MXPA98000917A - Systems initiators of polyamine organograne complexes and polymerizable compositions prepared with mis - Google Patents

Abstract

A composition comprising a polyamine organoborane complex and a polyol is described. The composition can form a part of a polymerization initiator system, which also includes a polyisocyanate. The system can be used to initiate the polymerization of the acrylic monomer and form a polyurethane / polyurea acrylic adhesive which has an exceptionally good adhesion to low surface energy polymers.

Description

STARTING SYSTEMS OF ORGANOBORAN POLYAMINE COMPLEX AND POLYMERIZABLE COMPOSITIONS PROCESSED WITH THEM BACKGROUND OF THE INVENTION Field of the invention This invention relates in general to the initiator systems of the organoborane po-amine complex and more specifically to the systems in which the complex it is carried in a polyol and with systems that include polyisocyanate. The invention further relates to the polymerizable compositions made therefrom, in particular the two-part adhesive compositions having separate components of polyurethane / polyurea and acrylics when cured. Adhesive compositions have excellent adhesion to a variety of substrates, especially low surface energy polymers.

Description of the Related Art An efficient, effective means for adhesively bonding low surface energy plastic substrates, such as polyethylene, polypropylene and polytetrafluoroethylene (e.g., TEFLON) has been sought for a long time. The difficulties in bonding these materials together : < ? They are well known. See for example "Adhesion Problems at Polymer Surfaces" by D. M Brewis, which appeared in Progress in Rubber and Plastic Technology, Vol. 1. pp. 1 (1985). Conventional procedures normally operate by (1) increasing the surface energy of the substrate (to more closely match the surface energies of the substrate and the REF: 26719 adhesive, to promote by this a better wetting of the substrate by means of the adhesive) and / or (2) remove additives and low molecular weight polymeric fractions in the substrate, which may migrate to the surface of the substrate and adversely affect adhesion by forming a weak border layer As a result, conventional procedures often use complex and expensive substrate surface preparation techniques, such as flame treatment, corona discharge, plasma treatment, oxidation by ozone or acids oxidants and attack by electronic deposition Alternatively the surface of the substrate can be primed by coating it with a high surface energy material. However, to obtain adequate adhesion of the primer, it may be necessary to first use the surface preparation techniques described above. All these techniques they are well known c as reported in Treatise on Adhesion and Adhesives (J D Mmford editor Marcel Decker, 1991, New York, Vol 7. pp 333 to 435) Known procedures are frequently adjusted for use with specific substrates. As a result they may not be useful for bonding plastic substrates of low surface energy in general.

In addition, the complexity and cost of the presently known procedures do not make them particularly suitable for retail consumer use (eg do-it-yourself home repairs, etc.) or in low volume operations. An annoying problem is the repair of many items. daily non-expensive household items that are made of polyethylene. polypropylene or polystyrene, such as garbage baskets for laundry and laundry baskets Consequently, there has been a considerable and long-felt need for a simple, easy-to-use adhesive that can easily adhere to a wide variety of substrates, especially low-energy materials surface adhesives such as polyethylene, polytetrafluoroethylene fluoroethylene without requiring complicated surface preparation, priming and the like. While an adhesive that can bond low surface energy plastics is certainly advantageous, the commercial utility of such an adhesive would be improved if components of it could be combined into one Convenient mixing ratio This would allow easy application of the adhesive when using conventional adhesive dispensers or dispensers, without the need for laborious manual weighing and mixing of different components However the convenient mixing ratio should not come at the expense of stability in storage or performance? s significantly reduced Thus, there is not only a need for an adhesive that can bind low surface energy plastics, but also a need for an adhesive that can be easily combined in a convenient mixing ratio without a reduction of material in the capacity of storage performance or stability 0 It may be desirable that such adhesives have other attributes For example, in certain applications it may be important that the adhesive is hard elastomeric or abrasion resistant properties normally associated with polyurethane adhesives It may also be important to remove or reduce the low molecular weight components in the adhesives, which could migrate to the interface between the adhesive and the substrate. This could adversely affect the adhesion by forming a weak boundary layer. In addition, if the low molecular weight components can be removed by solvents, the volume of adhesive could be lost, voids or gaps could be created in the adhesive and the adhesive and the cohesive strength of the joint could be weakened, if the article joined was exposed to solvents Also, the low molecular weight components may be sensitive to water and their migration to the adhesive / substrate interface could decrease the hydrolytic stability of the adhesive bond. As explained more fully hereinafter, the initiator systems of the polyamine organoborane complex and the related compositions of the invention (which may include pol- nocyanate, polyol and acrylic monomer, which can polymerize acrylic polyurethane / polyurea adhesives) do not they only satisfy these demands, but offer many other advantages Organoboranees such as tributylborane and tpethylborane have been reported to initiate and catalyze the polymerization of vinyl monomers (see, eg, GS Kolesnikov et al. Bull Acad Sci. USSR, Div. Chem. Sci. 1957. p 653. J Furakawa et al., Journal of Polymer Science, volume 26, No. 113. p 234. 1957; and J Furakawa et al., Journal of Polymer Science, volume 28, No. 116, 1958) . It is known that organoborane compounds of the type described in these references are quite pyrophoric in air, which complicates their use. Chemical Abstracts No. 134385q (Vol 80, 1974) "Bonding Polyolefin or Vinyl Polymers" reports a mixture of 10 parts of methyl methanolate. 0 2 parts of tributylborane and 10 parts of poly (methyl methacrylate) was used to join (or paste) polyethylene vanes. polypropylene and poly (vinyl acetate). U.S. Patent No. 3,275,611, issued to E. H. Mottus et al. describes a process for the polymerization of olefinic compounds (eg, meta-plate monomers) with a catalyst comprising an organoboron compound. a peroxygen compound and an amine The organoboron compound and the amine can be added to the reaction mixture separately or can be added as a preformed complex. British Patent Specification No. 1, 113,722"Aerobically Polymerisable Compositions", published on 15 May 1968, describes the polymerization of acrylate monomers by the use of a free radical catalyst (eg, peroxides) and triarylborane complexes having the general formula (R) 3B-Am, wherein R is a aryl radical and Am is an amine It is reported that the resulting compositions are useful as adhesives Chemical Abstracts No. 88532r (vol 73, 1970) "Dental self- I cupng-resin" and all the complete text to which it refers, reports that the tpbutilborano can be made stable in air by complexing it with ammonia or certain amines and that the t-butylborane can be reactivated with an amine acceptor, such as an isocyanate. an acid chloride, a sulfonyl chloride or anhydrous acetic acid As a result the complex can be used to or polymerize mixtures of methyl methanolate and poly (methylmethacrylate) to provide a dental adhesive A series of patents issued to Skoultchi or Skouitchi et al. (U.S. Patent Nos. 5,106,928; 5,143,884; 5,286,821; 5,310,835 and 5,376,746), describe a two-part initiator system, which is reported as useful in acrylic adhesive compositions, especially elastomeric acrylic adhesives. parts includes a stable organoborane amine complex and the second part includes a destabilizer or activator such as an organic acid or an aldehyde. It is reported that the adhesive compositions are particularly useful in structural and semi-structural applications., such as loudspeaker magnets metal-metal junction glass-metal junction (automotive) glass-glass union joining of circuit board components union of selected plastics to metal glass wood etc and electric motor magnets Those plastics that can be joined (or glued) are not further described. US Pat. No. 4 043,982 (O'Sullivan et al) discloses a composition useful as an adhesive and which includes an acyl or silyl peroxide type polymerization initiator (generally dissolved in a volatile solvent). a polymerizable acrylate-isocyanate monomer or oligomer and an amine polymerization initiator The polymerizable acrylic-isocyanate monomer is the reaction product of an organic polnosocyanate with a polymesable acrylate ester having a primary or secondary hydroxy or amino group in the alcoholic portion U.S. Patent No. 4,721,751 (Schappert et al) discloses polyurea-urea dispersions an acrylate which are reported as useful as adhesives and sealants. The materials can be prepared by reacting a polnsocyanate with a funicidal amine in the presence of a polyol an ethnically unsaturated diluent. free of active hydrogens and an ethically unsaturated polymerizable compound containing active hydrogen. U.S. Patent No. 4,731,416 (Saunders) discloses a polyurethane-type adhesive, comprising the reaction product of: (1) a true solution of; (a) a copolymer of a α- β • ethylenically unsaturated carboxylic acid and a hydroxyalkyl ester of a β-ethylenically unsaturated acid in (b) a polyol having a molecular weight of at least 200; (2) an organic polyisocyanate; and (3) an agent that extends the polyahl chain. having a molecular weight less than 200. U.S. Patent No. 5,021,507 (Stanley et al.) discloses a reactive, urethane-modified urethane thermal fusion adhesive, which can be obtained by the addition of a prepolymer of urethane to low molecular weight polymers, formed from ethylenically unsaturated monomers which do not contain active hydrogen BRIEF DESCRIPTION OF THE INVENTION In general, this invention relates to polymerization initiator systems, which are particularly useful for providing two-part curable compositions, especially those that cure (this is polimenzan) to polyurethane / polyurea acrylic adhesives.

