MXPA06007149A - Accelerated organoborane amine complex initiated polymerizable compositions - Google Patents

Abstract

The invention is a two part polymerizable composition comprising in one part an organoboron compound capable of forming free radical generating species amine complex and in the second part one or more compounds capable of free radical polymerization and a cure accelerator comprising a) at least one compound containing a quinone structure or b) at least one compound containing at least one aromatic ring and one or more, preferably two substituents on the aromatic ring selected from hydroxyl, ether and both, where there are two substituents they are located either ortho or para with respect to one another and a peroxide containing compound. The second part may further contain an agent capable of causing the organoboron compound to form free radical generating species upon contacting the two parts. The first part may further comprises one or more compounds capable of free radical polymerization. This facilitates formulating compositions that have commercially desirable volumetric ratios of the two parts. Adhesive compositions of the present formulation provide excellent adhesion to low surface energy substrates, such as plastics.

Description

IMERIZABLE PO COMPOSITIONS INITIATED WITH ORGANOBORANUM ACCELERATED AMINO COMPLEX BACKGROUND OF THE INVENTION This invention relates to accelerated polymerizable compositions comprising compounds capable of free radical polymerization moieties, organoboron compounds capable of forming free radical generating species capable of initiating free radical polymerization and adhesives based on such compositions. In another embodiment, the invention relates to a method for polymerizing compounds containing portions capable of free radical polymerization and to methods for bonding substrates using such compositions. Low surface energy olefins, such as polyethylene, polypropylene and polytetrafluoroethylene have a variety of attractive properties in a variety of uses, such as toys, automotive parts, furniture applications and the like. Due to the low surface energy of these plastic materials, it is very difficult to find adhesive compositions that bind to these materials. The commercially available adhesives that are used for these plastics require extensive or slow pretreatment of the surface before the adhesive binds to the surface. Such pretreatments include corona treatment, flame treatment, the application of primaries and the like. The requirement of extensive surface pretreatment results in significant limitations for designers of automotive components, toys, furniture and the like. A series of patents issued for Skoultchi, U.S. Patent Nos. 5, 106,928; 5,143,884; 5,286,821; 5,310,835 and 5,376,746 (all incorporated in the present by reference) and for Zharov, et al. U.S. Patent Nos. 5,539,070; 5,690,780; and 5,691, 065 (all incorporated herein by reference), describe polymerizable acrylic compositions, which are particularly useful as adhesives, wherein the orbanoboro amine complexes are used to initiate curing. It is disclosed that these complexes are good for initiating the polymerization of an adhesive that binds to substrates of low surface energy. Pocius in a series of patents, U.S. 5,616,796; US 5,621, 143; US 5,681, 91 0; US 5,686,544; U.S. Patent 5,718,977; and U.S. Patent 5,795,657 (all incorporated herein by reference), describe organoboron amine complexes with a variety of amines used to complex the organoboron, such as polyoxyalkylene polyamines and polyamines, which are the reaction product of diprimary amines and a compound having at least two groups that react with a primary amine. A series of patents by Sonnenschein et al. U.S. Patent Nos. 6,806,330; 6,730,759; 6,706, 831; 6,713,578; 6,713,579 and 6,710, 145, describe organoboron amine compounds, wherein the organoboron is a trialkyl borane and the amine is selected from the group of amines having a structural amidine component; the aliphatic heterocycles having at least one nitrogen in the heterocyclic ring; an alicyclic compound having attached to the ring a substituent having an amine moiety; primary amines, which also have one or more hydrogen-binding acceptance groups, wherein there are at least two carbon atoms, preferably at least three carbon atoms, between the primary amine and the hydrogen-binding acceptance group; e conjugated mines. These patent applications describe polymerizable compositions containing the organoboron amine complexes, one or more of monomers, oligomers or polymers having olefinic unsaturation, which are capable of polymerization by free radical polymerization and which the polymerizable compositions can be used as adhesive compositions. , sealer, coating or ink. Some of the references discussed above describe the use of phenolic compounds, such as hydroquinones, to stabilize the compositions against unwanted polymerization. See Pocius, US Pat. No. 5,684, 102 in column 18, lines 45-53.; Pocius, U.S. Patent 5,861, 910 in column 13, lines 17 to 24. Jennes, U.S. Patent 3,236,823 discloses the use of hydroquinones, phentantiazine or tert-butyl pyrocatechol as stabilizers in acrylate systems initiated with alkyl borane. Many of the compositions described polymerize more slowly than desired for use in industrial processes. This results in processes that exhibit low productivity. Therefore, there is a need for adhesive systems that are capable of bonding to substrates of low surface energy, and initiator systems which facilitate such bonding. Polymeric compositions and adhesive systems are also needed, which are thermally stable at, or close to, ambient temperatures and which will undergo polymerization when the user desires. Adhesive compositions are also needed, which are capable of binding to substrates of low surface energy, and which bind to substrates of low surface energy to other substrates, without the need for extensive or expensive pretreatment. Additional compositions that can be used in existing commercial equipment at mixing ratios of 4: 1 or less are needed. Also desired are compositions that have stability, strength and adhesion at elevated temperatures. In addition, compositions that cure quickly are needed since many industrial processes require fast cycle times.

BRIEF DESCRIPTION OF THE INVENTION The invention is a two-part polymerizable composition, comprising on one hand an organoboron compound capable of forming an amine complex of a free radical generating species and in the second part one or more compounds capable of polymerization of free radicals. free radicals and a curing accelerator comprising a) at least one compound containing a quinone structure, or b) at least one compound containing at least one aromatic ring and one or more, preferably two substituents, on the selected aromatic hydroxyl ring , ether and both. Where there are two substituents, they are located either ortho or para with respect to each other and a compound containing peroxide. The second part may also contain an agent capable of causing the organoboron compound to form a free radical generating species by contacting the two parts. The first part may further comprise one or more compounds capable of free radical polymerization. This makes it easy to formulate compositions having commercially desirable volumetric proportions of the two parts. The adhesive compositions of the present formulation provide excellent adhesion to low surface energy substrates, such as plastics. The invention is also a polymerization method which comprises contacting the components of the polymerizable composition under conditions such that the polymerizable compounds undergo polymerization. In one modality, the contact occurs at or near room temperature. In another embodiment, the additional method comprises the step of heating the polymerized composition to an elevated temperature under conditions such that the organoboron compound forms a free radical generating species. In yet another embodiment, the invention is a method of joining two or more substrates together, which comprises contacting the components of the polymerizable composition together under such conditions, that the polymerization is initiated; contacting the polymerizable composition with the two or more substrates; positioning the two or more substrates, so that the polymerizable composition is located between the two or more substrates; and allowing the polymerizable composition to polymerize and join the two or more substrates together. In still another embodiment, the invention is a method for coating a substrate, which comprises contacting a composition according to the invention with one or more surfaces of a substrate, and initiating the polymerization of the composition according to the invention. In another embodiment, the invention is a laminate comprising two substrates having arranged between the substrates and joined to each substrate, a composition according to the invention. The polymerizable compositions of the invention are stable at, or close to, room temperature, and can be cured upon demand by contacting the two parts of the composition, or alternatively, by contacting the two parts of the composition and subsequently heating the components. compositions above the temperature at which the organoboron compound forms a free radical generating species. Additionally, the polymerizable compositions of the invention can form good bonds to low surface energy substrates without the need for primers or surface treatment. The polymerizable compositions of the invention can be formulated to be dispensed in commercial equipment at volume ratios of the two parts of 4: 1 or less. The polymerized compositions demonstrate excellent cohesive and adhesive strength at elevated temperatures and thus demonstrate excellent stability at high temperatures. The polymerizable compositions of the invention exhibit rapid curing and preferably exhibit an overlap cutting force in accordance with ASTM 03165.81 of 3,515 kg / cm2 (50 psi) or greater 1 hour after application. Preferably, the polymerizable compositions demonstrate excellent adhesion to substrates together with fast curing as discussed.

