Patent Application
20220025150
The present invention relates to a new polyolefin composition, which comprises a high quantity, such as greater than or equal to 80 wt.-%, of a recycled polypropylene rich material.
Polyolefins, in particular polyethylene and polypropylene are increasingly consumed in large amounts in a wide range of applications, including packaging for food and other goods, fibres, automotive components, and a great variety of manufactured articles. The reason for this is not only a favourable price/performance ratio, but also the high versatility of these materials and a very broad range of possible modifications, which allows tailoring of end-use properties in a wide range of applications. Chemical modifications, copolymerisation, blending, drawing, thermal treatment and a combination of these techniques can convert common-grade polyolefins into valuable products with desirable properties. This has led to huge amounts of polyolefin materials being produced for consumer applications.
During the last decade, concern about plastics and the environmental sustainability of their use in current quantities has arisen. This has led to new legislation on disposal, collection and recycling of polyolefin materials. There, in addition, have been efforts in a number of countries to increase the percentage of plastic materials, which are recycled instead of being sent to landfill.
In Europe, plastic waste accounts for approximately 27 million tons of waste a year; of this amount in 2016, 7.4 million tons were disposed of in landfill, 11.27 million tons were burnt (in order to produce energy) and around 8.5 million tons were recycled (http://www.plasticsrecyclers.eu/plastic-recycling accessed August 2018). Polypropylene is used in a wide variety of consumer applications, including pipes, specialised packaging and laboratory materials; consequently, a large amount of plastic waste is polypropylene. Taking into account the huge amount of waste collected compared to the amount of waste recycled back into the stream (only about 30%), there is still a huge potential for intelligent reuse of plastic waste streams and for mechanical recycling of plastic wastes.
Taking the automobile industry as an example. In Europe the end of life (ELV) directive from the EU states, that 85%/95% of materials from vehicles should be a recyclable or recoverable. The present rate of recycling of automobile components is significantly below this target. On average vehicles consist of 9 wt.-% plastics, out of this 9 wt.-% only 3 wt.-% is currently recycled. Therefore, there is still a need to be met if targets for recycling plastics in the automobile industry are to be achieved. This invention particularly focuses on mechanically recycled waste streams as opposed to “energetic recycling” where polyolefins are burnt and used for energy. However, due to cost reasons, poor mechanical properties and inferior processing properties waste streams containing cross-linked polyolefins are often used for energy recovery (e.g. incineration in a district heating plant or for heat generation in the cement industry) and are less often recycled into new products.
One major trend in the field of polyolefins is the use of recycled materials, which are derived from a wide variety of sources. Durable goods streams such as those derived from waste electrical equipment (WEE) or end-of-life vehicles (ELV) contain a wide variety of plastics. These materials can be processed to recover acrylonitrile-butadiene-styrene (ABS), high impact polystyrene (HIPS), polypropylene (PP) and polyethylene (PE) plastics. Separation can be carried out using density separation in water and then further separation based on fluorescence, near infrared absorption or raman fluorescence. However, it is commonly quite difficult to obtain either pure recycled polypropylene or pure recycled polyethylene. Generally, recycled quantities of polypropylene on the market are mixtures of both polypropylene (PP) and polyethylene (PE); this is especially true for post-consumer waste streams. Commercial recyclates from post-consumer waste sources have been found generally to contain mixtures of PP and PE, the minor component reaching up to <50 wt.-%.
The better the quality, i.e. the higher the purity, of the recycled polyolefin the more expensive the material is. Moreover, recycled polyolefin materials are often cross-contaminated with non-polyolefin materials, such as polyethylene terephthalate, polyamide, polystyrene or non-polymeric substances like wood, paper, glass or aluminium. Polyethylene and polypropylene are themselves not particularly compatible and additional impurities result in extremely poor compatibility between the main polymer phases.
In addition, recycled polypropylene rich materials normally have properties, which are much worse than those of the virgin materials, unless the amount of recycled polyolefin added to the final compound is extremely low. For example, such materials often have poor performance in odour and taste, limited stiffness, limited impact strength and poor mechanical properties (such as e.g. brittleness) thus, they do not fulfil customer requirements. For several applications, e.g. pipes, containers, automotive components or household articles. It is of high importance that polypropylene blends show high stiffness (tensile modulus) as well as high impact strength and relatively high elasticity (tensile strain at break). This normally excludes the application of recycled materials for high quality parts, and means that they are only used in low-cost, non-demanding applications, such as e.g. in construction or in furniture. In order to improve the mechanical properties of these recycled materials, it has been proposed to add relatively large amounts of filler, together with compatibilizing/coupling agents and elastomeric polymers. These materials are generally virgin materials, which are produced from petroleum.
US 2009/0048403 relates to polyolefin compositions comprising by weight A) 30 to 80% of a polyolefin component containing not less than 80% of a waste material selected from polyethylene, polypropylene or their mixtures and B) 20 to 70% of a heterophasic polyolefin composition having a flexural modulus equal to or lower than 600 MPa. Component B) comprises one or more propylene polymers selected from crystalline propylene homopolymers or copolymers of propylene with up to 10% of ethylene or other alpha-olefin comonomer(s) or their combinations, and (b) a co-polymer or a composition of co-polymers of ethylene with other alpha-olefins and optionally with minor amounts of a diene (typically from 1 to 10% with respect to the weight of (b)), said copolymer or composition containing 15% or more, in particular from 15% to 90%, preferably from 15 to 85% of ethylene. This application aims at materials with particular tensile properties, which can be used in flexible foils such as geo-membranes for agriculture, roofing and municipal pond applications. This application particularly demonstrates the use of heterophasic polyolefins to improve the properties of recycled polymer materials.
