymer composition obtained in step d) comprises the at least one polyethylene polymer in an amount from 1.0 to 99.5 wt.-%, preferably from 30 to 99 wt.-%, more preferably from 50 wt.-% to 99 wt.-%, still more preferably from 70 to 99 wt.-%, even more preferably from 70 to 98 wt.-% and most preferably from 70 to 95 wt.-%, based on the total weight of the polymer in the filled polymer composition.
Additionally or alternatively, the filled polymer composition obtained in step d) comprises a total amount of polymer being derived from waste polymers of at least 20 wt.-%, preferably at least 50 wt.-%, more preferably at least 70 wt.-%, still more preferably at least 85 wt.-%, and most preferably at least 95 wt.-%, based on the total amount of polymer in the filled polymer composition.
Additionally or alternatively, the filled polymer composition obtained in step d) comprises at least one further polymer in an amount of at most 50 wt.-%, preferably at most 30 wt.-%, more preferably at most 15 wt.-%, and most preferably at most 5 wt.-%, based on the total amount of the polymer in the filled polymer composition.
Additionally or alternatively, the filled polymer composition obtained in step d) comprises at least one additive in an amount of up to 30 wt.-%, preferably up to 5 wt.-%, more preferably up to 2 wt.-%, based on the total weight of the filled polymer composition. The total amount of additives may be up to 35 wt.-%, preferably up to 5 wt.-%, more preferably up to 2 wt.-%, based on the total weight of the filled polymer composition.
In a preferred embodiment of the process of the present invention, mixing step c) and compounding step d) are performed simultaneously, wherein the surface-treated calcium carbonate-containing filler material of step a) is admixed after mixing the polyethylene polymer and the polypropylene polymer and/or the polymer mixture of step b), more preferably wherein the mixture of the polyethylene polymer and the polypropylene polymer and/or the polymer mixture of step b) is at least partially in the molten state. For example, the inventive filler may be injected directly into the injection zone of the extruder, e.g., at any split-feed inlet port along the kneading screw of the extruder. A suitable process is disclosed in EP2981568 A1.
In another preferred embodiment of the process of the present invention, compounding step d) is performed at a temperature in the range from 150 to 260° C., more preferably from 170 to 240° C., and most preferably from 180 to 230° C., and/or compounding step d) is an extrusion step.
In a preferred embodiment of the present invention, the mixing step c) comprises the sub-steps of
It is to be understood that the at least one polyethylene polymer or the at least one polypropylene polymer of step c1) may be the same or different from the at least one polyethylene polymer or the at least one polypropylene polymer provided in step b). However, the at least one polyethylene polymer or the at least one polypropylene polymer of step c1) are as described hereinabove.
Preferably, the masterbatch obtained in step c1) comprises at least one polyethylene polymer or at least one polypropylene polymer being a virgin polymer. In this embodiment, it is preferred that the treated masterbatch obtained in step c2) is mixed in step c3) with a polymer mixture comprising polyethylene and polypropylene and being derived from waste polymers.
Step c1) may be performed by any compounding method known to the skilled person. Preferably, step c1) is performed by a kneading process, wherein a premix of the surface-treated calcium carbonate-containing filler material of step a) and at least one polyethylene polymer or at least one polypropylene polymer of step b) is continuously fed to an extruder, such as a single screw or twin screw extruder. The extruder is heated to a temperature sufficiently high to allow for efficient mixing of the surface-treated calcium carbonate-containing filler material and the at least one polyethylene polymer or the at least one polypropylene polymer. A suitable temperature range is 150 to 260° C.
Alternatively, the surface-treated calcium carbonate-containing filler material may be added during step c1) to the at least partially molten at least one polyethylene polymer or the at least one polypropylene polymer, e.g., at any split-feed inlet port along the kneading screw of the extruder.
During step c1), at least one further additive as described hereinabove may be added.
