CA2011871A1 - Impact modified thermoplastic polyurethane molding compositions, a process for their preparation and their use - Google Patents
Impact modified thermoplastic polyurethane molding compositions, a process for their preparation and their useInfo
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- CA2011871A1 CA2011871A1 CA002011871A CA2011871A CA2011871A1 CA 2011871 A1 CA2011871 A1 CA 2011871A1 CA 002011871 A CA002011871 A CA 002011871A CA 2011871 A CA2011871 A CA 2011871A CA 2011871 A1 CA2011871 A1 CA 2011871A1
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- thermoplastic polyurethane
- weight
- molding compositions
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- methylstyrene
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- 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
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
IMPACT MODIFIED THERMOPLASTIC POLYURETHANE MOLDING
COMPOSITIONS, A PROCESS FOR THEIR PREPARATION AND THEIR USE
ABSTRACT OF DISCLOSURE
The subject of the instant invention is impact modified thermoplastic polyurethane molding compositions, comprising:
A) 70 to 99 parts by weight of at least one thermoplastic polyurethane elastomer (A);
B) 1 to 30 parts by weight of at least one graft polymer (B), comprising:
B1) an elastomer (B1) serving as a grafting basis having a glass temperature less than -40° C; and, B2) a grafting basis (B2) prepared in one or two steps, comprising; .alpha.-methylstyrene and acrylonitrile; or .alpha.-methylstyrene, styrene, and acrylonitrile;
whereby in grafting basis (B2);
i) the amount of .alpha.-methylstyrene units polymerized in situ is greater than the styrene units, ii) the weight ratio of the .alpha.-methylstyrene units or .alpha.-methylstyrene styrene units polymerized in situ to the acrylonitrile units is from 60:40 to 90:10; and, iii) the grafting degree lies between 15 and 30, the parts by weight of (A) and (B) total 100 parts by weight, C) 0 to 60 weight percent of at least one additive, based on the weight of (A) and (B).
, .. . .. .. . .. . .. .
COMPOSITIONS, A PROCESS FOR THEIR PREPARATION AND THEIR USE
ABSTRACT OF DISCLOSURE
The subject of the instant invention is impact modified thermoplastic polyurethane molding compositions, comprising:
A) 70 to 99 parts by weight of at least one thermoplastic polyurethane elastomer (A);
B) 1 to 30 parts by weight of at least one graft polymer (B), comprising:
B1) an elastomer (B1) serving as a grafting basis having a glass temperature less than -40° C; and, B2) a grafting basis (B2) prepared in one or two steps, comprising; .alpha.-methylstyrene and acrylonitrile; or .alpha.-methylstyrene, styrene, and acrylonitrile;
whereby in grafting basis (B2);
i) the amount of .alpha.-methylstyrene units polymerized in situ is greater than the styrene units, ii) the weight ratio of the .alpha.-methylstyrene units or .alpha.-methylstyrene styrene units polymerized in situ to the acrylonitrile units is from 60:40 to 90:10; and, iii) the grafting degree lies between 15 and 30, the parts by weight of (A) and (B) total 100 parts by weight, C) 0 to 60 weight percent of at least one additive, based on the weight of (A) and (B).
, .. . .. .. . .. . .. .
Description
2011871.
IMPACT MODIFIED THERMOPLASTIC POLYURETHANE MOLDING
COMPOSITIONS, A PROCESS FOR THEIR PREPARATION AND THEIR USE
-The present invention deals with impact modified molding compositions, comprising:
(A) at least one thermoplastic polyurethane, hencef~rth abbreviated TPU; and, (B) at least one graft rubber synthesized in a special fashion.
Molding compositions from polyurethane elastomers and graft rubbers are well known. It is also known that the cold flexibility of TPU can be improved by modification with a graft rubber.
United States Patent 3 049 505 discloses, for example, a molding composition from a crosslinked, rigid polyurethane elastomer and ABS rubber, whose grafting basis comprises styrene acrylonitrile units polymerized in situ, and which has a degree of grafting greater than 40. According to DE-A-2 854 407 (US 4 317 890) there are thermoplastic molding compositions, comprising: (A) 75 to 97 weight percent of a TPU, and (B) 25 to 3 weight percent of a graft polymer whereby this is synthesized from (Ba) 5 to 35 weight percent, based on (B) of one or more graft monomers and (Bb) 65 to 95 weight percent, based on (B) of an elastomer component serving as a grafting basis, having a glass transition temperature less than -30 C and whereby the total graft polymer ~B) contain~ less than 50 weight percent of the monomers styrene, -methylstyrene, and acrylonitrile; the 20~1871.
grafting basis preferably comprises styrene and acrylonitrile in a weight ratio of from 9:1 to 1:1 and the degree of grafting is from 5 to 35. The resulting molding compositions demonstrate unsatisfactory impact resistance at low temperatures and are not free of evidence of segregation; that is, the so called pearlescent effect. In addition, the mechanical strength of the molding compositions is reduced by the segregation.
In order to overcome this pearlescent effect, EP-A-O-152 ~49 (CA-A-l 213 488) discloses ABS-graft rubbers having a grafting basis comprising styrene and acrylonitrile in a weight ratio of 9:10 to 50:50 and a degree of grafting from 50 to 70, mixed with a specially synthesized TPU having a low density and a Shore D hardness of from 55 to 80, prepared from selected starting components, preferably from polytetramethylene ether glycol and a mixture of primary chain extending agents co-chain extending agents in a mole ratio of from 97:3 to 72:28 whereby 1,4-butanediol or 1,6-hexanediol are used as the primary chain extending agents; and, preferably 1,6-hexanediol, 1,4-butanediol, diethylene glycol, dipropylene glycol, and tri-propylene glycol, or hydroquinone-di-(B-hydroxyl ethyl ether) are used as the co-chain extending agents.
~ owever, even the aforesaid measures do not significantly improve the low temperature impact resistance of the molding compositions, especially at temperatures of -30 C.
The object of the present invention was to prepare molding compositions from TPU having improved low temperature impact resistance.
IMPACT MODIFIED THERMOPLASTIC POLYURETHANE MOLDING
COMPOSITIONS, A PROCESS FOR THEIR PREPARATION AND THEIR USE
-The present invention deals with impact modified molding compositions, comprising:
(A) at least one thermoplastic polyurethane, hencef~rth abbreviated TPU; and, (B) at least one graft rubber synthesized in a special fashion.
Molding compositions from polyurethane elastomers and graft rubbers are well known. It is also known that the cold flexibility of TPU can be improved by modification with a graft rubber.
United States Patent 3 049 505 discloses, for example, a molding composition from a crosslinked, rigid polyurethane elastomer and ABS rubber, whose grafting basis comprises styrene acrylonitrile units polymerized in situ, and which has a degree of grafting greater than 40. According to DE-A-2 854 407 (US 4 317 890) there are thermoplastic molding compositions, comprising: (A) 75 to 97 weight percent of a TPU, and (B) 25 to 3 weight percent of a graft polymer whereby this is synthesized from (Ba) 5 to 35 weight percent, based on (B) of one or more graft monomers and (Bb) 65 to 95 weight percent, based on (B) of an elastomer component serving as a grafting basis, having a glass transition temperature less than -30 C and whereby the total graft polymer ~B) contain~ less than 50 weight percent of the monomers styrene, -methylstyrene, and acrylonitrile; the 20~1871.
grafting basis preferably comprises styrene and acrylonitrile in a weight ratio of from 9:1 to 1:1 and the degree of grafting is from 5 to 35. The resulting molding compositions demonstrate unsatisfactory impact resistance at low temperatures and are not free of evidence of segregation; that is, the so called pearlescent effect. In addition, the mechanical strength of the molding compositions is reduced by the segregation.
In order to overcome this pearlescent effect, EP-A-O-152 ~49 (CA-A-l 213 488) discloses ABS-graft rubbers having a grafting basis comprising styrene and acrylonitrile in a weight ratio of 9:10 to 50:50 and a degree of grafting from 50 to 70, mixed with a specially synthesized TPU having a low density and a Shore D hardness of from 55 to 80, prepared from selected starting components, preferably from polytetramethylene ether glycol and a mixture of primary chain extending agents co-chain extending agents in a mole ratio of from 97:3 to 72:28 whereby 1,4-butanediol or 1,6-hexanediol are used as the primary chain extending agents; and, preferably 1,6-hexanediol, 1,4-butanediol, diethylene glycol, dipropylene glycol, and tri-propylene glycol, or hydroquinone-di-(B-hydroxyl ethyl ether) are used as the co-chain extending agents.
~ owever, even the aforesaid measures do not significantly improve the low temperature impact resistance of the molding compositions, especially at temperatures of -30 C.
The object of the present invention was to prepare molding compositions from TPU having improved low temperature impact resistance.
2~ 87~
~ ccordingly, the subject of the invention is impact modified thermoplastic polyurethane molding compositions, comprising:
A) 70 to 99 parts by weight, more preferably 75 to 90 parts by weight, of at least one thermoplastic polyurethane elastomer IA);
B) 1 to 30 parts by weight, more preferably 10 to 25 parts by weight, of at least one graft polymer (B) which is synthesized from:
Bl) an elastomer (Bl) serving as a grafting basis having a glass transition temperature below -40C, preferably below -50 C; and B2) a grafting basis (B2) prepared in one or two steps from ~-methylstyrene and acrylonitrile, or -methylstyrene, styrene, and acrylonitrile;
whereby the parts by weight of ~A) and (B) total 100 parts by weight; and, i) the total weight of -methylstyrene units polymerized in situ is greater than the total weight of the styrene units polymerized in situ;
ii) the total weight of the -methylstyrene units polymerized in situ or the total of the -methylstyrene units and styrene units polymerized in situ to the acrylonitrile units polymerized in situ, is from 60:40 to 90:10, more preferably 65:35 to 80:20; and, iii) the degree of grafting is between 15 and 30, 37~.
more preferably between 20 and 30 (C) 0 to 60 weight percent, more preferably 0 to 40 weight percent, based on the total weight of (A) and (B) of at least one additive;
wherein in grafting basis (B2):
The subject of the present invention is also a process for the preparation of impact modified thermoplastic polyurethane molding compositions comprising: melting together components (A) and (B) and optionally incorporating component ~C) in a conventional mixing device, preferably in an extruder at a temperature of from 160 to 250 C and with residency time of from 0.5 to 10 minutes. The subject of the present invention is also using the impact modified, thermoplastic, polyurethane molding compositions in the preparation of injection molded articles, preferably ski boots and automobile trim parts as well as molded articles prepared while using the impact modified polyurethane thermoplastic polyurethane molding compositions as an essential starting component.
