Raft agent, polymerization method, polymer, rubber mixture, and use thereof

Patent metadata

Field	Value
Publication number	US-10442877-B2
Application number	US-201715810561-A
Country	US
Kind code	B2
Filing date	Nov 13, 2017
Priority date	May 12, 2015
Publication date	Oct 15, 2019
Grant date	Oct 15, 2019

Abstract

Disclosed are RAFT agents, a method of polymerizing alkenes, dienes, vinyl compounds, and/or vinylidene compounds using at least one RAFT agent, polymers prepared by the methods, sulfur-crosslinkable rubber mixtures prepared by the methods, and motor vehicle tires, cords, belts, or hoses incorporating the sulfur-crosslinkable rubber mixtures. In one embodiment, the RAFT agent has the formula Z—C(═S)—S—R—S—P or P—S—Z—C(═S)—S—R—S—P, wherein P is a protecting group, and Z and R are typical RAFT Z and R groups.

First claim

What is claimed is:

1. A RAFT agent of formula I):
Z—C(═S)—S—R—S—P,  I)

wherein
Z is a Z group typical of RAFT polymerization,
R is an R group typical of RAFT polymerization,
C is a carbon atom,
S is a sulfur atom,
P is a protecting group selected from the group consisting of: S(═O) 2 —R 1 , S—C(═S)—N—R 2 R 3 , C(═O)—R 4 , N—R 5 R 6 , SiR 7 R 8 R 9 , and S(═O) 2 —OM,
R 1 =alkyl, benzyl, or phenyl,
R 2 and R 3 =alkyl, benzyl, or phenyl,
R 4 =alkyl,
R 5 =hydrogen atom (H), alkyl, benzyl, or phenyl,
R 6 =alkyl, benzyl, or phenyl,
R 7 , R 8 and R 9 =alkyl or benzyl, and
M=Na, K, or H.

2. A RAFT agent of formula II):

wherein n is between 13 and 22.

3. The RAFT agent of claim 1 , wherein Z is selected from the following groups:

wherein Ph is phenyl, Me is methyl, and Et is ethyl.

4. The RAFT agent of claim 1 ,
wherein Z is selected from the group consisting of:
a) phenyl,
b) phenoxy,
c) alkoxy (O-alkyl) having 1 to 30 carbon atoms, wherein the alkyl is branched or unbranched,
d) alkyl having 1 to 30 carbon atoms, wherein the alkyl is branched or unbranched,
e) S-alkyl having 1 to 30 carbon atoms, wherein attachment to the —C(═S)—S—R—S—P radical of the RAFT agent is via the sulfur atom, and wherein the alkyl is branched or unbranched,
f) a heterocyclic group,
g) alkyl(phenyl)amino, wherein alkyl is 1 to 30 carbon atoms, wherein attachment to the —C(═S)—S—R—S—P radical of the RAFT agent is via the nitrogen atom, and wherein the alkyl is branched or unbranched, and
h) dialkylamino, wherein alkyl is 1 to 30 carbon atoms, wherein each alkyl is independently branched or unbranched, wherein attachment to the —C(═S)—S—R—S—P radical of the RAFT agent is via the nitrogen atom, and wherein each alkyl group is the same or different,
and

wherein R is selected from the group consisting of: cyanoisopropyl, 2-phenylpropan-2-yl, cyano(phenyl)methyl, 1-ethoxy-2-methyl-1-oxopropan-2-yl, 2,4,4-trimethylpentan-2-yl, 1-cyanoethyl, 1-phenylethyl, tert-butyl, cyanomethyl, and benzyl.

5. The RAFT agent of claim 1 , wherein R is a polymethacrylate group comprising at least a first methacrylate unit that optionally comprises a carbamate group or a dithiocarbamate group, wherein attachment to the Z—C(═S)—S— radical of the RAFT agent is via a secondary carbon atom of the first methacrylate unit of the polymethacrylate group.

6. A RAFT agent of formula III):
P—S—Z—C(═S)—S—R—S—P,  III)

wherein
Z is a Z group typical of RAFT polymerization,
R is an R group typical of RAFT polymerization,
C is a carbon atom,
S is a sulfur atom,
P is a protecting group selected from the group consisting of: S(═O) 2 —R 1 , S—C(═S)—N—R 2 R 3 , C(═O)—R 4 , N—R 5 R 6 , SiR 7 R 8 R 9 , and S(═O) 2 —OM,
R 1 =alkyl, benzyl, or phenyl,
R 2 and R 3 =alkyl, benzyl, or phenyl,
R 4 =alkyl,
R 5 =hydrogen atom (H), alkyl, benzyl or phenyl,
R 6 =alkyl, benzyl, or phenyl,
R 7 , R 8 and R 9 =alkyl or benzyl, and
M=Na, K, or H.

