CA1231488A - Process for the production of thermoplastic polyurethane elastomers - Google Patents
Process for the production of thermoplastic polyurethane elastomersInfo
- Publication number
- CA1231488A CA1231488A CA000473527A CA473527A CA1231488A CA 1231488 A CA1231488 A CA 1231488A CA 000473527 A CA000473527 A CA 000473527A CA 473527 A CA473527 A CA 473527A CA 1231488 A CA1231488 A CA 1231488A
- Authority
- CA
- Canada
- Prior art keywords
- component
- diol
- molecular weight
- dill
- mixture
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
- C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
- C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
- C08G18/7685—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing two or more non-condensed aromatic rings directly linked to each other
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
- C08L75/08—Polyurethanes from polyethers
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
A PROCESS FOR THE PRODUCTION OF
THERMOPLASTIC POLYURETHANE ELASTOMERS
ABSTRACT OF THE DISCLOSURE
Thermoplastic polyurethane elastomers which are flexible at low temperatures, have high mechanical strength, a density of from 1.10 to 1.17 Mg/m3 and a Shore-D hardness of from 55 to 80 are produced by reacting: a) 4,4'-diisocyanatodiphenylmethane or an isomer mixture thereof with b) a polytetramethylene ether diol having a molecular weight of from 800 to 3,000 in the presence of c) a mixture of diol chain extenders, d) a graft rubber polymer and optionally e) an antioxidant and/or UV-absorber/light stabilizer.
The molar ratio of a) to b) is between 6:1 and 50:1.
The mixture of diol chain extenders is made up of (1) 1,4-butane diol or 1,6-hexane diol and (2) a diol different from (1) having a molecular weight of from 62 to 399. The molar ratio of diol (1) to diol (2) is from 97:3 to 72:28. These elastomers are particularly useful in the production of automobile and ski boot components.
THERMOPLASTIC POLYURETHANE ELASTOMERS
ABSTRACT OF THE DISCLOSURE
Thermoplastic polyurethane elastomers which are flexible at low temperatures, have high mechanical strength, a density of from 1.10 to 1.17 Mg/m3 and a Shore-D hardness of from 55 to 80 are produced by reacting: a) 4,4'-diisocyanatodiphenylmethane or an isomer mixture thereof with b) a polytetramethylene ether diol having a molecular weight of from 800 to 3,000 in the presence of c) a mixture of diol chain extenders, d) a graft rubber polymer and optionally e) an antioxidant and/or UV-absorber/light stabilizer.
The molar ratio of a) to b) is between 6:1 and 50:1.
The mixture of diol chain extenders is made up of (1) 1,4-butane diol or 1,6-hexane diol and (2) a diol different from (1) having a molecular weight of from 62 to 399. The molar ratio of diol (1) to diol (2) is from 97:3 to 72:28. These elastomers are particularly useful in the production of automobile and ski boot components.
Description
i Rio Moe Lea 22,892 A PROCESS FOR THE PRODUCTION OF
THEP~IOPLASTIC POLYURETHANE ELASTOMERS
BACKGROUND OF THE INVENTION
This invention relates to a process for the production of rigid, elastic, homogeneously Diablo, substantially non-yellowing, hydrolysis-resistant polyp urethane elastomers which show low-temperature phlox ability and outstanding impact strength at low tempera-lures, tensile strength and a high modulus without any nickers segregation of the hard segments an which have a relatively low density of from 1.10 to 1.17 Mg/m3 and a high Shore-D hardness of from 55 to 80.
The synthesis of polyurethane elastomers from polytetramethylene ether dills, diisocyanates and chain extenders is known in principle. However, attempts to produce highly rigid polyurethane elastomers from polyp tetramethylene ether dills (e.g., polytetrahydrofuran dills) of relatively high molecular weight (molecular weight of the polyether approx. 1200 to 1500), hove generally produced elastomers having a high degree of segregation between hard and soft segments when the molar ratio of diisocyanates (diphenylmethane dozes Nate "MID") to polyether dills was greater than about 8:1. Such segregation is evidenced by a distinct nickers effect or, in the case of dyed or pigmented materials, by serious streaking in the molding. The strength values particularly tear propagation resist-ante, are greatly reduced by such segregation. Cons-quaintly, molded articles with reduced wall thickness (for example sky boot fastenings have much zoo low resistance to detachment for many practical applique-lions.
German Offenle~ungsschrlft 2,854,409 discloses polyester urethane elastomers chain-extended with 1,4-butane dill in its Examples. However, when the Moe Jut rigidity of products such as these is increased to around 40 Ma, their impact strength at low temperatures is extremely moderate (approx. 20 to 40% in impact/
tensile tests). When polyeth~r urethane elastomers are chain-extended with Boone dill as the sole chain extender in the manner disclosed in the Examples of German Offenlegungsschrift 2,854,409, the elastomers obtained show a pronounced nickers structure and cannot be used in applications such as ski boots. The products obtained by this process also are highly yellow.
German Offenlegungsschrift 2,854,407 discloses thermoplastic blends of thermoplastic polyurethane based on polyethers or polyesters and a graft product of I to 95 wit % of an elastomers component serving as the graft base and 5 to 35 wit % of one or more grafted on monomers. The blends obtained with these polyethers show poor impact strength at low temperatures and also exhibit the segregation phenomena tithe nickers effect).
The strengths of these products are reduced as a result of such segregation.
The nickers effect is also encountered in products made by the process described in European Patent Application 12,343. In this disclosed process, relatively high molecular weight polypropylene oxide and polyethylene oxide ether polyols are used as the rota-lively high molecular weight polyhydroxyl compounds.
The yellowing of these products is very high their impact strength at low temperatures is inadequate and their strengths/moduli need i~pro~ement. In this disclosed process, certain copol~ners or graft polymers are used together with stabilizers to preappoint degrade-lion of the products during extrusion.
owe Jo According to U.S. Patent 4,179,479, ABS-graft copolymers together with from 0.5 to 10 it % of process-in aids in the form of an acrylate polymer having a molecular weight of from 500,000 to 1,500,000 thomopoly-mews of methylmethacrylate and butylmethacrylate,copolymers of methylmethacrylate and ethylacrylate and terpolymers of methylmethacrylate, n-butylacrylate and styrenes), optionally in admixture with finlike anti-oxidants and UV-absorbers, may be used in addition to thermoplastic polyurethane. The acrylate polymer processing aids make it possible to improve processing by extrusion. This process also gives nickers products with relatively poor strength values, even at low temperatures. The ABS-types used had high styrenes contents.
European Patent Application 4,939 describes a dill chain extending mixture (for example of 1,4-butane dill and 1,6-hexane dill) in which one component is present in a quantity of from I to 99 wit % and the other component in a quantity of from 1 to 10 wit % which is useful in the production ox extruded and calendered PU-elastomers. There is no suggestion in European Patent Application 4,939 to use graft rubber. Where a rigid polyurethane is used in this disclosed process, the products still show a distinct nickers effect and also yellow very seriously. Polyurethane thermoplasts made from the hexamethylene diisocyanate disclosed therein show excessively reduced strength values after exposure to ultraviolet light.
SIAM JO TUG I~VEK!ION
It is an object of the present invention to provide a process for the production of thermoplastic polyurethane elastomers which are flexible at lo temperatures, have high mechanical strength, a density Moe of from 1.10 to 1.17 Mg/m3 and a Shore-D hardness of from 55 to 80.
It is also an object of the present invention to provide a process for the production of homogeneously Diablo, substantially non-yellowing thermoplastic polyurethane elastomers in which segregation of the hard segments is substantially completely eliminated.
It is another object of the invention to provide a process for the production of thermoplastic polyurethane elastomers having outstanding impact strength at low temperatures and high strength and tear propagation resistance values.
It is a further object of the present invention to provide a process for the production of thermoplastic polyurethane elastomers which may be readily extruded or injection molded to form automobile components and ski boot components.
These and other objects which will be readily apparent to those skilled in the art are accomplished by reacting in quantities which meet specific ratio requirements 4,4-diisocyanatodiphenylme~hane or mixtures thereof containing 2,4'-diisocyanatodipheT~ylmethane with certain polytetramethylene ether dills having molecular weights of from 800 to 3Q00 in thy presence of a certain mixture of dill chain extenders, a graft rubber polymer and optionally, an antioxidant and/or US absorber/light stabilizer.
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to a process for the production of thermoplastic polyurethane elastomers by reacting a diisocyanate, a relatively high molecular weight polyol and dill chain-extending agents in substantially equivalent ratios of NCO-groups to the OH-groups of the polyol and dill components in the Moe I
presence of a thermoplastic polymer and, optionally, antioxidant and/or W-absorbers/light stabilizers.
More specifically, rigid-elastic, homogeneous thermos plastic polyurethane elastomers showing flexibility at low temperature and high mechanical strength without any nickers effect through segregation of the hard segments and having a low density of from 1,10 to 1.17 Mum and a Shore-D hardness of from 55 to 80 are produced from the components more fully described below.
The diisocyanate employed in the process of the present invention is 4,4'-diisocyanatodiphenylmethane or an isomer mixture with up to 5 mole percent of
THEP~IOPLASTIC POLYURETHANE ELASTOMERS
BACKGROUND OF THE INVENTION
This invention relates to a process for the production of rigid, elastic, homogeneously Diablo, substantially non-yellowing, hydrolysis-resistant polyp urethane elastomers which show low-temperature phlox ability and outstanding impact strength at low tempera-lures, tensile strength and a high modulus without any nickers segregation of the hard segments an which have a relatively low density of from 1.10 to 1.17 Mg/m3 and a high Shore-D hardness of from 55 to 80.
