Accelerated organoborane amine complex initiated polymerizable compositions
View Patent ↗The invention is a two part polymerizable composition comprising in one part an organoboron compound capable of forming free radical generating species amine complex and in the second part one or more compounds capable of free radical polymerization and a cure accelerator comprising a) at least one compound containing a quinone structure or b) at least one compound containing at least one aromatic ring and one or more, preferably two substituents on the aromatic ring selected from hydroxyl, ether and both, where there are two substituents they are located either ortho or para with respect to one another and a peroxide containing compound. The second part may further contain an agent capable of causing the organoboron compound to form free radical generating species upon contacting the two parts. The first part may further comprises one or more compounds capable of free radical polymerization. This facilitates formulating compositions that have commercially desirable volumetric ratios of the two parts. Adhesive compositions of the present formulation provide excellent adhesion to low surface energy substrates, such as plastics.
1. A method of polymerization comprising contacting the components of a polymerizable composition comprising in one part an organoboron compound comprising an organoboron amine complex and in the second part one or more compounds capable of free radical polymerization and a cure accelerator comprising (a) at least one substituted or unsubstituted benzoquinone present in an amount of about 0.02 to about 0.4 percent by weight of the two part composition and a decomplexing agent capable of decomplexing the organoboron amine complex upon contacting of the two parts, wherein the cure accelerator is located only in the second part and wherein the parts of the composition prior to contacting of the two parts exhibit a viscosity increase of less than 150 percent over 30 days when stored at 40° C. or less and the polymerizable composition exhibits a lap shear strength according to ASTM 03165-91 of 50 psi or greater 2 hours after contacting and application to a polypropylene substrate:
wherein:
the organoboron compounds comprise a complex of trialkyl borane and a compound having a primary amine and one or more hydrogen accepting grows, wherein the one or more hydrogen bond accepting groups is selected from ether or polyether, and there are at least two carbon atoms between primary amine and the hydrogen bond accepting groups, wherein the compound having a primary amine and one or more hydrogen accepting groups is selected from the group of consisting of methoxypropylamine, methoxybutylamine, methoxyethylamine, ethoxypropylamine, propoxypropylamine, and amine terminated polyalkylene ethers: and
the compounds capable of free radical polymerization comprise acrylate or methacrylate monomers, polymers or a mixture thereof.
2. The method of claim 1 wherein the contacting occurs at, or near, ambient temperature.
3. A method of bonding two or more substrates together which comprises:
contacting the components of a composition, comprising in one part an organoboron compound comprising an organoboron amine complex and in the second part one or more compounds capable of free radical polymerization and a cure accelerator comprising (a) one or more substituted or unsubstituted benzoquinones present in an amount of about 0.02 to about 0.4 percent by weight of the two part composition and a decomplexing agent capable of decomplexing the organoboron amine complex upon contacting of the two parts, wherein the cure accelerator is located only in the second part and under conditions such that polymerization is initiated
contacting the contacted composition with the two or more substrates;
positioning the two or more substrates such that the contacted composition is located between the two or more substrates wherein they are in contact with one another; and
allowing the contacted composition to cure so as to bind the two or more substrates together:
wherein the parts of the composition prior to contacting of the two parts exhibit a viscosity increase of less than 150 percent over 30 days when stored at 40° C. or less and the composition exhibits a lap shear strength according to ASTM 03165-91 of 50 psi or greater 2 hours after application to a polypropylene substrates:
wherein:
the organoboron compounds comprise a complex of trialkyl borane and a compound having a primary amine and one or more hydrogen accepting groups, wherein the one or more hydrogen bond accepting groups is selected from ether or polyether, and there are at least two carbon atoms between primary amine and the hydrogen bond accepting groups, wherein the compound having a primary amine and one or more hydrogen accepting groups is selected from the group of consisting of methoxypropylamine, methoxybutylamine, methoxyethylamine, ethoxypropylamine, propoxypropylamine and amine terminated polyalkylene ethers; and
the compounds capable of free radical polymerization comprise acrylate or methacrylate monomers, polymers or a mixture thereof.
4. A method of bonding two or more substrates according to claim 3 which further comprises heating the composition to a temperature such that the organoboron amine complex disassociates.
5. A method of coating a substrate which comprises contacting the components of a composition comprising in one part an organoboron compound comprising an organoboron amine complex and in the second part one or more compounds capable of free radical polymerization and a cure accelerator comprising (a) at least one substituted or unsubstituted benzoquinone present in an amount of about 0.02 to about 0.4 percent by weight of the two part composition and a decomplexing agent capable of decomplexing the organoboron amine complex upon contacting of the two parts, wherein the cure accelerator is located only in the second part and; contacting the contacted composition with one or more surfaces of a substrate; and allowing the contacted composition on the substrate to cure; and
wherein the parts of the composition prior to contacting of the two parts exhibit a viscosity increase of less than 150 percent over 30 days when stored at 40° C. or less and the composition exhibits a lap shear strength according to ASTM 03165-91 of 50 psi or greater 2 hours after application to a polypropylene substrate:
wherein:
the organoboron compounds comprise a complex of trialkyl borane and a compound having a primary amine and one or more hydrogen accepting groups, wherein the one or more hydrogen bond accepting groups is selected from ether or polyether, and there are at least two carbon atoms between primary amine and the hydrogen bond accepting groups, wherein the compound having a primary amine and one or more hydrogen accepting groups is selected from the group of consisting of methoxypropylamine, methoxybutylamine, methoxyethylamine, ethoxypropylamine, propoxypropylamine, and amine terminated polyalkylene ethers; and
the compounds capable of free radical polymerization comprise acrylate or methacrylate monomers, polymers or a mixture thereof.
6. A method according to claim 1 wherein the first part further comprises one or more compounds capable of free radical polymerization selected from acrylate or methacrylate monomers, polymers and mixtures thereof.
7. A method according to claim 3 wherein the first part further comprises one or more compounds capable of free radical polymerization selected from acrylate or methacrylate monomers, polymers and mixtures thereof.
8. A method according to claim 1 wherein the decomplexing agent comprises an acid.
9. A method according to claim 3 wherein the decomplexing agent comprises an acid.
10. A method according to claim 5 wherein the decomplexing agent comprises an acid.
11. A method according to claim 5 wherein the first part further comprises one or more compounds capable of free radical polymerization selected from acrylate or methacrylate monomers, polymers and mixtures thereof.