INITIATOR SYSTEM AND ADHESIVE COMPOSITION MADE THEREWITH

Abstract: Systems for initiating the polymerization of acrylic monomers comprising (1) organoborane amine complexes and (2) decomplexers comprising at least one anhydride group. Adhesive compositions prepared from the initiator systems advantageously exhibit low levels of mobile constituents, excellent solvent resistance, and good adhesion to low energy surfaces.

Description: INITIATOR SYSTEM AND ADHESIVE COMPOSITION MADE THEREWITH Field ofthe Invention This invention relates generally to systems capable of initiating the polymerization of acrylic monomers. More specifically, the invention relates to those initiator systems comprising (1) organoborane amine complexes and (2) decomplexers comprising at least one anhydride group. The invention further relates to the use of these systems for initiating the polymerization of acrylic monomers, as well as acrylic adhesive compositions made therewith. Adhesive compositions having low levels of mobile constituents, excellent solvent resistance, and good adhesion to low energy surfaces are advantageously provided. Description ofthe Related Art Systems for initiating the polymerization of acrylic monomers to make adhesive compositions are known in the art. U.S. Patent Nos. 5,106,928, 5,286,821, and 5,310,835, for example, disclose a two part initiator system that is reportedly useful in acrylic adhesive compositions. The first part of this two part system includes a stable organoborane amine complex and the second part includes an activator. The activator liberates the organoborane compound by removing the amine group, thereby allowing the organoborane compound to initiate the polymerization process. Activators are also sometimes referred to as liberators or decomplexers. The organoborane compound ofthe complex has the general formula: where R, R and R 2 are either alkyl groups having 1 to 10 carbon atoms or phenyl groups. Useful amine compounds for the complex include n-octylamine, 1,6- diaminohexane, diethylamine, dibutylamine, diethylenetriamine, dipropylenediamine, ammonia, 1,3-propylenediamine, and 1,2-propylenediamine. U.S. Patent No. 5,286,821 reports that suitable activators for liberating the organoborane compound include aldehydes having the general structure: wherein R is alkyl of 1 to 10 carbon atoms or aryl having 6 to 10 carbon atoms and x is 1 to 2. Examples include benzaldehyde, o-, m-, p-nitrobenzaldehyde, 2,4- dichlorobenzaldehyde, p-tolylaldehyde, and 3-methoxy-4 hydroxybenzaldehyde. U.S. Patents 5,310,835 and 5,106,928 reports that suitable activators also include organic acids having the structure: R— COOH wherein R is H, alkyl, or alkenyl having 1 to 8 carbon atoms. Examples include acrylic acid, methacrylic acid, benzoic acid, and p-methoxybenzoic acid. Fujisawa, Imai, and Mashuhara also describe a system for initiating the polymerization of methyl methacrylate. See Reports ofthe Institute for Medical and Dental Engineering. 3, 64 (1969). The system comprises a trialkylborane amine complex and an activator such as the chloride of methacrylic or n-butane sulfonic acid, terephtalic acid chloride, benzoyl chloride, p-toluene sulfonic acid chloride, benzene sulfonic acid chloride, methane sulfonic acid chloride, toluene diisocyanate, adipic acid chloride, o-tolyl isocyanate, acetyl chloride, and anhydrous acetic acid. The initiator system is reportedly useful in providing fast curing resins for dental applications. Activators (sometimes also referred to as decomplexers) liberate the organoborane compound by bonding (either covalently or ionicaily) to the amine to form an activator-amine constituent. Most activator-amine constituents remain in the adhesive composition as a mobile constituent that is not incorporated into the polymerized adhesive per se. In general, mobile constituents in adhesive compositions may cause performance problems when, for example, they migrate to the surface ofthe adhesive thereby disrupting the bond interface. Mobile constituents are also susceptible to attack by solvents, thereby making the adhesive composition less suitable for applications where exposure to solvents is unavoidable. A need exists for initiator systems which provide acrylic adhesive compositions having reduced levels of mobile constituents and improved solvent resistance. Such adhesives are less susceptible to performance problems due to migration of mobile constituents to the bond interface and can also be used in various manufacturing applications where adhesives are exposed to organic vapors, oils, fuels, and other solvents such as methylethylketone, tetrahydrofuran, and the like. SUMMARY OF THE INVENTION This invention provides systems capable of initiating the polymerization of acrylic monomers. More specifically, the invention provides initiator systems comprising (1) an organoborane amine complex and (2) a decomplexer comprising at least one anhydride group. The term "decomplexer" means a compound capable of liberating the organoborane compound, thereby allowing the organoborane to initiate the polymerization process. Decomplexers are also sometimes referred to as "activators" or "liberators." As used herein, each of these terms has the same meaning. In the present invention, the anhydride group ofthe decomplexer is capable of forming a covalent bond with the amine portion ofthe organoborane amine complex to liberate the organoborane compound. The decomplexer ofthe invention comprises at least one anhydride group. Preferably, the anhydride has one ofthe following structures: or Each ofthe Ri and R 2 groups may independently be an aliphatic group (i.e., a straight- or branched-chain arrangement of carbon atoms falling into one of three subgroups, namely, alkane, alkene and alkyne groups); a cycloaliphatic group (i.e., a non-aromatic cyclic hydrocarbon structure); or an aromatic group (i.e., a cyclic hydrocarbon structure that is fully unsaturated). Of these three, aliphatic and aromatic groups are preferred. Preferred aliphatic groups comprise 1 to 17 carbon atoms, more preferably 2 to 9 carbon atoms. Preferred aromatic groups include benzene and benzene substituted with aliphatic groups comprising 1 to 4 carbon atoms. R 3 is a divalent organic radical that completes a cyclic structure with the anhydride group to form, for example, a 5 or 6 member ring. The term "divalent organic radical" means an organic moiety wherein the available valencies are on carbon atoms. R3 may be substituted with aliphatic, cycloaliphatic or aromatic groups, preferably aliphatic groups comprising 1 to 12, more preferably 1 to 4, carbon atoms. R3 may also contain a heteroatom such as oxygen or nitrogen with the proviso that the heteroatom is not adjacent to the anhydride functionality. R 3 may also be part of a fused ring structure. The fused ring structure may be cycloaliphatic or aromatic. The term "aromatic" in reference to a fused ring structure means that at least one carbonyl group is attached to an aromatic group. The term "cycloaliphatic" is intended to include all other non-aromatic fused ring structures. The fused ring may further be substituted with aliphatic groups, preferably those groups having 1 to 4 carbon atoms, most preferably 1 carbon atom. The organoborane amine complex ofthe system ofthe invention comprises an amine portion and an organoborane portion. The amine portion ofthe complex may comprise one or more amine groups. The anhydride group ofthe decomplexer reacts with the amine portion ofthe organoborane amine complex to form a decomplexer-amine reaction product. The organoborane is thereby liberated whereupon it is capable of initiating polymerization of the acrylic monomer(s). Preferably, the decomplexer comprises at least one free radically polymerizable group that is capable of forming a covalent bond with acrylic monomer. In this case, the decomplexer-amine reaction product is capable of forming covalent bonds with acrylic monomer(s) and can be incoφorated into the polymerized adhesive per se. This results in a reduced level of mobile constituents (i.e., those materials capable of migrating or diffusing through the cured adhesive). Even more preferably, the decomplexer reacts with the amine portion ofthe organoborane amine complex to form a decomplexer-amine reaction product comprising more than one free radically polymerizable group. In this case, the decomplexer not only provides a reduced level of mobile constituents, but also provides polymerized adhesive compositions having good solvent resistance. As stated previously, the system ofthe invention can be used to initiate the polymerization of acrylic monomer(s). Consequently, the invention also relates to a polymerizable acrylic composition that comprises at least one acrylic monomer, an effective amount of an organoborane amine complex, and an effective amount ofthe decomplexer ofthe invention for liberating the organoborane to initiate polymerization ofthe at least one acrylic monomer. A wide variety of acrylic monomers may be used, for example, monofunctional acrylate ester, monofunctional methacrylate ester, substituted derivatives ofthe foregoing, and blends ofthe foregoing. Acrylic compositions ofthe invention are uniquely useful in providing adhesives, and adhesive compositions ofthe invention advantageously provide reduced levels of mobile constituents, excellent solvent resistance, and adhesion to low surface energy plastics such as polyethylene and polytetrafluroethylene. The term "low energy surface" means those materials having a surface energy of less than 45 mJ/m 2 , more typically less than about 35-40 mJ/m 2. In another aspect, the invention relates to a method of initiating the polymerization of an acrylic monomer, the method comprising the steps of providing at least one acrylic monomer, blending the at least one acrylic monomer with the components ofthe polymerization initiator system according to the invention, and initiating polymerization ofthe at least one acrylic monomer. As indicated above, a decomplexer-amine reaction product is formed when the decomplexer is combined with the organoborane amine complex. When the decomplexer-amine reaction product comprises at least one free radically polymerizable group capable of forming a covalent bond with acrylic monomer, polymerized acrylic compositions having a reduced level of mobile constituents are advantageously provided. Furthermore, when the decomplexer-amine reaction product comprises more than one free radically polymerizable group, this method may be used to prepare a polymerized adhesive composition having improved solvent resistance. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Decomplexer The decomplexer ofthe invention comprises at least one anhydride group. Preferably, the anhydride has one ofthe following structures: or Each ofthe Ri and R 2 groups may independently be an aliphatic group (i.e., a straight- or branched-chain arrangement of carbon atoms falling into one of three subgroups, namely, alkane, alkene and alkyne groups); a cycloaliphatic group (i.e., a non-aromatic cyclic hydrocarbon structure); or an aromatic group (i.e., a cyclic hydrocarbon structure that is fully unsaturated). Of these three, aliphatic and aromatic groups are preferred. Preferred aliphatic groups comprise 1 to 17 carbon atoms, more preferably 2 to 9 carbon atoms. Preferred aromatic groups include benzene and benzene substituted with aliphatic groups comprising 1 to 4 carbon atoms. R 3 is a divalent organic radical that completes a cyclic structure with the anhydride group. The term "divalent organic radical" means an organic moiety wherein the available valencies are on carbon atoms. The cyclic structure may comprise, for example, a 5 or 6 member ring. R 3 may be substituted with aliphatic, cycloaliphatic or aromatic groups, preferably aliphatic groups comprising 1 to 12, more preferably 1 to 4, carbon atoms. R 3 may also contain a heteroatom such as oxygen or nitrogen. R 3 may also be part of a fused ring structure. The fused ring structure may be cycloaliphatic or aromatic. The term "aromatic" in reference to a fused ring structure means that at least one carbonyl group is attached to an aromatic group. The term "cycloaliphatic" is intended to include all other non- aromatic fused ring structures. The fused ring may further be substituted with aliphatic groups, preferably those groups having 1 to 4 carbon atoms, most preferably 1 carbon atom. Examples of useful anhydrides include propionic anhydride, methacrylic anhydride, crotonic anhydride, butyric anhydride, isobutyric anhydride, valeric anhydride, trimethylacetic anhydride, hexanoic anhydride, heptanoic anhydride, decanoic anhydride, lauric anhydride, stearic anhydride, oleic anhydride, benzoic anhydride, succinic anhydride, methylsuccinic anhydride, isobutenylsuccinic anhydride, 2,2-dimethylsuccinic anhydride, itaconic anhydride, maleic anhydride, citraconic anhydride, 2,3-dimethylmaleic anhydride, 2-octen-l-ylsuccinic anhydride, 2-dodecen-l-ylsuccinic anhydride, glutaric anhydride, 3-methylglutaric anhydride, 3,3-dimethylglutaric anhydride, 3-ethyl-3-methylglutaric anhydride, 2-phenylglutaric anhydride, diglycolic anhydride, ethylenediaminetetraacetic dianhydride, and poly(styrene-co-maleic anhydride), cyclohexanedicarboxylic anhydride, cis- 1,2,3, 6- tetrahydrophthalic anhydride, hexahydro-4-methylphthalic anhydride, cis-5- norbornene-endo-2, 3 -dicarboxylic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, exo-3,6-epoxy-l,2,3,6-tetrahydrophthalic anhydride, 3,3- tetramethyleneglutaric anhydride, phthalic anhydride, 4-methylphthalic anhydride, 1,8-naphthalic anhydride, diphenic anhydride, and homophthalic anhydride. These materials are commercially available from a variety of