Broadly and in one aspect of the invention, the polymerization initiator systems include a complex of organoborane and polyol amine. Preferably the complex and the polyol form a solution (even more preferably a liquid solution) at room temperature. A variety of polyamine organoborane complexes can be used in the invention. The following structure is representative of those that are appropriate In this structure R1 is an alkyl group having from 1 to 10 carbon atoms. R2 and R3 are independently selected from alkyl groups having from 1 to 10 carbon atoms and groups containing phenyl, Am is a polyamine selected from the group consisting of alkylpolyamine polyoxyalkylenepolyme amine and the reaction product of an amine-terminated material dippmapa and a material having at least two groups reactive with primary amine, wherein the number of primary amine groups in the reaction mixture is greater than the number of groups reactive with the primary amine and the value of v is selected to provide a effective ratio of nitrogen atoms of primary amine to boron atoms in the complex which is broadly a ratio of about 0 5 1 to 4 1. although a ratio of 1 1 is more preferred A wide variety of polyols can be used, in those which include polyether polyols and polyester polyols. Preferably the polyol has a hydroxyl functionality of from 2 to 3. Among those polyols the Particularly preferred are alkylene oxide polyols such as polyol of oleoeene oxide, polypropylene oxide, polyol of polytetrameene oxide, derivatives of eene oxide and propylene oxide of these materials and mixtures. of poh-e-caprolactone is a particularly preferred polyester polyol. The polymerization initiator systems of the invention further include a polnsocyanate (preferably a dnsocyanate). The polnosocyanate is reactive with the polyamine of the complex and can release the Organoborane for initiating the polymerization of the acrylic monomer Preferably the number of equivalents of isocyanate functionality is equal to the sum of the number of equivalents of amine functionality plus the number of equivalents of hydroxyl functionality in the composition As a result and quite advantageously the polymerization by condensation of the remaining polnsocyanate is presented by reaction with the polyol, to form independent but co-existing linear polymers or networks of acrylic and polyurethane / polyurea The amount of the polyisocyanate / polyamide migratory product of low molecular weight in the composition is reduced by the formation of a linear polymer or polyurethane / polyurea network. Otherwise, such migratory components could flourish at the interface between the adhesive composition and a substrate which could result in a weak boundary layer a decreased hydrolytic stability an adhesive Reduced ion and a loss of cohesive strength especially if these components can or can be extracted by solvents In certain applications this could be undesirable In another aspect the invention relates to a polymerizable composition comprising a complex of polyamine organoborane, polyol, polnsocyanate and acrylic monomer polimepable The acrylic monomer < The polymetazable is preferably a monofunctional acrylic ester or a monofunctional metaplatter ester (in which substituted derivatives and mixtures of these materials are included) A mixture of an alkyl acnlate and an alkyl metaplatte is particularly preferred Optionally the portable composition may include a * This is a compound that contains a free radical polymerizable group (preferably (meth) acrylic functionality) and an amine reactive group. The bireactive compound can be directly included in the adhesive composition or it can be generated in situ, by example, by reacting a hydroxylated (meth) acrylate with polnosocyanate The polymerizable compositions are particularly useful for providing a curable (at room temperature) adhesive composition at 100% two-part solids. One part comprises a organoborane and polyol amine complex (preferably as a solution). The other part comprises a monomer polimepazable acrylic polnsocianato and optionally a bireactive compound Polnsocianato is provided in an amount sufficient to release the organoborane to initiate the polymerization of the acrylic monomer and to react with the polyamma and the polyol to form urethane / polyurea The two parts of the adhesive can be easily combine in a mixing ratio of a convenient commercially useful integer of 1 10 or 2 < »Smaller, more preferably 1 4, 1 3 1 2 1 1. such that they can be easily used with two-part adhesive dispensers or dispensers. When cured, these compositions produce a linear polymer or network of a linear acrylic polymer. or polyurethane / polyurea network which is independent, but coexists with the polymerized and residual acrylic organoborane and / or byproducts of < degradation (for example by oxidation) of organoborane If a bireactant compound has been included, it can bind the polimeparated acrylic and the urethane / polyurea The compositions of the invention have excellent adhesion to substrates of low surface energy such as polyethylene polypropylene and 5 polytetrafluoroethylene , in another aspect, the invention relates to attached (or glued) compounds comprising a first substrate and a second substrate (preferably low energy surface polymeric materials) bonded (or glued) together adhesively, by a layer of a cured adhesive composition according to the invention The? or adhesion to such substrates is promoted by using an effective amount of the polyamine organoborane complex. which is broadly about 0.03 to 1.5% by weight of boron based on the weight of the acrylic group-containing components and the organic thickener in the polyepable composition more preferably of about 0.08 to 0.5% by weight of i * boron more preferably from 0 1 to 0 3% by weight of boron The solubility of the polyamine organoborane complex in polyol allows the provision of two-part adhesives as described above. The complexes can be separated from the constituents with which they can be used. This may improve the stability in the or parking of the adhesive composition. Accordingly, the invention also relates to a method for improving the storage stability of a two-part polishable adhesive composition, comprising acp 'co polymerizable monomer, a complex of organoborane polyamine and a material that reacts with the pohamine to release the organoborane to initiate the polymerization of the acrylic onomer (e.g. polyisocyanate) The method comprises the steps of (a) providing the polyamine organoborane complex; (b) providing a polyol in which the polyamine-organoborane complex is soluble; (c) forming a solution of the polyol and the organoborane complex; Y (d) preparing a two part polymerizable adhesive composition, in which one part comprises the material that reacts with the polyamide and all the polymerizable acrylic monomer and the other part comprises the solution of the polyol and the polyamine organoborane complex. As indicated above, the amount of the migrant pol- nocyanato-polyamine reaction product is reduced by the formation of polyurethane / po urea. Consequently, the invention also relates to a method for reducing the amount of migratory material in the adhesive compositions of the type described. previously. The method comprises the steps of. (a) providing a polyisoanate that is reactive with the polyamide component of the complex, (b) providing a polyol that is reactive with the polusocyanate; (c) allowing the polusocyanate to react with the pohamine to release the organoborane, (d) initiating the polymerization of the acrylic monomer with the released organoborane and polimeprating the acrylic monomer to form a linear polymer or acrylic network. and (e) allow the polyamine. the polyisocyanate and the polyol react to form a linear polymer or polyurethane / polyurea network that is independent of, but coexists with. the linear polymer or acrylic network.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS In general, this invention relates to polymerization initiator systems that are particularly useful for providing two-part curable compositions, especially those that cure (ie, polymerize) polyurethane / polyurea acrylic adhesives. Broadly and in one aspect of the invention, the polymerization initiator systems include a polyamine organoborane complex and polyol. As explained below, the polyol is advantageously a carrier for the polyamine organoborane complex and reactive with the other constituents of the polymerization initiator system. More specifically, the polymerization initiator systems of the invention comprise and more preferably consist essentially of a polyamine organoborane complex, polyol and polyisocyanate. The organoborane component of the complex initiates the free radical polymerization of the acrylic monomer to form an acrylic component. stabilizing the organoborane against premature oxidation, complexed with polyamide The organoborane is released from the complex by reacting a portion of the polyisocyanate with the polyamine to form polyurea. Advantageously, the condensation polymerization of the remaining polyisocyanate occurs by reaction with the polyol to form a polyurethane / polyurea component that is independent but coexists with the acrylic. That is, a linear independent polymer or polyurethane / polyurea network is formed and an independent linear polymer or acrylic network is formed (which coexist with each other), as opposed to generating a hybrid "urethane-acrylate" material (ie, a material having a fundamental urethane chain with acrylic functionality either on the fundamental chain or terminally or a material having a fundamental acrylic chain with urethane or isocyanate functionality either in the fundamental or terminal chain). Advantageously, the incorporation of the polyamine into the polymerized composition reduces the level of low molecular weight components that could flourish or migrate to the adhesive / substrate interface. In the case of an adhesive, this could result in a weak boundary layer, reduced adhesion and an increased level of removable components. As explained below, the polyurethane / polyurea and separate acrylic components can be linked together by a birective compound (ie, a monomer having both amine-reactive functionalities and free radical scalable functionalities) to provide a more robust build up of strength. fast and one level further reduce the level of low molecular weight migratory components. The polyurethane / polyurea acrylic adhesives of the invention can bind a wide variety of substrates, but provide exceedingly good adhesion to low surface energy plastic substrates (eg, polyethylene, polypropylene, polytetrafluoroethylene, etc.) which have hitherto been bonded (or glued) by using complex and expensive surface preparation techniques Polymerized acrylic urethane / polyurea compositions derive their adhesion, especially to low surface energy plastics, from free radical polymerization initiated by acrylic monomer organoborane The compositions derive their cohesive strength from the polymerization initiated by the simultaneous organoborane of the acrylic monomer and the condensation polymerization of the polnsocyanate with the pohol carrier for the complex and the polyamine of the complex. More advantageously the compositions of the invention offer good adhesion of the acrylic. pohmepzado lico and an elastomeric hard abrasion resistant junction of polyurethane / polyurea The polnsocianato and acrylic monomer are individually reactive materials, with molecular weights or (weight average molecular weights) less than about 3, 000, more preferably less than about 1,000, and more preferably less than about 750. As a result, the invention provides a fully reactive polymeric adhesive composition at 100% solids. In addition, the polyol carrier allows for the provision of a storage stable initiator system which can be combined directly with the portable monomers for a two-part adhesive in a convenient commercially useful integer mixing ratio of 1 10 or less The polyamine organoborane complexes useful in the invention are complex of organoborane and polyamma They preferably have the following general structure wherein R1 is an alkyl group having from 1 to 10 carbon atoms and R2 and R3 are independently selected from alkyl groups having from 1 to 10 carbon atoms and phenyl containing groups More preferably, R1, R2 and R3 are alkyl groups having from 1 to 5 carbon atoms such as methyl ethyl, propyl. iso-propyl, n-butyl. iso-butyl and pentyl "independently selected" means that R2 and R3 may be the same or may be different R1 may be the same as R2 or R3 or may be different from Preferably R1 R2 and R3 are the same. The most preferred are the complexes in which R1 R2 and R3 are each ethyl groups. The value of v is selected to provide an effective ratio of primary amine hydrogen atoms to boron atoms in the complex The ratio of the primary amine nitrogen atom to the boron atom in the complex ion is broadly about 1 1 to 4 1 However, preferably the ratio is 1 1 to 2 1 more preferably 1 1 to 1 5 1 and more preferably about 1 1 (In the case of a polyamine containing primary and secondary amine groups the ratio of primary amine nitrogen atom to boron atom could be as low as 0 5 1) One? < ratio of the nitrogen atom of the primary amine to the boron atom of less than 1 1 could leave free organoborane a material that tends to be pyrophoric A ratios of the primary amine nitrogen atom to the boron atom of more than 2 1 the practical utility of the complex in, for example, an adhesive system decreases as the amount of the complex that must be used to or improve a useful adhesive becomes larger. "Am" represents the polyamide portion of the complex and can be provided by a wide variety of materials that have more than one amine group in which combinations of different amines are included. More preferably, the pohamine has cor. to four amine groups, although the polyamines with two mine groups (ie diammas) are more preferred. In one embodiment, the polyamide can be described by the structure H2N-R4-NH2 in which R4 is a bivalent organic radical containing a alkyl, aryl or alkylaryl group Preferred among these materials are the alkanediamines which may be branched or linear and which have the general structure RJ wherein x is an integer greater than equal to 1, more preferably from 2 to 12, R 5 is hydrogen or an alkyl group, preferably methyl Particularly preferred examples of alkanemames include 1,2-ethanediamine. 1,3-propanediamine, 1,5-pentane-amine, 1,6-hexanediamine, 1,1-dodecanediamine, 2-methyl-1,5-pentanediamine, 3-methyl-1,5-pentanediamine and isomers of these materials . While the alkanediamines are preferred, other alkyl polyamines may be used such as triethylenetetraamine and diethylenetriamine. The polyamine can also be provided by a polyoxyalkylene polyamide. The polyoxyalkylene polyamine useful in the preparation of the complexes for the invention can be selected from the following structures H2NR6O- (R7O) - (R10), - (R7O) and -R6NH2 (ie, polyoxyalkyleneamyams) ). or [H7 * 0- (R70 _- R, R7 or R] are alkylene groups having from 1 to 10 carbon atoms and may be the same or different. Preferably R6 is an alkyl group having from 2 to 4 carbon atoms. carbon such as ethyl n-propyl, iso-propyl, n-butyl or iso-butyl Preferably R7 and R8 are alkyl groups having 2 or 3 carbon atoms such as ethyl n-propyl or isopropyl R9 is the residue of a • polyol used to prepare the oxoalkylene polyamine (this is the organic structure that remains if the hydroxyls are removed or separated) R9 can be branched or linear and substituted or unsubstituted (although the substituents can not interfere with the oxyalkylation reactions) value of w> 1 more preferably from about 1 to 150 and more preferably about 1 to 20 The structures in which w is 2 3 or 4 are also useful The value of x and y are both >; 0 The value of z is > 2 more preferably 3 or 4 (to provide, respectively, polyoxyalkylene triamines and tetraamines) It is preferred that the values of w, x, y and z be chosen such that the resulting complex is liquid at room temperature, since this simplifies the handling and Mixing it Usually, the? polyoxyalkylene polyamine is itself a liquid Molecular weights of less than about 5,000 can be used for the polyoxyalkylene although molecular weights of about 1000 or less are more preferred and molecular weights of about 250 to 1000 are more preferred or examples of polyoxyalkylene amines Particularly preferred include polyethylene oxide diamine polypropylene dioxide polypropylene dioxide triamine diethylene glycol propylene diamine triethylene glycol propylene diamine, polytetrapeptidenoxy: polyethylene oxide polyethylene oxide co-polypropylene dioxamine and polyethylene oxide co-polyopropanyl idotriamma Examples of commercially available polyoxyalkylene polyamines. appropriate, include several JEFAMINES from Huntsman Chemical Company, such as diameters of the series D. ED and EDR (for example, D-400, D-2000, D-5000. ED-600, ED-900, ED-2001 and EDR-148) and the triamines of Se T (for example T-403). also as H221 of Union Carbide Company. The polyamine may also comprise the product of the condensation reaction of a diprimary amine-terminated material (that is, the two terminal groups are primary amine) and one or more materials containing at least two primary amine-reactive groups (referred to in or sometimes present as "diffunctional primary amine reactive material"). Such materials 3 are preferably substantially linear to have the following general structure E- (LE) uLE in which E is the residue of the amine dippmapa-terminated material and each L is a linking group which is the residue of the amine reactive material primary difuncional. ("Residue" means those 5 portions of the dippmarine amine-terminated material and the difunctional primary amine reactive material remaining after the reaction to form the polyamine adduct) The E and L groups are independently selected. This is. each group E can be the same or it can be different, as it can be each or group L. Although it is preferred that each group E is the same and that each group L is the same Preferably E and L are selected to form a complex that is soluble in acrylic monomer Most (more than 50%) of the terminal groups in the polyamine should be primary amine The value of u is selected to provide a polyamine and a < useful viscosity complex Preferably the polyamine and the complex are liquid at room temperature ("Room temperature" herein refers to a temperature of about 20 to 22 ° C). Consequently, the value of u may be greater than or equal to zero, although a value of approximately 0 to 5 is more preferred and a value of 0 or 1 is more preferred.