DETAILED DESCRIPTION OF THE INVENTION The polymerization initiator is an organoboron-containing compound, which is capable of forming a trivalent organoboron compound. In a preferred embodiment, the free radical generating species is a free radical generating species of trivalent organoboron compound. The preferred boron-containing compounds are tetravalent since they have four boron bonds of which three are covalent and one may be covalent or is in the form of an electronic association with a complexing agent. The free radical generating species, such as a trivalent boron compound, is formed when the boron-containing compound is contacted with another substance, referred to herein as a complex uncoupling agent or initiator. The free radical generating species generates free radicals by reacting with ambient oxygen. In the embodiment wherein the boron-containing compound is tetravalent, such contact causes the abstraction of one of the ligands bound to or in complex with the boron atom to convert it to a trivalent borane. The free radical generating species is a compound that contains or generates free radicals under polymerization conditions. The complex uncoupling agent or initiator can be any compound that reacts with the complex uncoupling agent or which abstract a cation from the boron-containing compound. Preferably, the boron-containing compound is an organoborate or an obranoboro amine complex. An organoborate is a salt of a positive cation and an anionic tetravalent boron. Any organoborate, which can be converted to an organoboron by contact with a complex uncoupling agent or initiator can be used. A class of preferred organoborates, (also known as quaternary boron salts), is described in Kenafsey et al. , U.S. 2003/0226472 and Kneafsey et al. , U.S. 2004/0068067, both incorporated herein by reference. The preferred organoborates described in these two US patent applications are described by the following for R > wherein R2 is alkyl; R3 is independently at each occurrence CrC10 alkyl, C3-C10 cycloalkyl, phenyl, C ^ C ^ phenyl-substituted alkyl or C3-C10 phenyl-substituted cycloalkyl, provided that any two of R2 and / or R3 may optionally be part of a carbocyclic ring; and M + is a metal ion or a quaternary ammonium ion. Preferred examples of organoborts include sodium tetraethyl borate, lithium tetraethyl borate, phenyl triethyl borate lithium and phenyl triethyl borate tetramethylammonium. In another embodiment, the organoborate is an internally blocked borate as described in Kendall et al., U.S. Pat. 6,630,555, incorporated herein by reference. Borate internally blocked borates of four coordinates are described in this patent, wherein the boron atom is part of a ring structure which also contains an oxa or thio moiety. The internally blocked heterocyclic borates preferably have the following structure: R ° l? Nlví m + where J is oxygen or sulfur; when J represents oxygen, n is the integer 2, 3, 4 or 5; when J represents sulfur, n is the integer 1, 2, 3, 4 or 5; R4, R5, R6 and R7 are independently substituted or unsubstituted alkyl or alkylene groups containing 1 to 10 carbon atoms, substituted aryl groups having up to 7 to 12 carbon atoms or unsubstituted aryl groups; R5, R6 and R7 can be hydrogen; R4 can be part of a second substituted or unsubstituted cyclic borate; R4 may comprise a spiro ring or a spiro-ether ring; R4 together with R5 can be linked to form a cycloaliphatic ring; or R4 together with R5 may comprise a ring of cyclic ether and M is a positively charged species; with m being a number greater than 0.

The term "internally blocked" with reference to the organoborates described herein means a four-coordinate boron atom that is part of an internal ring structure bridged through two of the four boron coordinates or valences. The internal block includes a single ring or a i-ring structure, where boron is part of structures of a ring or multiple rings. In the embodiment wherein the organoboron compound is in the form of an amine complex, the free radical generating species used in the invention is a trialkyl borane or an alkyl cycloalkyl borane. The organoboro used in the complex is a trialkyl borane or an alkyl cycloalkyl borane. Preferably, such a borane corresponds to the Formula: B- (R1). wherein B represents boron; and R1 is separately in each occurrence a C? _10 alkyl, C3.10 cycloalkyl, or two or more of R1 can be combined to form a cycloaliphatic ring. Preferably R1 is C1-4 alkyl, even more preferably C2-4 alkyl, and most preferably C3.4 alkyl. Among the preferred organoboros are tri-ethyl borane, tri-isopropyl borane and tri-n-butylborane. In the embodiment, wherein the organoboron compound is an organoboron amine complex, the organoboron is a trivalent organoboron and the amine can be any amine that reversibly complexes with the organoboron. Such complexes are represented by the formula B-fR1) 3-Am wherein R1 is described hereinbefore and Am is an amine. The amines used to complex the organoboron compound can be any amine or mixture of amines, which complex with the organoboron and which can be decoupled from the complex when exposed to a decoupling agent. The desirability of using a given amine in an amine / organoboron complex can be calculated from the energy difference between the Lewis Acidobase complex and the sum of energies of isolated Lewis acid (organoboron) and base (amine) known as bonding energy. The more negative the binding energy, the more stable the complex.