The synthesis of polyurethane elastomers from polytetramethylene ether dills, diisocyanates and chain extenders is known in principle. However, attempts to produce highly rigid polyurethane elastomers from polyp tetramethylene ether dills (e.g., polytetrahydrofuran dills) of relatively high molecular weight (molecular weight of the polyether approx. 1200 to 1500), hove generally produced elastomers having a high degree of segregation between hard and soft segments when the molar ratio of diisocyanates (diphenylmethane dozes Nate "MID") to polyether dills was greater than about 8:1. Such segregation is evidenced by a distinct nickers effect or, in the case of dyed or pigmented materials, by serious streaking in the molding. The strength values particularly tear propagation resist-ante, are greatly reduced by such segregation. Cons-quaintly, molded articles with reduced wall thickness (for example sky boot fastenings have much zoo low resistance to detachment for many practical applique-lions.
German Offenle~ungsschrlft 2,854,409 discloses polyester urethane elastomers chain-extended with 1,4-butane dill in its Examples. However, when the Moe Jut rigidity of products such as these is increased to around 40 Ma, their impact strength at low temperatures is extremely moderate (approx. 20 to 40% in impact/
tensile tests). When polyeth~r urethane elastomers are chain-extended with Boone dill as the sole chain extender in the manner disclosed in the Examples of German Offenlegungsschrift 2,854,409, the elastomers obtained show a pronounced nickers structure and cannot be used in applications such as ski boots. The products obtained by this process also are highly yellow.
German Offenlegungsschrift 2,854,407 discloses thermoplastic blends of thermoplastic polyurethane based on polyethers or polyesters and a graft product of I to 95 wit % of an elastomers component serving as the graft base and 5 to 35 wit % of one or more grafted on monomers. The blends obtained with these polyethers show poor impact strength at low temperatures and also exhibit the segregation phenomena tithe nickers effect).
The strengths of these products are reduced as a result of such segregation.
The nickers effect is also encountered in products made by the process described in European Patent Application 12,343. In this disclosed process, relatively high molecular weight polypropylene oxide and polyethylene oxide ether polyols are used as the rota-lively high molecular weight polyhydroxyl compounds.
The yellowing of these products is very high their impact strength at low temperatures is inadequate and their strengths/moduli need i~pro~ement. In this disclosed process, certain copol~ners or graft polymers are used together with stabilizers to preappoint degrade-lion of the products during extrusion.
owe Jo According to U.S. Patent 4,179,479, ABS-graft copolymers together with from 0.5 to 10 it % of process-in aids in the form of an acrylate polymer having a molecular weight of from 500,000 to 1,500,000 thomopoly-mews of methylmethacrylate and butylmethacrylate,copolymers of methylmethacrylate and ethylacrylate and terpolymers of methylmethacrylate, n-butylacrylate and styrenes), optionally in admixture with finlike anti-oxidants and UV-absorbers, may be used in addition to thermoplastic polyurethane. The acrylate polymer processing aids make it possible to improve processing by extrusion. This process also gives nickers products with relatively poor strength values, even at low temperatures. The ABS-types used had high styrenes contents.
European Patent Application 4,939 describes a dill chain extending mixture (for example of 1,4-butane dill and 1,6-hexane dill) in which one component is present in a quantity of from I to 99 wit % and the other component in a quantity of from 1 to 10 wit % which is useful in the production ox extruded and calendered PU-elastomers. There is no suggestion in European Patent Application 4,939 to use graft rubber. Where a rigid polyurethane is used in this disclosed process, the products still show a distinct nickers effect and also yellow very seriously. Polyurethane thermoplasts made from the hexamethylene diisocyanate disclosed therein show excessively reduced strength values after exposure to ultraviolet light.
SIAM JO TUG I~VEK!ION
It is an object of the present invention to provide a process for the production of thermoplastic polyurethane elastomers which are flexible at lo temperatures, have high mechanical strength, a density Moe of from 1.10 to 1.17 Mg/m3 and a Shore-D hardness of from 55 to 80.
It is also an object of the present invention to provide a process for the production of homogeneously Diablo, substantially non-yellowing thermoplastic polyurethane elastomers in which segregation of the hard segments is substantially completely eliminated.
It is another object of the invention to provide a process for the production of thermoplastic polyurethane elastomers having outstanding impact strength at low temperatures and high strength and tear propagation resistance values.
It is a further object of the present invention to provide a process for the production of thermoplastic polyurethane elastomers which may be readily extruded or injection molded to form automobile components and ski boot components.
These and other objects which will be readily apparent to those skilled in the art are accomplished by reacting in quantities which meet specific ratio requirements 4,4-diisocyanatodiphenylme~hane or mixtures thereof containing 2,4'-diisocyanatodipheT~ylmethane with certain polytetramethylene ether dills having molecular weights of from 800 to 3Q00 in thy presence of a certain mixture of dill chain extenders, a graft rubber polymer and optionally, an antioxidant and/or US absorber/light stabilizer.
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to a process for the production of thermoplastic polyurethane elastomers by reacting a diisocyanate, a relatively high molecular weight polyol and dill chain-extending agents in substantially equivalent ratios of NCO-groups to the OH-groups of the polyol and dill components in the Moe I
presence of a thermoplastic polymer and, optionally, antioxidant and/or W-absorbers/light stabilizers.
More specifically, rigid-elastic, homogeneous thermos plastic polyurethane elastomers showing flexibility at low temperature and high mechanical strength without any nickers effect through segregation of the hard segments and having a low density of from 1,10 to 1.17 Mum and a Shore-D hardness of from 55 to 80 are produced from the components more fully described below.
The diisocyanate employed in the process of the present invention is 4,4'-diisocyanatodiphenylmethane or an isomer mixture with up to 5 mole percent of
2,4-diisocyanatodiphenylmethane, preferably from 0.5 to 5 mole percent and, more preferably, from 0.5 to 3.5 15 mole percent. This diisocyanate may be modified with small quantities of the chain extender mixture.
The relatively high molecular weight polyol is a polytetramethylene ether dill having a molecular weight of from 800 to 3000 and preferably from lG00 to 1500, optionally in admixture with other relatively high molecular weight polyhydroxyl compounds having a molecular weight in the range from 800 Jo 3000. Polyp tetrahydrofuran dill is an example of such a doll.
The mixture of chain extenders employed in the I process of the present invention is made up of a prince-pal chain extender and one or more co-chain extender dills in a molar ratio of from 97:3 Jo 7~:28 and prefer-ably from 94:6 to 87:13. The principal chain extender may be either 1,4-butane dill or ennui dill and the 30 co-chain extender Jay be one or Gore other dill.
Preferred co-chain extenders are 1,6-hexane dill, 1,4-butane dill, diethylene glycol, dip and tripropylene glycol and hydroquinone di-~-hydroxyethyl ether.
Moe I
The thermoplastic polymer used in the present invention is a butadiene-based graft rubber, preferably a graft rubber containing from 30 to 50 wit % of but-dine as the raft base and a thermoplastic resin combo-next of styrenes and acrylonitrile as the graft monomer This thermoplastic polymer is generally used in quanta-ties of from 5 to 25 wit % and preferably in quantities of from 6 to 15 wit Jo based on total diisocyanate, high molecular weight polyol and chain extender mixture.
Finlike antioxidant and/or W -absorbers/light stabilizers in quantities of from Owe to 3 wit % based on total diisocyanate, high molecular weight pull and chain extender mixture) may optionally be used.
Other relatively high molecular weight polyp hydroxyl compounds, for example other polyethers or polyesters or polycarbonates may by added to and mixed with the polytetramethylene ether dill in a quantity of up to 60 wit % and preferably in a quantity of less than 4Q wit %. Relatively high molecular weight polyols such as these are described, for example, in Genuine Offend legungsschrift 2,854,409. However, these other polyols may have an adverse effect upon impact strength at low temperatures so combination of such polyols with the tetramethylene ether dill is not preferred. Other relatively high molecular weight polyols which have proven to be particularly advantageous when used in combination with a ~e~ramethylene ether dill are 1,4-butane dill adipate and 1,4 butane Dylan dill mixed adipate. The molecular weight of polyether diol/polyester dill mixtures such as these is preferably in the range from 1~00 to 2500.
The molar ratio of diocesan to te~ramethyl-one ether dill and any other high molecular weight polyp hydroxyl compound should amount to between Al and oily, preferably 6:1 and 50:l.
and more preferably to between 6,5:1 and 15:1. Ratios of from I to 13:1 are particularly preferred. Such molar ratios result in elastomers having a Shore-D hardness of from 55 to 80 and preferably from 63 to I
Chain extending mixtures containing 1,4-butane dill or 1,6-hexane dill as the principal component and one or more (for example 2, 3 or 4) other dills having a molecular weight in the range from 62 to 399 as co-chain extenders (e.g. 1,6-hexane dill, 1,4-butane dill, diethylene glycol, dipropylene glycol, tripropylene glycol and hydroquinone Dow hydroxyethyl ether) may be used as the chain-extending mixture It is preferred to use a mixture of from 97 to 72 mole percent of 1,4-butane dill and from 3 to 28 mole percent of 1,6-hexane dill. A molar ratio of 94-87:6-13 is particularly preferred. If 1,6-hexane dill is used as the principal component and 1,4-butane dill as the co-chain extender, the products obtained are less elastic and do not have the same physical properties obtained ho 1,4-butane dill is the principal chain extender. At least 5 moles of chain extending mixtures are used for each mole of polytetramethylene ether dill to insure production of a rigid product. The co-chain extender may also be introduced through the dozes-natodiphenylmethane (MID). Thus, mixtures of dip or tripropylene gawkily and MID which are liquid at room temperature may be used in accordance with the invent lion.