The material finished in amine diprimana can be alkyl amine dippmapa. anl amina dippmapa. alkylamine amine diprimapa a polyoxyalkylene diamine (such as those described above) or mixtures thereof Useful dippmaryl alkyl amines include those having the structure NHr-R10-NH2. wherein R10 is a linear or branched alkyl group. or having about 1 to 12 carbon atoms, such as 1,3-propanediamma 1.6-hexanedi amine 1.12-dodecanediamine. Other useful diprimaproalkylamines include triethylene tetraamma and diethylene tinamine. Examples of useful diplyme aryl amines include 1,3- and 1,4-phenanthin diamine. also as the various isomers of diammonaphthalene. An example of an alkylaryl amine? useful dippmapa is m-tetramethylxylene diam The reactive materials containing diffunctional primary amine contain at least two groups reactive with primary amine. The reactive groups may be different but it is preferred that they be the same. Difunctional primary amine reactive materials having a functionality of 2 (ie, 2 groups reactive with primary amine) are preferred. The materials reactive with difunaonal primary amine. Useful can be generally represented by the formula Y-R1, -Z. wherein R 11 is a divalent organic radical such as an aryl or alkylaryl alkyl group or combination thereof and Y and 7 are primary amine reactive groups and which may be the same or may be different Examples of Y and Z groups useful, reagents with primary amine include carboxylic acid (-COOH), carboxylic acid halide (-COX, wherein X is a halogen for example chlorine), ester (-COOR), aldehyde (-COH). epoxy alcohol amine (-NHCH2OH) and acrylic (-C-CH = CH3) I o Suitable carboxylic acid functional materials are preferably those which are useful in the formation of pohamines. for example, c-clohexan-1,4d-carboxylic acid and dicarboxylic acids having the structure HOOC-R 12 -COOH. wherein R12 is a linear alkyl group having about 2 to 21 carbon atoms. The aromatic dicarboxylic acids (for example terephthalic and isophthalic acids) can be used as well as the alkylaryl dicarboxylic acids can be used. especially in combination with alkyl dicarboxylic acids. Useful carboxylic acid halide materials and functional ester materials include those which are obtained by derivatizing the carboxylic acid functional materials described above. Suitable aldehyde functional materials include alkyl., aryl and alkylaryl dialdehydes such as oxaldehyde propandialdehyde, succmaldehyde. adipalaehicO 2-h? drox? hexanod? al. phthalaldehyde 1, 4-benzenediacetaldehyde 4 4-tet lend? O?) D? Benzaldehyde and 2,6-naphthalene dicarbaldehyde The most preferred are glutalaldehyde and adipaldehyde.

