Organoborane amine complex polymerization initiators and polymerizable compositions

• US 6,740,716 B2
• Filed: 10/30/2001
• Issued: 05/25/2004
• Est. Priority Date: 10/30/2001
• Status: Expired due to Fees

• Current Assignee: Dow Global Technologies, Inc. (Dow, Inc.)
• Original Assignee: Dow Global Technologies, Inc. (Dow, Inc.)
• Inventors: Sonnenschein, Mark F., Webb, Steven P.
• Primary Examiner(s): Zalukaeva, Tatyana
• Application Number:
  US10/012,629
• Publication Number:
  US 20030120005A1
• Time in Patent Office: 938 Days
• Field of Search: 428/421, 428/515, 428/516, 428/500, 526/196, 526/197, 526/198, 526/208, 525/130, 525/131, 525/134, 525/459
• US Class Current: 526/196
• CPC Class Codes: C08G 18/3268 Salt complexes of polyamines
• CPC Class Codes: C08G 18/8038 with compounds of C08G18/3225
• CPC Class Codes: Y10T 428/31855 Of addition polymer from unsaturated monomers
• CPC Class Codes: Y10T 428/31909 Next to second addition polymer from unsaturated monomers
• CPC Class Codes: Y10T 428/31913 Monoolefin polymer

Abstract

The invention is a two part composition useful for initiating cure of one or more polymerizable monomers which cure when exposed to free radicals comprising in one part an organoboraneamine complex and in a second part an isocyanate which is capable of decomplexing the organoborane complex wherein the ratio of amine nitrogen atoms to boron atoms is greater than 4.0:1.0. In another embodiment the invention is a two part polymerizable composition comprising

part 1, a) an organoborane amine complex; and

part 2, b) one or more of monomers, oligomers or polymers having olefinic unsaturation which is capable of polymerization by free radical polymerization

c) an effective amount of a compound which causes the complex to disassociate thereby freeing the borane to initiate polymerization of the one or more monomers, oligomers or polymers having olefinic unsaturation wherein the compound which causes disassociation of the complex is kept separate from the complex until initiation of polymerization is desired; and

d) a material which manages the heat of the polymerization reaction such that adhesion to the substrate is maintained, which material can be located in either part 1, part 2 or both parts.

Claims

1. A two part composition useful for initiating cure of one or more polymerizable monomers which cure when exposed to free radicals, the composition comprising in one part an organoboraneamine complex and in a second part an isocyanate which is capable of decomplexing the organoborane complex wherein the equivalent ratio of amine nitrogen atoms to boron atoms is greater than 4.0:

1 wherein the equivalents ratio of isocyanate to amine is greater than 1;

0;

1.0.

2. The two part composition according to claim 1 wherein the equivalent ratio of amine to isocyanate is 1.25:

1.0 or less.

3. The two part composition according to claim 2 wherein the amine to isocyanate equivalent ratio is less than 1.0:

1.0.

4. The two part composition according to claim 3 wherein the organoborane comprises a trialkyl borane or an alkyl cycloalkyl borane and the amine comprises a primary amine;

a secondary amine;

a polyamine having primary or secondary amines or both;

ammonia;

polyoxyalkylene amines;

the reaction product of a diamine and a difunctional compound having moieties which react with an amine, wherein the reaction product has terminal amine groups;

aryl amities;

heterocyclic amines;

a compound having an amidine structural component;

aliphatic heterocycles having at least one secondary nitrogen in the heterocyclic ring wherein the heterocyclic compound may also contain one or more additional secondary or tertiary nitrogen atoms, oxygen atoms, sulfur atoms, or double bonds in the heterocycle;

alicyclic compounds having bound to the alicyclic ring one or more substituents containing an amine moiety;

conjugated imines or a mixture thereof.

5. A composition according to claim 4 wherein the complex of the organoborane and the amine corresponds to the formula

the organoborane heterocyclic amine complex corresponds to the formula;

the organoborane amidine complex corresponds to the formula

the organoborane conjugated imine complex corresponds to the formula

the organoborane alicyclic compound with an amine containing substituent

corresponds to the formula

wherein B is boron;

R¹ is separately in each occurrence hydrogen, a C_1-10 alkyl or C_3-10 cycloalkyl;

R² Is separately in each occurrence a C_1-10 alkyl, C_3-10 cycloalkyl or two or more of R² may combine to form a cycloaliphatic ring structure;

R³ is separately in each occurrence hydrogen, a C_1-10 alkyl or C_3-10 cycloalkyl;

R⁴ is separately in each occurrence hydrogen, C_1-10 alkyl, C_3-10 cycloalkyl, C_6-10 aryl or C_6-10 alkaryl;

R⁵ is separately in each occurrence hydrogen, C_1-10 alkyl, or C_3-10 cycloalkyl;

R⁶ is separately in each occurrence hydrogen, a C_1-10 alkyl, C_3-10 cycloalkyl or —

N(R⁵)₂;