The graft rubbers used in the present invention are preferably butadiene-based graft rubbers containing from 30 to 50 wit % of butadiene in the elastomers component and styrenes acrylonitrile and, optionally, methacrylates as the graft monomer component. Mixtures of the monomers styrenes and acrylonitrile in a ratio by Moe weight of from 90:10 to 50:50 are preferably used as the graft monomer component.
Where antioxidant and/or UV-absorbers/light stabilizers are used in the present invention, they are used in quantities of from 0.1 to 3 wit %, based on the total quantity of all the components. It is preferred to use mixtures of stabilizers.
Suitable antioxidant are known to those in the art and are described in European Patent Applique-lo lion 12,343. Preferred antioxidant are those base don starkly hindered phenols such as 2,6-di-t-butyl-4-methylphenol and pentaerythritol-tetrakis-3-~3,5-di-t-butyl-4-hydroxyphenyl)-propiona~e (Irganox 1010, a product of Ciba-Geigy).
The W -absorbers used may be state-of-the-ar~
products, such as 2-(~'-hydroxyphenyl)-benztriazole derivatives (e.g. those sold under the trademark Tinuvin~ 326, 327, 328 or Tinuvin P (products of Cuba-Geigy), hydroxybenzophenone derivatives and others.
Other examples of appropriate hydroxyphenyl benztriazole derivatives are given in German Auslegeschrif~ 1J794,144 at columns 5-7. Particularly preferred UV-absorbers are the cyanoacrylate derivatives described in German Patentschrift 1,793,797, for example the compound corresponding to the formula SHEA
Cluck COOK
which is sold by Bayer A under the designation W -absorber 340.
Examples of suitable fight stabilizers are the bis-ester of sebacic acid with 4-hydroxy-2,2~6,6-tetra-~10-~644 I ho go methylpiperidine (Tinuvin 770), but especially pent-methyl derivatives represented by the formula SHEA
C-O ON -SHEA
twill / Ho --HAYAKAWA C - alkyd - (Cluck) t-butyl \ I SHEA
C-O ~7~N-CH3 The product sold under the trademark Tinuvin~l44 is one such stabilizer. Oligomeric or polymeric, N-substituted derivatives such as those corresponding to the formula O O R I
R' - C (SHEA) x C O OH SHEA - OWE
SHEA Ho m on which x represents a number from 2 to lo lo R represents hydrogen or a methyl group and R' represents an alkyd or a cycloalkyl group may also be used as light stabilizers. In the above-given formula, when n represents 2, R represents hydrogen and R' r presents a methyl group, the formula lo represents the composition sold under the designation Tinuvin~622.
Preferred light stabilizers are those based on 2,2,6,6-tetraalkyl piperidines. Light stabilizers based on l,2,2,6,6-pentaalkyl pip~ridines are particularly 20 preferred.
Moe I
Where the light stabilizers used contain a group of a finlike antioxidant (a starkly hindered phenol group, such as 2,6-di~t-butylphenol) in addition Jo a tetraalkyl or (preferably) pentaalkyl (for example pentamethyl) group in the same molecule, as is the case with the material designated Tenon, there is no need for finlike antioxidant Jo be used.
The polyurethane reaction may ox course be carried out in the presence of the usual catalysts, release agents, antistatic agents, flame proofing agents, fillers, glass fibers and pigments employed in this art.
Such materials are described in greater detail in, for example, German Offenlegungsschriften 2,854,409 and 2,~20,501 and in Herman Patentschrift 3,329 9 775.
Suitable catalysts are, for example, tertiary amine, organometallic compounds, particularly organic tin, lead and titanium compounds such as tin acetate, Tony) ethyl hexoate, dibutyl tin dilaurate or lead acetate.
Suitable release agents include waxes, oils and long-chain compounds containing carboxyl~ ester, aside, urethane or urea groups such as those described in German Offenlegungsschrift 2,~04,470, The quantities of diocesan polytetra-ethylene ether deluge other polyhydroxyl compounds and chain extender dills used in the process o. the present invention are generally selected in such a way that the NCO:OH ratio of diisocyanate to OH-compounds amounts to between 0.9 and 1.2 and, preferably, to between 1.01 and 1.08.
The polyurethane according to the invention may be produced by forming a polyurethane in known manner and by subsequently mixing ~co-extruding) the polyurethane thus-formed with the graft rubber in Moe I
another stage. It is preferred however to use a one-shot procedure (described, for example, in German Offend legungsschrift 2,814,409) in which the graft rubber is initially introduced into a seli-cleaning twin-screw kneader and the remaining polyurethane components added thereto. Before it is introduced into the reactor, the polyol may even have been reacted with the diisocyanate to form an NCO-containing prepolymer. The elastomeric materials may be further processed in the processing 10 machines normally used for thermoplasts, preferably injection-molding machines.
A major advantage of the polyurethane elect-mews of the present invention lies in the fact that they do not show any troublesome separation of the hard segments, ire no opalescent nickers effect. This enables satisfactory dyeing or pigmenting of relatively large injection moldings without any troublesome color streaks. By contrast, when the graft rubber and chain extender mixture are not used in the production of the elastomers hard, thermoplastic polyurethane based on polytetramethylene ether dills (molecular weight of the polyether approximately 1500) showing impact resistance a low temperatures and Shore-D hardness values ox from 63 to 72 show this troublesome nickers effect.
The new polyurethane elastomers of the present invention show excellent impact strength at low temperatures. In contrast to thermoplastic polyester urethanes, they withstand the shattering test according to DIN 53 443 (weight of 50 kg dropped from a height of 1 meter) at a temperature of -~0C. Very good breaking elongation values are obtained in the impact/tensile strength test. Elastomers according to the invention based on polyte~ramethylene ether diol/polyester dill show a breaking elongation of from 40 to 100~ whereas Moe pure polytetramethylene ether dill products show a breaking elongation of from 100 to more than 200%. The antioxidant-UV absorber/light stabilizer combination also has a favorable effect upon the breaking elongation values particularly where the product is to be extruded because thermal damage during extrusion is minimized.
The stiffening factor of the polyurethane elastomers according to the invention measured at +20C
as against -20C amounts to approximately 1:1.7 to 1:2.5 (determined from the flexural stress at a given deflect lion in accordance with DIN 53 445). Thermoplastic polyester urethanes which do not correspond to the invention show a distinctly higher stiffening factor of, in general, from 1:2.5 to 1:3 or higher.
The new materials, particularly those based on polytetramethylene other dill, have a density of from 1.10 to 1.17 Mg/m3. This has considerable advantages in the case of ski boot shells. Compared with thermos plastic polyester urethanes (density approximately 1.24 Mg/m3), density is reduced by around 10%.
The elasticity of the polyurethane elastomers according to the invention is distinctly increased.
Whereas thermoplastic polyester urethanes show a resilience of at most 40%, the thermoplastic polyether polyurethane copolymers according to the invention show increased resilience values of approximately 50~.
The polyurethane elastomers according to the invention show high tear propagation resistance. This is extremely important in the case of automobile or ski boot components. I the mixture of chain extenders according to the invention is replaced by a single chain extender, however, tear propagation resistance is distinctly reduced, even in cases where the graft rubber is used.
-264l~
The invention is illustrated by the following Examples in which quantities are expressed in parts by weight, unless otherwise indicated.
EXAMPLES
Production of the thermoplastic PU-elastomers according to the invention using a twin-screw kneader A Werner & Pfleiderer ASK 53 V twin-screw kneader (Werner & Pfleiderer, Stuttgart) with self-cleaning screws and an approximately 20~ quota of knead-in elements was used in each of these Examples. The processing section was made up of 12 separately hatable housings and corresponded in length to approximately 20 times the screw diameter.
The function and mode of operation of the screw kneader and of the kneading and conveying elements of the screws etc. are described in detail in Werner Pfleiderer Brochures and in Gunman Auslegeschrift 2,302,564.
The residence times of the reaction melt in the Kneader were generally between 0.3 and 30 minutes and preferably between 0.5 and 4 minutes. The temperature of the screw housing was between about 60C and 300C
(approximately 80 to 280C in the feed zone; approxi-mutely 100 to 300C in the middle of the extrude and approximately 120 to 250C in the discharge zone). The melt issuing from the Pxtruder was quenched and size-reduced by known methods.
_ A thermoplastic polyurethane elastomers was produced from the following starting materials in the quantities (parts by weight) indicated:
Moe 15.27 wit % of polytetramethylene ether dill, molecular weight 1000 15.27 wit % of polytetram~thylene ether dill, molecular weight 2000 a) 0.12 wit JO of 2,6-di-t-butyl-4-methylphenol 0.21 wit % of pentaerythritol-tetrakis-3-(3,5 di-t-butyl-4-hydroxyphenyl)-preappoint (Irganox-1010, a product of Ciba-Geigy~
0.15 wit % of cyanoacrylic acid ester (US-absorber 340, a product of Bayer AGO
b) f 12.22 wit % of 1,4-butane dill 1.37 wit % of 1,6-hexane dill c) 45.21 wit of 4,4'-diisocyanatodiphenylme~hane containing 2.5 wit of isomer d) 0.15 wit of stearylamide and e) 10.00 wit % of graft rubber (containing 50 wit % of butadiene, 36 wit % of styrenes and 14 wit % acrylonitrile).
The NCO:OH-ratio was 1.06:1.
By means of a gear pump, component a) was pumped from the storage vessel kept at 120C into housing 2 of a twin-screw extrude. The dill mixture b) was also introduced into housing 2 at room temperature by means of a small piston pump. Component I was pumped into housing 3 at a temperature of 60C by means of a gear pump. Components d) and e) were introduced into housing 1 in powder form by means of metering screws.