sources. Further examples of useful anhydrides include the partial adducts of active hydrogen compounds (such as hydroxyl, amine and thiol compounds) with polyanhydrides (i.e., compounds having at least two anhydride groups such as ethylenediaminetetraacetic dianhydride and poly(styrene-co-maleic anhydride)). The term "partial adduct" means that the resulting adduct retains at least one anhydride group after reaction with the active hydrogen containing compound. Examples of hydroxyl compounds useful for preparing the partial adducts include aliphatic alcohols such as methanol, ethanol, propanol, and butanol; higher alkane alcohols such as hexanol and octanol; ether alcohols such as 2-methoxyethanol, 2- (2-propoxy)ethanol, 2-butoxyethanol, and 2-ethoxyethanol; and alicyclic alcohols such as cyclohexylmethanol. Other hydroxyl compounds which may be used include those having the following structure: R-i O r II CH 2 =C— C-X-Rs— OH wherein R 4 is hydrogen, methyl, ethyl or chlorine; R 5 is an alkyl group preferably having 2 to 16 carbon atoms; and X is oxygen or R wherein B- 6 is hydrogen or an alkyl group preferably having 1 to 4 carbon atoms. More preferably, R is hydrogen or methyl, R 5 is an alkyl group having 2 to 4 carbon atoms, and X is oxygen. Still other active hydrogen containing compounds useful for preparing the partial adducts ofthe invention include the adducts ofthe above-mentioned hydroxylated (meth)acrylates with lactones. The adducts, hydroxyacrylate polyesters, may be represented by the following structure: wherein R 4 , R 5 and X are defined above, R 7 is an alkyl group preferably having 2 to 11 carbon atoms, and m is an integer greater than or equal to 1. More preferably, R- t is hydrogen or methyl, R 5 is an alkyl group having 2 to 4 carbon atoms, X is oxygen, R 7 is an alkyl group having 3 to 5 carbon atoms, and m is an integer from 1 to 4. Examples of amine compounds useful for preparing the partial adducts include aliphatic primary amines such as ethylamine, butylamine, hexylamine, and allylamine; aliphatic secondary amines such as diethylamine, dihexylamine, and N- methylbutylamine; aromatic primary amines such as aniline, the ortho-, meta- or para-toluidines, and xylylamines; and aromatic secondary amines such as n-alkyl anilines and toluidines. Examples of thiols include butanethiol; dodecyl mercaptan; esters of 3 -mercaptopropionic acid such as isooctyl 3-mercaptopropionate; and esters of thioglycolic acid such as 2-ethylhexyl thioglycolate. The partial adducts are typically prepared by first dissolving the polyanhydride in a solvent that is non-reactive with the polyanhydride and that provides a pourable medium for the subsequent dissolution of co- reactants. Examples of suitable solvents include butyl acetate, toluene, xylene, tetrahydrofuran, ethylene glycol dimethyl ether and the like. Preferably, the solvent is free radically polymerizable with acrylic monomer so that once the partial adduct is made, the solution of partial adduct in solvent can be used to prepare adhesives without the need for solvent removal. Examples of solvents which are free radically polymerizable with acrylic monomer include the esters of acrylic or methacrylic acid such as butyl methacrylate, ethoxyethyl methacrylate, benzyl methacrylate, and tetrahydrofurfuryl methacrylate. After the polyanhydride is dissolved in a solvent, a free radical inhibitor (for example, a phenolic compound such as hydroquinone monomethylether or butylated hydroxytoluene) is typically added at a level of 300-600 parts by weight per million parts by weight partial adduct. After the addition ofthe free radical inhibitor, the active hydrogen containing compound is added. A molar excess ofthe anhydride groups is necessary to achieve anhydride functionality in the resulting partial adduct. Once the active hydrogen containing compound is added, the mixture is then typically heated for a length of time (for example, 80°C to 110°C for several hours) When the reaction is complete, the mixture is cooled. If a free radically polymerizable solvent was used to carry out the reaction, the solution (with solvent) may be used to prepare adhesive compositions. Otherwise, the solvent is typically removed using various evaporation methods known in the art. Preferably, the decomplexer comprises at least one free radically polymerizable group that is capable of forming a covalent bond with acrylic monomer(s). In this case, the decomplexer-amine reaction product is capable of forming a covalent bond with acrylic monomer(s) and can be incoφorated into the polymerized adhesive per se. This results in a reduced level of mobile constituents (i.e., those materials capable of migrating or diffusing through the cured adhesive). Examples of polymerizable groups that may be present in the decomplexer ofthe invention include monosubstituted alkene groups, 1,1 -disubstituted alkene groups, and 1,2-disubstituted alkene groups which are part of an α,β-unsaturated carbonyl structure. Examples of anhydrides that comprise such groups include itaconic anhydride, maleic anhydride, isobutenyl succinic anhydride, and methacrylic anhydride. Even more preferably, the decomplexer reacts with the amine portion ofthe organoborane amine complex to form a decomplexer-amine reaction product comprising more than one free radically polymerizable group. In this case, the decomplexer not only provides a reduced level of mobile constituents, but also provides polymerized adhesive compositions having good solvent resistance. For example, the reaction of itaconic anhydride, maleic anhydride, isobutenyl succinic anhydride, or methacrylic anhydride with an organoborane amine complex comprising more than one amine group provides a decomplexer-amine reaction product comprising more than one free radically polymerizable group. Organoborane Amine Complex In general, complexes ofthe invention are complexes of organoborane and amine. Such complexes may be represented by the structure: Rg is an alkyl group having 1 to 10 carbon atoms. R and Rio are independently selected from alkyl groups having 1 to 10 carbon atoms and phenyl-containing groups. Preferably, Re, R and Rio are independently selected alkyl groups having 1 to 5 carbon atoms. Most preferably, they are the same. The value of v is selected so as to provide an effective ratio of primary or secondary amine nitrogen atoms to boron atoms in the complex. The ratio of primary or secondary amine nitrogen atoms to boron atoms in the complex should broadly be about 0.5: 1 to 4: 1. The amine, Am, may comprise a variety of structures, for example, any primary or secondary amine, polyamine containing a primary or secondary amine, or ammonia. When solvent resistance in the ultimate polymerized acrylic composition is desired, Am preferably comprises a polyamine. For example, Am may represented by the structure: where Rn and R 1 2 are