By using graft polymer (B), whose grafting basis (B2~, comprises; an -methylstyrene-acrylonitrile polymer or an ~-methylstyrene~styrene-acrylonitrile copolymer; suprisingly TPU
molding compositions result having a substantially improved impact resistance ~ith high strength especially at low temperatures. Another advantage is that starting component TPU
(A) and graft polymer ~) do not separate either in the melt nor in the molded article, and the molding compositions of the present invention can easily be processed into molded articles 20~L1871.
which have an excellent surface character.
TPU ~A) used according to the invention corresponds to the state-of-the-art and can be prepared by reacting:
a) organic, more preferably aromatic diisocyanates, most preferably 4,4'-dipenylmethyl diisocyanate with;
b) polyhydroxyl compounds, preferably essentially linear polyhydroxyl compounds having molecular weights of from 500 to 8,000, most preferably polyalkylene glycol polyadipates having 2 to 6 carbon atoms in the alkylene radical and molecular weights of from 500 to 6,000 or hydroxyl groups containing polytetrahydrofuran having a molecular weigh~ of from 500 to B,000; and, c) diols as chain extending agents having molecular weights of from 60 to 400, most preferably 1,4-butanediol;
in the presence of:
d) catalysts and optionally;
e) auxiliaries and/or;
f) additives;
at elevated temperatures.
The following should be noted with respect to the starting components (a) through (d) and optionally (e) and/or (f):
a) organic diisocyanates (a) are, for example, aliphatic, cycloaliphatic, or more preferably aromatic diisocyanates. Individual examples are: aliphatic diisocyanates, such as hexamethylene-1,6-diisocyanate, 2-methyl-pentamethylene-1,5-diisocyanate, 2-ethyl-20118~1 butylene-1,4-diisocyanate, or mixtures of of least two of the aforesaid aliphatic diisocyanates; cycloaliphatic diisocyanates such as, for example, isophorone diisocyanate, 1,4-cyclohexane diisocyanate, l-methyl-2,4-cyclohexane diisocyanate, and 1-methyl-2,6-cyclohexane diisocyanate, as well as the corresponding isomeric mixtures, 4,4'-, 2-4'-, and 2,2'-dicycohexyl-methane diisocyanate as well as the corre~ponding isomeric mixtures, and preferably aromatic diisocyanates such as, for example, 2,4-toluene diisocyanate, mixtures of 2,4-, and 2,6-toluene diisocyanate, 4,4'-, 2,4'-, and 2,2'-diphenylmethane diisocyanate; mixtures of 2,4'-, and 4,4'-diphenylmethane diisocyanate, urethane modified liquid 4,4'-, and/or 2,4'-diphenylmethane diisocyanate, 4,4'-diisocyanato-1,2-diphenylethane, mixtures of 4,4'-, 2,4'-, and 2,2'-diisocyanato-1,2-diphenylethane, advantageously those comprising at least 95 weight percent of 4,4'-diisocyanato-1,2-diphenylethane and 1,5-naphthylene diisocyanate. Preferably used are diphenylmethane diisocyanate isomeric mixtures having a 4,4'-diphenylmethane diisocyanate content greater than 96 weight percent, and most preferably essentially pure 4,4'-diphenylmethane diisocyanate.
The organic diisocyanates can optionally be replaced to a lesser degree, for example, in quantities up to 3 mole percent, more preferably to 1 mole percent, based on the organic diisocyanate by a trifunctional polyisocyanate or a higher functional polyisocyanate, however, ~he1 ~ 8 71.
quantities must be limited so that polyurethanes are obtained which are still thermoplastic in nature when processed.
Quantities of isocyanates considered more than difunctional are best compensated for by using less than difunctional compounds with reactive h~drogen atoms so that extensive chemical crosslinking of the polyurethane is avoided. Examples of isocyanates regarded as more than difunctional are mixtures of diphenylmethane diisocyanates and polyphenyl polymethylene polyisocyanates, the so-called polymeric-MDI and liquid 4,4'-, and/or 2,4'-diphenylmethane diisocyanate modified with the following groups: isocyanurate, urea, biuret, allophanate, urethane and/or carbodiimide.
Typical monofunctional compounds having reactive hydrogen atoms which also are used as molecular weight regulators are, for example, monoamines such as, for example, butyl-, dibutyl-, octyl-, stearyl-, N-methylstearylamine, pyrrolidone, piperidine, and cyclohexylamine; and monoalcohols such as, for example, butanol, amyl alcohol, l-ethylhexanol, octanol, dodecanol, cyclohexanol, and ethylene glyrol monoethyl ether.
b) Higher molecular weight polyhydroxyl compounds (b) having molecular weights of from 500 to 8,000 are preferably polyether polyols and most preferably, :' :
pslyester polyols. However, other example~ are:
hydroxyl group containing polymers with ether and/or ester groups as bridge members, for example, polyacetels such as polyoxymethylenes and particularly water insoluble formals, for example, polybutanediol formal and polyhexanediol formal, and polycarbonates preferably, those from diphenyl carbonate and 1,~-hexanediol prepared by transesterification. The polyhydroxyl compounds must be predominantly linear, i.e., difunctional in the sense that the isocyanate reaction. The aforesaid polyhydroxyl compounds can be used as individual components or in the form of mixtures.
Typical polyether polyols can be prepared according to known processes, for example, by the anionic polymerization with alkali hydroxides such as sodium or potassium hydroxide or alkali alcolates such as sodium methylate, sodium or potassium methylate, or potassium isopropylate as catalysts and while using at least one initiator molecule which contains in bonded form 2 to 3, more preferably 2 active hydrogen atoms; or by the cationic polymerization with Lewis acids such as, for example, antimony pentachloride, boron fluoride etherate, etc., or bleaching earth as catalysts from one or more alkylene oxides having 2 to 4 carbon atoms in the alkylene radical.
Typical alkylene oxides are, for example, ~, ... . . . . . ..
201187~
preferably tetrahydrofuran, 1,3-propylene oxide, 1,2-, and/or 2,3-butylene oxide, and most preferably ethylene oxide and 1,2-propylene oxide. The alkylene oxides can be used individually, alternating one after another, or as mixtures. Typical initiator molecules are, for example, water, organic dicarboxylic acids such as succinic acid, adipic acid, and/or glutaric acids;
alkanolamines, such as, for example, ethanolamine, N-alkylalkanolamine, N-alkyldialkanolamines, such as, for example, N-methyldiethanolamine, and N-ethyldiethanolamine, and preferably, divalent alcohols optionally containing ether bridges in bonded form such as, for example, ethanediol, 1,2-propanediol, and 1,3-propanediol, 1,4-butanediol, diethylene glycol, 1,5-pentanediol, 1,6-hexanediol, dipropylene glycol, 2-methyl-1,5-pentanediol, and 2-ethyl-1,4-butanediol. The initiator molecules can be used individually or as mixtures.
Preferably used are polyether polyols from 1,2-propylene oxide and ethylene oxide in which more than 50 percent, more preferably 60 to 80 percent, of the OH groups are primary hydroxyl groups and in which at least a portion of the ethylene oxide is situated as a terminal block. Such polyether polyols can be obtained, for example, by first polymerizing 1,2-propylene oxide onto the initiator molecule then subsequently polymerizing the ethylene oxide, or first .,,,, - --- - ---8'~:L
polymerizing the entire 1,2-propylene oxide mixed with a portion of the ethylene oxide and then subsequently polymerizing the remainder of the ethylene oxide, or stepwise that is first a portion of the ethylene oxide then the entire 1,2-propylene oxide and the remainder of the ethylene oxide onto the initiator molecule.
Also preferably used are hydroxyl group containing polymerization products of tetrahydrofuran.
The essentially linear polyether polyols have molecular weights of from 500 to 8,000, more preferably 600 to 6,000, and most preferably 800 to 3,500. They can be used individually or mixed with one another.
Typical polyester polyols can be prepared, for example, from dicarboxylic acids having 2 to 12, more preferably 4 to 6 carbon atoms and from multivalent alcohols.
Typical dicarboxylic acids are, for example:
aliphatic dicarboxylic acids, such as, succinic acid, glutaric acid, adipic acid, subaric acid, azelaic acid, and sebacic acid, and aromatlc dicarboxylic acids, such as, phthalic acid, isophthalic acid and terephthalic acid. The dicarboxylic acids can be used individually or as mixtures, for example, a mixture of succinic, glutaric, and adipic acids. When preparing the polyester polyols, it optionally can be advantageous to use the corresponding carboxylic acid derivatives in place of the carboxylic acids such as carboxylic acid 201~871 esters having 1 to 4 carbon atoms in the alcohol radical, carboxylic acid anhydrides, or carboxylic acid chlorides. Examples of multivalent alcohols are:
glycols having 2 to 10, more preferably 2 to 6 carbon atoms such as ethylene glycol, diethylene glycol, 1,4-butanediol, l,S-pentanediol, 1,6-nexanediol, 1,10-decanediol, 2,2-dimethyl-1,3-propanediol, 1,3-propanediol, and dipropylene glycol. Depending on the desired properties, the multivalent alcohols can be u~ed individually or optionally mixed with one another.
Also suitable are esters of carboxylic acids with the aforesaid dio~s, most preferably those having 4 to 6 carbon atoms such as 1,4-butanediol and/or 1,6-hexanediol; condensation products of ~-hydroxycarboxylic acids, for example, ~-hydroxycaproic acid, and preferably polymerization products from lactones, preferably optionally substituted ~-caprolactones.
Polyester polyols preferably used are:
ethanediol polyadipates, 1,4-butanediol polyadipates, ethanediol- 1,4-butanediol polyadipates, 1,6-hexanediol neopentylglycol polyadipates, 1,6-hexanediol, 1,4-butanediol polyadipates, and polycaprolactones. The polyester polyols have molecular weights of from 500 to 6,0Q0, more preferably 800 to 3,500.
c) Typical chain extending agents (c) having molecular weights of from 60 to 400, more preferably 60 to 300, are, for example, preferably aliphatic diols having 2 to _, .. ... . . . . .. . . .. . .. . . .