The various housings of the kneader were adjusted to the following temperatures:
Housing 1 2 3 7 9 11 12 he'd Temperature 100 210 21~ 200 180 16Q 100 190 C
owe Aster storage for 3 days, injection molding in conventional injection molding machines and tempering of the test specimens for 15 h at 110C, the thermoplastic polyurethane elastomers obtained showed the mechanical properties set out in Table 1. The solidification behavior of the iniection~molded test specimens was favorable and their green strength high. Coloring did not produce any of the otherwise troublesome separation streaks of the hard segment. The low-temperature impact strength values were very good for a thermoplast as rigid as this (impactltensile strength test: 158%
breaking elongation).
Table 1 Test DIN Standard Value Unit Muddles 53 5Q4 31.6 Ma Muddles 53 504 51.2 Ma Tensile strength 53 504 53.3 Ma Breaking elongation 53 504 310 %
Shore hardness A/D 53 505 aye (A/D) Elasticity 53 512 51 %
Abrasion 53 516 19 mm3 Tear propagation resistance 53 515 170 Kim Flexural stress at a given deflection 23C 53 452 34.9 Ma Flexural stress at a given deflection -20C 53 452 69.7 Ma Impact/tensile strength test -10C 158 %
Density 53 ~79 1.11 Mg/m3 30 Shrinkage 0.5 %
At 1.11 Mg/m3, density was low, tear propaga-lion resistance high. The stiffening factor, determined from the flexural stress at a given deflection at ~23C
as against the value at -20C was 1:2.
Moe Relatively high molecular weight polyols made up of a mixture of polytetramethylene ether dill and 1,4-butane diol/adipic acid polyester dill were used to produce an elastomers The reaction components were as follows:
14.53 wit % of polytetramethylene ether dill (OH
number 56.2) 14.53 wit % of 1,4-butane diolladipic acid polyester dill (OH number 51.9) a) 0.12 wit % of 2,6-di-t-butyl-4-methylphenol 0.20 wit % of Irganox-1010 products of 0.15 wit % of Tinuvin-622 J Ciba-Geigy 0.15 wit of 2,2'-6,6'-tetraisopropyl diphenyl carbodiimide 13.08 wit % of Boone dill 1.45 wit % of 1,6-hexane dill c) 45.64 wit % of 4l4'-diisocyanatodiphenylme~hane d) 0.15 wit % of Carnauba wax 20 e) 10.00 wit % of the graft rubber used in Example 1.
The NCO:OH-ratio was 1.06:1.
Production and further processing were carried out in the same way as in Example 1, The mechanical properties are shown in Table 2.
Moe Table 2 Test DIN standard Value Unit Muddles% 53 504 31.4 Ma Modulus/300% 53 504 54.4 Ma Tensile strength 53 504 54.9 Ma Breaking elongation 53 504 301 %
Shore hardness A/D 53 505 98/69 Elasticity 53 512 49 %
lo Tear propagation resistance 53 515 197 Kim Flexural stress at a given deflection 23~C 53 452 38.7 Ma Flexural stress at a given deflection -20C 53 452 80.3 Ma 15 Impact/tensile strength test -10C 52 %
Density 53 479 1.13 Mg/m3 This thermoplast was injection-molded to form satisfactory moldings without any n~creous effect.
Tensile strength and tear propagation resistance were both high. The low-temperature properties were good, although not as good as in the preferred polyol range according to the invention as indicated in Example l (pure polytetramethylether dill).
EXAMPLES 3 to 11 Thermoplastic polyurethane according to the invention were produced in the same manner as described in Examples 1 and 2 using formulations 3 to if shown in 30 Table 3. Examples 3 to 10 represent variations of the chain extenders and OX the type and quantity of graft rubber, the ratio of the two chain extellders to one another being varied in Examples 8 and 9.
owe In Example 11, par of the polytetramethylene ether dill was replaced by a polyester cliol ox rota-lively high molecular weight.
The polyurethane elastomers described in Examples 3 to 11 were thermoplastic ally processed in standard commercially available injection molding machines. They showed little, if any, separation of the hard segment and, accordingly, were pigmented without any problems. They showed high flexibility and high impact strength at low temperatures for a thermoplastic polyurethane. In addition, they were distinguished by good initial elasticity during processing. Their mechanical properties are shown in Table 4.
Examples 3 and 4 according to the invention are characterized by a content of 5 wit % of graft rubber.
This reduced separation in the polyurethane, although not as much as in Examples 1, 5 to 7 according to the invention which are characterized by the preferred graft rubber content of 10 wit %.
Slight separation of the hard segment was evident, even where the content of co-chain extender was low. This occurred, for example, in formulation 8 according to the invention which contained 4 mule percent of 1 t 6-hexane dill (and 96 mole percent of 1,4-butane dill) and which was therefore outside the preferred co-chain extender range of 6 to 13 mole percent. If more than 13 mole percent of co-chain extender were used (Example 9), the initial elasticity of the moldings suffered slightly and the injection cycle on the injection molding machine became longer.
The same effect also occurred with a relatively high content of graft rubber (Example 10, I wit % of graft rubber).
Example 11 according to the invention core-spends to a "soft" variant of Example 2.
Moe Jo I
_ `~= _ o ox o o o o o I, a If Lo GUN N Kiwi _ I
C I 'it JO O O C`J
o 3 r ED No to Cal I
I Jo OX Jo O ox an I
Lo Jo r_ I ox O
c O I I Jo N I) I I JO O O I
a r-E eel clue I C~J lo ) x LLlc~ -I o o o E Jo to Jo us I
s I if) . L
a Jo a v to r--a N a . a E
I Jo ,_ or Jo ox ,_ .--L) Jo I I to Jo O
I ._ Cal a .
En E ~:1 Lo) Jo I 1.
E I= c L o Q _ v --I O E l x x I_ E E
I Jo I ,_ J roll I W
o C ox o I
I 'o us a 3 a o.-- owe Jo ~=~
ill clue I _ _ Lowe o o ox O
o o o o Cal o o O
at I o I
I O et Jo o o , Us o o C
0 I ._ O O I I.
I_ I> OX N O O C .-1 I tl)~ ._ "it O I_ O Jo eye C`J o So I Us O O I
. - CUD I) E---Lo O O Lo Cal O O
I Jo o Jo E E I O I o o an--., ox a,) E c ox so v) c owe * Jo Jo c I ._ 'Jo Jo Jo xc a I 5- a a o Jo us QJ
c EYE o En us I>
._ o no i s_ Jo x a o o I I: C
tug O _ *
eye E I o 7 z .-~ *
Moe I. 7 I
~21--Lo O d j_ KIWI o Jo l o Cal Us ox In CO Al C~J
O ED Al I O an ONE do to) O l it Lo vow a as. us a O N C~J O CO r-l ESSAY I) Urn a I l ,_, I
pa o O I dud I) N '1 Jo I) N Lo C~J I C~J it I N
CJ I I) Us an I l to N
. CO C7~ an I an Ox Lo In g CO I c`J ox I Lo) us cry on i 00 E N Ox Clue I I r-1 O
O I ennui o Lo D gnu 1~ l Jo ED
J I C I CO I m us us us l l Tao . O-. I Jo I
. . JO cr. .
n ox a o I I o O N Ox Lo I t CO
V
cc I
on ED I CO I I Us I Lo l I_ Cal E E
._ us I
Lo no_ is z 4-s_ of Irk N I ) Cal 5~J
O Z I I IS Us Us I q' eat I I I C~J
Us Lo Us LO Lo Us U
O I O Us c Al . ulc TV
I a) Jo t'77 I O So 1:7-O O ~:~` Us I:
Jo I Us O L .. C O C I- > a O
U) C:J .1 O I ISSUE r I) a a v .,. Q an S_ C
'I a I L or- X
It I o o ITS I
5J O O 3J I_ r- a ox I: TV Lo or " 0 I
Moe .3 _ o o I =~, _ o:
Cal O
C:
Jo Us Jo I,, s O ;:
Moe EXAMPLES 12 to 16 (Comparison Examples) Comparison Examples 12 to 16 are set out in Table 5. The mechanical properties associated with these Comparison Examples are shown in Table 6.
The test specimens produced from the thermos plastic polyurethane of Example 12 without thy co-chain extender showed clear signs of separation. In addition, the mechanical properties, such as breaking elongation, resilience, tear propagation resistance and low lo temperature behavior, were poorer than in the comparable Example 1 according to the invention.
Without the stabilizers according Jo the invent lion, the test specimens associated with Example 13 showed poor low temperature flexibility compared with Example 10 according to the invention due to the thermal degradation of the polyol.
Comparison Example 14 contained only one chain extender (1,6-hexane dill). The thermoplastic process-in cycle was extremely long, resilience minimal and shrinkage very high.
Without the graft rubber according to the invention, the test specimens associated with Comparison Examples 15 and 16 showed serious separation of the hard segment. They could not be pigmented without streaking and showed serious shrinkage of up to 3.2% coupled with poor low-tempera~ure properties.
Moe ED O O O Ox s Jo
The relatively high molecular weight polyol is a polytetramethylene ether dill having a molecular weight of from 800 to 3000 and preferably from lG00 to 1500, optionally in admixture with other relatively high molecular weight polyhydroxyl compounds having a molecular weight in the range from 800 Jo 3000. Polyp tetrahydrofuran dill is an example of such a doll.
The mixture of chain extenders employed in the I process of the present invention is made up of a prince-pal chain extender and one or more co-chain extender dills in a molar ratio of from 97:3 Jo 7~:28 and prefer-ably from 94:6 to 87:13. The principal chain extender may be either 1,4-butane dill or ennui dill and the 30 co-chain extender Jay be one or Gore other dill.
