Fluorine-containing diblock copolymer

Patent metadata

Field	Value
Publication number	US-10196473-B2
Application number	US-201415107677-A
Country	US
Kind code	B2
Filing date	Dec 22, 2014
Priority date	Dec 25, 2013
Publication date	Feb 5, 2019
Grant date	Feb 5, 2019

Abstract

Provided is a fluorine-containing diblock copolymer having good water and oil repellency by using, as a raw material, a fluorine-containing (meth)acrylic ester having low bioaccumulation potential. The fluorine-containing diblock copolymer is produced by: process (A) a process for producing a fluorine-containing diblock copolymer by polymerizing a fluorine-containing (meth)acrylic ester represented by the following formula (1) in the presence of a trithiocarbonic ester compound and a radical polymerization initiator and then polymerizing a non-fluorine vinyl-based monomer, or process (B) a process for producing a fluorine-containing diblock copolymer by polymerizing a non-fluorine vinyl-based monomer in the presence of a trithiocarbonic ester compound and a radical polymerization initiator and then polymerizing a fluorine-containing (meth)acrylic ester represented by the following formula (1).

First claim

The invention claimed is:

1. A production process for a fluorine-containing diblock copolymer, being either the following process (A) or the following process (B):
Process (A)
a production process comprising
[first step] a step of polymerizing a fluorine-containing (meth)acrylic ester represented by the following formula (1) in the presence of a trithiocarbonic ester compound and a radical polymerization initiator to give a polymer of the fluorine-containing (meth)acrylic ester, and
[second step] a step of polymerizing a non-fluorine vinyl-based monomer in the presence of the polymer of the fluorine-containing (meth)acrylic ester obtained in the first step to give a fluorine-containing diblock copolymer;

Process (B)
a production process comprising
[first step] a step of polymerizing a non-fluorine vinyl-based monomer in the presence of a trithiocarbonic ester compound and a radical polymerization initiator to give a polymer of the non-fluorine vinyl-based monomer, and
[second step] a step of polymerizing a fluorine-containing (meth)acrylic ester represented by the following formula (1) in the presence of the polymer of the non-fluorine vinyl-based monomer obtained in the first step to give a fluorine-containing diblock copolymer;

wherein R 1 is a hydrogen atom or a methyl group,
a is an integer of 1 to 3, b is an integer of 1 to 2, n is an integer of 1 to 6,
—C n F 2n+1 group is bonded to CH 2 group of(CF 2 CH 2 ) b — group, and
—(CF 2 CF 2 ) a — group is bonded to CF 2 group of —(CF 2 CH 2 ) b — group;

wherein the trithiocarbonic ester compound is a compound represented by the following formula (2):

wherein R 2 and R 3 are each independently a hydrogen atom or an alkyl group of 1 to 3 carbon atoms, and any one of R 2 and R 3 may contain one carboxyl group, and
R 4 is a straight-chain alkyl group of 6 to 18 carbon atoms; and
wherein the process (A) and the process (B) are carried out in a borosilicate tempered glass reaction container.

2. The production process as defined in claim 1 , wherein the radical polymerization initiator is an azo-based radical polymerization initiator.

3. The production process as defined in claim 1 , wherein the fluorine-containing diblock copolymer has a number-average molecular weight of 5,000 to 200,000.

Assignees

• Unimatec Co Ltd

Inventors

• Saito Satoru
• Sato Katsuyuki
• Sonoi Takehiro

Classifications

• C08F293/005 Primary

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

• C08F220/24

  containing perhaloalkyl radicals · CPC title

• 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

• C08F2438/01

  Atom Transfer Radical Polymerization [ATRP] or reverse ATRP · CPC title