Claims
- 1. A method of polymerization comprising contacting the components of the polymerizable composition of
a) an organoborane/amine complex wherein the organoborane is a trialkyl borane or an alkyl cycloalkyl borane and the amine is selected from the group of amines having an amidine structural component; aliphatic heterocycles having at least one nitrogen in the heterocyclic ring wherein the heterocyclic compound may also contain one or more nitrogen atoms, oxygen atoms, sulfur atoms, or double bonds in the heterocycle; an alicyclic compound having bound to the ring a substituent having an amine moiety wherein the alicyclic compound may have a second substituent which can contain one or more nitrogen, oxygen or sulfur atoms and/or one or two double bonds; primary amines which in addition to a primary amine have one or more hydrogen bond accepting groups of an ether, polyether, thioether or halogen wherein there is an alkylene chain of at least two carbon atoms between the primary amine and the hydrogen bond accepting group; and conjugated imines; and, 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 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 under conditions such that the one or more monomers, oligomers, or polymers undergo polymerization.
- 2. The method of claim 1 wherein the contacting occurs at, or near, ambient temperature.
- 3. A method according to claim 2 wherein the complex of the organoborane and the primary amine corresponds to the formula
- 4. A method according to claim 3 wherein:
R1 is separately in each occurrence hydrogen or methyl; R2 is separately in each occurrence a C2-4 alkyl group; R3 is separately in each occurrence hydrogen, methyl, or forms a double bond with an R3 or R4 on an adjacent atom; R4 is separately in each occurrence hydrogen, C1-4 alkyl or; R5 and R6 are separately in each occurrence hydrogen, C1-4 alkyl, C5-6 cycloalkyl group, or N(R4)2, R7 is separately in each occurrence hydrogen or methyl, with the proviso that two or more of R5, R6, and R7 can combine in any combination to form a single or multiple ring structure and can include one or more of nitrogen, oxygen or unsaturation in the ring; X is separately in each occurrence a SR10 or —OR10; Y is separately in each occurrence SR4, N(R4)2 or OR4, an alkylene group which can also form a cyclic ring with R7 or R9; R9 is separately in each occurrence hydrogen, a C1-10 alkyl, Y, —C(R9)2—(CR9═CR9)c—Y, or two or more of R9 can form a cyclic ring one or more of R9 or one or more of R9 can combine with Y to form a ring structure provided the ring structure is conjugated with respect to the double bond of the amine nitrogen; and a is an integer of about 2 to about 6; b is separately in each occurrence an integer of about 0 to about 1; c is separately in each occurrence an integer of from about 1 to about 5; and d is separately in each occurrence an integer of about 2 to about 4.
- 5. A method according to claim 3 comprising an aliphatic heterocylic amine wherein the amine is a five or six membered heterocylic compound.
- 6. A method according to claim 4 wherein the amine is a conjugated imine.
- 7. A method according to claim 4 wherein the amine is a compound with an amidine structural component.
- 8. A method according to claim 4 wherein the amine is an alicyclic compound having bound to the ring a substituent having an amine moiety wherein the alicyclic compound may have a second substitutent which can contain one or more nitrogen, oxygen or sulfur atoms and/or one or two double bonds.
- 9. A polymerizable composition according to claim 8 wherein the alicyclic ring is a 5 or 6 membered ring.
- 10. A method according to claim 4 wherein the decomplexing agent is an acid.
- 11. A method according to claim 1 which comprises
a) from about 0.2 to about 8 percent by weight of complex; b) from about 20 to about 95 percent by weight or less of monomers, oligomers or polymers; c) from about 1 to about 8 percent by weight of decomplexing agent; d) from about 10 to about 60 percent by weight of a thickener; and e) from about 5 to about 35 percent by weight of an elastomeric material.
