CA2025010A1 - Polyurethane elastomers of low hardness - Google Patents

Polyurethane elastomers of low hardness

Info

Publication number
CA2025010A1
CA2025010A1 CA 2025010 CA2025010A CA2025010A1 CA 2025010 A1 CA2025010 A1 CA 2025010A1 CA 2025010 CA2025010 CA 2025010 CA 2025010 A CA2025010 A CA 2025010A CA 2025010 A1 CA2025010 A1 CA 2025010A1
Authority
CA
Canada
Prior art keywords
thermoplastic polyurethane
polyester
omega
alpha
dicarboxylic acid
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.)
Abandoned
Application number
CA 2025010
Other languages
French (fr)
Inventor
Richard Weider
Thomas Scholl
Ulrich Eisele
Rolf Dhein
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Bayer AG
Original Assignee
Individual
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Publication of CA2025010A1 publication Critical patent/CA2025010A1/en
Abandoned legal-status Critical Current

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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
    • C08G18/28—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
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/664—Compounds of group C08G18/42 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
    • 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
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • 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
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4205—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups
    • C08G18/423—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing cycloaliphatic groups
    • C08G18/4233—Polycondensates having carboxylic or carbonic ester groups in the main chain containing cyclic groups containing cycloaliphatic groups derived from polymerised higher fatty acids or alcohols

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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)
  • Polyurethanes Or Polyureas (AREA)
  • Materials For Medical Uses (AREA)

Abstract

Mo3449 LeA 27,126 POLYURETHANE ELASTOMERS OF LOW HARDNESS
ABSTRACT OF THE DISCLOSURE
This invention relates to substantially linear thermoplastic polyurethanes prepared by a process comprising reacting organic polyisocyanates; at least one polyester derivative having at least two isocyanate reactive hydrogen atoms, wherein said polyester derivative is a polyester of an .alpha.,.omega.-dicarboxylic acid containing a total of at least 16 carbon atoms and a non-vicinal diol, in an amount such that the proportion of the .alpha.,.omega.-dicarboxylic acid is greater than 35% by weight based on the total quantity of thermoplastic polyurethane; and chain lengthening agents having no phenolic OH groups. This invention also relates to the process used to prepare such thermoplastic polyurethanes.
This invention further relates to the use of the thermoplastic polyurethanes for medical purposes.

Mo3449

Description

2Q2~9 Mo3449 LeA 27,126 POLYURETHANE ELASTOMERS OF LOW HARDNESS
BACKGROUND OF THE INVENTION
This invention relates to polyurethane elastomers of low hardness, to a process for their preparation, and to their 5 use.
The hardness values obtainable with polyurethane elastomers prepared according to known methods are in the range of about 80 Shore A to 75 Shore D and thus cover a range from typical rubber elastomers (20 to 80 Shore A) to rigid synthetic resins (greater than 55 Shore D).
Hardness is determined mainly by the proportion of the hard phase formed by the isocyanate and chain lengthening agent. At values below 80 Shore A, properties are markedly deteriorated. If the proportion of hard phase is reduced while 15 the polydiol content is kept constant, the dimensional - stability under heat deteriorates because of the partial miscibility of the hard phase with the polydiol component. If the hard phase component is reduced due to an increase in the mGlecular weight of the polydiol component, the flexibility of 20 the product in the cold deteriorates because of the increasing tendency to crystallization of the polydiols with increasing molecular weight. See also Becker/Braun, Kunststoffhandbuch, Volume 7, Polyurethane, page 36, Carl Hanser Verlag, Munich, Vienna, 1983.
2s Matrix materials of great hardness are disclosed in German Offenlegungsschrift 3,513,980. These materials are obtainable by the reaction of isocyanates, phenolic chain lengthening agents, and soft segment formers based on dimerized and/or trimerized fatty acids. The use of a dimeric fatty acid 3~ polyol with a high trimer content in a polyurethane lacquer which has improved resistance to chemicals is described in U.S.
Patent 3,349,049. The introduction of small proportions of dimeric fatty acid polyols is described in European Application 35376RH0609 . .
2~25~ ~

