Carbinol-terminated polymers containing allylamine

Patent metadata

Field	Value
Publication number	US-9718912-B2
Application number	US-201314399101-A
Country	US
Kind code	B2
Filing date	Apr 29, 2013
Priority date	May 9, 2012
Publication date	Aug 1, 2017
Grant date	Aug 1, 2017

Abstract

The present invention relates to diene polymers or diene copolymers, wherein the diene polymers or diene copolymers have, at the start of the polymer chains, tertiary amino groups of the formula (Ia), (Ib), (IIa) or (IIb)

where
R 1 , R 2 are the same or different and are each alkyl, cycloalkyl, aryl, alkaryl and aralkyl radicals which may contain heteroatoms such as O, N, S and/or Si, Z is a divalent organic radical which, as well as C and H, may contain heteroatoms such as O, N, S and/or Si, and, at the end of the polymer chains, silane-containing carbinol groups of the formula (III)

or metal salts thereof or semimetal salts thereof, where
R 3 , R 4 , R 5 , R 6 are the same or different and are each an H or alkyl, cycloalkyl, aryl, alkaryl and aralkyl radicals which may contain heteroatoms such as O, N, S and/or Si,
A is a divalent organic radical which, as well as C and H, may contain heteroatoms such as O, N, S and/or Si.

First claim

What is claimed is:

1. Diene polymers comprising:
at the start of the polymer chains, tertiary amino groups of the formula (Ia), (Ib), (IIa) or (IIb)

where
R 1 , R 2 are the same or different and are each alkyl, cycloalkyl, aryl, alkaryl and aralkyl radicals which may contain heteroatoms, and
Z is a divalent organic radical which, as well as C and H, may contain heteroatoms, and

at the end of the polymer chains, silane-containing carbinol groups of the formula (III)

 or
metal salts thereof or semimetal salts thereof, where
R 3 , R 4 , R 5 , R 6 are the same or different and are each an H or alkyl, cycloalkyl, aryl, alkaryl and aralkyl radicals which may contain heteroatoms, and
A is a divalent organic radical which, as well as C and H, may contain heteroatoms.

2. The diene polymers according to claim 1 , wherein the silane-containing carbinol groups of the formula (III) are in the form of metal salts of the formula (IV)

where
R 3 , R 4 , R 5 , R 6 are the same or different and are each an H or alkyl, cycloalkyl, aryl, alkaryl and aralkyl radicals which may contain heteroatoms,
A is a divalent organic radical which, as well as C and H, may contain heteroatoms,
N is an integer from 1 to 4, and
M is a metal or semimetal of valency 1 to 4.

3. The diene polymers according to claim 1 or 2 , 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. The diene polymers according to claim 2 , wherein:
the heteroatoms are selected from the group consisting of O, N, S, Si, and any combination thereof, and
M is selected from the group consisting of Li, Na, K, Mg, Fe, Co, Ni, Al, Nd, Ti, Si, Sn, and any combination thereof.

5. The diene polymers according to claim 1 , wherein:
the diene polymers have mean molar masses (number-average) of 10,000 to 2,000,000 g/mol,
the diene polymers have glass transition temperatures of −110° C. to +20° C., and
the diene polymers have Mooney viscosities [ML 1+4 (100° C.)] of 10 to 200 Mooney units.

6. The diene polymers according to claim 1 , wherein:
the diene polymers have mean molar masses (number-average) of 100,000 to 1,000,000 g/mol,
the diene polymers have glass transition temperatures of −110° C. to 0° C., and
the diene polymers have Mooney viscosities [ML 1+4 (100° C.)] of 30 to 150, Mooney units.

7. A process for preparing diene polymers according to claim 1 , the process comprising:
introducing functional groups at the end of the polymer chains by reaction of the polymer chains with functionalization reagents of one or more 1-oxa-2-silacycloalkanes, and
introducing the tertiary amino groups at the start of the polymer chains by reaction of the polymer chains with tertiary allylamine-containing polymerization initiators of the general formula (Va), (Vb), (VIa) or (VIb)

 where
R 1 , R 2 are the same or different and are each alkyl, cycloalkyl, aryl, alkaryl and aralkyl radicals which may contain heteroatoms,
Z is a divalent organic radical which, as well as C and H, may contain heteroatoms, and
M is Li, Na, K.

