Catalyst for living radical polymerization and polymerization method

Patent metadata

Field	Value
Publication number	US-9546226-B2
Application number	US-201013388811-A
Country	US
Kind code	B2
Filing date	May 10, 2010
Priority date	Aug 6, 2009
Publication date	Jan 17, 2017
Grant date	Jan 17, 2017

Abstract

Provided is a low-cost, highly active, environmentally friendly living radical polymerization catalyst which does not require a radical initiator. An organic compound having an oxidation-reduction capability is used as a catalyst. Even if a radical initiator is not used, a monomer can be subjected to a radical polymerization to obtain a polymer having narrow molecular weight distribution. The cost of the living radical polymerization can be remarkably reduced. It is made possible to prevent adverse effects of using a radical initiator. The present invention is significantly more environmentally friendly and economically excellent than conventional living radical polymerization methods, due to advantages of the catalyst such as low toxicity of the catalyst, low amount of the catalyst necessary, high solubility of the catalyst, mild reaction conditions, and no coloration/no odor (which do not require a post-treatment for a molded article), etc.

First claim

The invention claimed is:

1. A method of polymerization comprising:
polymerizing, in a living radical polymerization, a monomer of the formula CH 2 ═CR 5 R 6 , hydrogen or a C 1-3 alkyl group and R 6 is a carbon/late, C 1-10 aryl or a C 6-10 aromatic group, by contacting the monomer with an organic halide and an organic compound
wherein:
the organic halide is of the formula CR 2 R 3 R 4 X 3 , wherein R 2 and R 3 are each independently hydrogen or C 1-10 , R 4 is halogen, hydrogen, C 1-10 alkyl, a C 6-10 aromatic group, a C 5-10 heteroaryl group containing at least one heteroatom or cyano, and X 3 is halogen, and
the organic compound is selected from the group consisting of:

triethylamine;
tributylamine;
tetrakis(dimethylamino) amine;
1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane;
Tributylphosphine;
N,N,N′,N″,N″-pentamethyl diethylenetriamine;
ethylenediamine;
dimethyl ethylenediamine;
tetramethylethylenediamine;
tetramethyldiaminomethane;
tris(2-aminoethyl)amine;
tris(2-(methylamino)ethyl)amine;
1,2-bis(diphenylphosphino)methane;
hematoporphyrin;
triethylphosphine;
triphenylphosphine;
phosphonic acid;
1,2-bis(diphenylphosphino)methane;
thiophene;
oligothiophene;
polythiophene;
tetrathiofulvalene;
bis(ethylenedithio)tetrathiafulvalene;
3,4-ethylenedioxythiophene; and
poly(3,4-ethylenedioxythiophene);
the living radical polymerization is conducted without the use of a catalyst other than the organic compound,
a raw material composition which is used in the method does not include a raw material containing a transition metal, and
a radical initiator is not added to a reaction mixture at the time of conducting the living radical polymerization.

2. The method of claim 1 , wherein R 6 is a carboxylate or a C 6 aromatic group.

3. The method of claim 2 , wherein R 6 is carboxylate, phenyl or naphthyl.

4. The method of claim 1 , wherein R 2 is and R 3 are each independently hydrogen or C 1-5 alkyl.

5. The method of claim 1 , wherein R 4 is halogen, hydrogen, C 1-5 alkyl, a C 6-10 aromatic group, a C 5-10 heteroaryl group containing at least one heteroatom or cyano.

6. The method of claim 1 , wherein R 4 is a C 6-10 aromatic group,
a C 5-10 heteroaryl group containing at least one heteroatom or cyano.

7. The method of claim 5 , wherein R 4 is a C 6-10 aromatic group,
a C 5-10 heteroaryl group containing at least one heteroatom or cyano.

8. The method of claim 1 , wherein R 5 is hydrogen or a C 1-3 alkyl group and R 6 is a carboxylate or a C 6 aromatic group.

9. The method of claim 1 , wherein the monomer is selected from the group consisting of (meth)acrylic acid ester; a styrene monomer; (meth)acrylonitrile; (meth)acrylamide; a vinyl ester monomer; (meth)acrylic acid; and vinyl halide.

10. The method of claim 1 , wherein the organic compound is selected from the group consisting of:
triethylamine;
tributylamine;
tetrakisdimethylaminoethene;
1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane;
tributylphosphine;
triphenylphosphine;
bis(ethylenedithio)tetrathiafulvalene;
ethylenediamine;
dimethylethylenediamine;
tetramethylethylenediamine;
tetramethyldiaminomethane;
tris(2-aminoethyl)amine;
tris(2-(methylamino)ethyl)amine;
1,2-bis(diphenylphosphino)methane; and
hematoporphyrin.

Assignees

• Goto Atsushi
• Tsujii Yoshinobu
• Fukuda Takeshi
• Univ Kyoto

Inventors

• Goto Atsushi
• Tsujii Yoshinobu
• Fukuda Takeshi

Classifications

• C08F12/08

  Styrene · 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

• C08F120/14

  Methyl esters {, e.g. methyl (meth)acrylate} · CPC title

• C08F4/40 Primary

  Redox systems · CPC title