Joining energy = - (Complex energy - (Lewis acid energy + Lewis base energy)) Such binding energies can be calculated using theoretical ab-initio methods, such as the Hartree Fock method and the base set 3-21 G. These computational methods are commercially available using computer program and commercial equipment, such as SPARTAN programs and Gaussian 98 with a Silicon Graphics workstation. Amines having amine / organoboron binding energies of 1.0 kilocalories per mole or greater are preferred, amines having a binding energy of 15 kilocalories per mole or greater are more preferred, and even more preferred are amines with a bond of 20 kilocalories per mole or greater. In the embodiment where the polymerization of the compositions of the invention is initiated by the use of a decoupling agent, the binding energy of the amine to the organoboron is preferably about 50 kcal / mole or less and most preferably about 30 kcal / mole or less. In the embodiment where the polymerization of the compositions of the invention is initiated by the use of heat, the binding energy of the amine is preferably about 100 kcal / mole or less, more preferably about 80 kcal / mole or less and most preferably approximately 50 kcal / mol or less. Preferred amines include primary or secondary amines or polyamines containing groups, primary or secondary amine, or ammonia as described in Zharov, US Patent 5,539,070 in column 5, lines 41 to 53, incorporated herein by reference, Skoultchi, US Patent 5, 106,928 in column 2, line 29 to 58, incorporated herein by reference, and Pocius, US patent 5,686,544 in column 7, line 29 to column 10 line 36, incorporated herein by reference; ethanolamine, dialkyl diamines or secondary or polyoxyalkylene polyamines; and amine-terminated reaction products of diamines and compounds having two or more amine-reactive groups as described in Deviny, US Patent 5,883,208 in column 7, line 30 to column 8 line 56, incorporated herein by reference. With respect to the reaction products described in Deviny, the preferred diprimary amines include diprimary alkyl amines, aryl amines diprimary, alkylaryl amines diprimary and polyoxyalkylene diamines; and amine-reactive compounds include compounds containing two or more carboxylic acid moieties, carboxylic acid esters, carboxylic acid halides, aldehydes, epoxides, alcohols and acrylate groups. Preferred amines described in Deviny include n-octylamine, 1,6-diaminohexane (1,6-hexane diamine), diethylamine, dibutyl amine, diethylene triamine, dipropylene diamine, 1,3-propylene diamine (1,3-propane diamine). , 1,2-propylene diamine, 1,2-ethanediamine, 1,5-pentane diamine, 1,12-dodecanediamine, 2-methyl-1,5-pentane diamine, 3-methyl-1,5-pentane diamine, triethylene tetraamine, diethylene triamine. Preferred polyoxyalkylene polyamines include polyethylene oxide diamines, polypropylene oxide diamines, triethylene glycol propylene diamine, polytetramethylene oxide diamine and polyethylene oxide hydroxypropylene oxide diamines. In a preferred embodiment, the amine comprises a compound having a primary amine and one or more groups that accept hydrogen bond, wherein at least two carbon atoms, preferably at least about three, exist between the primary amine and groups that They accept hydrogen bond. Preferably, a portion of alkylene is located between the primary amine and the group accepting hydrogen bond. The group that accepts hydrogen bonding means in the present a functional group that through either the inter- or intramolecular interaction with a hydrogen of the amine complexed with borane, increases the electronic density of the nitrogen of the amine group in complex with the borano. Preferred hydrogen bonding groups include primary amines, secondary amines, tertiary amines, ethers, halogen, polyethers, thioethers and polyamines. Preferred compounds having a primary amine and one or more groups accepting hydrogen bonding are described in Sonnenschein et al. , US Patent Nos. 6,730,759, (column 4, line 60 to column 5, line 67); 6,706,831; 6,713,578; 6,713,579 and 6,710, 145 relevant portions, incorporated herein by reference. In another embodiment, the amine is an aliphatic heterocycle having at least one nitrogen in the heterocycle. The heterocyclic compound may also contain one or more nitrogen, oxygen, sulfur or double bond atoms. In addition, the heterocycle can comprise multiple rings, wherein at least one of the rings has nitrogen in the ring. Preferred aliphatic heterocyclic amines are described in Sonnenschein et al., U.S. Patent Nos. 6,730,759 (column 6, lines 1 to 45); 6,706,831: 6,713,578; 6,71 3,579 and 6,710, 145 relevant portions, incorporated herein by reference. In still another embodiment, the amine which forms complex with the organoboron is an amidine. Any compound with an amidine structure, wherein the amidine has sufficient binding energy as described hereinabove with the organoboron, can be used. Preferred amidine compounds are described in Sonnenschein et al., U.S. Patents 6,730,759, (column 6, line 4 to column 7, line 21); 6,706,831; 6,713,578; 6,713,579 and 6,710, 145 relevant portions, incorporated herein by reference. In still another embodiment, the amine that complexes with the organoboron is a conjugated imine. Any compound with a conjugated imine structure, wherein the imine has sufficient binding energy as described hereinabove with the organoboron, can be used. The conjugated imine can be a linear or branched chain imine or a cyclic imine. Preferred imine compounds are described in Sonnenschein et al. U.S. Patent Nos. 6,730,759 (column 7, line 22 to column 8, line 24), 6,706,831; 6,713,578; 6,713,579 and 6,710, 145 relevant portions, incorporated herein by reference. In another embodiment, the amine may be an alicyclic compound having attached to the alicyclic ring a substituent containing an amine moiety. The alicyclic compound containing amine may have a second substituent containing one or more nitrogen, oxygen, sulfur or double bond atoms. The alicyclic ring may contain one or two double bonds. The alicyclic compound can be a single ring structure or multiple rings. Preferably, the amine in the first substituent is primary or secondary. Preferably, the alicyclic ring is a 5- or 6-membered ring. Preferably, the functional groups in the second substituent are amines, ethers, thioethers or halogens. The preferred alicyclic compound with one or more amines containing substituents Sonnenschein et al. U.S. Patent Nos. 6,730,759 (column 8, line 25 to line 59); 6,706,831; 6,713,578; 6,714,579 and 6.71 0. 145 relevant portions, incorporated herein by reference. In another preferred embodiment, the amine also contains siloxane, which is an amino siloxane. Any compound with both amine and siloxane units, wherein the amine has sufficient binding energy as described hereinbefore with the organoboron, can be used. Preferred amines with siloxane portions are further described in U.S. Patent 6,777,512 and entitled AMINE ORGANOBORANE COMPLEX INITIATED POLYMERIZABLE COMPOSITIONS CONTAINING SILOXANE POLYMERIZABLE COMPONENTS (polymerizable compositions initiated with organoborane amine complex containing polymerizable siloxane components), (column 10, line 14 to column 1 1, line 29), incorporated herein by reference. In the embodiment wherein the organoboron compound is an organoboron amine complex, the equivalent ratio of amine compound (s) to borane compound in the complex is relatively important. An excess of amine is preferred to enhance the stability of the complex and in the embodiment where the complex decoupling agent is an isocyanate functional compound to react with the isocyanate functional compound, thereby resulting in the presence of polyurea in the final product. The presence of polyurea improves the high temperature properties of the composition. Compounds capable of free radical polymerization can be used in the polymerizable compositions of the invention include any monomer, oligomer, polymer or mixtures thereof, which contain olefinic unsaturation, which can be polymerized by free radical polymerization. Such compounds are well known to those skilled in the art. Mottus, US Patent 3,275.61 1, provides a description of such compounds in column 2, line 46 to column 4, line 16, incorporated herein by reference. Preferred classes of compounds containing olefinic unsaturation are Sonnenschein et al. U.S. Patent Nos. 6,730,769 (column 9, line 7 to line 54); 6,706,831; 6,713,578; 6.71 3.579 and 6.71 0. 145 relevant portions, incorporated herein by reference. Examples of preferable acrylates and methacrylates are described in Skoultchi, US Pat. No. 5,268,681 in column 3, lines 50 to column 6, line 12, incorporated herein by reference, and Pocius, US patent 5,681, 910 in column 9. , line 28 to column 12, line 25, incorporated herein by reference. Also úitles in these compositions crosslinking molecules including ethylene glycol dimethacrylate acrylate, ethylene glycol diacrylate, triethylene glycol dimethacrylate, diethylene glycol bismethacryloxy carbonate, polyethylene glycol diacrylate, tetraethylene glycol dimethacrylate, diglycerol diacylate, diethylene glycol dimethacrylate, pentaerythritol triacrylate, trimethylolpropane trimethacrylate, isobornylmethacrylate and tetrahydrofurfuryl methacrylate. In the embodiment where the composition is used as an adhesive, the compounds based on acrylate and / or methacrylate are preferably used as the compounds capable of free radical polymerization. More preferred acrylate and methacrylate compounds include methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate and cyclohexylmethyl methacrylate. The preferred amounts of compounds capable of free radical polymerization are preferably about 10 weight percent or greater, based on the weight of the total formulation, more preferably about 20 weight percent or more and most preferably about 30 weight percent. weight or greater. Preferred amounts of compounds capable of free radical polymerization are preferably about 90 weight percent or less based on the weight of the total formulation, more preferably about 85 weight percent or less and most preferred 80 weight percent or less. The compositions of the invention include two-part polymerizable compositions comprising on one part an organoboron compound and one or more compounds containing one or more ring-opening heterocyclic portions, and in a second part, compounds capable of being polymerized by radical polymerization. Free, a catalyst capable of polymerizing