WO 03/087215 A1 is extremely general and relates to techniques for creating recycled plastic materials from waste plastic materials from a variety of sources such as office automation equipment (printers, computers, copiers, etc.), white goods (refrigerators, washing machines, etc.), consumer electronics (televisions, video cassette recorders, stereos, etc.), automotive shredder residue, packaging waste, household waste, building waste and industrial moulding and extrusion scrap. Pre-determined properties of the recycled plastic material can be controlled by selecting the types of waste plastic materials used in the recycling feed, determining the types and amounts of recycled plastic material recovered from a separation process and blending the recycled plastic material with other materials. This document relates to Acrylonitrile butadiene styrene (ABS) materials, High Impact Polystyrene (HIPS) materials, Polypropylene (PP) materials and Polycarbonate (PC) materials. This disclosure primarily relates to mixtures of different grades of polymers. Furthermore, this disclosure relates to materials containing a range of other additives such as carbon black and metals such as Cd, Pb, Hg, Cr and Ni.
WO 2013/025822 A1 relates to a process for creating polyolefin blends from waste streams with controlled rheological properties. In particular, specific MFR2 values. In general, this document focuses on mixtures comprising polypropylene and polyethylene and compounding the mixture with one or more peroxides to produce a polyolefin blend. This document refers to the difficulties involved in separating polypropylene (PP) from high-density polyethylene (HDPE) and that this process is expensive. Furthermore, higher density plastics such as ABS and HIPS can also be found in these streams in small, but measurable amounts. The ratio of PP to HDPE in the PP products can be controlled by the mix of materials in the feed stream and/or by the degree of separation of the two plastic types.
EP 14167409 refers to blends of polypropylene and polyethylene, particularly recycled blends of polypropylene and polyethylene, which contain a specific kind of compatibilizer. The specific compatibilizer can lead to an increase in stiffness as well as impact strength and heat deflection resistance. Unfortunately, PP and PE are highly immiscible resulting in a blend with poor adhesion among its phases, coarse morphology and consequently poor mechanical properties. The compatibility between the phases of a blend can be improved by the addition of compatibilizers, which results in a finer and more stable morphology, better adhesion between the phases of the blends and consequently better properties of the final product.
There is, consequently, a deeply felt need in the art for improving recycled materials in terms of their mechanical performances, i.e. improving the balance between stiffness (Tensile modulus ISO 1873-2), impact strength at +23° C. and at −30° C. (Charpy Notched Impact Strength ISO 179-1 eA) and tensile strain at break (ISO 527-2), while having a material that is also easily processable (e.g. it has a reasonable MFR2 value). In addition, there is still a need in the art for developing methods to increase the use of recycled material in higher value products e.g. in automotive applications and in food packaging.
In order to improve the quality of recycled olefins, generally a quantity of virgin polyolefin is added to the recycled material, to give a polymer blend. The properties of the blend are often dependent on the composition, roughly according to equation 1 (Eq.1).
P(X1)=X1P(1)+(1−X1)P(2) Eq. 1
where, P(X) is the particular property of the blend, P(1) is the property of the recycled material (blend (A)) and P(2) is the property of polymer 2 (compatibilizer (B)). This equation describes a linear relationship between the properties of materials and the weight fractions of each material added.
It is, therefore, important to find the concentration range (X1) in which the properties of the components optimally fulfil the requirements for a particular use of the polymer blend.
The use of compositions comprising high amounts (e.g. greater than 80 wt.-%) of recycled polypropylene materials comprising greater than 80 wt.-% PP, show some drawbacks. In particular, it is presumed by persons skilled in the art that the use of high levels of recycled polyolefins, may lead to poor mechanical properties compared to those of virgin polyolefin materials. This prejudice must be overcome before recycled PP materials will be accepted by industry. Furthermore, in order for a recycling process to be viable the properties of the recycled PP must be acceptable, particularly as PP is a very cheap material and so from an economic perspective there is an immense pressure to produce high quality PP with a low cost.
The present invention insofar provides a polypropylene-polyethylene composition, obtainable by blending
The polypropylene-polyethylene composition of the present invention generally has improved mechanical properties, such as improved tensile strain at break and improved impact strength, compared to the raw recycled polypropylene rich material (blend(A)).
A significant finding of the present invention is that the polypropylene-polyethylene composition as described above has a good balance of stiffness (as determined by the tensile modulus measured according to ISO 527-2), impact strength at both low and ambient temperatures and strain at break. This is particularly surprising given the relatively low xylene soluble content XCS (measured according to ISO 16152, 1 ed, 25° C.) of the compatibilizer. Generally, a higher degree of XCS is related to a higher amorphous content of a polymer. Using a compatibilizer with a high degree of XCS is therefore, generally seen as advantageous when seeking to improve the mechanical properties of polyolefin materials with high polypropylene contents. Furthermore, the compatibilizer has a relatively low intrinsic viscosity of the xylene soluble content IV(XCS) (measured in decalin according to DIN ISO 1628/1 at 135° C.).
The composition of the present invention shows mechanical properties, which at least have reduced the gap between the properties of virgin polypropylene and the recycled material with a high polypropylene content. An additional advantage of the composition of the present invention is that the carbon footprint of the article manufactured from recycled polyolefin materials is significantly lower than products made from virgin materials. This means that the polypropylene-polyethylene compositions of the present invention use significantly less petroleum and less energy than is generally required to create virgin plastics from petroleum. Importantly, the polypropylene-polyethylene composition obtained is stiff, but not brittle and is resistant to impact forces. This is important for a number of potential applications for polypropylene such as e.g. piping and packaging applications.
