# US 9,518,140 B2 · Process for production of fluorine-containing block copolymer

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- Number: US 9,518,140 B2
- Document ID: US9518140B2
- Status: Granted
- Kind: B2
- Application number: 15/041,285
- Filed: 2016-02-11
- Published: 2016-06-09
- Granted: 2016-12-13
- Earliest claimed: 2009-07-16
- Assignees: Daikin Industries, Ltd.
- Applicants: Daikin Industries, Ltd.
- Inventors: Yuzo Komatsu; Kenichi Katsukawa; Haruhiko Mohri; Takashi Kanemura
- Web page: https://patentgrep.com/patent/US9518140B2

## CPC

- C08F 293/005: {using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent}
- C08F 259/08: on to polymers containing fluorine
- C08F 293/00: Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule (on to polymers modified by introduction of unsaturated end groups C08F290/02)
- C08J 3/24: Crosslinking, e.g. vulcanising, of macromolecules (mechanical aspects B29C35/00; crosslinking agents C08K)
- C08F 214/22: Vinylidene fluoride
- C08F 214/262: {with fluorinated vinyl ethers}
- C08J 2327/22: modified by chemical after-treatment
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08J: WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H (working, e.g. shaping, of plastics B29)

## Abstract

Provided is a process for the production of a fluorine-containing block copolymer, which suppresses the formation of a homopolymer as a by-product and which, regardless of whether the chain transfer constant of the iodine end is large or small, achieves nearly 100% conversion into a block copolymer. The process is characterized by reacting (A) a fluorine-containing polymer which has an iodine atom or a bromine atom at either or both terminals of the backbone chain and/or at a side-chain terminal with (M) a radical-polymerizable monomer in the presence of (C) a sulfur compound represented by general formula (2): (Y1)nH2-nS2O4 (wherein Y1 is a mono- or divalent metal ion or an ammonium ion; and n is an integer of 0 to 2).

## Claims

### Claim 1

A method for producing a fluorine-containing block copolymer, comprising
reacting a fluoropolymer (A) having an iodine atom at either or both ends of its main chain and/or an end of its side chain with a radical polymerizable monomer (M) in the presence of a sulfur compound (C) represented by formula (2):
(Y1)nHmS2O4 (2)
wherein Y1 is a monovalent metal ion or an ammonium ion, n is 1 and m is 1;
Y1 is a monovalent metal ion or an ammonium ion, n is 2 and m is 0; or
Y1 is a divalent metal ion, n is 1 and m is 0,
said fluoropolymer (A) further having a terminal structure represented by —CH2I and being a fluoropolyether having a repeating unit represented by formula (6):
—(R8—O)n— (6)
wherein R8 is a C1-C6 linear or branched fluoroalkylene group; n is an integer of 1 to 500.

### Claim 2 (depends on 1)

The production method according to claim 1,
wherein the fluoropolymer (A), excluding both end groups thereof, has a structure of a fluoropolyether chain which includes at least one structural unit selected from the group consisting of —CF2O—, —CF2CF2O—, —CF2CF2CF2O—, CF(CF3)CF2O—, —CH2CF2CF2O— and —C(CF3)2O— and which has a number average molecular weight of 300 to 300,000.

### Claim 3 (depends on 1)

The production method according to claim 1,
wherein the radical polymerizable monomer (M) is a monomer which is different from a fluoromonomer (N) giving a structural unit of the fluoropolymer (A) and which is at least one monomer selected from the group consisting of vinyl fluoride monomers, nonfluoro ethylenic monomers, (meth)acrylic monomers, styrenic monomers, vinyl etheric monomers, and vinyl ester monomers.

### Claim 4 (depends on 1)

The production method according to claim 1,
wherein the sulfur compound (C) is selected from the group consisting of Na2S2O4, K2S2O4, Li2S2O4, NaHS2O4, KHS2O4, LiHS2O4, ZnS2O4, MgS2O4, CaS2O4, (NH4)2S2O4 and (NH4)HS2O4.