Aminosilyl-substituted diarylethene compounds for anionic polymerisation

Patent metadata

Field	Value
Publication number	US-9938305-B2
Application number	US-201415326832-A
Country	US
Kind code	B2
Filing date	Jul 14, 2014
Priority date	Jul 14, 2014
Publication date	Apr 10, 2018
Grant date	Apr 10, 2018

Abstract

The invention related to novel compounds useful as modifying monomers and precursors for polymerization initiators. The invention further relates to a method of making the polymerization initiators and resulting polymers. The invention also relates to polymer compositions comprising the polymer of the invention and further components such as extender oils, fillers, vulcanizing agents etc., and to corresponding vulcanized polymer compositions and articles comprising vulcanized parts made from the vulcanized polymer composition.

First claim

The invention claimed is:

1. A compound represented by the following Formula 1:

wherein
each R is independently selected from an optionally substituted organic group having from 1 to 12 carbon atoms, wherein R may be connected to one of the two benzene rings of Formula 1 to form a ring together with the Si atom of the aminosilyl group;

R′ is an optionally substituted methylene group;
each R 1 is independently selected from an optionally substituted organic group having from 1 to 12 carbon atoms;
each R 2 is independently selected an optionally substituted organic group having from 1 to 12 carbon atoms, wherein the R 2 groups may be connected to each other to form a ring together with the Si-bonded nitrogen atom;
R 3 and R 4 are each independently selected from hydrogen, methyl, ethyl, propyl, butyl and vinyl;
each R 5 is independently selected from an optionally substituted hydrocarbon group having from 1 to 12 carbon atoms, a C 1 -C 6 alkoxy group, a C 1 -C 6 alkylthio group, and an amine group carrying two substituents independently selected from a C 1 -C 6 alkyl group and a silyl group carrying three substituents independently selected from a C 1 -C 6 alkyl group and a phenyl group;
a≥1; b≥0; a+b≤10;
m=0 or 1;
n=0 to 12;
x=0, 1 or 2; y=1, 2 or 3; z=0, 1 or 2; x+y+z=3; or x+y+z=2 when the silicon atom of the aminosilyl group is bonded twice to the benzene rings via groups R′ or single bonds;
with the proviso that when m=1, then n=1 to 12, and when m=n=0, then x=1 or 2;
wherein the aminosilyl group(s) may be bonded to any of the two benzene rings, plural aminosilyl groups may be different from each other, and the R 5 group(s) may be bonded to any of the two benzene rings.

2. A polymerization initiator represented by the following Formula 2:

wherein
each R is independently selected from an optionally substituted organic group having from 1 to 12 carbon atoms, wherein R may be connected to one of the two benzene rings of Formula 1 to form a ring together with the Si atom of the aminosilyl group;
R′ is an optionally substituted methylene group;
each R 1 is independently selected from an optionally substituted organic group having from 1 to 12 carbon atoms;
each R 2 is independently selected an optionally substituted organic group having from 1 to 12 carbon atoms, wherein the R 2 groups may be connected to each other to form a ring together with the Si-bonded nitrogen atom;
R 3 and R 4 are each independently selected from hydrogen, methyl, ethyl, propyl, butyl and vinyl;
each R 5 is independently selected from an optionally substituted hydrocarbon group having from 1 to 12 carbon atoms, a C 1 -C 6 alkoxy group, a C 1 -C 6 alkylthio group, and an amine group carrying two substituents independently selected from a C 1 -C 6 alkyl group and a silyl group carrying three substituents independently selected from a C 1 -C 6 alkyl group and a phenyl group;
R 6 is selected from C 1 -C 6 alkyl, phenyl and benzyl;
M is an alkali metal selected from lithium, sodium and potassium;
a≥1; b≥0; a+b≤10;
m=0 or 1;
n=0 to 12;
x=0, 1 or 2; y=1, 2 or 3; z=0, 1 or 2; x+y+z=3; or x+y+z=2 when the silicon atom of the aminosilyl group is bonded twice to the benzene rings via groups R′ or single bonds;
with the proviso that when m=1, then n=1 to 12, and when m=n=0, then x=1 or 2;
wherein the aminosilyl group(s) may be bonded to any of the two benzene rings, plural aminosilyl groups may be different from each other, and the R 5 group(s) may be bonded to any of the two benzene rings.

3. A method of making the polymerization initiator of Formula 2 as defined in claim 2 , comprising the step of reacting (i) a compound of Formula 1

with (ii) at least one compound of the following Formula 3
R 6 M   Formula 3

wherein Formula 1 is as defined in claim 1 and R 6 and M are as defined in claim 2 .

