Methanol-terminated polymers containing silane

Patent metadata

Field	Value
Publication number	US-9587059-B2
Application number	US-201113885073-A
Country	US
Kind code	B2
Filing date	Nov 11, 2011
Priority date	Nov 16, 2010
Publication date	Mar 7, 2017
Grant date	Mar 7, 2017

Abstract

The present invention relates to polymers functionalized by terminal groups, where these have, at the chain end, a silane-containing carbinol group of the formula (I)

where
R 1 , R 2 , R 3 , R 4 are identical or different and are H, alkyl moieties, cycloalkyl moieties, aryl moieties, alkaryl moieties and aralkyl moieties, where these can comprise heteroatoms such as O, N, S, Si,
A is a divalent organic moiety which can comprise, alongside C and H, heteroatoms such as O, N, S, Si.

First claim

The invention claimed is:

1. Polymers functionalized by terminal groups, the polymers comprising, at a chain end, a silane-containing carbinol terminal group of the formula (I)

or a metal salt thereof of the formula (II)

where
R 1 , R 2 , R 3 , R 4 are identical or different and are H, alkyl moieties, cycloalkyl moieties, aryl moieties, alkaryl moieties and aralkyl moieties, where these optionally comprise heteroatoms selected from O, N, S, and Si,
A is a divalent organic moiety optionally comprising heteroatoms selected from O, N, S, and Si,
n is an integer from 1 to 4, and
M is a metal or semimetal of valency from 1 to 4,

wherein the polymers are diene polymers or diene copolymers of dienes and vinylaromatic monomers.

2. The polymers functionalized by terminal groups according to claim 1 , wherein M is Li, Na, K, Mg, Ca, Fe, Co, Ni, Al, Nd, Ti, Si, or Sn.

3. The polymers functionalized by terminal groups according to claim 1 , wherein the diene polymer is a polybutadiene, a polyisoprene, a butadiene-isoprene copolymer, a butadiene-styrene copolymer, an isoprene-styrene copolymer or a butadiene-isoprene-styrene terpolymer.

4. Polymers functionalized by terminal groups, the polymers comprising diene polymers or diene copolymers of dienes and vinylaromatic monomers functionalized with functionalization reagent comprising one or more 1-oxa-2-silacycloalkanes, and the terminal groups are of the formula (I) and/or (II)

where
R 1 , R 2 , R 3 , R 4 are identical or different and are H, alkyl moieties, cycloalkyl moieties, aryl moieties, alkaryl moieties and aralkyl moieties, where these optionally comprise heteroatoms selected from O, N, S, and Si,
A is a divalent organic moiety optionally comprising heteroatoms selected from O, N, S, and Si,
n is an integer from 1 to 4, and
M is a metal or semimetal of valency from 1 to 4.

5. The polymers functionalized by terminal groups according to claim 4 , wherein the 1-oxa-2-silacycloalkanes are compounds of the general formula (III)

where
R 1 , R 2 , R 3 , R 4 are identical or different and are H, alkyl moieties, cycloalkyl moieties, aryl moieties, alkaryl moieties and aralkyl moieties, where these optionally comprise heteroatoms selected from O, N, S, and Si, and
A is a divalent organic moiety optionally comprising heteroatoms selected from O, N, S, and Si.

6. The polymers functionalized by terminal groups according to claim 5 , wherein the polymers have average molar masses (number average) of 10,000 to 2,000,000 g/mol.

7. The polymers functionalized by terminal groups according to claim 6 , wherein the polymers have glass transition temperatures of −110° C. to +20° C.

8. The polymers functionalized by terminal groups according to claim 7 , wherein the polymers have Mooney viscosities [ML 1+4 (100° C.)] of 10 to 200.

9. A process for producing the polymers functionalized by terminal groups according to claim 1 , the process comprising functionalizing reactive polymer chain ends of diene polymers or diene copolymers of dienes and vinylaromatic monomers with one or more 1-oxa-2-silacycloalkanes (functionalization reagents).

10. The process according to claim 9 , further comprising functionalizing the polymers after conclusion of polymerization, wherein the 1-oxa-2-silacycloalkanes are compounds of the general formula (III)

where
R 1 , R 2 , R 3 , R 4 are identical or different and are H, alkyl moieties, cycloalkyl moieties, aryl moieties, alkaryl moieties and aralkyl moieties, where these optionally comprise heteroatoms selected from O, N, S, and Si, and
A is a divalent organic moiety optionally comprising heteroatoms selected from O, N, S, and Si.

11. The process according to claim 9 , further comprising using an excess of the functionalization reagents.

12. The process according to claim 9 , further comprising using stoichiometric amounts or substoichiometric amounts of the functionalization reagents.

13. The process according to claim 9 , wherein the process comprises functionalizing the polymers with 0.005 to 2% by weight of the functionalization reagents based on the amount of polymer having reactive polymer chain ends.

14. The process according to claim 9 , further comprising adding coupling reagents for reaction with the reactive polymer chain ends.

15. Vulcanizable rubber compositions comprising the polymers according to claim 1 , and one or more of antioxidants, oils, fillers, rubbers and/or rubber auxiliaries.

16. Vulcanizable rubber compositions comprising polymers functionalized by carbinol terminal groups of the formula (I)

or metal salts thereof of the formula (II)

where
R 1 , R 2 , R 3 , R 4 are identical or different and are H, alkyl moieties, cycloalkyl moieties, aryl moieties, alkaryl moieties and aralkyl moieties, where these optionally comprise heteroatoms selected from O, N, S, and Si,
A is a divalent organic moiety optionally comprising heteroatoms selected from O, N, S, and Si,
n is an integer from 1 to 4,
M is a metal or semimetal of valency from 1 to 4, and

wherein the polymers are diene polymers or diene copolymers of dienes and vinylaromatic monomers.

17. The polymers functionalized by terminal groups according to claim 6 , wherein the average molar masses are 100,000 to 1,000,000 g/mol.

18. The polymers functionalized by terminal groups according to claim 7 , wherein the glass transition temperatures are −110° C. to 0° C.

19. The polymers functionalized by terminal groups according to claim 8 , wherein the Mooney viscosities are from 30-150 Mooney units.

Assignees

• Steinhauser Norbert
• Arlanxeo Deutschland Gmbh

Inventors

• Steinhauser Norbert

Classifications

• C08K3/36

  Silica · CPC title

• C08L15/00

  Compositions of rubber derivatives (C08L11/00, C08L13/00 take precedence) · CPC title

• C08F2/38

  Polymerisation using regulators, e.g. chain terminating agents {, e.g. telomerisation} · CPC title

• C08F236/10 Primary

  with vinyl-aromatic monomers · CPC title

• C08L9/00

  Compositions of homopolymers or copolymers of conjugated diene hydrocarbons · CPC title