MX2008004512A - Amido-organoborate initiator systems - Google Patents

Abstract

In one embodiment, the invention is a system for initiating free radical polymerization comprising:a) in one part, one or more amido-borate compounds containing one or more anionic amido-borate moieties comprising an organoborate wherein the boron atom is bonded to a nitrogen atom of ammonia or an organic compound containing one or more nitrogen atoms, such as a hydrocarbyl amine, a hydrocarbyl polyamine, or an aromatic heterocycle containing one or more nitrogen atoms, and a cationic counter ion and b) in a second part, a liberating compound which reacts with the nitrogen atom(s) bound to the boron atom upon contact with the amido-borate to form an organoborane radical. In another embodiment, the invention is a two part polymerizable composition comprising in one part, one or more amido-borate compounds and in the second part, a liberating compound which reacts with the nitrogen atoms bound to the boron atom upon contact with the amido-borate to form an organoborane radical and one or more compounds capable of free radical polymerization. The first part may further comprise one or more compounds capable of free radical polymerization. This facilitates formulating compositions that have commercially desirable volumetric ratios of the two parts.

Description

INITIATING SYSTEMS OF AMIDO-ORGANOBORATO Field of the Invention The present invention relates to amido-organoborate initiator systems which are useful for polymerizable compositions containing such systems. Background of the Invention Organoborane based systems are known to initiate free radical polymerization and promote adhesion of low surface energy substrates due to their ability to generate radicals to polymerize compounds susceptible to free radical polymerization such as compounds containing unsaturated portions. Oxidation of organoborane-based systems with molecular oxygen forms energetic peroxides that are exothermic and can be pyrophoric if not carefully controlled. Due to the high reactivity of organoboranes with oxygen, systems have been developed that block the organoborane center to stabilize the organoborane and which unblocks the organoborane center to initiate the formation of free radicals. The role of the blocking group is to make the center of the organoborane less susceptible to the insertion of oxygen and the initiation of radicals.

Patent EP 1, 201, 722 describes the use of L-selectride and phenyl borate as the precursors of borane with hydride and phenyl anions as the blocking groups. A series of patents for Skoultchi, US Patent Nos. 5, 106,928; 5,143,884; 5,286,821; ,310,835 and 5,376,746 (all incorporated herein 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 organoboron amine complexes are used to initiate healing. Pocius in a series of US Patents Nos. 5,616,796; 5,621, 143; 5,681, 910; 5,686,544; 5,718,977; and 5,795,657 (all incorporated herein by reference) describe organoboro amine complexes using a variety of amines to form complexes with the organoboron, such as polyoxyalkylene polyamines and polyamines which are the reaction product of diprimary amines and a compound having at least two groups which 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 complexes wherein oraganoboro is a trialkyl borane and the amine is selected from the group of amines having an amidine structural component; 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 groups that accept hydrogen bond where there are at least two carbon atoms between the primary amine and the group accepting hydrogen bonds; e conjugated mines. These patents describe polymerizable compositions containing the organoboron amine complexes, one or more monomers, oligomers or polymers having olefinic unsaturation which are amenable to polymerization by free radical polymerization and which the polymerizable compositions can be used as adhesives, sealants, coatings or ink compositions. Kendall et al. , U.S. Patent No. 6,630,555 (incorporated herein by reference) discloses boron containing compounds useful for initiating polymerization which are internally blocked organoborates, incorporated herein by reference. The term "internally blocked" in reference to organoborates is described as four coordinated boron atoms that are part of a bridged inner ring structure through two of the four coordinate or boron valencies. Kneafsey et al., U.S. Patent Publication No. 2003/0226472 and Kneafsey et al., U.S. Patent Publication No. 2004/0068067 describe another class of organoborates useful in the initiation of polymerization, is tetrahydrocarbyl borates (also known as quaternary boron salts), both incorporated herein by reference. Low surface energy olefins such as polyethylene, polypropylene, and polytetrafluoroethylene have a variety of attractive properties in a variety of uses, such as toys, auto 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 join these materials. The commercially available adhesives that are used for these plastics require time consuming or extensive pre-treatments of the surface before the adhesive attaches to the surface. Such pre-treatments include light discharge treatment, flame treatment, the application of primer paints, and the like. The requirement for extensive surface pre-treatment results in significant limitations for designers of automobile, toy, furniture and the like components. There is a continuing need for free radical polymerization initiator systems that are stable under storage conditions, that initiate rapid cure once polymerization is initiated and that are useful in polymerizable systems which are capable of bonding substrates of low surface energy. . Brief Description of the Invention In one embodiment, the invention is: a) amido-borate compounds containing one or more anionic portions of amido-borate comprising an organoborate wherein the boron atom is linked to at least one atom of ammonia nitrogen, or an organic compound containing a nitrogen atom, such as a hydrocarbyl amine, a hydrocarbyl polyamine, or an aromatic heterocycle containing one or more nitrogen atoms and optionally one or more heteroatoms or heteroatom-containing functional portions, and one or more cationic counterions. In another embodiment the amido-borate is a compound comprising one or more tetravalent boron anions and one or more of: i) an organic compound containing a nitrogen atom and a cation or ii) an ammonium cation; wherein each of the one or more tetravalent boron atoms is bonded to the nitrogen atom of an ammonium cation or to an organic compound containing a nitrogen atom. In another embodiment the amido-borate is a compound comprising at least one tetravalent boron anion wherein the boron anion is bonded to the nitrogen atom or to an organic compound containing a nitrogen atom and one or more cations and the number of borate anions and cations is the same. In another embodiment, amido-borate is a compound comprising one or more tetravalent boron anions bonded to an ammonium cation. In another embodiment the amido-borates comprise two or more amido-borates, each comprising a tetravalent boron anion wherein at least one of the borate anions is bonded to the nitrogen atom of an organic compound; and at least one of the borate anions is bonded to the nitrogen of an ammonium cation; and one or more additional cations wherein the number of additional cations is the same as the number of tetravalent boron atoms bonded to the nitrogen atom of an organic compound containing at least one nitrogen atom. Amido-borates are useful in two-part polymerizable compositions comprising, in one part, one or more amido-borate compounds and in the second part, a release compound that reacts with the nitrogen atoms bonded to the boron atom while being present. in contact with the amido-borate to form an organoborane radical and one or more compounds susceptible to free radical polymerization. Amido-borates allow polymerizable compositions that are stable at or near room temperature and can be cured on demand by contacting the two parts of the composition. Additionally, the polymerizable compositions containing the amido-borates can form good bonds for substrates of low surface energy without the need for primer paints or surface treatments. The polymerized compositions based on amido-borates show excellent cohesive and adhesive strength at elevated temperatures and thus demonstrate excellent stability at high temperatures. Detailed Description of the Invention Amido-borates comprise one or more amido-borate anions and one or more corresponding cations which neutralize the amido-borate anion. A borate