High strength polyisobutylene polyurethanes

Patent metadata

Field	Value
Publication number	US-9926399-B2
Application number	US-201314433974-A
Country	US
Kind code	B2
Filing date	Nov 21, 2013
Priority date	Nov 21, 2012
Publication date	Mar 27, 2018
Grant date	Mar 27, 2018

Abstract

An elastomeric polymer, comprising (1) a hard segment in the amount of 10% to 60% by weight of the elastomeric polymer, wherein the hard segment includes a urethane, urea, or urethaneurea; and (2) a soft segment in the amount of 40% to 90% by weight of the elastomeric polymer, wherein the soft segment includes a polyisobutylene macrodiol and/or diamine. Additionally disclosed is a method of forming a polyisobutylene-based thermoplastic urethane, comprising the steps of (a) reacting a polyisobutylene macrodiol and/or diamine with a diisocyanate to form a first reaction mixture; (b) combining a metal catalyst and a chain extender with the first reaction mixture to create a second reaction mixture, a molar ratio of the metal catalyst to the diisocyanate being greater than 0.0:1 and less than or equal to 0.4:1; and (c) reacting the second reaction mixture for a period of time sufficient to form the polyisobutylene-based thermoplastic urethane.

First claim

What is claimed is:

1. A polyisobutylene-based thermoplastic polyurethane, comprising:
(1) a hard segment in the amount of 10% to 60% by weight of the polyisobutylene-based thermoplastic polyurethane, wherein the hard segment includes a urethane, urea, or urethaneurea, and is the product of a reaction of a diisocyanate with a chain extender; and
(2) a soft segment in the amount of 40% to 90% by weight of the polyisobutylene-based thermoplastic polyurethane, wherein the soft segment consists essentially of a polyisobutylene macrodiol;

wherein the number average molecular weight of the polyisobutylene-based thermoplastic polyurethane is greater than or equal to about 40 kilodaltons; and
wherein the polydispersity index of the hard segment is between 2.04 and 2.29, inclusive.

2. The polyurethane of claim 1 , wherein the number average molecular weight of the elastomeric polymer is greater than or equal to 50 kilodaltons.

3. The polyurethane of claim 1 , wherein the polyisobutylene macrodiol or diamine is of the formula:

wherein:
each X is independently —OH, —NH 2 , or —NHR 4 ;
R 1 is an initiator residue;
R 2 , R 3 , and R 4 is, each independently, a C 1 -C 16 alkyl, a C 3 -C 16 cycloalkyl, a C 2 -C 16 alkenyl, a C 3 -C 16 cycloalkenyl, a C 2 -C 16 alkynyl, a C 3 -C 16 cycloalkynyl, or a C 6 -C 18 aryl, wherein, for each occurrence, R 2 or R 3 is, independently, optionally substituted with one or more groups selected from halo, cyano, nitro, dialkylamino, trialkylamino, C 1 -C 16 alkoxy, and C 1 -C 16 haloalkyl; and
n and m are each, independently, integers from 1 to 500.

4. The polyurethane of claim 1 , wherein the hard segment is present in the amount of from about 30% to about 50% by weight of the elastomeric polymer.

5. The polyurethane of claim 1 , wherein the polyisobutylene macrodiol is hydroxyallyl telechelic polyisobutylene.

6. The polyurethane of claim 1 , wherein the polyisobutylene macrodiol is hydroxyalkyl telechelic polyisobutylene.

7. The polyurethane of claim 6 , wherein the polyisobutylene macrodiol is hydroxypropyl telechelic polyisobutylene.

8. The polyurethane of claim 1 , wherein the polyisobutylene macrodiamine is aminoallyl telechelic polyisobutylene.

9. The polyurethane of claim 1 , wherein the number average molecular weight of the polyisobutylene macrodiol is about 400 Da to about 6000 Da.

10. The polyurethane of claim 1 , wherein the number average molecular weight of the polyisobutylene macrodiol is about 1000 Da to about 3000 Da.

11. The polyurethane of claim 1 , wherein the diisocyanate includes at least one member selected from the group consisting of 4,4′-methylenephenyl diisocyanate; methylene diisocyanate; p-phenylene diisocyanate; cis-cyclohexane-1,4-diisocyanate; trans-cyclohexane-1,4-diisocyanate; a mixture of cis-cyclohexane-1,4-diisocyanate and trans-cyclohexane-1,4-diisocyanate; 1,6-hexamethylene diisocyanate; 2,4-toluene diisocyanate; cis-2,4-toluene diisocyanate; trans-2,4-toluene diisocyanate; a mixture of cis-2,4-toluene diisocyanate and trans-2,4-toluene diisocyanate; p-tetramethylxylene diisocyanate; and m-tetramethylxylene diisocyanate.

12. The polyurethane of claim 1 , wherein the chain extender includes at least one member selected from the group consisting of 1,4-bunatediol; 1,5-pentanediol; 1,6-hexanediol; 1,8-octanediol; 1,9-nonanediol; 1,10-decanediol; 1,12-dodecanediol; 1,4-cyclohexane dimethanol; p-xyleneglycol; and 1,4-bis(2-hydroxyethoxy)benzene.

13. The polyurethane of claim 1 , wherein the chain extender includes at least one member selected from the group consisting of 1,4-diaminobutane; 1,5-diaminopentane; 1,6-diaminohexane; 1,8-diaminooctane; 1,9-diaminononane; 1,10-diaminodecane; 1,12-diaminododecane; 1,4-diaminocyclohexane; 2,5-diaminoxylene; and isophoronediamine.

14. The polyurethane of claim 1 , wherein the diisocyanate is 4,4′-methylenephenyl diisocyanate and wherein the chain extender is 1,4-butanediol.

15. The polyurethane of claim 1 , wherein:
the polyisobutylene macrodiol is hydroxyallyl telechelic polyisobutylene; and
the hard segment includes a product of a reaction of 4,4′-methylenephenyl diisocyanate and 1,4-butanediol.

Assignees

• Univ Massachusetts

Inventors

• Faust Rudolf
• Wei Xinyu

Classifications

• C08G18/6511

  compounds of group C08G18/3203 · CPC title

• C08G18/10

  Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step · CPC title

• C08F293/00 Primary

  Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule (on to polymers modified by introduction of unsaturated end groups C08F290/02) · CPC title

• C08G18/6204 Primary

  Polymers of olefins (unsaturated polymers of conjugated dienes C08G18/69) · CPC title

• C08G18/32

  Polyhydroxy compounds; Polyamines; Hydroxyamines · CPC title