The masterbatch may be obtained as a material having a defined shape, such as pellets, spheres, pearls, beads, prills, flakes, chips or slugs, or a non-defined shape, such as, for example, crumbles. Alternatively, the polymer composition may be a mixture of both defined and non-defined shape materials. Preferably, a pelletizing step is performed after the kneading process to provide the masterbatch in the form of pellets.
In a further embodiment of the present invention, the masterbatch obtained in step c1) consists of the surface-treated calcium carbonate-containing filler material of step a) and the polypropylene polymer or the polyethylene polymer of step b).
It is appreciated that in treating step c2), the masterbatch material is mixed with the peroxide agent such that the peroxide agent is soaked onto the masterbatch material, i.e., is dispersed or dissolved on the surface of the masterbatch material. Preferably, step c2) is performed such that the shape of the masterbatch material is essentially retained, e.g., by using standard mixing equipment that does not impart high shear forces onto the material (as would be the case, e.g., when using high-shear mixers or ball mills).
In the case that the peroxide agent is solid at room temperature, it is preferred that treating step c2) is performed at a temperature in the range from the melting point of the peroxide agent to slightly below the decomposition temperature of the peroxide agent to prevent premature reaction of the peroxide agent with the components of the masterbatch. For the purposes of the present invention, the “decomposition temperature” refers to the temperature at which the peroxide agent begins to decompose thermally, e.g., by cleavage of the oxygen-oxygen single bond. The decomposition temperature may be determined by differential scanning calorimetry or thermogravimetrical analysis and may be defined therein as an onset temperature.
For example, the peroxide agent may be pre-heated to a desired temperature and added to the masterbatch material. Alternatively, the mixing equipment itself may be heated to the desired temperature. Preferably, treating step c2) is performed at a temperature in the range from 0° C. to 90° C., preferably 20° C. to 75° C., more preferably 25° C. to 70° C.
Alternatively, step c) may comprise the sub-step c1) of forming a masterbatch, but does not comprise sub-step c2) of treating the masterbatch. Thus, in mixing step c3), the masterbatch of step c1) and the peroxide agent of step a) may be mixed separately, in any order, with the the same or different at least one polyethylene polymer and/or at least one polypropylene polymer and/or polymer mixture comprising polyethylene and polypropylene of step a) to obtain a mixture comprising polyethylene and polypropylene.
In yet another embodiment of the present invention, mixing step c) comprises the sub-steps of
In the case that the peroxide agent is solid at room temperature, it is preferred that treating step c4) is performed at a temperature in the range from the melting point of the peroxide agent to slightly below the decomposition temperature of the peroxide agent to prevent premature reaction of the peroxide agent with the components of the masterbatch.
For example, the peroxide agent may be pre-heated to a desired temperature and added to the masterbatch material. Alternatively, the mixing equipment itself may be heated to the desired temperature. Preferably, treating step c4) is performed at a temperature in the range from 0° C. to 90° C., preferably 20° C. to 75° C., more preferably 25° C. to 70° C.
In another embodiment of the present invention, the process comprises at least one further step e) of forming the filled polymer composition obtained in step d) into an article, preferably by injection moulding or film or sheet formation. Preferred film formation processes include blown film formation and cast film formation.
In an exemplary embodiment of the present invention, the process comprises the steps of
In another exemplary embodiment of the present invention, the process comprises the steps of
In still another preferred embodiment of the present invention, the process comprises the steps of
A third aspect of the present invention relates to a filled polymer composition obtainable by reacting the inventive filled polymer mixture or obtainable by the inventive process.
It is appreciated that the “filled polymer composition” relates to a reaction product, which may be obtained by reacting the filled polymer mixture, e.g., by heating it to a certain temperature, for example above the decomposition temperature of the peroxide agent or by a process as described hereinbelow. Thus, the filled polymer composition comprises reaction products of the peroxide agent with the surface-treatment layer of the surface-treated calcium carbonate-containing filler material and/or the polyethylene polymer and/or the polypropylene polymer. The inventive filled polymer mixture and the inventive process for obtaining the filled polymer composition has been described in detail hereinabove.