4. The compound of claim 1 , wherein each R is independently selected from a C 1 -C 12 aliphatic group and a C 3 -C 12 aromatic group, each of which may optionally be substituted.

5. The compound of claim 4 , wherein the C 1 -C 12 aliphatic group is linear, branched or cyclic and may be saturated or unsaturated.

6. The compound of claim 4 , wherein the C 3 -C 12 aromatic group is a homocyclic aromatic group or heterocyclic aromatic group.

7. The compound of claim 1 , wherein each R 1 is independently selected from a C 1 -C 12 aliphatic group and a C 3 -C 12 aromatic group, each of which may optionally be substituted.

8. The compound of claim 7 , wherein the C 1 -C 12 aliphatic group is linear, branched or cyclic and may be saturated or unsaturated.

9. The compound of claim 7 , wherein the C 3 -C 12 aromatic group is a homocyclic aromatic group or heterocyclic aromatic group.

10. The compound of claim 1 , wherein each R 2 is independently selected from a C 1 -C 12 aliphatic group and a C 3 -C 12 aromatic group, each of which may optionally be substituted and wherein the R 2 groups may be connected to each other to form a ring together with the Si-bonded nitrogen atom.

11. The compound of claim 10 , wherein the C 1 -C 12 aliphatic group is linear, branched or cyclic and may be saturated or unsaturated.

12. The compound of claim 10 , wherein the C 3 -C 12 aromatic group is a homocyclic aromatic group or heterocyclic aromatic group.

13. The compound of claim 1 , wherein each R 5 is independently selected from a C 1 -C 12 aliphatic group and a C 3 -C 12 aromatic group, each of which may optionally be substituted.

14. The compound of claim 13 , wherein the C 1 -C 12 aliphatic group is linear, branched or cyclic and may be saturated or unsaturated.

15. The compound of claim 13 , wherein the C 3 -C 12 aromatic group is a homocyclic aromatic group or heterocyclic aromatic group.

16. The compound of claim 1 , wherein the optional substituents are independently selected from a C 1 -C 12 alkyl group, a C 6 -C 12 aryl group, a C 4 -C 12 heteroaryl group, C 1 -C 6 alkoxy group, C 1 -C 6 alkylthio group, a di(C 1 -C 6 alkyl)amino group, a diphenylamino group, a di(C 1 -C 6 alkyl)phosphino group, a diphenyl phosphine group, a C 6 -C 12 aryloxy group, a C 6 -C 12 arylthio group, a tri(C 1 -C 6 alkyl)silyl group, a tri(C 6 -C 12 aryl)silyl group and a tri(mixed C 1 -C 6 alkyl and C 6 -C 12 aryl)silyl group.

17. The compound of claim 1 , wherein R 3 and R 4 are each independently selected from hydrogen, methyl and vinyl.

18. The polymerization initiator of claim 2 , wherein R 6 is selected from methyl, n-butyl, sec-butyl, tert-butyl, benzyl and phenyl.

19. The polymerization initiator of claim 2 , wherein M is lithium.

20. The polymerization initiator of claim 2 , wherein each R is independently selected from C 1 -C 5 alkyl and C 6 aryl, each R 1 is independently selected from C 1 -C 4 alkyl and C 6 aryl, each R 2 is independently selected from C 1 -C 8 alkyl and C 7 -C 10 alkylaryl, R 3 and R 4 are each hydrogen, each R 5 is independently selected from C 1 -C 4 alkyl, R 6 is selected from methyl, ethyl, tert-butyl, n-butyl, sec-butyl, phenyl and benzyl, M is lithium, a=1 or 2, b=0 or 1, m=0 and R′ is methylene and n=1, 2 or 3, x=0 o

Assignees

• Trinseo Europe Gmbh

Inventors

• Rössle Michael
• Döring Christian
• Thiele Sven
• Heidenreich Daniel
• Schübel Nadine
• Jacobi Christiane

Classifications

• C07F7/12

  Organo silicon halides · CPC title

• C07F7/10 Primary

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

• C08K5/01

  Hydrocarbons {(C08K5/0091 takes precedence)} · CPC title

• C07F7/0849

  Chemistry & Metallurgy · mapped topic

• C08J3/24

  Crosslinking, e.g. vulcanising, of macromolecules (mechanical aspects B29C35/00; crosslinking agents C08K) · CPC title