In a preferred aspect, the present invention relates to the use of a compatibilizer (B) in the polypropylene-polyethylene composition,
for increasing the strain at break properties of a blend (A) comprising
In a preferred aspect, the present invention relates to the use of a compatibilizer (B),
for increasing the impact properties of a blend (A) comprising
In a preferred aspect, the current invention relates to an article comprising a polypropylene-polyethylene composition obtainable by blending
In a preferred aspect, the polypropylene-polyethylene composition according to the current invention has a tensile modulus of at least 1000 MPa (measured according to ISO 527-2 using injection moulded specimens as described in EN ISO 1873-2 (dog bone shape, 4 mm thickness)).
In a preferred aspect, the compatibilizer (B) according to the current invention has tensile strain at break (MD) of at least 400%, more preferably of at least 500% and most preferably of at least 600%. Usually, the compatibilizer (B) according to the current invention will not have tensile strain at break (MD) of above 800%.
In a preferred aspect, the compatibilizer (B) according to the current invention has a content of units derived from ethylene in the XCI (xylene insoluble) fraction of from 2.0 to 6.0 wt.-%.
In a further preferred aspect, the compatibilizer (B) according to the current invention has a content of units derived from ethylene in the XCS (xylene soluble) fraction of from 25.0 to 38.0 wt.-%.
In yet a further preferred aspect, the compatibilizer (B) according to the current invention has an MFR2 (ISO1133; 2.16 kg; 230° C.) of from 5 to 15 g/10 min.
In a preferred aspect, the compatibilizer (B) according to the current invention has a total content of units derived from ethylene of from 5.0 to 10.0 wt.-%.
In a preferred aspect, according to the current invention the xylene soluble XCS of compatibilizer (B) has an intrinsic viscosity (measured in decalin according to DIN ISO 1628/1 at 135° C.) of from 1.3 to less than 2.2 dl/g.
In a preferred aspect, according to the current invention the compatibilizer (B) has flexural modulus of from 400 to 550 MPa (ISO 178, measured on injection-moulded specimens, 23° C.).
In a preferred aspect, the polypropylene-polyethylene composition according to the current invention has a notched Charpy impact strength (1eA) (non-instrumented, ISO 179-1 at +23° C.) of at least 6.0 kJ/m2 and/or a notched Charpy impact strength (1eA) (non-instrumented, ISO 179-1 at −30° C.) of at least 4.0 kJ/m2 and/or a tensile strain at break (ISO 527-1,2) of at least 20%.
In a preferred aspect, the ratio of the tensile modulus of the final polypropylene-polyethylene composition versus the tensile modulus of blend (A) is at least 0.9, preferably at least 0.95.
In a preferred aspect, blend (A) has a content of limonene as determined by solid phase micro-extraction (HS-SPME-GC-MS) of from 1 ppm to below 100 ppm, preferably from 1 ppm to below 50 ppm, more preferably from 2 ppm to below 35 ppm, most preferably from 2 ppm to below 10 ppm.
In a preferred aspect, blend (A)
In a further preferred aspect, blend (A) contains
In a preferred aspect, the present invention relates to an article comprising the polypropylene-polyethylene composition according to the present invention, for use in a consumer application, such as e.g. in packaging or automobile applications. Preferably, the article comprises at least 50 wt-% of the polypropylene-polyethylene composition according to the present invention, more preferably the article comprises at least 80 wt-% of the polypropylene-polyethylene composition according to the present invention, most preferably the article comprises at least 95 wt-% of the polypropylene-polyethylene composition according to the present invention.
In a preferred aspect, the present invention relates to a process for the manufacture of a polypropylene-polyethylene composition according to any one of claims 1 to 13, wherein the process comprises the steps of:
In a preferred aspect, the present invention relates to the use of a polypropylene-polyethylene composition according the present invention, for automotive articles, pipes, films, geo-membranes, roofing applications, pond liners, packaging, caps and closures as well as core layers of a multilayer polyolefin sheet or film.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the invention pertains. Although, any methods and materials similar or equivalent to those described herein can be used in practice for testing of the present invention, the preferred materials and methods are described herein. In describing and claiming the present invention, the following terminology will be used in accordance with the definitions set out below.
Unless clearly indicated otherwise, use of the terms “a,” “an,” and the like refers to one or more.
For the purposes of the present description and of the subsequent claims, the term “recycled waste” is used to indicate a material recovered from both post-consumer waste and industrial waste, as opposed to virgin polymers. Post-consumer waste refers to objects having completed at least a first use cycle (or life cycle), i.e. having already served their first purpose; while industrial waste refers to manufacturing scrap, which does not normally reach a consumer.
The term “virgin” denotes newly produced materials and/or objects prior to first use, which have not already been recycled.
Many different kinds of polyethylene or polypropylene can be present in “recycled waste”. In particular, the polypropylene fraction can comprise: isotactic propylene homopolymers, random copolymers of propylene with ethylene and/or C4-C8 α-olefins, hetrophasic copolymers comprising a propylene homopolymer and/or at least one C2, C4-C8 α-olefin copolymer and an elastomeric fraction comprising copolymers of ethylene with propylene and/or a C2, C4-C8 α-olefin, optionally containing minor amounts of a diene.
The term “recycled material” such as used herein denotes materials reprocessed from “recycled waste.”
A polymer blend is a mixture of two or more polymeric components. In general, the blend can be prepared by mixing the two or more polymeric components. Suitable mixing procedures known in the art are post-polymerization blendings.
Post-polymerization blendings can be dry-blendings of polymeric components such as polymer powders and/or compounded polymer pellets or melt blending by melt mixing the polymeric components.
A propylene random copolymer is a copolymer of propylene monomer units and comonomer units in which the comonomer units are distributed randomly over the polypropylene chain.
A “compatibilizer” is a substance in polymer chemistry, which is added to an immiscible blend of polymers in order to increase their stability.
“Polypropylene-polyethylene composition” refers to a composition containing both polypropylene and polyethylene in a mole ratio of from 9:1 to 13:7, wherein the relative amount of units derived from propylene is greater than 50 wt.-% with respect to the total weight of the composition.