156,665 (corresponding to U.S. Patent 4,602 079). The proportion of dimeric fatty acid is at most 35% by weight. The use of higher proportions of predominantly dimeric fatty acid is not obvious since it is known that large proportions of polydiols having a predominantly aliphatic character, such as OH-terminated polybutadiene or its hydrogenated form, give rise to materials that have only moderate mechanical properties ("strength") caused by poor miscibility with the hard phase.
Houben-Weyl, Handbuch der organischen Chemie, Volume E20, pages o 1569 and 1599.
Isocyanate-modified polyesters based on a glycol and a polymeric fatty acid are disclosed in U.S. Patent 3,264,236.
Soft polyurethane elastomers having high dimensional stability under heat, excellent flexibility in the cold, and high elasticity have not, however, been previously known in the art.
It is an object of the present invention to provide soft, highly elastic polyurethane elastomers having high dimensional stability under heat and excellent flexibility in the cold.
SUMMARY OF THE INVENTION
This invention relates to thermoplastic polyurethanes that are at least substantially linear in structure prepared by a process comprising reacting (aJ organic polyisocyanates;
(b) at least one polyester derivative having at least two isocyanate reactive hydrogen atoms, wherein said polyester derivative is a polyester of an ~ dicarboxylic acid containing a total of at least 16 carbon atoms and a non-vicinal diol, in an amount such that the proportion of the ~,~-dicarboxylic acid is greater than 35% by weight based on the total quantity of thermoplastic polyurethane;
and (c) chain lengthening agents having no phenolic OH groups.

Mo3449 2 ~ 2 ~

Catalysts, other known addltives, and other isocyanate-reactive compounds having a molecular weight greater than 400 may optionally be included in the preparation of the thermoplastic polyurethanes of the invention.
This invention further relates to a process for the preparation of thermoplastic polyurethanes having a substantially linear structure by the reaction of the organic polyisocyanates (a) with the polyester derivatives (b) and the chain lengthening agents (c).
Yet another object of this invention is the use of the thermoplastic polyurethanes according to the invention for medical purposes.
DETAILED DESCRIPTION OF THE INVENTION
In a preferred embodiment, the thermoplastic polyurethanes according to the invention have a hardness of less than about 80 Shore A, preferably less than 75 Shore A.
These thermoplastic polyurethanes are substantially linear and preferably have a volume flow index ("MVI") of at least 0.3 cm3/10 min (preferably at least 1 cm3/10 min), as determined at l9O-C with a testing force of 10 kp (DIN 53735; ISO 1132).
Preferred polyester derivatives (b) are polyesters, polyester carbonates, polyetheresters, and polyetherester carbonates containing terminal OH or NH2 groups. Particularly preferred polyesters (b) have an acid number below about 2 and a hydroxyl number of from about 11 to about 170.
Preferred ~ dicarboxylic acids used to prepare the polyester derivatives (b) include dimeric fatty acids obtained by reductive dimerization of unsaturated aliphatic monocarboxylic acids, preferably monocarboxylic acids having about 8 to about 22 carbon atoms and most preferably oleic acids. The trimer content formed in the reaction is no more than about 5% by weight based on the dimeric fatty acid, preferably no more than 1.5% by weight.
The polyester derivatives (b) to be used according to the invention may be obtained in known manner by condensation Mo3449 2~2~

