Benzoxazine-thiol adducts

Patent metadata

Field	Value
Publication number	US-9441144-B2
Application number	US-201313753681-A
Country	US
Kind code	B2
Filing date	Jan 30, 2013
Priority date	Jun 5, 2009
Publication date	Sep 13, 2016
Grant date	Sep 13, 2016

Abstract

Novel benzoxazine-thiol adducts are described, which may be may be cured to produce compositions useful in coating, sealants, adhesive and many other applications.

First claim

What is claimed is:

1. A B-stagable adhesive composition comprising:
a) 30 to 90 mole % of one or more N-aryl benzoxazines;
b) 10 to 70 mole % of one or more N-alkyl benzoxazines;
c) one or more non-polymeric thiol compounds, the molar amounts ratio of benzoxazine groups to thiol groups is about 1.1:1 to 50:1.

2. The adhesive of claim 1 wherein the thiol compound is of the formula R 4 —(S—H) n , wherein R 4 is a non-polymeric aliphatic, cycloaliphatic, aromatic or alkyl-substituted aromatic moiety having from 1 to 30 carbon atoms and optionally 1 to four catenary heteroatoms of oxygen, nitrogen or sulfur.

3. An adhesive composition comprising a thermal reaction product of the composition of claim 1 formed by heating the composition to at least a first temperature.

4. The adhesive composition of claim 3 wherein the thermal reaction product of the composition of claim 1 is capable of further thermal reaction upon heating to a second temperature, wherein the second temperature is higher than the first temperature.

5. The adhesive composition of claim 1 wherein the benxoxazines are of the formula:

wherein
each of R 1 is H or an alkyl group;
R 2 is H, a covalent bond, or a polyvalent (hetero)hydrocarbyl group;
R 5 is a mixture of aromatic and aliphatic groups, and
x is at least 1.

6. The adhesive composition of claim 1 wherein the benzoxazines are of the formula:

wherein
each of R 1 is H or an alkyl group;
R 2 is H, a covalent bond, or a divalent (hetero)hydrocarbyl group;
R 5 is a mixture of aromatic and aliphatic groups.

7. The adhesive composition of claim 1 wherein the benzoxazines are of the formula:

each of R 1 is H or an alkyl group;
R 2 is a covalent bond, or a divalent (hetero)hydrocarbyl group;
R 5 is a mixture of aromatic and aliphatic groups.

8. The adhesive composition of claim 1 wherein the benzoxazines are of the formula:

wherein,
each of R 1 is H or an alkyl group;
R 2 is a covalent bond, or a divalent (hetero)hydrocarbyl group;
R 5 is a mixture of aromatic and aliphatic residues of a primary diamino compounds; and
z is at least 2.

9. The adhesive composition of claim 1 wherein the thiol compound is of the formula:
R 6 —[(CO 2 ) x —R 7 —SH] y , where

R 6 is an alkylene group, an aryl group, an oxyalkylene group, or combination thereof,
R 7 is a divalent hydrocarbyl group,
x is 0 or 1,
y is 1 to 6.

10. The adhesive composition of claim 1 wherein the thiol compound is of the formula:

wherein
R 6 is an alkylene group, an aryl group, an oxyalkylene group, or combination thereof,
R 7 is a divalent hydrocarbyl group,
x is 0 or 1,
y is 1 to 6.

11. The adhesive composition of claim 1 wherein the thiol compound is of the formula:

wherein
R 6 is an alkylene group, an aryl group, an oxyalkylene group, or combination thereof,
R 7 is a divalent hydrocarbyl group,
x is 0 or 1,
y is 1 to 6.

12. The adhesive composition of claim 1 wherein the thiol compound is of the formula:

wherein
R 6 is an alkylene group, an aryl group, an oxyalkylene group, or combination thereof,
R 7 is a divalent hydrocarbyl group,
y is 1 to 6.

13. A method for assembly comprising: providing the adhesive composition of claim 1 ; providing a substrate and an adherent; applying said adhesive composition to one of said substrate and said adherent; heating said applied adhesive composition to a first temperature; optionally cooling said adhesive composition; applying the other of said substrate and said adherent to said heated adhesive composition; and heating said adhesive composition to a second temperature to further advance the cure of the adhesive composition, wherein the second temperature is higher than the first temperature.

14. A method for assembly comprising: providing the adhesive composition of claim 1 ; providing a substrate and an adherent; applying said adhesive composition to one of said substrate and said adherent; heating said adhesive composition to a first temperature; applying the other of said substrate and said adherent to said heated adhesive composition; and heating said adhesive composition to a second temperature to further advance the cure of the adhesive composition, wherein the second temperature is higher than the first temperature.

15. A method for assembly comprising: providing the adhesive composition of claim 1 ; providing a substrate and an adherent; applying said adhesive composition to one of said substrate and said adherent; heating said applied adhesive composition to a first temperature; applying the other of said substrate and said adherent to said heated adhesive composition; and continuing heating of said adhesive composition to a second temperature, higher than the first temperature to further advance the cure of the adhesive composition.

Assignees

• 3M Innovative Properties Co

Inventors

• Gorodisher Ilya
• Webb Robert J
• Devoe Robert J

Classifications

• C09J181/02 Primary

  Polythioethers; Polythioether-ethers · CPC title

• C08K5/37

  Thiols · CPC title

• C08G73/06 Primary

  Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule · CPC title

• C09J5/06

  involving heating of the applied adhesive · CPC title

• C08L79/04

  Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors · CPC title