Patent Application
20230399482
The present invention relates to processes and reactive foam formulations for forming a polyurethane-polyurea comprising water blown foam having an apparent density in the range 30-700 kg/m3 measured according to ISO 845 and having a tensile strength (measured according to DIN 53504) over apparent density ratio of at least 10 kPa·m3/kg.
The present invention further relates to foams having elastomeric behaviour and improved mechanical properties such as tensile strength and ball rebound which make them very suitable for use in footwear and automotive and more in particular in applications aiming for consumer comfort.
Current state-of-the-art elastomeric flexible foams having densities in the range 200-300 kg/m3 suffer from rather disappointing mechanical properties such as tensile strength and ball rebound. Typical examples of these elastomeric flexible foams can be found in US2012/0095122A1.
Furthermore, conventional low-density elastomeric flexible polyurethane foams are typically produced using isocyanate reactive compounds with a functionality higher than 2 and with very high-water contents in order to have stability during foaming and to achieve the required mechanical properties and density. It is known that the use of isocyanate reactive compounds with a functionality higher than 2 will give rise to a cross-linked polyurethane matrix. This renders conventional low-density flexible polyurethane foams behaving as thermoset materials rather than thermoplastic materials. Furthermore, the combination of typical compounds used to form said foams result in materials having very low tensile strength. Typical examples of low-density foams can be found in CA2337913A1.
To solve above problems, there is a need to produce an elastomeric flexible foam which has improved mechanical properties such as tensile strength and ball rebound for a given density. The solution provided to solve this problem still allows formulators a large degree of freedom. Optionally a specific version of the elastomeric polyurethane flexible foam can be made which is thermoplastic and thereby is thermally recyclable (e.g., via extrusion) and/or melt reprocessable after its service-life.
The goal is to achieve an elastomeric polyurethane flexible foam which has for a given density a higher tensile strength (measured according to DIN 53504) and higher ball rebound (measured according to ISO 8307 and also referred to as resilience) compared to state-of-the-art elastomeric polyurethane foams. Especially for foams in the range 200-300 kg/m3 there is a need to develop foams having higher tensile strength and higher ball rebound while maintaining hardness and angle tear.
The ultimate goal is to develop an elastomeric polyurethane flexible foam having a density in the range 200-300 kg/m3 which has a tensile strength, a ball rebound and/or compression set which is typical for state-of-the-art elastomeric polyurethane flexible foams having densities in the range 300-500 kg/m3.
Throughout the description, the improved characteristic of the foam according to the invention having a higher tensile strength at a given density is indicated as a tensile strength over apparent density ratio.
It is a further goal to develop a reactive mixture suitable for making an elastomeric polyurethane flexible foam which has an apparent density in the range 30-700 kg/m3 measured according to ISO 845 and having a tensile strength (measured according to DIN 53504) over apparent density ratio of at least 10 kPa·m3/kg.
Additionally, it is the goal to develop an elastomeric thermoplastic polyurethane flexible foam which is thermally recyclable (e.g., via extrusion) and/or melt reprocessable after its service-life.
In the context of the present invention, the following terms have the following meaning:
In other words, the NCO-index expresses the percentage of isocyanate actually used in a formulation (reactive mixture) with respect to the amount of isocyanate theoretically required for reacting with the amount of isocyanate-reactive hydrogen used in a formulation (reactive mixture). In the specific case where an isocyanate prepolymer is used in the reactive mixture, it is clear that a part of the NCO-equivalents and equivalents of isocyanate-reactive hydrogen atoms is no longer available to participate in the reaction. Theses “consumed” equivalents used in the making of the isocyanate prepolymer should thus not be considered in the calculation of the isocyanate index.
The present invention discloses polyurethane-polyurea comprising water blown foams which have surprisingly good mechanical properties such as tensile strength and ball rebound and are easily melt-reprocessable and recyclable after use. These flexible polyurethane foams are foams which are polymerised and blown in-situ and which can be recycled after service-life (use) by means of a thermal treatment above the melt temperature of the (thermoplastic) polyurethane material.
The present invention discloses a method and reactive mixture for making the elastomeric polyurethane-polyurea comprising water blown foams. The reactive mixture of the invention used to make said foam is blown using predominantly water as blowing agents.
The use of the reactive mixture according to the invention will lead to a micro-phase separated polymer morphology, more in particular the formation of distinctive crystalline hard block phases and a soft block phase. This phase separation contributes to the superior properties of the foam compared to state-of-the-art elastomeric flexible foams.