hydrogen, alkyl of 1 to 10 carbon atoms, hydroxyethyl or where R 13 and R 14 are hydrogen or alkyl of 1 to 10 carbon atoms, m is greater than 2, and n is 1 to 6. The alkyl groups in these formulae may comprise straight or branched chains. Illustrative compounds include n-octylamine, 1 ,6-diaminohexane, diethylamine, dibutylamine, dipropylenediamine, diethylenetriamine, ammonia, 1,3- propylenediamine, and 1 ,2-propylenediamine. Alternatively, Am may be a polyoxyalkylenepolyamine having a structure such as H 2 NR 15 O-<R, 6 OV-{R, 7 O) X — (R 16 O) ^ι 5 NH 2 (I) or [H 2 NR, 5 O— (Rι 6 O)w]r-Λi8 (H). R 1 5, Ri 6 and R 17 are preferably alkylene groups having 1 to 10 carbon atoms which may be the same or different. More preferably, R 15 is an alkyl group having 2 to 4 carbon atoms, Rj 6 is an alkyl group of 2 or 3 carbon atoms, and Rn is an alkyl group of 2 or 3 carbon atoms. Rjg is a residue of a polyol used to prepare the polyoxyalkylenepolyamine (i.e., the organic structure that remains when the hydroxyl groups are removed). Ru may be branched or linear, saturated or unsaturated, and substituted or unsubstituted. The value of w is > 1 (more preferably about 1 to 150, and most preferably about 1 to 20). The value of x and y are > 0. The value of z is > 2 (more preferably 3 or 4). Examples of useful polyoxyalkylenepo-yamines include polyethyleneoxidediamine, polypropyleneoxidediamine, diethyleneglycolpropylenediamine, triethyleneglycolpropylenediamine, polytetramethyleneoxidediamine, and polyethyleneoxide-co- polypropyleneoxidediamine. Examples of useful commercially available polyoxyalkylenepo-yamines include various JEFF AMINES from Huntsman Chemical Company such as the D, ED, EDR, and T series diamines (e.g., D-400, D-2000, D-5000, ED-600, ED-900, ED-2001, EDR- 148 and T403), as well as DCA-221 from Dixie Chemical Company. Alternatively, the amine, Am, may comprise the reaction product of one or more diprimary amine-terminated materials (i.e., the two terminal groups are primary amine) and one or more materials containing at least two groups reactive with the primary amine (the latter may be referred to as a "difunctional primary amine-reactive" material). In this case, Am may be represented by the structure: E— <L- ) q — L— E (III) in which each E group is the residue ofthe diprimary amine-terminated material and each L is a linking group that is the residue ofthe material having at least two groups reactive with primary amine. The term "residue" means those portions of the diprimary amine-terminated material and the difunctional primary amine-reactive material that remain after reaction to form the polyamine adduct. The integral value of q is ≥ 0 (more preferably, it is from 0 to 5, and most preferably it is 0 or 1). Useful diprimary amine-terminated materials (E) include alkyl diprimary amines, aryl diprimary amines, alkaryl diprimary amines, polyoxyalkylenediamines such as those represented by structure I described above, and mixtures thereof. A particularly preferred material for E is an aliphatic oxyalkylene diamine sold as DCA-221 from Dixie Chemical Company. Suitable candidates for the material having at least two groups reactive with primary amine (L) may be represented by the general structure W-R-Z, wherein W and Z are moieties independently selected from the group consisting of carboxylic acid, carboxylic acid halide, ester, aldehyde, epoxide, amino alcohol, and acrylic, and R is a divalent organic radical. Most preferably W and Z are the same. A particularly preferred material for L is hexanedioldiacrylate. Initiator Svstem The initiator systems ofthe invention are especially useful in polymerizing acrylic monomers, particularly for making polymerizable acrylic adhesives. The organoborane amine complex is employed in an effective amount, which is an amount large enough to permit polymerization to readily occur to obtain a polymer (preferably, an acrylic polymer) ofhigh enough molecular weight for the desired end use. If the amount of organoborane amine complex is too low, then the polymerization may be incomplete or, in the case of adhesives, the resulting composition may have poor adhesion. On the other hand, if the amount of organoborane amine complex is too high, then the polymerization may proceed too rapidly to allow for effective mixing and use ofthe resulting composition. Large amounts of complex could also lead to the generation of large volumes of borane, which, in the case of an adhesive, could weaken the bondline. The useful rate of polymerization will depend in part on the method of applying the composition to a substrate. Thus, a faster rate of polymerization may be accommodated by using a high speed automated industrial adhesive applicator rather than by applying the composition with a hand applicator or by manually mixing the composition. Within these parameters, an effective amount ofthe organoborane amine complex is an amount that preferably provides about 0.03 to 1.5 weight % boron, based on the total weight ofthe adhesive composition, more preferably about 0.06 to 0.60 weight % boron. The weight % of boron in a composition is equal to the following: (weight of complex (weight % of boron in the composition . X in the complex^ (Total weight of composition) The organoborane decomplexer liberates organoborane by reacting with the amine, thereby removing the organoborane from chemical attachment with the amine. The decomplexer is employed in an effective amount; that is, an amount effective to promote polymerization by liberating organoborane from the complex but without materially adversely affecting the properties ofthe ultimate polymerized composition. Larger amounts of decomplexer may permit the polymerization to proceed too quickly and, in the case of adhesives, the resulting materials may demonstrate inadequate adhesion to low energy surfaces. If small amounts of decomplexer are employed, the rate of polymerization may be too slow and the monomers that are being polymerized may not adequately increase in molecular weight. However, a reduced amount of decomplexer may be helpful in slowing the rate of polymerization if it is otherwise too fast. Within these parameters, the decomplexer is typically provided in an amount such that the ratio of anhydride groups to amine groups is in the range of 0.5: 1.0 to 1.0: 1.0. The number of amine groups includes both primary and secondary amine groups if the amine is a polyamine. Compositions The initiator systems ofthe invention are useful in providing polymerizable acrylic monomer compositions. "Acrylic monomers" are polymerizable monomers having one or more acrylic or substituted acrylic moieties, chemical groups or functionality; that is, groups having the general structure wherein R 19 and R 2 o are hydrogen or organic radicals, and X is oxygen or NR 21 where R 2 ι is hydrogen or an alkyl group preferably having 1 to 4 