of ~ dicarboxylic acids with non-vicinal diols, optionally with the addition of diaryl or dialkyl carbonates or phosgene.
The OH end groups obtained in the reaction may optionally be replaced by NH2 groups.
~he polyester derivatives to be used according to the invention may contain other aliphatic dicarboxylic acids in addition to the dimeric acids (for example, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, dodecane diacid, or mixtures thereof), but pure dimeric acid is o preferably used. Examples of non-vicinal diols suitable for the condensation reaction include ethylene glycol, 1,3- and 1,2-propanediol, di-, tri-, tetra-, and octa-ethylene glycol, dipropylene glycol, tripropylene glycol, 1,4-butanediol, 1,3-and 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol, 1,6-hexanediol, and higher, optionally branched, aliphatic diols. The molecular weights of components (b) may be from about 700 to about 10,000.
The organic polyisocyanates (a) include those used in previously known processes and are described e.g. in 20 . Kunststoff-handbuch, Volume VII, Polyurethane, Hanser Verlag, Munich, 1983, or in Houben-Weyl, Makromolekulare Stoffe, Volume E20. Aromatic or aliphatic diisocyanates, especially bis(iso-cyanatophenyl)methane, are preferably used. Other diiso-cyanates, however, may also be used, including aliphatic diisocyanates such as tetra- or hexamethylene diisocyanate, trimethylhexamethylene diisocyanate; cycloaliphatic diiso-cyanates such as cyclohexyl diisocyanate, isophorone diiso-cyanate or dicyclohexylmethane diisocyanate; or aromatic diiso-cyanates such as benzene diisocyanate, toluene diisocyanate, dichlorodiphenylmethane diisocyanate, dimethyldiphenylmethane diisocyanate, or dibenzyldiisocyanate.
The chain lengthening agents (c) are preferably bifunctional polyols such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclo-hexanedimethanol, hydroquinone-bis(2-hydroxyethyl) ether, and Mo3449 2~2 1,5-bis(2-hydroxyethoxy)naphthalene. The preferred ch~in lengthening agents have a molecular weight of from about 32 to about 399~ preferably from 62 to 220.
In one particularly preferred embodiment~ polyiso-cyanate (a~ is an isocyanate based on diphenylmethane and the chain lengthening agent (c) is butanediol.
In another preferred embodiment, components (a), (b), and (c) are substantially bifunctional and from about 0.9 to about 1.2 equivalents of isocyanate-reactive compounds are used per isocyanate equivalent.
Known catalysts, such as organic or inorganic tin compounds, amines, or alkali metal compounds, are optionally used for the preparation of polyurethanes. Other additives, such as blowing agents, stabilizers, emulsifiers, dyes, pigments, and fillers may also be used in known manner.
The thermoplastic polyurethanes according to the invention may be prepared by various methods. In one preferred embodiment, the polyurethane thermoplast is prepared by the band or screw process. See Becker/Braun, Kunststoff-Handbuch, Volume 7, Polyurethane, Chapter 8.2.1, pages 428 et seq, Carl Hanser Verlag, Munich, Vienna, 1983. A double screw kneading machine is used in a preferred embodiment.
The polyurethane-forming components may be introduced into the extruder at one feed point or at several feed points.
The components may be introduced into the screw machine either separately or as a pre-mix. See German Offenlegungsschrift 2,842,806. In a particularly preferred process, a prepolymer is first formed from isocyanate (a) and polyester derivative (b) and the chain lengthening agent is then added to the 30 prepolymer.
Apart from the low hardness and high elasticity compared with polyurethane elastomers prepared without dimeric fatty acids or with only small proportions of dimeric fatty acids, the polyurethane elastomers according to the invention 35 are also distinguished by their good compatibility with body Mo3449 2~ 2 ~. Q ~ ~

tissues and blood, which is due to the reduced surface tension, and their great durability when in contact with body fluids.
The elastomers of the invention are therefore particularly suitable for the manufacture of medical equipment such as blood bags, catheters, pacemaker leads, and artificial blood vessels or tubes to be inserted intravenously. Pharmacologically valuable substances may be incorporated in the materials, in particular anti-coagulants such as heparin, immunosuppressive drugs, antibiotics, or other known pharmacologically active o ingredients described, for example, in Polymer Science and Technology, Volume 34, "Polymers in Medicine IIn, Plenum Press, New York, 1983.
The following examples further illustrate details for the preparation of the compositions of this invention. The invention, which is set forth in the foregoing disclosure, is not to be limited either in spirit or scope by these examples.
Those skilled in the art will readily understand that known variations of the conditions and processes of the following preparative procedures can be used to prepare these 20 - compositions. Unless otherwise noted, all temperatures are degrees Celsius and all percentages are percentages by weight.
EXAMPLES
General Method of Preparation: Polyester component (b) (having compositions as described below) (0.~5 mole) was reacted with the total quantity of bis(4-isocyanatophenyl)-methane ("MDI~) (or other polyisocyanate, if indicated) at 100-C to form a prepolymer. The quantity of chain lengthening agent (c) equivalent to the remaining NCO groups was added to the melt at 110 C and the mi~ture was briefly degassed, poured into a mold, and tempered at llO-C for 8 hours. Plates 1 or 2 mm in thickness were produced by compression molding at 200-C
for determination of mechanical properties.
Comparison examples were prepared using a polyester diol of adipic acid and butanediol (OH number of 49.7) instead of component (b).
Mo3~49 2~23~ ~