12 carbon atoms more preferably 2, 4, or 6 carbon atoms, for example, ethanediol, 1,6-hexanediol, diethylene glycol, dipropylene glycol, and most preferably 1,4-butanediol. However, also suitable are diesters of terephthalic acids with glycols having 2 to 4 carbon atoms such as, for example, terephthalic acid bis-ethylene glycol or terephthalic acid bis-1,4-butanediol, and hydroxyalkylene ether from hydroquinone, for example, 1,4-di-(~-hydroxyethyl) hydroquinone as well as polytetramethylene glycols having molecular weights of from 162 to 378.
The starting components can be varied in relatively broad molar ratios to adjust hardness and melt index, whereby the hardness and melt viscosity increase with an increasing amount of chain extending agent (c) while the melt index decreases.
When preparing TPU (A) the essentially linear difunctional polyhydroxyl compounds (b) and diols (c) are advantageously used in mole ratios of from 1:3 to 1:12, more preferably 1:6 to 1:12 so that the resulting TPU's have a Shore D hardness of from 40 to 80, more preferably 40 to 75.
d) Typical catalysts which accelerate the reaction between the NCO groups of the diisocyanates (a) and the hydroxyl groups of starting components (b) and (c) are those ~tate-of-the-art catalysts and also conventional tertiary amines such as, ~or example, triethylamine, 20~871 dimethylcyclohexylamine, ~-methylmorpholine, ~,N'-diethylpiperazine, diazabicyclo[2.2.2]octane and the like, as well as preferably organic metal compounds such as titanium acid ester, iron compounds, tin compounds, for example, tin diacetate, tin dioctoate, tin dilaurate, or tin dialkyl salts of aliphatic carboxylic acids such as, for example, dibutyltin acetate, dibutyltin dilaurate, or the like. Catalysts are generally used in quantities of from 0.001 to 0.1 parts by weight per 100 parts by weight of the mixture of polyhydroxyl compounds (b) and diols ~c).
Auxiliaries (e) and /or additives (f) in addition to the catalysts can also be added to the starting components.
Typical examples are: lubricants, inhibitors, stabilizers against hydrolysis, light, heat, or discoloration, flame retardants, dyes, pigments, inorganic and/or organic fillers, and reinforcing agents.
The auxiliaries (e) and/or additives (f) as already Rtated can be added to the starting components or to the reaction mixture when preparing TPU (A). Following another process variation, auxiliaries (e) and/or additives (f), which can be identical to (C), can be mixed with TPU (A) and/or graft polymer (B) and subsequently melted together or directly incorporated to the melt comprising components (A) and (B). The later method is particularly used for adding reinforcing fillers as additive (C).
Additional information concerning auxiliaries and/or additives can be found in the technical literature, for example, ., ,, . , .. , , . ., ,, , . _ _ _, , . _,; .. . , _ .. ,, . , ", _ . , ~ . _ . _ . . . . . . .. . ... ..
. .
2011871.
in the monograph of J. H. Saunders and K. C. Frisch ~igh Polymers, Vol. XVI, Polyurethanes, Parts 1 and 2, Interscience Publishers 19~2 and 1964, or in the The Plastics Handbook, Vol.
7, Polyurethanes, First and Second Editions, Carl Hanser Publishers, 1966 and 1983 or in DE-OS 29 01 774.
When preparing the TPU, starting components (a), (b), and (c) are reacted in the presence of catalysts (d) and optionally auxiliaries (e) and/or additives (f) in such quantities so that the equivalent ratio of NCO groups from said diisocyanates to the total of the hydroxyl groups from components (b) and (c) is from 0.80 to 1.20:1, more preferably 0.95 to 1.05:1, and most preferably about 1:1.
TPU (A) used according to the present invention, which typically contains 8 to 20 weight percent, more preferably 8 to 16 weight percent, based on the total weight, of urethane groups in bonded form, and which has a melt index at 210 C of 500 to 1, more preferably 100 to 1, can be prepared following an extruder process or more preferably a conveyor process batchwise or by continuously mixing starting components ~a) through (d) as well as optionally (e) and (f); allowing t~e reaction mixture to cure in an extruder or on a conveyor belt at temperatures of from 60 to 250 C, more preferably 70 to 150 C, and subsequently granulating the resulting TPU (A). Optionally it also can be advantageous to temper the resulting TPU (A) before further processing into TPU molded articles of the present invention at 80 to 120 C, more preferably 100 to 110~ C from 1 to 24 hours.
TPU (A) as already cited is preferably prepared Z01187~
according to a conveyor process. Here the starting components (a) through (d) and optionally le) and/or tf) are mixed at temperatures above the melt point of starting components (a) through (c) continuously with the help of a mix head. The reaction mixture is applied onto a carrier preferably a conveyor belt made of, for example, metal at a rate of from 1 to 20 meters per minute, more preferably 4 to 10 meters per minute, and is fed through a heating zone 1 to 20 meters in length, more preferably 3 to lO meters in length. The reaction temperature in the heating zone is 60 to 200 C, more preferably 80 to 180 C.
Depending on the diisocyanate portion in the reaction mixture, the reaction i9 controlled by heating or cooling so that at least 90 percent, more preferably at least 98 percent, of the isocyanate groups of the diisocyanates react and the reaction mixture cures at the selected reaction temperature. Due to the free isocyanate groups in the cured reaction product, which based on the total weight range from 0.05 to 1 weight percent, more prefe~ably 0.1 to 0.5 weight percent, TPU (A) is obtained having a very low melt viscosity and/or a high melt index.
TPU molding compositions of the present invention containing starting (B) as already stated, comprise; 1 to 30 parts by weight, more preferably lQ to 25 parts by weight, based on lO0 parts by weight of (A) and (B), of one or more graft polymers, preferably a rubber elastic graft polymer (B), comprising:
Bl~ preferably 70 to 85 weight percent, most preferably 70 to 80 weight percent, based on the weight of (B), of a . _ _., .. .. . , , _ , . __ . _ , . . .. . ... ,_. . _ , . .. . . . . . .
20~187~.
rubber elastic grafting basis (Bl) from a butadiene homopolymer or butadiene copolymer having a glass temperature less than -40 C, more preferably -5~ C;
and, B2) preferably 30 to 15 weight percent, most preferably 30 to 20 weight percent, based on the weight of (B), of a grafting basis (B2) prepared in one or two steps, comprising; ~-methylstyrene and acrylonitrile or -methylstyrene, styrene, and acrylonitrile.
Grafting basis (Bl) comprises a 1,3-butadiene homopolymer, or 1,3-butadiene copolymer whereby the copolymer can contain in bonded form up to 30 weight percent, more preferably up to 20 weight percent, based on the weight of (Bl) of units of olefinic unsaturated monomers polymerized in situ selected from the group consisting of isoprene, styrene, acrylic acid, and methacrylic acid alkylesters having 1 to 8, more preferably 1 to 6 carbon atoms in the alkyl radical. The grafting basis is preferably at least partially crosslinked. To increase the degree of crosslinking in addition to the aforesaid diols other crosslinking monomers can be added such as, for example, triallylcyanurate, triallyl isocyanurate, triacryloylhexahydro-5-triazine, and trialkylene benzene.
If the crosslinking monomers have more than two polymerizable double bonds, it is useful to restrict their quantity to less than 1 weight percent, based on weight of grafting basis (Bl).
Grafting basis (B2) ~the grafting shell) can be 201~7?
synthesized in one or two steps. In a two step synthesis, the first step (the first shell), preferably comprises polymerized styrene and the second step ~the second shell) comprises and ~-methylstyrene a~rylonitrile copolymer. On the other hand, the grafting basis prepared in one step comprises an ~-methylstyrene acrylonitrile copolymer or an ~-methylstyrene, styrene, acrylonitrile copolymer whereby:
i) the total weight of -methylstyrene units polymerized in situ is greater than the styrene units polymerized in situ which also may be 0; and, ii) the weight ratio of the -methylstyrene units polymerized in situ or the total from the -methylstyrene styrene units and styrene units polymerized in situ to the acrylonitrile units polymerized in situ is from 60:40 to 90:10, more preferably 65:35 to 80:20.
The grafting basis defined as the weight share of grafting basis (B2) to the total mass of graft polymer (B), when multiplied times 100, lies between 15 and 30, more preferably between 20 and 30.
The graft yield, i.e., the quotient from the quantity of the grafted monomer and quantity of the graft monomer used lies generally in a range of from 20 to 90 percent, more preferably 50 to 90 percent.
The average particle size d5~ of the rubber elastic graft polymer B, which is defined as the particle diameter greater than exactly 50 percent of the particles, lies between 80 , . , , ., . , _, , , _ _ . , _ .. ... . .. . .. . . . ... . .. .. . . . . . . .... .
201~8~
and 300 nm, more preferably between 90 and 250 nm.
Preparing graft polymer B used according to the present invention, is done in a conventional fashion by emulsion polymerization, for example, analagous to the teachings of DE-A 2 035 390, DE A-2 248 242, and most preferably according to EP-A-22 216.
In addition to the TPU (A) components and rubber elastic graft polymer (B), the TPU molding compositions can also contain additives (C).
As already indicated, the additives (C) can be identical to auxiliaries (e) and/or additives (f) typically u~ed in the preparation of TPU and therefore already incorporated into TPU IA). The amount of the (C) component typically is from 0 to 60 weight percent, more preferably 2 to 50 weight percent, and most preferably 5 to 40 weight percent, based on the weight of the IA) and (B) components. Additives of the aforesaid type are, for example, fillers, reinforcing agents, and flame retardants.
Typical fillers are, for example, organic fillers such as, for example, carbon black, chlorinated polyethylenes and melamine, and inorganic fillers such as, for example, wollastonite, calcium carbonate, magnesium carbonate, amorphous ~ilicic gel, calcium silicate, calcium metasilicate, quartz powder, talc, kaolin, mica, feldspar, glass spheres, silicon nitride, or boron nitride as well as mixture of these fillers.