compounds containing heterocyclic ring-opening moieties, a curing accelerator of the invention and optionally a component that will cause the organoboron compound to form a free radical generating species. In a modality, the invention is a two-phase system comprising a first phase containing one or more polymers prepared from the compounds that polymerize by free radical polymerization and a second phase comprising polymerized or partially polymerized compounds derived from one or more compounds containing heterocyclic portions that open ring. In one embodiment, the polymer prepared from the compounds containing heterocyclic ring-opening moieties is immiscible with the polymer prepared by free radical polymerization and thus, the resulting polymerized composition has at least two regions each rich in one of the two polymers formed. In one embodiment, the two-part invention compositions include a polymerized portion comprising polymerized compound capable of free radical polymerization and a second portion comprising unpolymerized or partially polymerized compounds having heterocyclic ring-opening moieties. The two portions can be miscible, partially miscible or immiscible. In a preferred embodiment, the polymerized composition comprises two phases, one based on the compounds that polymerize through olefinic bonds and a second one that polymerizes by a ring-opening reaction of a heterocyclic portion. The cured compositions of the invention preferably contain two regions which in many cases are not miscible. In some embodiments, the two regions are separate phases or are interpenetrating networks of two different polymers. The two regions can chemically bind to each other if the composition includes a crosslinking compound. The compound containing a heterocyclic ring opening portion can be any monomer, oligomer or prepolymer containing a heterocyclic portion capable of ring opening and polymerization. The heteroatom in the heterocyclic portion is preferably nitrogen, oxygen or sulfur, with nitrogen and oxygen being preferred and oxygen being most preferred. Preferably, the heterocyclic portion is a 3-membered ring. Preferred heterocyclic portions are oxirane and aziridine portions, with oxirane portions being more preferred. Preferred heterocyclic ring-opening compounds are described further in Sonnenschein et al. , U.S. Patent 6,762,260 (column 10, line 34 to column 11, line 22), incorporated herein by reference. The presence of the polymer derived from the heterocyclic ring-opening polymerizable compound, such as oxirane and aziridine, improves the adhesion to plastics of higher surface energy, such as nylon, and also the thermal properties of the polymerized or partially polymerized compositions of the invention. . A sufficient amount of the heterocyclic ring opening compound is used to improve bonding to larger surface energy substrates and to improve the high temperature properties of the polymerized or partially polymerized composition. The thermal properties are referred to herein at glass transition temperatures greater than the polymerized compositions and improved cohesive strength at elevated temperatures, as evidenced by higher overlap cutting forces at elevated temperature, such as 125 and 150 ° C. A significant improvement of glass transition temperature is 5 ° C. A significant improvement in the overlap cutting force is approximately 3.515 kg / cm2 (50 psi) or greater at 125 ° C. The total polymerizable formulation may contain about 2 percent by weight of heterocyclic polymerizable compound or greater; more preferably about 5 weight percent or more and more preferred about 10 weight percent or more. The polymerizable formulation may contain about 50 weight percent or less, more preferably about 45 weight percent less and most preferably about 40 weight percent or less of heterocyclic polymerizable compound. In some cases, it may be useful to crosslink the free radical polymerizable compound phase to the phase derived from polymerizable compound that opens the heterocyclic ring as described in Sonnenschein et al, U.S. Patent 6,762,260 (column 11, line 53 to column 1, line 1 1), incorporated herein by reference. The amount of crosslinker used is that amount which gives the desired properties, that is, sufficient overlap cutting force at 125 ° C or above, and still does not cause the adhesive force at room temperature to go below the desired value. Preferred amounts of crosslinker are about 0 percent by weight or greater based on the weight of the polymerizable formulation, more preferably about 1 percent by weight or greater; even more preferably about 3 weight percent or more and most preferably about 5 weight percent or more. Preferably, the amount of crosslinker used is about 20 weight percent of the total or less polymerizable formulation; even more preferably about 15 weight percent or less and most preferably about 12 weight percent or less. It is preferable that the polymerizable compound that opens the heterocyclic ring polymerizes at a rate similar to the polymerization rate of the compounds containing portions capable of free radical polymerization. If the reaction of a polymerizable component is too slow, the composition may vitrify before obtaining the acceptable monomer to polymer conversion of both phases. Unreacted components can act as a plasticizer and degrade properties, such as adhesion, thermal performance and the like. The properties of the final polymerized composition can be enhanced by post-heating the polymerized composition to prevent the termination of the polymerization of the heterocyclic polymerizable compounds. This is accomplished by heating the polymerized composition to a temperature above the glass transition temperature of the polymerized polymer (s) incompletely. In this embodiment, post-curing is preferred at the expected use temperature of the structure, more preferred at 5 ° C above the expected use temperature of the composition and it is more preferred to provide a thermal post-cure of 10 °. C above the expected use temperature of the polymerized composition. Examples of post-curing process are described in Briggs (U.S. Patent 4,426,243) and Ersun-Hallsby, et al. (U.S. Patent 5,204,386), incorporated herein by reference. A preferred embodiment of the ring-opening polymerization of heterocyclic compounds is described in Sonnenschein et al. , U.S. Patent 6,762,260 (column 12, line 24 to line 65), incorporated herein by reference. The organoboron compounds useful for polymerization of the compounds having portions capable of free radical polymerization, can be converted to compounds capable of forming free radical generating species by the application of a complex uncoupling agent that will cause the formation of compounds capable of forming species. generating free radicals, such as a trivalent borane compound, such as when displacing the borane amine. The formation of compounds capable of forming the free radical generating species such as, trivalent borane. The displacement of the alkyl borane amine can occur with any chemical for which the exchange energy is favorable, such mineral acids, organic acids, Lewis acids, isocyanates, acid chlorides, sulfonyl chlorides, aldehydes and the like. Preferred complex decoupling agents are acids and isocyanates. In those embodiments, where the initiator for the ring-opening polymerization is a Lewis acid, the dog decoupling agent can be omitted since the Lewis acids can also function as the complex decoupling agent. If the Lewis acid is used as the polymerization initiator and complex uncoupling agent that opens the heterocyclic ring, additional amounts over those amounts necessary to initiate the polymerization are not necessary. The choice of initiator can be impacted through the use of the polymerizable composition. In particular, where the polymerizable composition is an adhesive and the material to which it will be bound is polypropylene, the preferred class of initiators is isocyanate initiators and where the substrate is nylon the preferred initiators are acids. The polymerization can also be thermally initiated. The temperature at which the composition is heated to initiate the polymerization is dictated by the binding energy of the complex. In general, the temperature used to initiate the polymerization upon decoupling the complex is about 30 ° C or greater and preferably about 50 ° C or higher. Preferably, the temperature at which the thermally initiated polymerization is initiated is about 120 ° C or less and more preferably about 100 ° C or less. Any heat source that heats the composition to the desired temperature can be used, provided that the heat source does not negatively impact the components of the composition or its function. In this manner, the composition can be contacted with the substrates either before or after the composition is exposed to heat. If the composition is heated before contact with the substrates, the composition should be contacted with the substrates before the composition has polymerized to the point at which the composition is no longer capable of adhering to the substrates. It may be necessary in the thermally initiated reaction to control the oxygen content, so that there is adequate oxygen to create favorable conditions for radical formation, but not so much as to inhibit polymerization. In one embodiment, the invention of the polymerizable compositions may further comprise one or more compounds, oligomers or prepolymers having a siloxane skeleton and reactive portions capable of polymerization, a catalyst for the polymerization of the one or more compounds, oligomers or prepolymers having a siloxane skeleton and reactive portions capable of polymerization as described in US Pat. No. 6,777,512, entitled AMINE ORGANOBORANE COMPLEX INITIATED POLYMERIZABLE COMPOSITIONS CONTAINING SILOXANE POLYMERIZABLE COMPONENTS (polymerizable compositions initiated with organoborane amine complex containing polymerizable siloxane components), ( column 12, line 66 to column 15, line 54), incorporated herein by reference. The compositions of the invention may also contain a stabilizing amount of a dihydrocarbyl hydroxyl amine. Stabilize, as used herein, refers to preventing polymerization until it is desired. In general, this means that the polymerization is inhibited under normal storage conditions. Normal storage conditions mean storage at a temperature from about 0 ° C to about 40 ° C, where the adhesive is stored in a sealed container. A stable