A fourth aspect of the present invention relates to the use of a surface-treated calcium carbonate-containing filler material and a peroxide reagent for reacting a polymer mixture comprising at least one polyethylene polymer and at least one polypropylene polymer,
The present inventors realized that by reacting the polymer mixture comprising the at least one polyethylene polymer and the at least one polypropylene polymer by use of the surface-treated calcium carbonate-containing filler material and the peroxide reagent, the mechanical properties of the resulting polymer composition can be improved.
It is appreciated that the surface-treated calcium carbonate-containing filler material, the calcium carbonate-containing filler material, the at least one surface-treatment agent and/or salty reaction products thereof, the peroxide agent, the at least one polyethylene polymer and at least one polypropylene polymer are as defined hereinabove.
In a preferred embodiment of the present invention, the at least one polyethylene polymer and the at least one polypropylene polymer are at least partially derived from waste polymers. Thus, the filled polymer composition may comprise a mixture of virgin and recycled polymers.
More preferably, the total amount of polymer being derived from waste polymers in the filled polymer composition is at least 20 wt.-%, more preferably at least 50 wt.-%, even more preferably at least 70 wt.-%, still more preferably at least 85 wt.-%, and most preferably at least 95 wt.-%, based on the total amount of polymer in the filled polymer composition.
Furthermore, the filled polymer composition may comprise further polymers, e.g., polyethylene terephthalate (PET), polytrimethylene terephthalate (PTT), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN), but also degradable polyesters, such as polylactic acid (polylactide, PLA) and polyethylene-2,5-furandicarboxylate, polyvinyl chloride, polyvinylidene chloride (PVDC), polyvinylidene fluoride (PVDF) and polytetrafluoroethylene (PTFE), polybutadiene, polyacrylonitrile, polymethylmethacrylate, polyamides, polyurethanes, and mixtures thereof.
In one embodiment of the present invention, the at least one polypropylene polymer is present in the filled polymer composition in an amount from 0.5 to 99 wt.-%, preferably from 1 to 70 wt.-%, more preferably from 1 wt.-% to 50 wt.-%, still more preferably from 1 to 30 wt.-%, even more preferably from 2 to 30 wt.-% and most preferably from 5 to 30 wt.-%, based on the total weight of the polymer in the filled polymer composition. Additionally or alternatively, the at least one polyethylene polymer is present in the inventive filled polymer composition in an amount from 1.0 to 99.5 wt.-%, preferably from 30 to 99 wt.-%, more preferably from 50 wt.-% to 99 wt.-%, still more preferably from 70 to 99 wt.-%, even more preferably from 70 to 98 wt.-% and most preferably from 70 to 95 wt.-%, based on the total weight of the polymer in the filled polymer composition. In the case that the at least one polyethylene polymer and the at least one polypropylene polymer are at least partially derived from waste polymers, it is to be understood that the amounts of the at least one polyethylene polymer and the at least one polypropylene polymer are determined at least partially by the source and/or composition of the waste polymer. In view thereof, it is appreciated that the invention is not limited to specific amounts of polyethylene polymer and polypropylene polymer.
As an illustrative example, the filled polymer composition may comprise a polymer mixture being derived from waste polymers, which comprises, e.g., from 50 to 99 wt.-%, preferably from 70 to 99 wt.-%, more preferably from 70 to 98 wt.-%, most preferably from 70 to 95 wt.-%, based on the total weight of the polymer mixture, of at least one polyethylene polymer and, e.g., from 1 to 50 wt.-%, preferably from 1 to 30 wt.-%, more preferably from 2 to 30 wt.-%, most preferably from 5 to 30 wt.-%, based on the total weight of the polymer mixture, of at least one polypropylene polymer. The polymer mixture being derived from waste polymers may be present in an amount of at least 20 wt.-%, preferably at least 50 wt.-%, more preferably at least 70 wt.-%, still more preferably at least 85 wt.-%, and most preferably at least 95 wt.-%, based on the total amount of polymer in the filled polymer composition. Additionally, the filled polymer composition may comprise at least one further polyethylene polymer being a virgin polymer and/or at least one further polypropylene polymer being a virgin polymer, e.g., such that the polymer mixture and the at least one further polyethylene polymer being a virgin polymer and/or at least one further polypropylene polymer being a virgin polymer add up to 100 wt.-%, based on the total amount of polymer in the filled polymer composition.
