Multivinylaminosilanes as branching agents for functionalized elastomeric polymers

Patent metadata

Field	Value
Publication number	US-2020055881-A1
Application number	US-201916663975-A
Country	US
Kind code	A1
Filing date	Oct 25, 2019
Priority date	Feb 18, 2015
Publication date	Feb 20, 2020
Grant date	—

Abstract

The present invention relates to novel polymerizable multivinylaminosilanes which are useful as branching agents for synthetic and natural rubber. The compounds of the invention can be used as such in the polymerization of conjugated diene monomers, optionally together with aromatic vinyl monomers, thus producing polymers, specifically elastomeric polymers, which can favorably be used in rubber articles such as tires.

First claim

1 . A multivinylaminosilane of the following Formula 1:
(A)-B n   (Formula 1)
wherein
A is an organic group having at least two amino groups;
each B is independently selected from a group —Si(R 1 )(R 2 )(R 3 ), wherein R 1 , R 2 and R 3 are each independently selected from vinyl, butadienyl, methyl, ethyl, propyl, butyl, hexyl, octyl, and benzyl, with the proviso that at least one of R 1 , R 2 and R 3 is selected from vinyl and butadienyl, wherein each group B is a substituent of an amino group of group A;
at least two of the amino groups of group A are each substituted with at least one group B;
n is an integer of at least 2;
all amino groups in group A are tertiary amino groups; and
wherein the multivinylaminosilane is not N,N′-bis(ethenyldimethylsilyl)-N,N′-dimethyl-1,2-ethanediamine.

2 . The multivinylaminosilane according to claim 1 , which is a compound selected from the following Formulas 1-1 to 1-5:

wherein
each of R 11 , R 12 , R 13 , R 14 and R 15 is independently selected from group B, C 1 -C 18 alkyl, C 6 -C 18 aryl, optionally C 1 -C 4 alkyl-substituted C 3 -C 12 heteroaryl, C 7 -C 18 aralkyl, —(R 4 ) a —O—(R 5 ) b , wherein each R 4 is independently C 1 -C 6 alkylene or C 6 -C 18 arylene, each R 5 is independently C 1 -C 6 alkyl or C 6 -C 18 aryl, and a and b are each 1, and —Si(R 6 )(R 7 )(R 8 ), wherein each of R 6 , R 7 and R 8 is independently selected from methyl, ethyl, propyl, butyl, hexyl, octyl, and benzyl, and wherein at least two of R 11 , R 12 , R 13 , R 14 and R 15 are group B;

each of R 9 and R 10 is independently selected from divalent ethylene, propylene, butylene, phenylene and —(CH 2 ) a′ —C 6 H 5 —(CH 2 ) b′ —, wherein each of a′ and b′ is an integer independently selected from 0 and 1; and
c is an integer selected from 0, 1, 2 and 3;

wherein the group —N< >N— is a 5- to 18-membered heterocyclic group which may be saturated or unsaturated and which may be substituted on any carbon atom of the ring with a C 1 -C 6 alkyl group, wherein heteroatomic groups, if present in the heterocyclic group, other than the two N atoms expressly shown in Formula 1-2 are selected from —N═, >NR 16 , —O—, —S— and >SiR 17 R 18 , wherein R 16 is selected from group B, C 1 -C 6 alkyl, phenyl and benzyl, and wherein each of R 17 and R 18 is independently selected from C 1 -C 6 alkyl, phenyl and benzyl;

wherein each of R 20 , R 21 and R 22 is independently selected from a single bond and a C 1 -C 10 alkylene group, d is an integer selected from 0, 1 and 2, d′ is an integer selected from 0 and 1, wherein d is 0 when d′ is 0, each group —N< >X— is independently selected from a 5- to 10-membered heterocyclic group which may be saturated or unsaturated and which may be substituted on any carbon atom of the ring with a C 1 -C 6 alkyl group, wherein each X is independently selected from —N—, —C═ and —CH—, and heteroatomic groups other than the two groups N and X expressly shown in Formula 1-3 are selected from —N═, >NR 16 , —O—, —S— and >SiR 17 R 18 , wherein R 16 is selected from C 1 -C 6 alkyl, group B, phenyl and benzyl, and wherein each of R 17 and R 18 is independently selected from C 1 -C 6 alkyl, phenyl and benzyl;