Suitable epoxy-functional materials include phthalic, cycloaliphatic and glycidyl ether diepoxides. More preferred are diepoxides based on bis-phenol A and bis-phenol. The useful acrylic functional materials are preferably diacnlates and a wide variety of such materials can be successfully employed in the invention The organoborane pohamin complex can be easily prepared using known techniques Normally, the polyamine is combined with the organoborane in an inert atmosphere with slow stirring. Frequently a heat release is observed consequently the cooling of the mixture It is recommended If the ingredients have a high vapor pressure it is desirable to keep the reaction temperature at a temperature less than about 70 to 80 ° C. Once the materials have been mixed well the complex is allowed to cool to room temperature. require specific storage conditions Although the complex is required to be kept in a covered container in a dark cold place, the polyamine organoborane complex is employed in an effective amount which is an amount large enough to allow the polymerization of the acrylic monomer to be easily presented. to obtain a sufficiently high molecular weight acrylic polymer for the desired end use If the amount of the organoborane polyamine complex is too low then the polymerization may be incomplete or in the case of the adhesives the resulting composition may have poor adhesion For another ^ If the amount of the organoborane polyamine complex is too high then the polymerization can proceed too fast, to allow effective mixing and use of the resulting composition. Large amounts of the complex could also lead to the generation of large volumes of borane, the which in the case of an adhesive, pod It will weaken the bond line. The useful polymerization rate will depend largely on the method of application of the composition to a substrate. Thus a faster polymerization rate can be obtained by using a high-speed automated industrial adhesive applicator instead of the application of the composition with a manual applicator or by manually mixing the composition Within these parameters, an effective amount of the organoborane polyamine complex is an amount that preferably provides about 0.03 to 1.5% by weight of boron, more than preference 0 08 to 0 5 wt% boron, more preferably at about 0 1 to 0 wt% boron Weight% boron in a composition is based on the total weight of the acrylic group containing materials plus the inorganic thickening agent (for example poh (methyl methacrylate) or a core-shell polymer) if present and does not include the pohol or polnsocianato It can be calculated by the following equation (Weight of the complex in X (% by weight of boron in the composition) complex) (Total weight of the materials containing acphco group + organic thickener) The polyamine organoborane complex is fairly advantageously transported by (for example, dissolved in or diluted by) polyol or mixture of isocyanate-reactive polyols The polyol should not be reactive towards, coordinate or complex the pohamina. Any of a wide variety of polyols that are used to make the polyurethane can be used in the invention in which polyether poles and polyester polyols are included. Such materials are described in various publications such as Polyuretane Elastomers. published by Elsevier Applied Science, London, 1992: Advances tn Polyuretane Technology, chapter 3, edited by Buist and Gudgeon published by John Wiley and Sons. New York, 1968: and Poly? Rethane Handbook edited by Oertel, published by Hanser Publishers, Munich, 1985. As useful materials they have broadly a hydroxyl functionality greater than 1. it is preferred that the functionality be in the range of 2 to 3 The pohol must be soluble in acrylic monomers included in the composition Soluble "means that no overt evidence of phase separation at room temperature is visible to the naked eye Similarly, the organoborane po-amine complex must be soluble in the po, although the slight heating of a mixture of the complex and the pohol may be useful in the formation of a solution of the two at room temperature. The liquid is more preferably the polyamine organoborane complex and the pohol form a liquid solution. Substantially advantageous amounts (for example, more than 75% by weight) of the complex can be dissolved in the pohol. of two-part adhesives that can be combined into a useful mixing ratio 2 Preferably, the pohol is selected to provide a polyurethane / polyurea component having a glass transition temperature greater than room temperature, more preferably greater than 30 ° C While the hydroxyl groups in the polyol may be secondary or tertiary , poles having primary hydroxyl groups are preferred to adjust the polymerization rate of the polyurethane to a more useful level. Polyether polyols are particularly preferred for use in the invention and may comprise the epoxide polymerization product with either water or water alcohol. Exemplary epoxides that can be employed in the preparation of the polyether polyols useful in the invention include short chain alkylene oxides (eg, from about 2 to 6 carbon atoms) such as ethylene oxide, propylene oxide, oxide of butylene and amylene oxide ghcidyl ethers such as t-butyl glycidyl ether and phenyl glycidyl ether and random or block copolymers of 2 or more of these epoxides Exemplary hydrocarbon alcohols which can be used in the preparation of appropriate pohter pohols Use in the invention preferably have from 2 to 8 hydroxyl groups and include short chain diols (having about 2 to 7 carbon atoms) such as ethylene glycol. 1.2-propanod? Ol. 1.4-butanod? Ol. 1.3-butanod? Ol. 1.5-pentapodiol and 1,7-heptanediol, compounds derived from phenols such as bis-phenol A: and materials having more than 2 hydroxyl groups such as g cerol, 1,1,1-trimethylolpropane. 1 1 1-tr? Met? Loletano. hexan-1.2.6-tr? ol a-metiiglucosido, pentaeptritol, pentatoles. hextols and various sugars (e.g., glucose, fructose sucrose and maltose) As a subclass, polyalkylene polyether polyols (sometimes referred to herein as polyalkylene oxide polyols (or polyalkylene oxide polyols)) are preferred. They can be prepared from the short chain alkylene oxides previously described, also as other starting materials, such as tetrahydrofuran and epihalohydrins, such as epichlorohydrin. The alkylene oxide tetrahydrofuran copolymers can also be used. arylene, such as styrene oxide. which may be used to form polyarylene oxide polyols. The most preferred polyalkylene ether polyols are polyol or polypropylene oxide, polyethylene oxide polyol and polyethexylene oxide polyol, including derivatives terminated in ethylene oxide. or propylene oxide thereof. More preferred are the polypropylene oxide polyols. Examples of useful disposable polyalkylene polyether polyols include the REZOL family of 5 Witco Chemical Co materials (eg ET-700) and the ARCOL family of materials from ARCO Chemical Co (e.g. PPG 425 and PPG 1000) Poyester polyesters are also useful and can be prepared by reacting one or more diols with one more dicarboxylic acids. The diols which can be used to make the polyester poles useful or in the invention include saturated diols, having the general structure HO- (CH2), -OH, wherein the integral value of x is from about 2 to 6. , examples of which include ethileng col. propylene glycol, 1,4-butanediol and 1,6-hexanediol The dicarboxylic acids which can be used to make the poyester polyesters useful in the invention include acids < saturated dicarboxyhcs having the general structure HOOC- (CH2) y -COOH, where the integral value of y is from about 4 to 8 examples of which include adipic acid and sebacoic acid The aromatic dicarboxylic acids can also be used in both that the organoborane polyamyria complex remains soluble in the same Examples of commercially available suitable po 5-ester polyols include the family of FOMREZ materials from Witco Chemical Company (eg 1066-167) Poh-e-caprolactone-based pohie pohols are particularly preferred and can be obtained from ring-opening polymerization of e-caprolactone The TONE family of poh- and e-caprolactone pohols from Union Carbide Corp (eg TONE 0210 0305 and 0310) are particularly useful. As indicated above, the polymerization initiator systems of the invention include a pol- nocyanate (this is a material having a isocyanate functionality greater than 1 more preferably an isocyanate functionality of 2 to 4, more preferably an isocyanate functionality of 2) The pohisoaanate reacts with the pohamin of the organoborane po amin complex to thereby separate the organoborane from the linkage chemistry with pohamine and form po urea The organoborane is available to initiate the free radical polymerization of monomers or acnhc However, advantageously, polnosocyanate is also reactive with the pohol which carries the organoborane and pohmenza pohamma complex to a linear polymer or polyurethane / pohurea network., the invention provides a 100% fully reactive polymerizable composition. Desirable polyisocyanates readily form reaction products with polyamine and polyol at room temperature or at a lower temperature (and more preferably at room temperature) to provide a composition such as as an adhesive, which can be easily used and cured under ambient conditions. The polyisocyanates useful in the invention are soluble in acrylic monomers used in the adhesive composition, which means that no strong evidence of phase separation at room temperature is visible to the naked eye. The polyisocyanates useful in the invention include various aliphatic cycloaliphatic, aromatic, and (cyclo) aliphatic-aromatic mixed diisocyanates. In general, aliphatic diisocyanates are preferred, especially in conjunction with polyamine organoborane complexes incorporating aliphatic polyamines. The useful ones are ethylene diisocyanate. ethylene diisocyanate propylene diisocyanate, butylene diisocyanate. hexamethylene dnsocyanate (in which dimers and trimers thereof are included), dichlorohexamethylene diisoanate. c? Clopentylene-1,3-diisocyanate. c? clohex? len-1.4-diisoc? anato c? clohex? len-1.2-d? soc? anato. isophorone diisocyanate. toluene furfunhdene diisoanate diisoanate, 2 2-d? phen? lpropan-4,4'-d? femmethylene p-phenylene diesocyanate, m-phenylene diisocyanate. xihleno diisocyanate. 1,4-naphthylene dnsocyanate. 1-5-naphthylene diisocyanate, m-tetramethyl xylylene diisocyanate. polymeric versions of 4-4-methylene diphenyl diphenyl-4,4'-d-isocyanate dnsocyanate. azobenzene-4,4'-dnsocyanate d? phen? lsulfon-4 4 -diisocyanate and 1-chlorobenzene-2,4-diisocyanate. Highly crystalline aromatic materials that are more soluble in acrylic monomer (for example, 4,4'-pure methylene diphenyldicyanoate) would not be used. Various tp- and tetraisocyanates can also be used such as 4 4'4"-tr ?? soc. ? anatotr? fen? methane 1 3 5 -tr? soc? anato benzene 2 4 6- ^ trnsocianato tolueno and 4 4'-d? met? ld? fen? metmetano-2 2 ', 5,5'-tetra? Soc. The hexamethylene dnsocyanate (and its dimers) isophorone dnsocyanate and m-tetramethyl xylene dnsocyanate are preferred. The polnosocyanate is employed in an effective amount that is an amount effective to promote the polymerization of the acrylic monomer at or release the organoborane. of the complex and allow the formation of a pohurethane / pohurea of sufficient molecular weight for the proposed end use (but without materially adversely affecting the properties of the final pohmepzada composition) The amount of polnsocyanate employed is normally in the same range as that used convince nally for the i >; condensation polymerization of pohurethane / pohurea Larger amounts of polnsoaanate may allow the polymerization of acrylic monomer to proceed too quickly and in the case of adhesives the resulting materials may demonstrate inadequate adhesion to low energy surfaces. 2 undesirable secondary that adversely affect the performance properties of the polymerized composition or an undesirably high level of components that can be extracted in the pohmepzada composition can also result from the use of large amounts of pohisocyanate that would otherwise remain unreacted. amounts of * • «polusocyanate the polymerization rate can be too slow and the M) monomers that are polimepzan may not adequately increase in molecular weight. However, a reduced amount of polyisocyanate may be useful to slow down the polymerization rate if it is otherwise too fast. Within these parameters, the polyisocyanate may be provided in an amount where the number of isocyanate equivalents is stoichiometic with the number of amine functionality equivalents, plus the number of equivalents of hydroxyl functionality in the polymerizable composition (whether or not it is provided by the polyamine, polyol and polnsocyanate or other functional amine-, hydroxyl- or isocyanate materials in the composition) Opaonally the adhesive composition may contain a bireactive compound in order to bind the polyurethane / polyurea and the acrylic. The bireactive compound preferably comprises at least one free radical-scalable group and at least one amine-reactive group. Examples of useful birective compounds in the invention can be represented by the following general structure (Fp). - ALREADY). where "Fp" is a group pohmepzable by free radicals. "A" is a reactive amine group "Y" is a polyvalent organic linking group; "a" represents the number of groups pohmepzables by free radicals, and "b" represents the number of groups reactive with amine The group po mepzable by free radicals Fp "preferably comprises an alkene group The alkene group can be unsubstituted or substituted or may be part of a cyclic ring structure The substituted alkenes include those alkenes having an alkyl or aryl group substitution Preferred alkenes are those having terminal non-substituted double bonds, such as halo groups The most preferred alkenes are The most preferred alkenes are the materials that contain an acrylic group The amine reactive group, "A" preferably comprises an isocyanate group, because the bioreactive compound comprises at least one movable group by free radicals and by at least one group reactive with amine, the value of each of "A" and "b" is at least one. Preferably, the sum of "a" and "b" is less than or equal to 6, more than preference less than or equal to 4. more preferably 2. The polyvalent organic linking group "Y" may comprise a wide variety of different chemical structures, depending on the reagents used for prepare the birective compound Preferably, the birective compound comprises the product of? reaction of a polnsocyanate and a hydroxyl compound containing a free radical free poWmerable group Polnsocyanates useful in the formation of the bioreactive compound include those discussed above as being suitable for reacting with the polyamine portion of the organoborane pohamma complex or the adducts prepared by reacting a molar excess of polnsocyanate with a compound having active hydrogen (for example polyols, polythiols and pohamines) are also useful in the preparation of the bireactive compound Useful polyols include alkylene glycols, alkylene ether glycols and polyhydric alkanes Useful polyethylene include 1. propanod? thiol, 5 2 2 -dimercapto diethyl ether 2.2 -dimercapto diethyl sulphide, tpetylene glycol dimercaptan and tnmethylol ethane tr? (- mercapto propionate) Useful polyamines include ethylene diamine, 1,3-d? am? nopropane, 1,6-hexanod? amna and 4 7.10-tr? oxa-1 13-tr? decand? am? na _r The preferred hydroxyl compounds in cluyen (met) acplatos and ^ (met) acr? lam? das hidroxilados where the use of the expression (met) indicates that the substitution of methyl is optional The adducts of (met) acr? iat o (meth) acylates which are hydroxylated with lactones (e.g. e-caprolactone) to form hydroxyl (meth) acrylate pothanes are also particularly useful The most preferred birezactive compounds comprise the? or reaction product of the preferred polnsiocyanates a those referenced above and a hydroxylated (meth) acrylate such as hydroxyethylmethacrylate hydroxyethylplatoxyhydroxybutylcarbonate or adducts thereof (met) acrylates hydroxylated with e-caprolactone The birective compound can be included in the composition? < adhesive as a preformed material or can be generated in situ. If the pre-formed material is provided as a starting material (for example hydroxylated (meth) acrylate and dionesocyanate) they are reacted in the presence of a catalyst for the formation of urethane ( as dibutyltin dilaurate) and optionally a free radical inhibitor (e.g., or hydroquinone). As an example when the starting ingredients are a mono-hydroxylated (meth) acrylate and dionesocyanate the molar ratio of the first to the last is prefa from 0 9 - 1 1 1 more preferably 1 1 to provide < The equivalent amount of NCO to OH of 2 1 l of the amino acid can be formed in situ by the inclusion, for example, of the hydroxylated (meth) acrylate, with the polyisocyanate and acrylic monomer (as explained more fully in below), in the presence of a catalyst for the formation of urethane In this instance, the total amount of polyisocyanate must be increased to take into account the additional hydroxyl functionality added by the hydroxylated (meth) acutate. Thus the compositions of the invention may also include a compound such as a hydroxylated (meth) acrylate or the others described above, which react with polyisocyanate to produce a bireactive compound. As indicated above, the released organoborane initiates the free radical polymerization of the acrylic monomer "Acrylic monomer" means suitable monomers. that have one or more portions, chemical or functional groups acrylic or substituted acrylic. That is, groups having the general structure RO • I l H ^ CCCOR 'wherein R is hydrogen or an organic radical and R' is an organic radical Where R and R are organic radicals, they may be the same or different. they can use mixtures of acrylic monomers The pohmepzable acrylic monomer can be monofunctional. functional or a combination of the same The most useful monomers are monofunctional acplato and metacplato esters and substituted derivatives thereof, such as hydroxy. amide, cyano, chloro and silane derivatives, as well as mixtures of substituted and unsubstituted monofunctional acrylate and meta-platelet esters Particularly preferred monomers include lower molecular weight meta-plate esters such as methyl meta-platelet, ethyl methacrylate, methoxy ethyl meta-platelet, hydroxyethyl meta-platelet meta-plate Hydroxypropyl Methanolate, Cyclohexyl, Tetrahydrofurfuplo Metacrate, and Combinations The higher-molecular weight metacplate esters of achalate and meta-plate esters are less preferred for use alone, but can be especially useful as modifying monomers with predominant amounts of more molecular weight metacrate esters to improve for example the softness or flexibility of the final adhesive composition. Examples of such higher molecular weight metacplate esters and acrylic esters include methyl acrylate ethyl acyllate isobornyl meta-platelet hydroxypropyl acrylate butyl acrylate, -octyl, 2-et? lhex acplato? the meta-plate of 2-et? lhex? decilmetacplato 11 dodecilmetacplato metaplatto of tert-butyl acplamide, N-methylacplamide, diacetonacplamide N-tert-butylacplamide N-tert-octylacplamide N-butoxyarphamide gamma-metacploxypropyl tpmethoxysilane acrylate 2-aanoethyl acrylate 3-c? Anopropyl chloroacetate tetrahydrofurfuplo glycidyl acrylate glycidyl methacrylate and Particularly preferred are mixtures of any of the lower molecular weight alkylmethacrylate esters described above with alkyl achalates having from 4 to 10 carbon atoms in the alkyl group such as mixtures of meta-platelet and methyl butacrylate. Pozmezables of this type can comprehend widely in : < based on the total weight of the composition about 2 to 40% by weight of the alkyl acrylic and correspondingly, about 60 to 98% by weight of the alkyl methacrylate Another class of polymerizable monomers which are especially useful as modifiers, such as for improve the slip resistance or temperature resistance of