Fibers are examples of reinforcing fillers which have proven effective and therefore are preferably used. The fibers are, for example, carbon fibers or mo~t preferably glass fibers . . , , ,,, . ~
2~11871.
and if a high heat dimensional stability is required, then the fiber can be coated with adhesion promoters and/or sizing.
Typical glass fibers are, for example, in the form of woven glass fabric, glass mats, glass fleece, and/or preferably glass filament rovings, or cut glass filaments from alkali-low E-fibers having a diameter of from 5 to 200 microns, more preferably 6 to 15 microns. Following their incorporation into the TPU
composition they generally have an average fiber length of ~rom O.05 to 1 mm, more preferably 0.1 to 0.5 mm.
Flame retardants are, for example: melamine, polyhalidediphenyl, polyhalidediphenylether, polyhalidephthalic acid, and their derivatives, polyhalide oligocarbonates and polyhalide polycarbonates whereby the corresponding bromine compounds are particularly effective. Also suitable as flame retardants are phosphorus compounds such as elemental phosphorus or organic phosphorus compounds. In addition, generally the flame retardants also contain a synergist, for example, antimony trioxide.
As already indicated auxiliaries and/or additives can be incorporated in~o the impact modified TPU molding compositions or the TPU ~A) or graft polymer (B) suitable therefore. If such materials are used their share, based on the total weight of (A) and (B), generally is up to 20 weight percent, more preferably up to 10 weight percent, and most preferably 0.01 to 5 weight percent. Such additives are, for example, nucleating agents, oxidation retardants, stabilizers, lubricants, release agents, and dyes.
. . . ~., 2~187~, Nucleating agents are, for example, talc, calcium fluoride, sodium phenylphosphinate, ammonium oxide, and finely divided polytetrafluoroethylene in quantities up to 5 weight percent, based on the weight of TPU (A) and graft polymer (B).
Typical oxidation retardants and heat stabilizers which can be added to the TPU molding compositions are, for example, halides of metals from group I of the periodic chart, for example, sodium, potassium, and lithium halides optionally used in conjunction with copper (I) halides, for example, chlorides, bromides, or iodides; sterically hindered phenols, hydroquinones, as well as substituted compounds of this group and mixture~
thereof, which are preferably used in concentrations up to 1 weight percent, based on the weight of (A) and (B) components.
Typical W stabilizers are different substituted resorcines, salicylates, benzotriazoles, and benzophenones as well as sterically hindered amines which generally are used in quantities up to 2.0 weight pe~cent, based on the weight of the (A) and (B) components.
Lubricants and demolding agents which generally are added in quantities up to 1 weight percent, based on the weight on the (A) and (B) components, include: stearic acids, stearic alcohol, stearic acid esters, and stearic acid amides, as well as the fatty acid ester of pentaerythitol. In addition organic dyes such as Nigrosin, and pigments such as, for example, titar.ium dioxide, calcium sulfide, calcium sulfide selenide, phthalocyanine, Ultramarine blue or carbon black can be added.
The impact modified TPU molding compositions can be 201~18~
prepared according to any process in which essentially homogeneous compositions are obtained from TPU (A), graft polymer (B), and optionally additive (C). For example, starting components (A), (B), and (C) can be mixed at temperature of from 0 to 150 C, more preferably 15 to 30 C, and then melted together or the components can be mixed together directly in the melt. According to another process variation, (A) can be mixed with (C) or (B) with (C), and then the mixture can be incorporated into (B) and/or (AJ.
Preparing the TPU molding compositions of the present invention is done at temperatures ranging from 160 to 250 C, more preferably 210 to 240 C employing a residency time of from 0.5 to 10 minutes, more preferably 0.5 to 3 minutes, in, for example, a flowable, softened or preferably molten state of TPU
(A) and graft polymer (B), for example, by stirring, milling, kneading, or preferably, extruding, for example, while using conventional plastification equipment such as, for example, Brabender or Banbury mills, kneaders and extruders, preferably a double-screw extruder or an injection mixing extruder.
Following the most practical and thus the most preferably used production process, TPU (A) and graft polymer (B) are melted together at a temperature of from 160 to 250 C, preferably in an extruderi optionally the (C) component is added to the melt; this is allowed to cool and the resulting TPU
molding composition is reduced in ~ize.
According to another preferred production variation, suitable pulverized graft polymer (B) can be emulsified or Z01187~
dispersed in at least one of starting components (A) through (C) to prepare TPU (A), preferably the higher molecular weight polyhydroxyl compound (B), and this starting component containing graft polymer (B) then can be converted in a conventional fashion into the TPU molding composition.
The TPU molding compositions of the present invention can be easily pxocessed into molded articles having a good surface character and improved impact resistance with high rigidity particularly a~ low temperatures whereby the (A) and (B) components do not separate either in the melt nor in the molded articles.
The TPU molding compositions are preferably used in the preparation of molded articles, most preferably ski ~oots and large planar injection molded parts for automobiles, preferably automobile exterior parts such as, for example, bumpers, front aprons, rear spoilers, and side impact trim.
The compositions are also suitable for molded articles in the interior of automobiles, for example, as console coverings, arm rests, and handles.
Exam~les The following thermoplastic polyurethane elastomers (A) were used in the preparation of the impact modified TPU molding compositions of the present invention:
Al: TPU having a Shore D hardness of 74, prepared by reacting a mixture of 0.5 moles of a 1,4-butanediol polyadipate having a molecular weight of 2,000 and 5.86 moles of 1,4-butanediol with 4,4'-diphenylmethane diisocyanate in a 201~87~.
NCO:OH group ratio of 1 at temperatures ranging from 80 to 170 C following a conveyor process.
A2: TPU having a Shore D hardness of 74, prepared analogous to paragraph Al, however, while using a NCO:OH group ratio of 1.04.
A3: TPU having a Shore D hardness of 64, prepared analogous to paragraph Al, however, while using 3.87 moles of 1,4~
butanediol.
A4: TPU having a Shore A hardness of 90, prepared analogous to paragraph Al, however, while using 1.7 mole~ of 1,4-butanediol.
A5: TPU having a Shore D harness of 74, prepared by reacting a mixture of 0.5 moles of a 1,4-butanediol ethylene glycol polyadipate with 1,4-butanediol:ethylene glycol in a mole ratio of 1:1 and having a molecular weight of 2,000 and 5.66 moles of 1,4-butanediol with 4,4'-diphenylmethane diisocyanate in a NCO:OH group ratio of 1.
The TPU's described as Al through A5 contained, based on the weight of the alkanediol polyadipate, 1 weight percent of diisopropylphenylcarbodiimide as a stabilizer hydrolysis.
A6: TPU having a Shore D hardness of 74, prepared by reacting a mixture of 1 mole of polytetramethyleneglycol having a molecular weight of 1,000 and 5.9 moles of 1,4-butanediol with 4,4'-diphenylmethane diisocyanate in an NCO:OH group ratio of 1 at temperatures ranging from 90 to 170 C
following a conveyor process.
201~871.
The following were used in graft polymers:
BI: (A comparison product) A rubber elastic graft polymer having a grafting basis (75 weight percent) of polybutadiene and a grafting basis (25 weight percent) of a copolymer from styrene and acrylonitrile in a weight ratio of from 75:25, prepared by emulsion polymerization in a conventional fashion. The average particle diameter d50 which is defined as the diameter which lies above and below the diameter of 50 percent of the particles, was 200 nm.
BII: ~ rubber elastic graft polymer prepared analagous to paragraph BI, however, the grafting basis was a copolymer from u-methylstyrene acrylonitrile in a weight ratio of 75:25.
BIII: A rubber elastic graft polymer having a grafting basis (70 weight percent) of polybutadiene and a grafting basis ~a total of 30 weight percent) prepared in a second step;
whereby the first grafting ba~is (10 weight percent) was polystyrene and the second grafting basis (20 weight percent) was a copolymer from ~-methylstyrene and acrylonitrile in a weight ratio of 70:30. The graft polymer was prepared by emulsion polymerization in a conventional fashion and had an average particle diameter d50 of 150 nm.
In preparing the TPU molding compositions, TPU (A) and graft polymer (B) were intensively mixed together at 23 C: the mixture was introduced into a twin-screw extruder; melted at 230 C; homogenized within two minutes at the same temperature; and then extruded into a water bath.
Following granulation and drying, the TPU molding composition was process into test articles using an injection molding machine at 230 C. The notched bar impact strength according to DIN 53 453 and the modulus of elasticity according to DIN 53 457 were measured on the test articles without any post treatment.
The following table illustrates the type and quantity of TPU (A) and graft polymer ~) used and the mechanical properties measured on the test articles.
. . . . .. .. . .. .. .
871.
.1 ~ o ._ o o o o o o o o ~ o a L~ o ~o ~ ~ 3 ~ à u~ Lr~ 3 1~ ~ ~ U~
OC,~
~ S ~ ~
a~ ~ Y
V V--L '~
O Oo t~.l 3 ~ ~ _ ~ 3 ~
a o o o o S m m m m m m m m m m m m m m b~
2 ~ N
g ~ ~ ~ 2 2 _ ~ ~ ~
D~
a~ Y
O,~ -- ~ ~) 3 1~ -- 3 3 --L -- a~
~S 3 . ~ :~
E~ ~ cq . Il ~ 0~ 0 a) 0 ~ ~ ~ c~ 0 CD a~ o E- ~ -- N 0 3 In ~ ~ 0 O~
, .. . . , _, _ _ . .. , ., ., _ _ , , _ ., , _ _ .. _ _ _ _ _ _ _ , , . . _ _ , , ~ . , . _, _ .. , . . ~ .
. . . ..
