Organoborane polyamine complex initiator systems and polymerizable compositions made therewith
AssigneeMinnesota Mining and Manufacturing Company
InventorAlphonsus V. Pocius
Life of this patent
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Abstract
A composition comprises organoborane polyamine complex and polyol. The composition can form a part of a polymerization initiator system that also includes polyisocyanate. The system can be used to initiate polymerization of acrylic monomer and to form a polyurethane/polyurea acrylic adhesive that has exceptionally good adhesion to low surface energy polymers.
Claims42
An adhesive composition that can be applied and cured at room temperature comprising:
- (a) a polymerizable blend of alkyl acrylate monomer and alkyl methacrylate monomer;
- (b) an optional organic thickener;
- (c) an organoborane polyamine complex which provide about 0.08 to 0.5 wt. % boron, based on the weight of the acrylic-group containing materials and optional organic thickener in the adhesive composition, the complex having the structure:
- ##STR14## wherein:
- R.sup.1 is an alkyl group having 1 to 10 carbon atoms;
- R.sup.2 and R.sup.3 are independently selected from alkyl groups having 1 to 10 carbon atoms and phenyl-containing groups;
- Am is a polyamine selected from the group consisting of alkyl polyamine, polyoxyalkylenepolyamine, and the reaction product of a diprimary amine-terminated material and a material having at least two groups reactive with primary amine, wherein the number of primary amine groups in the reaction mixture was greater than the number of groups reactive with primary amine;
- and
- the value of v is selected so as to provide an effective ratio of primary amine nitrogen atoms to boron atoms in the complex;
- (d) a polyol in which the organoborane polyamine complex is soluble and which is selected from the group consisting of polyethylene oxide polyol, polypropylene oxide polyol, polytetramethylene oxide polyol, ethylene oxide- and propylene oxide-terminated derivatives of these materials, poly-.epsilon.-caprolactone, and blends of the foregoing;
- and
- (e) an effective amount of a diisocyanate that reacts with the polyamine to liberate the organoborane for initiating polymerization of the polymerizable blend, and that reacts with the polyamine and the polyol to form polyurethane/polyurea.
A 100% solids, two-part curable adhesive composition comprising:
- (a) a first part comprising a solution of organoborane polyamine complex and polyol, wherein the polyol is not reactive with the polyamine;
- and
- (b) a second part comprising:
- (1) polymerizable acrylic monomer;
- and
- (2) a polyisocyanate that is soluble in the acrylic monomer, wherein the polyisocyanate is provided in an amount sufficient to react with the polyamine to liberate the organoborane for intitiating polymerization of the acrylic monomer, and to react with the polyol and the polyamine to form polyurethane/polyurea;
- (3) a polyurethane formation catalyst;
- and
- (4) optionally, either a compound that has both a free-radically polymerizable group and a group reactive with amine, or a material that reacts with the polyisocyanate to form a compound that has both a free-radically polymerizable group and a group reactive with amine.
A cured adhesive composition comprising:
- (a) a polymerized acrylic;
- (b) polyurethane/polyurea independent from the polymerized acrylic;
- and
- (c) organoborane and/or organoborane degradation by-product.
A method of improving the storage stability of a two-part polymerizable adhesive composition that comprises polymerizable acrylic monomer, organoborane polyamine complex, and a material that reacts with the polyamine for liberating the organoborane to initiate polymerization of the acrylic monomer, the method comprising the steps of:
- (a) providing an organoborane polyamine complex;
- (b) providing a polyol in which the organoborane polyamine complex is soluble;
- (c) forming a solution of the polyol and the organoborane polyamine complex;
- and
- (d) preparing a two-part polymerizable adhesive composition in which one part comprises (i) material that reacts with the polyamine and (ii) all of the polymerizable acrylic monomer, and the other part comprises the solution of the polyol and the organoborane polyamine complex.
In a two-part polymerizable adhesive composition that comprises polymerizable acrylic monomer, organoborane polyamine complex, and a material that reacts with the polyamine for liberating the organoborane to initiate polymerization of the acrylic monomer, a method for reducing the amount of material that can migrate in the polymerized adhesive composition, said material comprising the reaction product of the polyamine and the material that reacts with polyamine, the method comprising the steps of:
- (a) providing a polyisocyanate that is reactive with the polyamine component of the complex;
- (b) providing a polyol that is reactive with the polyisocyanate;
- (c) permitting the polyisocyanate to react with the polyamine to liberate the organoborane;
- (d) initiating polymerization of the acrylic monomer with the liberated organoborane and polymerizing the acrylic monomer to form acrylic polymer;
- and
- (e) permitting the polyamine, polyisocyanate and polyol to react to form polyurethane/polyurea independent from but coexisting with the acrylic polymer.
Dependencies are inferred from the claim text.