Polymer production method and radical polymerization initiating group-containing compound

Patent metadata

Field	Value
Publication number	US-11746178-B2
Application number	US-202117206489-A
Country	US
Kind code	B2
Filing date	Mar 19, 2021
Priority date	Feb 29, 2016
Publication date	Sep 5, 2023
Grant date	Sep 5, 2023

Abstract

The present invention provides: a novel production technique that enables production of a polymer whose molecular weight and molecular weight distribution are controlled and production of a polymer having a complicated structure in a desirably controlled manner using commercially available materials without using a radical polymerization initiator or a special material for use in living radical polymerization and without the need for strict polymerization conditions; and a radical polymerization initiating group-containing compound for use in the technique. The present invention relates to: a method for producing a polymer, the method including a polymerization step of mixing and warming (1) a radically polymerizable monomer, (2) an organic compound wherein at least one group that functions as a group for initiating polymerization of the monomer and that has a structure represented by formula 1 or formula 2 (X in the formula represents Cl or Br) is introduced in a molecule of the organic compound, and (3) an iodine-containing compound, thereby initiating, from the group having the structure, radical polymerization accompanied by a termination reaction; and the organic compound of (2) for use in the method.

First claim

The invention claimed is:

1. A composition for radical polymerization of a radically polymerizable monomer, the composition comprising:
(1) the radically polymerizable monomer having an unsaturated bond;
(2) a radical polymerization initiating group-containing compound;
(3) at least one iodine ion-containing compound, the at least one iodine ion-containing compound being at least one iodide salt or triiodide salt selected from the group consisting of metal iodides, quaternary ammonium iodides, quaternary phosphonium iodides, and quaternary ammonium triiodides,
wherein the metal iodides in the group for the at least one iodine ion-containing compound (3) are lithium iodide, sodium iodide, potassium iodide, calcium iodide, and magnesium iodide; and

(4) the at least one material selected from the group consisting of iodine, N-iodoimide-based compounds as iodinated organic compounds capable of releasing iodine, and compounds each having an organic base,
wherein the compounds each having an organic base are triethylamine, tributylamine, diazabicycloundecene, diazabicyclooctane, and phosphazene bases,

wherein the radical polymerization initiating group-containing compound (2) is a compound that conducts the radical polymerization accompanied by a termination reaction without using any initiator selected from the group consisting of azo-based radical polymerization initiators, peroxide-based radical polymerization initiators, and photo-radical polymerization initiators,
the radical polymerization initiating group-containing compound (2) has in a molecule thereof, at least one group having a structure represented by following formula [1] or formula [2], and is a copolymer of monomers comprising: a monomer in a molecule of which the at least one group having the structure represented by the formula [1] or the formula [2] is introduced, and a monomer having a reactive group that bonds to a surface of a base material,
the radical polymerization initiating group-containing compound (2) functions as a group for initiating polymerization of the radically polymerizable monomer (1) by using the radical polymerization initiating group-containing compound (2) with the at least one iodine ion-containing compound (3) in the presence of the at least one material (4),
the at least one material (4) is present in an amount at a ratio of the at least one material (4) relative to a total amount of a functional group of formula [1] and a functional group of formula [2] in the radical polymerization initiating group-containing compound (2) being in a range from 0.001 to 0.1 (mol/mol), and
a metal catalyst used in living radical polymerization is not present in the radical polymerization,

wherein R 1 represents H, an alkyl group, an acyl group, or a phenyl group, R 2 represents an alkyl group or an aryl group, X represents Cl or Br, and Y represents O or NH, and

wherein R 3 represents H, an alkyl group, or an aryl group, R 4 represents an aryl group, a cyano group, a carboxyl group, an ester group, or an amide group, and X represents Cl or Br.

2. The composition for radical polymerization according to claim 1 ,
wherein the group having the structure represented by the formula [1] is a group having a structure represented by following formula [3]:

wherein Y represents O or NH.

3. The composition for radical polymerization according to claim 1 ,
wherein the radical polymerization initiating group-containing compound (2) is a polymer in a molecule of which two groups each having the structure represented by the formula [1] or the formula [2] are introduced.

4. The composition for radical polymerization according to claim 1 ,
wherein the radical polymerization initiating group-containing compound (2) is a compound in a molecule of which three or more groups each having the structure represented by the formula [1] or the formula [2] are introduced.

5. The composition for radical polymerization according to claim 1 ,
wherein the radical polymerization initiating group-containing compound (2) is a vinyl polymer in a molecule of which three or more groups each having the structure represented by the formula [1] or the formula [2] are introduced in a molecule of the vinyl polymer.

6. The composition for radical polymerization according to claim 1 ,
wherein the radical polymerization initiating group-containing compound (2) is a copolymer of monomers consisting of: the monomer in a molecule of which the at least one group having the structure represented by the formula [1] or the formula [2] is introduced, and the monomer having a reactive group that bonds to a surface of a base material.

7. The composition for radical polymerization according to claim 1 ,
wherein the monomer that is the at least one group having the structure represented by the formula [1] or the formula [2] is introduced is 2-(2-bromo-2-methylpropionyloxy)ethyl 2-methacrylate.

8. The composition for radical polymerization according to claim 1 ,
wherein the monomer having a reactive group that bonds to a surface of a base material is 3-methacryloxy propyl triethoxy silane.

9. The composition for radical polymerization according to claim 1 ,
wherein the monomer that is the at least one group having the structure represented by the formula [1] or the formula [2] is introduced is 2-(2-bromo-2-methylpropionyloxy)ethyl 2-methacrylate, and
the monomer having a reactive group that bonds to a surface of a base material is 3-methacryloxy propyl triethoxy silane.

10. The composition for radical polymerization according to claim 1 ,
wherein the radical polymerization initiating group-containing compound (2) has in a molecule thereof, at least one group having a structure represented by the formula [1],
the at least one material (4) is present in an amount at a ratio of the at least one material (4) relative to an amount of the functional group of formula [1] in the radical polymerization initiating group-containing compound (2) being in a range from 0.001 to 0.1 (mol/mol), and
in the formula [1], Y represents NH.

11. The composition for radical polymerization according to claim 1 ,
wherein in the formula [1], R 2 represents an aryl group, X represents Cl or Br, and Y represents O or NH, and
in the formula [2], R 4 represents an aryl group, a cyano group, a carboxyl group, or an amide group.

Assignees

• Dainichiseika Color Chem

Inventors

• Shimanaka Hiroyuki
• Tagi Yoichi
• Murakami Yoshikazu

Classifications

• Y02P20/54

  using solvents, e.g. supercritical solvents or ionic liquids · CPC title

• C08F293/005 Primary

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

• C08F2/06

  Organic solvent · CPC title

• C08F2/38 Primary

  Polymerisation using regulators, e.g. chain terminating agents {, e.g. telomerisation} · CPC title

• C08F4/08

  of alkali metals · CPC title