~ ccordingly, the subject of the invention is impact modified thermoplastic polyurethane molding compositions, comprising:
A) 70 to 99 parts by weight, more preferably 75 to 90 parts by weight, of at least one thermoplastic polyurethane elastomer IA);
B) 1 to 30 parts by weight, more preferably 10 to 25 parts by weight, of at least one graft polymer (B) which is synthesized from:
Bl) an elastomer (Bl) serving as a grafting basis having a glass transition temperature below -40C, preferably below -50 C; and B2) a grafting basis (B2) prepared in one or two steps from ~-methylstyrene and acrylonitrile, or -methylstyrene, styrene, and acrylonitrile;
whereby the parts by weight of ~A) and (B) total 100 parts by weight; and, i) the total weight of -methylstyrene units polymerized in situ is greater than the total weight of the styrene units polymerized in situ;
ii) the total weight of the -methylstyrene units polymerized in situ or the total of the -methylstyrene units and styrene units polymerized in situ to the acrylonitrile units polymerized in situ, is from 60:40 to 90:10, more preferably 65:35 to 80:20; and, iii) the degree of grafting is between 15 and 30, 37~.
more preferably between 20 and 30 (C) 0 to 60 weight percent, more preferably 0 to 40 weight percent, based on the total weight of (A) and (B) of at least one additive;
wherein in grafting basis (B2):
The subject of the present invention is also a process for the preparation of impact modified thermoplastic polyurethane molding compositions comprising: melting together components (A) and (B) and optionally incorporating component ~C) in a conventional mixing device, preferably in an extruder at a temperature of from 160 to 250 C and with residency time of from 0.5 to 10 minutes. The subject of the present invention is also using the impact modified, thermoplastic, polyurethane molding compositions in the preparation of injection molded articles, preferably ski boots and automobile trim parts as well as molded articles prepared while using the impact modified polyurethane thermoplastic polyurethane molding compositions as an essential starting component.
By using graft polymer (B), whose grafting basis (B2~, comprises; an -methylstyrene-acrylonitrile polymer or an ~-methylstyrene~styrene-acrylonitrile copolymer; suprisingly TPU
molding compositions result having a substantially improved impact resistance ~ith high strength especially at low temperatures. Another advantage is that starting component TPU
(A) and graft polymer ~) do not separate either in the melt nor in the molded article, and the molding compositions of the present invention can easily be processed into molded articles 20~L1871.
which have an excellent surface character.
TPU ~A) used according to the invention corresponds to the state-of-the-art and can be prepared by reacting:
a) organic, more preferably aromatic diisocyanates, most preferably 4,4'-dipenylmethyl diisocyanate with;
b) polyhydroxyl compounds, preferably essentially linear polyhydroxyl compounds having molecular weights of from 500 to 8,000, most preferably polyalkylene glycol polyadipates having 2 to 6 carbon atoms in the alkylene radical and molecular weights of from 500 to 6,000 or hydroxyl groups containing polytetrahydrofuran having a molecular weigh~ of from 500 to B,000; and, c) diols as chain extending agents having molecular weights of from 60 to 400, most preferably 1,4-butanediol;
in the presence of:
d) catalysts and optionally;
e) auxiliaries and/or;
f) additives;
at elevated temperatures.
The following should be noted with respect to the starting components (a) through (d) and optionally (e) and/or (f):
a) organic diisocyanates (a) are, for example, aliphatic, cycloaliphatic, or more preferably aromatic diisocyanates. Individual examples are: aliphatic diisocyanates, such as hexamethylene-1,6-diisocyanate, 2-methyl-pentamethylene-1,5-diisocyanate, 2-ethyl-20118~1 butylene-1,4-diisocyanate, or mixtures of of least two of the aforesaid aliphatic diisocyanates; cycloaliphatic diisocyanates such as, for example, isophorone diisocyanate, 1,4-cyclohexane diisocyanate, l-methyl-2,4-cyclohexane diisocyanate, and 1-methyl-2,6-cyclohexane diisocyanate, as well as the corresponding isomeric mixtures, 4,4'-, 2-4'-, and 2,2'-dicycohexyl-methane diisocyanate as well as the corre~ponding isomeric mixtures, and preferably aromatic diisocyanates such as, for example, 2,4-toluene diisocyanate, mixtures of 2,4-, and 2,6-toluene diisocyanate, 4,4'-, 2,4'-, and 2,2'-diphenylmethane diisocyanate; mixtures of 2,4'-, and 4,4'-diphenylmethane diisocyanate, urethane modified liquid 4,4'-, and/or 2,4'-diphenylmethane diisocyanate, 4,4'-diisocyanato-1,2-diphenylethane, mixtures of 4,4'-, 2,4'-, and 2,2'-diisocyanato-1,2-diphenylethane, advantageously those comprising at least 95 weight percent of 4,4'-diisocyanato-1,2-diphenylethane and 1,5-naphthylene diisocyanate. Preferably used are diphenylmethane diisocyanate isomeric mixtures having a 4,4'-diphenylmethane diisocyanate content greater than 96 weight percent, and most preferably essentially pure 4,4'-diphenylmethane diisocyanate.
The organic diisocyanates can optionally be replaced to a lesser degree, for example, in quantities up to 3 mole percent, more preferably to 1 mole percent, based on the organic diisocyanate by a trifunctional polyisocyanate or a higher functional polyisocyanate, however, ~he1 ~ 8 71.
quantities must be limited so that polyurethanes are obtained which are still thermoplastic in nature when processed.
Quantities of isocyanates considered more than difunctional are best compensated for by using less than difunctional compounds with reactive h~drogen atoms so that extensive chemical crosslinking of the polyurethane is avoided. Examples of isocyanates regarded as more than difunctional are mixtures of diphenylmethane diisocyanates and polyphenyl polymethylene polyisocyanates, the so-called polymeric-MDI and liquid 4,4'-, and/or 2,4'-diphenylmethane diisocyanate modified with the following groups: isocyanurate, urea, biuret, allophanate, urethane and/or carbodiimide.
Typical monofunctional compounds having reactive hydrogen atoms which also are used as molecular weight regulators are, for example, monoamines such as, for example, butyl-, dibutyl-, octyl-, stearyl-, N-methylstearylamine, pyrrolidone, piperidine, and cyclohexylamine; and monoalcohols such as, for example, butanol, amyl alcohol, l-ethylhexanol, octanol, dodecanol, cyclohexanol, and ethylene glyrol monoethyl ether.
b) Higher molecular weight polyhydroxyl compounds (b) having molecular weights of from 500 to 8,000 are preferably polyether polyols and most preferably, :' :
pslyester polyols. However, other example~ are:
hydroxyl group containing polymers with ether and/or ester groups as bridge members, for example, polyacetels such as polyoxymethylenes and particularly water insoluble formals, for example, polybutanediol formal and polyhexanediol formal, and polycarbonates preferably, those from diphenyl carbonate and 1,~-hexanediol prepared by transesterification. The polyhydroxyl compounds must be predominantly linear, i.e., difunctional in the sense that the isocyanate reaction. The aforesaid polyhydroxyl compounds can be used as individual components or in the form of mixtures.
Typical polyether polyols can be prepared according to known processes, for example, by the anionic polymerization with alkali hydroxides such as sodium or potassium hydroxide or alkali alcolates such as sodium methylate, sodium or potassium methylate, or potassium isopropylate as catalysts and while using at least one initiator molecule which contains in bonded form 2 to 3, more preferably 2 active hydrogen atoms; or by the cationic polymerization with Lewis acids such as, for example, antimony pentachloride, boron fluoride etherate, etc., or bleaching earth as catalysts from one or more alkylene oxides having 2 to 4 carbon atoms in the alkylene radical.
Typical alkylene oxides are, for example, ~, ... . . . . . ..
201187~
preferably tetrahydrofuran, 1,3-propylene oxide, 1,2-, and/or 2,3-butylene oxide, and most preferably ethylene oxide and 1,2-propylene oxide. The alkylene oxides can be used individually, alternating one after another, or as mixtures. Typical initiator molecules are, for example, water, organic dicarboxylic acids such as succinic acid, adipic acid, and/or glutaric acids;
alkanolamines, such as, for example, ethanolamine, N-alkylalkanolamine, N-alkyldialkanolamines, such as, for example, N-methyldiethanolamine, and N-ethyldiethanolamine, and preferably, divalent alcohols optionally containing ether bridges in bonded form such as, for example, ethanediol, 1,2-propanediol, and 1,3-propanediol, 1,4-butanediol, diethylene glycol, 1,5-pentanediol, 1,6-hexanediol, dipropylene glycol, 2-methyl-1,5-pentanediol, and 2-ethyl-1,4-butanediol. The initiator molecules can be used individually or as mixtures.
Preferably used are polyether polyols from 1,2-propylene oxide and ethylene oxide in which more than 50 percent, more preferably 60 to 80 percent, of the OH groups are primary hydroxyl groups and in which at least a portion of the ethylene oxide is situated as a terminal block. Such polyether polyols can be obtained, for example, by first polymerizing 1,2-propylene oxide onto the initiator molecule then subsequently polymerizing the ethylene oxide, or first .,,,, - --- - ---8'~:L
polymerizing the entire 1,2-propylene oxide mixed with a portion of the ethylene oxide and then subsequently polymerizing the remainder of the ethylene oxide, or stepwise that is first a portion of the ethylene oxide then the entire 1,2-propylene oxide and the remainder of the ethylene oxide onto the initiator molecule.
Also preferably used are hydroxyl group containing polymerization products of tetrahydrofuran.
The essentially linear polyether polyols have molecular weights of from 500 to 8,000, more preferably 600 to 6,000, and most preferably 800 to 3,500. They can be used individually or mixed with one another.
Typical polyester polyols can be prepared, for example, from dicarboxylic acids having 2 to 12, more preferably 4 to 6 carbon atoms and from multivalent alcohols.
Typical dicarboxylic acids are, for example:
aliphatic dicarboxylic acids, such as, succinic acid, glutaric acid, adipic acid, subaric acid, azelaic acid, and sebacic acid, and aromatlc dicarboxylic acids, such as, phthalic acid, isophthalic acid and terephthalic acid. The dicarboxylic acids can be used individually or as mixtures, for example, a mixture of succinic, glutaric, and adipic acids. When preparing the polyester polyols, it optionally can be advantageous to use the corresponding carboxylic acid derivatives in place of the carboxylic acids such as carboxylic acid 201~871 esters having 1 to 4 carbon atoms in the alcohol radical, carboxylic acid anhydrides, or carboxylic acid chlorides. Examples of multivalent alcohols are:
glycols having 2 to 10, more preferably 2 to 6 carbon atoms such as ethylene glycol, diethylene glycol, 1,4-butanediol, l,S-pentanediol, 1,6-nexanediol, 1,10-decanediol, 2,2-dimethyl-1,3-propanediol, 1,3-propanediol, and dipropylene glycol. Depending on the desired properties, the multivalent alcohols can be u~ed individually or optionally mixed with one another.
