Synthesis of functional polyisobutylene-containing oligomers and polymers

Patent metadata

Field	Value
Publication number	US-9828454-B2
Application number	US-201514806237-A
Country	US
Kind code	B2
Filing date	Jul 22, 2015
Priority date	Jan 28, 2013
Publication date	Nov 28, 2017
Grant date	Nov 28, 2017

Abstract

Disclosed are single step and multi-step methods of making functional polyisobutylene (PIB)-containing oligomers and polymers and the materials made thereby. In the single step method a functional group containing PIB oligomer or polymer is made under cationic polymerization conditions in a direct, one step reaction. In the multi-step method a functional group containing PIB oligomer or polymer is made in a two-step process. The first step is performed under cationic polymerization conditions. The second step is performed under non-cationic polymerization conditions.

First claim

What is claimed:

1. A direct capping method of preparing a PIB oligomer or polymer in a one step reaction, comprising reacting components as shown below:

where:
R 1 is an initiator core structure independently selected from alkyl, heteroalkyl, aryl, heteroaryl, alkenyl, heteroalkenyl, alkynyl, heteroalkynyl and alkoxy and R 1 can be substituted or unsubstituted;
X is an initiating site bonded to the initiator core structure independently selected from halide, alkoxy, and ester;
m is an integer from about 2 to about 1,000;
n is an integer from about 1 to about 20;

CAP is a capping reagent selected from structure I;
I Ar-(EDG-R 2 —Y) q
where EDG is an electron donating group selected from NR 3 , S, and R 4 ;
R 2 can be independently selected from alkylene, heteroalkylene, alkenylene, heteroalkenylene, alkynylene, heteroalkynylene, arylene and heteroarylene;
R 3 can be independently selected from H, alkyl, heteroalkyl, alkenyl, heteroalkenyl, alkynyl, heteroalkynyl, aryl, and heteroaryl;
R 4 can be independently selected from alkylene, heteroalkylene, alkenylene, heteroalkenylene, alkynylene, heteroalkynylene, arylene and heteroarylene;

q is an integer from about 1 to about 20; and
Y can be independently selected from (meth)acrylate, OH, epoxy, oxetane, cyanate, isocyanate, urethane, urea, NR 5 R 6 , SR 7 , and Si(OR 8 ) i R 9 3-i , where i is an integer from 0 to 3 and R 5 , R 6 , R 7 , R 8 , R 9 can be independently selected from H, alkyl, heteroalkyl, alkenyl, heteroalkenyl, alkynyl, heteroalkynyl, aryl, and heteroaryl; or
from one or more of following structures II to III;
II (Ar) p -Ar-(EDG-R 2 —Y) q
III PAr-(EDG-R 2 —Y) q
where EDG is an electron donating group selected from O, NR 3 , S, and R 4 ;
R 2 can be independently selected from alkylene, heteroalkylene, alkenylene, heteroalkenylene, alkynylene, heteroalkynylene, arylene and heteroarylene;
R 3 can be independently selected from H, alkyl, heteroalkyl, alkenyl, heteroalkenyl, alkynyl, heteroalkynyl, aryl, and heteroaryl;
R 4 can be independently selected from alkylene, heteroalkylene, alkenylene, heteroalkenylene, alkynylene, heteroalkynylene, arylene and heteroarylene;

p is an integer from about 1 to about 20;
q is an integer from about 1 to about 20; and
Y can be independently selected from (meth)acrylate, OH, epoxy, oxetane, cyanate, isocyanate, urethane, urea, NR 5 R 6 , SR 7 , and Si(OR 8 ) i R 9 3-i , where i is an integer from 0 to 3 and R 5 , R 6 , R 7 , R 8 , R 9 can be independently selected from H, alkyl, heteroalkyl, alkenyl, heteroalkenyl, alkynyl, heteroalkynyl, aryl, and heteroaryl.