The term “elastomer” denotes a natural or synthetic polymer having elastic properties.
The term “XCS” refers to the Xylene cold soluble fraction (XCS wt %) determined at 23° C. according to ISO 6427
The term “XCI” refers to the xylene insoluble content determined at 25° C. according to ISO 16152, 1 ed
If not indicated otherwise “%” refers to weight-%.
In the following, the details and preferred embodiments of the inventive polyolefin composition will be described in more detail. It is to be understood that these technical details and embodiments also apply to the inventive process and uses, as far as applicable.
The present invention is based on the findings that the addition of a soft, random heterophasic copolymer (RAHECO, referred to throughout as compatibilizer (B)), to a recycling stream with poor properties containing polypropylene-rich materials results in a material with a surprising degree of strain at break improvement, improved impact properties and a surprisingly low loss of stiffness. These properties are important particularly in applications where the materials are required to be stiff without being brittle and where the material needs to be resistant to deformation such as e.g. in water pipe manufacture. Compatibilizer (B) has a high tensile strain at break and also good impact properties and is characterised by a relatively low ethylene content, relatively low xylene soluble content (XCS), wherein the xylene soluble fraction has a low intrinsic viscosity (IV(XCS)).
In particular, given the relatively low amount of compatibilizer (B) used in the present invention, large improvements are seen in the tensile strain at break. Furthermore, the present invention is related to the use of a polypropylene-polyethylene composition as described hereinbefore for reducing the carbon footprint of polypropylene-based articles. This is especially advantageous in the field of infrastructure, engineering applications and packaging.
Blend (A)
The polypropylene-polyethylene composition according to the present invention comprises 80 wt.-% or more, preferably from 80 to 97 wt.-% of blend (A). It is the essence of the present invention that blend (A) is obtained from a recycled waste stream. Blend (A) can be either recycled post-consumer waste, post-industrial waste, such as for example from that the automobile industry, or alternatively, a combination of both.
Blend (A) is a polypropylene rich recycled material, meaning that it comprises significantly more polypropylene than polyethylene. Recycled waste streams, which are high in polypropylene can be obtained for example from the automobile industry, particularly as some automobile parts such as bumpers are sources of fairly pure polypropylene material in a recycling stream.
Preferably, the polypropylene rich recycled material is obtained from recycled waste by means of plastic recycling processes known in the art. Such recyclates are commercially available, e.g. from Corepla (Italian Consortium for the collection, recovery, recycling of packaging plastic wastes), Resource Plastics Corp. (Brampton, ON), Kruschitz GmbH, Plastics and Recycling (AT), Vogt Plastik GmbH (DE), Mtm Plastics GmbH (DE) etc. None exhaustive examples of polypropylene rich recycled materials include: Purpolen®PP (Mtm Plastics GmbH), Axpoly® recycled polypropylene pellets (Axion Ltd) and PolyPropylene Copolymer (BSP Compounds). It is considered that the present invention could be applicable to a broad range of recycled polypropylene materials or materials or compositions having a high content of recycled polypropylene. The polypropylene-rich recycled material may be in the form of granules. In a certain preferred embodiment, Purpolen®PP (Mtm Plastics GmbH) is used as blend (A).
Blend (A) may have a relative amount of units derived from propylene of greater than 50 wt.-%, preferably greater than 53 wt.-%, more preferably greater than 60 wt.-%, more preferably greater than 70 wt.-%, more preferably greater than 75 wt.-%, more preferably greater than 80 wt.-%, with respect to the total weight of the composition.
In addition, blend (A) may have a relative amount of units derived from ethylene of less than 47 wt.-%, more preferably less than 40 wt.-%, more preferably less than 30 wt.-%, more preferably less than 20 wt.-%, most preferably less than 10 wt.-%.
Usually, the relative amount of units derived from ethylene is more than 5 wt.-% with respect to the total weight of the composition.
The recycled material can comprise recycled high-density polyethylene (rHDPE), recycled medium density polyethylene (rMDPE), recycled low-density polyethylene (rLDPE) and mixtures thereof.
According to the present invention, blend (A) preferably has a content of limonene as determined by solid phase micro-extraction (HS-SPME-GC-MS) of from 1 ppm to 100 ppm, preferably from 1 ppm to 50 ppm, more preferably from 2 ppm to 35 ppm, most preferably from 2 ppm to 10 ppm. Limonene is conventionally found in recycled polyolefin materials and originates from packing application in the field of cosmetics, detergents, shampoos and similar products. Therefore, blend (A) contains limonene, when blend (A) contains material that originates from domestic waste streams.
In a further aspect, the presence of fatty acids is another indication for the polyolefins to originate from recycling streams.
Preferably, blend (A) of the polypropylene-polyethylene composition of the present invention contains:
Compatibilizer (B)
Recycled polyolefin materials generally contain a mixture of PE and PP. Unfortunately, PP and PE are highly immiscible resulting in a blend with poor adhesion among its phases, coarse morphology and consequently poor mechanical properties. The compatibility between the phases of a blend can be improved by the addition of compatibilizers, which results in a finer and more stable morphology, better adhesion between the phases of the blends and therefore better properties of the final product.
In the literature several kinds of compatibilizers are known, such as block copolymers, e.g. ethylene-propylene block copolymers and styrene-ethylene/butylene-styrene or triblock copolymers, or ethylene propylene rubber (EPR), ethylene/propylene diene copolymer (EPDM) or ethylene/vinyl acetate copolymer (EVA).
The compatibilizer (B) of the present invention is a heterophasic random copolymer (RAHECO) comprising a random polypropylene copolymer matrix phase and an elastomer phase dispersed therein. Compatibilizer (B) is preferably a virgin polypropylene. The addition of the compatibilizer (B) according to the present invention to the recycled polypropylene material results in a surprising degree of strain at break improvement and an improvement in impact properties, while maintaining a relatively stiff material.