Also suitable are esters of carboxylic acids with the aforesaid dio~s, most preferably those having 4 to 6 carbon atoms such as 1,4-butanediol and/or 1,6-hexanediol; condensation products of ~-hydroxycarboxylic acids, for example, ~-hydroxycaproic acid, and preferably polymerization products from lactones, preferably optionally substituted ~-caprolactones.
Polyester polyols preferably used are:
ethanediol polyadipates, 1,4-butanediol polyadipates, ethanediol- 1,4-butanediol polyadipates, 1,6-hexanediol neopentylglycol polyadipates, 1,6-hexanediol, 1,4-butanediol polyadipates, and polycaprolactones. The polyester polyols have molecular weights of from 500 to 6,0Q0, more preferably 800 to 3,500.
c) Typical chain extending agents (c) having molecular weights of from 60 to 400, more preferably 60 to 300, are, for example, preferably aliphatic diols having 2 to _, .. ... . . . . .. . . .. . .. . . .
12 carbon atoms more preferably 2, 4, or 6 carbon atoms, for example, ethanediol, 1,6-hexanediol, diethylene glycol, dipropylene glycol, and most preferably 1,4-butanediol. However, also suitable are diesters of terephthalic acids with glycols having 2 to 4 carbon atoms such as, for example, terephthalic acid bis-ethylene glycol or terephthalic acid bis-1,4-butanediol, and hydroxyalkylene ether from hydroquinone, for example, 1,4-di-(~-hydroxyethyl) hydroquinone as well as polytetramethylene glycols having molecular weights of from 162 to 378.
The starting components can be varied in relatively broad molar ratios to adjust hardness and melt index, whereby the hardness and melt viscosity increase with an increasing amount of chain extending agent (c) while the melt index decreases.
When preparing TPU (A) the essentially linear difunctional polyhydroxyl compounds (b) and diols (c) are advantageously used in mole ratios of from 1:3 to 1:12, more preferably 1:6 to 1:12 so that the resulting TPU's have a Shore D hardness of from 40 to 80, more preferably 40 to 75.
d) Typical catalysts which accelerate the reaction between the NCO groups of the diisocyanates (a) and the hydroxyl groups of starting components (b) and (c) are those ~tate-of-the-art catalysts and also conventional tertiary amines such as, ~or example, triethylamine, 20~871 dimethylcyclohexylamine, ~-methylmorpholine, ~,N'-diethylpiperazine, diazabicyclo[2.2.2]octane and the like, as well as preferably organic metal compounds such as titanium acid ester, iron compounds, tin compounds, for example, tin diacetate, tin dioctoate, tin dilaurate, or tin dialkyl salts of aliphatic carboxylic acids such as, for example, dibutyltin acetate, dibutyltin dilaurate, or the like. Catalysts are generally used in quantities of from 0.001 to 0.1 parts by weight per 100 parts by weight of the mixture of polyhydroxyl compounds (b) and diols ~c).
Auxiliaries (e) and /or additives (f) in addition to the catalysts can also be added to the starting components.
Typical examples are: lubricants, inhibitors, stabilizers against hydrolysis, light, heat, or discoloration, flame retardants, dyes, pigments, inorganic and/or organic fillers, and reinforcing agents.
The auxiliaries (e) and/or additives (f) as already Rtated can be added to the starting components or to the reaction mixture when preparing TPU (A). Following another process variation, auxiliaries (e) and/or additives (f), which can be identical to (C), can be mixed with TPU (A) and/or graft polymer (B) and subsequently melted together or directly incorporated to the melt comprising components (A) and (B). The later method is particularly used for adding reinforcing fillers as additive (C).
Additional information concerning auxiliaries and/or additives can be found in the technical literature, for example, ., ,, . , .. , , . ., ,, , . _ _ _, , . _,; .. . , _ .. ,, . , ", _ . , ~ . _ . _ . . . . . . .. . ... ..
. .
2011871.
in the monograph of J. H. Saunders and K. C. Frisch ~igh Polymers, Vol. XVI, Polyurethanes, Parts 1 and 2, Interscience Publishers 19~2 and 1964, or in the The Plastics Handbook, Vol.
7, Polyurethanes, First and Second Editions, Carl Hanser Publishers, 1966 and 1983 or in DE-OS 29 01 774.
When preparing the TPU, starting components (a), (b), and (c) are reacted in the presence of catalysts (d) and optionally auxiliaries (e) and/or additives (f) in such quantities so that the equivalent ratio of NCO groups from said diisocyanates to the total of the hydroxyl groups from components (b) and (c) is from 0.80 to 1.20:1, more preferably 0.95 to 1.05:1, and most preferably about 1:1.
TPU (A) used according to the present invention, which typically contains 8 to 20 weight percent, more preferably 8 to 16 weight percent, based on the total weight, of urethane groups in bonded form, and which has a melt index at 210 C of 500 to 1, more preferably 100 to 1, can be prepared following an extruder process or more preferably a conveyor process batchwise or by continuously mixing starting components ~a) through (d) as well as optionally (e) and (f); allowing t~e reaction mixture to cure in an extruder or on a conveyor belt at temperatures of from 60 to 250 C, more preferably 70 to 150 C, and subsequently granulating the resulting TPU (A). Optionally it also can be advantageous to temper the resulting TPU (A) before further processing into TPU molded articles of the present invention at 80 to 120 C, more preferably 100 to 110~ C from 1 to 24 hours.
TPU (A) as already cited is preferably prepared Z01187~
according to a conveyor process. Here the starting components (a) through (d) and optionally le) and/or tf) are mixed at temperatures above the melt point of starting components (a) through (c) continuously with the help of a mix head. The reaction mixture is applied onto a carrier preferably a conveyor belt made of, for example, metal at a rate of from 1 to 20 meters per minute, more preferably 4 to 10 meters per minute, and is fed through a heating zone 1 to 20 meters in length, more preferably 3 to lO meters in length. The reaction temperature in the heating zone is 60 to 200 C, more preferably 80 to 180 C.
Depending on the diisocyanate portion in the reaction mixture, the reaction i9 controlled by heating or cooling so that at least 90 percent, more preferably at least 98 percent, of the isocyanate groups of the diisocyanates react and the reaction mixture cures at the selected reaction temperature. Due to the free isocyanate groups in the cured reaction product, which based on the total weight range from 0.05 to 1 weight percent, more prefe~ably 0.1 to 0.5 weight percent, TPU (A) is obtained having a very low melt viscosity and/or a high melt index.
TPU molding compositions of the present invention containing starting (B) as already stated, comprise; 1 to 30 parts by weight, more preferably lQ to 25 parts by weight, based on lO0 parts by weight of (A) and (B), of one or more graft polymers, preferably a rubber elastic graft polymer (B), comprising:
Bl~ preferably 70 to 85 weight percent, most preferably 70 to 80 weight percent, based on the weight of (B), of a . _ _., .. .. . , , _ , . __ . _ , . . .. . ... ,_. . _ , . .. . . . . . .
20~187~.
rubber elastic grafting basis (Bl) from a butadiene homopolymer or butadiene copolymer having a glass temperature less than -40 C, more preferably -5~ C;
and, B2) preferably 30 to 15 weight percent, most preferably 30 to 20 weight percent, based on the weight of (B), of a grafting basis (B2) prepared in one or two steps, comprising; ~-methylstyrene and acrylonitrile or -methylstyrene, styrene, and acrylonitrile.
Grafting basis (Bl) comprises a 1,3-butadiene homopolymer, or 1,3-butadiene copolymer whereby the copolymer can contain in bonded form up to 30 weight percent, more preferably up to 20 weight percent, based on the weight of (Bl) of units of olefinic unsaturated monomers polymerized in situ selected from the group consisting of isoprene, styrene, acrylic acid, and methacrylic acid alkylesters having 1 to 8, more preferably 1 to 6 carbon atoms in the alkyl radical. The grafting basis is preferably at least partially crosslinked. To increase the degree of crosslinking in addition to the aforesaid diols other crosslinking monomers can be added such as, for example, triallylcyanurate, triallyl isocyanurate, triacryloylhexahydro-5-triazine, and trialkylene benzene.
If the crosslinking monomers have more than two polymerizable double bonds, it is useful to restrict their quantity to less than 1 weight percent, based on weight of grafting basis (Bl).
Grafting basis (B2) ~the grafting shell) can be 201~7?
synthesized in one or two steps. In a two step synthesis, the first step (the first shell), preferably comprises polymerized styrene and the second step ~the second shell) comprises and ~-methylstyrene a~rylonitrile copolymer. On the other hand, the grafting basis prepared in one step comprises an ~-methylstyrene acrylonitrile copolymer or an ~-methylstyrene, styrene, acrylonitrile copolymer whereby:
i) the total weight of -methylstyrene units polymerized in situ is greater than the styrene units polymerized in situ which also may be 0; and, ii) the weight ratio of the -methylstyrene units polymerized in situ or the total from the -methylstyrene styrene units and styrene units polymerized in situ to the acrylonitrile units polymerized in situ is from 60:40 to 90:10, more preferably 65:35 to 80:20.
The grafting basis defined as the weight share of grafting basis (B2) to the total mass of graft polymer (B), when multiplied times 100, lies between 15 and 30, more preferably between 20 and 30.
The graft yield, i.e., the quotient from the quantity of the grafted monomer and quantity of the graft monomer used lies generally in a range of from 20 to 90 percent, more preferably 50 to 90 percent.
The average particle size d5~ of the rubber elastic graft polymer B, which is defined as the particle diameter greater than exactly 50 percent of the particles, lies between 80 , . , , ., . , _, , , _ _ . , _ .. ... . .. . .. . . . ... . .. .. . . . . . . .... .
201~8~
and 300 nm, more preferably between 90 and 250 nm.
Preparing graft polymer B used according to the present invention, is done in a conventional fashion by emulsion polymerization, for example, analagous to the teachings of DE-A 2 035 390, DE A-2 248 242, and most preferably according to EP-A-22 216.
In addition to the TPU (A) components and rubber elastic graft polymer (B), the TPU molding compositions can also contain additives (C).
