Thioester-functional organic polymers, method for preparing and compositions thereof

Patent metadata

Field	Value
Publication number	US-11230620-B2
Application number	US-202016878096-A
Country	US
Kind code	B2
Filing date	May 19, 2020
Priority date	May 22, 2019
Publication date	Jan 25, 2022
Grant date	Jan 25, 2022

Abstract

An organic polymer comprising an organic polymer fragment and at least one S-alkylsilyl hydrocarbonthioate group or at least one S-alkylstannyl hydrocarbonthioate group bonded to the backbone of the organic polymer fragment through a C—Si covalent bond and their methods or production are provided. The organic polymer backbone can be derived from the anionic polymerization of monomers containing C—C unsaturation. The silicon or tin atom can be further bonded to two alkoxy groups, two hydrocarbon groups or to one alkoxy group and one hydrocarbon group.

First claim

What is claimed is:

1. An organic polymer comprising an organic polymer fragment and at least one S-alkylsilyl hydrocarbonthioate group or at least one S-alkylstannyl hydrocarbonthioate group bonded to the backbone of the organic polymer fragment through a C—Si covalent bond.

2. The organic polymer of claim 1 , wherein the backbone of the organic polymer fragment is derived from the anionic polymerization of monomers containing C—C unsaturation.

3. The organic polymer of claim 1 , wherein the silicon atom of the S-alkylsilyl hydrocarbonthioate group or the tin atom of the S-alkylstannyl hydrocarbonthioate group is further bonded to two alkoxy groups, two hydrocarbon groups or to one alkoxy group and one hydrocarbon group.

4. The organic polymer of claim 1 , wherein the organic polymer has the general formula (I):
[R 1 C(═O)SR 2 -M(OR 3 ) a (R 4 ) 2−a -] b G 1 -[R 5 ] 2−b   (I)

wherein
each M is independently a silicon or tin atom;
each R 1 is independently a monovalent alkyl, cycloalkyl, alkenyl, aryl or aralkyl group having 1 to 24 carbon atoms;
each R 2 is independently a divalent alkyl group of from 2 to 6 carbon atoms;
each R 3 is independently a monovalent alkyl, cycloalkyl, alkenyl, aryl or aralkyl group having 1 to 12 carbon atoms, or a monovalent group having the structure —R 6 (OR 7 ) c (OR 8 ) d R 9 , where R 6 is a divalent alkyl group having from 2 to 6 carbon atoms, R 7 is ethylene, each R 8 is independently propylene or butylene, R 9 is a monovalent alkyl, cycloalkyl, alkenyl, aryl or aralkyl group having 1 to 20 carbon atoms or —(C═O)R 4 , and the subscripts c and d are integers, wherein c is from 0 to 6 and d is from 0 to 6, with the proviso that c+d is from 1 to 10;
each R 4 is independently methyl or phenyl;
R 5 is a monovalent alkyl, cycloalkyl, alkenyl, aryl or aralkyl group having 1 to 24 carbon atoms;
G 1 is an organic polymer fragment having a backbone of carbon atoms covalently bonded together by C—C single bond, C—C double bond or a combination of C—C single bonds and C—C double bonds; and
the subscripts a and b are integers, where a is 0, 1 or 2 and b is 1 or 2.

5. The organic polymer of claim 4 , wherein G 1 is an organic polymer fragment having the general formula (III):

wherein
each R 11 , R 12 , R 13 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 and R 26 is independently a monovalent alkyl group having from 1 to 6 carbon atoms or hydrogen;
each R 14 is independently hydrogen or a monovalent alkyl of from 1 to 24 carbon atoms, cylcoalkyl of from 3 to 24 carbon atoms, alkenyl of from 1 to 24 carbon atoms, cycloalkenyl of from 5 to 24 carbon atoms, aralkyl of from 7 to 24 carbon atoms or aryl group of from 6 to 25 carbon atoms;
the subscripts e, f and g are integers, wherein e is equal to or greater than 0, f is equal to or greater than 0 and g is equal to or greater than 0, with the proviso that e+f+g is equal to or greater than 1.

6. The organic polymer of claim 5 , wherein e is from 0 to 10,000.

7. The organic polymer of claim 5 , wherein e is from 100 to 2,500.

8. The organic polymer of claim 5 , wherein f is from 0 to 10,000.

9. The organic polymer of claim 7 , wherein f is from, 100 to 2,500.

10. The organic polymer of claim 8 , wherein g is from 0 to 10,000.

11. The organic polymer of claim 5 , wherein g is from 100 to 2,500.

12. The organic polymer of claim 5 , wherein e+f+g is from 1,000 to 5,000.

13. The organic polymer of claim 5 , wherein each R 11 , R 12 , R 13 , R 15 , R 16 , R 17 , R 18 , R 19 , R 20 , R 21 , R 22 , R 23 , R 24 , R 25 and R 26 is hydrogen, methyl or ethyl.