Generally, a heterophasic random copolymer of propylene is a propylene copolymer comprising a propylene random copolymer matrix component (1) and an elastomeric copolymer component (2) of propylene with one or more of ethylene and/or C4-C8 alpha olefin co-monomers, wherein the elastomeric copolymer component (2) is dispersed in said propylene random copolymer matrix polymer (1). Preferably, the 02, C4-C8 alpha olefin co-monomers are ethylene co-monomers.
Compatibilizer (B) has a xylene cold solubles content (XCS) (measured according to ISO 161521 ed at 25° C.) of from 12 to 35 wt.-%, preferably from 15 to 30 wt.-%, most preferably from 18 to 25 wt.-%, such as around 20 wt.-%.
Moreover, the xylene soluble content (XCS) of the compatibilizer (B) may have an intrinsic viscosity (measured in decalin according to DIN ISO 1628/1 at 135° C.) of 1.2 dl/g to less than 3.0 dl/g, preferably from 1.3 dl/g to less than 2.2 dl/g, more preferably from 1.5 dl/g to less than 2.0 dl/g, most preferably from 1.6 dl/g to 1.8 dl/g.
In an aspect of the present invention, the compatibilizer (B) has a total content of units derived from ethylene of 1.0 to 20.0 wt.-%, preferably from 5.0 to 10.0 wt.-% such as about 8 wt.-%. In the polypropylene-polyethylene composition according to the present invention, the compatibilizer (B) preferably has a content of units derived from ethylene in the XCS fraction of 25.0 to 38.0 wt.-%, preferably between 30.0 and 35.0 wt.-%.
In yet a further aspect of the present invention, the compatibilizer (B) preferably has a content of units derived from ethylene in the XCI fraction of 1.5 to 6.0 wt.-%, more preferably 2.0 to 5.5 wt.-%.
This compatibilizer (B) of the present invention preferably has density of from 800 to 1000 kg m−3, preferably from 850 to 950 kg m−3, more preferably from 890 to 920 kg m−3, such as from 900 to 910 kg m−3.
The present invention, preferably, provides a polypropylene-polyethylene composition, wherein the compatibilizer (B) has tensile strain at break (MD) of at least 400%, preferably at least 600%, most preferably between 650 and 850%. Optionally, the tensile-strain at break (MD) of the compatibilizer (B) is less than 1000%. Without wishing to be bound by any theory, addition of a material with very high tensile strain at break is believed to improve the properties of the composition leading to a rigid/stiff material, which is not brittle.
The present invention, preferably, provides a polypropylene-polyethylene composition, wherein the compatibilizer (B) has an MFR2 (ISO1133; 2.16 kg; 230° C.) of from 5 to 25 g/10 min, preferably from 5 to 20 g/10 min, such as about 7 g/10 min.
In addition, the compatibilizer (B) may have a flexural modulus of from 350 to 550 MPa (ISO 178, measured on injection moulded specimens, 23° C.), preferably around 400 to 500 MPa. Compatibilizers with a flexural modulus of 300 MPa or lower shall not be used in the current invention as the stiffness/impact balance of compositions produced using such compatibilizers is often rather moderate.
The compatibilizer (B) as defined in the instant invention, may contain up to 2.0 wt.-% additives, selected from the group of nucleating agents, antioxidants, slip agents and talc among others. The same additives as described in more detail below with respect to the polypropylene-polyethylene composition may also be present in compatibilizer (B).
The compatibilizer (B) can be a commercially available grade of a heterophasic random copolymer or can be produced e.g. by conventional polymerisation processes and process conditions using e.g. a conventional catalyst system known in the literature.
Production of Compatibilizer (B)
One feasible polymerisation process including the conditions and catalyst system is generally described below for compatibilizer (B) according to the present invention, i.e. for production of a heterophasic random copolymer.
The polymers can be polymerised e.g. in an optional pre-polymerisation reactor following first reactor (preferably loop reactor) and then in a second reactor (preferably first gas phase reactor) using preferably the conditions as described below.
As to polymerisation of the heterophasic random copolymer of propylene, the individual components (matrix and elastomeric components) of the PP copolymer can be produced separately and blended mechanically by mixing in a mixer or extruder. However, it is preferred that the random polypropylene copolymer comprising the matrix component and the elastomeric component are produced in a sequential process, using reactors in serial configuration and operating at different reaction conditions. Consequently, each fraction prepared in a specific reactor can have its own molecular weight distribution, MFR2 and/or comonomer content distribution.
The heterophasic random copolymer according to this invention is preferably produced in a sequential polymerisation process, i.e. in a multistage process, known in the art, wherein the matrix component is produced at least in one slurry reactor, preferably at least in one slurry reactor, and optionally and preferably, in a subsequent gas phase reactor, and subsequently the elastomeric component is produced at least in one, i.e. one or two, gas phase reactor(s) (gpr), preferably in one gpr.
Accordingly, it is preferred that the heterophasic random copolymer is produced in a sequential polymerisation process comprising the steps of
Optionally, the elastomeric component of the heterophasic random copolymer can be produced in two reactors, whereby after above step (e), the process further comprises the following steps:
A preferred multistage process is a “loop-gas phase”-process, such as developed by Borealis NS, Denmark (known as BORSTAR® technology) described e.g. in patent literature, such as in EP 0887379, WO 92/12182 WO 2004/000899, WO 004/111095, WO 99/24478, WO 99/24479 or in WO 00/68315.
The compositions of the present invention can be prepared by mechanically blending the components using techniques used in the art for the preparation of polyolefin blends. For example, one can use Banbury, Buss, or Brabender mixers, single-screw or twin-screw extruders.