carbon atoms. Where R 19 and R 2 o are organic radicals, they may be the same or they may be different. Blends of acrylic monomers may also be used. The polymerizable acrylic monomer may be monofunctional, polyfunctional or a combination thereof. The most useful monomers are monofunctional acrylate and methacrylate esters or amides and substituted derivatives thereof such as cyano, chloro, and silane derivatives as well as blends of substituted- and unsubstituted monofunctional acrylate and methacrylate esters and amides. Particularly preferred monomers include lower molecular weight methacrylate esters and amides such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, methoxy ethyl methacrylate, cyclohexyl methacrylate, tetrahydrofurfuryl methacrylate, N,N-dimethyl methacrylamide and blends thereof. Acrylate esters and amides and higher molecular weight methacrylate esters and amides are less preferred for use alone, but can be especially usefully employed as modifying monomers with predominating amounts of lower molecular weight methacrylate esters and amides so as to, for example, enhance the softness or flexibility ofthe ultimate composition. Examples of such acrylate esters and amides and higher molecular weight methacrylate esters and amides include methyl acrylate, ethyl acrylate, isobomyl methacrylate, butyl acrylate, n-octyl acrylate, 2- ethylhexyl acrylate, 2-ethylhexyl methacrylate, decylmethacrylate, dodecyl methacrylate, tert-butyl methacrylate, acrylamide, N-methyl acrylamide, diacetone acrylamide, N-tert-butyl acrylamide, N-tert-octyl acrylamide, N-decyl methacrylamide, gamma-methacryloxypropyl trimethoxysilane, 2-cyanoethyl acrylate, 3-cyanopropyl acrylate, tetrahydrofurfuryl chloroacrylate, glycidyl acrylate, glycidyl methacrylate, and the like. Dimethylaminoethyl acrylate and dimethylaminoethyl methacrylate may also be used as modifying agents although additional organoborane liberator may be required due to the extra amine groups Particularly preferred are blends of any ofthe lower molecular weight alkyl methacrylate esters described above with alkyl acrylates having 4 to 10 carbon atoms in the alkyl group, such as blends of methyl methacrylate and butylacrylate. Polymerizable compositions of this type may broadly comprise, based on the total weight ofthe composition, about 2 to 50 wt. % ofthe alkyl acrylate and, correspondingly, about 50 to 98 wt. % ofthe alkyl methacrylate. Other useful monomers that can be used include di- or higher functional (meth)acιylates (for example, hexanedioldiacrylate, ethylene glycol dimethacrylate, ethylene glycol diacrylate, triethylene glycol dimethacrylate, polyethylene glycol diacrylate, tetraethylene glycol di(meth)acrylate, glycerol diacrylate, diethylene glycol dimethacrylate, pentaerythritol triacrylate, trimethylolpropane trimethacrylate, as well as other polyether diacrylates and dimethacrylates). The above-discussion of acrylic monomers is not intended to be exhaustive. Other acrylic monomers are known in the art and may be used in the present invention. The compositions may further comprise a variety of optional additives. One particularly useful additive is a thickener such as medium (about 40,000) molecular weight polybutyl methacrylate which may be incoφorated in an amount of about 10 to 40 weight %, based on the total weight ofthe composition. Thickeners may be employed to increase the viscosity ofthe composition to a more easily applied viscous syrup-like consistency. Another particularly useful additive is an elastomeric material. These materials can improve the fracture toughness of compositions made therewith which can be beneficial when, for example, bonding stiff, high yield strength materials such as metal substrates that do not mechanically absorb energy as easily as other materials, such as flexible polymeric substrates. Such additives can be incoφorated in an amount of about 5% to 35% by weight, based on the total weight ofthe composition. Useful elastomeric modifiers include chlorinated or chlorosulphonated polyethylenes such as HYPALON 30 (commercially available from E. I. duPont de Nemours and Co., Wilmington DE). Also useful, and even more preferred, are certain graft copolymer resins such as particles that comprise 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. In addition to improving the fracture toughness ofthe composition, core- shell polymers can also impart enhanced spreading and flow properties to the uncured composition. These enhanced properties may be manifested by a reduced tendency for the composition to leave an undesirable "string" upon dispensing from a syringe-type applicator, or sag or slump after having been applied to a vertical surface. Use of more than about 20% of a core-shell polymer additive is desirable for achieving improved sag-slump resistance. Peroxides may be optionally included (typically in an amount of about 2 % by weight or less, based on the total weight ofthe composition), for example, to adjust the speed at which the compositions polymerize or to complete the polymerization. Small amounts of inhibitors such as hydroquinone monomethylether may be used, for example, to prevent or reduce degradation ofthe acrylic monomers during storage. Inhibitors may be added in an amount that does not materially reduce the rate of polymerization or the ultimate properties of an adhesive or other composition made therewith, typically about 100 - 10,000 ppm based on the weight ofthe polymerizable monomers. Other possible additives include non-reactive colorants, fillers (e.g., carbon black), etc. provided they are dried sufficiently to reduce moisture content below about 0.1 % by weight based on the total weight ofthe additives. The various optional additives are employed in an amount that does not significantly adversely affect the polymerization process or the desired properties of compositions made therewith. Polymerizable acrylic compositions according to the invention may be used in a wide variety of ways, including as sealants, coatings, and injection molding resins. They may also be used as matrix resins in conjunction with glass and metal fiber mats such as in resin transfer molding operations. They may further be used as encapsulants and potting compounds such as in the manufacture of electrical components, printed circuit boards and the like. Quite desirably, they provide polymerizable acrylic adhesive compositions that can bond a diverse myriad of substrates, including polymers, wood, ceramics, concrete, and primed metals. The polymerizable compositions ofthe invention can be easily used as two- part adhesives. The components ofthe polymerizable composition are blended as would normally be done when working with such materials. The decomplexer of the polymerization initiator system is usually included in this blend so as to separate it from the organoborane amine complex, thus