IP Library Granted Patent US 9,441,144
Granted Patent B2
US 9,441,144 · App. 13/753,681 · Granted Sep 13, 2016

Benzoxazine-thiol adducts

Inventors: Ilya Gorodisher (Stillwater, MN); Robert J. Webb (Hudson, WI); Robert J. Devoe (Minneapolis, MN)
Assignee: 3M Innovative Properties Company
C09J181/02C08G73/06C08L79/04C09J5/06C09J179/04C08K5/37
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Quick Facts
Patent No.
US 9,441,144
App. No.
13/753,681
Granted
Sep 13, 2016
Kind
B2
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.

Claims (54)

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.

Continuity (3)
Division 12685707
Provisional Application 61184328 · Jun 5, 2009
Related Publication 20130139965A1 · Jun 6, 2013