Polypropylene-Polyethylene Composition
The polypropylene-polyethylene composition according to the present invention is composed of a blend of recycled polypropylene (component (A)) and a compatibilizer (compatibilizer (B)).
In a preferred aspect, the polypropylene-polyethylene composition contains 15 wt.-% or less of compatibilizer (B), preferably 10 wt.-% or less, more preferably 5 wt.-% or less. In a preferred aspect, the polypropylene-polyethylene composition contains at least 83 wt.-% of blend (A), preferably at least 85 wt.-% of blend (A), more preferably at least 90 wt.-% of blend (A). Generally, a rather high amount of compatibilizer (B) is desirable for producing materials with desirable properties for end consumer applications.
In a preferred aspect, the polypropylene-polyethylene composition according to the current invention may also contain:
Examples of inorganic fillers for use in the composition can include ash, talc, glass fibres or wood fibres.
Examples of additives for use in the composition are pigments or dyes (for example carbon black), stabilizers (anti-oxidant agents), anti-acids and/or anti-UVs, antistatic agents, nucleating agents and utilization agents (such as processing aid agents). Generally, the amount of these additives is in the range of 0 to 5.0 wt.-%, preferably in the range of 0.01 to 3.0 wt.-%, more preferably from 0.01 to 2.0 wt.-% based on the weight of total composition.
Examples of antioxidants which are commonly used in the art, are sterically hindered phenols (such as CAS No. 6683-19-8, also sold as Irganox 1010 FF™ by BASF), phosphorous based antioxidants (such as CAS No. 31570-04-4, also sold as Hostanox PAR 24 (FF)™ by Clariant, or Irgafos 168 (FF)™ by BASF), sulphur based antioxidants (such as CAS No. 693-36-7, sold as Irganox PS-802 FL™ by BASF), nitrogen-based antioxidants (such as 4,4′-bis(1,1′-dimethylbenzyl)diphenylamine), or antioxidant blends.
Anti-acids are also commonly known in the art. Examples are calcium stearates, sodium stearates, zinc stearates, magnesium and zinc oxides, synthetic hydrotalcite (e.g. SHT, CAS-No. 11097-59-9), lactates and lactylates, as well as calcium stearate (CAS No. 1592-23-0) and zinc stearate (CAS No. 557-05-1); Common antiblocking agents are natural silica such as diatomaceous earth (such as CAS No. 60676-86-0 (SuperfFloss™), CAS-No. 60676-86-0 (SuperFloss E™), or CAS-No. 60676-86-0 (Celite 499™)), synthetic silica (such as CAS-No. 7631-86-9, CAS-No. 7631-86-9, CAS-No. 7631-86-9, CAS-No. 7631-86-9, CAS-No. 7631-86-9, CAS-No. 7631-86-9, CAS-No. 112926-00-8, CAS-No. 7631-86-9, or CAS-No. 7631-86-9), silicates (such as aluminium silicate (Kaolin) CAS-no. 1318-74-7, sodium aluminum silicate CAS-No. 1344-00-9, calcined kaolin CAS-No. 92704-41-1, aluminum silicate CAS-No. 1327-36-2, or calcium silicate CAS-No. 1344-95-2), synthetic zeolites (such as sodium calcium aluminosilicate hydrate CAS-No. 1344-01-0, CAS-No. 1344-01-0, or sodium calcium aluminosilicate, hydrate CAS-No. 1344-01-0).
Anti-UVs are, for example, Bis-(2,2,6,6-tetramethyl-4-piperidyl)-sebacate (CAS-No. 52829-07-9, Tinuvin 770); 2-hydroxy-4-n-octoxy-benzophenone (CAS-No. 1843-05-6, Chimassorb 81).
Alpha nucleating agents like sodium benzoate (CAS No. 532-32-1); 1,3:2,4-bis(3,4-dimethylbenzylidene)sorbitol (CAS 135861-56-2, Millad 3988).
Suitable antistatic agents are, for example, glycerol esters (CAS No. 97593-29-8) or ethoxylated amines (CAS No. 71786-60-2 or 61791-31-9) or ethoxylated amides (CAS No. 204-393-1).
Usually these additives are added in quantities of 100-2.000 ppm for each individual component of the polymer
The polypropylene-polyethylene composition preferably contains between 1.0 and 2.0 wt.-% PO ash.
The polypropylene-polyethylene composition according to the invention has a good balance of stiffness (tensile modulus) and ductility (tensile strain at break) as compared to the pure recycled material (i.e. it is stiff, but not brittle). It should be noted, that the composition in the present invention is characterized not by any single one of the defined mechanical property features, but by their combination. By this combination of features, the inventive composition can advantageously be used in many application fields, such as in pipes, bottles and films.
The present invention preferably provides a polypropylene-polyethylene composition having a tensile modulus measured according to EN ISO 1873-2 (dog bone shape, 4 mm thickness) of at least 1000 MPa, preferably of at least 1050 MPa, most preferably of at least 1100 MPa. Usually, the tensile modulus of the polypropylene-polyethylene composition according to the present invention will not be higher than 1500 MPa.
Preferably, the notched Charpy impact strength (1eA) (non-instrumented, ISO 179-1) measured at 23° C. is at least 5 kJ/m2, more preferably at least 5.5 kJ/m2, most preferably at least 6 kJ/m2. Usually the notched Charpy impact strength (1eA) (non-instrumented, ISO 179-1) measured at 23° C. will not be higher than 20 kJ/m2. In addition, the notched Charpy impact strength (1eA) (non-instrumented, ISO 179-1) measured at −30° C. is preferably at least 3.5 kJ/m2, more preferably at least 4.0 kJ/m2 and most preferably at least 4.5 kJ/m2. Usually the notched Charpy impact strength (1eA) (non-instrumented, ISO 179-1) measured at −30° C. will not be higher than 7.0 kJ/m2.
