Living radical polymerization method using zinc phthalocyanine dye as near-infrared photocatalyst

Patent metadata

Field	Value
Publication number	US-12098223-B2
Application number	US-202017427640-A
Country	US
Kind code	B2
Filing date	Aug 20, 2020
Priority date	Jul 29, 2020
Publication date	Sep 24, 2024
Grant date	Sep 24, 2024

Abstract

The invention provides a living radical polymerization method using a zinc phthalocyanine dye as a near-infrared photocatalyst, including subjecting a free radical polymerizable monomer to a near-infrared light-controlled polymerization reaction, in the presence of a chain transfer agent, a cocatalyst and a zinc phthalocyanine dye containing a carbon-carbon double bond, in a solvent at 0-30° C. under the air atmosphere, to obtain a living radical polymerization product. The free radical polymerizable monomer is an acrylate monomer, a methacrylate monomer, an acrylamide monomer or a methacrylamide monomer; the chain transfer agent includes a thiocarbonate; and the cocatalyst includes an organic amine with or without a carbon-carbon double bond. A near-infrared light-responsive functional zinc phthalocyanine dye is used as a near-infrared photocatalyst for the polymerization reaction, and after the polymerization is completed, the polymerizable zinc phthalocyanine dye remains on the polymer chain by polymerization, thereby realizing the cyclic utilization of the near-infrared photocatalyst.

First claim

What is claimed is:

1. A near-infrared light-controlled living radical polymerization method, comprising steps of:
subjecting a free radical polymerizable monomer to a near-infrared light-controlled polymerization reaction, in the presence of a chain transfer agent, a cocatalyst and a zinc phthalocyanine dye with a carbon-carbon double bond as a catalyst, in a solvent at 0-30° C. under the air atmosphere, to obtain a living radical polymerization product after complete reaction,
wherein the free radical polymerizable monomer is selected from an acrylate monomer, a methacrylate monomer, an acrylamide monomer or a methacrylamide monomer;
the chain transfer agent comprises a thiocarbonate;
the cocatalyst comprises an organic amine with a carbon-carbon double bond or an organic amine without a carbon-carbon double bond; and
the living radical polymerization product has a structure of Formula (1) or (2):

in which co represents a random copolymer;
R 1 and R 1 ′ are each independently selected from the group consisting of

R 2 and R 2 ′ are each independently selected from a C2-C12 alkyl group or a C2-C12 alkyl group substituted with carboxyl;
R 3 , R 3 ′, R 5 and R 5 ′ are each independently selected from hydrogen or methyl;
R 4 is selected from benzyl, a C1-C6 alkyl group, a C1-C6 alkyl group substituted with hydroxyl, a polyethylene glycol chain, a C1-C6 alkylene oxide, or a C1-C6 alkyl group substituted with dimethylamino;
R 6 and R 6 ′ are each independently selected from

R 7 and R 7 ′ are each independently selected from hydrogen or methyl;
R 8 and R 9 are each independently selected from hydrogen, a C1-C6 alkyl group, or a C1-C6 alkyl group substituted with hydroxyl; and
X=3-1000; y is lower than 10; and z=0-20.

2. The living radical polymerization method according to claim 1 , wherein when z=0, the cocatalyst is an organic amine without a carbon-carbon double bond; and the organic amine without a carbon-carbon double bond is triethylamine and/or tributylamine.

3. The living radical polymerization method according to claim 1 , wherein when z=1−20, the cocatalyst comprises an organic amine with a carbon-carbon double bond; and the organic amine with a carbon-carbon double bond is dimethylaminoethyl acrylate and/or dimethylaminoethyl methacrylate.

4. The living radical polymerization method according to claim 1 , wherein R 2 and R 2 ′ are each independently selected from the group consisting of ethyl, n-dodecyl, and —CH 2 CH 2 COOH.

5. The living radical polymerization method according to claim 1 , wherein R 4 is selected from the group consisting of: —CH 3 ,

in which n=5-22.

6. The living radical polymerization method according to claim 1 , wherein R 8 and R 9 are each independently selected from the group consisting of hydrogen, methyl, ethyl, isopropyl and 2-hydroxypropyl.

7. The living radical polymerization method according to claim 1 , wherein the molar ratio of the free radical polymerizable monomer to the zinc phthalocyanine dye is 1:0.00001-0.01.

8. The living radical polymerization method according to claim 1 , wherein the molar ratio of the thiocarbonate to the cocatalyst is 1:0.5-20.

9. The living radical polymerization method according to claim 1 , wherein the near-infrared light-controlled polymerization reaction takes place at a near-infrared light with a wavelength of 650-900 nm.

10. A living radical polymerization product prepared by the method according to claim 1 , having a molecular weight of 1000-200000 g/mol and a molecular weight distribution of 1.07-1.5.

Assignees

• Univ Soochow

Inventors

• Cheng Zhenping
• Tian Chun
• Zhang Lifen
• Zhu Xiulin

Classifications

• 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

• C08F230/04

  containing a metal · CPC title

• C08F220/14 Primary

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

• C08F4/50

  selected from alkaline earth metals, zinc, cadmium, mercury, copper or silver · CPC title

• C08F2/46

  Polymerisation initiated by wave energy or particle radiation · CPC title