the final composition, corresponds to the general formula R can be selected from the group consisting of hydrogen, methyl, ethyl and CH j- O-? C- C- CH2 i ?? R14 can be selected from the group consisting of chlorine, methyl and ethyl R15 can be selected from the group consisting of hydrogen and O fl -OCC-CH, I R'5 The value of a is an integer greater than or equal to 1 more than preferably from 1 to about 8 and more preferably from 1 to 4 The integral value of b is 1 greater than or equal to 1. more preferably from 1 to about 20. The value of c is 0 or 1 Other acrylic monomers useful as modifying monomers, include ethylene dimetacplato col. d? acr? l3to of ethylene glycol. diacnlate from po ethilenghcol. dimetacplato of tetraetileng cabbage dighcerol diacnlate. > diethylene glycol dimethacrylate. pentaentptol triacplate. tnmetacplato of tpmetilol propane. also as other polyether diaclettes and dimethacrylates Other suitable monomers which are useful in the invention particularly as modifying monomers have the general formula R'6 can be hydrogen chloro methyl or ethyl. R1 can be an alkylene group with 2 to 6 carbon atoms and R18 is (CH2) e in which e is an integer from 0 to 8 or one of the isolates / C-C 0 = C H CM 3 X the phenyl group is substitutable in any of the positions ortho, meta or for the value of. is an integer from 1 to 4 The typical monomers of this class include bimeta (et? lenghcol) dimetacplato ad? duck dimethacrylate bis (et? legl? col) maleate. dimetacplato of bis (et? lenghcol) phthalate dimetacplato de b? s (tetraet? legl? col) phthalate. dimetacplato de b? s (tetraet? lenghcol) sebacate dimethacrylates of b? süetraet? lengl? col) maleate and the diacnlates and chloroacplats corresponding to dimethacrylates and the like Also useful as modifying agents are the monomers which are isocyanate reaction products. Hydroxyacid or isocyanato-aminoachnlate These can be characterized as polyurethanes and polyureas or polyureas terminated in acnlate. Such monomers have the following general formula Where W is selected from the group consisting of -O- and R "I -N-R19 is selected from the group consisting of hydrogen and lower alkyl groups (for example from 1 to 7 carbon atoms) T is the organic residue of or an acrylic ester containing active hydrogen the active hydrogen is separated and the ester is hydroxy or substituted ammo on the alkyl portion thereof (in which the homologs of methyl ethyl and chlorine are included) The integral value of e is 1 to 6 Q is a mono- or polyvalent organic radical selected from the group consisting of alkylene alkyl alkenyl cycloalkyl radicals? < cycloalkylene aryl aralkyl alkanol pol? (Ox? Alkylene) pol? (Carboalkox? -alkylene) and heterocyclic radicals Substituted and unsubstituted monomers Typical monomers of this class include the reaction product of mono- or pol- nocyanates for example toluene dnsocyanate with an acrylic ester containing a hydroxy group or an ami- ppo group in the portion or not. acnlate thereof for example hydroxyethyl metacrate The compositions may further comprise a variety of optional additives. A particularly useful additive is a thickening agent, such as polymethyl methacrylate of average molecular weight (about 100,000) which can be incorporated in an amount of about 1 to 0 to 40% by weight, based on the total weight of the composition. Thickening agents can be employed to increase the viscosity of the composition to a syrup-like, viscous consistency, applied at room temperature more easily. Another particularly useful additive is an elastomeric material. These materials can improve the hardness at fracture of the compositions made with them, which can be beneficial when, for example, materials with high resistance to cadence, are rigidly joined, such as metal substrates that do not mechanically absorb energy. as easily as other materials such as flexible polymeric substrates. Such additives may be incorporated in an amount of about 5% to 35% by weight, based on the total weight of the composition. Certain graft copolymer reams, such as particles comprising rubber or rubber-like cores or networks that are surrounded by relatively hard covers these materials are often referred to as shell-shell polymers, they are particularly useful elastomeric additives. More preferred are acrylic-butadiene-styrene graft copolymers. In addition to improving the hardness at fracture of the composition the core-shell polymers , they can also impart improved dispersion and flow properties to the uncured composition. These improved properties can be manifested by a reduced tendency of the composition to leave an undesirable "string" after the assortment or supply, of a syringe-type applicator, or to run or to flow after having been applied to a super vertical ficie The use of more than about 20% of a core-shell polymer additive is desirable to obtain improved creep-flow resistance. Another useful adjuvant is a monomeric acrylic crosslinking agent (crosslinking). Acrylic monomer can be used to improve the solvent resistance of the adhesive bond, although certain compositions of the invention have good resistance to solvents even in the absence of externally aggregated acrylic monomer crosslinking agents. Employed normally in an amount of about O 2 to 10% by weight, based on the total weight of the composition, useful acrylic monomer crosslinking agents include the various diacnlates referred to herein as possible acrylic modifying monomers, as well as other materials. Particular examples of crosslinking agents of acrylic monomer co appro piados include ethylene glycol dimethacrylate, ethylene glycol dimethacrylate of tnetileng cabbage, bismetacploxycarbonate of diethylene glycol, diatchet of pohetilenghcol. tetraethylene glycol dimethacrylate. dighcerol diaccolate. diethylene glycol dimethacrylate. pentaerythritol tpacplate, trimethylolpropane tpmetacplate, as well as other polyether diaclettes and dimethanedielates. The peroxides may be optionally included (commonly in an amount of about 2% by weight or less, based on the total weight of the acrylic and methacrylate components) by example, to adjust the speed at which the compositions polimepzan or to consummate the polymerization of the acrylic monomer Catalysts that promote the formation of polyurethane (for example dibutyl tin dilaurate stannous octoate and tpetilentpamine such as DABCO from Air Products And Chemicals Co etc. ). they can also be 5 employed. A catalytically effective amount is used which is a sufficient amount to increase the polymerization rate of the polyurethane but without accelerating the polymerization in such a way that the adhesive composition cures so quickly that it becomes difficult to spread it under application conditions. Normal room temperature A typical amount The catalyst for the formation of polyurethane is less than about 20% by weight of the alcohol. Other additives which can be included in the compositions are those which are associated with the formation of polyurethane such as chain-extending agents, weight Molecular (for example 1 4-butanediol or 1 3-propanod? am? na etc) which could be included to influence the nature of the polyurethane / pohurea especially the hard segment component thereof. The hard segment of the polyurethane can also be modified by proper selection of the po-amine component of the complex Thus the pohamin can serve for or the double function of stabilizing the organoborane against oxidation and providing a hard segment of urethane. Small amounts of inhibitors such as hydroquinone can be used for example for prevent or reduce the degradation of acrylic mopomeros during storage. The inhibitors can be * added in an amount that does not materially reduce the polymerization rate or the final properties of an adhesive or other composition made therefrom typically of about 100-10. 000 ppm based on the weight of the polymerizable monomers Other possible additives include and in non-reactive dyes filled (for example carbon black) etc. The various optional additives are employed in an amount that does not significantly adversely affect the polymerization process or the desired properties of the compositions made therewith. According to the dimension they can be used in a wide variety of ways in which they are included as sealants coatings and injection molding reams They can also be used as matrix resins in conjunction with fiberglass and metal mats such as in operations Resin transfer molding can also be used additionally as encapsulating and filler compounds such as in the manufacture of electrical components and printed circuit boards and the like. They quite desirably provide porous adhesive compositions which can be attached to a variety of substrates in which include concrete ceramic wood polymers and primed metals. The pocheable compositions of the invention are? > especially useful for adhesively bonding plastic substrates or low-energy surface substrates that historically have been very difficult to adhere without using surface preparation techniques complicated priming etc. Substrates b? ja surface energy means materials that have a surface energy of less than 45 mJ / m2 more commonly less * of 40 mJ / m2 or less than 35 mJ / m2 Included among such materials are polyethylene, polypropylene acplonitplo-butadiene-styrene and fluorinated polymers such as polytetrafluoroethylene (TEFLON) which has a surface energy less than 20 mJ / m2 (The term 'surface energy' is often used as a synonym for 'critical wetting tension by others.) Other polymers of somewhat higher surface energy that can be joined (or glued) together Compositions of the invention include polycarbonate pohmetilmetacplato and pohvinylchloride Compositions Pozmepzable compositions of the invention can easily be used as two-part adhesives Acrylic monomers are combined as would normally be done when working with such materials although they must be thoroughly dried to prevent undesirable reaction between the polnsocyanate and the moisture that the formation could cause. of foam and carbon dioxide evolution Polnsocyanate is usually included in this mixture to separate it from the organoborane po-amine complex to thereby provide a part of the two-part composition. The optional reactive compound (if present) also is added to the first part of the adhesive composition The polyamine organoborane polyolamine complex and any catalyst for the formation of polyurethane provide the second part of the composition The first and second parts are combined briefly before it is desired for use of the composition a two-part adhesive such as those of the invention to be used more easily in commercial and industrial environments the ratio to which the two Darts are combined should be a convenient whole number. This facilitates the application of the adhesive with commercially available conventional dispensers or dispensers. Such dispensers are shown in US Pat. Nos. 4, 538,920 and 5,082,147 and are available from Conprotec, Inc. (Salem NH) under the brand name "Mixpac." Normally these jets use a pair of tubular receptacles 5 arranged side by side each tube which is designed to receive one of the two parts of the adhesive Two plungers, one for each tube, are advanced simultaneously (for example manually or by a ratchet mechanism) hand-operated) to evacuate the contents of the tubes in an elongated, common hollow mixing chamber, which may also contain a static mixer to facilitate the combination of the two parts. The mixed adhesive is extruded from the mixing chamber onto a substrate. Once the tubes have been emptied, they can be replaced with new tubes and the application process continues. The ratio to which the two parts of the adhesive are combined is? >; controlled by the diameter of the tubes (Each plunger is sized to be received inside a fixed diameter tube and the plungers are advanced to the tubes at the same speed) A single spout is often designed for use with a variety of different adhesives of two parts and the plungers are dimensioned to supply the two parts of the adhesive in a convenient mixing ratio. Some common mixing ratios are 1 1 1 2 1 4 and 1 10 If the two parts of the adhesive are combined in an unequal mixing ratio (For example 3 5 100). then the end user would probably weigh the two parts of the adhesive manually. Thus for a "better commercial and industrial utility and for ease of use with the currently available dispensing equipment, the two parts of the adhesive must have the ability to be combined in a mixing ratio of a common whole number, such as 10: 1 or minor, more preferably 1: 4, 1: 3, 1: 2 or 1: 1. The adhesive compositions of the invention are uniquely suitable for use with conventional assortment equipment, commercially available. for two-part adhesives. The unique solubility of the polyamine organoborane complex polyol can be advantageously used to modify the mixing ratio of the two parts of the adhesive composition to the values of commercially most important whole numbers, for example. 1 10. 1.4. 1.3. 1: 2 or 1: 1. In addition, the excellent solubility of the organoborane pohamin complex in the polyol allows the complex to be stored separately from the part containing the acrylic monomer of the two-part composition. As a result, the two parts of the composition have excellent storage stability ( at least several weeks) but can still be combined in a commercially useful mixing ratio. In addition, the polnosocyanate reacts with the pohol and the amine to form a linear polymer or polyurethane / polyurea network independent of the linear polymer or acp'hco network. Once the two parts have been combined, the composition should be used quickly, since the useful life can be short, depending on the monomeric mixture acquiring the amount of the complex, the temperature at which the union is going to be carried out. the presence or absence of a pohurethane formation catalyst and the type of hydroxyl groups in the pohol. The openable composition can be easily applied and cured at room temperature. Normally, it is applied to one or both substrates and then the substrates are joined together with pressure to force the excess composition out of the bond line. This also has the advantage of displacing the composition that has been exposed to the air and that may have begun to rust. In general, the joints must be made briefly after the composition has been applied preferably in the course of about 10 minutes The thickness of the typical bond line is from about 0 1 to 0 3 mm The bonding process can be carried out easily at room temperature and for to improve the degree of polymerization it is desirable to maintain the temperature at a level of less than or about 40 ° C, preferably less than 30 ° C and more preferably less than approx. 25 ° C Once applied, the composition develops a cohesive strength of the simultaneous polymerization of the acrylic monomer (to form a linear polymer or acrylic network) and the polnsocyanate po and polyamine (to? < form a linear polymer or network polyurethane / polyurea independent of but coexisting with the linear polymer or acrylic network) Adhesion is provided by the acrylic component The joints will cure to a reasonable green or premature strength to allow handling of the bonded components in the course of about 6 hours. at 7 hours Full resistance will or will be obtained in approximately 24 hours under ambient conditions, post-curing with heat (Normally around 80 ° C) can be used if desired An even more rapid integration of resistance is facilitated by the inclusion of a bi-reactive compound in the polymerization mixture to crosslink (or cross-link) acrylic and the polyurethane / polyurea < between them and the use of aromatic polnosocyanate In such situations, resistance to handling can be obtained in less than 1 hour. The acrylic monomer. the polyamine portion of the complex, the polyol and the polyisocyanate should be selected to produce a cured adhesive in which the independent urethane / po urea and the acrylic components are compatible. "Compatible" means that no clear evidence of phase separation of the acrylic and polyurethane / polyurea is visible to the naked eye at room temperature such that the resulting adhesive bonds are characterized by low cohesive strength and inconsistent adhesion. The invention will be more fully appreciated with reference to the following non-limiting examples in which the weights are they give either as percentages by weight (percent by weight) based on the total weight of the composition which is nominally 100% by weight or grams, the weights (except for boron) are reported to two significant digits after the decimal point Several brand names and abbreviations used in the examples are defined according to the following list Abbreviation or trade name Description BA n-butyl acnlate BLENDEX B467 acplonitrile-butadiene-styrene terpolymer from General Electric Specialty Chemicals Parkersburg, WV cm centimeter DBTL Dibutyl tin dilaurate DESMOPHEN 1150 Polio! of polyether-based polyol of castor oil, from Bayer DYTEK A 2-met? l-1 5-d? am? nopentane available from E I duPont de Nemours and Co FOMERZ 1066-187 Reaction product of polyphenol of tpmethylol propane and 1,6-hexanod? O? Co acid, available from Witco Chemical Co FOMREZ UL-28 Catalyst for the formation of polyl urethane. available from Witco Chemical Co HA N-Hexylplate HEMA Hydroxymethylmethacrylate HMDA 1 6-Hexanedi amine I * in inches IPDI isoforopa isoforopa Lo-PMMA poly (methyl methacrylate) low molecular weight from Aldrich Chemical Company or μm microns mm millimeters MMA methylmethacrylate PMMA poh (methyl tacrolimethylacrylate etheric acid ethoxy 101,000 with less than 5% ethylacrylate from Aldrich Chemical Company PPG 425 polypropylene oxide pohol having a approximate average molecular weight number of about 425, available from Aldrich Chemical Company PPG 1000 Polypropylene Oxide Pohol having an approximate average molecular weight number of about 1000, available from Aldrich Chemical Company REZOL ET-700 Polyoxyalkylene Pohol commercially available by Witco Chemical Co? <; TEB Tpetilborano THFMA Tetrahydrofurfurylmetacplato TMXDI Tetramethylxylenedosociapato TONE 0210 Poh-e-caprolactane diol. available from Union Carbide Corp or TONE 0305 Poly-e-caprolactone triol, available from Union Carbide Corp. TONE 0310 Tri-po-e-caprolactone. available from Union Carbide Corp Synthesis of the pohamin organoborane complex All glass equipment was washed and subjected to the flame at 538 ° C (1000 ° F) or subjected to the flame by means of a Bunsen burner until the articles of glass shone with an orange color A box of 5 handling with gloves was installed and washed with a nitrogen discharge The concentration of oxygen in the glove box was verified by a Servomex Oxygen analyzer and the synthesis was carried out in a nitrogen environment containing less than 100 ppm oxygen io The glove compartment contained a faucet funnel (or wrench) or dropper that equalizes the pressure an electric scale, a flask with appropriate plugs, a stand and an ice bath The organoborane was weighed in the funnel with tap that equals the pressure and the amine was weighed in the flask. Then the organoborane was added dropwise to the polyamine with stirring and? < cooling A moderate heat evolution was observed and the addition of the organoborane was moderate to control the heat evolution. If the smoke formation appeared the addition of organoborane was stopped until the smoke formation stopped When all the organoborane had been added, The flask was allowed to reach room temperature and either a crystalline mass or a liquid was obtained. If it results in a crystalline mass it is heated to 55 ° C by means of an oil bath outside the box for the manipulation with gloves until a liquid is obtained. Then the liquid is transferred to a bottle that had been flushed with nitrogen. Unless indicated otherwise, the complexes were synthesized cleanly with a ratio of the primary nitrogen atom to the atom. of boron of 1: 1.

