Trifunctional olefinic-capped polymers and compositions that include such polymers

• US 6,515,078 B1
• Filed: 08/21/2002
• Issued: 02/04/2003
• Est. Priority Date: 06/11/1999
• Status: Expired due to Fees

• Current Assignee: Lord Corporation (Parker-Hannifin Corporation)
• Original Assignee: Lord Corporation (Parker-Hannifin Corporation)
• Inventors: Righettini, Robin F.
• Primary Examiner(s): PEZZUTO, HELEN LEE
• Application Number:
  US10/224,785
• Time in Patent Office: 167 Days
• Field of Search: 525/54.3, 525/54.4, 525/59, 525/293, 525/302, 525/330.3, 525/331.9, 525/440, 525/445, 525/479, 526/279, 526/310, 526/313, 526/320, 526/328, 526/332, 526/335
• US Class Current: 525/302
• CPC Class Codes: C08C 19/28 Reaction with compounds containing carbon-to-carbon unsaturated bonds graft polymers C08F279/00
• CPC Class Codes: C08F 8/30 Introducing nitrogen atoms or nitrogen-containing groups
• CPC Class Codes: C08F 8/34 Introducing sulfur atoms or sulfur-containing groups

Abstract

A polymer having at least one reactive terminal or pendant functional group that has been capped with a trifunctional olefinic compound. The polymer can be made by contacting a base polymer having at least one reactive terminal or pendant functional group with a trifunctional olefinic compound under conditions effective to react at least one of the terminal or pendant functional groups with the trifunctional olefinic compound. The capped polymers are particularly suitable as crosslinking toughening agents in multi-components compositions such as adhesives, coatings and matrices for composites.

Claims

1. A composition comprising (a) a polymerizable component and (b) a polymer having at least one reactive terminal or pendant functional group that has been capped with a trifunctional olefinic compound having a structure represented by:

wherein A represents said polymer;

X is an electron withdrawing group;

Y is —

R¹, —

Ar or an electron withdrawing group; and

Z is a moiety selected from the first or second row elements of the Periodic Chart in the form of either a single element or linearly bonded multiple elements; and

R¹ is an alkyl, alkoxy, alkyl ether, alkenyl, alkyl ester, amino, alkylamino, alkylimino, or alkylamimidoyl, wherein Ar is an aryl or substituted aryl group.

2. A composition according to claim 1 wherein the curable component comprises at least one ethylenically unsaturated compound selected from a styrenic compound, a vinyl ether and a conjugated diene.

3. A composition according to claim 2 wherein the ethylenically unsaturated compound is selected from a styrenic monomer.

4. A composition according to claim 3 wherein the styrenic monomer is selected from styrene or vinyl toluene.

5. A composition according to claim 4 wherein the styrenic monomer is vinyl toluene.

6. A composition according to claim 2 wherein the trifunctional olefinic compound has a structure represented by formula A

wherein X is an electron withdrawing group; Y is —

R¹, —

Ar or an electron withdrawing group;

Z is a moiety selected from the first or second row elements of the Periodic Chart in the form of either a single element or linearly bonded multiple elements; and

R¹ is an alkyl, alkoxy, alkyl ether, alkenyl, alkyl ester, amino, alkylamino, alkylimino, or alkylamimidoyl, wherein Ar is an aryl or substituted aryl group.

7. A composition according to claim 6 wherein the electron withdrawing group is —

SO₂R¹, —

CN, SO₂Ar, —

(C═

O)R², or halogen, wherein Ar is an aryl or substituted aryl group;

R¹ is an alkyl, alkoxy, alkyl ether, alkenyl, alkyl ester, amino, alkylamino, alkylimino, or alkylamimidoyl; and

R² is an alkyl, —

N(H)R¹, or —

NH₂.

8. A composition according to claim 2 wherein the trifunctional olefinic compound comprises a benzylidenecyanoacetate.

9. A composition according to claim 2 wherein the polymer with the reactive terminal or pendant functional group is selected from polyether polyol, hydroxy-terminated diene, hydroxy-terminated silicone, hydroxy-terminated polyester, amine-terminated polyether, polymer or copolymer of 2-hydroxy(meth)acrylate, poly(vinyl alcohol), poly(vinyl acetal), poly(vinyl phenol), cellulose, chitin or oligomerized castor oil.

10. A composition according to claim 6 wherein the curable component comprises at least one styrenic monomer.

11. A composition according to claim 10 wherein the polymer with the reactive terminal or pendant functional group is selected from polyether polyol, hydroxy-terminated diene, hydroxy-terminated silicone, hydroxy-terminated polyester, amine-terminated polyether, polymer or copolymer of 2-hydroxy(meth)acrylate, poly(vinyl alcohol), poly(vinyl acetal), poly(vinyl phenol), cellulose, chitin or oligomerized castor oil.

12. A composition according to claim 10 wherein the trifunctional olefinic compound comprises a benzylidenecyanoacetate and the ethylenically unsaturated compound comprises vinyl toluene.

13. A polymer according to claim 1 wherein the electron withdrawing group is —

SO₂R¹, —

CN, SO₂Ar, —

(C═

O)R², or halogen, wherein Ar is an aryl group;

R¹ is an alkyl, alkoxy, alkyl ether, alkenyl, alkyl ester, amino, alkylamino, alkylimino, or alkylamimidoyl; and

R² is an alkyl, —

N(H)R¹, or —

NH₂.

14. A polymer according to claim 1 wherein X is —

CN;

Y is —

CN or —

Ar;

Z is hydrogen and R¹ is a primary or secondary alkyl having 1 to 18 carbon atoms.

15. A polymer according to claim 1 wherein the trifunctional olefinic compound comprises a benzylidenecyanoacetate.

16. A polymer according to claim 1 wherein the reactive terminal or pendant functional group of the polymer is selected from at least one of hydroxyphenyl, hydroxy or amino.

17. A polymer according to claim 1 wherein the polymer having the reactive terminal or pendant functional group is selected from polyether polyol, hydroxy-terminated diene, hydroxy-terminated silicone, hydroxy-terminated polyester, amine-terminated polyether, polymer or copolymer of 2-hydroxy(meth)acrylate, poly(vinyl alcohol), poly(vinyl acetal), poly(vinyl phenol), cellulose, chitin or oligomerized castor oil.