The low hardness of the polyurethanes according to the invention is evident from the following Examples.
~xamPle 1 The procedure described above was carried out using 5 butanedio~ as the chain lengthening agent (c) and as component (b) a polyester having an OH number of 49.2 prepared from (1) hydrogenated dimeric fatty acid with acid number 197 (trimer content 1% and monomer content 0.1%) and (2) butanediol. The dimeric fatty acid had been obtained by dimerization of fatty acids and contains 36 carbon atoms (CAS Registry Number 68783-41-5, iodide value of 7).
The data listed in the following Table show that the thermoplastic polyurethanes obtained were surprisingly soft, in view of the percentage content of hard segment.

g MDI g Butane- Polyester X Hard Hardness diol OH number segment Shore A Shore D

37.5 9 49.2 28.92 80 28 13.5 49.2 35.71 85 30 62.5 18 50.7 41.32 89 39 22.5 50.7 46.88 92 44 Similar properties were obtained using as component ~b) a similar polyester having an OH number of 50.7.
When an adipic acid polyester having an OH number of 49.7 is used instead of the polyester derivative to be used according to the invention, the product obtained with the same proportion of hard segment is less soft.
Example 2 A thermoplastic polyurethane was prepared as described in Example 1 except that the polyester (b) was a polyester having an OH number 37. The resultant thermoplastic polyurethane had the following properties:

Mo344g 2 ~

% Hard segment: 23.5 Shore A hardness: 72 Tensile strength: 17 MPa Melting point of hard segment: 150C
Brittleness point: -40C
Example 3 A thermoplastic polyurethane was prepared as described in Example 1 except that the polyester (b) was a polyester having an OH number 28 prepared from the dimeric fatty acid from Example 1 and neopentyl glycol. The resultant thermoplastic polyurethane had the following properties:
% Hard segment: 19 Shore A hardness: 61 Tensile strength: 12 MPa Melting point of hard segment: 145C
Brittleness point: -40C
Thermoplastic polyurethanes having the degree of softness shown in Examples 2 and 3 are not obtained when conventional polyols are used. A polyurethane prepared from 20 the comparison polyester of Example 1 and containing a hard segment proportion of 20.8% by weight had a Shore A hardness of 94.
Example 4 A polyester having an OH number of 34.8 prepared from 25 the dimeric acid from Example 1 and ethylene glycol was used as component (b). The resultant polyurethane had a hard segment content of 22.4% and a Shore A hardness of 60.
Example 5 A polyester having an OH number of 27.0 prepared from 30 the dimeric acid from Example I and hexanediol was allowed to react with hexamethylene diisocyanate instead of bis(4-iso-cyanatophenyl)methane with the aid of butanediol as chain lengthening agent. The resultant product had a hard segment content of 14.2% and a Shore A hardness of 66.