Preferred co-chain extenders are 1,6-hexane dill, 1,4-butane dill, diethylene glycol, dip and tripropylene glycol and hydroquinone di-~-hydroxyethyl ether.
Moe I
The thermoplastic polymer used in the present invention is a butadiene-based graft rubber, preferably a graft rubber containing from 30 to 50 wit % of but-dine as the raft base and a thermoplastic resin combo-next of styrenes and acrylonitrile as the graft monomer This thermoplastic polymer is generally used in quanta-ties of from 5 to 25 wit % and preferably in quantities of from 6 to 15 wit Jo based on total diisocyanate, high molecular weight polyol and chain extender mixture.
Finlike antioxidant and/or W -absorbers/light stabilizers in quantities of from Owe to 3 wit % based on total diisocyanate, high molecular weight pull and chain extender mixture) may optionally be used.
Other relatively high molecular weight polyp hydroxyl compounds, for example other polyethers or polyesters or polycarbonates may by added to and mixed with the polytetramethylene ether dill in a quantity of up to 60 wit % and preferably in a quantity of less than 4Q wit %. Relatively high molecular weight polyols such as these are described, for example, in Genuine Offend legungsschrift 2,854,409. However, these other polyols may have an adverse effect upon impact strength at low temperatures so combination of such polyols with the tetramethylene ether dill is not preferred. Other relatively high molecular weight polyols which have proven to be particularly advantageous when used in combination with a ~e~ramethylene ether dill are 1,4-butane dill adipate and 1,4 butane Dylan dill mixed adipate. The molecular weight of polyether diol/polyester dill mixtures such as these is preferably in the range from 1~00 to 2500.
The molar ratio of diocesan to te~ramethyl-one ether dill and any other high molecular weight polyp hydroxyl compound should amount to between Al and oily, preferably 6:1 and 50:l.
and more preferably to between 6,5:1 and 15:1. Ratios of from I to 13:1 are particularly preferred. Such molar ratios result in elastomers having a Shore-D hardness of from 55 to 80 and preferably from 63 to I
Chain extending mixtures containing 1,4-butane dill or 1,6-hexane dill as the principal component and one or more (for example 2, 3 or 4) other dills having a molecular weight in the range from 62 to 399 as co-chain extenders (e.g. 1,6-hexane dill, 1,4-butane dill, diethylene glycol, dipropylene glycol, tripropylene glycol and hydroquinone Dow hydroxyethyl ether) may be used as the chain-extending mixture It is preferred to use a mixture of from 97 to 72 mole percent of 1,4-butane dill and from 3 to 28 mole percent of 1,6-hexane dill. A molar ratio of 94-87:6-13 is particularly preferred. If 1,6-hexane dill is used as the principal component and 1,4-butane dill as the co-chain extender, the products obtained are less elastic and do not have the same physical properties obtained ho 1,4-butane dill is the principal chain extender. At least 5 moles of chain extending mixtures are used for each mole of polytetramethylene ether dill to insure production of a rigid product. The co-chain extender may also be introduced through the dozes-natodiphenylmethane (MID). Thus, mixtures of dip or tripropylene gawkily and MID which are liquid at room temperature may be used in accordance with the invent lion.
The graft rubbers used in the present invention are preferably butadiene-based graft rubbers containing from 30 to 50 wit % of butadiene in the elastomers component and styrenes acrylonitrile and, optionally, methacrylates as the graft monomer component. Mixtures of the monomers styrenes and acrylonitrile in a ratio by Moe weight of from 90:10 to 50:50 are preferably used as the graft monomer component.
Where antioxidant and/or UV-absorbers/light stabilizers are used in the present invention, they are used in quantities of from 0.1 to 3 wit %, based on the total quantity of all the components. It is preferred to use mixtures of stabilizers.
Suitable antioxidant are known to those in the art and are described in European Patent Applique-lo lion 12,343. Preferred antioxidant are those base don starkly hindered phenols such as 2,6-di-t-butyl-4-methylphenol and pentaerythritol-tetrakis-3-~3,5-di-t-butyl-4-hydroxyphenyl)-propiona~e (Irganox 1010, a product of Ciba-Geigy).
The W -absorbers used may be state-of-the-ar~
products, such as 2-(~'-hydroxyphenyl)-benztriazole derivatives (e.g. those sold under the trademark Tinuvin~ 326, 327, 328 or Tinuvin P (products of Cuba-Geigy), hydroxybenzophenone derivatives and others.
Other examples of appropriate hydroxyphenyl benztriazole derivatives are given in German Auslegeschrif~ 1J794,144 at columns 5-7. Particularly preferred UV-absorbers are the cyanoacrylate derivatives described in German Patentschrift 1,793,797, for example the compound corresponding to the formula SHEA
Cluck COOK
which is sold by Bayer A under the designation W -absorber 340.
Examples of suitable fight stabilizers are the bis-ester of sebacic acid with 4-hydroxy-2,2~6,6-tetra-~10-~644 I ho go methylpiperidine (Tinuvin 770), but especially pent-methyl derivatives represented by the formula SHEA
C-O ON -SHEA
twill / Ho --HAYAKAWA C - alkyd - (Cluck) t-butyl \ I SHEA
C-O ~7~N-CH3 The product sold under the trademark Tinuvin~l44 is one such stabilizer. Oligomeric or polymeric, N-substituted derivatives such as those corresponding to the formula O O R I
R' - C (SHEA) x C O OH SHEA - OWE
SHEA Ho m on which x represents a number from 2 to lo lo R represents hydrogen or a methyl group and R' represents an alkyd or a cycloalkyl group may also be used as light stabilizers. In the above-given formula, when n represents 2, R represents hydrogen and R' r presents a methyl group, the formula lo represents the composition sold under the designation Tinuvin~622.
Preferred light stabilizers are those based on 2,2,6,6-tetraalkyl piperidines. Light stabilizers based on l,2,2,6,6-pentaalkyl pip~ridines are particularly 20 preferred.
Moe I
Where the light stabilizers used contain a group of a finlike antioxidant (a starkly hindered phenol group, such as 2,6-di~t-butylphenol) in addition Jo a tetraalkyl or (preferably) pentaalkyl (for example pentamethyl) group in the same molecule, as is the case with the material designated Tenon, there is no need for finlike antioxidant Jo be used.
The polyurethane reaction may ox course be carried out in the presence of the usual catalysts, release agents, antistatic agents, flame proofing agents, fillers, glass fibers and pigments employed in this art.
Such materials are described in greater detail in, for example, German Offenlegungsschriften 2,854,409 and 2,~20,501 and in Herman Patentschrift 3,329 9 775.
Suitable catalysts are, for example, tertiary amine, organometallic compounds, particularly organic tin, lead and titanium compounds such as tin acetate, Tony) ethyl hexoate, dibutyl tin dilaurate or lead acetate.
Suitable release agents include waxes, oils and long-chain compounds containing carboxyl~ ester, aside, urethane or urea groups such as those described in German Offenlegungsschrift 2,~04,470, The quantities of diocesan polytetra-ethylene ether deluge other polyhydroxyl compounds and chain extender dills used in the process o. the present invention are generally selected in such a way that the NCO:OH ratio of diisocyanate to OH-compounds amounts to between 0.9 and 1.2 and, preferably, to between 1.01 and 1.08.
The polyurethane according to the invention may be produced by forming a polyurethane in known manner and by subsequently mixing ~co-extruding) the polyurethane thus-formed with the graft rubber in Moe I
another stage. It is preferred however to use a one-shot procedure (described, for example, in German Offend legungsschrift 2,814,409) in which the graft rubber is initially introduced into a seli-cleaning twin-screw kneader and the remaining polyurethane components added thereto. Before it is introduced into the reactor, the polyol may even have been reacted with the diisocyanate to form an NCO-containing prepolymer. The elastomeric materials may be further processed in the processing 10 machines normally used for thermoplasts, preferably injection-molding machines.
A major advantage of the polyurethane elect-mews of the present invention lies in the fact that they do not show any troublesome separation of the hard segments, ire no opalescent nickers effect. This enables satisfactory dyeing or pigmenting of relatively large injection moldings without any troublesome color streaks. By contrast, when the graft rubber and chain extender mixture are not used in the production of the elastomers hard, thermoplastic polyurethane based on polytetramethylene ether dills (molecular weight of the polyether approximately 1500) showing impact resistance a low temperatures and Shore-D hardness values ox from 63 to 72 show this troublesome nickers effect.
The new polyurethane elastomers of the present invention show excellent impact strength at low temperatures. In contrast to thermoplastic polyester urethanes, they withstand the shattering test according to DIN 53 443 (weight of 50 kg dropped from a height of 1 meter) at a temperature of -~0C. Very good breaking elongation values are obtained in the impact/tensile strength test. Elastomers according to the invention based on polyte~ramethylene ether diol/polyester dill show a breaking elongation of from 40 to 100~ whereas Moe pure polytetramethylene ether dill products show a breaking elongation of from 100 to more than 200%. The antioxidant-UV absorber/light stabilizer combination also has a favorable effect upon the breaking elongation values particularly where the product is to be extruded because thermal damage during extrusion is minimized.
The stiffening factor of the polyurethane elastomers according to the invention measured at +20C
as against -20C amounts to approximately 1:1.7 to 1:2.5 (determined from the flexural stress at a given deflect lion in accordance with DIN 53 445). Thermoplastic polyester urethanes which do not correspond to the invention show a distinctly higher stiffening factor of, in general, from 1:2.5 to 1:3 or higher.
The new materials, particularly those based on polytetramethylene other dill, have a density of from 1.10 to 1.17 Mg/m3. This has considerable advantages in the case of ski boot shells. Compared with thermos plastic polyester urethanes (density approximately 1.24 Mg/m3), density is reduced by around 10%.
