Living radical polymerization initiator, method for producing polymer, and polymer

Patent metadata

Field	Value
Publication number	US-10414848-B2
Application number	US-201515508313-A
Country	US
Kind code	B2
Filing date	Aug 7, 2015
Priority date	Sep 2, 2014
Publication date	Sep 17, 2019
Grant date	Sep 17, 2019

Abstract

A living radical polymerization initiator represented by the following:

wherein, R 1 represents an aromatic, an alkylcarbonyl, an alkoxycarbonyl, an aminocarbonyl, an alkylaminocarbonyl, a dialkylaminocarbonyl, an arylcarbonyl, an alkylsulfonyl, an aryl sulfonyl or combinations thereof; R 2 , R 3 , R 4 and R 5 are a hydrogen, an aliphatic, an aromatic, an alkylcarbonyl, an alkoxycarbonyl, an aminocarbonyl, an alkylaminocarbonyl, a dialkylaminocarbonyl, an arylcarbonyl, a carboxy, an alkylsulfonyl or an aryl sulfonyl; X and Y are a halogen; m and n are an integer of 1 or more, and

are non-symmetrical so that X and Y have different reactivities to initiate a living radical polymerization.

First claim

The invention claimed is:

1. A method for producing a polymer, comprising:
(i) carrying out a first polymerization step comprising mixing a living radical polymerization reaction initiator with a first monomer having an unsaturated bond at reaction conditions to initiate a living radical polymerization reaction, the living radical polymerization initiator being represented by the following formula (1):

wherein in the formula (1), R 1 represents a substituted or unsubstituted organic group having a valency of two or more, and is selected from the group consisting of an aliphatic group having 1 to 12 carbon atoms, an aromatic group, an alkylcarbonyl group having 1 to 12 carbon atoms, an alkoxycarbonyl group having 1 to 12 carbon atoms, an aminocarbonyl group, an alkylaminocarbonyl group having 1 to 12 carbon atoms, a dialkylaminocarbonyl group having 1 to 12 carbon atoms, an arylcarbonyl group, an alkylsulfonyl group having 1 to 12 carbon atoms, an aryl sulfonyl group and an organic group in which two or more of said groups are combined,
R 2 , R 3 , R 4 and R 5 are a hydrogen atom or a substituted or unsubstituted organic group selected from the group consisting of an aliphatic group having 1 to 12 carbon atoms, an aromatic group, an alkylcarbonyl group, an alkoxycarbonyl group, an aminocarbonyl group, an alkylaminocarbonyl group, a dialkylaminocarbonyl group having 1 to 12 carbon atoms, an arylcarbonyl group, a carboxy group, an alkylsulfonyl group having 1 to 12 carbon atoms and an aryl sulfonyl group,
X and Y are each a halogen atom,
m and n are an integer of 1 or more, and

are non-symmetrical so that X and Y have different reactivities to initiate a living radical polymerization,
wherein one of halogen atoms X and Y is reacted to obtain a first polymer product having at one end thereof the other of the halogen atoms X and Y which is unreacted and which is attached to the following skeleton structure:

and
(ii) carrying out a second polymerization step comprising mixing the first polymer product with a second monomer at reaction conditions to initiate a living radical polymerization reaction to obtain a polymer having at one end thereof one of the halogens X and Y and having at an opposite end thereof the other of the halogens X and Y, and disposed therebetween polymerized monomers and the following skeleton structure:

2. The living radical polymerization initiator according to claim 1 , wherein the halogen atom is iodide, chloride, or bromide.

3. The method for producing a polymer according to claim 1 , wherein the first polymerization step and the second polymerization step are carried out in the presence of a catalyst, and the first polymerization step and the second polymerization step are carried out such that at least one of reaction temperature and type of the catalyst is changed depending on the type of the monomer.

4. The method for producing a polymer according to claim 3 , wherein the catalyst is (i) a transition metal complex-based catalyst which is operable for an atom transfer radical polymerization; (ii) a catalyst consisting of a compound containing at least one center element selected from the group consisting of phosphorus, nitrogen, carbon, oxygen, germanium, tin and antimony, and a halogen atom bound to the center element, which is operable for reversible chain transfer catalyst polymerization; (iii) an organic amine compound catalyst which is operable for a reversible complexation mediated polymerization; (iv) or a catalyst comprising a non-metal compound having an ionic bond with a halide ion, wherein a non-metal atom in the non-metal compound is in a cationic state and forms the ionic bond with the halide ion.

5. The method for producing a polymer according to claim 1 , wherein the first polymerization step and the second polymerization step are each carried out at a temperature of 180° C. or lower.

6. The method for producing a polymer according to claim 1 , wherein the first polymerization step and the second polymerization step are each carried out for a reaction time of 30 minutes to 24 hours.

7. The method for producing a polymer according to claim 1 , further comprising, before the second polymerization step, carrying out one or more living polymerization reactions with one or more third monomers at reaction conditions to carry out a living polymerization reaction.

8. The method for producing a polymer according to claim 1 , wherein the first monomer and the second monomer are different from each other and are selected from the group consisting of methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, nonyl methacrylate, benzyl methacrylate, glycidyl methacrylate, cyclohexyl methacrylate, lauryl methacrylate, n-octyl methacrylate, 2-methoxyethyl methacrylate, butoxyethyl methacrylate, methoxytetraethylene glycol methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate, tetrahydrofurfuryl methacrylate, 2-hydroxy 3-phenoxypropyl methacrylate, diethylene glycol methacrylate, polyethylene glycol methacrylate and 2-(dimethylamino)ethyl methacrylate.

9. The method for producing a polymer according to claim 1 , wherein the first monomer and the second monomer are different from each other and are selected from the group consisting of methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, t-butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, benzyl acrylate, glycidyl acrylate, cyclohexyl acrylate, lauryl acrylate, n-octyl acrylate, 2-methoxyethyl acrylate, butoxyethyl acrylate, methoxytetraethylene glycol acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-chloro 2-hydroxypropyl acrylate, tetrahydrofurfuryl acrylate, 2-hydroxy 3-phenoxypropyl acrylate, diethylene glycol acrylate, polyethylene glycol acrylate, and 2-(dimethylamino)ethyl acrylate.

10. The method for producing a polymer according to claim 1 , wherein the living radical polymerization initiator is selected from the group consisting of methyl 2-iodo-2-(4′-(2″-iodopropionyloxy) phenyl) acetate, 4-iodobutyl 2-iodoisobutyrate, methyl 2-iodo-2-(4′-(4″-iodobutanoyloxy) phenyl) acetate, 4-iodobutyl 2-iodophenylacetate and 2-(iodoacetoxy) ethyl 2-iodo-2-phenylacetate.

11. The method for producing a polymer according to claim 3 , wherein the catalyst is tributylmethyl phosphonium iodide.

Assignees

• Univ Kyoto
• Godo Shigen Co Ltd
• Good Shigen Co Ltd

Inventors

• Goto Atsushi
• Miyamoto Michihiko
• Komatsu Hiroto
• Yamaguchi Yu
• Jitsukawa Takuya

Classifications

• C07C69/65

  of unsaturated acids · CPC title

• C08F293/005 Primary

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

• C07C69/635

  containing rings in the acid moiety · CPC title

• C07C69/73

  of unsaturated acids · CPC title

• C07C69/63

  of saturated acids · CPC title