Thus, in a preferred embodiment of the present invention, the filled polymer composition comprises a total amount of polymer being derived from waste polymers of at least 20 wt.-%, preferably at least 50 wt.-%, more preferably at least 70 wt.-%, still more preferably at least 85 wt.-%, and most preferably at least 95 wt.-%, based on the total amount of polymer in the filled polymer composition.
Preferably, the filled polymer composition comprises the at least one polyethylene polymer and the at least one polypropylene polymer in a combined amount of at least 50 wt.-%, preferably at least 80 wt.-%, more preferably at least 95 wt.-%, and most preferably at least 98 wt.-%, based on the total weight of the polymer in the filled polymer composition.
Preferably, the mechanical properties of the so-obtained filled polymer composition are improved.
The expression “improving the mechanical properties” is to be understood in that at least one of the mechanical properties of the polymer composition, e.g., impact strength or resilience, tensile modulus or elongation at break, is improved, compared to either the same polymer composition not comprising the surface-treated calcium carbonate-containing filler material or to the same polymer composition comprising the same calcium carbonate-containing filler material lacking a surface-treatment layer or to the same polymer composition not comprising the peroxide agent or to the same polymer composition comprising neither the surface-treated calcium carbonate-containing filler material nor the peroxide agent. By “the same polymer composition”, it is meant that a polymer composition not comprising the surface-treated calcium carbonate-containing filler material, or comprising the same calcium carbonate-containing filler material lacking a surface-treatment layer or not comprising the peroxide agent, all else being equal, is produced in the same way as the inventive polymer composition, i.e., following the same method steps for its production and using the same remaining compounds in the same relative amounts other than the omitted material (the surface-treated calcium carbonate-containing filler material or the surface-treatment layer or the peroxide agent, respectively).
Preferably, the tensile modulus of the polymer composition is essentially maintained or increased, preferably by at least 5%, more preferably at least 10%, and most preferably at least 15%, compared to the same polymer composition not comprising the surface-treated calcium carbonate-containing filler material. The tensile modulus is measured according to ISO 527-1:2019.
Preferably, the tensile modulus of the polymer composition is essentially maintained or increased, preferably by at least 5%, more preferably at least 10%, and most preferably at least 15%, compared to the same polymer composition comprising the same calcium carbonate-containing filler material lacking a surface-treatment layer. The tensile modulus is measured according to ISO 527-1:2019.
Preferably, the tensile modulus of the polymer composition is essentially maintained or increased, preferably by at least 5%, more preferably at least 10%, and most preferably at least 15%, compared to the same polymer composition comprising the same surface-treated calcium carbonate-containing filler material but lacking the peroxide agent. The tensile modulus is measured according to ISO 527-1:2019.
Preferably, the tensile modulus of the polymer composition is essentially maintained or increased, preferably by at least 5%, more preferably at least 10%, and most preferably at least 15%, compared to the same polymer composition comprising neither the surface-treated calcium carbonate-containing filler material nor the peroxide agent.
In a preferred embodiment of the present invention, the impact strength or resilience of the polymer composition is increased, preferably by at least 10%, more preferably by at least 20%, even more preferably by at least 25%, or by at least 50%, for example at least 100%, determined by ISO 179-1eA:2010-11, compared to the same polymer composition not comprising the surface-treated calcium carbonate-containing filler material.