Preferably, a higher value of notched Charpy impact strength (1eA) (non-instrumented, ISO 179-1) at 23° C. is obtained for the polypropylene-polyethylene composition following addition of compatibilizer (B), than for raw blend (A).
Preferably, the polypropylene-polyethylene composition according to the present invention has a tensile modulus of at least 1000 MPa and a notched Charpy impact strength (1eA) (non-instrumented, ISO 179-1) measured at 23° C. of at least 5.5 kJ/m2 and more preferably at least 6 kJ/m2. In a preferred embodiment, the polypropylene-polyethylene composition according to the present invention has a tensile modulus of at least 1000 MPa and a notched Charpy impact strength (1eA) (non-instrumented, ISO 179-1) measured at −30° C. of at least 2.5 kJ/m2, preferably at least 3.5 kJ/m2, more preferably at least 4 kJ/m2, most preferably at least 4.5 kJ/m2. Having this combination of features is particularly advantageous such as e.g. in piping applications, as it is important to have a pipe which is both stiff, but which is also resistant to impact at both ambient and low temperatures.
Furthermore, the polypropylene-polyethylene composition according to the present invention may have a notched Charpy impact strength (1eA) (non-instrumented, ISO 179-1) of at least 6.0 kJ/m2 at 23° C. or a tensile strain at break (ISO 527-1,2) of at least 75%. Again, this is important for applications where the polyolefin is impact resistant; but, is also able to extend without breaking.
Preferably, the polypropylene-polyethylene composition according to the present invention has a tensile strain at break measured according to ISO 527-1,2 of at least 15%, or at least 20%, or at least 30%, or at least 35%. Usually tensile strain at break measured according to ISO 527-1,2 will not be higher than 50%.
The polypropylene-polyethylene composition according to the present invention preferably has a tensile strain at break measured according to ISO 527-1,2 of at least 20% and a tensile modulus of at least 1000 MPa.
The ratio of the tensile modulus of the final polypropylene-polyethylene composition to the tensile modulus of blend (A) is preferably at least 0.90, more preferably at least 0.95.
In a preferred embodiment the polypropylene-polyethylene composition according to the present invention has a reasonable high melt flow rate (MFR2), of 10 to 20 g/10 min. Such ranges renders the polypropylene-polyethylene composition particularly suitable for injection moulding applications.
Furthermore, the composition in the present invention preferably has a tensile stress at break determined according to ISO 527-2 of greater than 10 MPa, or greater than 12 MPa, or greater than 14 MPa. Still further, the composition in the present invention preferably has a tensile strength determined according to ISO 527-2 of greater than 20 MPa, preferably greater than 22 MPa, more preferably greater than 24 MPa and optionally up to a maximum of 28 MPa. The tensile stress does not decrease significantly in comparison to the recycled polypropylene material.
Process
It is appreciated that the present invention also refers to a process for producing the polypropylene-polyethylene compositions as defined herein. The process comprises the steps of
For the purposes of the present invention, any suitable melting and mixing means known in the art may be used for carrying out the melting and mixing step c). However, the melting and mixing step c) preferably takes place in a mixer and/or blender, high or low shear mixer, high-speed blender, or a twin-screw extruder. Most preferably, the melting and mixing step c) takes place in a twin-screw extruder such as a co-rotating twin-screw extruder. Such twin-screw extruders are well known in the art and the skilled person will adapt the melting and mixing conditions (such as melting temperature, screw speed and the like) according to the process equipment.
In certain embodiments, optionally prior to the melting and mixing step (c) an additional dry mixing step of all components can be applied.
Typically, the melt temperature in step (C) is around 140-170° C. for polypropylene compounds, preferably between 140° C. and 165° C.
Particularly for recycled material, which often contains additional, contaminating ingredients, the target would be to carry out the melting step at the lowest possible temperature. This would allow the cost of production to be kept low, (this is particularly important for polypropylene as a commodity polyolefin) and helps to increase the sustainability effort and to minimize the additional odour, smell and toxic fumes that are often generated with recyclate containing compounds at high temperatures from e.g. contaminating ingredients in the recyclate, such as e.g. PVC.
Additionally, the extruder or compounding unit may be equipped with one or more vacuum degassing units along the screw or screws, with or without the use of water stripping units. The function of a water-stripping unit is to add small amounts of water into the melt upfront of a mixing, a decompression and vacuum degassing section. The result of this is to bring down both the odour, smell and toxic fumes, as well as to reduce the amount of volatiles in the final compound.
Uses
The present invention relates to a polypropylene-polyethylene composition, which may be used for a wide range of applications, for example in automotive articles or applications, in pipes, for construction applications, in packaging and caps, and in closures. Additionally, due to the satisfactory tensile properties of the compositions of the present invention, they may be employed as films (with a thickness of 400 microns or less) or for flexible foils (with a thickness of more than 400 microns) such as geo-membranes for agriculture, roofing applications and as pond liners. Typically, the compositions described herein are used as a core layer of a multilayer sheet (e.g. a three layer geo-membrane sheet), where the external layers are made of various kinds of polyolefin materials.
In the following, the present invention is described in more detail with respect to particularly preferred embodiments. All preferred aspects as discussed above shall also apply for these specifically preferred embodiments as far as appropriate.
In the first preferred embodiment of the present invention, the composition comprises from 90 wt.-% to 95 wt.-% of recycled polypropylene blend, wherein the blend contains 80 wt.-% to 99 wt.-% of polypropylene. This embodiment aims at a polypropylene composition demonstrating acceptable mechanical properties, but containing a maximum amount of recycled polymer. In general, such a composition would be expected to have a high tensile modulus; while achieving a nominal tensile strain at break of greater than 20% i.e. the material should be stiff, but not brittle.
