Method of producing methacrylate block copolymer

Patent metadata

Field	Value
Publication number	US-10626210-B2
Application number	US-201815995749-A
Country	US
Kind code	B2
Filing date	Jun 1, 2018
Priority date	Dec 1, 2017
Publication date	Apr 21, 2020
Grant date	Apr 21, 2020

Abstract

A method of producing a methacrylate block copolymer includes operations of (a) preparing a polymer solution comprising a methacrylate polymer block by polymerizing a methacrylate monomer using a polymerization initiator and a reversible addition-fragmentation chain transfer (RAFT) agent in the presence of water or an organic solvent; (b) preparing a polymer solution comprising an acrylate polymer block-containing methacrylate diblock copolymer by adding an acrylate monomer and a styrene monomer to the polymer solution prepared in operation (a); (c) preparing a polymer solution comprising a methacrylate polymer block-containing methacrylate triblock copolymer by adding a methacrylate monomer to the polymer solution prepared in operation (b); and (d) collecting a polymer prepared after operations (b) and (c) and removing the RAFT agent present at a terminal of the polymer by using an amine-based organic material.

First claim

What is claimed is:

1. A method of producing a methacrylate block copolymer, the method comprising operations of:
(a) preparing a first polymer solution comprising a methacrylate polymer block by polymerizing a methacrylate monomer in the presence of a polymerization initiator and a reversible addition-fragmentation chain transfer (RAFT) agent in the presence of water or an organic solvent;
(b) preparing a second polymer solution comprising an acrylate polymer block-containing methacrylate diblock copolymer by adding an acrylate monomer and a styrene monomer to the polymer solution prepared in the operation (a);
(c) preparing a third polymer solution comprising a methacrylate polymer block-containing methacrylate triblock copolymer by adding a methacrylate monomer to the polymer solution prepared in the operation (b); and
(d) collecting a polymer prepared after the operations (b) and (c) and removing the RAFT agent present at a terminal of the polymer with an amine-based organic material.

2. The method of claim 1 , wherein a collected polymer in the operation (d) comprises 60 to 90% by weight of the methacrylate monomer, 10 to 40% by weight of the acrylate monomer, and 0.1 to 10% by weight of the styrene monomer based on a total weight of the collected polymer in the operation (d).

3. The method of claim 1 , wherein the RAFT agent used in the operation (a) comprises at least one selected from the group consisting of dithioester and trithiocarbonate.

4. The method of claim 3 , wherein the dithioester comprises a compound represented by Formula 1 below:

wherein R1 comprises at least one selected from the group consisting of an alkyl group, a cycloalkyl group, and an aryl group having 1 to 20 carbon atoms, and
R2 is an alkyl group having 1 to 8 carbon atoms,
at least one hydrogen atom of the alkyl group of R1 or R2 is substituted with at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, and a cyano group.

5. The method of claim 3 , wherein the trithiocarbonate comprises a compound represented by Formula 2 below:

wherein R1 comprises at least one selected from the group consisting of an alkyl group, a cycloalkyl group, and an aryl group having 1 to 20 carbon atoms, and
R2 is an alkyl group having 1 to 8 carbon atoms,
at least one hydrogen atom of the alkyl group of R1 or R2 is substituted with at least one functional group selected from the group consisting of a hydroxyl group, a carboxyl group, and a cyano group.

6. The method of claim 1 , wherein a molar ratio of the RAFT agent to each of the methacrylate monomer of the operation (a), the acrylate monomer and the styrene monomer of the operation (b), and the methacrylate monomer of the operation (c) is in a range of 1:100 to 500.

7. The method of claim 1 , wherein a molar ratio of the RAFT agent to the polymerization initiator is in a range of 1:5 to 10.

8. The method of claim 1 , wherein the methacrylate monomers used in the operations (a) and (c) comprise at least one selected from the group consisting of methyl methacrylate (MMA), ethyl methacrylate, and cyclohexyl methacrylate.

9. The method of claim 1 , wherein the acrylate monomer used in the operation (b) comprises at least one selected from the group consisting of methylacrylate, ethylacrylate, butylacrylate, and hexylacrylate, and
the styrene monomer comprises at least one selected from the group consisting of styrene, α-methylstyrene, p-bromostyrene, p-methylstyrene, p-chlorostyrene, and o-bromostyrene.

10. The method of claim 1 , wherein the amine-based organic material used in the operation (d) comprises at least one selected from the group consisting of
a primary amine comprising propyl amine, n-butyl amine, t-butyl amine, n-hexyl amine, and n-octylamine,
a secondary amine comprising pyridine, pyrrolidine, piperidine, and pyrrole, and 2 equivalents of amines comprising imidazole, pyrimidine, and hydrazine.

11. The method of claim 1 , wherein the polymerization initiator comprises at least one selected from the group consisting of azobisisobutyronitrile, 1,1′-azobis(cyclohexanecarbonitrile), a water soluble azo initiator 2,2′-azobis(2-(2-imidazolin-2-yl)propane, a water soluble azo initiator 4,4′-azobis(4-cyanovaleric acid), sodium persulfate, potassium persulfate, ammonium persulfate, and sodium dodecyl sulfate.

Assignees

• Hyundai Motor Co Ltd
• Kia Motors Corp
• Univ Inha Res & Business Found

Inventors

• Hwang Duckhyoung
• Kim Seok Hwan
• Kwon Yong Ku
• Hwang Daehyeon

Classifications

• C08F220/1804

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

• C08F293/005 Primary

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

• C08F212/08

  Styrene · CPC title

• C08F220/1806

  C6-(meth)acrylate, e.g. (cyclo)hexyl (meth)acrylate or phenyl (meth)acrylate · CPC title

• C08K2003/3054

  Ammonium sulfates · CPC title