In a particularly preferred embodiment of the present invention, the impact strength or resilience of the polymer composition is increased, preferably by at least 10%, more preferably by at least 20%, even more preferably by at least 25%, or by at least 50%, for example at least 100%, determined by ISO 179-1eA:2010-11, compared to the same polymer composition comprising the same calcium carbonate-containing filler material lacking a surface-treatment layer.
In a preferred embodiment of the present invention, the impact strength or resilience of the polymer composition is increased, preferably by at least 10%, more preferably by at least 20%, even more preferably by at least 25%, or by at least 50%, for example at least 100%, determined by ISO 179-1eA:2010-11, compared to the same polymer composition comprising the same surface-treated calcium carbonate-containing filler material but lacking the peroxide agent.
Preferably, the impact strength or resilience of the polymer composition is increased, preferably by at least 10%, more preferably by at least 20%, even more preferably by at least 25%, or by at least 50%, for example at least 100%, determined by ISO 179-1eA:2010-11, compared to the same polymer composition comprising neither the surface-treated calcium carbonate-containing filler material nor the peroxide agent.
A fifth aspect of the present invention relates to an article comprising the inventive filled polymer mixture or the inventive filled polymer composition as defined hereinabove.
Preferably, the inventive article may comprise the inventive filled polymer composition inventive filled polymer mixture or the in the form of fibers, filaments, films, threads, sheets, pipes, profiles, molds, injection molded compounds and blow molded compounds.
The inventive article may be used in packaging applications, (in the form of plastic bags, films, containers, bottles, food packagings, microwavable containers, trays etc.), building and construction applications, automotive applications, electrical and electronic applications, agricultural applications, household applications and leisure and sports applications.
The article is preferably selected from the group comprising hygiene products, medical and healthcare products, filter products, geotextile products, agriculture and horticulture products, clothing, footwear and baggage products, household and industrial products, packaging products, construction products and the like. For example, the article may be selected from the group comprising pipes, paint pots, flower pots, garden chairs, bottles, plastic bags, films, containers, food packagings, microwavable containers, trays, automotive parts, bank notes, hinged caps, sweet and snack wrappers, agricultural film, toys, houseware, window frames, profiles, floor and wall covering, cable insulation, garden hoses, garbage bins and the like.
Preferably, the mechanical properties of the inventive article are improved as defined hereinabove.
Preferably, the impact strength or resilience of the article is increased, preferably by at least 10%, more preferably by at least 20%, even more preferably by at least 25%, or by at least 50%, for example at least 100%, determined by ISO 179-1eA:2010-11, compared to the same article not comprising the peroxide agent or compared to the same article comprising the same calcium carbonate-containing filler material lacking a surface-treatment layer.
The following examples are meant to additionally illustrate the invention. However, the examples are not meant to restrict the scope of the invention in any way.
Throughout the present document, the specific surface area (in m2/g) of the mineral filler is determined using the BET method (using nitrogen as adsorbing gas), which is well known to the skilled man (ISO 9277:2010). The total surface area (in m2) of the mineral filler is then obtained by multiplication of the specific surface area and the mass (in g) of the mineral filler prior to treatment.
The amount of the treatment layer on the calcium carbonate-comprising filler material is calculated theoretically from the values of the BET of the untreated calcium carbonate-containing filler material and the amount of at least one hydrophobizing agent that are used for the surface-treatment.
As used herein and as generally defined in the art, the “d50” value is determined based on measurements made by using a Sedigraph™ 5100 of Micromeritics Instrument Corporation and is defined as the size at which 50% (the median point) of the particle mass is accounted for by particles having a diameter equal to the specified value.
The method and the instrument are known to the skilled person and are commonly used to determine grain size of fillers and pigments. The measurement is carried out in an aqueous solution of 0.1 wt.-% Na4P2O7. The samples are dispersed using a high speed stirrer and supersonics.
The impact properties are measured according to ISO 179-1eA:2010-11 on a HIT5.5P device from Zwick Roell. Measurements are performed on notched samples with a hammer of 2 J. All measurements are performed on samples that have been stored under similar conditions after preparation.