composition is one that does not experience unwanted viscosity increase over a defined period. The increase in viscosity is evidence of polymerization of the monomers present. In a preferred embodiment, a composition is stable if the viscosity does not increase more than 150 percent over a period of 30 days when stored at temperatures of 40 ° C or less, more preferably 100 percent or less over a period of 30 days and most preferably 50 percent or less over a period of 30 days. The dihydrocarbyl hydroxyl amines useful herein include any such compound, which when included in the compositions of this invention; improve the stability of the compositions as described herein. The preferred dihydrocarbyl amines correspond to the formula (R 1) 2 N-OH wherein R 1 1 is independently in each occurrence a hydrocarbyl portion. Preferably, R 3 is independently at each occurrence a C2.30 alkyl, alkaryl or aryl moiety; more preferably a C? 0-2 or alkyl, alkaryl or aryl portion; the C10-alkyl portions being still more preferred. Among the preferred dihydrocarbyl hydroxyl amines is the hydroxylamine free base of BASF, hydroxylamine derivatives of Mitsui Chemicals America, Inc. and Irgastab FS Products of Ciba Specialty Chemical, containing oxidized tallow alkyl hydrogenate, also described as bis (N-dodecyl) N-hydroxyl amine. The dihydrocarbyl hydroxyl amines are used in sufficient amounts to stabilize the compositions of the invention. Preferably, the dihydrocarbyl hydroxyl amines are used in an amount of about 1 part per million of the compositions of the invention or greater, more preferably about 2 parts per million or greater and most preferably about 5 parts per million or greater. Preferably, the dihydrocarbyl hydroxyl amines are used in an amount of about 1,000,000 parts per million of the compositions of the invention or less, more preferably about 50,000 parts per million or less, even more preferably about 10,000 parts per million or less and very much preferably about 3,000 parts per million or less. The compositions of the invention further comprise an accelerator for curing the polymerizable compositions. Accelerators comprise at least one compound containing a quinone structure or at least one compound containing at least one aromatic ring and one or more preferably two substituents, on the aromatic ring selected from hydroxyl, ether and both when two substituents are used and they are located either ortho or para with respect to each other. In one embodiment, the accelerator is any compound that contains a quinone structure, said compound accelerates the curing of the polymerizable compositions. For adhesive compositions, the preferred quinones also facilitate the adhesion of the polymerizable compositions to the substrate surfaces. The preferred quinone compounds contain the following structure: The preferred classes of quinone compounds are substituted or unsubstituted quinone, naphthaquinone or anthraquinones. The substituent can be any substituent that does not interfere with the formation of free radicals or the reaction of free radicals with other compounds. The preferred quinone-containing compounds correspond to one of the formulas containing compound corresponding to one of the structures: wherein R8 is separately in each occurrence any substituent that does not prevent the formation of free radicals or reaction of free radicals with other compounds; and d is separately in each occurrence an integer from 0 to 4. The preferred quinone-containing compounds are quinone compounds. The quinone compounds correspond preferably to the formula: Preferably, R8 is separately in each occurrence R9, OR9 or SR9, wherein R9 is separately in each occurrence substituted or unsubstituted hydrocarbyl; more preferably alkyl, aryl, substituted or unsubstituted aralkyl, still more preferably C? .80 C6.6 alkyl or substituted or unsubstituted aryl, C6- or aralkyl and most preferably C1-10 alkyl and C6-? 4 aryl. Preferably d is 0 to 2, even more preferably 0 to 1, and most preferably 0. Among the preferred quinone structure-containing compounds are benzoquinone and ortho, meta, or substituted benzoquinine, and ortho and quinone. Preferably R8 is R9 or OR9. The most preferred quinones include anthraquinone, benzoquinone, 2-phenylbenzoquinone, orthoquinone and substituted benzoquinone. The most preferred quinone-containing compounds include benzoquinone. The amount of quinone used is that amount which accelerates the curing of the compositions and does not inhibit the adhesion of the composition to the substrate surface. If too little is used, there is no significant increase in curing speed. If too much is used, the composition will not adhere to a substrate surface. Preferably, the quinone is used in an amount of about 0.01 weight percent of the polymerizable composition or greater, more preferably about 0.02 weight percent or greater, and most preferably about 0.04 weight percent or greater. Preferably, the quinone is in an amount of about 0.1 percent by weight of the polymerizable composition or less, more preferably about 0.8 percent by weight or less, and most preferably about 0.4 percent by weight or less. In another embodiment, the accelerator comprises at least one compound containing at least one harmonic ring and at least one, preferably two substituents in the selected hydroxyl ring, ether or both, wherein the substituents are located either ortho or para with respect to each other, hereinafter a compound containing a substituted aromatic ring and a compound having a peroxy portion. The substituted aromatic compound may contain any aromatic portion, including those with multiple ring structures. The compounds preferably contain two or more functional groups selected from hydroxy and ether. Preferably, the substituted aromatic compounds contain at least one hydroxy and another hydroxy or ether portion. More preferably, the substituted aromatic compound contains at least one hydroxy and at least one portion of ether. Preferably, the substituted compounds contain aromatic ring structures of benzene, anthracene or naphthalene. The substituted aromatic compounds can be substituted with any substituent, which does not interfere with the formation of free radicals or the reaction of free radicals with other compounds. Preferred substituents include alkyl, aryl or aralkyl groups, and heteroatom containing groups selected from the group comprising oxygen and sulfur. More preferred substituents include aryl groups and heteroatom containing groups. Preferably, the substituted aromatic compounds correspond to one of the formulas wherein R10 is separately in each occurrence hydrogen or any substituent which does not prevent the formation of free radicals or reaction of free radicals with other compounds; and R8 and d are as previously defined. Preferably, R10 is separately in each occurrence substituted or unsubstituted hydrocarbyl; more preferably substituted or unsubstituted alkyl, aryl, or aralkyl; even more preferably C1-10o C6-alkyl or substituted or unsubstituted aryl, or C6-9o aralkyl and most preferably C1-20 alkyl, e is 0 or 1, preferably 1. More preferably, the substituted aromatic containing compounds correspond to The formulas: wherein R8, R10, d and e are described above. Among the most preferred substituted aromatic ring-containing compounds are anthrahydroquinones, naphthahydroquinones, methyl ether of hydroquinone and alkyl ethers of hydroquinone. The amount of the substituted aromatic ring-containing compound used is that amount which accelerates the curing of the compositions, and which does not inhibit the adhesion of the composition to the substrate surface. If very little is used, there is no significant increase in curing speed. If too much is used, the composition will not adhere to a substrate surface. Preferably, the substituted aromatic ring containing compound is used in an amount of about 0.1 weight percent of the polymerizable composition or greater, more preferably about 1 weight percent or greater, and most preferably about 2 weight percent or more . Preferably, the substituted aromatic ring-containing compound is used in an amount of about 4 weight percent of the polymerizable composition or less, more preferably about 3 weight percent or less, and most preferably about 2.5 weight percent or less . In conjunction with the substituted aromatic ring containing compound, a peroxy containing compound is used. Any peroxy containing compound that reacts with the substituted aromatic ring-containing compound to form free radicals can be used. Preferred peroxy-containing compounds include dialkyl peroxides, diaryl peroxides, diacyl peroxides, alkyl hydroperoxides, aryl hydroperoxides and aryl hydroperoxides. More preferred peroxy-containing compounds include t-butyl peroxides, benzoyl peroxide, t-butyl perbenzoate. More preferred peroxy-containing compounds include benzoyl peroxide and t-butyl perbenzoate. The amount of peroxy-containing compound used is that amount which accelerates the curing of the compositions. If very little is used, there is no significant increase in curing speed. If too much is used, the adhesive does not bind to the polyolefins. Preferably, the peroxy containing compound is used in an amount of about 0.1 percent by weight of the polymerizable composition or greater, more preferably about 1 percent by weight or greater, and most preferably about 2 percent by weight or more. Preferably, the peroxy-containing compound is used in an amount of about 4 weight percent or less of the polymerizable composition, more preferably about 3 weight percent or less, and most preferably about 2.5 weight percent or less. Preferably, the relative amount of compound containing peroxy to substituted aromatic ring containing compound is selected so that the majority of the resulting free radicals generated by the peroxy compound are reacted with the substituted aromatic ring compound. In this way, a molar ratio of peroxy containing compound to aromatic ring compound is one or less. If the proportion is too high, then no adhesion to polyolefins would be observed. If the ratio is very low, then the curing speed of the adhesive is not increased. Preferably, the amount of compound proportion containing peroxy to compound containing substituted aromatic ring is about 1: 4 or greater, and most preferably about 2: 3 or greater. Preferably, the proportion amount of compound containing peroxy to compound containing substituted aromatic ring is about 1: 1 or less.