R⁷ is separately in each occurrence hydrogen, C_1-10 alkyl or C_3-10 cycloalkyl;

two or more of R⁵, R⁶ and R⁷, in any combination, can combine to form a ring structure which can be a single ring or a multiple ring structure and the ring structure can Include one or more of nitrogen, oxygen or unsaturation in the ring structure;

R⁹ is independently in each occurrence hydrogen, C_1-10 alkyl or C_3-10 cycloalkyl, Y, —

(C(R⁹)₂—

(CR⁹═

CR⁹)_c—

Y or two or more of R⁹ can combine to form a ring structure, or one or more of R⁹ can form a ring structure with Y provided the electron rich group in

Y is conjugated with respect to the double bond of the imine nitrogen;

X is a hydrogen-bond accepting group,;

Y is independently in each occurrence hydrogen, —

N(R⁴)₂, —

OR⁴, —

C(O)OR⁴, a halogen or an alkylene group which forms a cyclic ring with it R⁹;

Z is separately in each occurrence oxygen or —

NR⁴;

a is separately in each occurrence an integer of from about 1 to about 10;

b is separately in each occurrence 0 or 1, with the proviso that the sum of a and b should be from about 2 to about 10;

c is separately in each occurrence an integer of from about 1 to about 10;

x is separately in each occurrence an integer of about 1 to about 10, with the proviso that the total of all occurrence of x is from about 2 to about 10; and

y is separately in each occurrence about 0 or 1.

6. A two part polymerizable composition comprising

part 1, a) an organoboraneamine complex wherein the ratio of amine nitrogen atoms to boron atoms is greater than 0:

1; and

part 2, b) one or more of monomers, oligomers or polymers having olefinic unsaturation which is capable of polymerization by free radical polymerization, and c) an effective amount of an isocyanate which causes the complex to disassociate, treeing the borane to initiate polymerization of the one or more monomers, oligomers or polymers having olefinic unsaturation;

wherein the compound which causes disassociation of the complex is kept separate from the complex until initiation of polymerization is desired.

7. A two part polymerizable composition according to claim 6 wherein the ratio of amine to boron atoms is about 5.0:

1 or greater.

8. A two part polymerizable composition according to claim 7 wherein the equivalent ratio of amine to isocyanate is 1.25:

1.0 or less.

9. A two part polymerizable composition according to claim 8 wherein the amine to isocyanate equivalent ratio is less than about 1.0:

1.0.

10. A two part polymerizable composition according to claim 9 wherein the organoborane comprises a trialkyl borane or an alkyl cycloalkyl borane and the amine comprises a primary amine;

a secondary amine;

a polyamine having primary and/or secondary amines;

ammonia;

polyoxyalkylene amines;

the reaction product of a diamine and a difunctional compound having moieties which react with an amine wherein the reaction product has terminal amine groups;

aryl amines;

heterocyclic amines;

a compound with an amidine structural component;

aliphatic heterocycles having at least one secondary nitrogen in the heterocyclic ring wherein the heterocyclic compound may also contain one or more additional secondary or tertiary nitrogen atoms, oxygen atoms, sulfur atoms, or double bonds in the heterocycle;

alicyclic compounds having bound to the alicyclic ring one or more substituents containing an amine moiety;

conjugated imines and mixtures thereof.

11. A two-part composition according to claim 6 wherein the equivalents ratio of isocyanate to amine is greater than 1.0:

1.0.

12. A method of polymerization comprising contacting the components of the polymerizable composition of claim 11 under conditions such that the one or more monomers, oligomers, or polymers undergo polymerization.

13. The method of claim 12 wherein the contacting occurs at, or near, ambient temperature.

14. The method claim 13 which further comprises the step of heating the composition to an elevated temperature under conditions such that the amine and isocyanate may react further.

15. A method of bonding two or more substrates together which comprises

a. contacting the components of the composition of claim 11 together under conditions such that polymerization is initiated;

b. contacting the adhesive composition with the two or more substrates;

c. positioning the two or more substrates such that the adhesive composition is located between the two or more substrates wherein they are in contact with one another; and

c. allowing the adhesive to cure so as to bind the two or more substrates together.

16. A method of bonding two or more substrates according to claim 15 which further comprises heating the adhesive composition to a temperature such that the amine and isocyanate react further.

17. The method of claim 16 wherein the adhesive composition is heated to a temperature at or above the expected maximum use temperature of the adhesive.

18. A method of modifying the surface of a low surface energy polymer by contacting a composition according to claim 11 with at least a portion of the surface of the low surface energy polymer and causing the complex to disassociate thereby initiating polymerization of the monomer, oligomers, polymers or mixture thereof such that the polymer formed is on the surface of the low surface energy polymer.

19. A method at coating a substrate which comprises contacting the components of the composition of claim 11;

contacting the contacted composition with one or more surfaces of a substrate; and

allowing the coating Composition to cure.

20. A coating composition which comprises the composition of claim 11.

21. A laminate comprising at least two substrates having disposed between the substrates and bound to each substrate a composition according to claim 11.