Multivinylaminosilanes as branching agents for functionalized elastomeric polymers

Patent metadata

Field	Value
Publication number	US-10858377-B2
Application number	US-201615551519-A
Country	US
Kind code	B2
Filing date	Jan 20, 2016
Priority date	Feb 18, 2015
Publication date	Dec 8, 2020
Grant date	Dec 8, 2020

Abstract

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

First claim

The invention claimed is:

1. A multivinylaminosilane which is a compound selected from

wherein
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, phenyl and benzyl, with the proviso that at least one of R 1 , R 2 and R 3 is selected from vinyl and butadienyl, and
R is a C 1 -C 6 alkyl group;
or from one of Formulas 1-1, 1-3, 1-4 and 1-5:

wherein
each of R 11 , R 12 , R 13 , R 14 and R 15 is independently selected from 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, —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, phenyl and benzyl, and —Si(R 1 )(R 2 )(R 3 ), wherein R 1 , R 2 and R 3 are each independently selected from vinyl, butadienyl, 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 at least two of R 11 , R 12 , R 13 , R 14 and R 15 are —Si(R 1 )(R 2 )(R 3 ),
each of R 9 and R 19 is independently selected from ethylene (—C 2 H 4 —), propylene (—C 3 H 6 —) and butylene (—C 4 H 8 —), 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
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, phenyl and benzyl, with the proviso that at least one of R 1 , R 2 and R 3 is selected from vinyl and butadienyl,
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, and d′ is an integer selected from 0 and 1, wherein d is 0 when d′ is 0, and
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 as defined above, phenyl and benzyl, wherein each of R 17 and R 18 is independently selected from C 1 -C 6 alkyl, phenyl and benzyl;

wherein
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, phenyl and benzyl, with the proviso that at least one of R 1 , R 2 and R 3 is selected from vinyl and butadienyl,
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 in the heterocyclic group 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 as defined above, phenyl and benzyl, and 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 C 1 -C 10 alkylene group, and
e is an integer selected from 2, 3 and 4;

wherein
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, phenyl and benzyl, with the proviso that at least one of R 1 , R 2 and R 3 is selected from vinyl and butadienyl,
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 group B as defined above, C 1 -C 4 alkyl and benzyl, and
f is an integer selected from 2 and 3.

2. The multivinylaminosilane according to claim 1 , wherein in Formula 1-1, each of R 11 , R 12 , R 13 , R 14 and R 15 is independently selected from methyl and —Si(R 1 )(R 2 )(R 3 ), wherein R 1 , R 2 and R 3 are each independently selected from vinyl, butadienyl, 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; each of R 9 and R 19 is ethylene; c is an integer selected from 0, 1, 2 and 3; and at least two of R 11 , R 12 , R 13 , R 14 and R 15 are —Si(R 1 )(R 2 )(R 3 ).

3. The multivinylaminosilane according to claim 1 , which is selected from

wherein
each B is independently selected from —Si(R 1 )(R 2 )(R 3 ), wherein R 1 , R 2 and R 3 are each independently selected from vinyl, butadienyl, 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
each R is independently selected from B as defined above, C 1 -C 6 alkyl and benzyl, and at least two of R 11 , R 12 , R 13 , R 14 an d R 15 are —Si(R 1 )(R 2 )(R 3 );

or from

wherein each B is as defined above and at least two of R 11 , R 12 , R 13 , R 14 and R 15 are —Si(R 1 )(R 2 )(R 3 ).

4. The multivinylaminosilane according to claim 1 , 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.

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

6. A process for preparing the multivinylaminosilane as defined in claim 1 , the 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, phenyl 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 group.

7. An initiator compound obtainable by reacting a multivinylaminosilane of the following Formula 1 with an organo-alkali

Assignees

• Trinseo Europe Gmbh

Inventors

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

Classifications

• C08L21/00

  Compositions of unspecified rubbers · CPC title

• C08J2347/00

  Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds; Derivatives of such polymers (C08J2345/00 takes precedence; of conjugated diene rubbers C08J2309/00 - C08J2321/00) · CPC title

• C08F2810/20

  leading to a crosslinking, either explicitly or inherently · CPC title

• C08F2438/00

  Living radical polymerisation · CPC title

• C08F293/005

  using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent · CPC title