wherein D is a 5- to 10-membered carbocyclic or heterocyclic group which may be saturated or unsaturated and which may be substituted on any carbon atom of the ring with a C 1 -C 6 alkyl group, wherein heteroatomic groups are selected from —N═, >NR 16 , —O—, —S— and >SiR 17 R 18 , wherein R 16 is selected from C 1 -C 6 alkyl, group B, phenyl and benzyl, and wherein each of R 17 and R 18 is independently selected from C 1 -C 6 alkyl and phenyl, each group —N< >X— is independently selected from a 5- to 10-membered heterocyclic group which may be saturated or unsaturated and which may be substituted on any carbon atom of the ring with a C 1 -C 6 alkyl group, wherein each X is independently selected from —N—, —C═ and —CH—, R 23 is selected from a single bond and a divalent C 1 -C 10 alkylene group, and e is an integer selected from 2, 3 and 4;

wherein E is a 6- to 10-membered cycloaliphatic or aromatic group, each R′ is independently selected from a single bond and C 1 -C 2 alkylene, each R is independently selected from B, C 1 -C 4 alkyl and benzyl, and f is an integer selected from 2 and 3.

3 . The multivinylaminosilane according to claim 2 , wherein in Formula 1-1 each of R 11 , R 12 , R 13 , R 14 and R 15 is independently selected from group B and methyl; each of R 9 and R 10 is divalent ethylene; and c is an integer selected from 0, 1, 2 and 3.

4 . The multivinylaminosilane according to claim 2 , which is selected from

wherein each R is independently selected from B, C 1 -C 6 alkyl and benzyl;

wherein R is a C 1 -C 6 alkyl group; and

5 . The multivinylaminosilane according to claim 2 , wherein in Formula 1-4 D is selected from cyclopentyl, cyclohexyl, phenyl and tetrahydrofuranyl; each group —N< >X— is selected from piperidinyl and piperazinyl; R 23 is a single bond; and e is an integer selected from 2 and 3.

6 . The multivinylaminosilane according to claim 2 , wherein in Formula 1-5 E is selected from cyclohexyl and phenyl; R′ is a single bond; R is selected from B, C 1 -C 4 alkyl and phenyl; and f is an integer selected from 2 and 3, wherein each R is independently selected from B, C 1 -C 4 alkyl and phenyl.

7 . An initiator compound obtainable by reacting a multivinylaminosilane of the following Formula 1 with one or more organo-alkali metal compounds
(A)-B n   (Formula 1)
wherein
A is an organic group having at least two amino groups;
each B is independently selected from a group —Si(R 1 )(R 2 )(R 3 ), wherein R 1 , R 2 and R 3 are each independently selected from vinyl, butadienyl, methyl, ethyl, propyl, butyl, hexyl, octyl, and benzyl, with the proviso that at least one of R 1 , R 2 and R 3 is selected from vinyl and butadienyl, wherein each group B is a substituent of an amino group of group A;
at least two of the amino groups of group A are each substituted with at least one group B;
n is an integer of at least 2; and
all amino groups in group A are tertiary amino groups.

8 . A process for preparing the multivinylaminosilane of Formula 1 as defined in claim 1 , said process comprising reacting an amine with a silane of the following Formula 2 in the presence of a base:
X—Si(R 1 )(R 2 )(R 3 )  (Formula 2)
wherein
X is selected from Cl, Br, I, trifluoromethanesulfonate (OTf) and tosylate (OTos);
R 1 , R 2 and R 3 are each independently selected from vinyl, butadienyl, methyl, ethyl, propyl, butyl, hexyl, octyl, and benzyl, with the proviso that at least one of R 1 , R 2 and R 3 is selected from vinyl and butadienyl; and
the amine is a compound having at least two groups independently selected from a primary amino group and a secondary amino grou

Assignees

• Trinseo Europe Gmbh

Inventors

• Rossle Michael
• Doring Christian
• Thiele Sven K H
• Thielemann Dominique

Classifications

• C08F2/38

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

• C07F7/10 Primary

  containing nitrogen {having a Si-N linkage} · CPC title

• C08F236/10

  with vinyl-aromatic monomers · CPC title

• C08C19/44 Primary

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

• C08F297/044

  using a coupling agent · CPC title