Therefore, the present invention discloses a method for making an elastomeric polyurethane-polyurea comprising water blown foam (referred herein after as “PU/PUR foam”) having an apparent density in the range 30-700 kg/m3 measured according to ISO 845 and having a tensile strength (measured according to DIN 53504) over apparent density ratio of at least 10 kPa·m3/kg, said method comprising mixing at an isocyanate index in the range 75 up to 125 in situ at least following ingredients to form a reactive foam formulation:
According to embodiments, the D equivalents of low molecular weight (MW) urethane forming compounds containing hydroxyl functional groups and having a molecular weight<500 g/mol and having a hydroxy functionality in the range 1 up to 8 (referred to as low MW urethane forming compounds further on) refers to the sum of the urethane forming equivalents of polyol chain extender compounds and/or polyol crosslinker compounds and/or mono-alcohol compounds used.
According to embodiments, the E equivalents of low molecular weight (MW) urea forming compounds containing amine functional groups and having a molecular weight<500 g/mol and having a functionality in the range 1 up to 8, (referred to as low MW urea forming compounds further on) refers to the sum of the urea forming equivalents of amine chain extender compounds and/or amine crosslinker compounds and/or mono-amine compounds used.
According to embodiments, the required equivalents of compounds B up to E are first combined (to form the so-called “b-side”) and then reacted with the polyisocyanate composition.
According to embodiments, the isocyanate index of the reactive foam formulation is in the range up to 125, in the range 80 up to 120, in the range 85 up to 120, in the range 88 up to 120, in the range 90 up to 120, in the range 90 up to 110, in the range 92 up to 110, in the range 95 up to 110, in the range 95 up to 105, in the range 98 up to 105, in the range 98 up to 102.
According to embodiments, the process for making the elastomeric PU/PUR foam according to the invention comprises at least the steps of:
According to embodiments, the step of mixing of the polyisocyanate composition with the pre-mixed composition obtained in step i) to form a reactive foam formulation is performed using a 2-component mixing system. According to embodiments, the mixing system is a pressure mixing system. According to embodiments, the pressure mixing system is a high-pressure mixing system that uses impingement to mix materials.
According to embodiments, the step of mixing of the polyisocyanate composition with the pre-mixed composition obtained in step i) to form a reactive foam formulation is performed using a 2-component dynamic mixing system.
According to embodiments, the step of mixing of the polyisocyanate composition with the pre-mixed composition obtained in step i) to form a reactive foam formulation is performed using a combination of impingement and dynamic mixing.
According to embodiments, no external heat is preferably added to the reactive foam formulation, the reaction exotherm is sufficient to obtain a foamed structure.
According to embodiments, the step of allowing the reactive foam formulation obtained in step ii) to foam is performed in a mould and the mould temperature may be altered to affect skin properties. Elevated mould temperature may also prevent excessive heat loss, hereby helping conversion/molecular weight build-up during polymerisation.
According to embodiments, the method for making the elastomeric PU/PUR foam according to the invention is performed at an isocyanate index in the range 75 up to 125, in the range 80 up to 120, in the range 85 up to 120, in the range 88 up to 120, in the range 90 up to 120, in the range 90 up to 110, in the range 92 up to 110, in the range 95 up to 110, in the range 95 up to 105, in the range 98 up to 105, in the range 98 up to 102.
According to embodiments, the number of urea forming equivalents of water C is smaller than smaller than 0.07, smaller than 0.06, smaller than 0.055, smaller than 0.05, smaller than 0.045, smaller than 0.04, in the range 0.02 up to 0.04 calculated on 100 gram reactive foam formulation.
According to embodiments, the number of equivalents low 1\4W urethane forming compounds D is greater than 0, greater than 0.005, greater than 0.008, greater than 0.01, greater than 0.012, greater than 0.015, greater than 0.017, greater than 0.02 or greater than 0.025 calculated on 100 gram reactive foam formulation.
According to embodiments, the number of equivalents low 1\4W urethane forming compounds D is smaller than 0.06, smaller than 0.055, smaller than 0.05, smaller than 0.045, smaller than 0.04 or smaller than 0.035 calculated on 100 gram reactive foam formulation.
According to embodiments, the number of urea forming equivalents of low molecular weight (MW) urea forming compounds containing amine functional groups E is greater than 0 calculated on 100 gram reactive foam formulation (not optional). The amount of low MW urea forming compounds might be at least 5%, 10%, 15%, 20%, 25%, or 30% by weight calculated on the total amount of low MW urea forming compounds and low MW urethane forming compounds in the reactive formulation. Increasing the amount of low MW urea forming compounds in the reactive formulation might be beneficial to lower the free rise density of the foam.