is a salt of a positive cation and a tetravalent anionic boron. Amido-borates are organoborates wherein one of the ligands in the boron atom is ammonia nitrogen or an organic compound that contains a nitrogen atom and which may contain a heteroatom or functional portions containing heteroatom wherein the nitrogen may be quaternary and cationic. In some embodiments, the cation may be nitrogen bound to boron in the form of a quaternary nitrogen. This is especially true where the nitrogen compound used to form the amido-borate has more than one nitrogen which is bonded to more than one boron atom of organoborane to form the amido-borate. The organoborane bonded to the nitrogen atom to form the amido-borate comprises a boron atom with three bonds to hydrocarbyl portions wherein the hydrocarbyl portions may further comprise one or more heteroatoms or functional groups containing a heteroatom which do not interfere in the described function of the amido-borate compounds. Preferred heteroatoms that may be present in the hydrocarbyl moieties disclosed herein include oxygen, sulfur, nitrogen, silicon, halogens, and the like, with oxygen being most preferred. Preferred heteroatom-containing functional groups that may be present as part of the hydrocarbyl moieties disclosed herein include ethers, thioethers, amines, silanes, siloxanes and the like, the ethers being the most preferred. The boron atom can be bonded to three separate hydrocarbyl moieties or it can be bonded to two hydrocarbyl moieties wherein one hydrocarbyl moiety has two bonds to the boron atom thereby forming one or more cyclic ring (s). The organoborane used to prepare the amido-borate is preferably a trialkyl borane or an alkyl cycloalkyl borane. Preferably, such organoborane corresponds to the formula: B- (R1) 3 wherein B represents boron; and R1 is separately in each occurrence hydrogen, an alkyl or cycloalkyl group, or two or more of R1 may be combined to form a cycloaliphatic ring; preferably R1 is a C1.10 alkyl, C3.10 cycloalkyl, or two or more of R1 may be combined to form a cycloaliphatic ring; with the proviso that only 1 or 2 of R1 can be hydrogen. More preferably, none of R1 is hydrogen. More preferably, R1 is C1-4 alkyl, and more preferably C2- alkyl. Among the preferred organoborates are tri-ethylborane, tri-isopropyl borane and tri-n-butylborane. The nitrogen-containing portion of the amido-borate can be derived from ammonia or any organic compound containing a nitrogen atom which is capable of binding to boron and is preferably derived from ammonia, an amine or a hydrocarbyl polyamine. The nitrogen atoms of such compounds bonded to the boron atoms to form the borates may be primary, secondary, or quaternary, preferably secondary or tertiary or quaternary. In another preferred embodiment the nitrogen atom bonded to the organoborane to prepare the amido-borate is a nitrogen placed in or on the ring of a heteroaromatic cyclic compound. In those embodiments wherein the nitrogen is quaternary, the quaternary nitrogen portion of the amido-borate is the cationic counter ion for the borate anion portion of the compound to which the quaternary nitrogen atom is attached. The hydrocarbyl amine or polyamine and the nitrogen-containing aromatic heterocyclic compound may contain heteroatoms as described hereinbefore or may be further substituted with substituents that do not interfere with the operation of such compounds in the compositions of the invention described hereinbefore. The hydrocarbyl amines preferably correspond to the formula H2.r-N- (R2) r wherein R2 is independently in each occurrence an alkyl, cycloalkyl, aryl, alkaryl, or aralkyl group; wherein such a group may optionally contain one or more heteroatoms, one or more functional groups containing a heteroatom, as described hereinbefore or protons. R 2 is preferably C 1-10 alkyl C 3-10 cycloalkyl, C 6 ar 2 aryl, C 7-20 alkaryl or C 7-20 aralkyl; wherein such a group may optionally contain one or more heteroatoms of O or S, preferably O, or heteroatom functional portions containing O or S. R 2 is more preferably C 1 - alkyl or C 1. 0 alkoxyalkyl; even more preferably methyl, ethyl, propyl, methoxypropyl, ethoxypropyl or propoxypropyl. Referring to the alkoxyalkyl, the number of carbon atoms refers to the total carbon atoms in the portion. The hydrocarbyl polyamines preferably correspond to the formula wherein R2 is as described here above; R4 is independently in each occurrence a divalent hydrocarbyl portion which may contain one or more heteroatoms or one or more heteroatom-containing functional portions as described hereinbefore; r is independently in each occurrence 0, 1 or 2; and q is independently in each occurrence 1 or 2. Heterocyclic compounds containing aromatic nitrogen preferably correspond to the formula wherein R3 is independently at each occurrence hydrogen, an alkyl group, an alkoxy, aralkyl or an aryl group; wherein such a group may optionally contain one or more heteroatoms, one or more heteroatom-containing functional portions, as described hereinbefore, or protons; Z is independently in each occurrence N, Si, P or C and w is 0 or 1 with the proviso that when Z is N or P, w can only be 0, whereas when Z is C or Si; w can only be 1 Preferably Z is N or C. R3 is preferably hydrogen, Ci-10 alkyl, C3.10 cycloalkyl, C6.12 aryl, C7-20 alkaryl or C7.20 aralkyl; wherein such a group may optionally contain one or more heteroatoms of O or S, preferably O, or one or more functional portions containing heteroatom O or S. R3 is more preferably hydrogen, C1- alkyl or an alkoxyalkyl of C? -10 , even more preferably hydrogen, methyl, ethyl, propyl and more preferably hydrogen. Preferably R4 is independently at each occurrence alkylene of C2.20, cycloalkylene of C3-20, arylene of C6.20, alkarylene of C7.20 or aralkylene of C7-2o; more optionally containing one or more heteroatoms or functional portions containing heteroatom; more preferably C2.20 alkylene or C2.2o alkylene groups containing one or more oxygen atoms and even more preferably C2-4 alkylene. The preferred heteroatoms are O or S, with O being most preferred. The cation that forms the salt with the amido-borate can be any cation that forms a salt with the amido-borate. The cation can be any metal of group IA and group NA, any inorganic cation or organic cation. Preferably the cation is an onium ion or an alkali metal ion. More preferably the cation is sodium, potassium, a phosphonium ion or an ammonium ion. The preferred ammonium ions are tetraalkyl ammonium ions, the tetramethyl ammonium ion being the most preferred. Preferred phosphonium ions are tetraalkyl phosphonium or tetraaryl phosphonium; tetrabutyl phosphonium and tetraphenyl phosphonium being preferred. The amido-borates preferably correspond to one of the formulas: (R f-N-Ofc2 ^ (R3) » wherein R1, R2, R3, R4 and w are as described here above; X is independently in each occurrence a cation; p is independently in each occurrence 0 or 1; q is independently in each occurrence 1 or 2 where q is 2, the nitrogen atom is the cation that balances the borate anion; with the proviso that the sum of p and q in each pair of bound boron and nitrogen is 2; and the sum of p is 1 or 2. Where q is 2, the nitrogen to which it is bound is quaternary and carries a positive charge that balances the negative charge found in boron boron and a cation is not necessary to neutralize the borate. Preferably, X is independently on each occurrence an onium or a meta-alkali ion; more preferably X is a cation of ammonium, phosphonium, potassium or Sodium; even more preferably X is tetraalkyl ammonium, tetraalkyl phosphonium, tetraaryl phosphonium or Sodium and more preferably X is tetramethyl ammonium, tetrabutyl ammonium, tetrabutyl phosphonium or tetraphenyl phosphonium. In another embodiment the cationic species may have more than one cationic species that forms salts with the borate anions. Thus, the cationic species can form a salt with more than one borate species. Preferably, cationic species with more than one cation have 2 to 4, preferably 2 or 3 cations and even more preferably 2. Among the preferred cationic species having more than one cation are the compounds having 2 or more ammonium or phosphonium cations, with the compounds having two ammonium cations being preferred. Examples of such compounds include 1,2 (di (trimethylammonio)) ethane. In the embodiment wherein the cationic species have more than one cation, the amido-borates preferably correspond to the formulas: wherein R1, R2, R3, R4, w, X, p and q as described here above; R5 is independently in each occurrence a t-valent hydrocarbyl group