As already indicated, the additives (C) can be identical to auxiliaries (e) and/or additives (f) typically u~ed in the preparation of TPU and therefore already incorporated into TPU IA). The amount of the (C) component typically is from 0 to 60 weight percent, more preferably 2 to 50 weight percent, and most preferably 5 to 40 weight percent, based on the weight of the IA) and (B) components. Additives of the aforesaid type are, for example, fillers, reinforcing agents, and flame retardants.
Typical fillers are, for example, organic fillers such as, for example, carbon black, chlorinated polyethylenes and melamine, and inorganic fillers such as, for example, wollastonite, calcium carbonate, magnesium carbonate, amorphous ~ilicic gel, calcium silicate, calcium metasilicate, quartz powder, talc, kaolin, mica, feldspar, glass spheres, silicon nitride, or boron nitride as well as mixture of these fillers.
Fibers are examples of reinforcing fillers which have proven effective and therefore are preferably used. The fibers are, for example, carbon fibers or mo~t preferably glass fibers . . , , ,,, . ~
2~11871.
and if a high heat dimensional stability is required, then the fiber can be coated with adhesion promoters and/or sizing.
Typical glass fibers are, for example, in the form of woven glass fabric, glass mats, glass fleece, and/or preferably glass filament rovings, or cut glass filaments from alkali-low E-fibers having a diameter of from 5 to 200 microns, more preferably 6 to 15 microns. Following their incorporation into the TPU
composition they generally have an average fiber length of ~rom O.05 to 1 mm, more preferably 0.1 to 0.5 mm.
Flame retardants are, for example: melamine, polyhalidediphenyl, polyhalidediphenylether, polyhalidephthalic acid, and their derivatives, polyhalide oligocarbonates and polyhalide polycarbonates whereby the corresponding bromine compounds are particularly effective. Also suitable as flame retardants are phosphorus compounds such as elemental phosphorus or organic phosphorus compounds. In addition, generally the flame retardants also contain a synergist, for example, antimony trioxide.
As already indicated auxiliaries and/or additives can be incorporated in~o the impact modified TPU molding compositions or the TPU ~A) or graft polymer (B) suitable therefore. If such materials are used their share, based on the total weight of (A) and (B), generally is up to 20 weight percent, more preferably up to 10 weight percent, and most preferably 0.01 to 5 weight percent. Such additives are, for example, nucleating agents, oxidation retardants, stabilizers, lubricants, release agents, and dyes.
. . . ~., 2~187~, Nucleating agents are, for example, talc, calcium fluoride, sodium phenylphosphinate, ammonium oxide, and finely divided polytetrafluoroethylene in quantities up to 5 weight percent, based on the weight of TPU (A) and graft polymer (B).
Typical oxidation retardants and heat stabilizers which can be added to the TPU molding compositions are, for example, halides of metals from group I of the periodic chart, for example, sodium, potassium, and lithium halides optionally used in conjunction with copper (I) halides, for example, chlorides, bromides, or iodides; sterically hindered phenols, hydroquinones, as well as substituted compounds of this group and mixture~
thereof, which are preferably used in concentrations up to 1 weight percent, based on the weight of (A) and (B) components.
Typical W stabilizers are different substituted resorcines, salicylates, benzotriazoles, and benzophenones as well as sterically hindered amines which generally are used in quantities up to 2.0 weight pe~cent, based on the weight of the (A) and (B) components.
Lubricants and demolding agents which generally are added in quantities up to 1 weight percent, based on the weight on the (A) and (B) components, include: stearic acids, stearic alcohol, stearic acid esters, and stearic acid amides, as well as the fatty acid ester of pentaerythitol. In addition organic dyes such as Nigrosin, and pigments such as, for example, titar.ium dioxide, calcium sulfide, calcium sulfide selenide, phthalocyanine, Ultramarine blue or carbon black can be added.
The impact modified TPU molding compositions can be 201~18~
prepared according to any process in which essentially homogeneous compositions are obtained from TPU (A), graft polymer (B), and optionally additive (C). For example, starting components (A), (B), and (C) can be mixed at temperature of from 0 to 150 C, more preferably 15 to 30 C, and then melted together or the components can be mixed together directly in the melt. According to another process variation, (A) can be mixed with (C) or (B) with (C), and then the mixture can be incorporated into (B) and/or (AJ.
Preparing the TPU molding compositions of the present invention is done at temperatures ranging from 160 to 250 C, more preferably 210 to 240 C employing a residency time of from 0.5 to 10 minutes, more preferably 0.5 to 3 minutes, in, for example, a flowable, softened or preferably molten state of TPU
(A) and graft polymer (B), for example, by stirring, milling, kneading, or preferably, extruding, for example, while using conventional plastification equipment such as, for example, Brabender or Banbury mills, kneaders and extruders, preferably a double-screw extruder or an injection mixing extruder.
Following the most practical and thus the most preferably used production process, TPU (A) and graft polymer (B) are melted together at a temperature of from 160 to 250 C, preferably in an extruderi optionally the (C) component is added to the melt; this is allowed to cool and the resulting TPU
molding composition is reduced in ~ize.
According to another preferred production variation, suitable pulverized graft polymer (B) can be emulsified or Z01187~
dispersed in at least one of starting components (A) through (C) to prepare TPU (A), preferably the higher molecular weight polyhydroxyl compound (B), and this starting component containing graft polymer (B) then can be converted in a conventional fashion into the TPU molding composition.
The TPU molding compositions of the present invention can be easily pxocessed into molded articles having a good surface character and improved impact resistance with high rigidity particularly a~ low temperatures whereby the (A) and (B) components do not separate either in the melt nor in the molded articles.
The TPU molding compositions are preferably used in the preparation of molded articles, most preferably ski ~oots and large planar injection molded parts for automobiles, preferably automobile exterior parts such as, for example, bumpers, front aprons, rear spoilers, and side impact trim.
The compositions are also suitable for molded articles in the interior of automobiles, for example, as console coverings, arm rests, and handles.
Exam~les The following thermoplastic polyurethane elastomers (A) were used in the preparation of the impact modified TPU molding compositions of the present invention:
Al: TPU having a Shore D hardness of 74, prepared by reacting a mixture of 0.5 moles of a 1,4-butanediol polyadipate having a molecular weight of 2,000 and 5.86 moles of 1,4-butanediol with 4,4'-diphenylmethane diisocyanate in a 201~87~.
NCO:OH group ratio of 1 at temperatures ranging from 80 to 170 C following a conveyor process.
A2: TPU having a Shore D hardness of 74, prepared analogous to paragraph Al, however, while using a NCO:OH group ratio of 1.04.
A3: TPU having a Shore D hardness of 64, prepared analogous to paragraph Al, however, while using 3.87 moles of 1,4~
butanediol.
A4: TPU having a Shore A hardness of 90, prepared analogous to paragraph Al, however, while using 1.7 mole~ of 1,4-butanediol.
A5: TPU having a Shore D harness of 74, prepared by reacting a mixture of 0.5 moles of a 1,4-butanediol ethylene glycol polyadipate with 1,4-butanediol:ethylene glycol in a mole ratio of 1:1 and having a molecular weight of 2,000 and 5.66 moles of 1,4-butanediol with 4,4'-diphenylmethane diisocyanate in a NCO:OH group ratio of 1.
The TPU's described as Al through A5 contained, based on the weight of the alkanediol polyadipate, 1 weight percent of diisopropylphenylcarbodiimide as a stabilizer hydrolysis.
A6: TPU having a Shore D hardness of 74, prepared by reacting a mixture of 1 mole of polytetramethyleneglycol having a molecular weight of 1,000 and 5.9 moles of 1,4-butanediol with 4,4'-diphenylmethane diisocyanate in an NCO:OH group ratio of 1 at temperatures ranging from 90 to 170 C
following a conveyor process.
201~871.
The following were used in graft polymers:
BI: (A comparison product) A rubber elastic graft polymer having a grafting basis (75 weight percent) of polybutadiene and a grafting basis (25 weight percent) of a copolymer from styrene and acrylonitrile in a weight ratio of from 75:25, prepared by emulsion polymerization in a conventional fashion. The average particle diameter d50 which is defined as the diameter which lies above and below the diameter of 50 percent of the particles, was 200 nm.
BII: ~ rubber elastic graft polymer prepared analagous to paragraph BI, however, the grafting basis was a copolymer from u-methylstyrene acrylonitrile in a weight ratio of 75:25.
BIII: A rubber elastic graft polymer having a grafting basis (70 weight percent) of polybutadiene and a grafting basis ~a total of 30 weight percent) prepared in a second step;
whereby the first grafting ba~is (10 weight percent) was polystyrene and the second grafting basis (20 weight percent) was a copolymer from ~-methylstyrene and acrylonitrile in a weight ratio of 70:30. The graft polymer was prepared by emulsion polymerization in a conventional fashion and had an average particle diameter d50 of 150 nm.
In preparing the TPU molding compositions, TPU (A) and graft polymer (B) were intensively mixed together at 23 C: the mixture was introduced into a twin-screw extruder; melted at 230 C; homogenized within two minutes at the same temperature; and then extruded into a water bath.
Following granulation and drying, the TPU molding composition was process into test articles using an injection molding machine at 230 C. The notched bar impact strength according to DIN 53 453 and the modulus of elasticity according to DIN 53 457 were measured on the test articles without any post treatment.
The following table illustrates the type and quantity of TPU (A) and graft polymer ~) used and the mechanical properties measured on the test articles.
. . . . .. .. . .. .. .
871.
.1 ~ o ._ o o o o o o o o ~ o a L~ o ~o ~ ~ 3 ~ à u~ Lr~ 3 1~ ~ ~ U~
OC,~
~ S ~ ~
a~ ~ Y
V V--L '~
O Oo t~.l 3 ~ ~ _ ~ 3 ~
a o o o o S m m m m m m m m m m m m m m b~
2 ~ N
g ~ ~ ~ 2 2 _ ~ ~ ~
D~
a~ Y
O,~ -- ~ ~) 3 1~ -- 3 3 --L -- a~
~S 3 . ~ :~
E~ ~ cq . Il ~ 0~ 0 a) 0 ~ ~ ~ c~ 0 CD a~ o E- ~ -- N 0 3 In ~ ~ 0 O~
, .. . . , _, _ _ . .. , ., ., _ _ , , _ ., , _ _ .. _ _ _ _ _ _ _ , , . . _ _ , , ~ . , . _, _ .. , . . ~ .