According to embodiments, the ratio
in the reactive foam formulation is smaller than 1.4, smaller than 1.3, smaller than 1.2, smaller than 1.1, smaller than 1 or smaller than 0.9.
According to embodiments, the ratio
in the reactive foam formulation is larger than 0, greater than 0.05, greater than 0.1, greater than 0.13, greater than 0.15, greater than 0.2, greater than 0.25, greater than 0.3, greater than 0.40, greater than 0.50, greater than 0.55, greater than 0.6, greater than 0.65 or greater than 0.7.
According to embodiments, the blowing agent composition comprises at least 20 wt %, preferably >40 wt %, more preferably >60 wt %, more preferably >80 wt %, more preferably >90 wt % water based on the total weight of all blowing agents used.
In preferred embodiments physical blowing agents may be added to the reactive foam formulation used to make the elastomeric PU/PUR foam according to the invention. Addition of physical blowing agents may help to further reduce the density of the foam formulation while maintaining an optimal ratio
According to embodiments, suitable physical blowing agents may be selected from isobutene, methylformate, dimethyl ether, methylene chloride, acetone, t-butanol, argon, krypton, xenon, chloro fluoro carbons (CFCs), hydro fluoro carbons (HFCs), hydro chloro fluoro carbons (HCFCs), hydro fluoro olefins (HFO's), Hydro Chloro Fluoro Olefins (HCFO's), and hydrocarbons such as pentane, isopentane and cyclopentane and mixtures thereof. According to preferred embodiments, the physical blowing agents are selected from at least CO2 and/or N2.
According to preferred embodiments, the physical blowing agents may be selected from HFO blowing agents and/or HCFO blowing agents and/or hydrocarbons such as cyclo-pentane. HFO blowing agents may be selected from 3,3,3-trifluoropropene, 1,2,3,3,3-pentafluoropropene, cis-and/or trans-1,3,3,3-tetrafluoropropene and/or 2,3,3,3-tetrafluoropropene, and/or 1,1,1,4,4,4-hexafluorobut-2-ene, and/or 1-chloro-3,3,3-trifluoropropene, and/or 2-chloro-3,3,3-trifluoropropene and mixtures thereof. Preferred examples of commercially available suitable HFO blowing gases are Honeywell HFO-1234ze (Honeywell's trade name for trans—1,3,3,3-tetrafluoropropene) or Opteon 1100 (Chemours' trade name for cis-1,1,1,4,4,4-hexafluorobut-2-ene, CF 3CH═CHCF3). A preferred example of a commercially available suitable HCFO blowing gas is Honeywell Solstice® 1233zd (Honeywell's trade name for trans-1-chloro-3,3,3-trifluoropropene, CHCl=CHCF3) or Forane® 1233zd (Arkema's trade name for trans-1-chloro-3,3,3-trifluoropropene, CHCl=CHCF3).
According to embodiments, the amount of blowing agents used in the reactive foam formulation can vary based on, for example, the intended use and application of the foam product and the desired foam stiffness and density.
According to embodiments, the amount of water and optionally further blowing agents used in the reactive foam formulation is in the range 0.1 to 25 parts by weight, more preferably from 0.25 to pbw per hundred weight parts isocyanate reactive compounds (polyol) in order to produce a low-density flexible foam having a density<500 kg/m3, e.g., a low-density foam having densities in the range 50-500 kg/m3.
According to embodiments, the isocyanate composition used to make the PU/PUR foam according to the invention has a molecular number average isocyanate functionality in the range 1.8 up to 2.4, in the range of 1.8 up to 2.2, more preferably in the range of 1.9-2.1, more preferably in the range of 1.95-2.05, more preferably in the range of 1.95-2.02, more preferably in the range of 1.95-2.015, more preferably in the range of 1.95-2.012, even more preferably in the range of 1.98-2.01 and most preferably in the range of 1.98-2.005.
According to embodiments, the isocyanate composition has an NCO value in the range 3 up to 50, an NCO value in the range 5 up to 33.56, an NCO value in the range 8 up to 30, an NCO value in the range 10 up to 26 or an NCO value in the range 13 up to 23.
According to embodiments, the isocyanate composition used to make the elastomeric PU/PUR foam according to the invention comprises at least 80% by weight, at least 85% by weight, at least 90%, at least 95% by weight difunctional isocyanate compounds calculated on the total weight of all isocyanate compounds in the isocyanate composition. Most preferably the isocyanate composition contains at least 80 wt %, at least 85 wt %, at least 90 wt %, at least 95 wt %, and most preferably at least 98 wt % 4,4′-diphenylmethane diisocyanates calculated on the total weight of the isocyanate composition.