optionally containing one or more heteroatoms or heteroatom-containing functional portions as described hereinbefore; And it is independently in each occurrence-i ^ R ^ or -P (R2) 3; and t is independently in each occurrence 2 or greater. Preferably, t is 2 to 4, still more preferably 2 or 3 and more preferably 2. More preferably R5 is independently at each occurrence a C2.20 alkylene t-valent; C3.20 cycloalkylene; C6-2o arylene; C7 alkarylene. or; or C7.20 aralkylene optionally containing one or more heteroatoms or heteroatom-containing functional portions, preferred heteroatoms are sulfur and oxygen with oxygen being most preferred; and More preferably R5 is a t-valent alkylene group, and more preferably a t-valent alkylene group of C2-6. More preferably R5 is an alkylene group of C2-divalent. The amido-borates are used in the polymerizable compositions of the invention in an amount sufficient to initiate the polymerization when the amine is released and to facilitate the binding of the polymerizable compositions where desired. Preferably, the amido-borate is present in the polymerizable compositions in an amount of about 0.1 part by weight based on 100 parts by weight of the composition or greater, more preferably about 0.5 part by weight or greater and more preferably about 1 part per weight or greater. Preferably, the amido-borate is present in the polymerizable compositions in an amount of about 30 parts by weight or less based on 100 parts by weight of the composition, more preferably about 20 parts by weight or less and more preferably about 10 parts by weight. weight or less. The amido-borates can be prepared from the base amines described above, such amines are commercially available. The amine can be contacted with a base, in a solvent and without solvent if the amine is liquid, resulting in a salt. Inert organic solvents such as tetrahydrofuran can be used. An amine salt and the cation of the base are formed. The resulting salt is contacted with a trivalent organoborane to form the amido-borate. The contact is preferably carried out under vacuum or under an inert atmosphere. Preferably, the process is carried out at ambient temperatures. If a solvent is used, it can be removed under vacuum. Amido-borate is capable of forming a trivalent organoboron compound. Amido-borates are tetravalent in that they have four bonds to boron. The species that generates free radicals, the trivalent boron compound, is formed when the amido-borate is contacted with a release compound. Trivalent borane generates free radicals by reacting with oxygen from the environment. The trivalent organoborane is easily attacked by oxygen to form radicals that initiate polymerization by free radicals in contact with the compounds that polymerize in the presence of free radicals. Upon contacting the amido-borate with the release compound causes the abstraction of one of the ligands bound to the boron atom to convert it to a trivalent borane. The release agent can be any compound that reacts with the nitrogen atom of the amido-borate. Generally, the release agent has a higher affinity for the nitrogen of the amido-borate than that which the boron atom has for the nitrogen atom. The amine-ammonium or ammonium-borate release can occur with any chemical compound for which the exchange energy is favorable, such as mineral acids, organic acids, Lewis acids, isocyanates, acid chlorides, sulfonyl chlorides, aldehydes, and the like. The preferred release compounds are acids and isocyanates. In those embodiments wherein a compound having a heterocyclic compound susceptible to ring-opening polymerization is present and the initiator for the ring-opening polymerization is a Lewis acid, the release compound can be omitted since the Lewis acids they can also function as the release compound. If the Lewis acid is used as the release compound and the initiator of the heterocyclic ring opening polymerization, no additional amounts are required with respect to the amounts necessary to initiate the polymerization. The compositions of the invention will comprise a sufficient amount of the release compound to initiate the polymerization in an acceptable ratio. Preferably the release compound is present in a molar equivalent base, or higher, compared to the amido-borate. Preferably, the release compound is present in an amount of about 0.5 molar equivalent or greater based on the molar equivalents of the organoborane, more preferably in an amount of about 1.0 molar equivalents or greater and more preferably about 1.5 molar equivalents or greater. Preferably, the release compound is present in an amount of about 100 molar equivalents or less based on the molar equivalents of the organoborane, more preferably in an amount of about 50 molar equivalents or less and more preferably about 25 molar equivalents or less. Preferably, the polymerizable compositions based on the amido-borates of the invention further comprise a second amine which may further comprise functional polar groups. The second amine may be any amine that stabilizes the compositions of the invention against unwanted polymerization. Preferred functional polar groups are ether groups, thioether groups, secondary and tertiary amines and the like. Preferably, the second amine comprises an alkoxy alkylamine or a polyamine, that is, a compound having two or more amino groups. The alkyl main chain of the second amine is preferably a C2.8 alkyl group and more preferably C- alkyl. Preferably, the alkyl group in the alkoxy group is a C 1-8 alkyl, more preferably a C 1 alkyl and more preferably a methyl group. Preferred alkoxy alkylamines include methoxypropyl amine, methoxyethylamine and ethoxypropylamine; with methoxypropyl amine being the most preferred. The second amine is present in an amount sufficient to stabilize the compositions of the invention to prevent premature polymerization. Preferably, the second amine is present in an amount of about 1 mole percent or greater based on the moles of the amido-borate present and more preferably an amount of about 10 mole percent or greater. Preferably, the second amine is present in an amount of about 1,000 mole percent or less based on the moles of the amido-borate present or less and more preferably about 300 mole percent or less. The compounds susceptible to free radical polymerization which can be used in the polymerizable compositions include any monomers, oligomers, polymers or mixtures thereof containing an olefinic unsaturation which can be polymerized by free radical polymerization. Such compounds are well known to those skilled in the art. Mottus, U.S. Patent No. 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 an olefinic unsaturation are described in Sonnenschein et al. , US Patent Nos. 6,730,759 (column 9, line 7 to line 54); 6,706,831; 6,713,578; 6,713,579 and 6,710, 145, the relevant portions are incorporated herein by reference. Examples of preferred acrylates and methacrylates are described in Skoultchi, U.S. Patent No. 5,286,821 in column 3, line 50 to column 6, line 12, incorporated herein by reference and Pocius, U.S. Patent No. 5,681, 910 in column 9, line 28 to column 12, line 25, incorporated herein by reference. These compositions are also useful molecules crosslinking acrylate include ethyleneglycol dimethacrylate, ethyleneglycol diacrylate, triethylene glycol dimethacrylate, bismethacryloxy diethylene carbonate, polyethylene glycol diacrylate, tetraethylene glycol dimethacrylate, diglycerol diacrylate, diethylene glycol dimethacrylate, pentaerythritol triacrylate, trimethylolpropane trimethacrylate, isobornylmethacrylate and tetrahydrofurfuryl methacrylate. In the embodiment wherein the composition is used as an adhesive, the compounds based on acrylate and / or methacrylate are preferably used as the compounds susceptible to free radical polymerization. The most preferred acrylate and methacrylate compounds include methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexylmethyl methacrylate and (tetrahydrofurfuryl) methacrylate. The preferred amounts of the compounds susceptible to free radical polymerization are about 10 parts by weight or greater based on 100 parts of the total weight of the formulation, more preferably about 20 parts by weight or greater and more preferably about 30 parts by weight or more. higher. The preferred amounts of the compounds susceptible to free radical polymerization are preferably about 90 parts by weight or less based on 100 parts of the total weight of the formulation, more preferably about 85 parts by weight or less and more preferably 80 parts by weight or more. less. In another embodiment, the invention