Photochemical preparation of hydroxyl-terminated polyisobutylenes and related methods and uses

Patent metadata

Field	Value
Publication number	US-9701781-B2
Application number	US-201414771021-A
Country	US
Kind code	B2
Filing date	Mar 4, 2014
Priority date	Mar 4, 2013
Publication date	Jul 11, 2017
Grant date	Jul 11, 2017

Abstract

The present invention relates to novel hydroxyl-terminated polyisobutylenes and methods of making and using them. The hydroxyl-terminated polyisobutylenes contain a sulfur unit, —S—, within each terminal end group. The well-defined, sulfur containing, primary hydroxyl-terminated polyisobutylenes of the present invention can be simply, rapidly, and essentially quantitatively obtained by subjecting the unsaturated telechelic PIBs and mercapto alcohols to UV light-activated thiol-ene reactions. The resultant sulfur containing, primary hydroxyl-terminated polyisobutylenes can then be used in the production of polyurethanes and like materials.

First claim

What is claimed is:

1. A telechelic polyisobutylene composition having at least one
primary alcohol end group, a single sulfur atom being present within each of the at least one primary alcohol end group.

2. The telechelic polyisobutylene composition of claim 1 wherein the sulfur atom is present within 3 carbon atoms of the alcohol unit in the primary alcohol end group.

3. The telechelic polyisobutylene composition of claim 2 , wherein the sulfur atom is present within 2 carbon atoms of the alcohol unit in The primary alcohol end group.

4. The telechelic polyisobutylene composition of claim 1 , further comprising an initiator core and at least two polyisobutylene chains extending from the initiator core, wherein each one of the at least two polyisobutylene chains is terminated with a primary alcohol end group having a sulfur atom contained therein.

5. The telechelic polyisobutylene composition of claim 4 wherein each one of the at least two polyisobutylene chains comprises an —S—CH 2 CH 2 —OH moiety within the primary alcohol end group.

6. The telechelic polyisobutylene composition of claim 4 wherein said initiator core is a difunctional aromatic initiator core and the telechelic polyisobutylene composition is linear and di-telechelic.

7. The telechelic polyisobutylene composition of claim 1 wherein the at least one primary alcohol end group has a chemical structural formula selected from the group consisting of:

wherein R comprises a polyisobutylene polymer chain.

8. The telechelic polyisobutylene composition of claim 1 having a formula selected from the group consisting of:

wherein n and n′ are each an integer from 2 to 5,000.

9. A telechelic polyisobutylene composition comprising the photochemical thiol-ene reaction product of:
a polyisobutylene polymer having at least one end group selected from —CH 2 —CH(CH 3 )═CH 2 , —CH═C(CH 3 ) 2 , and —CH 2 —CH═CH 2 and combinations; and
a mercapto alcohol, in the presence of UV light.

10. The telechelic polyisobutylene composition of claim 9 wherein the mercapto alcohol is 2-mercapto ethanol.

11. The telechelic polyisobutylene composition of claim 10 wherein said polyisobutylene polymer has a formula selected from the group consisting of:

wherein n and n′ are each an integer from 2 to 5,000.

12. A polyurethane composition having improved hydrolytic-oxidative stability comprising the reaction products of:
one or more telechelic polyisobutylenes having at least two alcohol-terminated end groups, the at least two alcohol-terminated end groups each having a single sulfur atom present therein; and
one or more diisocyanates.

13. The polyurethane composition of claim 12 wherein the one or more diisocyanates are selected from the group consisting of 4,4-methylene dicyclohexyl diisocyanate (HDMI), 4,4-methylene diphenyl diisocyanate (MDI), and combinations thereof.

14. The polyurethane composition of claim 13 , wherein each of the at least two alcohol-terminated end groups of the one or more telechelic polyisobutylenes includes an —S—CH 2 CH 2 —OH moiety.

15. The polyurethane composition of claim 12 , wherein the one or more telechelic polyisobutylenes are selected from the group consisting of:

wherein n and n′ are the same or different and are each an integer ranging from to 5,000.

16. A method of making a telechelic polyisobutylene composition having one or more alcohol-terminated end groups, each having a single sulfur atom contained therein, the method comprising:
(a) providing a polyisobutylene polymer having at least one end group selected from the end groups —CH 2 —CH(CH 3 )═CH 2 , —CH 2 ═C(CH 3 ) 2 , and CH 2 —CH═CH 2 , and combinations thereof;
(b) combining the polyisobutylene polymer with a stoichiometricly sufficient quantity of a mercapto alcohol to provide a mixture;
(c) irradiating the mixture with UV light.

17. The method of claim 16 wherein said mercapto alcohol is 2-mercapto ethanol.

18. The method of claim 16 , wherein the polyisobutylene polymer has a formula selected from the group consisting of:

wherein n and n′ are each an integer from 2 to 5,000.

19. A method for the production of a polyisobutylene-based polyurethane having improved hydrolytic-oxidative stability, the method comprising:
(a) providing a photochemically-prepared telechelic polyisobutylene having at least two primary alcohol-terminated end groups, wherein a single sulfur atom is present within each of the primary alcohol-terminated end groups;
and
(b) adding a diisocyanate selected from the group consisting 4,4-methylene dicyclohexyl diisocyanate (HDMI), 4,4-methylene diphenyl diisocyanate (MDI),
and combinations thereof, and a catalyst, to the photochemically-prepared telechelic polyisobutylene, to provide a polyurethane having improved hydrolytic-oxidative stability.

Assignees

• Kennedy Joseph
• Nugay Nihan
• Nugay Turgut
• Univ Akron

Inventors

• Kennedy Joseph
• Nugay Nihan
• Nugay Turgut

Classifications

• C08F110/10 Primary

  Isobutene · CPC title

• C08K5/5403

  containing no other elements than carbon or hydrogen · CPC title

• C08F2810/30

  leading to the formation or introduction of aliphatic or alicyclic unsaturated groups · CPC title

• C08G18/696 Primary

  containing heteroatoms other than oxygen and other than the heteroatoms of copolymerised vinyl monomers · CPC title

• C08G18/3206

  aliphatic · CPC title