Preparation of the monomer mixtures More specific details about the monomer mixtures used in the examples are given below in conjunction with the individual examples. In general, however, the monomer mixtures were generated by weighing methyl methacrylate, p-butyl acrylate. thickening agent (for example, poly (methyl methacrylate) or core-shell polymer) and the bireactive compound (if included) in a bottle. First the monomers were dried on 4A molecular sieves. The bottle was sealed placed on a roller / mixer and heated under an infrared heating lamp that heated the bottle but did not heat on contact until a solution was obtained. After cooling, the pohisoanate was added. Usually a clear, colorless, viscous liquid is obtained. In the tables, the monomeric ratios are given as one percent by weight of the monomer mixture.

Preparation of the curing mixtures More specific details about the curing mixtures used in the examples are given below in conjunction with the individual examples. In general, however, certain curing mixtures were made by dissolving the polyamine organoborane compound in pohol. using moderate heat as necessary to dissolve the complex. The catalyst (if included) was also added for the formation of the polyurethane. The polyols were first heated under vacuum to a temperature of over 100 ° C to separate the water and then stored on 4A molecular sieves.

Overlap Cut Test Method The examples that were subsequently evaluated to measure the overlap cut resistance of the adhesive bonds were tested as described below. The dimensions in English units are nominal and the conversion to the metric units is approximate. More specifically, the test samples used were similar to those described in ASTM D-1002, except that they were generated using protection panels of nominal dimensions of 2.5 cm X 10 2 cm X 0 3 cm thick (1 inch by 4 inches by 1/8 inch thick) 1.3 cm red lithograph tape was applied. (0 5 inches) \ width to the end of one of the adhered ones in order to fix the joint and also to help make the overlap region of 1 3 cm. (0.5 inches). Short pieces of piano wire measuring 150 microns (0.006 inches) in diameter for examples 1 and 2 and 200 microns (0.008 inches) in diameter for all other examples were used as separators to control the thickness of the line Bonding of adhesive The adhesive composition was made by weighing the monomer mixture prepared previously in a bottle that had the ability to be sealed with a polyethylene cap. Then the previously prepared curing mixture was added, combined with the monomeric mixture using a wooden rod and the jar was sealed with the polyethylene lid. In general, the addition of the curing mixture to the monomer mixture caused the mixture to warm slightly and in some cases to turn yellow. A spot of the mixed adhesive was applied to each adhered and spread to ensure that an area of 2 5 cm. X 1 3 cm (1 inch by 0 5 inches) outside covered at the end of each adhered Two pieces of piano wire were placed in the adhesive on an adhered one and the joint was closed and repaired with the lithograph tape The joint was also made with two binding clips and was allowed to cure at room temperature for 48 hours at which time the fasteners and the tape were removed. Overlap cutting tests were carried out with three types of TEFLON adhered mechanical grade ethylene high density and polypropylene as available Precision Punch and Plastic Co (M neapohs MN) Three adhesive joints were made with each adhered and? >; each adhesive combination For each adhesive the TEFLON was first adhered then the high density polyethylene and then the polypropylene After the curing the joints were tested for faults when using a tensile testing machine The transversal speed was 2 5 mm / min (0 1 inch / minute) and the tests were carried out at room temperature. The overlap shear strengths are an average of the three measurements and are reported in psi (pounds / square inch) to the nearest whole number. were visually inspected after being loaded as to faults to determine the failure mode. The failure of the < Adhered is the most preferred although the cohesive failure of the adhesive composition makes a useful formulation evident. Failure modes are reported in the examples based on a series of coded abbreviations which can be interpreted as follows Abbreviation Failure Mode Good mesh adhesion b One or more stretched joints to cause 1 the yield of the adhered without failure. 1 c Blending mode failure! d Adhesive failure i e Cohesive failure in the adhesive i f adhesive adhesion failure í 9 Incomplete humidification: pudelado del 1 1 adhesive Example 1 Two adhesive compositions according to the invention were prepared by using the formulations shown below in Table 1 In Table 1. As in many of the other tables the information pertaining to the adhesive composition is provided in condensed form. with the ingredients identified by the abbreviations shown in the above list and with the relative amounts of each ingredient that are given in parentheses. Thus the first entry in table 1 describes an adhesive composition in which the monomer mixture comprises 34.80% by weight of methyl methacrylate (MMA). 25.20% by weight of n-butyl acrylate (BA). 10.00% by weight of m-tetramethyl xylene diisocyanate (TMXDI) and 30 00% by weight of poly (methyl meta-plate) (PMMA). The curing mixture comprised 17.50% by weight of triethylborane complex * 1.6-hexanediamine (TEB * HMDA) and 82.50% by weight of DESMOPHEN 1150 pohol. Then the adhesive compositions were tested for overlap and failure mode using the procedure described above and with the results shown below in Table 1 The cohesive failure mode for most joints indicates that adhesion was promoted by the acrylic polymer initiated by organoborane. The compositions of Example 1 are useful in applications where a softer material is desired, for example, a sealant. A useful mix ratio of 10 1 was obtained. The resistance of the overlap cut could be increased by providing a higher amount of polyurethane / polyurea. Table 1 Example 2 A series of adhesive compositions according to the invention were prepared following the procedure described above and having the formulations shown below in table 2. The last entry in table 2 is a comparative example which did not contain any monomer acrylic or organoborane pohamina complex. The ratios are given in percent by weight (% by weight) The resistance to cut to overlap of the adhesive compositions was tested and the failure mode analyzed as described above and with the results shown in table 2. Table 2 Adhesive position Pniebas 1 TEI Polyenneno Polypropylene Me/ .? Me / Ja Resistance Ratio Resistance Mode Resistance Mode \ kxJo 1 monon? Ep «.a Cured Me / cla of the cut of of to the cut of of to the cut of of ! (Relationship »(Relationship) Monomer overlap Fail overlap Fail overlap fault 1 a Me / cla of Kiicm Ka cm2 kg. cured i sii (psi) psi 1 \ t \ l B \ TEB'HMD ?. | n 1 2oX? 2'N »? ae 454 ((> 4 (»? a e 2 (^ 1 * 74) de | TMXDI TONE > 5 PMM \ FOMRE / 1 (> < < < < 2 2 < < "or LL-2X 1 ^ 2"; < »" • »> ('• * < t > so l 2oo » In general, the failure mode was cohesive in the adhesive or the adherent was stretched or failed. However, when the acrylic monomers and the organoborane pohamin complex were separated to provide the comparative example, the cut resistance to overlap fell significantly and the failure mode became adhesive for all substrates Table 2 shows the use of the tpfunctional pohol and the catalysts for the formation of pohurethane Table 2 also shows that commercially useful mixing ratios of 10 1 4 1 and 2 1 can be obtained with the compositions adhesives of the invention indicating that they can be easily filled with commercially available jets for two-part adhesives. Example 3 A series of adhesive compositions according to the invention were prepared following the procedure described above and having the foundations shown in FIG. continued in table 3 The mix? <; monomerica included the bi-reactive compound of hydroxyethylmethacrylate to crosslink the accrete pohmepzado to pohuretano / po urea The ratios of components (which are given in percent by weight) were adjusted in such a way that the stoichiometry of isocyanate groups to the combined amount of groups hydroxyl and amine was equal to 1 1 for each adhesive composition La < »Resistance to overlap cut of the adhesive compositions was tested and failure mode analyzed as described above and with the results shown in Table 3 5X Table 3 Table 3 shows the improved adhesion that can be obtained when the adhesive composition includes a birective compound. Preferably, the birezactive compound is employed in an amount of about 0 to 50% based on the ratio of hydroxyl equivalents to equivalents of polnosocyanate Table 3 also shows that isophorone diisocyanate can be used as the polnsocyanate and that the dibutyltin dilaurate can be used as the polyurethane forming catalyst.

Example 4 Example 4 shows an adhesive composition according to the invention, in which the core-shell polymer BLENDEX B467 was used as a thickening agent instead of poly (methyl methacrylate). The monomer mixture consisted of MMA / DA / TMXDI / BLENDEX B467 in which the relative percentages by weight of the different ingredients was: 52 00 / 11.30 / 6.80 / 30 00 The monomer mixture was prepared by mixing the different ingredients in the mixture. a mixer under high cut conditions until a white, opalescent, thixotropic mass is obtained. The curing mixture (prepared as described in the preparation of the curing mixture) consisted of TEB * HMDA / TONE 0305 / FOMREZ UL-28 in the which the relative percentages by weight of the different ingredients was 32 40/67 60/0 0010. The monomer mixture and the curing mixture were combined in a ratio of 10: 1 and test samples were prepared for the shear strength overlap and were tested as described above and with the results shown below in Table 4 Table 4 Example 5 A series of adhesive compositions according to the invention are prepared, in which the monomer mixtures described in Table 5 below were paired with the corresponding curing mixtures shown below in Table 6. The monomer mixtures and the mixtures of Cured were prepared as described above, although no heating was used. Tables 5 and 6 give the relative amounts of the different ingredients in grams (g). The overlap cut resistance of the adhesive compositions was tested and the failure mode was analyzed as described above and with the results shown below in Table 7 Table 5 The HEMA included 0 07% by weight of DBTDL Table 6 TONE 0305 included 0 047% by weight of DBTDL. N B refers to the ratio of primary amine nitrogen atoms to boron atoms > in the complex As shown below in Table 7, a series of adhesive compositions is prepared, in which a monomer mixture was combined with its corresponding curing agent in a weight ratio of 10 1 When manually weighed and mixed, the adhesive or compositions cured too quickly to be used. The adhesive compositions were then used in conjunction with a 10 1 tubular syringe-type adhesive dispenser that was equipped with a static mixer. The test samples for overlap cutting resistance were prepared as described above but with several exceptions Because the adhesive compositions cure quickly, one strip of adhesive was placed on the end of one adhered and on the other end adhered and the joints were matched and compressed by hand until the wire separators were resisting. additional compression. The joints were made in the following order. TEFLON polyethylene. Polypropylene: TEFLON. polyethylene, polypropylene: TEFLON, polyethylene, polypropylene. After all nine joints were made, they were fixed with fasteners and allowed to cure at room temperature for 48 hours before the tests of overlap cut resistance and joint failure analysis. The test results are shown below in table 7. Table 7 Table 7 shows that the adhesive compositions of the invention can be used in conjunction with a double-tubular syringe-type dispenser for two-part adhesives while providing adhesion to various polymer surfaces of low surface energy. Example 5 further shows how the adhesive compositions of the invention can quickly accumulate resistance. They cure rapidly to a high resistance to overlap cutting. Example 6 A series of adhesive compositions according to the invention was prepared in which the monomer mixtures described in the table 8 were then paired with corresponding curing mixtures as shown below in Table 9. The monomer mixtures and curing mixtures were prepared as described above. In tables 8 and 9 the relative amounts of the different ingredients are given in grams Table 8 Table 9 In curing mixtures C1 to C8. the polyol included 1% by weight of DBTDL. In curing mixtures C9 to C10 the polyol included 1% by weight of Fomrez UL-28. Each complex had a 1: 1 ratio of primary amine nitrogen atoms to boron atoms. As shown below in Table 10, a series of adhesive compositions were prepared in which a monomer mixture was combined with its corresponding curing mixture. at a ratio of 4: 1 by weight. The overlap cut resistance of the adhesive compositions was tested and the failure mode was analyzed as described above and with the results shown in Table 10. Table 10 6 Table 10 shows that different polymeric acrylic monomer polyols and polyurethane forming catalysts can be used in the adhesive compositions of the invention. C5, and C6 curing mixtures show a mixture of liquid and solid polyols which formed a solution Adhesive flexibility can be adjusted by proper selection of polyol and acrylic monomer The combination of the monomeric mixture M1 and the curing mixture C1 had adhesion but was flexible and elastomepca Other combinations also adhere but with more overlapping cut resistance high K? Example 7 A series of adhesive compositions according to the invention were prepared in which the monomer mixtures described in Table 11 below were paired with corresponding curing mixtures? shown in Table 12 below. Monomeck mixtures and curing mixtures were prepared as described above. In Tables 1 and 12 the relative amounts of the different ingredients are given in grams. The amount of the polyamine organoborane supplement was varied or in the adhesive compositions In order to maintain a 1 1 stoichiometry (this is a ratio of isoaanate groups to the combined number of hydroxyl and amine groups) the level of pohol and polnosocyanate was varied. The pohol included 0 05% by weight of DBTDL. of nitrogen atoms from primary amine to boron atoms in the complex was 1 1 Table 11 Table 12 Mc / cla Cure TONE COMPLEX (2) TEB * DVTEK A (2) C l * 92 ooxo C2 i 7 (> 024 <066 <, IS <X2 C <4 I 00 Co < 4X 252 C7 2 ^ X 2 CX I >? 4o2 As shown in Table 13 a series of adhesive compositions were prepared in which a monomer mixture was combined with its corresponding curing mixture in a weight ratio of 101 to show how the variation of the boron content in the adhesive composition affects the overlap cut resistance Overlap cut resistance of (> 7 The adhesive compositions were tested and the failure mode was analyzed as described above and with the results shown in Table 13 Table 13 Table 13 shows that at the boron levels (calculated as the percentage by weight of the portion containing the acrylic group of the adhesive composition plus the thickening agent this is acrylic monomers and pol (methyl methacrylate) less than about O 03% by weight, the adhesion is reduced To approximately 03% by weight of boron, the adhesion to the pohetylene is increased to more than approximately 08% by weight of boron the adhesion to all the substrates improves The curing mixture C8 also shows a solution comprising more than 757% by weight of the pohamin organoborane 6X complex Example 8 A series of adhesive compositions according to the invention were prepared in which the monomer mixtures described in Table 14 below were paired with corresponding curing mixtures shown below in Table 15. The monomer mixtures and the mixtures of cured were prepared as described above In tables 14 and 15 the relative amounts of the different ingredients are given in grams. The amount of the polyamine organoborane complex is varied in the adhesive compositions. In order to maintain a stoichiometry of 1 1 (ie ratio of isocyanate groups to the combined number of hydroxyl and amine groups) the level of polyol and polyisocyanate is varied. The polyol included 1% by weight of DBTDL. The ratio of primary amine nitrogen atoms to boron atoms in the complex was 1: 1. 15 Table 14 Table 15 Curing Mixture i TONE 0305 TEB'DYTEK Complex A (g) (g) C1 7 46 0.040 C2 7 39 0.1 1 C3 7 21 0 29 C4 7 13 0.37 is; 6 76 0.74 C6 | 6 38 1.12 C7 5 98 1.52 C8 5 58 1.92 As shown in Table 16 below, a series of adhesive compositions were prepared in which a monomeca mixture was combined with its corresponding curing mixture in a weight ratio of 4 1 to show as the variation of the Boron content in the Adhesive composition affects the overlap cut resistance The overlap cut resistance of the adhesive compositions was tested and the failure mode was analyzed as described above and with the results shown in Table 16 Adhesive compositions nominally comprise more than 40% polyurethane / polyurea Table 16 Table 16 shows that at the boron levels (calculated as a percentage by weight of the portion containing the acrylic group of the adhesive composition plus thickening agent) less than about 0.03% by weight the adhesion is reduced to about 0.03% by weight. boron weight adhesion to ethylene is increased To more than about 08% by weight of boron adhesion to all substrates is improved At high levels of the complex the overlap cut resistance was lower but adhesion was maintained Example 9 A series of adhesive compositions according to the invention were prepared, in which the monomer mixtures described in Table 17 below were paired with corresponding curing mixtures shown below in Table 18. Monomer mixtures and curing mixtures were prepared as described above In Tables 17 and 18 the relative amounts of the different ingredients are given in grams The amount of the pohamin organoborane complex was varied in the adhesive compositions In order to maintain a stoichiometry of 1 1 (this is the ratio of isocyanate groups to the combined number of hydroxyl and amine groups) the level of polyole and polusocyanate is varied The polyol included 1% by weight of DBTDL The ratio of the primary amine nitrogen atoms to the boron atoms in the complex was 1 1 Table 17 Table 18 As shown below in Table 19, a series of adhesive compositions were prepared, in which a monomer mixture was combined with its corresponding curing mixture at a weight ratio of 2 1 to show as the variation of the boron content in the adhesive composition affects the overlap cut resistance The overlap cut resistance of the adhesive compositions was tested and the failure mode was analyzed as described above and with the results shown in table 19 7" Table 19 Table 19 shows that at the boron levels (calculated as a percentage by weight of the portion containing the acrylic group of the adhesive composition plus thickening agent) less than about 0.03% by weight the adhesion is reduced to about 0.03% by weight. boron weight the adhesion to pohetylene is increased To more than about 08% by weight of boron the adhesion to all substrates improves The predominantly acphcos adhesives are frequently accompanied by a distinctive and pungent odor which makes them unpleasant to use. However, quite desirably adhesive compositions of Example 9 which with the exception of PMMA consisted of about 2/3 pohurethane / po urea and 1/3 acrylated pohmepzado had significantly less odor and still provided adhesion to several polymers of low surface energy Example 9 also becomes evident the ability to adjust the adhesive composition by varying the relative amounts of polyurethane / polyurea and acrylic in the cured composition. The relative amounts that are desirable will be influenced by the planned application, some applications benefit from a greater amount of acrylic. while others will benefit from a greater amount of polyurethane / polyurea However, it is possible to provide compositions having the associated advantages with a polyurethane adhesive (e.g., hardness, abrasion resistance) and still adhering to the polymers of low surface energy, although hard polyurethane adhesives are typically associated with the adhesion of high surface energy substrate In such compositions, the polyurethane / polyurea will comprise more than 50% of the adhesive. More in general.