of the polymerizable compositions may further comprise one or more compounds, oligomers or prepolymers having a siloxane backbone and reactive portions susceptible to polymerization, a catalyst for the polymerization of one or more compounds, oligomers or prepolymers that have a siloxane backbone and reactive portions susceptible to polymerization as described in U.S. Patent No. 6,777,512, entitled Amine Organoborane Complex Initiated Polymerizable Compositions Containing Siloxane Polymerizable Components (column 12)., line 66 to column 15, line 54), incorporated herein by reference. The polymerizable compositions of the invention may further contain a stabilizing amount of a dihydrocarbyl hydroxylamine or stable nitroxy radicals such as those described in Jialanella, U.S. Patent Publication No. 2005/0004332, incorporated herein by reference. Stabilize as used herein refers to avoiding polymerization until desired. Generally this means that polymerization is inhibited under normal storage conditions. Normal storage conditions means storing at a temperature of about 0 ° C to about 40 ° C, where the adhesive is stored in a sealed container. A stable composition is one that does not undergo undesired viscosity development for a defined period. The development of 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 for a period of 30 days when stored at temperatures of 40 ° C or less, more preferably 100 percent or less for a period of time of 30 days and more preferably 50 percent or less for a period of 30 days. Preferred dihydrocarbyl hydroxyl amines useful herein include any such compounds which, when included in the compositions of this invention, improve the stability of the compositions described herein. Among the preferred dihydrocarbyl hydroxyl amines are the hydroxylamine free base of BASF, the hydroxylamine derivatives of Mitsui Chemicals America, Inc. and IRGASTABMR FS Products of Ciba Specialty Chemicals which contain oxidized bis (hydrogenated tallow alkyl) amine, 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 by weight of the compositions of the invention or greater, more preferably about 2 parts per million or greater and more preferably about 5 parts per million or greater. Preferably, the dihydrocarbyl hydroxyl amines are used in an amount of about 100,000 parts per million by weight of the compositions of the invention or less, more preferably about 50,000 parts per million or less, even more preferably about 25,000 parts per million or less and more preferably about 10,000 parts per million or less. The compositions of the invention may 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 a compound is used, the substituents are placed either ortho or for one with respect to another. In one embodiment, the accelerator is any compound containing a quinone structure which compound accelerates the curing of polymerizable compositions, as described by Jialanella, U.S. Patent Publication No. 2005-0004332, incorporated herein by reference. For preferred adhesive compositions, preferred quinones also facilitate the adhesion of polymerizable compositions to substrate surfaces. 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 surface of the substrate. If very little is used, there is no significant increase in curing speed. If too much is used, the composition will not adhere to the surface of a substrate. Preferably, the quinone is used in an amount of about 0.01 part by weight based on 100 parts of the polymerizable composition or greater, more preferably about 0.02 parts by weight or greater, and more preferably about 0.04 parts by weight or greater. Preferably, the quinone is used in an amount of about 0.1 part by weight based on 100 parts of the polymerizable composition or less, more preferably about 0.8 parts by weight or less, and more preferably about 0.4 parts by weight or less. In another embodiment, the accelerator comprises at least one compound containing at least one aromatic ring and at least one, preferably two, substituents on the selected aromatic ring of hydroxyl, ether and both, wherein the two substituents are already placed be ortho or for one with respect to another. The substituted aromatic ring-containing compound is used in conjunction with a compound having a peroxy moiety as described by Jialanella, U.S. Patent Publication No. 2005-0004332, incorporated herein by reference. The substituted aromatic compound may contain any aromatic moiety, including those with multiple ring structures. The substituted aromatic compounds preferably contain two or more functional groups selected from hydroxide 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 aromatic compounds contain aromatic ring structures of benzene, anthracene or naphthalene. The substituted aromatic compounds can be substituted with any substituent that 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 oxygen or sulfur heteroatom containing groups. More preferred substituents include aryl groups and heteroatom containing groups. 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 surface of the substrate. If too little is used, there is no significant increase in curing speed. If too much is used, the composition will not adhere to the surface of a substrate. Preferably, the substituted aromatic ring-containing compound is used in an amount of about 0.1 part by weight or greater of the polymerizable composition based on 100 parts, more preferably about 1 part by weight or greater, and more preferably about 2 parts by weight or older. Preferably, the substituted aromatic ring containing compound is used in an amount of about 4 parts by weight or less of the polymerizable composition based on 100 parts, more preferably about 3 parts by weight or less, and more preferably about 2.5 parts by weight 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 used of the peroxy-containing compound is that amount which accelerates the curing of the compositions. If too little is used, there is no significant increase in curing speed. If too much is used, the adhesive does not bind polyolefins. Preferably, the peroxy-containing compound is used in an amount of about 0.1 part by weight or greater of the polymerizable composition based on 100 parts, more preferably about 1 part by weight or greater, and more about 2 parts by weight or more. Preferably, the peroxy-containing compound is used in an amount of about 4 parts by weight or less of the polymerizable composition based on 100 parts, more preferably about 3 parts by weight or less, and more preferably about 2.5 parts by weight or less. Preferably, the relative amount of the peroxy-containing compound with respect to the substituted aromatic ring-containing compound is selected such that most of the resulting free radicals generated by the peroxy compound react with the substituted aromatic ring compound. Thus, a molar ratio of the peroxy-containing compound to the aromatic ring-containing compound is one or less. If the ratio is very high, then no adhesion to polyolefins would be observed. If the ratio is very low, then the cure rate of the adhesive does not increase. Preferably, the molar ratio of the peroxy-containing compound to the substituted aromatic ring-containing compound is about 1: 4 or greater, and more preferably about 2: 3 or greater. Preferably, the molar ratio of the peroxy-containing compound to the substituted aromatic ring-containing compound is about 1: 1 or less. Preferably, the accelerator is placed in the part that does not contain the amido-borate. Frequently the part containing the amido-borate is referred to as the hardener side, and the other part is often referred to as the resin side because the larger part of the polymerizable compound is in this part. The hydrocarbyl as used herein refers to any portion having both carbon and hydrogen atoms and includes saturated and unsaturated, branched and unbranched hydrocarbon chains and aromatic and non-aromatic ring structures. Alkyl refers to branched and unbranched saturated hydrocarbon chains. Alkenyl refers to branched and unbranched unsaturated hydrocarbon chains. Aryl defines a portion of aromatic hydrocarbon. Alkaryl defines a portion of aromatic hydrocarbon with a linear or branched hydrocarbon chain attached. Aralkyl defines a straight or branched hydrocarbon chain with a linked aryl group. Acyl defines a portion of hydrocarbyl and carbonyl. Alkylene defines a divalent alkyl moiety. Unless otherwise indicated these portions may be substituted with any other substituent that 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 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 time (open