The elasticity of the polyurethane elastomers according to the invention is distinctly increased.
Whereas thermoplastic polyester urethanes show a resilience of at most 40%, the thermoplastic polyether polyurethane copolymers according to the invention show increased resilience values of approximately 50~.
The polyurethane elastomers according to the invention show high tear propagation resistance. This is extremely important in the case of automobile or ski boot components. I the mixture of chain extenders according to the invention is replaced by a single chain extender, however, tear propagation resistance is distinctly reduced, even in cases where the graft rubber is used.
-264l~
The invention is illustrated by the following Examples in which quantities are expressed in parts by weight, unless otherwise indicated.
EXAMPLES
Production of the thermoplastic PU-elastomers according to the invention using a twin-screw kneader A Werner & Pfleiderer ASK 53 V twin-screw kneader (Werner & Pfleiderer, Stuttgart) with self-cleaning screws and an approximately 20~ quota of knead-in elements was used in each of these Examples. The processing section was made up of 12 separately hatable housings and corresponded in length to approximately 20 times the screw diameter.
The function and mode of operation of the screw kneader and of the kneading and conveying elements of the screws etc. are described in detail in Werner Pfleiderer Brochures and in Gunman Auslegeschrift 2,302,564.
The residence times of the reaction melt in the Kneader were generally between 0.3 and 30 minutes and preferably between 0.5 and 4 minutes. The temperature of the screw housing was between about 60C and 300C
(approximately 80 to 280C in the feed zone; approxi-mutely 100 to 300C in the middle of the extrude and approximately 120 to 250C in the discharge zone). The melt issuing from the Pxtruder was quenched and size-reduced by known methods.
_ A thermoplastic polyurethane elastomers was produced from the following starting materials in the quantities (parts by weight) indicated:
Moe 15.27 wit % of polytetramethylene ether dill, molecular weight 1000 15.27 wit % of polytetram~thylene ether dill, molecular weight 2000 a) 0.12 wit JO of 2,6-di-t-butyl-4-methylphenol 0.21 wit % of pentaerythritol-tetrakis-3-(3,5 di-t-butyl-4-hydroxyphenyl)-preappoint (Irganox-1010, a product of Ciba-Geigy~
0.15 wit % of cyanoacrylic acid ester (US-absorber 340, a product of Bayer AGO
b) f 12.22 wit % of 1,4-butane dill 1.37 wit % of 1,6-hexane dill c) 45.21 wit of 4,4'-diisocyanatodiphenylme~hane containing 2.5 wit of isomer d) 0.15 wit of stearylamide and e) 10.00 wit % of graft rubber (containing 50 wit % of butadiene, 36 wit % of styrenes and 14 wit % acrylonitrile).
The NCO:OH-ratio was 1.06:1.
By means of a gear pump, component a) was pumped from the storage vessel kept at 120C into housing 2 of a twin-screw extrude. The dill mixture b) was also introduced into housing 2 at room temperature by means of a small piston pump. Component I was pumped into housing 3 at a temperature of 60C by means of a gear pump. Components d) and e) were introduced into housing 1 in powder form by means of metering screws.
The various housings of the kneader were adjusted to the following temperatures:
Housing 1 2 3 7 9 11 12 he'd Temperature 100 210 21~ 200 180 16Q 100 190 C
owe Aster storage for 3 days, injection molding in conventional injection molding machines and tempering of the test specimens for 15 h at 110C, the thermoplastic polyurethane elastomers obtained showed the mechanical properties set out in Table 1. The solidification behavior of the iniection~molded test specimens was favorable and their green strength high. Coloring did not produce any of the otherwise troublesome separation streaks of the hard segment. The low-temperature impact strength values were very good for a thermoplast as rigid as this (impactltensile strength test: 158%
breaking elongation).
Table 1 Test DIN Standard Value Unit Muddles 53 5Q4 31.6 Ma Muddles 53 504 51.2 Ma Tensile strength 53 504 53.3 Ma Breaking elongation 53 504 310 %
Shore hardness A/D 53 505 aye (A/D) Elasticity 53 512 51 %
Abrasion 53 516 19 mm3 Tear propagation resistance 53 515 170 Kim Flexural stress at a given deflection 23C 53 452 34.9 Ma Flexural stress at a given deflection -20C 53 452 69.7 Ma Impact/tensile strength test -10C 158 %
Density 53 ~79 1.11 Mg/m3 30 Shrinkage 0.5 %
At 1.11 Mg/m3, density was low, tear propaga-lion resistance high. The stiffening factor, determined from the flexural stress at a given deflection at ~23C
as against the value at -20C was 1:2.
Moe Relatively high molecular weight polyols made up of a mixture of polytetramethylene ether dill and 1,4-butane diol/adipic acid polyester dill were used to produce an elastomers The reaction components were as follows:
14.53 wit % of polytetramethylene ether dill (OH
number 56.2) 14.53 wit % of 1,4-butane diolladipic acid polyester dill (OH number 51.9) a) 0.12 wit % of 2,6-di-t-butyl-4-methylphenol 0.20 wit % of Irganox-1010 products of 0.15 wit % of Tinuvin-622 J Ciba-Geigy 0.15 wit of 2,2'-6,6'-tetraisopropyl diphenyl carbodiimide 13.08 wit % of Boone dill 1.45 wit % of 1,6-hexane dill c) 45.64 wit % of 4l4'-diisocyanatodiphenylme~hane d) 0.15 wit % of Carnauba wax 20 e) 10.00 wit % of the graft rubber used in Example 1.
The NCO:OH-ratio was 1.06:1.
Production and further processing were carried out in the same way as in Example 1, The mechanical properties are shown in Table 2.
Moe Table 2 Test DIN standard Value Unit Muddles% 53 504 31.4 Ma Modulus/300% 53 504 54.4 Ma Tensile strength 53 504 54.9 Ma Breaking elongation 53 504 301 %
Shore hardness A/D 53 505 98/69 Elasticity 53 512 49 %
lo Tear propagation resistance 53 515 197 Kim Flexural stress at a given deflection 23~C 53 452 38.7 Ma Flexural stress at a given deflection -20C 53 452 80.3 Ma 15 Impact/tensile strength test -10C 52 %
Density 53 479 1.13 Mg/m3 This thermoplast was injection-molded to form satisfactory moldings without any n~creous effect.
Tensile strength and tear propagation resistance were both high. The low-temperature properties were good, although not as good as in the preferred polyol range according to the invention as indicated in Example l (pure polytetramethylether dill).
EXAMPLES 3 to 11 Thermoplastic polyurethane according to the invention were produced in the same manner as described in Examples 1 and 2 using formulations 3 to if shown in 30 Table 3. Examples 3 to 10 represent variations of the chain extenders and OX the type and quantity of graft rubber, the ratio of the two chain extellders to one another being varied in Examples 8 and 9.
owe In Example 11, par of the polytetramethylene ether dill was replaced by a polyester cliol ox rota-lively high molecular weight.
The polyurethane elastomers described in Examples 3 to 11 were thermoplastic ally processed in standard commercially available injection molding machines. They showed little, if any, separation of the hard segment and, accordingly, were pigmented without any problems. They showed high flexibility and high impact strength at low temperatures for a thermoplastic polyurethane. In addition, they were distinguished by good initial elasticity during processing. Their mechanical properties are shown in Table 4.
Examples 3 and 4 according to the invention are characterized by a content of 5 wit % of graft rubber.
This reduced separation in the polyurethane, although not as much as in Examples 1, 5 to 7 according to the invention which are characterized by the preferred graft rubber content of 10 wit %.
Slight separation of the hard segment was evident, even where the content of co-chain extender was low. This occurred, for example, in formulation 8 according to the invention which contained 4 mule percent of 1 t 6-hexane dill (and 96 mole percent of 1,4-butane dill) and which was therefore outside the preferred co-chain extender range of 6 to 13 mole percent. If more than 13 mole percent of co-chain extender were used (Example 9), the initial elasticity of the moldings suffered slightly and the injection cycle on the injection molding machine became longer.
The same effect also occurred with a relatively high content of graft rubber (Example 10, I wit % of graft rubber).
Example 11 according to the invention core-spends to a "soft" variant of Example 2.
Moe Jo I
_ `~= _ o ox o o o o o I, a If Lo GUN N Kiwi _ I
C I 'it JO O O C`J
o 3 r ED No to Cal I
I Jo OX Jo O ox an I
Lo Jo r_ I ox O
c O I I Jo N I) I I JO O O I
a r-E eel clue I C~J lo ) x LLlc~ -I o o o E Jo to Jo us I
s I if) . L
a Jo a v to r--a N a . a E
I Jo ,_ or Jo ox ,_ .--L) Jo I I to Jo O
I ._ Cal a .
En E ~:1 Lo) Jo I 1.