14. The organic polymer of claim 12 , wherein R 1 is a monovalent straight chain alkyl group of from 2 to 14 carbon atoms.

15. The organic polymer of claim 5 , wherein R 1 is a branched chain alkyl group of from 5 to 11 carbon atoms.

16. The organic polymer of claim 12 , wherein R 1 is methyl, ethyl, propyl, pentyl, hexyl, heptyl, nonyl, unidecyl, octadecyl, dec-3-enyl, heptadec-5-enyl, heptadec-5,7-dienyl, heptadec-5,7,9-trienyl, 2-methylpentyl, 2-methylhexyl, 6-methylheptyl, 2-phenylmethyl, cyclohexyl, phenyl or tolyl.

17. The organic polymer of claim 5 , wherein R 2 is a divalent straight chain alkyl group of from 1 to 6 carbon atoms or a divalent branched chain alkyl group of from 3 to 6 carbon atoms.

18. The organic polymer of claim 16 , wherein R 2 is methyl, ethyl, propyl, 2-methylpropyl, 2,2-dimethylbutyl or hexyl.

19. The organic polymer of claim 5 , wherein R 3 is a monovalent alkyl group of from 1 to 4 carbon atoms.

20. The organic polymer of claim 4 , wherein the organic polymer has the general formula (IV):
R 1 C(═O)SCH 2 CH 2 CH 2 Si(OCH 2 CH 3 ) 2 G 1 Si(OCH 2 CH 3 ) 2 CH 2 CH 2 CH 2 SC(═O)R 1   (IV)

where R 1 is a monovalent straight chain alkyl group having from 1 to 18 carbon atoms, and G 1 is an organic polymer fragment having a backbone of carbon atoms covalently bonded together by C—C single bond, C—C double bond or a combination of C—C single bonds and C—C double bonds.

21. The organic polymer of claim 1 , wherein the number average molecular weight of the organic polymer is from about 2,000 to about 1,00,000 Daltons.

22. The organic polymer of claim 5 , wherein the number average molecular weight of the organic polymer is from about 90,000 to about 150,000 Daltons.

23. A method of making an organic polymer, comprising:
reacting a chain of C—C unsaturated carbon atom monomers with an anionic initiator to form a first living anionic polymer intermediate,
reacting the living anionic polymer intermediate with a compound containing a 2-thia-1-sila cycloalkane ring or 2-thia-1-stanna cycloalkane ring to form a second intermediate containing at least one thiolate group; and
reacting the second intermediate with an acyl reactive group having the general formula (II):
R 1 C(═O)X  (II)

wherein
R 1 is a monovalent alkyl, cycloalkyl, alkenyl, aryl or aralkyl group having 1 to 24 carbon atoms and X is chloride, bromide, iodide or a —SR 10 ,
R 10 is a monovalent alkyl, cycloalkyl, alkenyl, aryl or aralkyl group having 1 to 12 carbon atoms to form the reaction product
and a salt.

24. The method of claim 23 , wherein the monomers are conjugated or unconjugated C 4 -C 12 dienes, or C 8 -C 20 vinyl aromatics.

25. The method of claim 23 , wherein the monomers are selected from the group consisting of 1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 2,3-dimethyl-1,3-butadiene, 2-ethyl-1,3-butadiene, 2-methyl-1,3-pentadiene, 3-methyl-1,3-pentadiene, 4-methyl-1,3-pentadiene, 2,4-hexadiene, styrene, α-methyl styrene, p-methyl styrene, vinyl toluene, and vinyl naphthalene and combinations thereof.

26. The method of claim 23 , wherein the method comprises solution polymerization.

27. An S-alkylsilyl hydrocarbonthioate-terminated or S-alkylstannyl hydrocarbonthioate-terminated organic polymer.

28. An organic polymer composition comprising:
a S-alkylsilyl hydrocarbonthioate-terminated polymer or a S-alkylstannyl hydrocarbonthioate-terminated organic polymer or a combination thereof; and
a reinforcing material;
optionally a curative;
optionally a plasticizer; and
optionally one or more additives.

Assignees

• Momentive Performance Mat Inc

Inventors

• Kumar Vikram
• Pinnow Matthew

Classifications

• C08F8/34

  Introducing sulfur atoms or sulfur-containing groups · CPC title

• C08F2/04

  Polymerisation in solution (C08F2/32 takes precedence) · CPC title

• C08C19/44 Primary

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

• C08C19/25

  Incorporating silicon atoms into the molecule · CPC title

• C08C19/20

  Incorporating sulfur atoms into the molecule · CPC title