time) may be short depending on the monomer mixture, the amount of amido-borate, the amount of catalyst and the amount of temperature at which the union takes place. The adhesive compositions of the invention are applied to one or both substrates and subsequently the substrates are joined together, preferably with pressure to remove excess composition from the binding line. In general, the substrates should be contacted with the composition disposed therebetween shortly after the composition has been applied, preferably in about 10 minutes. The typical thickness of the bond line is approximately 0.13 mm (0.005 inches) to approximately 0.76 mm (0.03 inches). The joining line can be thicker if a space needs to be filled in since the composition of the invention can function as both adhesive and filling of a space. The bonding process can be easily carried out at room temperature, and to improve the degree of bonding, it is preferable to keep the temperature below about 55 ° C and more preferably below about 40 ° C. The compositions may further comprise a variety of optional additives. A particularly useful additive is a thickener such as a medium to high molecular weight polymethyl methacrylate (about 10,000 to about 1,000,000) which can be incorporated in an amount of about 10 to about 60 parts by weight, based on 100 parts 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 ductility at break of the compositions made with them which can be beneficial when, for example, materials with a high yield strength, of consistent bonding such as metal substrates that do not mechanically absorb energy as easily as other materials , such as flexible polymer substrates. Such additives may be incorporated in an amount of about 5 parts to about 35 parts by weight, based on 100 parts of the composition. Useful elastomeric modifiers include chlorinated or chlorosulfonated polyethylenes such as HYPALONMR 30 (commercially available from E. I. 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 coatings, these materials are often referred to as core-shell polymers. More preferred are the acrylonitrile-butadiene-styrene graft copolymers available from Rohm and Hass. In addition to improving the breakage ductility of the composition, the core-shell polymers can also impart improved flow properties and displacements to uncured compositions. These augmented properties can be manifested by a reduced tendency of the composition to leave an undesirable "bead" when dispensed from a syringe-type applicator, or detachment or bleeding after having been applied to a vertical surface. The use of more than about 20 parts of a core-shell polymer additive is desirable to obtain improved break-away resistance. Generally, the amount of the resistant polymer used in that amount gives the desired firmness to the polymer or prepared adhesive. The polymerizable compositions utilizing the amido-borates of the invention can be used in a wide variety of forms, including as adhesives, coatings, primer paints, to modify the surface of polymers and injection molding resins. They can also be used as matrix resins together with metal fiber or glass gratings such as in resin transfer molding operations. They can also be used as encapsulants and encapsulation compounds such as in the manufacture of electrical components, printed circuit boards, and the like. Most desirably, they provide polymerizable adhesive compositions that can bind a wide variety of substrates, including polymers, wood, ceramics, concrete, glass and primed or unprimed metals. Another desirable related application is its use in promoting adhesion of paints for low surface energy substrates such as polyethylene, polypropylene, polyethylene terephthalate, polyamides, and polytetrafluoroethylene, and their copolymers. In this embodiment, the composition is applied on the surface of the substrate to modify the surface to increase the adhesion of the final coating to the surface of the substrate. Subsequently the coating can be applied to the treated surface. The polymerizable compositions are especially useful for adhesively bonding low surface energy polymer or plastic substrates that have historically been very difficult to bond without using complicated surface preparation, priming, etc. techniques. By low surface energy substrates are meant materials having a surface energy of about 45 mJ / m2 or less, more preferably about 40 mJ / m2 or less and more preferably about 35 mJ / m2 or less. Included among these materials are polyethylene, polypropylene, acrylonitrile-butadiene-styrene, polyamides, syndiotactic polystyrene, block copolymers containing olefin, and fluorinated polymers such as polytetrafluoroethylene (TEFLON ™) which has a surface energy of less than about 20 mJ / m2 . (The expression "surface energy" is often used synonymously with "critical wetting tension" by others.) Other polymers of somewhat high surface energy that can be effectively bound with the compositions of the invention include polycarbonate, polymethylmethacrylate, and polyvinyl chloride . The polymerizable compositions using amido-borates of the invention can be easily used as two-part adhesives. The components of the polymerizable compositions are mixed as would normally be done when working with such materials. The amido-borate release compound is generally included with the free radical polymerizable component to separate it from amido-borate, thus providing a part of the composition of two parts. The amido-borates of the polymerization initiator system provide the second part of the composition and are 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 the 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 an appropriate carrier such as an olefin reactive monomer, i.e. , methyl methacrylate or a viscous solution of methyl methacrylate / polymethyl methacrylate. The adhesive compositions can be used to join two or more substrates together by contacting the parts of the composition together, contacting one of the substrates with the adhesive composition, contacting the substrates with the adhesive composition disposed between the substrates and allowing that the adhesive composition heals. In another embodiment, the invention is a sheet comprising two or more substrates having the cured composition of the invention disposed between the substrates. The cured adhesive composition contains the organoborane residue derived from amido-borate as described herein. Preferably, the two-part mixed compositions have a suitable viscosity to allow application without trickling. Preferably, the viscosities of the two individual components should be of the same order or magnitude. Preferably the mixed compositions have the viscosity of about 100 (0.1 Pa.S) centipoise or greater, more preferably about 5,000 (5.0 Pa.S), centipoise or greater and more preferably about 10,000 (10.0 Pa.S) centipoise or greater. Preferably, the adhesive compositions have a viscosity of about 500,000 (500 Pa.S) centipoise or less, more preferably 1 50,000 (150 Pa.S) centipoise or less, still more preferably about 100,000 (I00 Pa.S) centipoise or less and more preferably about 50,000 (50 Pa.S) centipoise or less. The viscosity as used in this section is measured using a Brookfield viscometer in accordance with ASTM D2196 using the conditions of needle number 7, 20 RPM and 25 ° C. Specific Modalities The following examples are included for illustrative purposes only and are not intended to limit the scope of the invention. Unless otherwise specified, all parts and percentages are by weight. Ingredients The following ingredients were used in the examples provided hereafter: Methyl methacrylate available from Rohm and Haas; Poly (methyl methacrylate) (MW 270,000) available from Rohm America Inc. under the trademark and designation, DEGALON LP51 / 07; poly (methylmethacrylate) pm of 996,000 available from Aldrich; fumed silica available from Cabot Corporation under the trademark and designation CAB-O-SILMR TS-720; acrylic acid available from Sigma Aldrich; methacrylate-butadiene-styrene PARALOIDMR BTA 753 (ER) and copolymer, available from Rohm & Haas Company; chlorosulfonated polyethylene HYPALONMR 20 available from Dupont-Dow Elastomers; glass bubbles SCOTCHLITEMR VS5500 available from 3M. Amido-borate 1 Amido-borate 2 Amido-borate 3 Amido-borate 4 F N (CH3) 4 Amido-borate 5 The Amido-borate 6 was amido-borate 5 mixed with 30 percent mole of methoxypropyl amine based on the boron equivalents present. Amido-borate 7 (CHjCH? - I i? N (CH Amido-borate 8 The Amido-borate 8 was mixed with 30 percent mole of methoxypropyl amine based on the boron equivalents present.