Materials used in the examples:
1. Polymer resin
Example 1: The polymer resins used are a virgin linear low density polyethylene (CAS No. 9002-88-4) Dowlex®2631.10UE (MFR = 7 g/10 min) commercially available from Resinex® and a virgin polypropylene PP (CAS No. 9003-07) Moplen™ HP525J (MFR = 3 g/10 min) from LyondellBasell®,
Example 2: The polymer resin used are a virgin linear low density polyethylene (CAS No. 9002-88-4) Dowlex2631.10UE (MFR = 7 g/10 min) commercially available from Resinex and a recycled polypropylene containing 20 wt.-% talc.
Example 3: The polymer resin used are KWR105M2 (MFR = 4 g/10 min), a mixture of high density polyethylene HDPE and 15% polypropylene derived from post-consumer waste polymer from KW Plastics as main matrix and a virgin linear low density polyethylene (CAS No. 9002-88-4) LLDPE 6101XR (MFR 20 g/10 min) commercially available from ExxonMobil® for masterbatches.
2. Calcium carbonate-containing filler material CC1
The calcium carbonate CC1 is a dry ground marble from Italy (d50 = 1.7 µm, d98 = 8 µm (measured with Sedigraph), BET SSA = 4.1 m2/g).
3. Hydrophobizing agent 01: ASA 1
Mono-substituted alkenyl succinic anhydride (2,5-Furandione, dihydro-, mono-C15-20-alkenyl derivs., CAS No. 68784-12-3) is a blend of mainly branched octadecenyl succinic anhydrides (CAS #28777-98-2) and mainly branched hexadecenyl succinic anhydrides (CAS #32072-96-1). More than 80% of the blend is branched octadecenyl succinic anhydrides. The purity of the blend is > 95 wt.-%. The residual olefin content is below 3 wt.-%.
4. Hydrophobizing agent 02: Fatty acids mixture 2
Fatty acid mixture 2 is a mixture of about 40% stearic acid and about 60% palmitic acid.
5. Hydrophobizing agent 03:
Hydrophobizing agent 03 is a grafted polybutadiene homopolymer comprising at least one succinic anhydride group obtained by grafting maleic anhydride onto a polybutadiene homopolymer (Mn = 3100 Da, Brookfield viscosity (25° C.) = 6500 cPs ± 3500, functional groups/chain = 2, anhydride equivalent weight 1238 g/mol; acid number: 40.1-51.5 meq KOH/g, total acid: 7-9 wt.-%, microstructure (molar% of butadiene): 20-35% 1-2 vinyl functional groups) commercially available from Cray Valley® under the trade name RICON® 130MA8.
6. Cross-linking agent: DCP
Dicumyl peroxide (bis(1-methyl-1-phenylethyl) peroxide, CAS No. 80-43-3) is a radical initiator obtained from Sigma-Aldrich.
Surface treatments were carried in a high speed mixer (Somakon MP-LB Mixer, Somakon Verfahrenstechnik, Germany), and conditioned by stirring for 10 minutes at the treatment temperature (600-1000 rpm). After that time, the additives were added to the mixture and stirring and heating is then continued for another 15 minutes for each step (600-1000 rpm). After that time, the mixture is allowed to cool and the powder is collected.
Compounds CP-1 to CP-7 were produced on a twin-screw extruder 25:1 from Three Tec (Extruder Type ZE12, die: 0.5 mm) with the following line settings:
Besides the conveyor belt a water bath is used to cool down the strand before cutting it.
The polymer matrix used is a mixture of a linear low-density polyethylene (LLDPE) that can be obtained from Resinex under the tradename Dowlex2631.10UE and a virgin polypropylene from LyondellBasell under the tradename Moplen HP525J. The composition of the polymer matrix is a ratio of 70 wt.-%LLDPE — 30 wt.-% PP.
All polymeric components (granules) were grinded on a Retsch® SR300 rotor beater mill before use. All components of the compounds are premixed together in a vessel before being extruded.