2. The method of claim 1 wherein EDG for capping reagent I is selected from NR 3 , S, and R 4 .

3. The method of claim 1 wherein CAP is shown in the following structure

4. The method of claim 1 wherein CAP is shown in the following structure

5. The method of claim 1 wherein CAP is shown in the following structure

6. A curable composition comprising the functionalized PIB containing oligomer or polymer of claim 1 and optionally further comprising one or more of a co-monomer, catalyst, filler, antioxidant, reaction modifier, adhesion promoter, rheology modifier.

7. A cured reaction product of a curable composition comprising the functionalized PIB containing oligomer or polymer of claim 1 .

8. A method of preparing a PIB polymer in a two step reaction, comprising
reacting components in step 1 under cationic reaction conditions as shown below,

reacting components in step 2 under non-cationic reaction conditions as shown below,

where:
R 1 is an initiator core structure selected from alkyl, heteroalkyl, aryl, heteroaryl, alkenyl, heteroalkeny, alkynyl, heteroalkynyl and alkoxy and R 1 can be substituted or unsubstituted;
X is an initiating site bonded to the initiator core structure and X can be selected from halide, alkoxy, and ester;
m is an integer from about 2 to about 1,000;
n is an integer from about 1 to about 20;
CAP is a capping reagent selected from one or more of following structures I to III;
I Ar-(EDG-R 2 —Y) q .
II (Ar) p -Ar-(EDG-R 2 —Y) q
III PAr-(EDG-R 2 —Y) q
where EDG is an electron donating group selected from O, NR 3 , S, and R 4 with the proviso that EDG for capping reagent I is selected from NR 3 , S, R 4 and excludes O;
R 2 can be independently selected from alkylene, heteroalkylene, alkenylene, heteroalkenylene, alkynylene, heteroalkynylene, arylene and heteroarylene;
R 3 can be independently selected from H, alkyl, heteroalkyl, alkenyl, heteroalkenyl, alkynyl, heteroalkynyl, aryl, and heteroaryl;
R 4 can be independently selected from alkylene, heteroalkylene, alkenylene, heteroalkenylene, alkynylene, heteroalkynylene, arylene and heteroarylene;

p is an integer from about 1 to about 20;
q is an integer from about 1 to about 20;
each Y can be independently selected from (meth)acrylate, OH, epoxy, oxetane, cyanate, isocyanate, urethane, urea, NR 5 R 6 , SR 7 ,and Si(OR 8 ) i R 9 3-i , where i is an integer from 0 to 3 and R 5 , R 6 , R 7 , R 8 , R 9 can be independently selected from H, alkyl, heteroalkyl, alkenyl, heteroalkenyl, alkynyl, heteroalkynyl, aryl, and heteroaryl;

each W can be independently selected from alkyl, heteroalkyl, alkenyl, heteroalkenyl, alkynyl, heteroalkynyl, aryl, and heteroaryl.

9. A curable composition comprising the functionalized PIB containing oligomer or polymer of claim 8 and optionally further comprising one or more of a co-monomer, catalyst, filler, antioxidant, reaction modifier, adhesion promoter, rheology modifier.

10. A cured reaction product of a curable composition comprising the functionalized PIB containing oligomer or polymer of claim 8 .

11. The method of claim 1 wherein CAP is a capping reagent selected from structure II or III.

Assignees

• Henkel IP & Holding GmbH

Inventors

• Burdzy Matthew
• Feng Dingsong
• Zhang Tianzhi

Classifications

• C08F4/16

  of silicon, germanium, tin, lead, titanium, zirconium or hafnium · CPC title

• C08F2810/40

  taking place solely at one end or both ends of the polymer backbone, i.e. not in the side or lateral chains · CPC title

• C08F8/00 Primary

  Chemical modification by after-treatment (graft polymers, block polymers, crosslinking with unsaturated monomers or with polymers C08F251/00 - C08F299/00; of conjugated diene rubbers C08C) · CPC title

• C08F110/10

  Isobutene · CPC title

• C08F2810/30

  leading to the formation or introduction of aliphatic or alicyclic unsaturated groups · CPC title