Insofar, the first preferred embodiment of the invention relates to a polypropylene-polyethylene composition having a tensile modulus of greater than 1000 MPa obtainable by blending
In a second preferred embodiment of the invention, from 80 wt.-% to 90 wt.-% of a recycled polypropylene is in blend (A), wherein blend (A) contains from 80 wt.-% to 99 wt.-% polypropylene. This embodiment aims at a composition with a high tensile modulus, but with enhanced nominal tensile strain at break from about 25 to about 40 compared to the compound in the first preferred embodiment.
Insofar, the second preferred embodiment of the invention relates to a polypropylene-polyethylene composition having a tensile modulus of at least 1000 MPa, which is obtainable by blending
The following Examples are included to demonstrate certain aspects and embodiments of the invention as described in the claims. It should be appreciated by those of skill in the art, however, that the following description is illustrative only and should not be taken in any way as a restriction of the invention.
Test Methods
Chalk content=100/44×WCO2
Ash content=(Ash residue)−56/44×WCO2−Wcb
A number of blends were produced with Purpolen PP a polypropylene-rich recycled plastic material (available from mtm plastics). In each of the blends 5 to 15 wt.-% of a reactor derived compatibilizer (B) was added. Compatibilizer (B) (compatibilizer 2) according to the present invention is a RAHECO. The comparative compatibilizer (compatibilizer 1) is random copolymer and therefore is not a RAHECO. Polymers were blended as described in WO2018141704. The compositions were prepared via melt blending on a co-rotating twin screw extruder with 0.15 wt.-% of Songnox 1010FF (Pentaerythrityl-tetrakis(3-(3′,5′-di-tert. butyl-4-5 hydroxyphenyl)), 0.15 wt.-% Kinox-68 G (Tris (2,4-di-t-butylphenyl) phosphite) from HPL Additives. The polymer melt mixture was discharged and pelletized.
1Butylated Hydroxy Toluene (BHT) available from for example Oxiris Chemicals S.A.
2A phosphorus based secondary antioxidant
supplied by Clariant International Ltd. 3A homo-polypropylene powder supplied by Borealis.
Purpolen PP properties:
The relevant specification for all materials relates to that available in August 2018.
Limonene Content in Purpolen
Measurement
Limonene quantification was carried out using solid phase micro-extraction (HS-SPME-GC-MS) by standard addition.
50 mg ground samples were weighed into 20 mL headspace vials and after the addition of limonene in different concentrations and a glass-coated magnetic stir bar, the vial was closed with a magnetic cap lined with silicone/PTFE. Micro capillaries (10 pL) were used to add diluted limonene standards of known concentrations to the sample. Addition of 0, 2, 20 and 100 ng equals 0 mg/kg, 0.1 mg/kg, 1 mg/kg and 5 mg/kg limonene, in addition standard amounts of 6.6, 11 and 16.5 mg/kg limonene were used in combination with some of the samples tested in this application. For quantification, ion-93 acquired in SIM mode was used. Enrichment of the volatile fraction was carried out by headspace solid phase micro-extraction with a 2 cm stable flex 50/30 pm DVB/Carboxen/PDMS fibre at 60° C. for 20 minutes. Desorption was carried out directly in the heated injection port of a GCMS system at 270° C.
GCMS Parameters:
Column: 30 m HP 5 MS 0.25*0.25
Injector: Splitless with 0.75 mm SPME Liner, 270° C.
Temperature program: −10° C. (1 min)
Carrier gas: Helium 5.0, 31 cm/s linear velocity, constant flow
MS: Single quadrupole, direct interface, 280° C. inter face temperature
Acquisition: SIM scan mode
Scan parameter: 20-300 amu
SIM Parameter: m/Z 93, 100 ms dwell time
1Headspace Soldiphase Microextraction. Materials available from mtm plastics GmbH according to August 2018 specifications.
Total Free Fatty Acid Content
Fatty acid quantification was carried out using headspace solid phase micro-extraction (HS-SPME-GC-MS) by standard addition.
50 mg ground samples were weighed in 20 mL headspace vial and after the addition of limonene in different concentrations and a glass coated magnetic stir bar the vial was closed with a magnetic cap lined with silicone/PTFE. 10 pL Micro-capillaries were used to add diluted free fatty acid mix (acetic acid, propionic acid, butyric acid, pentanoic acid, hexanoic acid and octanoic acid) standards of known concentrations to the sample at three different levels. Addition of 0, 50, 100 and 500 ng equals 0 mg/kg, 1 mg/kg, 2 mg/kg and 10 mg/kg of each individual acid. For quantification ion 60 acquired in SIM mode was used for all acids except propanoic acid, here ion 74 was used.
GCMS Parameter:
Column: 20 m ZB Wax plus 0.25*0.25
Injector: Split 5:1 with glass lined split liner, 250° C.
Temperature program: 40° C. (1 min) @6° C./min to 120° C., @15° C. to 245° C. (5 min)
Carrier: Helium 5.0, 40 cm/s linear velocity, constant flow
MS: Single quadrupole, direct interface, 220° C. inter face temperature
Acquisition: SIM scan mode
Scan parameter: 46-250 amu 6.6 scans/s
SIM Parameter: m/z 60.74, 6.6 scans/s
1The concentration of acetic acid, propionic acid, butyric acid, pentanoic acid, hexanoic acid, octanoic acid, nonanoic acid and decanoic acid in each sample was added together to give a totally fatty acid concentration value.
1ND = Not determined.
1Samples were measured after 96 hours.
2complete
| Number | Date | Country | Kind |
|---|---|---|---|
| 18198602.7 | Oct 2018 | EP | regional |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2019/076671 | 10/2/2019 | WO | 00 |