Compounds CP-8 to CP-16 were produced on a twin-screw extruder 25:1 from Three Tec (Extruder Type ZE12, die: 0.5 mm) with the following line settings:
Besides the conveyor belt a water bath is used to cool down the strand before cutting it.
The polymer matrix used is a mixture of a virgin linear low-density polyethylene (LLDPE) that can be obtained from Resinex under the tradename Dowlex2631.10UE and a recycled polypropylene containing 20 wt.-% talc. The composition of the polymer matrix is a ratio of 70 wt.-%LLDPE — 30 wt.-% rPP.
Some masterbatches are used for compounds 15 and 16.
Masterbatches 1 and 2 were produced on a twin-screw extruder 25:1 from Three Tec (Extruder Type ZE12, die: 0.5 mm) with the following line settings:
All polymeric components (granules) were grinded on a Retsch SR300 rotor beater mill before use. All components of the compounds or masterbatches are premixed together in a vessel before being extruded.
Samples containing 20 wt.-% filler in a polymer derived from post-consumer waste polymer. Filled polymer compositions CP-17 to CP-23 and masterbatches for CP-22 and CP-23 were produced on a twin-screw extruder from MARIS (Extruder Type TM 20HT (D=20 mm, L/D=48, D/d=1.55, 11 Nm/cc, 15 kW, die: 2 holes of 3 mm diameter) with the following line settings
The polymer matrix used is a mixture of high-density polyethylene (HDPE) and 15% polypropylene (PP) that can be obtained from KW Plastics under the tradename KWR105M2
Charpy samples were made by using a Xplore IM12 injection moulder from Xplore Instruments B.V with pellets produced as described in Table 2 and 4 with the settings indicated in Table 7:
The dimension of the produced samples are the following ones: 80 mm x 10 mm x 4 mm. These samples have been notched by using an Automatic NotchVis Plus from CEAST®. The radius of the notch is 0.25 mm with a depth of 2 mm.
Impact tests are made according to ISO179-1eA (notched).
As can be seen from table 8.1 the impact strength can be improved by a treatment comprising only a hydrophobizing agent (CP-6, comparative) when compared to a similar composition containing an untreated calcium carbonate (CP-4, comparative). By further addition of peroxide to the treated calcium carbonate (CP-7, inventive) the impact strength can be further improved which is not the case with an untreated calcium carbonate. Thus it is the combination of the hydrophobizing surface treatment agent and the peroxide that allows a more significant increase of impact strength.
As can be seen from table 8.2, this example confirms the impact strength / resilience can be improved by a treatment (CP-12) comprising only a hydrophobizing agent when compared to an untreated calcium carbonate (CP-11). By further addition of a peroxide (used as a co-treatment or as an additive, respectively CP-13 and CP-14) the impact strength can be further improved and even more by using a peroxide-coated masterbatch (CP-15). These further improvements are even more significant when the hydrophobizing agent is an unsaturated compound. Furthermore, adding the inventive calcium carbonate filler to a PE/PP mixture increases the impact strength compared to the unfilled PE/PP mixture.
As can be seen from table 8.3, this example confirms the impact strength / resilience can be improved by a treatment (CP-19) comprising only a hydrophobizing agent when compared to an untreated calcium carbonate (CP-18). By further addition of a peroxide (used as a co-treatment, CP-20) the impact strength can be further improved. These further improvements are even more significant when the hydrophobizing agent is an unsaturated compound. The use of a peroxide-coated masterbatch (CP-23) also provides an impact strength improvement when compared to the use of a masterbatch without the coating of peroxide (CP-22). Furthermore, adding the inventive calcium carbonate filler to a PE/PP mixture increases the impact strength compared to the unfilled PE/PP mixture.
| Number | Date | Country | Kind |
|---|---|---|---|
| 20200145.9 | Oct 2020 | EP | regional |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2021/077302 | 10/4/2021 | WO |