8. The process according to claim 7 , wherein the 1-oxa-2-silacycloalkanes are compounds of the general formula (VII)

where
R 3 , R 4 , R 5 , R 6 are the same or different and are each H, alkyl, cycloalkyl, aryl, alkaryl and aralkyl radicals which may contain heteroatoms, and
A is a divalent organic radical which, as well as C and H, may contain heteroatoms.

9. The process for preparing diene polymers according to claim 7 , further comprising:
obtaining the polymerization initiators by reaction of tertiary allylamines with organo-alkali metal compounds in situ or in a separate preforming step, and
reacting reactive ends of the polymer chains with one or more 1-oxa-2-silacycloalkanes.

10. The process according to claim 7 , wherein the 1-oxa-2-silacycloalkanes are added after completion of the polymerization.

11. The process according to claim 7 , wherein the anionic polymerization initiators are obtained by reaction of tertiary allylamines with organo-alkali metal compounds.

12. The process according to claim 9 , wherein the tertiary allylamine is N,N-dimethylallylamine, and the organo-alkali metal compound is butyllithium.

13. The process according to claim 9 , wherein:
the molar amount of tertiary allylamines is less than or equal to the molar amount of organo-alkali metal compounds, and
the amount of 1-oxa-2-silacycloalkanes is between 0.005-2% by weight, based on the amount of polymer having reactive ends of the polymer chains.

14. The process according to claim 9 , wherein:
the ratio of the molar amount of tertiary allylamines to the molar amount of organo-alkali metal compounds is 0.05-2.00:0.05-2.00, and
the amount of 1-oxa-2-silacycloalkanes is between 0.01-1% by weight, based on the amount of polymer having reactive ends of the polymer chains.

15. The process according to claim 7 , wherein coupling reagents are used for the reaction.

16. A method for producing vulcanizable rubber compositions, the method comprising producing the vulcanizable rubber compositions from diene polymers according to claim 1 .

17. Vulcanizable rubber compositions obtained according to claim 16 , wherein the vulcanizable rubber compositions additionally comprise ageing stabilizers, oils, fillers, rubbers and/or rubber auxiliaries.

18. Vulcanizable rubber compositions comprising diene polymers according to claim 1 or 2 .

19. Vulcanizable rubber compositions comprising functionalized diene polymers having tertiary amino groups of the formula (Ia), (Ib), (IIa) or (IIb) at the start of the polymer chains and functional groups of the formula (III) at the end of the polymer chains according to claim 1 .

20. Vulcanizable rubber compositions comprising functionalized diene polymers having tertiary amino groups of the formula (Ia), (Ib), (IIa) or (IIb) at the start of the polymer chains and functional groups of the formula (IV) at the end of the polymer chains according to claim 2 .

21. Vulcanizable rubber compositions comprising functionalized diene polymers having tertiary amino groups of the formula (Ia), (Ib), (IIa) or (IIb) at the start of the polymer chains and functional groups of the formula (III) and (IV) at the end of the polymer chains according to claim 2 .

22. A method for producing tyres, the method comprising producing at least tyre tread of the tyres from the vulcanizable rubber compositions according to claim 19 .

23. A method for producing moulded articles, the method comprising producing moulded articles from the vulcanizable rubber compositions according to claim 19 .

24. Tyres according to claim 22 .

25. Moulded articles obtainable according to claim 23 , wherein the moulded articles comprise ca

Assignees

• Arlanxeo Deutschland Gmbh

Inventors

• Steinhauser Norbert
• Gross Thomas
• Albino Fernanda

Classifications

• Y10T428/139

  Open-ended, self-supporting conduit, cylinder, or tube-type article · CPC title

• C08C19/44

  of polymers containing metal atoms exclusively at one or both ends of the skeleton · CPC title

• C08F236/10 Primary

  with vinyl-aromatic monomers · CPC title

• C08C19/25

  Incorporating silicon atoms into the molecule · CPC title

• B60C1/0016 Primary

  Compositions of the tread · CPC title