According to embodiments, the difunctional isocyanates (diisocyanates) may be selected from aliphatic diisocyanates selected from hexamethylene diisocyanate, isophorone diisocyanate, methylene dicyclohexyl diisocyanate and cyclohexane diisocyanate and or from aromatic diisocyanates selected from toluene diisocyanate (TDI), naphthalene diisocyanate, tetramethylxylene diisocyanate, phenylene diisocyanate, toluidine diisocyanate and, in particular, diphenylmethane diisocyanate (MDI).
According to embodiments, the isocyanate composition used in the process of the present invention contains essentially (at least 95% by weight, more preferably at least 98% by weight calculated on the total weight of the polyisocyanate composition) pure 4,4′-diphenylmethane diisocyanate.
According to embodiments, the isocyanate composition used in the process of the present invention contains mixtures of 4,4′-diphenylmethane diisocyanate with one or more other organic diisocyanates, especially other diphenylmethane diisocyanates, for example the 2,4′-isomer optionally in conjunction with the 2,2′-isomer.
According to embodiments, the isocyanate compounds in the polyisocyanate composition may also be an MDI variant derived from a isocyanate composition containing at least 95 wt % 4,4′-diphenylmethane diisocyanate. MDI variants are well known in the art and, for use in accordance with the invention, particularly include liquid products obtained by introducing carbodiimide groups into said polyisocyanate composition and/or by reacting with one or more polyols.
According to embodiments, the isocyanate compounds in the isocyanate composition may also be isocyanate-terminated prepolymer which is prepared by reaction of an excessive amount of the isocyanate having at least 80 wt %, at least 85 wt %, at least 90 wt %, at least 95% of 4,4′-diphenylmethane diisocyanate with a suitable difunctional polyol in order to obtain a prepolymer having the indicated NCO value. Methods to prepare prepolymers have been described in the art. The relative amounts of isocyanate and polyol depend on their equivalent weights and on the desired NCO value and can be determined easily by those skilled in the art. The NCO value of the isocyanate-terminated prepolymer is preferably above 3%, preferably above 5%, more preferably above 8% and most preferably above 10%.
According to embodiments, the molecular number average functionality of the total of the high MW isocyanate reactive compounds in the reactive formulation into account is in the range 1.8 up to 2.4, in the range of 1.8 up to 2.2, more preferably in the range of 1.9-2.1, more preferably in the range of 1.95-2.05, more preferably in the range of 1.95-2.02, more preferably in the range of 1.95-2.015, more preferably in the range of 1.95-2.012, even more preferably in the range of 1.98-2.01 and most preferably in the range of 1.98-2.005.
According to embodiments, the molecular number average functionality of the blend of all isocyanate reactive compounds is in the range of 1.8 up to 2.4, in the range of 1.8 up to 2.2, more preferably in the range of 1.9-2.1, more preferably in the range of 1.95-2.05, more preferably in the range of 1.95-2.02, more preferably in the range of 1.95-2.015, more preferably in the range of 1.95-2.012, even more preferably in the range of 1.98-2.01 and most preferably in the range of 1.98-2.005.
According to embodiments, the molecular number average functionality of the blend of all reactive components, including all isocyanate and isocyanate reactive compounds, is in the range of 1.8 up to 2.4, in the range of 1.8 up to 2.2, more preferably in the range of 1.9-2.1, more preferably in the range of 1.95-2.05, more preferably in the range of 1.95-2.02, more preferably in the range of 1.95-2.015, more preferably in the range of 1.95-2.012, even more preferably in the range of 1.98-2.01 and most preferably in the range of 1.98-2.005.
According to embodiments, the isocyanate reactive compounds in the reactive foam formulation comprising the high MW isocyanate reactive compounds, the low MW urethane forming compounds and low MW urea forming compounds are selected from at least 75% by weight difunctional polyols, more preferably at least 85% by weight difunctional polyols, most preferably at least 90% by weight difunctional polyols calculated on the total weight of all isocyanate reactive compounds in the reactive mixture.
According to embodiments, the isocyanate reactive compounds in the reactive foam formulation comprising the high MW isocyanate reactive compounds, the low MW urethane forming compounds and low 1\4W urea forming compounds are selected from at least 90% by weight difunctional polyols, more preferably at least 95% by weight difunctional polyols, most preferably at least 98% by weight difunctional polyols calculated on the total weight of all isocyanate reactive compounds in the reactive foam formulation.