Preferably, the accelerator is located in the part that does not contain the organoboron compound. Frequently, the part containing the organoboron compound is referred to as the hardening side, and the other part is referred to as the resin side because the larger part of the polymerizable compound is found in this part. The hydrocarbyl as used herein means any portion that has both carbon and hydrogen atoms and includes saturated and unsaturated, branched and unbranched hydrocarbon chains. Alkyl refers to branched and unbranched saturated hydrocarbon chains. "Alkenyl" refers to branched and unbranched unsaturated hydrocarbon chains. Aryl means a portion of aromatic hydrocarbon. Alkaryl means a portion of aromatic hydrocarbon with a bonded linear or branched hydrocarbon chain. Aralkyl means a straight or branched hydrocarbon chain with a linked aryl group. Acyl means a portion of hydrocarbyl and carbonyl. Unless otherwise noted, these portions may be substituted with any other substituent, which does not significantly interfere with the function of the compound to which the portion is bound or bound. The two-part polymerizable compositions or adhesive compositions of the invention are suitable only for use with commercially available, conventional dispensing equipment, for two-part compositions. Once the two parts have been combined, the composition should be used quickly, since the useful container life (opening time) may be short depending on the monomer mixture, the amount of the complex, the amount of catalyst and the amount of catalyst. temperature at which the union is made. The adhesive compositions of the invention are applied to one or both substrates and then the substrates are preferably bonded with pressure to force the excess composition out of the bond line. In general, the joints should be made shortly after the composition has been applied, preferably within about 10 minutes. The typical bond line thickness is approximately 0.1 3 mm (0.005 in) to approximately 0.76 mm (0.03 in). The bond line may be thicker if the aperture filler is necessary since the composition of the invention can function as both an adhesive and an aperture filler. The bonding process can be easily performed at room temperature and to improve the degree of bonding it is desirable to keep the temperature below 40 ° C, preferably below about 30 ° C and most preferably below 25 ° C. The compositions may additionally comprise a variety of optional additives. A particularly useful additive is a thickener, such as polymethyl methacrylate of medium to high molecular weight (about 1,000 to about 1,000,000), which can be incorporated in an amount of about 10 to about 60 percent by weight, based on in the total weight of the composition. The thickeners can be used to increase the viscosity of the composition to facilitate the application of the composition. Another particularly useful additive is an elastomeric material. The materials can improve the fracture toughness of compositions made with it, which can be beneficial when, for example, rigid, high-performance strength materials are attached, such as metal substrates that do not mechanically absorb energy as easily as other materials. , such as flexible polymer substrates. Such additives can be incorporated in an amount of about 5 percent to about 35 percent by weight, based on the total weight of the composition. Useful elastomeric modifiers include chlorinated or chlorosulfonated polyethylenes, such as HYPALON 30 (commercially available from E.l. Dupont de Nemours &; Co., Wilmington, Delaware) and styrene block copolymers and conjugated dienes (commercially available from Dexco Polymers under the trademark VECTOR, and Firestone under the trademark STEREON). Also useful, and even more preferred, are certain graft copolymer resins such as particles comprising rubber or rubber-like cores or networks that are surrounded by relatively hard shells, these materials often being referred to as "core-shell" polymers. . Most preferred are the acrylonitrile-butadiene-styrene graft copolymers available from Rohm and Haas. In addition to improving the fracture hardness of the composition, the core-shell polymers can also impart enhanced spreading and flow properties to the uncured composition. These enhanced properties can be manifested by a reduced tendency for the composition to leave an undesirable "chord" on the dispensing from a syringe-type applicator, or sag or depression after having been applied to a vertical surface. The use of more than about 20 percent of a core-shell polymer additive is desirable to achieve improved sink-depression resistance. In general, the amount of hardener polymer used is that amount which gives the desired hardness to the polymer or the prepared adhesive. In some embodiments, where a heterocyclic ring opening compound is present and is an oxirane, it may be desirable to include some compound containing aziridine in the formulation since aziridine enhances the stability of the formulation. In general, sufficient aziridine is added to improve the stability of the formulation. Preferably, about 1 weight percent or more of aziridine based on the weight of the formulation is used and more preferably about 2 weight percent or greater. Preferably, about 10 weight percent or less of aziridine is used based on the weight of formulation being used and more preferably about 7 weight percent or less. The polymerizable compositions according to the invention can be used in a wide variety of forms, including as adhesives, coatings, primers, to modify the surface of polymers and injection molding resins. They can also be used as matrix resins in conjunction with metal and glass fiber mats, such as in resin transfer molding operations. They can be used additionally as encapsulants and packaging compounds, such as in the manufacture of electrical components, printed circuit boards and the like. Quite desirably, they provide polymerizable adhesive compositions that can bind a wide range of substrates, including polymers, wood, ceramics, concrete, glass and metals with primary ones. Another desirable related application is its use to promote the adhesion of paints to low surface energy substrates, such as polyethylene, polypropylene, polyethylene terephthalate, polyamides and polytetrafluoroethylene and their co-polymers. In this embodiment, the composition is coated on the surface of the substrate to modify the surface to enhance the adhesion of the final coating to the surface of the substrate. The compositions of the invention can be used for coating applications. In such applications, the composition may further comprise a carrier, such as a solvent. The coating may contain additives well known to those skilled in the art for use in coatings, such as pigments for coloring the coating, inhibitors and UV stabilizers. The compositions may also be applied as powder coatings and may contain additives well known to those skilled in the art for use in powder coatings. The compositions of the invention can also be used to modify the surface of a polymer molded part, extruded film or contoured object. The compositions of the invention can also be used to change the functionality of a polymer particle by grafting polymer chains on the unmodified plastic substrate. The polymerizable compositions of the invention are especially useful for adhesively bonding low surface energy polymeric or plastic substrates that have historically been very difficult to bond without using complicated surface preparation techniques, primer application, etc. By "low surface energy substrates" is meant materials having a surface energy of about 45 mJ / m2 or less, more preferably about 40 mJ / m2 or less, and most preferably about 35 mJ / m2 or less. Included among such materials are polyethylene, polypropylene, acrylonitrile-butadiene-styrene, polyamides, syndiotactic polystyrene, block co-polymers containing olefin, and fluorinated polymers, such as polytetrafluoroethylene (TEFLON), which has a surface energy of less than approximately 20 mJ / m2. (The expression "surface energy" is often used synonymously with "critical wetting tension" by others.) Other polymers of somewhat higher surface energy that can be usefully linked with the compositions of the invention include polycarbonate, polymethyl methacrylate and polyvinylchloride.

