Graft copolymer, process for producing the graft copolymer, process for preparing a gel polymer electrolyte including the graft copolymer, and intermediate copolymer of the graft copolymer

Patent metadata

Field	Value
Publication number	US-2016043434-A1
Application number	US-201414456343-A
Country	US
Kind code	A1
Filing date	Aug 11, 2014
Priority date	Aug 11, 2014
Publication date	Feb 11, 2016
Grant date	—

Abstract

A graft copolymer comprising a backbone polymer and a branched-chain polymer, and represented by formula (I),

where A, B, R a , R b , R c , R d , R e , R f , G 1 , G 2 , G 3 , G 4 , Y 1 , Y 2 , and k are as defined in the specification. A process for producing the grate copolymer, a process for preparing a gel polymer electrolyte including the graft copolymer, and an intermediate copolymer of the graft copolymer are also disclosed.

First claim

What is claimed is:

1 . A graft copolymer comprising a backbone polymer and a branched-chain polymer, and represented by formula (I),

where:
A is represented by X 1  n and is independently of each repeating unit, in which n is an integral not less than zero, and X 1 is represented by

 and is independently of each repeating unit, in which
D 1 is a carbon atom or a silicon atom,
R 1 and R 2 are independently —CH 3 , H, or F when D 1 is a carbon atom, and are independently —CH 3 , -phenyl, —OCH 3 , or —OC 2 H, when D 1 is a silicon atom, and
m is 1 or 2;

B is represented by

 in which
D 2 is a carbon atom or a silicon atom,
R 3 , R 4 , R 5 , R 6 , R 7 , and R are independently —CH 3 , H, or F when D 2 is a carbon atom, and are independently —CH 3 , -phenyl, —OCH 3 , or —OC 2 H 5 when D 2 is a silicon atom,
p is 1 or 2,
q is an integral not less than 1,
Z 1 is

 in which R 15 and R 16 are independent for each repeating unit, R 15 , R 16 , and R 17 are independently H or alkyl, and r, s, and t are each an integral not less than 1, and
Z 2 is

in which R 18 and R 19 are independent for each repeating unit, R 18 , R 19 , and R 20 are independently H or alkyl, and u, v, and w are each an integral not less than 1;
R a , R b , R c , R d , R e , and R f are independently H or alkyl;
k is an integral not less than 1; and
G 1 , G 2 , G 3 , and G 4 are independent for each repeating unit, and G 1 , G 2 , G 3 , G 4 , Y 1 , and Y 2 are independently H, alkyl, or a polymer chain selected from the group consisting of polyacrylonitrile and a derivative thereof, polyvinylsulfonic acid and a derivative thereof, polyacrylate and a derivative thereof, and polyvinylphosphonic acid and a derivative thereof.

2 . The graft copolymer according to claim 1 , wherein A is represented by

where x, y, and z are each an integral not less than zero.

3 . The graft copolymer according to claim 1 , wherein B is represented by

4 . The graft copolymer according to claim 1 , wherein at least one of G 1 , G 2 , G 3 , and G 4 , in at least one of the repeating units is the polymer chain.

5 . The graft copolymer according to claim 1 , wherein the polymer chain is polyacrylonitrile.

6 . The graft copolymer according to claim 1 , wherein R a and R e are each a methyl group, and R b , R c , R d , and R f are each hydrogen atom.

7 . A process for preparing a gel polymer electrolyte,
comprising a step of soaking the graft copolymer as claimed in claim 1 with a lithium ion containing electrolyte.

8 . The process according to claim 7 , wherein the lithium ion containing electrolyte includes lithium hexafluorophosphate.

9 . A process for producing a graft copolymer comprising steps of:
(a) preparing a prepolymer having a formula (II),

where
A is represented by X 1  n , in which n is an integral not less than zero, and X 1 is represented by

 and is independently of each repeating unit, in which:
D 1 is a carbon atom or a silicon atom;
R 1 and R 2 are independently —CH 3 , H, or F when D 1 is a carbon atom, and are independently —CH 3 , -phenyl, —OCH 3 , or —OC 2 H 5 when D 1 is a silicon atom; and

m is 1 or 2, and R a , R b , R c , R d , R e , R f , R g , R h , R 11 , R 12 , R 13 , and R 14 are independently H or alkyl;
(b) subjecting a mixture of the prepolymer and monomers to a polymerization to form an intermediate copolymer, the monomers being selected from the group consisting of acrylonitrile and a derivative thereof,
vinylsulfonic acid and a derivative thereof, acrylate and a derivative thereof, vinylphosphonic acid and a derivative thereof, and combinations thereof; and
(c) using a crosslinking agent to bridge the intermediate copolymer and an additional prepolymer having the above formula (II), the crosslinking agent having a formula (III),

where
D 2 is a carbon atom or a silicon atom,
R 3 , R 4 , R 5 , R 6 , R 7 , and R 8 are independently —CH 3 , H, or F when D 2 is a carbon atom, and are independently —CH 3 , -phenyl, —OCH 3 , or —OC 2 H 5 when D 2 is a silicon atom,
p is 1 or 2,
q is an integral not less than 1,
Z 1 ′ is

 in which R 15 and R 16 are independent for each repeating unit, R 15 , R 16 , and R 17 are independently H or alkyl, and r, s, and t are each an integral not less than 1, and
Z 2 ′ is

in which R 18 and R 19 are independent for each repeating unit, R 18 , R 19 , and R 20 are independently H or alkyl, and u, v, and w are each an integral not less than 1.

10 . The process according to claim 9 , wherein the crosslinking agent is selected from the group consisting of polyethylene glycol diglycidyl ether, epoxy-modified poly(dimethylsiloxane), and a combination thereof.

11 . The process according to claim 9 , wherein the prepolymer is polyetheramine having a formula (IV),

where each of x, y, and z is an integral not less
than zero.

12 . The process according to claim 11 , wherein the monomers are acrylonitrile.

13 . An intermediate copolymer represented by formula (V),

where
A is represented by X 1  n , in which n is an integral not less than zero, and X 1 is represented by

 and is independently of each repeating unit, in which,
D 1 is a carbon atom or a silicon atom,
R 1 and R 2 are independently —CH 4 , H, or F when D 1 is a carbon atom, and are independently —CH 3 , -phenyl, —OCH 3 , or —OC 2 H, when D; is a silicon atom, and
m is 1 or 2;

R a , R b , R c , R d , R e , and R f are independently H or alkyl; and
G 1 , G 2 , G 3 , G 4 , Y 1 , and Y 2 are independently H, alkyl, or a polymer chain selected from the group consisting of polyacrylonitrile and a derivative thereof, polyvinylsulfonic acid and a derivative thereof, polyacrylate and a derivative thereof, and polyvinylphosphonic acid and a derivative thereof.

Assignees

• Univ Nat Cheng Kung

Inventors

• Kuo Ping-Lin
• Hou Sheng-Shu
• Lu Chung-Yu
• Wu Ching-An
• Tsao Chih-Hao
• Hsu Chun-Han

Classifications

• H01M10/052

  Li-accumulators · CPC title

• H01M10/0565 Primary

  Polymeric materials, e.g. gel-type or solid-type · CPC title

• H01M2300/0085

  Immobilising or gelification of electrolyte · CPC title

• C08G73/024

  Polyamines containing oxygen in the form of ether bonds in the main chain · CPC title

• B01J41/125

  Operations & Transport · mapped topic