According to embodiments, the high 1\4W isocyanate reactive compounds having a molecular weight>500 g/mol are selected from polyether based polyols wherein the polyether backbone is at least 50 w % based on a butyleneoxide polyol, preferably at least 70 w % based on a butyleneoxide polyol, more preferably at least 80 w % based on a butyleneoxide polyol and most preferably at least 90 w % based on a butyleneoxide polyol.
According to embodiments, the high 1\4W isocyanate reactive compounds having a molecular weight>500 g/mol are selected from polyester diols, polyether polyols and/or polyester polyether polyols having a molecular weight in the range 500 g/mol up to 10000 g/mol, preferably in the range 500 g/mol up to 5000 g/mol, more preferably in the range 650 g/mol up to 4000 g/mol.
According to embodiments, the high 1\4W polyols having a molecular weight>500 g/mol are selected from at least one linear high molecular weight difunctional polyol having a molecular weight in the range 500-20000 g/mol and the amount of linear high molecular weight difunctional polyol is at least 80 wt %, more preferably at least 85 wt %, most preferably at least 90 wt % calculated on the total weight of the high MW polyols. Preferably said difunctional polyols are selected from linear polyester polyols, polyether polyols, and/or polyether-polyester polyols (including speciality polyester diols such as polycaprolactone diols).
According to embodiments, the high MW (difunctional) polyol may comprise and/or may be selected from a silica based diol such as dihydroxyl-terminated polydimethylsiloxane (PDMS-diol), a dihydroxyl terminated polybutadiene (HTPB-diol), fatty acids dimer-based polyester diols and mixtures thereof.
According to embodiments, the elastomeric PU/PUR foam according to the invention may be fabricated using mainly high molecular weight difunctional polyol(s) selected from polyester diols. These elastomeric PU/PUR foam will have excellent compatibility with PVC and other polar plastics.
According to embodiments, the elastomeric PU/PUR foam according to the invention may be fabricated using mainly high molecular weight difunctional polyol(s) selected from polyether diols. These elastomeric PU/PUR foams will have excellent low temperature flexibility and hydrolysis resistance, making them suitable for applications where water is a consideration.
According to embodiments, the low MW urethane forming compounds have a molecular weight<500 g/mol, preferably a molecular weight in the range 45 g/mol up to 500 g/mol, more preferably in the range 50 g/mol up to 250 g/mol and are selected from 1,6-hexanediol, 1,4-butanediol, monoethylene glycol, diethyleneglycol, triethyleneglycol, tetraethyleneglycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-propanediol, 1, -3-butanediol, 1,5-pentanediol, Polycaprolactone diol, 2-methyl-1,3-propanediol, neopentyl glycol, 1,4-cyclohexanedimethanol, hydroquinone bis (2-hydroxyethyl) ether (HQEE), 1,3-Bis (2-hydroxyethyl) resorcinol (HER), ethanolamine, methyl di ethanol amine and/or phenyl di ethanol amine. Preferably the low 1\4W urethane forming compounds are selected from 1,6 hexanediol, 1,4-butanediol or ethylene glycol. 1,4-Butanediol is most preferred.
According to embodiments, the low MW urethane forming compounds or the low 1\4W urea forming compounds have a molecular weight in the range 45 g/mol up to 500 g/mol, more preferably in the range 100 g/mol up to 500 g/mol, more preferably in the range 200 g/mol up to 500 g/mol, more preferably in the range 300 g/mol up to 500 g/mol, more preferably in the range 350 g/mol up to 500 g/mol, most preferably in the range 350 g/mol up to 450 g/mol.
According to embodiments, the low MW urethane forming compounds are selected from at least 90 wt % of 1 type of compound which is beneficial for the phase separation. Preferably said low MW urethane forming compounds are selected from 1,6-hexanediol, 1,4-butanediol or ethylene glycol, most preferably 1,4-butanediol.
According to embodiments, the hardblock content of the reactive foam formulation is in the range 12 up to 65%, preferably in the range 12% up to 50%, more preferably in the range 12% up to 40%, more preferably in the range 14% up to 35%, more preferably in the range 14% up to 30%, more preferably in the range 14% up to 27%, more preferably in the range 15% up to 25%, most preferably in the range 17% up to 22%.
According to embodiments, the water, low 1\4W urea forming compounds (and possibly the low MW urethane forming compounds) will form urea hardblock units after reaction in the obtained foam and wherein at least 5% of the theoretical equivalents in said urea hardblock originate from water, more preferably 10%, 20%, 30%, 40%, 50%, 60%, 70%, 75% of the theoretical equivalents in said urea hardblock originate from water.