Mo3449 2 ~ Q ~ ~

Example 6 Example 5 was repeated but using 1,4-bis(2-hydroxy-ethoxy)benzene instead of butanediol as chain lengthening agent. The resultant polyurethane had a hard segment content of 13% and a Shore A hardness of 76.
Example 7 A polyether ester haYing an OH number of 34.7 prepared from the dimeric acid from Example I and diethylene glycol was used as component tb). The resultant polyurethane o had a hard segment content of 22.4% and Shore A hardness of 68.
Example 8 A polyester having an OH number of 20 prepared from the dimeric acid from Example I and hexanediol was used as component (b). The resultant polyurethane had a hard segment content of 14.2% and Shore A hardness of 53.
Example 9 A thermoplastic polyurethane was prepared as described in Example 1 except that the polyester derivative (b) had an OH number of 45.7. The resultant thermoplastic polyurethane had a hard segment content of 27.5%. The interfacial tension of this polyurethane with water was 24.6 mN/m.
Conventional thermoplastic polyurethanes have a higher interfacial tension and are therefore less suitable for 2S medical implants.
Examp,le~ 10 A polyester prepared from the dimeric fatty acid of Example 1 and hexanediol (OH number 30) was used. In addition, bis(4-isocyanatocyclohexyl)methane was used instead of MDI. As chain lengthening agent, butanediol was used. The following results were obtained for the resultant polyurethane:
% Hard segment: 31 Shore A hardness: 71 % Elongation 500 Tensile strength: 2~.7 MPa Mo3449 2 ~ ~'3 ~
-]O-The elastomer obtained was transparent.
Example 11 Polyurethanes were prepared as in Example 10 except for using MDI as the polyisocyanate and different percentages 5 by weight of the hard segment (as indicated). The resultant polyurethanes had the following properties:
ExamDle 11a Example 11b % Hard segmen~: 25.8 16.1 Shore A hardness: 65 34 % Elongation 744 822 Tensile strength: 17 MPa 12 MPa Tear resistance (DIN 53,515)25 KN/m20 KN/m % Compression set (24 h, 70C; DIN 53,517) 45 52 ExamDle 12 Example 11 was repeated using a hard segment percentage by weight of 18.3. The resultant polyurethane (compound 12a) had the following properties:
Shore A hardness: 59 20 . % Elongation 830 Tensile strength: 13 MPa As a comparison, a polyurethane elastomer (compound 12b) hav;ng a hard segment percentage of 29% was prepared by the general method described above from the polyesterdiol of 25 adipic acid (described in Example 1).
The permanent elongation of polyurethanes 12a and 12b were measured. The results are entered into the following Table:
12a 12b 12a 12b 12a 12b 12a 12b % Elongation100 100150 150 200 200 250 250 Permanent elongation 7 12 12 20 21 48 30 78 Mo3449

Claims (11)

1. A thermoplastic polyurethane that is at least substantially linear in structure prepared by a process comprising reacting (a) an organic polyisocyanate;
(b) at least one polyester derivative having at least two isocyanate reactive hydrogen atoms, wherein said polyester derivative is a polyester of an .alpha.,.omega.-dicarboxylic acid containing a total of at least 16 carbon atoms and a non-vicinal diol, in an amount such that the proportion of the .alpha.,.omega.-dicarboxylic acid is greater than 35% by weight based on the total quantity of thermoplastic polyurethane;
and (c) a chain lengthening agent having no phenolic OH groups.
2. A thermoplastic polyurethane according to Claim 1 wherein the polyester derivative (b) is a polyester, polyester carbonate, polyether ester, or polyether ester carbonate containing terminal OH or NH2 groups.
3. A thermoplastic polyurethane according to Claim 1 wherein the .alpha.,.omega.-dicarboxylic acid is a dimer of an unsaturated aliphatic monocarboxylic acid having at least 8 carbon atoms and having a trimer content of no more than 5% by weight.
4. A thermoplastic polyurethane according to Claim 1 wherein the polyester derivative (b) has an acid number below 2 and a hydroxyl number of from 11 to 170.
5. A thermoplastic polyurethane according to Claim 1 wherein polyisocyanate (a) is an isocyanate based on diphenylmethane and the chain lengthening agent (c) is butanediol.
6. A thermoplastic polyurethane according to Claim 1 wherein components (a) and (c) are substantially bifunctional and from about 0.9 to about 1.2 equivalents of isocyanate-reactive compounds are used per isocyanate equivalent.