Amido-borate 9 Amido-borate 10 Amido-borate 10 was mixed with 30 percent mole of methoxypropyl amine based on the boron equivalents present. Amido-borate 1 1 The Amido-borate 1 1 was mixed with 30 percent mole of methoxypropyl amine based on the boron equivalents present. Amido-borate 12 The Amido-borate 12 was mixed with 30 mole percent of methoxypropyl amine based on the boron equivalents present. Amido-borate 13? l? tfa Amido-borate 14 The Amido-borate 14 was mixed with 30 mole percent of methoxypropyl amine based on the boron equivalents present. Synthesis of Amido-borates It is understood that the present invention is operable in the absence of any component that has not been specifically described. Unless otherwise indicated, all parts and percentages are expressed on a weight basis. The term "overnight", if used refers to a time of about 16-18 hours, "room temperature", if used, refers to a temperature of about 20-25 ° C. All reagents were purchased from Aldrich and all solvents were purified using the technique described by Pangborn et al, Orsanometallics, 15, 1518-1520, (1996). All compounds, solutions and reactions were handled under an inert atmosphere (dry box), the NMR changes of 1 H and 13 C were referenced to internal solvent resonances and reported with respect to TMS. Example 1 Preparation of Amido-borate 1 Lithium dimethylamidotriethylborate To a slurry of solid lithium dimethylamide (2.55 g, 50 mmol) in 30 mL of THF was slowly added triethylborane (4.90 g, 50 mmol) by syringe and the resulting mixture was stirred for 5 hours at room temperature. The solvent was removed in vacuo to provide a white solid. The crude product was further washed with hexane and dried under vacuum for 2 hours to give the desired product (86 percent yield). The spectroscopic data are as follows: 1 H NMR (C6D6, 23 ° C): d 3.89 (s br, 6 H), 1.90 (t, 9 H, CH2Me), 0.42 (q, 6 H, CH2Me). Preparation of Amido-borate 5 To a slurry of the solid imidazole sodium salt, (4.5 g, 50 mmol) in 30 mL of THF was slowly added triethylborane (9.80 g, 100 mmol) by syringe for 45 minutes and the resulting mixture was stirred overnight at room temperature. The solvent was removed under vacuum to provide brown oil. The crude product was used without further purification (98 percent yield). Preparation of Amido-borate 8 To a slurry of sodium imidazole (9.006 g, 100 mmol) and tetramethylammonium chloride (10.96 g, 100 mmol) in 200 mL of THF was slowly added triethylborane (19.6 g, 200 mmol) by one syringe for 60 minutes and the resulting mixture was stirred overnight at room temperature. The formed salts were filtered and washed with 25 mL of THF twice. The filtrate solvent was removed in vacuo to provide the desired product as brown oil. The crude product was used without further purification (88 percent yield). Preparation of Amido-borate 9 To a slurry of the solid, sodium salt of 2-methyl imidazole, (5.205 g, 50 mmol), prepared by the reaction of 2-methyl imidazole with a stoichiometric amount of NaH in THF, in 30 mL of THF was added slowly triethylborane (9.81 g, 100 mmol) by syringe for 45 minutes and the resulting mixture was stirred overnight at room temperature. The solvent was removed under vacuum to provide brown oil (14.35 g, 95.6 percent yield). The crude product was used without further purification. Preparation of Amido-borate 10 To a slurry of sodium salt of imidazole (9.006 g, 100 mmol) and tetrabutylammonium chloride (27.90 g, 100 mmol) in 200 mL of THF was slowly added triethylborane (19.6 g, 200 mmol) via one syringe for 60 minutes and the resulting mixture was stirred overnight at room temperature. The formed salts were filtered and washed twice with 25 mL of THF. The filtrate solvent was removed in vacuo to provide the desired product as brown oil (43.9 g, 86.7 percent). Preparation of Amido-borate 1 1 To a slurry of sodium salt of imidazole (9.006 g, 100 mmol) and tetrabutyphosphonium bromide (34.1 g, 100 mmol) in 200 mL of THF was slowly added triethylborane (19.6 g, 200 mmol) by syringe for 60 minutes and the resulting mixture was stirred overnight at room temperature. The formed salts were filtered and washed twice with 25 mL of THF. The filtrate solvent was removed in vacuo to provide the desired product as brown oily solids. The crude product was used without further purification (46.6 g, 89.1 percent yield). Preparation of Amido-borate 12 To a slurry of sodium salt of imidazole (4.5 g, 50 mmol) and tetraphenylphosphonium bromide (21 g, 50 mmol) in 200 mL of THF was slowly added triethylborane (9.8 g, 100 mmol) by one syringe for 60 minutes and the resulting mixture was stirred overnight at room temperature. The formed salts were filtered and washed twice with 25 mL of THF. The filtrate solvent was removed in vacuo to provide the desired product as brown solids. The crude product was used without further purification (27 '.47 g, 91.2 percent yield). Preparation of Amido-borate 13 To a solution of triethylborane (4.9 g, 50 mmol) in 30 mL of THF was slowly added 3-methoxypropylamine (4.5 g, 50.5 mmol) by syringe for 15 minutes and then sodium hydride was added ( 1.22 g, 50.8 mmol) to the resulting mixture. The slurry was then gently refluxed overnight. The solvent was removed in vacuo to provide an off white solid which was washed with hexanes and dried (9.32 g, 89.1 percent yield). The crude product was used without further purification. Preparation of Amido-borate 14 To a slurry of sodium salt of imidazole (4.5 g, 50 mmol) and hexamethyl-l, 2-ethanediaminium diiodide (10.1 g, 25.2 mmol), prepared by reacting tetramethylethylenediamine with excess iodide of methyl, in 200 mL of THF, triethylborane (9.8 g, 100 mmol) was added slowly by syringe for 60 minutes and the resulting mixture was stirred overnight at room temperature. The formed salts were filtered and washed twice with 25 mL of THF. The filtrate solvent was removed in vacuo to provide the desired product as brown solids. The crude product was used without further purification (13.3 g, yield of 79.2 percent). Preparation of Adhesive Compositions Formulations of two parts were prepared by mixing the ingredients for each part, which were then placed in separate containers. Several different formulations of part B (hardener side) were prepared. Part A - Resin The following ingredients were added to a metal can of 3. 79 liters (1 gallon) were stirred in a ball mixer for 24 to 72 hours. For amido-borates 1 to 8, the ingredients were 63 parts of methyl methacrylate, 18 parts of polymethyl methacrylate (270,000 mw), and 5 parts of chlorosulfonated polyethylene (HYPALONMR 20 mw). 86 parts of the mixed ingredients were added to a 236 mL (8 oz) plastic cup. The ingredients were thoroughly mixed by hand using a tongue ablaze for 3 minutes. Two parts of glass bubbles and two parts of fumed silica were added and the ingredients were completely mixed by hand using a tongue swath for 3 minutes. 10 parts of acrylic acid were added and the ingredients were completely mixed by hand using a tongue-swath for 3 minutes. The resulting mixture was packed in a 236 mL (8 oz) plastic cup. For amido-borates 9 to 14, the ingredients were 58.7 parts of methyl methacrylate, 16.3 parts of methacrylate-butadiene-styrene copolymer, 15.2 parts of chlorosulfonated chlorinated polyethylene, 0.25 parts of methyl ether of hydroquinone and 9.5 parts of methacrylic acid. All resin formulations were mixed using a dual asymmetric centrifugal mixer FlackTek SpeedMixer ™ DAC 400 FVZ from Hauschild Engineering. The chlorinated polyethylene was combined with methyl methacrylate (MMA) in a premix in a ratio of 40 percent chlorinated chlorinated polyethylene to 60 percent MMA using a mixer or roll mill. The chlorosulfonated chlorinated polyethylene MMA premix was added to a mixing speed cup followed by methyl methacrylate and methoxyphenol (MEHQMR). The methacrylate-butadiene-styrene copolymer was then added to the speed mixing cup and was immediately incorporated with the other ingredients by hand using a tongue-swath. The speed mixing cup was placed in the speed mixer three times consecutively for 1 minute at a speed of 1, 800 rpm.