- 12. A process for polymerizing the composition comprising
a) an organoborane/amine complex wherein the organoborane is a trialkyl borane or an alkyl cycloalkyl borane and the amine is selected from the group of amines having an amidine structural component; aliphatic heterocycles having at least one nitrogen in the heterocyclic ring wherein the heterocyclic compound may also contain one or more nitrogen atoms, oxygen atoms, sulfur atoms, or double bonds in the heterocycle; an alicyclic compound having bound to the ring a substituent having an amine moiety wherein the alicyclic compound may have a second substituent which can contain one or more nitrogen, oxygen or sulfur atoms and/or one or two double bonds; primary amines which in addition to a primary amine have one or more hydrogen bond accepting groups of an ether, polyether, thioether or halogen wherein there is an alkylene chain of at least two carbon atoms between the primary amine and the hydrogen bond accepting group; and conjugated imines; and, b) one or more of monomers, oligomers or polymers having olefinic unsaturation which is capable of polymerization by free radical polymerization; which process comprises heating the composition to a temperature at or above the temperature at which the organoborane-amine complex disassociates.
- 13. The method of claim 12 wherein the composition is heated to a temperature of about 30° C. to about 120° C.
- 14. The method of claim 13 wherein the composition is heated to a temperature of about 50° C. to about 100° C.
- 15. A method according to claim 13 wherein the complex of the organoborane and the primary amine corresponds to the formula
- 16. A polymerizable composition according to claim 15 wherein:
R1 is separately in each occurrence hydrogen or methyl; R2 is separately in each occurrence a C2-4 alkyl group; R3 is separately in each occurrence hydrogen, methyl, or forms a double bond with an R3 or R4 on an adjacent atom; R4 is separately in each occurrence hydrogen, C1-4 alkyl or; R5 and R6 are separately in each occurrence hydrogen, C1-4 alkyl, C5-6 cycloalkyl group, or N(R4)2, R7 is separately in each occurrence hydrogen or methyl, with the proviso that two or more of R5, R6, and R7 can combine in any combination to form a single or multiple ring structure and can include one or more of nitrogen, oxygen or unsaturation in the ring; X is separately in each occurrence a SR10or —OR10; Y is separately in each occurrence SR4, N(R4)2 or OR4, an alkylene group which can also form a cyclic ring with R7 or R9; R9 is separately in each occurrence hydrogen, a C1-10 alkyl Y, —C(R9)2—(CR9═CR9)c—Y, or two or more of R9 can form a cyclic ring one or more of R9 or one or more of R9 can combine with Y to form a ring structure; and a is an integer of about 2 to about 6; b is separately in each occurrence an integer of about 0 to about 1; c is separately in each occurrence an integer of from about 1 to about 5; and d is separately in each occurrence an integer of about 2 to about 4.
- 17. A polymerizable composition according to claim 15 comprising an aliphatic heterocyclic amine wherein the amine is a five or six membered heterocyclic compound.
- 18. A polymerizable composition according to claim 15 wherein the amine is a conjugated imine.
- 19. A polymerizable composition according to claim 15 wherein the amidine is a compound with an amidine structural component.
- 20. A polymerizable composition according to claim 15 wherein the amine is an alicyclic compound having bound to the ring a substituent having an amine moiety wherein the alicyclic compound may have a second substituent which can contain one or more nitrogen, oxygen or sulfur atoms and/or one or two double bonds.
- 21. A polymerizable composition according to claim 20 wherein the alicyclic ring is a 5 or 6 membered ring.
- 22. A polymerizable composition according to claim 13 wherein the decomplexing agent is an acid.
- 23. A polymerizable composition according to claim 13 which comprises
a) from about 0.2 to about 8 to percent by weight of complex; b) from about 20 to about 95 percent by weight or less of monomers, oligomers or polymers; c) from about 10 to about 60 percent by weight of a thickener; and d) from about 5 to about 35 percent by weight of an elastomeric material.
CROSS REFERENCE TO RELATED APPLICATION
[0001] This application is a continuation-in-part (CIP) of copending application Ser. No. 09/466,321, filed Dec. 17, 1999.
Continuation in Parts (1)
|
Number |
Date |
Country |
Parent |
09466321 |
Dec 1999 |
US |
Child |
09881983 |
Jun 2001 |
US |