The polymerizable compositions of the invention can be easily used as two-part adhesives. The components of the polymerizable compositions are mixed as they normally would when working with such materials. The complex decoupler agent for the organoboron compound is usually included with the polymerizable, olefinic component, in order to separate it from the organoboron compound, thus providing a part of the two part composition. The organoboron compounds of the polymerization initiator system provides the second part of the composition and is added to the first part shortly before it is desired to use the composition. Similarly, the Lewis acid catalyst where it is used for the polymerization of heterocyclic ring opening compound is kept separate from the heterocyclic ring opening compound. The Lewis acid catalyst can be added to the first part directly or can be pre-dissolved in a suitable carrier, such as a reactive olefinic monomer, i.e., methyl methacrylate or a viscous solution of MMA / PMMA. For a two-part adhesive, such as those of the invention to be more easily used in commercial and industrial environments, the volume ratio at which the two parts are combined should be a convenient whole number. This facilitates the application of the adhesive with commercially available, conventional dispensers. Such dispensers are shown in U.S. Patent Nos. 4,538,920 and 5,082, 147 (hereby incorporated by reference) and are available from Conprotec, Inc. (Salem, New Jersey) under the trademark MIXPAC. Typically, these dispensers use a portion of tubular receptacles disposed side by side with each tube being intended 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 hand-operated ratchet mechanism) to evacuate the contents of the tubes in a hollow, common elongated mixing chamber, which may also contain a static mixer to facilitate the mixing 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 fresh tubes and the application process can be continued. The proportion at which the two parts of the adhesive are combined is controlled by the diameter of the tubes. (Each plunger is sized to be received within a fixed diameter tube, and the plungers are advanced towards the tubes at the same speed.) A simple dispenser is often intended for use with a variety of different two-part adhesives and plungers they are sized to deliver the two parts of the adhesive to a convenient mixing ratio. Some common mixing ratios are 1: 1, 2: 1, 4: 1 and 10: 1, but preferably less than about 10: 1, and more preferably less than about 4: 1. Preferably, the two-part mixed compositions of the invention have a suitable viscosity to allow application without dripping. Preferably, the viscosities of the two individual components should be made of the same order or magnitude. Preferably, the mixed compositions have the viscosity of about 100 (0.0 Pa.s centipoise or greater, more preferably about 1,000 (1.0 Pa.s) centipoise or greater and most preferably about 5,000 (5.0 Pa.s. ) centipoise or greater. Preferably, the adhesive compositions have a viscosity of about 150,000 (150 Pa.s) centipoise or less, more preferably about 100,000 (100 Pa.s) centipoise or less, and most preferably about 50,000 (50 Pa.s) centipoise or less ).