According to embodiments, the reactive foam formulation may further comprise solid polymer particles such as styrene-based polymer particles. Examples of styrene polymer particles include so-called “SAN” particles of styrene-acrylonitrile. Alternatively, small amounts of polymer polyols may be added as an additional polyol in the isocyanate reactive composition. An example of a commercially available polymer polyol is HYPERLITE® Polyol 1639 which is a Polyether polyol modified with a styrene-acrylonitrile polymer (SAN) with a solid content of approximately 41 wt % (also referred to as polymer polyol).
According to embodiments, the reactive foam formulation may comprise fillers such as wood chips, wood dust, wood flakes, wooden plates; paper and cardboard, both shredded or layered; sand, vermiculite, clay, cement and other silicates; ground rubber, ground thermoplastics, ground thermoset materials; honeycombs of any material, like cardboard, aluminium, wood and plastics; metal particles and plates; cork in particulate form or in layers; natural fibers, like flax, hemp and sisal fibers; synthetic fibers, like polyamide, polyolefin, polyaramide, polyester and carbon fibers; mineral fibers, like glass fibers and rock wool fibers; mineral fillers like BaSO4 and CaCO3; nanoparticles, like clays, inorganic oxides and carbons; glass beads, ground glass, hollow glass beads; expanded or expandable beads; untreated or treated waste, like milled, chopped, crushed or ground waste and in particular fly ash; woven and non-woven textiles; and combinations of two or more of these materials.
According to embodiments, other conventional ingredients (additives and/or auxiliaries) may be used in making the elastomeric PU/PUR foam according to the invention. These include surfactants, flame proofing agents, fillers, pigments, stabilizers and the like.
According to embodiments, the surfactant used is preferably selected from a silicon surfactant. Examples of suitable commercially available surfactants are Tegostab® B8494, Tegostab® B8905, TegostabR B8993, TegostabR B8948, TegostabR B8017, TegostabR B8930, TegostabR B8950, Tegostab B8960, Vorasurf® DC193, Vorasurf® 5382, Niax® L1500, Niax® L1550, Niax® L1542, Niax® UAX 7061, Niax® UAX 6897, Niax® UAX 6639, Niax® UAX 7061, Tegostab B8466 and Tegostab B8416.
According to embodiments, suitable catalysts accelerate in particular the reaction between the NCO groups of the diisocyanates a) and accelerate the hydroxyl groups of the isoreactive compounds and are selected from those known in the prior art such as metal salt catalysts, such as organotins, and amine compounds, such as triethylenediamine (TEDA), N-methylimidazole, 1,2-dimethylimidazole, N-methylmorpholine, N-ethylmorpholine, tri ethyl amine, N,N′-dimethylpiperazine, 1,3,5-tris(dimethylaminopropyl) hexahydrotriazine, 2,4,6-tri s(dimethylaminomethyl)phenol, N-methyldicyclohexylamine, pentamethyldipropylene triamine, N-methyl-N′-(2-dimethylamino)-ethyl-piperazine, tributylamine, pentamethyldiethylenetriamine, hexamethyltriethylenetetramine, heptamethyltetraethylenepentamine, dimethylaminocyclohexylamine, pentamethyldipropylene triamine, triethanolamine, dimethylethanolamine, bis(dimethylaminoethyl)ether, tris(3-dimethylamino)propylamine, or its acid blocked derivatives, and the like, as well as any mixture thereof. The catalyst compound should be present in the reactive composition in a catalytically effective amount, generally from about 0 to 5% by weight, preferably 0 to 2-% by weight, most preferably 0 to 1-% by weight, based on total weight of all reactive ingredients used.
All reactants in the reactive foam formulation can be reacted at once or can be reacted in a sequential manner. By prior mixing all or part of the isocyanate-reactive compounds solutions or suspensions or dispersions are obtained. The various components used in the manufacture of the compositions of the invention can in fact be added in any order. The process can be selected from a bulk process, either batch or continuous process including cast process.
The invention further discloses an elastomeric deformable PU/PUR comprising water blown foam made using the reactive formulation of the invention. Said foam having an apparent density in the range 30-700 kg/m3 measured according to ISO 845 and having a tensile strength (measured according to DIN 53504) over apparent density ratio of at least 10 kPa·m3/kg.