Mo3449
7. A thermoplastic polyurethane according to Claim 1 wherein the thermoplastic polyurethane has a hardness of less than 80 Shore A.
8. A process for the preparation of a thermoplastic polyurethane having a substantially linear structure comprising reacting (a) an organic polyisocyanate;
(b) at least one polyester derivative having at least two isocyanate reactive hydrogen atoms, wherein said polyester derivative is a polyester of an .alpha.,.omega.-dicarboxylic acid containing a total of at least 16 carbon atoms and a non-vicinal diol, in an amount such that the proportion of the .alpha.,.omega.-dicarboxylic acid is greater than 35% by weight based on the total quantity of thermoplastic polyurethane;
and (c) a chain lengthening agent having no phenolic OH groups.
9. A process according to Claim 8 comprising first reacting polyisocyanate (a) and polyester derivative (b) to form a prepolymer and then adding chain lengthening agent (c) to said prepolymer.
10. A method comprising manufacturing medical equipment from a thermoplastic polyurethane according to Claim 1.
11. A method comprising incorporating pharmacologically valuable substances into a thermoplastic polyurethane according to Claim 1.

Mo3449
CA 2025010 1989-09-13 1990-09-10 Polyurethane elastomers of low hardness Abandoned CA2025010A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19893930523 DE3930523A1 (en) 1989-09-13 1989-09-13 POLYURETHANE ELASTOMERS WITH LOW HOLDER
DEP3930523.6 1989-09-13

Publications (1)

Publication Number Publication Date
CA2025010A1 true CA2025010A1 (en) 1991-03-14

Family

ID=6389307

Family Applications (1)

Application Number Title Priority Date Filing Date
CA 2025010 Abandoned CA2025010A1 (en) 1989-09-13 1990-09-10 Polyurethane elastomers of low hardness

Country Status (4)

Country Link
EP (1) EP0417553A3 (en)
JP (1) JPH03119018A (en)
CA (1) CA2025010A1 (en)
DE (1) DE3930523A1 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6022939A (en) * 1994-12-23 2000-02-08 Bayer Aktiengesellschaft Thermoplastic polyurethanes with improved melt flow
US6790916B2 (en) 2002-02-23 2004-09-14 Bayer Aktiengesellschaft Process for the preparation of soft, low-shrinkage, thermoplastic polyurethane elastomers which can be easily released from the mold
WO2021110623A1 (en) * 2019-12-03 2021-06-10 Basf Se A medical tubing comprising thermoplastic polyurethane

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT1264880B1 (en) * 1993-06-24 1996-10-17 Tema Srl THERMOPLASTIC, ELASTIC, GUMMOUS POLYURETHANES WITH SHORE A HARDNESS LESS THAN 80
US5795633A (en) * 1994-08-22 1998-08-18 Nippon Zeon Co., Ltd. Material composition and shaped article
DE4446332A1 (en) * 1994-12-23 1996-06-27 Bayer Ag Thermoplastic polyurethanes with improved melt flow
DE19632925A1 (en) * 1996-08-16 1998-02-19 Bayer Ag Responsive masses with a long pot life
DE19939112A1 (en) * 1999-08-18 2001-02-22 Basf Ag Thermoplastic polyurethanes
CA2899226C (en) * 2013-02-04 2020-08-25 Lubrizol Advanced Materials, Inc. Clear hydrophobic tpu

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3264236A (en) * 1959-06-22 1966-08-02 Thiokol Chemical Corp p-tolylene dhsocyanate modified polyester polymer and method of making the same
US3689443A (en) * 1967-12-13 1972-09-05 Basf Wyandotte Corp Thermoplastically processable polyurethane elastomers
CA1030293A (en) * 1973-04-16 1978-04-25 Arthur J. Coury Polyurethanes and the coating of glass containers
US4423179A (en) * 1981-09-29 1983-12-27 Inmont Dimer acid based polyurethane coating compositions

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6022939A (en) * 1994-12-23 2000-02-08 Bayer Aktiengesellschaft Thermoplastic polyurethanes with improved melt flow
US6790916B2 (en) 2002-02-23 2004-09-14 Bayer Aktiengesellschaft Process for the preparation of soft, low-shrinkage, thermoplastic polyurethane elastomers which can be easily released from the mold
WO2021110623A1 (en) * 2019-12-03 2021-06-10 Basf Se A medical tubing comprising thermoplastic polyurethane

Also Published As

Publication number Publication date
JPH03119018A (en) 1991-05-21
EP0417553A2 (en) 1991-03-20
EP0417553A3 (en) 1991-05-02
DE3930523A1 (en) 1991-03-21

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