providing one part ofthe two-part composition. The organoborane amine complex ofthe polymerization initiator system provides the second part ofthe composition and is added to the first part shortly before it is desired to use the composition. The complex may be added to the first part directly or it may be predissolved in an appropriate carrier such as a small amount of methyl methacrylate. For a two-part adhesive such as those ofthe invention to be most easily used in commercial and industrial environments, the ratio at which the two parts are combined should be a convenient whole number. This facilitates application ofthe adhesive with conventional, commercially available dispensers. Such dispensers are shown in U.S. Patent Nos. 4,538,920 and 5,082, 147 and are available from Conprotec, Inc. (Salem NH) under the tradename "Mixpac." Once the two parts have been combined, the composition should be used quickly, as the useful pot life may be short depending upon the acrylic monomer mix, the amount of complex, and the temperature at which the bonding is to be performed. The polymerizable composition is applied to one or both substrates and then the substrates are joined together with pressure to force excess composition out of the bond line. This also has the advantage of displacing composition that has been exposed to air and that may have advanced too far in cure. In general, the bonds should be made shortly after the composition has been applied, preferably within about 10 minutes. The typical bond line thickness is about 0.1 to 0.3 mm but may exceed 1.0 mm when gap filling is needed. The bonding process can easily be carried out at room temperature and to improve the degree of polymerization it is desirable to keep the temperature below about 40°C, preferably below 30°C, and most preferably below about 25°C. The bonds will cure to a reasonable green strength to permit handling ofthe bonded components within about 1 hour. Full strength will be reached in about 24 hours under ambient conditions; post-curing with heat (typically about 80°C) may be used if desired. The invention will be more fully appreciated with reference to the following nonlimiting examples in which (unless noted otherwise) all weights are given as weight percents (weight %), based on the total weight ofthe composition which is 100 weight %. EXAMPLES Bond Strength Test Method The adhesive compositions described below were tested for bond strength. The base component of a given adhesive formulation (comprising a thorough mixture of thickened monomers and decomplexer) was combined with the organoborane polyamine complex (referred to as the accelerator component) and mixed with a spatula for one minute. The adhesive was then applied to a 2 inch (5.1 cm) wide, 6 inch long (15.2 cm), 8 mil (0.2 mm) thick film. The film was held flat using two 30 mil (0.8 mm) thick aluminum overlays, the overlays overlapping 0.5 inch (1.3 cm) along the entire length of each side ofthe film. Each adhesive formulation was tested on two different film substrates, skived polytetrafluoroethylene (PTFE) and skived ultrahigh molecular weight polyethylene (PE). Neither ofthe films had any surface treatment. Once the adhesive was applied to the first film, a second film comprising the same substrate was eased onto the adhesive using a 2.7 lb (1.2 kg) weighted glass plate. One side ofthe glass plate was applied to one side ofthe second film at an angle of about 30 degrees and then gradually lowered to a horizontal position so that the second film was applied incrementally to the first to avoid formation of bubbles in the adhesive. Sufficient adhesive was applied to the first film to provide minimum bond dimensions of 1 inch (2.5 cm) in width by 1.5 inch (3.8 cm) in length. The bonded adherends were allowed to cure for 24 hours at room temperature (21-25°C). The samples were then tested for bond strength in the T- peel mode using an Instron Tensile Tester set at a crosshead speed of 4 inches/min (10.2 cm/min). Two overlapping free ends ofthe sample were clamped into the jaws ofthe Instron tester, one free end in the upper jaw and one free end in the lower jaw. The jaws were then pulled apart until at least 1 inch (2.5 cm) of adhesive was exposed or until adherend failure was observed. The average force per width during the run after the adhesive was initially exposed was recorded as the Peel Strength in pounds/inch width (piw). The tensile strengths of PTFE and PE films were found to be 11 pounds inch width (20 N/cm width) and 25 pound/inch width (44 N/cm width), respectively. Preferably, the Peel Strength values approximate the tensile strength values, indicating substrate as opposed to adhesive failure. Solvent Resistance Cured adhesive films were obtained by removing the thin films of cured adhesive from the adherends after the bond strength peel tests were completed. When possible, the thin film was peeled from the remaining adherend. When this was difficult, the thin film plus adherend were immersed together in tetrahydrofuran (THF) solvent, and the adhesive was later scraped off the adherend. The weight of each adhesive film was determined and is denoted as Wl below. Each adhesive was placed in a 4 ounce (118 cm ) glass jar. Sufficient THF was added to the glass jar so that the contents comprised less than 5 parts by weight cured adhesive film and more than 95 parts by weight THF. The jar was capped and placed on a roll mixer for at least 24 hours at room temperature (21-25°C). The fluid mixture was then poured into a medium mesh conical gauze/paper paint filter (available from Foremost Co. and having a weight denoted below as W2) and thoroughly rinsed with THF. Filters were dried in an 80°C forced air oven for one hour. The filters were allowed to equilibrate ovemight at room temperature before being weighed to give the value denoted below as W3. Adhesive percent solids were then calculated as follows: Percent Solids = W3-W2 + 0.0299 XI 00 Wl It is noted that a correction factor of 0.0299 milligrams was added to W3-W2 in the equation above to account for that portion ofthe filter that was lost by virtue ofthe process conditions. Percent Gel was then calculated for samples ofthe invention by dividing the Percent Solids (calculated as described above) by the weight percent ofthe adhesive which is capable of addition polymerization. For those formulations whose Percent Solids never exceed 10%, the portion capable of addition polymerization is only the acrylic monomers. All other formulations include the portion derived from the acrylic monomers, the amine part ofthe complex and the decomplexer. A sample calculation is provided below for Example 30 ofthe invention: Percent Gel = Percent Solids X 100 Percent Capable of Addition Polymerization Percent Ge-Ex 30 = Percent Solids p x 30 X 100 (Wt.%MMA + Wt.% BMA + Wt.%MA = Wt%oc + Wt %A-nC where Wt.