Part B - Hardener For amido-borates 1 to 8, Part B (hardener side) comprised of 633 parts of methyl methacrylate, 180 parts of polymethylmethacrylate), 45 parts of styrene-butadiene-styrene block copolymers were placed in a can of half gallon paint and stirred in a cylinder mill overnight. Once the polymers were dissolved in a homogenous mixture, 85.8 parts were placed in a 236 mL (8 oz) plastic container and 2 parts of fumed silica and 2 parts of glass beads were added and mixed by hand using a abatelenguas Finally 10 parts of amido-borate were added to the vessel and mixed. For the amido-borates 6 and 8, 30 mol percent of methoxypropyl amine was added to the hardener side, based on the moles of amido-borate present. For amido-borates 9 to 14, Part B was comprised of 65 percent methyl methacrylate, 25 percent methacrylate-butadiene-styrene copolymer, 0.25 percent IRGASTABMR FS301 FF which is IRGASTABMR FS301 FF- A mixture of bis ( hydrogenated tallow alkyl) oxidized amines (IRGASTABMR FS042) and tris (2,4-di-tert-butylphenol) phosphate trademark of Ciba Specialty Chemicals and 10 parts of a complex of tri-n-butyl borane and methoxypropyl amine. Various formulations of Part A were prepared using the procedures described above. The formulations are described in the following Table 1. The adhesives as described above were tested to determine the splicing strength according to ASTM D3165-91 in the substrates listed below at different times of application as indicated below. The covered and superimposed surface area was 2.54 cm (1 inch) wide by 1.27 cm (Á inch) long. Union thickness of 0.76 mm (30 mils) was maintained using 0.76 mm (30 mil) glass beads. The samples were stretched on an Instron 5500 to a speed of 1.27 cm (Yt inch) per minute until failure and tension to failure was recorded in pounds per square inch. The results are summarized in the following Table 1. The surfaces of the substrates were not pre-treated. The samples were cured for three days at room temperature and evaluated at room temperature (approximately 23 ° C). The polypropylene substrate was 30 percent polypropylene filled with long glass fiber available from Dow Chemical Company under the designation, DLGF 9310. OOZ (30 percent filled with long fiberglass). The e-coated substrate is ACT cold rolled steel, ED 6100 from ACT Laboratories, Inc., Hillsdale, Michigan. Regarding the form of defect or failure: Cohesive failure means that the break occurred in the adhesive; and Adhesive failure means that the adhesive was torn off the substrate. Substrate failure means that the substrate broke before the bond of the adhesive failed or broke cohesively; and SD represents delamination of the substrate and means that a layer of the substrate is peeled off. Viscosities or some of the formulations were evaluated in accordance with the ASTM D2196 Brookfield viscometer procedure, 20 rpm, and needle number 7 at 25 ° C. The results are summarized in the Table.

SD means substrate delamination. PP means polypropylene is the substrate. E-coating means that the substrate is an e-coated metal panel. The examples illustrate that amido-borates are capable of curing acrylic adhesives and bonding substrates of low energy.

Claims (27)

1. CLAIMS 1. A compound comprising one or more tetravalent boron anions and one or more of: i) an organic compound containing a nitrogen atom and a cation or ii) an ammonium cation; wherein each of the one or more tetravalent boron atoms is bonded to the nitrogen atom of an ammonium cation or to an organic compound containing at least one nitrogen atom.
2. 2. A compound according to claim 1 comprising at least one amido-borate which comprises a tetravalent boron anion wherein the boron anion is bonded to the nitrogen atom or to an organic compound containing one or more carbon atoms. nitrogen and one or more cations with the proviso that the number of borate anions and cations is the same.
3. 3. A compound according to claim 1 comprising one or more amido-borates containing a tetravalent boron anion bonded to an ammonium cation.
4. A compound according to claim 1 comprising two or more amido-borates each comprising a tetravalent boron anion wherein at least one of the borate anions is bonded to the nitrogen atom of an organic compound; and at least one of the borate anions is bonded to the nitrogen of an ammonium cation; and one or more additional cations wherein the number of additional cations is the same as the number of tetravalent boron atoms bonded to the nitrogen atom of organic compounds containing at least one nitrogen atom.
5. 5. A compound according to claim 1 wherein the amido-borate corresponds to one of the formulas: (R3) * R1 is independently in each occurrence an alkyl or cycloalkyl group, or two or more of R1 may be combined to form a cycloaliphatic ring; R2 is independently in each occurrence an alkyl, cycloalkyl, aryl, alkaryl, or aralkyl group optionally containing one or more heteroatoms or protons; R3 is independently in each occurrence hydrogen, an alkyl or aryl group which may optionally contain one or more heteroatoms; R4 is independently in each occurrence a portion of divalent hydrocarbyl which may optionally contain one or more heteroatoms; R5 is independently in each occurrence a t-valent hydrocarbyl group; X is independently in each occurrence a cation; And it is independently in each occurrence-rHR ^ or -P (R2) 3; Z is independently in each occurrence N, P, Si or C; p is independently in each occurrence 0 or 1; q is independently in each occurrence 1 or 2; with the proviso that the sum of p and q in each pair of bound boron and nitrogen is 2 and the sum of p and q is 1 or 2; where q is 2, the nitrogen to which it is bound is quaternary and carries a positive charge that balances the negative charge found in boron boron and a cation is not necessary to neutralize the borate; t is independently in each occurrence 2 or greater; and w is independently in each occurrence either 0 or 1.
