Polymer production method and radical polymerization initiating group-containing compound

Patent metadata

Field	Value
Publication number	US-10982033-B2
Application number	US-201716066972-A
Country	US
Kind code	B2
Filing date	Feb 22, 2017
Priority date	Feb 29, 2016
Publication date	Apr 20, 2021
Grant date	Apr 20, 2021

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 method for producing a polymer, the method comprising radical polymerization of a radically polymerizable monomer by mixing and warming a composition,
wherein the composition comprises:
(1) the radically polymerizable monomer having an unsaturated bond;
(2) an organic compound having at least one functional group that functions as group for initiating the radical polymerization of the radically polymerizable monomer,
wherein the at least one functional group has a structure represented by following formula [1] or following formula [2] and is introduced in a molecule of the organic compound; and

(3) an iodine ion-containing compound being at least one iodide salt or at least one triiodide salt selected from the group consisting of metal iodides, quaternary ammonium iodides, quaternary phosphonium iodides, and quaternary ammonium triiodides; and
(4) at least one material selected from the group consisting of iodine, iodinated organic compounds capable of releasing iodine, and compounds each having an organic base,
wherein the radical polymerization is accompanied by a termination reaction and is initiated by the at least one functional group,
the metal iodides in the group for the iodine ion-containing compound (3) are lithium iodide, sodium iodide, potassium iodide, calcium iodide, and magnesium iodide,
the iodinated organic compounds capable of releasing iodine are N-iodoimide-based compounds, and the compounds each having an organic base are triethylamine, tributylamine, diazabicycloundecene, diazabicyclooctane, and phosphazene bases,
the at least one material (4) is present in amount at a ratio of the at least one material (4) relative to a total amount of the functional group of formula [1] and the functional group of formula [2] in the organic compound (2) being in a range from 0.001 to 0.1 (mol/mol), and
the method does not use a metal catalyst used in living 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 method for producing a polymer according to claim 1 ,
wherein the radical polymerization is performed 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.

3. The method for producing a polymer according to claim 1 ,
wherein an organic solvent is further used during the radical polymerization.

4. The method for producing a polymer according to claim 3 ,
wherein the organic solvent is at least one solvent selected from the group consisting of alcohol-based solvents, glycol-based solvents, amide-based solvents, sulfoxide-based solvents, and ionic liquids.

5. The method for producing a polymer according to claim 1 ,
wherein the N-iodoimide-based compounds are N-iodosuccinimide, N-iodophthalimide, N-iodocyclohexanylimide, 1,3-diiodo-5,5-dimethylhydantoin, and N-iodosaccharin.

6. The method for producing a polymer 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 0 or NH.

7. The method for producing a polymer according to claim 1 ,
wherein the organic compound (2) is a polymerization initiating group-containing polymer,
two groups each having the structure represented by the formula [1] or the formula [2] are introduced in a molecule of the polymerization initiating group-containing polymer, and
the polymer to be obtained in the radical polymerization is a polymer having a block structure or a comb-shaped structure.

8. The method for producing a polymer according to claim 1 ,
wherein the organic 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, and
the polymer to be obtained in the radical polymerization is a polymer having a branched structure, a star polymer, or a graft copolymer.

9. The method for producing a polymer according to claim 1 ,
wherein the organic compound (2) is a vinyl polymer in a molecule of which three or more groups each having a structure represented by the formula [1] or the formula [2] are introduced, and
the polymer to be obtained in the radical polymerization is (a) a polymer having a structure in which a polymer of the monomer (1) is grafted onto the vinyl polymer, or (b) a bottle brush polymer.

10. The method for producing a polymer according to claim 1 ,
wherein the organic compound (2) is a copolymer of a monomer in a molecule of which 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 surface of the base material is treated with the copolymer so as to modify the surface of the base material, and thereafter the monomer (1) and the iodine ion-containing compound (3) are mixed and warmed on the modified surface of the base material, thereby producing the polymer on the surface of the base material, and
the obtained polymer has a dense brush structure.

11. The method for producing a polymer according to claim 1 ,
wherein a temperature of the radical polymerization is in a range from 40° C. to 120° C.

12. A method for producing a polymer, the method comprising radical polymerization of a radically polymerizable monomer by mixing and warming a composition,
wherein the composition comprises:
(1) the radically polymerizable monomer having an unsaturated bond;
(2) an organic compound having at least one functional group that functions as group for initiating the radical polymerization of the radically polymerizable monomer,
wherein the at least one functional group has a structure represented by following formula [1] or following formula [2] and is introduced in a molecule of the organic compound; and

(3) an iodine ion-containing compound comprising at least one salt of quaternary ammonium triiodides; and
(4) at least one material selected from the group consisting of iodine, iodinated organic compounds capable of releasing iodine, and compounds each having an organic base,
wherein the radical polymerization is accompanied by a termination reaction and is initiated by the at least one functional group,
the iodinated organic compounds capable of releasing iodine are N-iodoimide-based compounds,
the compounds each having an organic base are triethylamine, tributylamine, diazabicycloundecene, diazabicyclooctane, and phosphazene bases,
the at least one material (4) is present in amount at a ratio of the at least one material (4) relative to a total amount of the functional group of formula [1] and the functional group of formula [2] in the organic compound (2) being in a range from 0.001 to 0.1 (mol/mol), and
the method does not use a metal catalyst used in living radical polymerization,

Assignees

• Dainichiseika Color Chem

Inventors

• Shimanaka Hiroyuki
• Tagi Yoichi
• Murakami Yoshikazu

Classifications

• C08F220/281

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• C08F220/1806

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• C08F220/1812

  C12-(meth)acrylate, e.g. lauryl (meth)acrylate · CPC title

• C08F220/1804

  C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate · CPC title

• C08L101/005

  Dendritic macromolecules · CPC title