%MMA is the weight percent of methyl methacrylate, Wt.%BM A is the weight percent of butyl methacrylate, Wt.%M A is the weight percent of methyl acrylate, Wt.%rχ, is the weight percent of decomplexer, and Wt.% A m C is the weight percent ofthe amine portion ofthe decomplexer used in Example 30. The Percent Solids of Example 30 can be found in Table VI to be 64.4. Example 30 comprised Initiator In-1 given in Table IV. The organoborane portion (triethylborane) has a molecular weight of 98, while the amine portion (1,6-hexanediamine) has a molecular weight of 116. Table VI indicates that the weight percent of initiator was 2.791. Thus the value ofthe Wt.% A π.c can be calculated as follows: Wt.%AmC = (2.791) (116) (312) Wt.%An,C = 1 038 The percent Gelεx 30 can now be calculated from the other weight percents listed in Table VI as follows: Percent GelEχ30 = 64.4 X 100 15.223 +23.786+23.786+2.067 +0.796 Percent GelEχ30 = 97.7% Small deviations from table values are due to rounding of Percent Solids values. Decomplexers Anhydride Decomplexers Anhydride decomplexers ofthe present invention include those commercially available compounds as listed as decomplexers A-M in Table I: TABLE I: Anhydride Decomplexers Decomplexer Name Source A Maleic Anhydride Aldrich Chemical Co. B Itaconic Anhydride Aldrich Chemical Co. C Phthalic Anhydride Aldrich Chemical Co. D cis-1, 2,3, 6-Tetrahydrophthalic Anhydride Aldrich Chemical Co. E cis- 1,2-Cyclohexanedicarboxylic Anhydride Aldrich Chemical Co. F Isobutenylsuccinic Anhydride (K-4) Zeeland Chemicals G Methacrylic Anhydride Aldrich Chemical Co. H Isobutyric Anhydride Aldrich Chemical Co. I Methyl Hexahydrophthalic Anhydride Milliken Chemical Co. (MHHPA) J Methyl-5-norbornene-2, 3 -dicarboxylic Aldrich Chemical Co. Anhydride K 2-Octen-l-ylsuccinic Anhydride Aldrich Chemical Co. L Milldride 5060 Anhydride Milliken Chemical Co. 1 M SMA-3000A Anhydride Atochem Inc. Preparation of Anhydride Partial Adducts Partial adducts of poly(styrene-co-maleic anhydride) were prepared for use as decomplexers. A 50 ml glass vial was charged with 2,6-di-t-butyl-4- methylphenol (BHT) inhibitor according to the weight ratios specified in Table II. This charge was followed with charges of dried hydroxyethyl acrylate (HEA); butyl methacrylate (BMA) solvent; and poly(styrene-co-maleic anhydride) (SMA-3000A, available from Atochem Inc.), according to the weight ratios specified in Table II. The HEA had been dried over a bed of 4A molecular sieves prior to charging. The glass vial was sealed, shaken to mix the contents, and placed in a 105°C circulating hot air oven. After reaching a temperature of 105°C, the contents were thoroughly remixed by shaking and returned to the oven. The glass vial remained in the oven for a 10-12 hour heating cycle, during which the glass vial was shaken periodically. The anhydride adduct decomplexers included in the present invention are designated as decomplexers N-Q in Table II. TABLE II: Anhydride Adduct Decomplexers Decomplexer Wt.% BUT Wt.% HEΞA Wt.% BMA Wt.% SMA N 0.03 3.00 49.98 46.99 0 0.03 4.89 49.98 45.10 P 0.03 5.65 49.99 44.33 Q 0.03 8.03 49.98 41.96 Comparative Decomplexer For comparative puφoses, methacrylic acid (available from Aldrich Chemical Co.) was used as a decomplexer in the following examples and has been designated as decomplexer R in Table III. TABLE III: Comparative Decomplexer Decomplexer Name Source Methacrylic Acid Aldrich Chemical Co. Initiators The organoborane amine complex initiators used in the present invention are listed in Table TV below. All were prepared with triethyl borane using a 1 : 1 boron to nitrogen ratio with the exception ofthe E-L-E type which used a boron to nitrogen ratio of 0.9: 1. The organoborane polyamine complexes may be readily prepared using known techniques. Typically, the polyamine is combined with the organoborane in an inert atmosphere with slow stirring. An exotherm is often observed and cooling ofthe mixture is therefore recommended. If the ingredients have a high vapor pressure, it is desirable to keep the reaction temperature below about 70° to 80°C. Once the materials have been well mixed the complex is permitted to cool to room temperature. No special storage conditions are required although it is preferred that the complex be kept in a capped vessel in a cool, dark location. Advantageously, the complexes can be prepared in the absence of organic solvents that would later have to be removed, although they could be prepared in solvent if so desired. Solvents used in the preparation ofthe complexes should, preferably be ones that do not coordinate amines, for example, tetrahydofuran or hexane. TABLE IV: Organoborane Amine Complex Initiators Initiator . Organoborane Amine ln-1 Triethylborane 1 ,6-Hexanediamine ln-2 Triethylborane Jeffamine ED-600 diamine (1) ln-3 Triethylborane Jeffamine T-403 triamine (1) ln-4 Triethylborane E-L-E diamine l (2a) ln-5 Triethylborane E-L-E diamine ll (2b) (1) Available from Huntsman Corp. (2) 2:1 Molar adduct of Dixie Chemical Co. DCA-221 diamine and: a = 1 ,6-hexanedio) diacrylate b = Shell Chemical Co. Epon 826 Adhesive Compositions (Examples 1-38 and Comparative Examples 39-41) Two part adhesive compositions were prepared according to Table V below. The weight percent of each component based upon total composition weight is shown in this table. The two part adhesives of this invention comprise an accelerator component and a base component. The accelerator component in all examples was solely the organoborane amine complex initiator. The base component comprised a thickened acrylic monomer mixture to which has been added an effective amount of decomplexer. The thickened monomer mixture comprises a 16:25:25:34 blend by weight of methyl methacrylate (MMA), butyl acrylate (BA), methyl acrylate (MA) and poly(butyl methacrylate) (PBMA), respectively. The thickened monomer mixture components are all available from Aldrich Chemical Co. Unless otherwise indicated, the standard formulation provided 3.0 moles of triethylborane for every 100 moles of free-radically polymerizable (meth)acrylate ester vinyl groups and an index of 0.75 moles of amine reactive anhydride groups for each mole of initiator amine groups. I fsJ (1) Moles of triethylborane 100 moles of (meth)acιylate ester vinyl groups -J I (2) Moles of methacrylic acid or anhydride groups/mole of initiator amine groups Bond Strength Free Filn: 1 PTFE PE Solvent Resistance Example Decomplexer piw N/cm piw N/cm % Solids % Gel Comp 39 R 7 12 4<D 6 (1 1.3 2.0 Comp 40 R 9 16 4<D β ™ 2.0 3.1 Comp 41 R „(2) , 9 (2) 6 3) 10 3) 0.4 0.6 ND = Not determined (1) Adherend tore (2) 1 inch (2.5 cm) wide adherend (3) 15 mil (0.4 mm) thick PE used Each bond strength value in Table VT is the average reading in pounds per inch width (piw) or Newtons per centimeter (N/cm) over the length ofthe bond which was pulled. In general, preferred bond