Specific Modalities The following examples are included for illustrative purposes only and are not intended to limit the scope of the claims. Unless otherwise stated, all parts and percentages are by weight.

Ingredients The following ingredients were used in the examples provided hereinafter; methyl methacrylate available from Rohm and Haas; poly (methylmethacrylate) of 350,000 molecular weight available from Aldrich; poii (methylmethacrylate) of molecular weight of 996,000 available from Aldrich; smoked silica available from Cabot Corporation under the trademark and designation Cab-o-sRR TS-720; acrylic acid available from Sigma Aldrich; Chlorosulfonated polyethylene Hypalon R 20 available from Dupont-Dow Elastomers; Scotchlite ™ VS5500 glass bubbles available from 3M; Hydroquinone methyl ether available from Sigma aldrich (MEHQ); t-butyl peroxybenzoate available from Aztec Peroxides Inc.; methacrylic acid available from Sigma Aldrich; Benzoquinone available from Aldrich; and tr-n-butyl borane and methoxypropyl amine complex. The two-part formulations were prepared by mixing the ingredients for each part and then placing them in separate containers. Several different formulations of part A (resin side) were made.

Process for preparing resin side containing benzoquinone as accelerator The following ingredients were added to a metal can of 3.79 liters (1 gallon) and rotated in a ball roller mill for 24 to 72 hours. The ingredients are 150 grams of methyl methacrylate, 45 grams of polymethyl methacrylate (350,000 mw), 9 grams of polymethyl methacrylate (996,000 mw) and 15 grams of chlorosulfonated polyethylene. 146 grams of the mixed ingredients were added to a 236 ml (8 oz.) Plastic cup to which were added 33.99 grams or methyl methacrylate and 0.024 grams of methyl ether of hydroquinone. The ingredients were thoroughly mixed by hand using a tongue ablaze for 3 minutes. Four grams of glass bubbles and 4 grams of smoked silica are added and the ingredients are completely mixed by hand using a tongue-swath for 3 minutes. Twenty-four grams of acrylic acid are added and the ingredients are completely mixed by hand using a chilling knife and tongue for 3 minutes. Up to 0.096 grams of benzoquinone are added and the ingredients are thoroughly mixed by hand using a tongue swath for 3 minutes. The resulting mixture is packed in a 236 ml (8 oz.) Plastic cup.

Process for preparing resin side containing methyl ether of hydroquinone The following ingredients are added to a metal can of 3.79 liters (1 gallon) and rotated in a ball roller mill for 24 to 72 hours. The ingredients are 150 grams of methyl methacrylate, 45 grams of polymethyl methacrylate (350,000 mw), 9 grams of polymethyl methacrylate (996,000 mw) and 15 grams of chlorosulfonated polyethylene. 146 grams of the mixed ingredients are added to a 236 ml (8 oz.) Plastic cup, to which are added 33.99 grams of methyl methacrylate and 4 grams of methyl ether of hydroquinone. The ingredients are completely mixed by hand using a tongue-twister for 3 minutes. Four grams of glass bubbles and 4 grams of fumed silica are added and the ingredients are completely mixed by hand using a tongue-swath for 3 minutes. Twenty-eight grams of acrylic acid are added and the ingredients are completely mixed by hand using a tongue-polisher for 3 minutes. Four grams of t-butyl peroxybenzoate are added and the ingredients are completely mixed by hand using a tongue-swath for 3 minutes. The resulting mixture is packed in a 236 ml (8 oz.) Plastic cup.

Part B Hardener Part B (hardener side) comprised 15 percent of a tri-n-butyl borane-methoxy propyl amine complex, 8.0 percent of Jeffamine T403 amine-terminated polyether polyol, 54 or one hundred methyl methacrylate, percent poly (methyl methacrylate), 7 percent poly (methyl methacrylate) polyacrylate copolymer and a stabilizer as listed below. Several Part A formulations were prepared using the procedures described above. The formulations are described below in Table 1. Table 1 The adhesives as described above were tested from an overlap cutting force in accordance with ASTM D3165-91 on the substrates listed below at various times of the application as listed below. The covered and overlapping surface area was 2.54 cm (1 in) wide by 1.27 cm (1/2 in) long. The bond thickness of 0.76 mm (30 mil) was maintained using 0.76 mm (30 mil) of glass beads. Samples were pulled on an Instron 5500 at a rate of 1 .27 cm (0.5 in) per minute until failure and strain at failure was recorded in pounds per square inch. The results are compiled in Table 2 below. The surfaces of the substrates were not pretreated. The samples were cured and tested at room temperature (approximately 23 ° C). The polypropylene substrate was 30 percent polypropylene filled with glass. In relation to failure mode: cohesive failure means that the break occurred in the adhesive; adhesive failure means that the adhesive separated from the substrate; and substrate means that the substrate broke.

Table 2 Table 2 (continued) Table 2 (continued) Table 2 (continued) Table 2 (continued) The examples illustrate that the use of oxidized bis (hydrogenated tallow) alkyl amines enhances the stability of other types of stabilizers. This situation is true whether they are used in a mixture or alone.

Claims (10)

1 . A two-part polymerizable composition comprising, in one part, an organoboron compound capable of forming ibres radical generating species and in the second part, one or more compounds capable of free radical polymerization and a curing accelerator comprising a) minus one compound containing a quinone structure, or b) at least one compound containing at least one aromatic ring and one or more substituents on the selected aromatic ring of hydroxyl, ether and both and a compound with a peroxide moiety.

2. A two-part composition according to claim 1, wherein the second part further contains a complex uncoupling agent capable of decoupling the organoboron compound compound by contacting the two parts.

3. The composition of claim 1 or 2, wherein the aromatic compound has two or more hydroxyl substituents, ether or both, wherein the substituents are located ortho or for each other.

4. The composition according to any of claims 1 to 3, wherein the organoboron compound is an organoborate or an organoborane amine complex.

5. A two-part composition according to any of claims 1 to 4, wherein the peroxide-containing compound is selected from the group of peroxides and hydroperoxides.

6. A two-part composition according to claims 1 to 5, wherein the accelerator is an aromatic compound with one or more hydroxyl substituents, ether or both and is present in an amount from about 0.1 percent to about 4 percent. 100 weight percent of the two part composition and the peroxide is present in an amount of about 0.5 percent to about 8 weight percent based on the weight of the two part composition. A two-part composition according to any of claims 1 to 5, wherein the accelerator is a quinna-containing compound and is present in an amount from about 0.1 percent to about 4.0 percent by weight of the part composition. of resin. A polymerization method comprising contacting the components of the polymerizable composition of any of claims 1 to 7 under conditions such that the one or more compounds capable of free radical polymerization undergo polymerization. The method of claim 8, which further comprises the step of heating the composition to an elevated temperature under conditions such that the organoboron amine complex dissociates. A method for joining two or more substrates together, which comprises: contacting the components of the composition of any one of claims 1 to 7 together under conditions such that polymerization is initiated; contacting the adhesive composition with the two or more substrates; positioning the two or more substrates so that the adhesive composition is located between the two or more substrates, where they are in contact with one another; and allowing the adhesive to cure in order to join the two or more substrates together. eleven . A method for modifying the surface of a low surface energy polymer by contacting a composition according to any one of claims 1 to 7, with at least a portion of the polymer surface of low surface energy and causing the complex of organoboro amine is dissociated, thereby initiating the polymerization of the monomer, oligomers, polymers or mixture thereof, such that the polymer formed is on the surface of the low surface energy polymer. 12. A method for coating a substrate, which comprises contacting the components of the composition of any of claims 1 to 7; contacting the contacted composition with one or more surfaces of a substrate; and allowing the coating composition to cure. 13. A coating composition, which comprises the composition of any of claims 1 to

7. 14. A laminate comprising at least two substrates having disposed between the substrates and attached to each substrate, a composition according to any of the claims 1 to 7.