According to embodiments, the elastomeric PU/PUR foam according to the invention is having a tensile strength (measured according to DIN 53504) over apparent density (ISO 845) ratio of at least 10 kPa·m3/kg, at least 10.5 kPa·m3/kg, at least 11 kPa·m3/kg, at least 11.5 kPa·m3/kg, at least 12 kPa·m3/kg, at least 12.5 kPa·m3/kg, at least 13 kPa·m3/kg, at least 13.5 kPa·m3/kg, at least 14 kPa·m3/kg.
According to embodiments, the elastomeric PU/PUR foam according to the invention has an apparent density in the range 30-700 kg/m3, in the range 30-600 kg/m3 or in the range 30-500 kg/m3 measured according to ISO 845.
According to embodiments, the elastomeric PU/PUR foam according to the invention has apparent density in the range 85-700 kg/m3, in the range 100-600 kg/m3, in the range 120-500 kg/m3, in the range 130-500 kg/m3, in the range 140-500 kg/m3, in the range 150-500 kg/m3 measured according to ISO 845.
According to embodiments, the elastomeric PU/PUR foam according to the invention has urethane hard-block species formed from urethane forming isocyanate reactive species having a molecular weight<500 g/mol and urea hard-block species formed from urea forming isocyanate reactive species having a molecular weight<500 g/mol.
According to embodiments, the elastomeric PU/PUR foam according to the invention has urethane and urea hard-block species formed from D equivalents urethane forming isocyanate reactive compounds having a molecular weight<500 g/mol, E equivalents urea forming isocyanate reactive compounds not being water having a molecular weight<500 g/mol, and C equivalents urea forming compounds selected from water and wherein the ratio calculated as D+E/C is smaller than 1.4, smaller than 1.2, smaller than 1.1, smaller than 1, smaller than 0.9.
According to embodiments, the elastomeric PU/PUR foam according to the invention has urethane and urea hard-block species formed from D equivalents urethane forming isocyanate reactive compounds having a molecular weight<500 g/mol, E equivalents urea forming isocyanate reactive compounds not being water having a molecular weight<500 g/mol, and C equivalents urea forming compounds selected from water and wherein the ratio calculated as D+E/C is larger than larger than 0.05, larger than 0.1, larger than 0.13, larger than 0.15, larger than 0.2, larger than larger than 0.3, larger than 0.4, larger than 0.5, larger than 0.55, larger than 0.6, larger than or larger than 0.7.
According to embodiments, the elastomeric PU/PUR foam according to the invention has urethane and urea hard-block species formed from D equivalents urethane forming isocyanate reactive species having a molecular weight<500 g/mol, E equivalents urea forming isocyanate reactive species not being water having a molecular weight<500 g/mol, and C equivalents urea forming compounds selected from water wherein the ratio calculated as D+E/C is in the range of 0.5 up to 1.4, in the range 0.55 up to 1.2 in the range 0.6 up to 1.1, in the range 0.65 up to 1.0, in the range up to 0.9.
According to embodiments, the elastomeric PU/PUR foam according to the invention is an injection moulded foam.
According to embodiments, the elastomeric PU/PUR foam according to the invention is a free risen foam or slabstock foam (performed in e.g., an open mould or conveyor belt).
According to embodiments, the elastomeric PU/PUR foam according to the invention is a sprayed foam using state-of-the-art spray technology for polyurethane foaming.
Due its good dynamic properties, the elastomeric PU/PUR foam according to the invention might be used in
The elastomeric foam according to the invention is having thermoplastic properties. The invention therefore further provides a process for recycling and/or remelting the elastomeric thermoplastic foam according to the invention into non-foamed thermoplastic materials without significantly deteriorating the thermoplastic polymer matrix compared to state-of-the-art recycled and/or remelted thermoplastic polyurethane (TPU) materials.
According to embodiments, the remelting/recycling of the thermoplastic elastomeric foam according to the invention is performed by a heat and/or compression process at temperatures above the melting temperature of the thermoplastic material of the elastomeric foam.
According to embodiments, the remelting/recycling of the thermoplastic elastomeric foam according to the invention is performed in an extruder at temperatures above the melting temperature of the thermoplastic material. By further addition of a blowing agent in the extruder a foamed recycled TPU foam might be achieved with closed cells.
The invention further discloses a thermally reformed material based on the foam according to the invention. The density of the thermally reformed material is at least >1.5 times the original density of the foam, more preferably >2 times the original density of the foam, more preferably >3 times the original density of the foam, most preferably >4 times the original density of the foam.