strengths are at least 5 piw (9 N/cm). The data in Table VI indicate good to outstanding bond formation for all ofthe formulations on either PE and PTFE, and for many formulations on both PE and PTFE. The data of Table VI also show that decomplexers ofthe present invention can advantageously provide both a reduced level of mobile constituents and improved solvent resistance compared to the comparative decomplexer (methacrylic acid). More specifically, Examples 17-38 provided % Solid values in the range of 14 to 64 and % Gel values in the range of 20 to 98, while the Comparative Examples 39-41 provided % Solid values in the range of 0.4-2.0 and % Gel values in the range of 0.6-3.1. It is noted that the decomplexers of Examples 17-38 comprised free radically polymerizable groups (namely, 1,1 -disubstituted alkenes and 1,2- disubstituted alkenes which are part of an α, β-unsaturated carbonyl structure). Such decomplexers are capable of covalently bonding with the polyamine portion of the organoborane amine complex to form decomplexer-amine reaction products comprising more than one free radically polymerizable group. As a consequence, these decomplexers provide adhesive compositions having both a reduced level of mobile consituents and good solvent resistance. Such decomplexers are preferred for the present invention. It is further noted that the decomplexer of Comparative Examples 39- 1 (methacrylic acid) comprised a 1,1 -disubstituted alkene group which is capable of ionicaily (as opposed to covalently) bonding with the polyamine portion ofthe organoborane amine complex. As a consequence, this decomplexer was unable to provide solvent resistance. Other observations from the data of Table VI include the following: Examples 24-29 illustrate that the initiator and anhydride concentrations can be independently varied to optimize adhesive bond strengths without adversely affecting solvent resistance. Examples 30-34 illustrate that a variety organoborane amine complexes may be utilized with the decomplexers ofthe invention to provide excellent adhesive bond strength values and solvent resistance. Various modifications and alterations of this invention will become apparent to those skilled in the art without departing from the scope and spirit ofthe invention. It should be understood that this invention is not limited to the illustrative embodiments set forth herein.

Claims: CLAIMS The embodiments for which an exclusive property or privilege is claimed are defined as follows: 1. An initiator system capable of initiating the polymerization of acrylic monomers comprising (1) an organoborane amine complex and (2) a decomplexer comprising at least one anhydride group. 2. An initiator system according to Claim 1 wherein said decomplexer comprises at least one free radically polymerizable group. 3. An initiator system according to Claim 1 wherein said decomplexer comprises at least one free radically polymerizable group and said organoborane amine complex comprises at least two amine groups. 4. An initiator system according to Claim 1 wherein said decomplexer has the structure: wherein each K \ and R 2 are independently selected from the group consisting of aliphatic, cycloaliphatic and aromatic groups. 5. An initiator system according to Claim 1 wherein said decomplexer has the following structure: wherein R 3 is a divalent organic radical. 6. An initiator system according to Claim 1 wherein said decomplexer is selected from the group consisting of methacrylic anhydride, itaconic anhydride, maleic anhydride and isobutenyl succinic anhydride. 7. An initiator system according to Claim 1 wherein said organoborane amine complex comprises at least two amine groups. 8. An initiator system according to Claim 1 wherein said complex has the structure: wherein Re is selected from the group consisting of alkyl groups having 1 to 10 carbon atoms; R 9 and Rio are independently selected from the group consisting of alkyl groups having 1 to 10 carbon atoms and phenyl-containing groups; the value of v is selected so as to provide a 0.5: 1 to 4: 1 ratio of primary or secondary amine nitrogen atoms to boron atoms in the complex; and Am is an amine. 9. A polymerizable acrylic composition comprising: a) at least one acrylic monomer; b) an effective amount of an organoborane amine complex; and c) an effective amount of a decomplexer comprising at least one anhydride group, said decomplexer being reactive with said amine to liberate the organoborane to initiate polymerization ofthe at least one acrylic monomer. 10. A polymerizable acrylic composition according to Claim 9 wherein said decomplexer comprises at least one free radically polymerizable group and said organoborane amine complex comprises at least two amine groups. 11. A polymerizable acrylic composition according to Claim 9 wherein said decomplexer has the structure: wherein each Ri and R 2 are independently selected from the group consisting of aliphatic, cycloaliphatic and aromatic groups. 12. A polymerizable acrylic composition according to Claim 9 wherein wherein said decomplexer has the following structure: wherein R 3 is a divalent organic radical. 13. A polymerized acrylic adhesive composition according to Claim 9. 14. A bonded composite comprising a first substrate, a second substrate and a polymerized acrylic adhesive composition according to Claim 9 that adhesively bonds the first and second substrates together. 15. A method of initiating the polymerization of at least one acrylic monomer, the method comprising the steps of: a) providing at least one acrylic monomer; b) blending the at least one acrylic monomer with the components of a polymerization initiator system, said system comprising: i) an organoborane amine complex, ii) an effective amount of a decomplexer comprising at least one anhydride group, said decomplexer being reactive with amine for liberating the organoborane to initiate polymerization ofthe at least one acrylic monomer; and c) initiating polymerization ofthe at least one acrylic monomer. 16. A method of increasing the solvent resistance of a polymerized acrylic adhesive composition obtained by organoborane-initiated polymerization of acrylic monomer, said method comprising the steps of a) providing at least one acrylic monomer; b) providing an organoborane amine complex comprising at least two amine groups; c) providing a decomplexer comprising at least one anhydride group and at least one free radically polymerizable group; d) blending components a), b) and c), and; e) initiating polymerization ofthe at least one acrylic monomer and continuing polymerization until a solvent resistant acrylic adhesive composition is obtained.

Inventors: DEVINY E JOHN, DEVINY, E., JOHN
Applicants: MINNESOTA MINING & MFG, MINNESOTA MINING AND MANUFACTURING COMPANY
Application year: 1996
Main classification: C08F20
IPC codes: C08F4, C08F20, C09J4, C09J133