However, the cured compositions of the invention may comprise from about 1 to 80% polyurethane / polyurea and correspondingly from about 20 to 99% acrylate these percentages may also be derived from the relative amounts of the acrylic monomer and the combined amount of the acrylic monomer. pohisocianato. pohol and pohamine in the com porable composition "Eiempl 10 Example 10 describes the performance of a conventional two-part acrylic adhesive that was modified to also include monomers that polychlorinated polyurethane Part A 14 70 grams of TONE 0305 (with 0 05% in weight of DBTDL) 28 60 grams of HYPALON 30 (chlorosulfonated polyethylene from EI duPont de Nemours and Compapy) 5 53 74 grams of methyl meta-plate 0 85 grams of eumeno hydroperoxide Part A was generated by dissolving the vain ingredients between each other Part B? 22 50 grams of BLENDEX B467 10 00 grams of TMXDI 67 50 grams of methyl meta-plate 4 50 grams of VANAX 808 (from Vanderbilt Chemical Co) 0 0045 grams of copper naphthenate 1 Part B was generated by weighing the ingredients in a container of metal and mixed at room temperature ambient conditions with a high-cut blender powered by nasta air that obtained a translucent coffee thixotropic fluid that has a minimal amount or does not have agglomerates of BLENDEX B467 (less than 5 minutes) or then the two parts of the adhesive were weighed into a container in a ratio of 1 wt.% and test samples were prepared to overlap cut resistance as aesc? t > e previously but with a curing at room temperature of 72 hoi as (this is cured over a weekend) The resistance to 'overlap cut was tested and the failure mode analyzed 5 as described above and with the results shown below in table 20 Table 20 The adhesive cured to a yellowish brown material, relatively hard to give low resistance to the overlap cut and failed adhesively. Example 10 shows a significant loss in performance, especially to substrates pohmepic low surface energy, which occurs when the adhesive composition does not include a polyamine organoborane complex Example 1 1 In example 11 a pair of two-part adhesives (each comprising a 'part A' and a part B) were formulated as follows Part A1 2 50 grams of PMMA 2 53 grams of BA 3 53 grams of MMA 1-44 grams of TEB'DYTEK A polyamine organoborane complex having a ratio of primary amine nitrogen atom to boron atom of 1 1 Part B1 10.00 grams of PMMA 1.25 grams of TMXDII 12 03 grams of BA 16.72 grams of MMA Part A 2 50 grams of PMMA 6 06 grams of MMA 1 44 grams of TEB'DYTEK A polyamine organoborane complex having a ratio of the primary amine nitrogen atom to the 1 1 boron atom Part B2 10 00 grams of PMMA 1 25 grams of TMXDI 14 56 grams of BA 14 19 grams of MMA Part A of each adhesive was prepared by dissolving the acrylic monomers and PMMA with each other and then adding the polyamine organoborane complex The viscosity The initial solution changed shortly after the addition of the complex. Part B was prepared by mixing the components together. Then each "part B" was combined with its "corresponding part A in a weight ratio of 4 1 to provide 0 002 parts of boron per part by weight of the two-part adhesive composition The overlap cut resistance of the two adhesive compositions was then tested immediately after combining the two parts and the failure mode of the joints was analyzed as described above and with the results shown below in table 21 Table 21 The two adhesive compositions could be used to make bonds immediately after the combination of "part A" with its corresponding part B. Changes in the viscosity of the two parts (before mixing together) under ambient conditions were observed visually. two days the viscosity of each "part B" had not changed appreciably after one day. Nevertheless, each "part A" had become extremely viscous After two days "part A1" had become rubberized and part A2 had become a hard solid, indicating that the organoborane pohamin complex whose presence is important to provide adhesion to low energy plastic substrates, it is not compatible in storage with acrylic monomers because it causes them to become hard or rubberized in only a couple of days. Example 12 Two adhesive compoons according to the invention comprising of example 8 a mixture monomer 4 (M4) combined with the curing mixture 4 (C4) and the monomer mixture 5 (M5) combined with the curing mixture 5 (C5) were stored in sealed bottles under ambient conditions for about 3 weeks. There was no visible change in the adhesive compoons at the end of the storage period The overlap cut resistance of the 2 adhesive compoons was tested at the end of the period of storage using the procedure described above and with the results shown below in Table 22 together with the determination of the failure mode For comparison purposes the test results for the corresponding adhesive compoons of Example 8 are shown in parentheses Table 22 | 5 Even after 3 weeks of storage, the resistances to the overlap cut were still very good and the mode of failure was not present. changed significantly. In contrast, the adhesive formulations of Example 11 had become hard or rubbery after only 2 days. Thus the two-part adhesive compositions of the invention can be combined in commercially useful mixing ratios but still have excellent storage stability.

Example 13 Two adhesive compositions were prepared to evaluate the rate of integration of the strength The monomer mixtures described in Table 23 below were paired with corresponding curing mixtures shown below in Table 24 Monomer mixtures and curing mixtures were prepared as described above In tables 23 and 24 the relative amounts of the different ingredients are given in grams Polio! included 1% by weight of DBTDL The ratio of the primary amine nitrogen atoms to the boron atoms in the complex was 1 1 Table 23 j Mc / cla M nomic M MA B V IPDI j HEMA PM MA i I I Ci); < «> I (• >) I I I 97 | S i - i I 92. OOO 7 50 j 1 1 - I 2 I s ls 2"« • • | 5 | | 7 5o 'I Table 24 As shown in Table 25 below, adhesive compositions were prepared in which the monomer mixture M1 was combined with the curing mixture C1 and the monomer mixture M2 was combined with the curing mixture C2 each in a weight ratio of 10.1. Using each adhesive composition, 15 adhesive joints were made with pohetylene adhered and 15 joints were made with polypropylene bonded. At several time intervals after the joints were made, the overlap cut resistance was tested following the procedure described above and with the results shown below in table 25 Table 25 Time (or position Hrv Ml-C 1 M2 + C2 Resistance to < Kcsisicnaa to Resistance to eope Resistance to cutting cope of overlap overlap overlap in overlapped polypropylene over polypropylene to full pulcii kgcm ípsn polictilcno g ^ i ípsu ke í sii kgcm ípsii. o2X «4?" I4? 2? 2X (4? 049 (7) _. 1 X (2o? 1 iili "~ .ll? n" 2 (4o) «1 (441 1 2? L7) 5 (. (XI!) X. "(1 IX) ''! X2 The rate of integration of the strength of the adhesive compositions of the invention may advantageously and surprisingly be accelerated by the presence of a bireactive compound such as hydroxyethylmethacrylate. Vanas modifications and alterations of this invention will become apparent to those skilled in the art without deviating from the scope and spirit of the invention It should be understood that this invention is not limited to the illustrative embodiments summarized herein. It is noted that with respect to this date the best method known by the applicant to carry out said invention is which is clear from the present description of the invention Having described the invention as above is claimed as property contained in the following

Claims (4)

1. 8"

   Claims 1 A composition characterized in that it comprises a complex of amine organoborane and polyol
2. 2 A composition according to claim 1 characterized in that it is a liquid solution at room temperature of the polyamine organoborane complex and the pohol.
3. 3 A composition according to claim 1 characterized in that the pohol has a hydroxyl functionality of 2 to 3

   A composition according to claim 1, characterized in that the po is selected from the group consisting of polyether pot and po po ester | 5 A composition according to claim 4 characterized in that the pohol is po-ol of polyalkylene oxide.

   6 A composition according to claim 4 characterized in that the pohol is selected from the group consisting of poholylene oxide pohol of polypropylene oxide pohol of tetraethylene oxide. Derivatives terminated in ethylene oxide and propylene oxide of these materials by poh-e-caorolactone and combinations of the above X4

   7. A liquid solution at room temperature, characterized in that it comprises: (a) a complex of: (i) an organoborane having the structure:

   wherein R1 is an alkyl group having from 1 to 10 carbon atoms: R: and R3 are independently selected from alkyl groups having from 1 to 10 carbon atoms and phenyl containing groups: and (i?) a po amma selected from the group consisting of alkylpohamma polyoxyalkylenepolyamine and the reaction product of a material finished in amine dippmana and a material having at least two groups reactive with primary amine, wherein the number of primary amine groups in the reaction mixture is greater than the number of groups reactive with primary amine, and (b) a pohol selected from the group consisting of polyethylene oxide polyol. polyol of polypropylene oxide polyol of tetramethylene oxide. Derivatives terminated in ethylene oxide and propylene oxide of these materials poh-e-caprolactone and combinations of the foregoing.

   8 A polymerization initiator system, characterized in that it comprises. (a) a polyamine organoborane complex: (b) a polnsocyanate reactive with the polyamine component of the X5

   complex for releasing the organoborane: and (c) a polyol.

