Fluorinated-containing macroinitiator and production process for the same

Patent metadata

Field	Value
Publication number	US-9587039-B2
Application number	US-201415107644-A
Country	US
Kind code	B2
Filing date	Dec 22, 2014
Priority date	Dec 25, 2013
Publication date	Mar 7, 2017
Grant date	Mar 7, 2017

Abstract

Provided is a fluorine-containing macroinitiator, particularly a fluorine-containing macroinitiator that enables production of a fluorine-containing block copolymer containing a non-fluorine vinyl-based monomer having a long side chain. The fluorine-containing macroinitiator includes a polymer represented by the following formula (1) and having a number-average molecular weight of 3,000 to 100,000. In the following formula (1), R 2 , R 3 and R 4 are each a specific group, and Q is a polymer segment composed of a structural unit represented by the following formula (2). In the following formula (2), R 1 is a hydrogen atom or a methyl group, Rf is a fluoroalkyl group having a specific structure, and k is an appropriate integer that is not 0.

First claim

The invention claimed is:

1. A fluorine-containing macroinitiator comprising:
a polymer represented by the following formula (1) and having a number-average molecular weight of 3,000 to 100,000,

wherein R 2 is a straight-chain alkyl group of 1 to 18 carbon atoms,
R 3 and R 4 are each independently a hydrogen atom or an alkyl group of 1 to 3 carbon atoms, and any one of R 3 and R 4 may contain one carboxyl group, and
Q is a polymer segment composed of a structural unit represented by the following formula (2):

wherein R 1 is a hydrogen atom or a methyl group,
Rf is a fluoroalkyl group represented by the following formula (3) or a fluoroalkyl group represented by the following formula (4), and
k is an appropriate integer that is not 0,

wherein n is an integer of 1 to 6,

wherein a is an integer of 0 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.

2. The fluorine-containing macroinitiator as defined in claim 1 , wherein in the formula (2), the Rf is a fluoroalkyl group represented by the formula (4), and a is 1 or 2.

3. The fluorine-containing macroinitiator as defined in claim 1 , wherein in the formula (2), the Rf is a fluoroalkyl group represented by the formula (3), and n is 4 or 6.

4. A production process for the fluorine-containing macroinitiator as defined in claim 1 , comprising:
a step of polymerizing a fluorine-containing (meth)acrylic ester represented by the following formula (6) by the use of an azo-based radical polymerization initiator in the presence of a trithiocarbonic ester compound represented by the following formula (5):

wherein R 2 is a straight-chain alkyl group of 1 to 18 carbon atoms, and
R 3 and R 4 are each independently a hydrogen atom or an alkyl group of 1 to 3 carbon atoms, and any one of R 3 and R 4 may contain one carboxyl group,

wherein R 1 is a hydrogen atom or a methyl group, and
Rf is a fluoroalkyl group represented by the following formula (3) or a fluoroalkyl group represented by the following formula (4),

wherein n is an integer of 1 to 6,

wherein a is an integer of 0 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.

5. The production process as defined in claim 4 , wherein the polymerization is carried out in one of a borosilicate tempered glass reaction container or a stainless steel reaction container.

6. The production process as defined in claim 4 , wherein in the formula (2), the Rf is a fluoroalkyl group represented by the formula (4), and a is 1 or 2.

7. The production process as defined in claim 4 , wherein in the formula (2), the Rf is a fluoroalkyl group represented by the formula (3), and n is 4 or 6.

Assignees

• Unimatec Co Ltd

Inventors

• Saito Satoru
• Sato Katsuyuki
• Sonoi Takehiro

Classifications

• C08F4/04

  Azo-compounds · CPC title

• C08F293/005

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

• C08F2/38 Primary

  Polymerisation using regulators, e.g. chain terminating agents {, e.g. telomerisation} · CPC title

• C08F20/22

  Esters containing halogen · CPC title