. . . ..
Claims (14)
1. Impact modified thermoplastic polyurethane molding compositions, comprising:
(A) 70 to 99 parts by weight of at least one thermoplastic polyurethane elastomer (A);
B) 1 to 30 parts by weight of at least one graft polymer (B), comprising;
B1) an elastomer (B1) serving as a grafting basis having a glass transition temperature below -40°C;
and, B2) a grafting basis (B2) prepared from .alpha.-methylstyrene and acrylonitrile, or .alpha.-methylstyrene-styrene copolymers and acrylonitrile; wherein i) the total weight of said .alpha.-methylstyrene is greater than said styrene;
ii) the weight ratio of the .alpha.-methylstyrene or .alpha.-methylstyrene-styrene copolymers to acrylonitrile is from 60:40 to 90:10; and iii) the degree of grafting is between 15 and 30 whereby (A) and (B) total 100 parts by weight; and C) 0 to 60 weight percent of an additive based on the total weight of (A) and (B).
(A) 70 to 99 parts by weight of at least one thermoplastic polyurethane elastomer (A);
B) 1 to 30 parts by weight of at least one graft polymer (B), comprising;
B1) an elastomer (B1) serving as a grafting basis having a glass transition temperature below -40°C;
and, B2) a grafting basis (B2) prepared from .alpha.-methylstyrene and acrylonitrile, or .alpha.-methylstyrene-styrene copolymers and acrylonitrile; wherein i) the total weight of said .alpha.-methylstyrene is greater than said styrene;
ii) the weight ratio of the .alpha.-methylstyrene or .alpha.-methylstyrene-styrene copolymers to acrylonitrile is from 60:40 to 90:10; and iii) the degree of grafting is between 15 and 30 whereby (A) and (B) total 100 parts by weight; and C) 0 to 60 weight percent of an additive based on the total weight of (A) and (B).
2. The impact modified thermoplastic polyurethane molding compositions of claim 1, wherein said graft polymer (B), comprises:
B1) 70 to 85 weight percent or a rubber elastic grafting basis; and B2) 30 to 15 weight percent of a grafting basis prepared in one or two steps;
whereby the weight percents are based on the total weight of (B1) and (B2).
B1) 70 to 85 weight percent or a rubber elastic grafting basis; and B2) 30 to 15 weight percent of a grafting basis prepared in one or two steps;
whereby the weight percents are based on the total weight of (B1) and (B2).
3. The impact modified thermoplastic polyurethane molding compositions of claim 2, wherein the rubber elastic grafting basis (B1) comprises a homopolymer of 1,3-butadiene.
4. The impact modified thermoplastic polyurethane molding compositions of claim 2, wherein the rubber elastic grafting basis (B1) comprises a copolymer of 1,3-butadiene and at least one olefinic unsaturated monomer selected from the group consisting of isoprene, styrene and methacrylic acid alkylesters having 1 to 8 carbon atoms in the alkyl radical.
5. The impact modified thermoplastic polyurethane molding compositions of claim 1, wherein the grafting basis (B2) is prepared in one step and comprises an .alpha.-methylstyrene-acrylonitrile copolymer or an .alpha.-methylstyrene-styrene-acrylonitrile copolymer.
6. The impact modified thermoplastic polyurethane molding compositions of claim 1, wherein the grafting basis (B2) is prepared in two steps from a styrene homopolymer in the first step and an .alpha.-methylstyrene-acrylonitrile copolymer in the second step.
7. The impact modified thermoplastic polyurethane molding compositions of claim 1, wherein the thermoplastic polyurethane elastomer (A) is prepared by reacting:
a) organic diisocyanates;
b) polyhydroxyl compounds having molecular weights of from 500 to 8,000; and c) chain extending agents having molecular weights of from 60 to 400;
in an equivalent ratio of NCO groups from said organic diisocyanate (a) to the total hydroxyl groups of component (b) and (c) of from 0.8:1.0 to 1.2:1Ø
a) organic diisocyanates;
b) polyhydroxyl compounds having molecular weights of from 500 to 8,000; and c) chain extending agents having molecular weights of from 60 to 400;
in an equivalent ratio of NCO groups from said organic diisocyanate (a) to the total hydroxyl groups of component (b) and (c) of from 0.8:1.0 to 1.2:1Ø
8. The impact modified thermoplastic polyurethane molding compositions from claim 7, wherein the thermoplastic polyurethane elastomer (A) is prepared by reacting:
a) aromatic isocyanates with;
b) polyhydroxy compounds selected from the group consisting of essentially linear polyhydroxyl compounds having 2 to 6 carbon atoms in the alkylene radical and molecular weights of 500 to 6,000 and hydroxyl group containing polytetrahydrofuran having a molecular weight of from 500 to 8,000; and c) aliphatic diols having from 2 to 12 carbon atoms.
a) aromatic isocyanates with;
b) polyhydroxy compounds selected from the group consisting of essentially linear polyhydroxyl compounds having 2 to 6 carbon atoms in the alkylene radical and molecular weights of 500 to 6,000 and hydroxyl group containing polytetrahydrofuran having a molecular weight of from 500 to 8,000; and c) aliphatic diols having from 2 to 12 carbon atoms.
9. The impact modified thermoplastic polyurethane molding composition from claim 8 wherein the thermoplastic polyurethane elastomer (A) is prepared by reacting:
a) 4,4'diphenylmethane diisocyanate with;
b) a polyalkylene glycol polyadipate having from 2 to 6 carbons in the alkylene radical; and c) 1,4-butanediol.
a) 4,4'diphenylmethane diisocyanate with;
b) a polyalkylene glycol polyadipate having from 2 to 6 carbons in the alkylene radical; and c) 1,4-butanediol.
10. The impact modified thermoplastic polyurethane molding compositions of claim 1, wherein the thermoplastic polyurethane elastomer (A) is prepared employing a conveyor process.
11. The impact modified thermoplastic polyurethane molding compositions of claim 1, wherein the thermoplastic polyurethane (A) has a Shore D hardness of from 40 to 80.
12. A process for the preparation of said impact modified thermoplastic polyurethane molding compositions of claim 1, comprising: melting together components (A) and (B) and optionally (C) in a conventional mixing device at temperatures ranging from about 160 to 250°C having a residency time of from 0.5 to 10 minutes.
13. A process for the preparation of said impact modified thermoplastic polyurethane molding compositions as claimed in claim 1, wherein said graft polymer (B) is emulsified or dispersed in component (A) and optionally (C).
14. The impact modified thermoplastic polyurethane molding compositions as claimed in claim 1, wherein said compositions are used in the preparation of molded products having improved cold temperature flexibility.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE3908237A DE3908237A1 (en) | 1989-03-14 | 1989-03-14 | IMPACT MODIFIED THERMOPLASTIC POLYURETHANE MOLDING MATERIALS, METHOD FOR THEIR PRODUCTION AND THEIR USE |
| DEP3908237.7 | 1989-03-14 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2011871A1 true CA2011871A1 (en) | 1990-09-14 |
Family
ID=6376290
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002011871A Abandoned CA2011871A1 (en) | 1989-03-14 | 1990-03-09 | Impact modified thermoplastic polyurethane molding compositions, a process for their preparation and their use |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0387590B1 (en) |
| JP (1) | JPH02281073A (en) |
| AT (1) | ATE109181T1 (en) |
| CA (1) | CA2011871A1 (en) |
| DE (2) | DE3908237A1 (en) |
| ES (1) | ES2057212T3 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6037409A (en) * | 1996-10-31 | 2000-03-14 | Bayer Corporation | Thermoformed article having low gloss and a composition for its preparation |
| WO2021110922A1 (en) * | 2019-12-05 | 2021-06-10 | Basf Se | Ultra-light skiing boots |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH03259947A (en) * | 1990-03-08 | 1991-11-20 | Sumitomo Dow Ltd | Resin composition excellent in antistatic property |
| DE4017571A1 (en) * | 1990-05-31 | 1991-12-05 | Bayer Ag | THERMOPLASTIC, FLEXIBLE POLYURETHANE COMPOSITIONS AND METHOD FOR THEIR PRODUCTION |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2436258A1 (en) * | 1974-07-27 | 1976-02-12 | Bayer Ag | Thermoplastic moulding-deep drawing compsn. - contg. aromatic polycarbonate-urethane and polymer obtd. by grafting monomers onto rubber |
| DE2854407A1 (en) * | 1978-12-16 | 1980-06-26 | Bayer Ag | THERMOPLASTIC CHEMICAL MATERIAL AND METHOD FOR THE PRODUCTION THEREOF |
-
1989
- 1989-03-14 DE DE3908237A patent/DE3908237A1/en not_active Withdrawn
-
1990
- 1990-02-26 EP EP90103744A patent/EP0387590B1/en not_active Expired - Lifetime
- 1990-02-26 AT AT90103744T patent/ATE109181T1/en not_active IP Right Cessation
- 1990-02-26 ES ES90103744T patent/ES2057212T3/en not_active Expired - Lifetime
- 1990-02-26 DE DE59006543T patent/DE59006543D1/en not_active Expired - Lifetime
- 1990-03-09 CA CA002011871A patent/CA2011871A1/en not_active Abandoned
- 1990-03-14 JP JP2061326A patent/JPH02281073A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6037409A (en) * | 1996-10-31 | 2000-03-14 | Bayer Corporation | Thermoformed article having low gloss and a composition for its preparation |
| WO2021110922A1 (en) * | 2019-12-05 | 2021-06-10 | Basf Se | Ultra-light skiing boots |
| US11766089B2 (en) | 2019-12-05 | 2023-09-26 | Basf Se | Ultra-light skiing boots |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0387590A3 (en) | 1990-10-24 |
| ATE109181T1 (en) | 1994-08-15 |
| ES2057212T3 (en) | 1994-10-16 |
| JPH02281073A (en) | 1990-11-16 |
| EP0387590A2 (en) | 1990-09-19 |
| DE3908237A1 (en) | 1990-09-20 |
| DE59006543D1 (en) | 1994-09-01 |
| EP0387590B1 (en) | 1994-07-27 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Discontinued |