In some cases, it is preferred to use the thermally reformed/recycled foam material in an identical application field as the original foam application. An example is the use of the thermoplastic PU/PUR foam according to the invention as a shoe sole cushioning material (footwear midsole) and wherein the thermally reformed/recycled foam material is used as a footwear outsole material.
The invention is illustrated with the following examples.
Chemicals used:
Preparation of the Isocyanate-Terminated Prepolymers
Isocyanate 2 is prepared by loading 53.5 w % isocyanate 1 to a reactor at 60° C., adding 0.001 w % thionylchloride and stirring the mixture. The reactor contains a rotating mixing blade, thermometer and is continuously flushed by nitrogen using an in- and out-let. Then 46.499 w % of Polymeg® 2000 at 60° C. is added in 30 minutes while stirring. After the addition of all components (100 w %) the mixture was heated to a temperature of 80° C. for 2 hours while continuously stirring. The reaction mixture was then cooled to room temperature and the NCO value of 16% was determined the next day.
Isocyanate 3 preparation can be found in US2012/0095122A1 and is incorporated herein as reference. It is prepared by loading 60 w % isocyanate 1 to a reactor together with 1.7w % of a 2000 g/mol polycarbonate polyol and 32.3 w % Bayflex® 2003E. The reactor contains a rotating mixing blade, thermometer and is continuously flushed by nitrogen using an in- and out-let. The material is stirred at 70° C. and allowed to react for 2 hours before being cooled to 65° C. Thereafter 6 w % carbodiimized MDI is charged to the reactor which is mixed for 30 minutes at 65° C. to obtain the full mixture (100 w %). The reaction mixture was then cooled to room temperature and the NCO value of 19.5% was determined the next day.
Test Methods
Test methods used for Comparative example 1D can be found in US2012/0095122A1 and are incorporated herein as reference.
All other examples (1A-1C) were tested/prepared using the methods described below:
The materials are made according to practical knowledge of those skilled in the art. This is done by varying the mixing ratio of the polyol blend and isocyanate blend and determining which mixing ratio provides the strongest foam after a given time (in our case 70 seconds) using an indentation drop test. The practical optimum was then used to make samples 1A, 1B and 1C and the theoretical isocyanate index was calculated on the used mixing ratio.
As can be seen, the practical optimum is very close to a theoretical isocyanate index of 100 which is important to obtain good elastomeric properties. The cream time and end of rise time was monitored as the time where the mixture starts to foam and the time the foam reaches its highest point respectively. Both free rise density and moulded density are determined as described in the definitions section.
The overpack factor (or ratio) is calculated by the ratio of the “moulded density” over the “free rise density” and is >1,0. To ensure the examples have a similar moulded density, even though they have a different free rise density, we varied the overpack ratio. To take into account any possible density variations in the examples, the tensile strength (measured according to DIN 53504) over apparent density ratio was calculated. The definition section includes the method of calculating the “urea forming equivalents” and “urethane forming equivalents” denoted by C, D and E; but also covers the other tested parameters shown in table 1 and the methods used.
The formulation of the examples is split in 2 separate blends, called the “isocyanate blend” and the “isocyanate reactive blend”. The isocyanate reactive blend (as shown in the examples) refers to all other ingredients besides the isocyanate and thus contains polyols, crosslinkers, chain extenders, catalysts and surfactants (but could also contain other ingredients as described in certain embodiments).
The foam samples (free rise & moulded) are made using a 2K PU casting Green machine with a DVM2408 mixing head. The “isocyanate blend” and “isocyanate reactive blend” were kept at and 53±1° C. respectively by the machine before the casting was done. Example 1A is according to the invention while examples 1B and 1C are comparative examples.
The composition and data of comparative example 1D taken from reference US2012/0095122A1 where it can be found as example 6 in Table 2
The experimental data shown in table 1 clearly shows the improved tensile strength and ball resilience of the foam according to the invention. This is clearly visible by the calculated tensile strength (measured according to DIN 53504) over apparent density ratio reaching values>10 kPa·m3/kg. The invention thereby allows to make significantly stronger foams at a given density, or a lower density foam with a similar tensile strength. The data also clearly shows that example 1A, having an optimal D/C ratio (or (D+E)/C ratio) allows to make the strongest foam with the highest resilience.
The recyclability of the foam from example 1A was also tested and it was very well recyclable via compression moulding using a Fontijne Lab-press TP400 at a temperature of 180° C. for 2×5 minutes using a pressure of 20 kN.
| Number | Date | Country | Kind |
|---|---|---|---|
| 20205808.7 | Nov 2020 | EP | regional |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2021/080677 | 11/4/2021 | WO |