7. The RAFT agent of claim 6 , wherein Z is selected from the following groups:

wherein Ph is phenyl, Me is methyl, and Et is ethyl.

8. The RAFT agent of claim 6 ,
wherein Z is selected from the group consisting of:
a) phenyl,
b) phenoxy,
c) alkoxy (O-alkyl) having 1 to 30 carbon atoms, wherein the alkyl is branched or unbranched,
d) alkyl having 1 to 30 carbon atoms, wherein the alkyl is branched or unbranched,
e) S-alkyl having 1 to 30 carbon atoms, wherein attachment to the —C(═S)—S—R—S—P radical of the RAFT agent is via the sulfur atom, and wherein the alkyl is branched or unbranched,
f) a heterocyclic group,
g) alkyl(phenyl)amino, wherein alkyl is 1 to 30 carbon atoms, wherein attachment to the —C(═S)—S—R—S—P radical of the RAFT agent is via the nitrogen atom, and wherein the alkyl is branched or unbranched, and
h) dialkylamino, wherein alkyl is 1 to 30 carbon atoms, wherein each alkyl is independently branched or unbranched, wherein attachment to the —C(═S)—S—R—S—P radical of the RAFT agent is via the nitrogen atom, and wherein each alkyl group is the same or different,
and

wherein R is selected from the group consisting of: cyanoisopropyl, 2-phenylpropan-2-yl, cyano(phenyl)methyl, 1-ethoxy-2-methyl-1-oxopropan-2-yl, 2,4,4-trimethylpentan-2-yl, 1-cyanoethyl, 1-phenylethyl, tert-butyl, cyanomethyl, and benzyl.

9. The RAFT agent of claim 6 , wherein R is a polymethacrylate group comprising at least a first methacrylate unit that optionally comprises a carbamate group or a dithiocarbamate group, wherein attachment to the Z—C(═S)—S— radical of the RAFT agent is via a secondary carbon atom of the first methacrylate unit of the polymethacrylate group.

10. A method of polymerizing alkene, diene, vinyl, and/or vinylidene, which comprises reacting an alkene, diene, vinyl, and/or vinylidene monomer with the RAFT agent of claim 1 .

11. A method of polymerizing alkene, diene, vinyl, and/or vinylidene, which comprises reacting an alkene, diene, vinyl, and/or vinylidene monomer with the RAFT agent of claim 6 .

12. A process for preparing an alkene, diene, vinyl, and/or vinylidene polymer chain, which comprises:
reacting an alkene, diene, vinyl, and/or vinylidene monomer with the RAFT agent of claim 1 ,
wherein the polymer chain comprises at least one —R—S—P molecular moiety of the RAFT agent at the start of the polymer chain, and
wherein the polymer chain comprises at least one molecular moiety Z—C(═S)—S— at the end of the polymer chain.

13. A process for preparing an alkene, diene, vinyl, and/or vinylidene polymer chain, which comprises:
reacting an alkene, diene, vinyl, and/or vinylidene monomer with the RAFT agent of claim 6 ,
wherein the polymer chain comprises at least one —R—S—P molecular moiety of the RAFT agent at the start of the polymer chain, and
wherein the polymer chain comprises at least one molecular moiety Z—C(═S)—S— at the end of the polymer chain.

14. A sulfur-crosslinkable rubber mixture comprising the polymer chain of claim 12 .

15. A sulfur-crosslinkable rubber mixture comprising the polymer chain of claim 13 .

16. A motor vehicle tire comprising the sulfur-crosslinkable rubber mixture of claim 14 .

17. A motor vehicle tire comprising the sulfur-crosslinkable rubber mixture of claim 15 .

18. A cord, belt, or hose comprising the sulfur-crosslinkable rubber mixture of claim 14 .

19. A cord, belt, or hose comprising the sulfur-crosslinkable rubber mixture of claim 15 .

Assignees

• Continental Reifen Deutschland Gmbh

Inventors

• Herzog Katharina
• Mueller Lena
• Recker Carla
• Pruss Noa
• Vana Phillipp
• Conrad Cathrin Sonja

Classifications

• C08F236/06

  Butadiene · CPC title

• C08F236/10

  with vinyl-aromatic monomers · CPC title

• C08F2438/03

  Use of a di- or tri-thiocarbonylthio compound, e.g. di- or tri-thioester, di- or tri-thiocarbamate, or a xanthate as chain transfer agent, e.g . Reversible Addition Fragmentation chain Transfer [RAFT] or Macromolecular Design via Interchange of Xanthates [MADIX] · CPC title

• C08F2810/40

  taking place solely at one end or both ends of the polymer backbone, i.e. not in the side or lateral chains · CPC title

• B60C1/0016

  Compositions of the tread · CPC title