6. 6. Compounds according to claim 5, wherein: R1 is independently at each occurrence a C1-10 alkyl, C3-10 cycloalkyl, or two or more of R1 can be combined to form a cycloaliphatic ring; R2 is independently at each occurrence C 1 -10 alkyl, C 3 - 0 cycloalkyl, C 6 - 2 aryl, C 7,20 alkaryl or C 7,20 aralkyl wherein such groups may optionally contain one or more O heteroatoms or S or functional portions containing O or S; R3 is independently at each occurrence hydrogen, C1_0 alkyl, C3.20 cycloalkyl, C6.20 aryl, C7-2alkaryl or C7.20 aralkyl optionally containing one or more heteroatoms or functional portions containing heteroatom; R5 is independently in each occurrence a t-valent alkylene group; X is independently on each occurrence an onium or an alkali metal ion; And it is independently in each occurrence -GHR2 ^; Z is independently in each occurrence N or C; and t is 2 or 3.
7. 7. Compounds according to claim 6 wherein: R1 is independently at each occurrence C1- alkyl; R 2 is independently at each occurrence C 1-4 alkyl, or C 1-10 alkoxyalkyl; R3 is independently in each occurrence hydrogen, C, alkyl. or C1.10 alkoxyalkyl; R4 is independently at each occurrence alkylene of C2-20, or alkylene of C2-20 containing one or more oxygen atoms; R5 is independently in each occurrence an alkylene portion of t-valent C2.e; X is an ammonium, phosphonium, sodium or lithium ion; and t is 2
8. 8. Compounds according to claim 7 wherein: R1 is independently at each occurrence C2.4 alkyl; R2 is independently at each occurrence methyl, ethyl, propyl, methoxypropyl, alkoxypropyl or propoxypropyl; R3 is independently in each occurrence hydrogen, methyl, ethyl or propyl; R4 is independently in each occurrence alkylene of C2-; R5 is a divalent C2-4 alkylene group; and X is tetraethyl ammonium, tetraethyl phosphonium, tetraphenyl phosphonium, sodium or lithium.
9. 9. Compounds according to claim 5 which correspond to one of the formulas (R3) * wherein R1 is independently at each occurrence an alkyl or cycloalkyl group, or two or more of R1 can be combined to form a cycloaliphatic ring; R2 is independently in each occurrence an alkyl, cycloalkyl, aryl, alkaryl, or aralkyl group optionally containing one or more heteroatoms or functional portions containing heteroatoms or protons; R3 is independently in each occurrence hydrogen, an alkyl or aryl group which may optionally contain one or more heteroatoms or heteroatom-containing functional portions; R4 is independently in each occurrence a divalent hydrocarbyl portion which may optionally contain one or more heteroatoms or heteroatom-containing functional portions; X is independently in each occurrence a cation; Z is independently in each occurrence N, P, Si or C; p is independently in each occurrence 0 or 1; q is independently in each occurrence 1 or 2; with the proviso that the sum of p and q in each pair of bound boron and nitrogen is 2; and the sum of p and q is 1 or 2 where q is 2, the nitrogen atom is the cation that balances the borate anion; w is independently in each occurrence either 0 or 1.
10. 10. Amido-borates according to claim 1 which correspond to one of the formulas: R1 is independently in each occurrence an alkyl or cycloalkyl group, or two or more of R1 may be combined to form a cycloaliphatic ring; R2 is independently in each occurrence an alkyl, cycloalkyl, aryl, alkaryl, or aralkyl group optionally containing one or more heteroatoms or functional portions containing heteroatoms or protons; R3 is independently in each occurrence hydrogen, an alkyl or aryl group which may optionally contain one or more heteroatoms or functional portions containing heteroatoms; R4 is independently in each occurrence a divalent hydrocarbyl portion which may optionally contain one or more heteroatoms or heteroatom-containing functional portions; R5 is independently in each occurrence a t-valent group; R5 is a t-valent hydrocarbylene group optionally containing one or more heteroatoms or heteroatom-containing functional portions; X is independently in each occurrence a cation; t is independently in each occurrence 2 or greater; And it is independently in each occurrence -IHR2 ^ or -P (R2) 3; Z is independently in each occurrence N, P, Si or C; p is independently in each occurrence 0 or 1; q is independently in each occurrence 1 or 2; with the proviso that the sum of p and q in each pair of bound boron and nitrogen is 2; and w is independently in each occurrence either 0 or 1.
11. Compounds according to claim 10 wherein: R1 is independently at each occurrence a C1-10 alkyl, C3.10 cycloalkyl, or two or more R1 they can be combined to form a cycloaliphatic ring; R 2 is independently at each occurrence C 1-10 alkyl, C 3-10 cycloalkyl, C 6-12 aryl, C 7,20 alkaryl or C 7-2 aralkyl wherein such groups may optionally contain one or more O or S heteroatoms or functional portions containing O or S; R3 is independently at each occurrence hydrogen, C1-10 alkyl, C3-2o cycloalkyl, C6-2o aryl, C7-2alkaryl or C7-2alkaryl optionally containing one or more heteroatoms or functional portions containing heteroatom; R5 is independently in each occurrence a t-valent alkylene group; X is independently on each occurrence an onium or an alkali metal ion; And it is independently in each occurrence -faR2; Z is independently in each occurrence N or C; and t is 2 or 3.
12. 12. Compounds according to claim 1 wherein: R1 is independently at each occurrence C1-4 alkyl; R2 is independently at each occurrence alkyl of C? 4, or alkoxyalkyl of C ^ o; R3 is independently at each occurrence hydrogen, C1-4 alkyl or C1-10 alkoxyalkyl; R4 is independently at each occurrence alkylene of C2.20, or alkylene of C2-20 containing one or more oxygen atoms; R5 is independently at each occurrence an alkylene portion of t-valent C2-6; X is an ammonium, phosphonium, sodium or lithium ion; and t is 2
13. 1 3. Compounds according to claim 12, wherein: R1 is independently at each occurrence C2- alkyl; R2 is independently at each occurrence methyl, ethyl, propyl, methoxypropyl, ethoxypropyl or propoxypropyl; R3 is independently in each occurrence hydrogen, methyl, ethyl or propyl; R4 is independently in each occurrence alkylene of C2-; R5 is an alkylene group of C2-divalent; and X is tetraethyl ammonium, tetraethyl phosphonium, tetraphenyl phosphonium, sodium or lithium.
14. 14. An amido-borate according to claim 1 corresponding to the formula
15. 15. A compound according to claim 5 corresponding to the formula
16. 16. A compound according to claim 1 corresponding to the formula
17. 17. A compound according to claim 5 corresponding to the formula F N (CH3) 4
18. 18. A compound according to claim 5 corresponding to the formula
19. 19. A compound according to claim 5 corresponding to the formula. N (CH
20. 20. A compound according to claim 5 corresponding to the formula
21. 21. An amido-borate according to claim 5 corresponding to the formula
22. 22. A compound according to claim 5 corresponding to the formula
23. 23. An amido-borate according to claim 5 corresponding to the formula
24. 24. An amido-borate according to claim 5 corresponding to the formula
25. 25. An amido-borate according to claim 5 corresponding to the formula
26. 26. An amido-borate according to claim 5 corresponding to the formula. (Cí% a ^ -t.Nita% -cife-c3r 0C? 3
27. 27. An amido-borate according to claim 5 corresponding to the formula