   9. A polymerization initiator system according to claim 8. characterized in that the pohol is selected from the group consisting of polyether polyol and polyester polyol

   10. A polymerization initiator system according to claim 8 characterized in that the polyisocyanate is soluble in acrylic monomer. 11. A polymerization initiator system according to claim 8, characterized in that the number of equivalents of isocyanate functionality is equal to the sum of the number of equivalents of amine functionality plus the number of equivalents of hydroxyl functionality | A system capable of initiating the polymerization of the acrylic monomer and of forming polyurethane / polyurea at room temperature, the system is characterized in that it comprises (a) a solution of the organoborane and amine polamine complex. wherein the polyol is not reactive with the pohamine and (b) a dnsocyanate which is reactive with the polyamine to release the organoborane to initiate the polymerization of the acyclic monomer. wherein the dnsocyanate is soluble in the acrylic monomer and is reactive with the polyamine and the polyol to form the pohurethane / pohurea. A system according to claim 12, characterized in that the pohol is selected from the group consisting of oxide pohol. polyethylene oxide polyethylene oxide, polyethylene oxide polyol, derivatives of ethylene oxide and propylene oxide of these materials poh-e-caprolactone and combinations of the above

   A system according to claim 12, characterized in that the number of equivalents of isocyanate functionality is equal to the sum of the number of equivalents of amine functionality plus the number of equivalents of hydroxyl functionality

   15 A pohmepzable composition. characterized in that it comprises (a) a pohmepzable acrylic monomer (b) a pohamin organoborane complex. (c) a polio! (d) a polyisocyanate and (e) optionally an organic thickening agent

   16. A pohmepzable composition according to claim 15. characterized in that the pohmepzable acrylic monomer is selected from the group consisting of monofunctional acyl ester. monofjncional ester metacplato derivatives substituted of the previous ones and combinations of the previous ones

   17. A water-soluble composition according to claim 15. characterized in that the composition comprises approximately 0.03 to 1.5% by weight of boron based on the weight of the components containing acrylic group and optional organic thickening agent in the polymerizable composition

   A polimepable composition according to claim 17. characterized in that the composition comprises about 0 1 to 0 3% by weight of boron, based on the weight of the components containing acrylic group and an optional thickening agent in the movable composition.

   A polimepable composition according to claim 15, characterized in that the pohamin organoborane complex has the structure

   wherein R 'is an alkyl group having from 1 to 10 carbon atoms. R: and R3 are independently selected from alkyl groups having from 1 to 10 carbon atoms and phenyl containing groups: Am is a pohamine selected from the group consisting of alkyl pohamin pohoxyalkylene amine and the reaction product of a finished material in amine dippmapa and a material having at least two groups reactive with primary amine wherein the number of primary amine groups in the reaction mixture is greater than the number of groups reactive with primary amine and the value of v is selected for provide an effective ratio of primary amine nitrogen atoms and boron atoms in the complex

   20 A pohmepzable composition according to claim 15 characterized in that the po is selected from the group consisting of polio! of po ether and pohol of polyester

   21 A pohmepzable composition according to claim 20, characterized in that the polio! it is polyol of polyalkylene oxide

   22 A pohmepzable composition according to claim 20, characterized in that the pohol is selected from the group consisting of poholylene oxide polyol of polypropylene oxide, pohtetramethylene oxide pohol derivatives terminated in ethylene oxide and propylene oxide of these pohol materials of pol? -e-ca? rolactone and combinations of the above

   A polimerizable composition according to claim 15, characterized in that the polnsocyanate is a dionesocyanate

   24 A polmepable composition according to claim 15, characterized in that the pogomine complex is bovine polyorganol soluble! and the polymer is soluble in the acrylic monomer. A polimepable composition according to claim 24, characterized in that the polnsocyanate is soluble in the acrylic monomer.

   _ •

   A polymerizable composition according to claim 15 characterized in that it further comprises either a compound having a free-radically polymerizable group and an amine-reactive group or a material that reacts with the polnosocyanate to form a compound having a movable group. by free radicals and a reactive group with amine

   A permeable composition according to claim 15, characterized in that it also comprises a hydroxylated (meth) actable

   28 A pohmepzable composition according to claim 15 characterized in that it also comprises a catalyst for the formation of polyurethane

   An adhesive composition that can be applied and cured at room temperature characterized in that it comprises (a) a pozable mixture of an alkyl acrylate monomer and alkyl meta-platelet monomer (b) an optional thickening agent (c) a polyamine organoborane complex which provides about 0.08 to 0.5% by weight of boron based on the weight of the materials containing the acrylate group and organic thickening agent, except that in the adhesive composition the complex has structure 9 (1).

   wherein R 'is an alkyl group having from 1 to 10 carbon atoms, R2 and R3 are independently selected from alkyl groups having from 1 to 10 carbon atoms and groups containing phenyl: Am is a polyamide selected from group consisting of alkyl pohamine. pohoxyalkylene amine and the reaction product of an amine dippmapa-terminated material and a matepal having at least two reactive groups with primary amine, wherein the number of primary amine groups in the reaction mixture is greater than the number of groups reagents with primary amine and the value of v is selected to provide an effective ratio of nitrogen atoms of primary amine and boron atoms in the complex (d) a polio! wherein the organoborane polyamine complex is soluble and which is selected from the group consisting of polyethylene oxide polyo! polypropylene oxide polio! of tetramethylene oxide derivatives terminated in ethylene oxide and propylene oxide of these materials and poh-e-caprolactone and combinations of the foregoing, and (e) an effective amount of a dnsocyanate that reacts with the pohamine to release the organoborane to initiate polymerization of the pohmepzable and reactive mixture with the amine and the polyol to form pohurethane / pohurea A 100% solids curable, two-part adhesive composition characterized in that it comprises (a) a first part comprising a complex of polyamine r organoborane and a pohol. where the po is not reactive with the polyamine. and (b) a second part comprising: (i) a polimepable acrylic monomer. and (i) a polyisocyanate which is soluble in the acrylic monomer wherein the pol- nosocyanate is provided in an amount sufficient to react with the pohamine to release the organoborane to initiate the polymerization of the acrylic monomer and react with the polio! and the polyamine to form polyurethane / pohurea. (iii) a catalyst for the formation of polyurethane: and (iv) optionally either a compound having a free radical polymerizable group and an amine reactive group or a material which reacts with the polnosocyanate to form a compound having a group polimepable by free radicals and an amine reactive group

   31 A curable adhesive composition of two parts at 100% solids, in accordance with claim 30 characterized in that the polio! it is selected from the group consisting of polio! of polyethylene oxide. pohol of polypropylene oxide polyol of pohtetramethylene oxide. Derivatives terminated in ethylene oxide and propylene oxide of these materials, polio! of poly-e-caprolactone and combinations of the above 32 A cured adhesive composition, characterized in that it comprises (a) a pohmepzado acrylic. (b) a polyurethane / po urea independent of the polimeparated acrylic and 5 (c) an organoborane or byproduct of degradation of organoborane

   A cured adhesive composition according to claim 34, characterized in that it also comprises a compound that bonds the acrylic polymeate and the urethane / polyurea

   A cured adhesive composition according to claim 34. characterized in that the polyurethane / po urea has a glass transition temperature greater than the ambient temperature | A bound compound comprising a first substrate and a second substrate characterized in that they are bonded (or bonded) together by a layer of a cured adhesive composition in accordance with claim 34 p 38 A compound bound in accordance with claim 37 characterized in that the first and second substrates are each independently selected from low surface energy polymeric materials

   A bound compound according to claim 38 characterized in that the first and second substrates are each independently selected from the group consisting of polyethylene polyethylene and polytetrafluoroethylene

   A method for improving the storage stability of a two-part pohmepzable adhesive composition comprising an acrylic monomer pohmepzable a organoborane pohamma complex and a material that reacts with the amine to release the organoborane to initiate the polymerization of the acrylic monomer the method is characterized in that or comprises the steps of ta) providing a polyamine organoborane complex. (b) provide a polio! wherein the organoborane po-amine complex is soluble (c) forming a solution of the polyol and the organoborane-amine complex and (d) preparing a two-part pohmepzable adhesive composition in which a part comprises (i) a material which reacts with the polyamine and (n) all the polymerizable acrylic monomer and the other part comprises the solution of the pohol and the pohamin organoborane complex < ? 41. A method for reducing the amount of material that can migrate in the adhesive composition impregnated in a two-part polishable adhesive composition comprising an acrylamide monomer that pohmepzable a pohamin organoboren complex. and a material that reacts with the polymer to react with the organuborbent. In order to initiate the polymerization of the acrylic monomer, the material comprises the reaction product of the pohamine and the material that reacts with the pohamma, the method is characterized in that it comprises the steps of (a) providing a polnsocyanate that is reactive with the polyamine component of the complex (b) providing a pohol that is reactive with the polysocyanate (c) allowing the polyisocyanate to react with the polyamine to release the organoborane (d) start polymerization of the acphco monomer with the liberated organoborane and pohmepzar the acrylic monomer to form acrylic polymer and (e) allow the pohamin polnsocianato and the polyol to react to form polyurethane / independent polyurea but coexisting with the acrylic polymer | A method according to claim 41, characterized in that the number of equivalents of isocyanate functionality is equal to the sum of the number of equivalents of amine functionality plus the number of equivalents of htdroxyl functionality

   SUMMARY OF THE INVENTION A composition comprising a complex of pohamin organoborane and a polyol is described. The composition can form a part of a polymerization initiator system that also includes a polnosocyanate. The system can be used to initiate the polymerization of the acrylic monomer and form a polyurethane / polyurea acrylic adhesive that has an exceptionally good adhesion to low surface energy polymers

   Claims Give Mexico. 1. A composition characterized in that it comprises a complex of polyamine organoborane and polyol, the weight ratio of the polyol to the complex is not greater than about 20: 1.

   2. A composition, characterized in that it comprises a complex of polyamine organoborane and polyol, the polyol is selected from the group consisting of polyether polyol and polyester polyol.

   3. A composition characterized in that it comprises a polyamine organoborane complex and a catalyst for the formation of polyurethane.
4. 4 A polymerization initiator system, characterized in that it comprises: (a) a pohamin organoborane complex; (b) a polnsocyanate reactive with the polyamine component of the complex to release the organoborane, and (b) a polio !.

   3 A system capable of initiating the polymerization of the acrylic monomer and of forming pohurethane / pohurea at room temperature, the system is characterized in that it comprises. (a) a solution of a polyamine organoborane and polio complex, where polio! it is not reactive with polyamine; and (b) a dnsocyanate that is reactive with the polyamine to release the organoborane to initiate the polymerization of the acrylic monomer, wherein the dnesocyanate is soluble in the acrylic monomer and is reactive with the pohamine and the pohol to form the pohurethane / pohurea

   6 A pohmepzable composition characterized in that it comprises (a) a polymerizable acrylic monomer; (b) a polyamine organoborane complex, (c) a polyol, (d) a polnsocyanate; and (e) optionally an organic thickening agent;

   A two-part curable adhesive composition, characterized in that it comprises (a) a first part comprising: (i) a solution of polyamine organoborane complex and polyol, wherein the polio! it is not reactive with pohamin, and (n) a catalyst for the formation of polyurethane; and (b) a second part comprising: (i) a water-soluble acrylic monomer; (n) a polnsocyanate which is soluble in the acrylic monomer, wherein the polyisocyanate is provided in an amount sufficient to react with the pohamine to release the organoborane, to initiate the polymerization of the acrylic monomer and to react the polio! with the polyamine to form a pohurethane / pohurea, and (ni) optionally, either a compound having a free radical free radical group and an amine reactive group or a material that reacts with the polnosocyanate to form a compound having a group po mepzable by free radicals and a group reactive with amine

   8. A composition or system according to any of claims 1, 2, and 4 to 7, characterized in that the pohol is poylene oxide of alkylene oxide.

   A composition or system according to claim 8, characterized in that the pohol is selected from the group consisting of polio! of polyethylene oxide, polypropylene oxide, pohtetramethylene oxide, polyethylene oxide and propylene oxide derivatives of these materials, polyo! of poh-e-caprolactone and combinations of the above

   A composition or system according to any of claims 1 and 4 to 7 characterized in that the polyol is selected from the group consisting of pohter pohol and pohol ester pohol

   11. A composition according to any of the preceding claims, characterized in that the pohamin organoborane complex has the structure

   wherein R1 is an alkyl group having from 1 to 10 carbon atoms; R2 and R3 are independently selected from alkyl groups having from 1 to 10 carbon atoms and groups containing phenyl; Am is a polyamine selected from the group consisting of alkyl polyamine, polyoxyalkylene polyamine and the reaction product of a diprimary amine-terminated material and a material having at least two reactive primary amine groups, wherein the number of primary amine groups in the reaction mixture is greater than the number of groups reactive with primary amine; and the value of v is selected to provide an effective ratio of nitrogen atoms of primary amine and boron atoms in the complex.

   12. A polymerizable composition according to claim 6, characterized in that the polyamine organoborane complex is soluble in the polyol and the polyol is soluble in the acrihco monomer.

   13 A polymerizable composition according to claim 12. characterized in that the polyisocyanate is soluble in the acrylic monomer.

   14. A polymerizable composition according to claim 6, characterized in that it comprises either a compound having a free radical free poWmepzable group and an amine reactive group or a material that reacts with the polyisocyanate to form a compound having a polymerizable group. free radicals and an amine-reactive group.

   15. A polymerizable composition according to claim 6, characterized in that it further comprises a catalyst for the formation of polyurethane.

   16. A two-part curable adhesive composition, according to claim 30, characterized in that the first part and the second part are combined in an integer ratio of 1: 1 to 1: 10.