E I= c L o Q _ v --I O E l x x I_ E E
I Jo I ,_ J roll I W
o C ox o I
I 'o us a 3 a o.-- owe Jo ~=~
ill clue I _ _ Lowe o o ox O
o o o o Cal o o O
at I o I
I O et Jo o o , Us o o C
0 I ._ O O I I.
I_ I> OX N O O C .-1 I tl)~ ._ "it O I_ O Jo eye C`J o So I Us O O I
. - CUD I) E---Lo O O Lo Cal O O
I Jo o Jo E E I O I o o an--., ox a,) E c ox so v) c owe * Jo Jo c I ._ 'Jo Jo Jo xc a I 5- a a o Jo us QJ
c EYE o En us I>
._ o no i s_ Jo x a o o I I: C
tug O _ *
eye E I o 7 z .-~ *
Moe I. 7 I
~21--Lo O d j_ KIWI o Jo l o Cal Us ox In CO Al C~J
O ED Al I O an ONE do to) O l it Lo vow a as. us a O N C~J O CO r-l ESSAY I) Urn a I l ,_, I
pa o O I dud I) N '1 Jo I) N Lo C~J I C~J it I N
CJ I I) Us an I l to N
. CO C7~ an I an Ox Lo In g CO I c`J ox I Lo) us cry on i 00 E N Ox Clue I I r-1 O
O I ennui o Lo D gnu 1~ l Jo ED
J I C I CO I m us us us l l Tao . O-. I Jo I
. . JO cr. .
n ox a o I I o O N Ox Lo I t CO
V
cc I
on ED I CO I I Us I Lo l I_ Cal E E
._ us I
Lo no_ is z 4-s_ of Irk N I ) Cal 5~J
O Z I I IS Us Us I q' eat I I I C~J
Us Lo Us LO Lo Us U
O I O Us c Al . ulc TV
I a) Jo t'77 I O So 1:7-O O ~:~` Us I:
Jo I Us O L .. C O C I- > a O
U) C:J .1 O I ISSUE r I) a a v .,. Q an S_ C
'I a I L or- X
It I o o ITS I
5J O O 3J I_ r- a ox I: TV Lo or " 0 I
Moe .3 _ o o I =~, _ o:
Cal O
C:
Jo Us Jo I,, s O ;:
Moe EXAMPLES 12 to 16 (Comparison Examples) Comparison Examples 12 to 16 are set out in Table 5. The mechanical properties associated with these Comparison Examples are shown in Table 6.
The test specimens produced from the thermos plastic polyurethane of Example 12 without thy co-chain extender showed clear signs of separation. In addition, the mechanical properties, such as breaking elongation, resilience, tear propagation resistance and low lo temperature behavior, were poorer than in the comparable Example 1 according to the invention.
Without the stabilizers according Jo the invent lion, the test specimens associated with Example 13 showed poor low temperature flexibility compared with Example 10 according to the invention due to the thermal degradation of the polyol.
Comparison Example 14 contained only one chain extender (1,6-hexane dill). The thermoplastic process-in cycle was extremely long, resilience minimal and shrinkage very high.
Without the graft rubber according to the invention, the test specimens associated with Comparison Examples 15 and 16 showed serious separation of the hard segment. They could not be pigmented without streaking and showed serious shrinkage of up to 3.2% coupled with poor low-tempera~ure properties.
Moe ED O O O Ox s Jo
3 N C`J
Lo I Jo .~. . Cal Jo I O O O
r r to I
a Lo) Lo Jo Cal N
Jo Jo O O O
C
I I'>
O Us Lo N
a at E N
E . . _, Cal I
X Cal Lo Lo . . .
Lo I X LLJ O O O ._ of a E o I no o a! a S_ L . -s a _ a a-- c" E
._ .- .
Jo on E
a I
. S_ S_ . O I Jo Eli s Jo a r r O U a. Eli a.) JO
'I I,_ I us E of c CLIP 115 Jo I Jo I Jo ' 3:: L I c t Lo E Jo E E c:
I> lo X o I-- I
I_ OX LOWE O
I- i I I So i QJ
.-- o .-- o clue ox aye ill S
O I_ 0 Jo c s_ Al a MCKEE
--25~
, Jo O O r-l r-l ., F E I o o ID L .,~
o Jo a to TO Roy. ~~~ .
a o so F A
to D
Al E
us to o a) x o Z
Moe I
ED CO JO Ott N O
Jo l N O`) I
Islet l N I ED D .--I) U') JO O`\ r-l I) O
Us O JO ED D .-1 JO
I> Al Lo ED Do I Cal N Lo It ._ Lo) en- ED Cal I ) I O O
E
X O
ED I N I_ I ED aye O Jo Kiwi l .-~ OX CO CO Lo`) I O
IJLI I I cr. I
Jo E
o I I z I.
Jo :~: .~: YE OF
I I> Cal m I I
O U- O Lo O Us to I_ ') I I) U O Inlay U > on Lo I Lo Lo in E
C o O Q ~3 o N
MU Jo d to C I: O Us O V7 O
I C1~ Us ., V) Al I_ c 1;: us a a O I* AL) O I no ' U
g O r- 'O Jo I
r-l Us S I) Q 4-on c c I) to 'aye I
._ IJ Us 'I C
I ~>~ TV awl S_ TV X a O Jo 'O C O 0 V) :' o Jo awl c , I_ I
Moe I
o o Us Jo I o E
E
a I: a Lo I a Us W
,-Jo Jo a , pa no .~.~ us , aye c ,5_ Q i_!_ I of) Moe I
Although the invention has been described in detail in the foregoing for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by the claims.
Moe
Lo I Jo .~. . Cal Jo I O O O
r r to I
a Lo) Lo Jo Cal N
Jo Jo O O O
C
I I'>
O Us Lo N
a at E N
E . . _, Cal I
X Cal Lo Lo . . .
Lo I X LLJ O O O ._ of a E o I no o a! a S_ L . -s a _ a a-- c" E
._ .- .
Jo on E
a I
. S_ S_ . O I Jo Eli s Jo a r r O U a. Eli a.) JO
'I I,_ I us E of c CLIP 115 Jo I Jo I Jo ' 3:: L I c t Lo E Jo E E c:
I> lo X o I-- I
I_ OX LOWE O
I- i I I So i QJ
.-- o .-- o clue ox aye ill S
O I_ 0 Jo c s_ Al a MCKEE
--25~
, Jo O O r-l r-l ., F E I o o ID L .,~
o Jo a to TO Roy. ~~~ .
a o so F A
to D
Al E
us to o a) x o Z
Moe I
ED CO JO Ott N O
Jo l N O`) I
Islet l N I ED D .--I) U') JO O`\ r-l I) O
Us O JO ED D .-1 JO
I> Al Lo ED Do I Cal N Lo It ._ Lo) en- ED Cal I ) I O O
E
X O
ED I N I_ I ED aye O Jo Kiwi l .-~ OX CO CO Lo`) I O
IJLI I I cr. I
Jo E
o I I z I.
Jo :~: .~: YE OF
I I> Cal m I I
O U- O Lo O Us to I_ ') I I) U O Inlay U > on Lo I Lo Lo in E
C o O Q ~3 o N
MU Jo d to C I: O Us O V7 O
I C1~ Us ., V) Al I_ c 1;: us a a O I* AL) O I no ' U
g O r- 'O Jo I
r-l Us S I) Q 4-on c c I) to 'aye I
._ IJ Us 'I C
I ~>~ TV awl S_ TV X a O Jo 'O C O 0 V) :' o Jo awl c , I_ I
Moe I
o o Us Jo I o E
E
a I: a Lo I a Us W
,-Jo Jo a , pa no .~.~ us , aye c ,5_ Q i_!_ I of) Moe I
Although the invention has been described in detail in the foregoing for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by the claims.
Moe
Claims (20)
1. A process for the production of a thermo-plastic polyurethane elastomer having flexibility at low temperatures, high mechanical strength, a density of from 1.10 to 1.17 Mg/m3 and a Shore-D hardness of from 55 to 80 comprising reacting (a) 4,4'-diisocyanatodiphenylmethane or an isomer mixture thereof which isomer mixture contains up to 5 mole percent 2,4'-diisocyanatodiphenylmethane and (b) a polytetramethylene ether diol having a molecular weight of from 800 to 3000 in quantities such that the molar ratio of component a) to component b) is between 5:1 and 300:1 and in the presence of (c) a mixture of chain extender diols made up of 1) 1,4-butane diol or 1,6-hexane diol and 2) a diol different from that of component (c)(l) having a molecu-lar weight of from 62 to 399 in which the molar ratio of (c)(l) to (c)(2) is from 97:3 to 72:28, (d) from 5 to 25 wt %, based on the total of components (a), (b) and (c), of thermoplastic polymer made up of a graft rubber base and a styrene-acrylonitrile thermoplastic resin component and optionally (e) 0.1 to 3 wt %, based on the total of components (a), (b) and (c), of anti-oxidant and/or UV-absorber/light stabilizer.
2. The process of Claim 1 in which component (a) is an isomer mixture containing from 0.5 to 5 mole percent of 2,4-diisocyanatodiphenylmethane.
3. The process of Claim 1 in which component (b) is a polytetramethylene ether diol having a molecular weight of from 800 to 3000 in admixture with other polyhydroxyl compounds having a molecular weight of from 800 to 3000.
4. The process of Claim 1 in which chain extender (c) component (2) is selected from the group consisting of 1,6-hexane diol, 1,4-butane diol, diethyl-ene glycol, dipropylene glycol, tripropylene glycol and hydroquinone di-.beta.-hydroxyethyl ether.
5. The process of Claim 1 in which the thermo-plastic polymer (d) contains from 30 to 50 wt % buta-diene as the graft rubber base.
6. The process of Claim 1 in which from 6 to 15 wt % of component (d) is employed.
7. The process of Claim 1 in which the chain extender mixture (c) is made up of 1) 85-93 mole percent 1,4-butane diol and 2) 15-7 mole percent 1,6-hexane diol.
8. The process of Claim 1 in which component (b) is a polytetramethylene ether diol in admixture with 1,4-butane diol adipate and/or 1,4-butane diol ethylene glycol adipate.
9. The process of Claim 8 in which up to 60 wt % of component (b) is 1,4-butane diol adipate and/or 1,4-butane diol ethylene glycol adipate.
10. The process of Claim 1 in which component (b) is polytetrahydrofuran having an average molecular weight of from 1000 to 1500.
11. The process of Claim 1 in which component (b) is a mixture of polytetramethylene ether diol and 1,4-butane diol having a molecular weight of from 1800 to 2500.
12. The process of Claim 1 in which an anti-oxidant is used as component (e).
13. The process of Claim 12 in which the anti-oxidant is selected from the group consisting of 2,6-di-t-butyl-4-methylphenol and pentaerythritol-tetrakis-3-(3,5-di-t-butyl-4-hydroxyphenyl)-proprionate.
14. The process of Claim 13 in which a UV-absorber/light stabilizer is also included in component (e).
15. The process of Claim 14 in which the UV-absorber/light stabilizer is a 1,2,2,6,6-pentaalkyl piperidine derivative or a cyanoacrylate derivative.
16. The process of Claim 1 in which the thermoplastic polymer (d) is used in a quantity of from 7 to 15 wt. %.
17. The process of Claim 1 in which the thermoplastic polymer (d) is used in a quantity of from 9 to 12 wt. %.
18. The process of Claim 1 in which the reaction is carried out in a reaction extruder.
19. The process of Claim 1 in which the reaction product is injection molded.
20. The process of Claim 1, wherein the molar ratio between component (a) and component (b) is between 6.5:1 and 15:1.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP3405531.2 | 1984-02-16 | ||
| DE19843405531 DE3405531A1 (en) | 1984-02-16 | 1984-02-16 | METHOD FOR PRODUCING THERMOPLASTIC POLYURETHANE ELASTOMERS AND THEIR USE |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1231488A true CA1231488A (en) | 1988-01-12 |
Family
ID=6227895
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000473527A Expired CA1231488A (en) | 1984-02-16 | 1985-02-04 | Process for the production of thermoplastic polyurethane elastomers |
Country Status (5)
| Country | Link |
|---|---|
| EP (1) | EP0152049B1 (en) |
| JP (1) | JPS60195116A (en) |
| AU (1) | AU566337B2 (en) |
| CA (1) | CA1231488A (en) |
| DE (2) | DE3405531A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5696205A (en) * | 1995-04-10 | 1997-12-09 | Bayer Aktiengesellschaft | Process for preparing TPU molding compositions |
| US5760133A (en) * | 1995-04-24 | 1998-06-02 | Bayer Aktiengesellschaft | Process for preparing TPU molding compositions |
| US6037409A (en) * | 1996-10-31 | 2000-03-14 | Bayer Corporation | Thermoformed article having low gloss and a composition for its preparation |
| CN110291126A (en) * | 2017-02-13 | 2019-09-27 | 巴斯夫欧洲公司 | Thermoplastic polyurethane |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0272682A3 (en) * | 1986-12-22 | 1989-01-25 | Kimberly-Clark Corporation | Superabsorbent thermoplastic compositions |
| US4994502A (en) * | 1987-07-01 | 1991-02-19 | Basf Corporation | Process for the preparation of integral skin polyurethane steering wheels |
| US4822827A (en) * | 1987-12-17 | 1989-04-18 | The Dow Chemical Company | Thermoplastic polyurethanes with high glass transition temperatures |
| DE4437586A1 (en) | 1994-10-20 | 1996-04-25 | Basf Schwarzheide Gmbh | Process for the preparation of thermoplastic polyurethanes |
| KR100343546B1 (en) * | 1994-12-30 | 2002-11-23 | 에스케이케미칼주식회사 | Non-yellowing polyurethane resin |
| US6521164B1 (en) | 1996-02-06 | 2003-02-18 | Parker-Hannifin Corporation | Injection-moldable thermoplastic polyurethane elastomer |
| US5627254A (en) * | 1996-05-03 | 1997-05-06 | The Dow Chemical Company | Rigid thermoplastic plyurethane comprising units of butane diol and a polyethylene glycol |
| WO2007118827A1 (en) * | 2006-04-19 | 2007-10-25 | Basf Se | Thermoplastic polyurethanes |
| JP5544944B2 (en) * | 2010-03-11 | 2014-07-09 | Ｎｏｋ株式会社 | Thermoplastic polyurethane elastomer for injection molding and method for producing the same |
| US9332802B2 (en) | 2011-12-30 | 2016-05-10 | Ticona Llc | Molded polymer articles for use in low temperatures having a low rigidity factor |
| US9328229B2 (en) | 2012-05-09 | 2016-05-03 | Ticona Llc | Polymer composition and articles for use in low temperature environments that are wear resistant |
| JP7368926B2 (en) * | 2018-06-06 | 2023-10-25 | ビーエーエスエフ ソシエタス・ヨーロピア | Ski boots with temperature-independent elastic modulus |
| CN112424250A (en) * | 2018-07-12 | 2021-02-26 | 巴斯夫欧洲公司 | Glass fiber reinforced TPU |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS51126245A (en) * | 1975-04-25 | 1976-11-04 | Sumitomo Naugatuck Co Ltd | Semi-rigid abs resin composition |
| US4010146A (en) * | 1975-09-29 | 1977-03-01 | Samuel Moore And Company | Polyol blends and polyurethane prepared therefrom |
| JPS5293465A (en) * | 1976-02-02 | 1977-08-05 | Sumitomo Naugatuck Co Ltd | Soft or semirigid composition |
| GB1577222A (en) * | 1977-02-17 | 1980-10-22 | Ici Ltd | Thermoplastic polyurethane elastomers |
| DE2817457A1 (en) * | 1978-04-21 | 1979-10-31 | Bayer Ag | THERMOPLASTIC POLYURETHANE FOR PROCESSING IN EXTRUDERS AND / AND ON CALENDARS |
| DE2854408A1 (en) * | 1978-12-16 | 1980-07-03 | Bayer Ag | THERMOPLASTIC POLYAETHERPOLYURETHANE WITH IMPROVED THERMOSTABILITY |
| JPS5714641A (en) * | 1980-06-30 | 1982-01-25 | Japan Synthetic Rubber Co Ltd | Softened resin composition |
| US4567236A (en) * | 1983-07-18 | 1986-01-28 | The Upjohn Co. | Novel polymer blends |
-
1984
- 1984-02-16 DE DE19843405531 patent/DE3405531A1/en not_active Withdrawn
-
1985
- 1985-02-04 CA CA000473527A patent/CA1231488A/en not_active Expired
- 1985-02-05 DE DE8585101169T patent/DE3572677D1/en not_active Expired
- 1985-02-05 EP EP85101169A patent/EP0152049B1/en not_active Expired
- 1985-02-12 AU AU38662/85A patent/AU566337B2/en not_active Ceased
- 1985-02-16 JP JP60027585A patent/JPS60195116A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5696205A (en) * | 1995-04-10 | 1997-12-09 | Bayer Aktiengesellschaft | Process for preparing TPU molding compositions |
| US5760133A (en) * | 1995-04-24 | 1998-06-02 | Bayer Aktiengesellschaft | Process for preparing TPU molding compositions |
| US5981655A (en) * | 1995-04-24 | 1999-11-09 | Bayer Aktiengesellschaft | Process for preparing TPU molding compositions |
| US6037409A (en) * | 1996-10-31 | 2000-03-14 | Bayer Corporation | Thermoformed article having low gloss and a composition for its preparation |
| CN110291126A (en) * | 2017-02-13 | 2019-09-27 | 巴斯夫欧洲公司 | Thermoplastic polyurethane |
Also Published As
| Publication number | Publication date |
|---|---|
| DE3572677D1 (en) | 1989-10-05 |
| EP0152049A2 (en) | 1985-08-21 |
| AU3866285A (en) | 1985-08-22 |
| JPS60195116A (en) | 1985-10-03 |
| AU566337B2 (en) | 1987-10-15 |
| EP0152049A3 (en) | 1987-01-28 |
| EP0152049B1 (en) | 1989-08-30 |
| DE3405531A1 (en) | 1985-08-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA1231488A (en) | Process for the production of thermoplastic polyurethane elastomers | |
| CA1208843A (en) | Polyurethanes useful as engineering plastics | |
| CA1269192A (en) | Polyurethane plastics with improved impact resistance | |
| US8680213B2 (en) | Thermoplastic polyurethanes | |
| CA2168938C (en) | A thermoplastic polyurethane resin | |
| US6740727B2 (en) | Injection-moldable, thermoplastic polyurethane elastomer | |
| US6538075B1 (en) | Thermoplastic polyurethane | |
| US6294638B1 (en) | Soft, transparent and processable thermoplastic polyurethane | |
| US5981655A (en) | Process for preparing TPU molding compositions | |
| CA2012761A1 (en) | Thermoplastic polyblends of aromatic polycarbonates and thermoplastic polyurethanes | |
| EP0852592B1 (en) | Thermoplastic polyurethanes containing units of an aromatic diol | |
| US6174959B1 (en) | Compatible blends of thermoplastic polyurethane with certain polyolefins | |
| KR101554261B1 (en) | Low melting polyurethane elastomers | |
| US5696205A (en) | Process for preparing TPU molding compositions | |
| US20030158365A1 (en) | Continuous production of thermoplastic polyurethane elastomers | |
| US5739250A (en) | Thermoplastic polyurethane-urea elastomers | |
| EP0276080A1 (en) | Process for producing polyoxymethylene-polyurethane type alloy | |
| CA2012763A1 (en) | Thermoplastic polyblends of aromatic polycarbonates and thermoplastic polyurethanes | |
| JP3345141B2 (en) | Resin composition | |
| CN116217882A (en) | Invisible car cover high-strength low-haze TPU and preparation method thereof | |
| JPH09202818A (en) | Composition for thermoplastic resin excellent in wear resistance, molding using the same and molded article | |
| MXPA97006695A (en) | Polyurethanes stabilizes | |
| JPH09291130A (en) | Composition for thermoplastic polyurethane resin having excellent abrasion resistance, production of resin from the composition, and molded product |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |