MXPA01006757A - Accelerators useful for energy polymerizable compositions - Google Patents

Abstract

Accelerators that can be useful for an energy polymerizable composition comprising a cationically curable material;energy polymerizable compositions comprising at least one cationically curable material and an initiation system therefor, the initiation system comprising at least one organometallic complex salt and at least one accelerator;and a method for curing the compositions. The cured compositions can provide useful articles. The invention also provides compositions of matter comprising an organometallic complex salt and at least one compound selected from the Class 1 and Class 2 compounds disclosed herein.

Description

USEFUL ACCELERATORS FOR ENERGY POLARIZABLE COMPOSITIONS FIELD OF THE INVENTION This invention is concerned with accelerators that may be useful for energy polymerizable compositions comprising a cationically curable material; energy-polymerizable compositions comprising a cationically curable material and a two-component initiator system, such an initiator system comprises at least one organometallic complex salt and at least one accelerator and with a method for curing the compositions. This invention is also concerned with the preparation of articles comprising the cured compositions. In addition to other uses, the compositions are useful as molded articles, as coating compositions including abrasion resistant coatings, as adhesives including structural adhesives and as binders for abrasives and magnetic media. The invention is also concerned with compositions of matter comprising an organometallic complex salt and at least one compound selected from the Class 1 and Class 2 compounds described herein. FEF: 130834 BACKGROUND OF THE INVENTION Transition metal salts comprising an organometallic cation and a non-nucleophilic counter anion have shown utility as photochemically activated initiators for cationic addition polymerization. These photoinitiator salts include salts of (cyclopentadienyl) (aren) iron * of the anions PF6 ~ and SbF6.

Similarly, it is known that certain classes of these salts are thermally activatable curing agents for cationic polymerizations. For many commercial applications, the monomers that are polymerized are often multifunctional (that is, they contain more than one polymerizable group per molecule), for example, epoxides, such as bisphenol A glycidyl ethers (DGEBA). Mixtures of multifunctional monomers such as epoxides and polyalcohols (polyols) or polyepoxides and polyalcohols can undergo acid-catalyzed polycondensation via a gradual mechanism. Also included in this description are multi-active monomers - those comprising two or more kinds of reactive groups. In many applications, photoinduced polymerization is impossible, is not practical or is undesirable.

For example many situations arise where the polymerization reactions in a closed environment (ie, in a mold or in a rolled product) or where the polymerizable compositions may contain opacifying pigments, the thermally activated initiators are preferred. The thermally activated initiators, such as the known organometallic salts, can be used to initiate the polymerization in these cases. There is a continuing need to have the ability to modify the polymerization rate and temperature of the polymerizable compositions by energy to meet the needs of specific applications.

BRIEF DESCRIPTION OF THE INVENTION The present invention is concerned with accelerators that can be used to influence the temperature at which the polymerization of a polymerizable composition by energy comprising a cationically curable material occurs. In particular, the accelerators of this invention can be used to reduce the polymerization temperature or allow modification of the rate or degree of polymerization at a given temperature of cationically polymerizable materials when organometallic salt initiators are used in cationic polymerization. Briefly, in one aspect, this invention provides a method comprising the step of using an accelerator and at least one salt of an organometallic complex cation to increase the speed or reduce the curing temperature of an energy polymerizable composition comprising a material cationically curable, wherein said cation comprises at least one carbon atom linked to a transition metal atom and wherein such an accelerator or an active portion thereof comprises at least one compound selected from Classes 1 and 2: the class 1 comprises compounds represented by Formula III and class 2 comprises compounds represented by Formula IV. In another aspect, this invention provides an energy polymerizable composition comprising: (a) at least one cationically curable material; (b) a two-component initiator system comprising: (1) at least one salt of an organometallic complex cation wherein said cation contains at least one carbon atom bonded to a transition metal atom. (2) at least one accelerator or active portion thereof of Classes 1 and 2 wherein class 1 comprises compounds represented by formula III herein and class 2 comprises compounds represented by formula IV herein.

In other aspects, the invention provides an energy polymerizable composition with one or more of the following optional components: (a) at least one of a material containing alcohol and additional adjuvants; (b) stabilizing ligands to improve shelf life; (c) at least one film-forming thermoplastic oligomer or polymer resin, essentially free of nucleophilic groups, such as amine, amide, nitrile, sulfur or phosphorous functional groups or metal complexing groups, such as carboxylic acid and sulfonic acid. (d) coupling agents to modify the adhesion. In another aspect, the invention provides a process for controlling or modifying the curing of a composition, comprising the steps of: (a) providing the energy polymerizable composition of the invention, (b) adding sufficient energy to the composition in the form of at least one of heat and light, in any combination and order, to polymerize the composition. In another aspect, this invention provides an article comprising a substrate having on at least one surface thereof a layer of the composition of the invention. The article can be provided by a method comprising the steps of: (a) providing a substrate, (b) coating the substrate with the curable composition of the invention and optionally adjuvant, and (c) providing sufficient energy to the composition in the form of at least one of heat and light in any combination and order to polymerize the composition. In another aspect, this invention provides a composition of matter comprising: (1) at least one salt of an organometallic complex cation, wherein said cation contains at least one carbon atom bonded to a transition metal atom and ( 2) at least one compound or active portion thereof, of classes 1 and 2 wherein class 1 comprises compounds represented by Formula III herein and class 2 comprises compounds represented by Formula IV herein. As used in this application: "energy-induced curing" means curing or polymerization by means of heat or electromagnetic radiation (ultraviolet, visible or electron beam) or electromagnetic radiation in combination with thermal means (infrared and heat), in such a manner that heat and light are used simultaneously or in any sequence, for example, heat followed by light, light followed by heat followed by light; "Catalytically effective amount" means a quantity sufficient to effect polymerization of the curable composition to a product polymerized at least to a degree to cause an increase in the viscosity of the composition under the specified conditions; "organometallic salt" means an ionic salt of an organometallic complex cation, wherein the cation comprises at least one carbon atom of an organic group that is bonded to a metal atom of the transition metal series of the periodic table of the elements ("Basic Inorganic Chemistry," FA Cotton, G. Wilkinson, Wiley, 1916, p.497); "initiator" and "catalyst" are used interchangeably and mean at least one salt of an organometallic complex cation which can change the rate of a chemical reaction; "cationically curable monomer" means at least one epoxide-containing material or material containing vinyl ether; "polymerizable composition" or "curable composition" as used herein means a mixture of the initiator system and the cationically curable monomer; alcohols and adjuvants may optionally be present; "polymerizing" or "curing" means supplying sufficient energy to a composition in the form of at least one of heat and light in any order or combination to alter the physical state of the composition, to cause it to transform from a fluid to a state less fluid, to advance from an adherent to a non-adherent state, to advance from a soluble to an insoluble state or to decrease the amount of polymerizable material by its consumption in a chemical reaction; "initiation system", "initiator system" or "two-component initiator" means at least one salt of an organometallic complex cation and at least one accelerator, the system is capable of initiating the polymerization; "accelerator" means at least one of the specified classes of compounds that moderate the curing of a composition of the invention by reducing the polymerization temperature or allowing an increase in the rate or degree of polymerization at a given temperature; "epoxy-containing" means a material comprising at least one epoxy and may further comprise accelerating additives, stabilizing additives, fillers, diols and other additives; "group" or "compound" or "ligand" means a chemical species that allows substitution or that can be substituted by conventional substituents that do not interfere with the desired product, for example the substituents may be alkyl, alkoxy, aryl, phenyl, halo (F, Cl, Br, I), cyano, nitro, etc. and "epoxy / polyol" and "catalyst / additive", etc., mean combinations of the substances on both sides of the diagonal ("/"). An advantage of at least one embodiment of the present invention is that the initiator system can initiate the curing of a thermally or photopolymerizable composition at temperatures lower than those required for the reactions initiated without the accelerators of the present invention. Another advantage of at least one embodiment of the invention is that the initiator system can provide improved curing of a thermally polymerizable or photopolymerizable composition at a given temperature. For example, at a given temperature, the curing time may be reduced compared to the cure times for the reactions initiated without the accelerators of the invention.

Yet another advantage of at least one embodiment of the invention is the ability to affect a color change in the curable composition upon activation of a catalyst in the composition or as the composition changes from an uncured state to a cured state. .

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 illustrates the change in start temperature, peak temperature, final temperature and final exothermic energy for a composition of the invention comprising a mixture of 88: 6: 6% by weight of EPON 288/1, 6-hexanediol / 1,4-CHDM cured with CpFeXylSbF6 catalyst and 0.1 and 2% by weight of propyl gallate. Peak temperatures of 115.3 ° C, 113.0 ° C and 98.74 ° C correspond to per hundred weight propyl gallate of 0.1 and 2 respectively.

DETAILED DESCRIPTION The present invention provides an energy polymerizable composition comprising at least one cationically polymerizable material and an initiation system therefor, the initiation system comprising at least one organometallic complex salt and at least one accelerator. The cured composition provides useful articles or coated articles.

The epoxy compounds which can be cured or polymerized by the process of this invention are those known to undergo cationic polymerization and include cyclic 1,2-, 1,3- and 1,4-ethers (also designated as 1,2- , 1,3- and 1,4-epoxides). See "Encyclopedia of Polymer Science and Technology", 6, (1986), p. 322, for a description of suitable epoxy resins. In particular, cyclic ethers that are useful include cycloaliphatic epoxies such as cyclohexene oxide and the type of ERL series resins available from Union Carbide, New York, NY, such as vinylcyclohexene oxide, vinylcyclohexene dioxide, carboxylate 3, 4 -epoxycyclohexylmethyl-3, 4-epoxycyclohexane, bis- (3,4-epoxycyclohexyl) adipate and 2- (3,4-epoxycyclohexyl-5, 5-spiro-3,4-epoxy) cyclohexen-meta-dio- xano; Also included are the glycidyl ether type epoxy resins such as propylene oxide, epichlorohydrin, styrene oxide, glycidol, the EPON type series of epoxy resins available from Shell Chemical Co. , Houston, TX, which include diglycidyl ether of bisphenol A and chain extender versions of this material such as EPON 828, EPON 1001, EPON 1004, EPON 1007, EPON 1009 and EPON 2002 or their equivalents from other manufacturers , cyclopentadiene dioxide, epoxidized vegetable oils such as epoxidized linseed oil and soybean oil available as VIKOLOX and VIKOFLEX resins from Elf Atochem North America, Inc., Philadelphia, PA, epoxidized KRATON LIQUID polymers, such as L-207 available from Shell Chemical Co. , Houston, TX, epoxidized polybutadienes such as POLY BD resins from Elf Atochem, Philadelphia, PA, 1,4-butanediol diglycidyl ether, phenol formaldehyde polyglycidylether, epoxidized phenolic novolac resins such as DEN 431 and DEN 438 available from Dow Chemical Co. , Midland MI, epoxidized cresol novolac resins such as ARALDITE ECN 1299 available from Ciba, Hawthorn, NY, resorcinol diglycidylether and epoxidized polystyrene / polybutadiene blends such as EPOFRIEND resins such as EPOFRIEND A1010 available from Daicel USA Inc., Fort Lee, NJ and diglycidyl ether of resorcinol. Preferred epoxy resins include the type of ERL resins especially 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, bis- (3,4-epoxycyclohexyl) adipate and 2- (3,4-epoxycyclohexyl-5,5-spiro- 3, 4-epoxy) cyclohexen-meta-dioxane and bisphenol A EPON-type resins in which 2, 2-bis- [p (2,4-epoxypropoxy) phenylpropane] and extended chain versions of this material are included. It is also within the scope of this invention to use a combination of more than one epoxy resin. It is also within the scope of this invention to use one or more epoxy resins combined together. The different kinds of resins can be present in any proportion. It is within the scope of this invention to use vinyl ether monomers as the cationically curable material. The monomers containing vinyl ether can be methyl vinyl ether, ethyl vinyl ether, tert-butyl vinyl ether, isobutyl vinyl ether, divinyl triethylene glycol ether (RAPI-CURE DVE-3, available from International Specialty Products, Wayne, NJ), 1,4-cyclohexanedimethanol divinyl ether (RAPI-CURE CHVE, International Specialty Products), trimethylolpropane trivinyl ether (TMPTVE, available from BASF Corp., Mount Olive, NJ) and VECTOMER divinyl ether resins from Allied Signal, such as VECTOMER 2010, VECTOMER 2020, VECTOMER 4010 and VECTOMER 4020, or their equivalents of other manufacturers. It is within the scope of this invention to use a combination of more than one vinyl ether resin. It is also within the scope of this invention to use one or more epoxy resins combined in combination with one or more vinyl ether resins. The different kinds of resins can be present in any proportion.

Bifunctional monomers can also be used and examples that are useful in this invention possess at least one cationically polymerizable functionality or a functionality that copolymerizes with cationically polymerizable monomers, for example functionalities that will allow a copolymerization of epoxy-alcohol. When two or more polymerizable compositions are present, they may be present in any proportion. Suitable salts of organometallic complex cations of the initiator system include, but are not limited to, those salts described in U.S. Patent No. 5,089,536 (column 2, line 48 to column 16, line 10). In preferred compositions of the invention, the organometallic complex salt of the initiator system is represented by the following formula: wherein: M is selected from the group containing Cr, Ni, Mo, W, Mn, Te, Re, Faith, Ru, Os, Co, Rh and Go; L1 represents the same or different ligands that contribute to pi electrons that can be selected from aromatic compounds and heterocyclic aromatic compounds and the ligand is capable of contributing six pi electrons to the valence shell of M; L2 represents the same or different ligands that contribute pi electrons that can be selected from cyclopentadienyl and indenyl anion groups and the ligand is capable of contributing six pi electrons to the valence shell of M; q is an integer that has a value of 1 or 2, the residual charge of the complex cation; y and z are integers that have a value of zero, one or two provided that the sum of y and z equals 2; X is an anion selected from tris- (highly fluorinated alkyl) sulfonyl, bis- (highly fluorinated alkyl) sulfonyl imide, tris- (fluorinated aryl) sulphonyl methanide, tetrakis- (fluorinated aryl) borate, organic sulfonate anions and complex anions containing halogen of a metal or metalloid and n is an integer having a value of 1 or 2, the number of complex anions required to neutralize the charge q on the complex cation. Ligands L1 and L2 are well known in the art of organometallic compounds of transition metals. Ligand L1 is provided by any monomeric or polymeric compound having an aromatic group accessible independently of the total molecular weight of the compound. "Accessible" means that the compound (or precursor compound from which the accessible compound is prepared) carrying the unsaturated group is soluble in a reaction medium, such as an alcohol, for example methanol; a ketone, for example methyl ethyl ketone; an ester, for example, amyl acetate; a halocarbon, for example, trichloro ethylene; an alkane, for example decalin; an aromatic hydrocarbon, for example anisole; an ether, for example tetrahydrofuran or that the compound is divisible into very fine particles of high surface area such that the unsaturated group (ie, the aromatic group) is sufficiently close to the metal to form a pi bond between the unsaturated group and M. Polymeric compound means as explained hereinafter, that the ligand can be a group on a polymer chain. Illustrative of ligand L1 are substituted and unsubstituted carbocyclic and heterocyclic aromatic ligands having up to 25 rings and up to 100 carbon atoms and up to 10 heteroatoms selected from nitrogen, sulfur, non-peroxygen, phosphorus, arsenic, selenium, boron, antimony, tellurium , silicon, germanium and tin, such as for example eta6-benzene, eta6-mesitylene, eta6-toluene, eta6-p-xylene, eta6-o-xylene, eta6-m-xylene, eta6-cumene, eta6-durene, eta6 -pentamethylbenzene, eta6-hexamethylbenzene, eta6-fluorene, eta6-naphthalene, eta6-anthracene, eta6-perylene, eta-criene, eta-pyrene, eta-triphenylmethane, etac-paracyclopane and eta -carbazole. Other appropriate aromatics can be found by consulting any of the many chemical manuals. Illustrative of L2 ligands are ligands derived from substituted and unsubstituted eta5-cyclopentadienyl anion, for example anion eta5-cyclopentadienyl, anion eta6-methylcyclopentadienyl, anion eta3-pentamethyl-cyan-pentadienyl, anion eta5-trimethylsilylcyclopenta-dienyl, anion eta5-trimethyltin cyclopentadienyl, anion eta5-tri-phenyltin cyclopentadienyl, anion eta5-triphenylsilyl-cyclopentadienyl and anion eta5 -indenyl. Each of the ligands L1 and L2 can be substituted by groups that do not interfere with the complexing action of the ligand on the metal atom or that do not reduce the solubility of the ligand to the extent that competition with the metal atom is not carried out . Examples of substituent groups, all of which preferably have less than 30 carbon atoms and up to 10 heteroatoms selected from nitrogen, sulfur, non-peroxygen, phosphorus, arsenic, selenium, antimony, tellurium, germanium, tin and boron, include hydrocarbyls such as methyl, ethyl, butyl, dodecyl, tetracosanyl, phenyl, benzyl, allyl, benzylidene, ethenyl and ethynyl; cyclohydrocarbyl such as cyclohexyl; hydrocarbyloxy groups such as methoxy, butoxy and phenoxy; hydrocarbyl mercapto groups such as methylmercapto (thiomethoxy), phenylmercapto (thiophenoxy); hydrocarbyloxycarbonyl such as methoxycarbonyl and phenoxycarbonyl; hydrocarbylcarbonyl such as formyl, acetyl and benzoyl, hydrocarbylcarbonyloxy such as acetoxy and cyclohexanecarbonyloxy; hydrocarbylcarbonamido, for example acetamido, benzamido; azo; borilo; halo, for example, chlorine, iodine, bromine and fluorine; hydroxy; cyano; nitro; nitrous; oxo; dimethylamino; diphenylphosphino; definilarsino; diphenylstein; trimethylgerman; tributyltin; methylselene; ethyltride and trimethylsiloxy. Ligands L1 and L2 can independently be a unit of a polymer. L1 for example may be the phenyl group in polystyrene or polymethylphenylsiloxane or the carbazole group in polyvinylcarbazole. L2 can be for example the cyclopentadiene group in poly (vinylcyclopentadienes). Polymers having a weight average molecular weight of up to 1,000,000 or more can be used. It is preferable that 5 to 50% of the aromatic groups present in the polymer be complexed with metal cations. In addition to those described above, the appropriate anions, X, in Formula I, for use as the counter ion in the ionic salts of the organometallic complex cation in the coating compositions are those in which X can be represented by the formula DQr (II) wherein: D is a metal of groups IB to VIIB and VIII or a metal or metalloid of groups 11LA to VA of the periodic table of the elements (CAS notation), Q is a halogen atom, hydroxyl group, a group substituted or unsubstituted phenyl or a substituted or unsubstituted alkyl group and r is an integer having a value of 1 to 6. Preferably, the metals are copper, zinc, titanium, vanadium, chromium, manganese, iron, cobalt or nickel and the metalloids are preferably boron, aluminum, antimony, "tin, arsenic and phosphorus.Preferably, the halogen atom Q is chlorine or fluorine Illustrative of appropriate anions are B (phenyl) 4 ~, B (phenyl) 3 ( alkyl) ", where alkyl it can be ethyl, propyl, butyl, hexyl and the like, BF4", PF6", AsF6 ~, SbF6 ~, FeCl4 ~, SnCl5", SbF5OH ~, A1C14- / A1F6", GaCl4-, InF4 ~, TiF6", ZrF6", B (C6F5) 4 ~, B (C6F3 (CF3) 2) 4-. Additional appropriate anions, X, in formula I, of use as the counter ion in the ionic salts of organometallic complex cations include those in which X is an organic sulfonate. Illustrative of suitable sulfonate-containing anions are CH3S03 ~, CF3S03 ~, C6H5S03", p-toluenesulfonate, p-chlorobenzenesulfonate and related isomers Additional suitable anions include highly fluorinated tris-alkyl methanide), sulfonyl, bis- (highly fluorinated alkyl) sulfonyl imide, tris- (fluorinated aryl) sulphonyl methanide, as described in U.S. Patent No. 5,554,664.Preferably, the anions are BF4", PF6", SbF6", SbF5OH", AsF6", SbCl6", CFI3S03" , C (S02CF3) 24-. Organometallic salts are known in the art and can be prepared as disclosed, for example in EPO Nos. 094,914, 094,915, 126,712 and U.S. Patent Nos. 5,089,536, 5,059,701, 5,191,101. Also, disubstituted ferrocene derivatives can be prepared by the general procedure described in J. Amer. Chem. Soc., 1978, 100, 7264. The ferrocene derivatives can be oxidized to prepare the corresponding ferrocenium salts by the general procedure described in Inorg. Chem., 1971, 10, 1559. Preferred salts of organometallic complex cations useful in the compositions of the invention are derived from formulas I wherein L1 is chosen from the class of aromatic compounds, preferably based on benzene and L2 is chosen of the class of compounds having a cyclopentadienyl anion group, M is Fe and X is selected from the group consisting of tetrafluoroborate, hexafluorophosphate, hexafluroarsenate, hexafluroantimonate, tris- (trifluoromethylsulfonyl) methanide, hydroxypenta-fluoroantimonate or trifluoromethanesulfonate. The most preferred salts of the organometallic complex cations useful in the invention are included in formula I wherein only L1 is present or where both L1 and L2 are present, M is Fe and X is selected from the group consisting of tetrafluoroborate, hexafluorophosphate, hexafluoroarsenate, hexafluroantimonate, hydroxypenta-fluroantimonate, trifluoromethanesulfonate and tris- (trifluoromethylsulfonyl) methanide. The organometallic complex cations can be used as mixtures and isomeric mixtures. In the preferred compositions of the invention, the salts of the organometallic complex cation include those described in U.S. Patent No. 5,089,536. Examples of the preferred salts of organometallic complex cations useful in the preparation of the compositions of the invention include complex cations of bis (eta6-arene) iron, complex cations of bis (eta5-cyclopentadienyl) iron and complex cations of (eta-5-) cyclopentadienyl) iron arene such as: bis- (eta6-cumene) iron hexafluoroantimonate bis- (eta6-durene) iron hexafluoroantimonate (2+), bis- (eta6-mesitylene) -iron trifluoromethanesulfonate (2+), bis- (eta6-mesitylene) iron (2+) hexafluoroantimonate, tris- (trifluoromethylsulfonyl) bis- (etas-mesitylene) methanide) iron (2+), bis- (eta6-hexamethyl-benzene) iron hexafluoroantimonate (2+), bis- (eta6-pentamethylbenzene) hexafluoroantimonate (2+), bis- (eta6-naphthalene) hexafluoroantimonate (2+), bis- (eta6-pyrene) iron hexafluoride (2+), (eta6-naphthalene) (eta5-cyclopentadienyl) iron hexafluoroantimonate (1+), (etae-pyrene) hexafluoroantimonate (eta5- cyclo-pentadienyl) iron (1+), bis- (eta-pentamethyl-cyclopentadienyl) iron hexafluoroantimonate (1+), bis- (eta 5 -methylcyclopentadienyl) iron hexafluoroantimonate (1+), bis- (eta 5) hexafluoroantimonate -trimethylsilyl-cyclopentadienyl) iron (1+), bis- (eta5-indenyl) iron hexafluoroantimonate (1+), (eta5-cyclopenta-dienyl) (eta5-methylcyclopentadienyl) iron hexafluoroantimonate (1+), bis- (eta5-cyclo-pentadienyl) iron trifluoromethanesulfonate (1+), bis- (eta5-cyclopenta) hexafluoroantimonate -dienyl) iron (1+), bis- (eta5-cyclopentadienyl) iron tris- (trifluoromethylsulfonyl) methanide (1+), hexafluoroantimonate (eta6-xylenes (mixed isomers) (eta5-cyclopentadienyl) iron (1+), hexafluorophosphate of (eta6-xylenes (mixed isomers)) (eta5-cyclopentadienyl) iron (1+), tris- (trifluoromethylsulfonylmetanide of (eta6-xylenes (mixed isomers)) (eta5-cyclopentadienyl) iron (eta6-xylenes (mixed isomers)) (eta5-cyclopen-tadienyl) iron (1+), (eta6-m-xylene) (eta5-cyclopen-thienyl) iron tetrafluoroborate (1+), hexafluoroantimonate (eta6-o) -xilen) (eta5-cyclopentadienyl) iron (1+), trifluoromethanesulfonate of (eta6-p-xylenes) (eta5-cyclopentadienyl) iron (1+), hexafluoroantimonate (eta6-toluene) (eta5-cyclo-pentadienyl) iron ( 1+), (eta6-cumen) (eta5-cyclo-pentadienyl) iron hexafluoroantimonate (1+), eta6-m-xylene) (eta5-cyclopentadienyl) iron hexafluoroantimonate (1+), (eta6-hexamethyl) hexafluoroantimonate bencen) (eta5-cyclopentadienyl) iron (1+), hexafluoroantimonate (eta6-mesitylene) (eta5-cyclopentadienyl) iron (1+), hexafluorophosphate (eta6-cumen) (eta5-cyclo-pentadienyl) iron (1+) , tris- (trifluoromethylsulfonyl) methanide (eta6-cumen) (eta5-cyclopentadienyl) iron (1+) and pentafluorohydroxyantimonate (eta6-mesitylene) - (eta5-cyclopentadienyl) iron (1+). In the polymerizable compositions of the present invention, the initiator salts may be present in a catalytically effective amount to initiate the polymerization, generally in the range of 0.01 to 20 weight percent (% by weight), preferably 0.1 to 10. % by weight, of the curable composition, that is, the total compositions that exclude any solvent that may be present. The accelerators of the present invention can be selected from two kinds of materials. The active portions of these materials (see Formulas III and IV) may be part of a polymer or included as part of any component in the compositions of the invention. Class 1 is described by Formula III Class 1 molecules comprise hydroxy aromatics wherein each R 1, independently, may be hydrogen or a radical portion selected from substituted and unsubstituted alkyl, alkenyl, alkynyl and alkoxy groups containing from 1 to 30 carbon atoms or groups of 1 to 4 substituted or unsubstituted aromatic rings wherein two to four rings may be fused or unbound or two R 1 taken together may form at least one ring that is saturated or unsaturated and the ring may be substituted or unsubstituted.

When the molecule contains more than two aromatic hydroxyl groups, at least two of the hydroxyl groups must be adjacent to each other, that is, in an ortho position. It is important that the substituent groups do not interfere with the complexing action of the accelerator additive with the complex metal or interfere with the cationic polymerization of the invention. Examples of substituent groups which may be present in any group R1, all of which preferably have less than 30 carbon atoms and up to 10 heteroatoms wherein the heteroatoms may interrupt the carbon chains to form, for example, ether or thio bonds selected of sulfur or non-peroxy oxygen, include hydrocarbyl groups such as methyl, ethyl, butyl, dodecyl, tetracosanyl, phenyl, benzyl, allyl, benzylidene, ethenyl and ethynyl; cyclohydrocarbyl groups such as cyclohexyl; hydrocarbyloxy groups such as methoxy, butoxy and phenoxy; hydrocarbyl mercapto groups such as methylmercapto (thiomethoxy); phenylmercapto (thiophenoxy); hydrocarbyloxycarbonyl such as methoxycarbonyl, propoxycarbonyl and phenoxycarbonyl; hydrocarbylcarbonyl such as formyl, acetyl and benzoyl; hydrocarbylcarbonyloxy such as acetoxy and cyclohexanecarbonyloxy; perfluorohydrocarbyl groups such as trifluoromethyl and pentafluorophenyl; azo; borilo; halo, for example, chlorine, iodine, bromine and fluoro, hydroxy; cyano; nitro; nitrous; trimethylsiloxy and aromatic groups such as cyclopentadienyl, phenyl, naphthyl and indenyl. Additionally the R1 can be a unit of a polymer. Examples of this type would be novolak catechol resins or polystyrene type polymers wherein the phenyl ring is substituted with at least ortho-dihydroxy groups. Examples of appropriate Class 1 accelerators are catechol; pyrogallol; Gallic acid; gallic acid esters (prepared from the condensation of the carboxylic acid of gallic acid with alcohols), such as methyl gallate, ethyl gallate, propyl gallate, butyl gallate; tannins such as tannic acid; alkyl catechols such as 4-tert-butylcatechol, nitrocatechols such as 4-nitrocatechol, methoxycatechol such as 3-methoxyicatecol; 2, 3, 4-trihydroxybenzophenone and 2,3,4-trihydroxyacetophenone. The Class 1 accelerators can be present in an amount ranging from 0.01 to 10.0 weight percent, preferably 0.1 to 4 weight percent of the total polymerizable composition. Class 2 is described by Formula IV Class 2 molecules comprise those compounds that have a ß-diketone portion where each R2 can be the same or different and excluding hydrogen, they can be the same as R1 described for Class 1 accelerators and where R3 can be an unsubstituted or substituted alkyl or aryl group. Examples of suitable accelerators of this class are 2, 4-pentanedione, 3,5-heptanedione, 1,3-diphenyl-1,3-propanedione, 1-phenyl-1,3-butanedione, 1, 1-trifluoro- 2, 4-pentanedione, 1,1,1,5,5,5-hexafluoro-2,4-pentanedione and 1- (4-methoxyphenyl) -3- (4-tert-butylphenyl) propane-1,3-dione available as PARSOL 1789 from Roch.e Vitamins, Inc., Parsippany, NJ, and EUSOLEX 9020 from EM Industries, Inc., Hawthorne, NY. The preferred Class 1 compound is 2,4-pentanedione. Class 2 accelerator additives are particularly useful with the bis-eta6-arene organometallic salts. The Class 2 accelerators can be present in an amount in the range of 0.05 to 10.00 weight percent, preferably 0.05 to 4 weight percent of the total polymerizable composition. It should be noted that accelerators of different classes or even within a class may not be equally effective with any given initiator. It may also be preferred and it is within the scope of this invention to add mono- or poly-alcohols as hardeners to the polymerizable composition. The alcohol or polyol aids in the extension of the chain and prevents over-crosslinking of the epoxide during curing.

Representative monoalcohols may include methanol, ethanol, 1-propanol, 2-propanol, 2-methyl-2-propanol, 1-butanol, 2-butanol, 1-pentanol, neopentyl alcohol, 3-pentanol, 1-hexanol, 1 -heptanol, 1-octanol, 2-phenoxyethanol, cyclopentanol, cyclohexanol, cyclohexylmethanol, 3-cyclohexyl-1-propanol, 3-norbornatemethanol and tetrahydrofurfuryl alcohol. The polyols useful in the present invention have two to five, preferably two to four, non-phenolic hydroxyl groups. Examples of useful polyols include, but are not limited to, 1,2-ethanediol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 2-methyl-1, 3- propanediol, 2,2-dimethyl-1,3-propanediol and 2-ethyl-l, 6-hexanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, neopentyl glycol, glycerol, trimethylol propane, 1, 2, 6-hexanotriol, trimethylolethane, pentaerythritol, quinitol, mannitol, diethylene glycol, triethylene glycol, tetraethylene glycol, glycerin, 2-ethyl-2- (hydroxymethyl) -1, 3-propanediol, 2-ethyl-2-methyl -l, 3-propanediol, pentaerythritol, 2-ethyl-l, 3-pentanediol and 2,2-oxydiethanol, sorbitol, 1,4-cyclohexanedimethanol, 1,4-benzenedimethanol, 2-buten-1,4-diol and polyalkoxylated bis-phenol A derivatives. Other examples of useful polyols are disclosed in U.S. Patent No. 4,503,211.

Higher molecular weight polyols include polyethylene oxide and polypropylene polymers in the molecular weight range of 200 to 20,000, such as the CARBOWAX polyethylene oxide materials supplied by Union Carbide, caprolactone polyols in the molecular weight range of 200 to 5,000, such as the TONE polyol materials supplied by Union Carbide, Polytetramethylene glycol ether in the molecular weight range of 200 to 4,000, such as TERATHANE materials supplied by Dupont (Wilmington, DE), hydroxy-terminated polybutadiene resins such as the POLY BD supplied by Elf Atochem, hydroxyl-terminated polyester materials such as copolyester materials DYNAPOL from Creanova Inc., Somerset, NJ or equivalent materials supplied by other manufacturers. The functional component of alcohol may be present as a mixture of materials and may contain mono- and polyhydroxyl-containing materials. The alcohol is preferably present in an amount sufficient to provide a ratio of epoxy to hydroxy in the composition between about 1: 0.1 and 1: 1, more preferably between about 1: 0.2 and 1: 0.8 and more preferably between about 1 : 0.2 and 1: 0.6. It is also within the scope of this invention to incorporate thermoplastic polymeric or oligomeric resins to aid in the production of film-based compositions. These thermoplastics can make it easier to form films, that is, they are used as film formers and in some cases they allow the re-working of a bond using an appropriate solvent. The thermoplastic resins include those which preferably have glass transition temperatures and / or melting points of less than 120 ° C. Useful thermoplastic resins are essentially free of groups that would interfere with the cationic polymerization of the cationically curable monomers. More particularly, useful thermoplastic resins are essentially free of nucleophilic groups, such as amine, amide, nitrile, sulfur or functional phosphorus groups. Further suitable thermoplastic resins are soluble in solvents such as tetrahydrofuran (THF) or methyl ethyl ketone (MEK) and exhibit compatibility with the epoxy resin used. This compatibility allows the combination of epoxy resin and thermoplastic resin to be molded by solvents without phase separation. Non-limiting examples of thermoplastic resins having these characteristics and useful in this invention include polyesters, copolyesters, acrylic and methacrylic resins, polysulfones, phenoxy resins such as PAPHEN materials available from Phenoxy Associates, Rock Hill, SC and polysulfones, phenoxy resins such as the PAPHEN materials available from Phenoxi Associates, Rock Hill, SC and novolac resins. It is also within the scope of this invention to use a combination of more than one oligomeric or polymeric thermoplastic resin in the preparation of the compositions. When it is desired to increase the shelf life of the compositions of this invention, it may be useful to include a stabilizing additive. Life-span stabilizing additives include basic Lewis ligands, nitrogen-chelate ligands such as 1, 10-phenanthroline, 2,2'-dipyridyl and 2,4,6-tripyridytriazine.; trialkyl, triaryl, tricycloalkyl and trialkylaryl amines, phosphines, phosphine oxides, phosphites, arsines and stilbenes, including triphenylphosphine, triphenylstyne, triphenylarsine and triphenylphosphite; macrocyclic cryptands and capped ethers such as 12-CROWN-4, 15-CROWN-5, 18-CROWN-6, 1-CROWN-7, KRYPTOFIX 211 and KRYPTOFIX 222, all available from Aldrich Chemical Company, Milwaukee, Wl; and basic Schiff derivatives, which are elaborated in general by the condensation of a ketone or aldehyde with a primary amine. Suitable stabilizing additives are described in U.S. Patent No. 5,494,943. An appropriate initiation system including organometallic complex ion salts described by Formula I and at least one accelerator taken from Classes 1 or 2 contains those combinations which, in the application of sufficient energy, generally in the form of heat and / or light, will catalyze the polymerization of the compositions of the invention. The level of catalytic activity depends on several factors such as the choice of ligands and counterions in the organometallic salt and the selection of the type and amount of at least one accelerator. The polymerization temperature and amount of initiator system used will vary depending on the particular polymerizable composition used and the desired application of the polymerized product. The addition of a xylan coupling agent is optional in the preparation of cured compositions of the invention. Preferably, the xylan coupling agent is added to the polymerizable composition to improve adhesion when at least one substrate surface consists of glass, an oxide or any other surface that would benefit from the addition of a xylan coupling agent. . When present, a xylan coupling agent contains a functional group that can react with an epoxy resin, for example, 3-glycidoxypropyltrimethoxysilane. The solvents, preferably organic, can be used to aid in the dissolution of the initiator system in the polymerizable monomers and as a processing aid. It may be advantageous to prepare a concentrated solution of the organometallic complex salt in a small amount of solvent to simplify the preparation of the polymerizable composition. Useful solvents are lactones, such as gamma-butyrolactone, gamma-valerolactone and epsilon-caprolactone; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone and cyclohexanone; sulfones such as tetramethylene sulfone, 3-methylsulfolane, 2,4-dimethylsulfolane, butadiene sulfone, methyl sulfone, ethyl sulfone, propyl sulfone, butyl sulfone, methyl vinyl sulfone, 2- (methylsulfunsil) ethanol, 2,2 '-sulfonyldiethanol; sulfoxides such as dimethyl sulfoxide; cyclic carbonates such as propylene carbonate, ethylene carbonate and vinylene carbonate; carboxylic acid esters such as ethyl acetate, methyl cellosolve acetate, methyl formate and other solvents such as methylene chloride, nitromethane, acetonitrile, glycol sulfite and 1,2-dimethoxyethane (glime). In some applications, it may be advantageous to absorb the initiator on an inert support such as silica, alumina, clays as described in the North American patent NO. 4,677,137. Suitable sources of heat for curing the compositions of the invention include induction heating coils, ovens, hot plates, heat gun, infrared sources which include lasers, microwave sources. Appropriate sources of electromagnetic radiation include ultraviolet light sources, visible light sources and electron beam sources. Suitable substrates useful for providing articles of the invention include, for example, metals (eg, aluminum, copper, cadmium, zinc, nickel, steel, iron, silver), glass, paper, wood, various thermoplastic films (e.g., polyethylene terephthalate, plasticized polyvinyl chloride, polypropylene, polyethylene), thermosettable films (eg, polyimide), cloth, ceramics and cellulosics, such as cellulose acetate. Adjuvants can optionally be added to the compositions such as colorants, abrasive granules, antioxidant stabilizers, stabilizers against thermal degradation, light stabilizers, conductive particles, tackifiers, flow agents, bulking agents, flattering agents, fillers or fillers. inerts, binders, blowing agents, fungicides, bactericides, surfactants or surfactants, plasticizers, rubber hardeners and other additives known to those skilled in the art. They may also be substantially non-reactive, such as fillers or fillers, present, are added in an effective amount for their intended purpose. The compositions of this invention are useful for providing abrasion resistant or protective coatings to articles and are useful as molded articles and as adhesives, in which thermal and structural fusion adhesives are included and as binders for abrasives. The compositions of this invention may also exhibit a color change in the activation of a catalyst in the composition or curing of the composition. Additional examples of compositions that may exhibit such a color change are disclosed in co-pending US Patent Application Serial No. 09 / 224,421 (Attorney File No. 54529USA1A). In general, the physical properties of a composition, that is, hardness, rigidity, modulus, elongation, strength, etc., are determined by the choice of epoxy resin and if a material containing alcohol is used, the proportion of epoxy to alcohol and the nature of alcohol. Depending on the particular use, each of these physical properties of the system will have a particular optimal value. In general, the material cured from a higher epoxy / alcohol ratio is stiffer than a lower epoxy / alcohol ratio. In general, an epoxy / alcohol composition, a shorter chain polyol epoxy / alcohol composition, a shorter chain polyol produces a cured composition that is more rigid than when using a longer chain polyol. The stiffness of a composition can also be increased by using a shorter chain monofunctional alcohol to replace a polyol. Epoxy / alcohol blends generally cure faster than epoxy-only compositions. Cycloaliphatic epoxies heal faster than glycidyl ether epoxies. Mixtures of these two types of epoxy can be used to adjust the cure rate to a desired level. To prepare a coated article using the materials of the present invention, the abrasive particles must be added to the curable composition. The general procedure is to select a suitable substrate such as paper, cloth, polyester, etc., coat the substrate with the "composition coating", which consists of the curable composition, apply the abrasive particles and then cure by applying a source of energy. A "sizing coating", which cures a material harder than the composition coating, is then coated onto the composition coating and cured. The sizing coating serves to fix the abrasive particles in place. For this and other applications, the coating is preferably provided by methods such as coatings by bar, knife or spatula, reverse roll, extrusion mold, knurled roller or by centrifugation or spray coating, brush application or rolling. To prepare a structural / semi-structural adhesive, the curable composition could contain additional adjuvants such as silica fillers, glass bubbles, curing agents. These adjuvants assist in hardening and reduce the density of the cured composition. In general, shorter chain polyols would be used to give hardness by means of chain extension of the cured epoxy. A chain diol that is too long would generally produce a too-soft cured composition that would not have the strength needed for structural / semi-structural applications. The use of polyols having a high hydroxyl functionality greater than three would produce an over-crosslinked material resulting in a brittle adhesive. To prepare magnetic media using the materials of the present invention, magnetic particles must be added to the curable composition. The magnetic media need to be coated on an appropriate substrate, generally a polymeric substrate such as polyester. In general, the coatings are very thin such that sufficient carrier solvent must be added to allow the production of an appropriately thin, uniform coating. The coating must cure quickly in such a way that a system of quick starter and curable materials must be chosen. The cured composition must have a moderately high modulus such that the curable materials must be selected appropriately. To prepare an abrasion resistant coating, clear from the materials of the present invention two important criteria for selecting the composition are the clarity and hardness of the cured composition. In general, particulate adjuvants would not be added since they would reduce the luster and clarity of the cured composition. Optionally, pigments or dyes could be added to produce a colored film. To prepare an electrically conductive adhesive, the curable composition is filled with conductive particles at the level that provides conduction by means of the adhesive between the desired contact points. A class of conductive adhesives are often referred to as "z-axis adhesives" or as "anisotropically conductive adhesives." This kind of adhesive is filled with conductive particles at the level that provides conduction between points of contact on the z-axis but not the x-y plane of the adhesive. Such z-axis adhesives are often produced as a thin film adhesive on a carrier substrate, such as a polymeric film. A description of suitable materials for z-axis adhesives is disclosed in U.S. Patent No. 5,362,421. Molded articles are made by means known to those skilled in the art, such as for example reaction injection molding, molding, etc. Objects and advantages of this invention are further illustrated by the following examples, but should not be construed as limiting the invention.

EXAMPLES In the examples, all parts, proportions and percentages are by weight unless specifically indicated otherwise. All materials used are commercially available from Aldrich Chemical Co. , Milwaukee, Wl unless stated otherwise. All examples were prepared in the ambient atmosphere (in the presence of usual amounts of oxygen and water vapor) unless otherwise indicated.

The general sample preparation procedure was as follows: the desired amount of accelerator additive was mixed with the epoxy-containing composition; The resulting mixture was heated, if necessary, to ensure complete dissolution of the components, allowing the mixture to cool to room temperature (23 ° C) before use. Curable mixtures were prepared by measuring the desired amount of cationic organometallic catalyst, adding the desired amount of solvent to dissolve the catalyst, then adding the appropriate amount of the epoxy-containing mixture and accelerator, followed by complete mixing manually using a bar wood applicator.

Differential Scanning Calorimetry (DSC) Differential Scanning Calorimetry (DSC) was carried out on a DSC 912 from TA Instruments Inc. (New Castle, DE) and was used to measure the exothermic heat of reaction associated with the thermal curing of the cationically polymerizable monomer. the DSC samples were commonly from 6 to 12 mg. The tests were carried out in aluminum, liquid, salted sample trays at a speed of 10 ° C / minute from room temperature (23 ° C) at 300 ° C. The data of the progress of the reaction were plotted on a table showing the flow of heat against the temperature. The integrated area below an exothermic peak represents the total exothermic energy produced during the reaction and is measured in joules / gram (J / g); the exothermic energy is proportional to the extent of curing, that is, degree of polymerization. The exothermic profile, that is, start temperature (the temperature at which the reaction will begin to present), peak temperature and final temperature, provides information regarding the conditions necessary to cure the material. For any particular reaction, a shift to a lower start and / or peak temperature for the exotherm indicates that the reactive material is being polymerized at lower temperatures, which correlates with the shorter gelation times.

Differential Photo-calorimetry (DPC) Differential photo-calorimetry was used to measure the exothermic heat of reaction associated with the photoinitiated curing of a cationically polymerizable monomer during exposure to light. The sample sizes of DPC were usually 6 to 12 mg. The tests were run on open aluminum trays, under nitrogen purge, on a DSC 912 base from TA Instruments Inc., equipped with a 930 differential photocalorimeter from TA Instruments Inc. (TA Instruments Inc. New Castle, DE). A 200-watt mercury lamp was used for the photolysis stage. In a typical experiment, the sample is maintained isothermally at the desired temperature throughout the CPD experiment. The sample is kept in the dark for 2 minutes, then a shutter is opened to allow the sample to be irradiated for 5 minutes after which the shutter is closed and the sample is kept in the dark for an additional 2 minutes. The data from the DPC experiment were plotted on a table showing the exothermic heat flow against time. The area below the exothermic peak represents the total exothermic energy produced during irradiation and is measured in Joules / gram (J / g). The exothermic energy is proportional to the extent of curing for any particular reaction, an increase in the exothermic energy of total DPC would indicate a higher degree of curing during irradiation. Immediately following the DPC experiment, the samples were capped and heated to 10 ° C / min in a DSC experiment as described above. The total exothermic energy is the combination of the DPC and DSC energies and is the total exothermic energy of polymerization.

GLOSSARY Identification of Components Used in the Examples Initiators Comparative Example Cl To determine the gel time for an epoxy-containing composition that did not contain an accelerator additive, O.O2 g of (mesitylene) 2Fe (SbF6) 2 were weighed on an aluminum weighing disk (VWR / Scientific Products Inc. ., West Chester, PA), followed by the addition of 0.04 g of propylene carbonate solvent. To aid in the dissolution of the initiator in the solvent, the mixture was stirred using a wood applicator bar (Puritan brand, available from Hardwood Products Company, Guilford, ME). To the resulting catalyst solution is added 2.0 g of a mixture of EPON 828/1, 6-hexanediol / CHDM (88: 6: 6 weight percent ratio based on the total weight of the mixture (weight / weight)), termed subsequently in the present as "monomeric mixture". The monomer mixture was prepared by first heating a 50:50 weight ratio mixture of 1,6-hexanediol and CHDM at 60 ° C, allowing the resulting liquid to cool to room temperature, then adding 12% by weight of this liquid to an appropriate amount of EPON 828. The resulting mixture was heated for 30 minutes at 80 ° C, then vigorously stirred for 30 seconds to obtain a homogeneous solution that turns milky white on cooling to room temperature over a period of 30 minutes . The addition of the monomer mixture to the catalytic solution was followed by complete mixing manually using a wood applicator bar. To measure the gel time the tray was then placed on a hot plate, which was preheated to 125 ° C. Samples were tested for curing periodically by scraping the sample with the end of a wood applicator bar. The presence of a gel was indicated by the solidification of the liquid resin. It was considered that the gelling time or curing time was the time in which the sample was no longer liquid. In this example, the gel was formed after 1:27 (minutes: seconds).

Examples 1-7 The effect of the addition of 1% by weight of a Class 1 accelerator additive to a thermally curable composition was examined. Concentrated solutions of accelerator additives ("additives") and epoxy resin were prepared by combining, in a glass container, 0.1 g of the additive with 10 g of a mixture of EPON 828 / 1,6-hexanediol / 1,4-CHDM ( 88: 6: 6 weight / weight) (prepared in the same manner as described in Comparative Example Cl). The glass vessel containing the epoxy / accelerator mixture was capped and placed in an LFD 1-42-3 oven from Despatch (Despatch industries, Inc. Minneapolis, MN), which had been preheated at 80 ° C, for about 30 minutes. minutes to ensure complete dissolution of the components; after heating, the vessel was shaken vigorously for 15 seconds and then the mixture was allowed to cool to room temperature (23 ° C) before use. This produced a 1% w / w solution of the additive in the epoxy-containing composition. For each example, 0.02 g of (mesitylene) 2Fe (SbF6) 2 were weighed into an aluminum disk, followed by the addition of 0.04 g of propylene carbonate solvent. To aid dissolution of the initiator in the solvent, the mixture was stirred using a wooden applicator bar. To the resulting catalyst solution is added 2.0 g of the appropriate concentrated solution followed by complete mixing, manually using a wood applicator bar. The gelation times were determined at 125 ° C following the procedure described in comparative example 1. The data in Table 1 show that, under the conditions used, the incorporation of a Class 1 accelerator additive decreases the gelling time of the coagulation, when compared to the gel time obtained in comparative example 1. For each example, it should be noted that the color of the formulations changed from pale orange to dark violet during normal curing.

TABLE 1 Gelification Time Experiments with 1% Accelerator Additive Examples 8-14 The effect of adding 2% by weight of a Class 1 accelerator additive to a thermally curable composition was examined. Concentrated solutions of epoxy resin accelerator additives were prepared by combining, in a glass container, 0.2 g of the additive with 10 g of a mixture of EPON 828/1, 6-hexanediol / l, 4-CHDM (88: 6: 6 weight / weight) (prepared in the same manner as described in Comparative Example Cl). The glass vessel containing the epoxy / accelerator mixture was capped and placed in an LFD 1-42-3 oven from Despatch (Despatch Industries, Inc. Minneapolis, MN), pre-heated to 80 ° C for approximately 30 minutes to ensure the complete dissolution of the components; after heating the vessel was vigorously agitated and then the mixture is allowed to cool to room temperature (23 ° C) before use. This produces a 2% w / w solution of the additive in the epoxy. For each example 0.02 g of (mesitylene) 2Fe / SbF6) 2 were weighed into an aluminum disk, followed by the addition of 0.04 g of propylene carbonate solvent. To aid dissolution of the initiator in the solvent, the mixture was stirred using a wooden applicator bar. To the resulting catalyst solution is added 2.0 g of the appropriate concentrated solution followed by complete mixing, manually, using a wood applicator bar. The gelation times were determined at 125 ° C following the procedure described in comparative example 1. The data in table 2 show that, under the conditions used, the incorporation of a Class 1 accelerator additive reduced the gelling time of the formulation, when compared to the gel time obtained in comparative example 1. Additionally, when compared to examples 1-7, the data in table 2 show that the incorporation of 2% accelerator additive provides gelling times faster than formulations containing 1% accelerator additive. As seen in Examples 1-7, the color of the formulations changed from orange to dark violet during thermal curing.

TABLE 2 Gelification Time Experiment with 2% Accelerator Additive Comparative Examples C2-C5 Meta- and para-dihydroxy substituted benzene compounds were evaluated as accelerator additives.

Concentrated solutions of the additives were prepared following the procedure described in general for examples 2-14.

For each comparative example, 0.02 g of (mesitylene) 2Fe (Sbfe) 2 were weighed into an aluminum disk, followed by the addition of 0.04 g of propylene carbonate solvent. To aid dissolution of the initiator in the solvent, the mixture was stirred using a wooden applicator bar. To the resulting catalyst solution was added 2.0 g of the appropriate concentrated solution followed by complete mixing, manually, using a wooden applicator bar. The gelation times were determined at 125 ° C following the procedure described in Comparative Example 1, with the results listed in Table 3. When compared with the data of Comparative Example 1 and Examples 1-14, the data in Table 3 show that these additives, having only meta- or para-dihydroxy groups, in contrast to the ortho-dihydroxy groups of the accelerators of the present invention, were not effective as accelerator additives. TABLE 3 Examples 15-22 and Comparative Example C6 The effect of the addition of a Class 2 accelerator additive to a thermally curable composition was examined. Concentrated solutions of accelerator / epoxy mixtures were prepared having 0.125%, 0.25%, 0.5%, 1%, 2%, 4%, 8% and 12% of 2,4-pentanedione by the addition of 0.0125 g, 0.025 g , 0.05 g, 0.1 g, 0.2 g, 0.4 g, 0.8 g and 1.2 g respectively of 2,4-pentanedione, to separate flasks containing 10 g of a mixture of EPON 828 / 1,6-hexanediol / CHDM (88: 6: 6 w / w) (prepared in the same manner as described in comparative example Cl), and mixed complete manually, using a wooden applicator. For each example, 0.02 g of (mesitylene) Fe (SbF6) 2 were weighed into an aluminum disk, followed by the addition of 0.04 solvent of propylene carbonate. To aid dissolution of the initiator in the solvent, the mixture was stirred using a wooden applicator bar. To the resulting catalyst solution was added 2.0 g of the appropriate concentrated solution followed by complete mixing, manually, using a wooden applicator bar. Two samples for each example were prepared, with the gelation times determined at 125 ° C and 80 ° C. The results in Table 4 show that small amounts of the accelerator additive significantly decrease the gelling time and that the increase in the amount of additive correlates in general with the faster gelation times. It was found with concentrations of accelerator additives greater than 4%, the cured materials, although completely solid, were significantly softer than the control materials or materials made with lower concentrations of the additives, as determined by observing and manipulating the samples . It was also noted that for each example, the color of the formulations changed from pale orange to dark red during thermal curing.

TABLE 4 Accelerator Additive Concentration Effect on the Examples 23-24 and Comparative Examples C7-C8 The effect of the addition of a Class 1 accelerator additive to a photocurable composition was examined using differential photo-calorimetry (DPC). For both the comparative examples and the examples, the photoinitiated polymerization of an epoxy composition, with and without accelerator additive, was investigated using differential calorimetry (DPC), at 40 ° C, followed by differential scanning calorimetry (DSC). For the Comparative Examples, 0.02 g of the selected photoinitiator was weighed into an aluminum disk, followed by the addition of 0.04 g of 3-methylsulpholane solvent. To aid dissolution of the initiator in the solvent, the mixture was stirred using a wooden applicator bar. To the resulting catalyst solution is added 2.0 g of ERL 4221 followed by complete mixing, manually, using a wood applicator bar. The resulting solution was subjected to light, then heat according to the DPC and DSC test methods described herein. The results are shown in Table 5. After the completion of the DPC and DSC tests for the comparative examples, the samples for Examples 23-24 were prepared by adding 0.08 g of 3-methoxyicatecol to each formulation of the comparative examples and complete mixing at room temperature until the 3-methoxy-potcol was completely dissolved. The resulting composition was examined using DPC and DSC, with the results shown in Table 5. The data in Table 5 shows that the addition of the accelerator additive increases the degree of polymerization during exposure to light, as is evident from a increase in the exothermic energy of DPC in the addition of accelerators.

TABLE 5 Photopolymerization DPC and DSC Measurements Comparative Example C9 To determine the gel time for a photo-initiated epoxy composition not containing an accelerator additive, 0.02 g of CpFeXylSbF6 were weighed into an aluminum disk, followed by the addition of 0.04 g of propylene carbonate solvent. To aid the dissolution of the initiator in the solvent, the mixture was stirred using a wooden applicator bar. To the resulting catalyst solution is added 2.0 g of a mixture of EPON 828 / 1,6-hexanediol / CHDM (88: 6: 6 w / w) (prepared in the same manner as described in Comparative Example Cl), followed by by complete mixing, manually, using a wooden applicator bar. Then the resulting sample was placed under a 500-watt tungsten-halogen lamp, with the sample positioned 12 cm (4.72 inches) away from the light source and continuously irradiated until gelation was observed. The presence of a gel was indicated by the solidification of the liquid resin. In this comparative example, the gel was formed after 3:35 (minutes: seconds).

Examples 25-31 The gelling time for a photo-initiated epoxy composition containing a Class 1 accelerator additive was examined. Concentrated solutions of different Class 1 accelerator additives and epoxy resin were prepared by combining, in a glass container, 0.1 g of the additive with 10 g of a mixture of EPON 828 / 1,6-hexanediol / 1,4-CHDM ( 88: 6: 6 weight / weight) (prepared in the same manner as described in Comparative Example Cl.) The glass container containing the epoxy / accelerator mixture was capped and placed in an LFD 1-42-3 oven. Despatch (Despatch Industries, Inc., Minneapolis, MN), pre-heated at 80 ° C, for approximately 30 minutes to ensure complete dissolution of the components, after heating, the vessel was vigorously stirred for 15 minutes and then allowed The mixture is cooled to room temperature (23 ° C) before use.This produces a 1% w / w solution of the additive in the epoxy., 0.02 g of CpFeXylSbFd were weighed into an aluminum disk, followed by the addition of 0.04 g of propylene carbonate solvent. To aid dissolution of the initiator in the solvent, the mixture was stirred using a wooden applicator bar. To the resulting catalyst solution is added 2.0 g of the appropriate concentrated solution followed by complete mixing, manually, using a wood applicator bar. The gelation times were determined following the procedure in Comparative Example 9, with the results shown in Table 6. The data in Table 6 show that the addition of Class 1 accelerator additives to an epoxy-containing formulation decreases the time of gelation TABLE 6 Gelification Time Experiment with 1% Accelerator Additive Examples 32-33 and Comparative Example CÍO The effect of the addition of several levels of a Class 1 accelerator additive to a photoinitiated composition was examined. For these examples, the photoinitiated polymerization of an epoxy composition, with and without accelerator additive, was investigated using differential photocalorimetry (DPC) followed by differential scanning calorimetry (DSC). Concentrated solutions having 1% and 2% propyl gallate in epoxy resin were prepared by combining, in a glass container, 0.1 and 0.2 g, respectively, of the additive with 10 g of a mixture of EPON 828/1, 6- hexanediol / L, 4-CHDM (88: 6: 6 w / w) (prepared in the same manner as described in Comparative Example Cl). The glass vessel containing the epoxy / accelerator mixture was capped and placed in a Despatch 1-42-3 LFD oven preheated to 80 ° C, for approximately 30 minutes to ensure maximum dissolution of the accelerator; after heating, the vessel was vigorously stirred for 15 seconds and the mixture allowed to cool to room temperature (23 ° C) before use. This produces a solution at 1% w / w and 2% w / w respectively, of the additive in the epoxy. For each example, 0.02 g of CpFeXylSbF6 were weighed into an aluminum disk, followed by the addition of 0.04 g of propylene carbonate solvent. To aid dissolution of the initiator in the solvent, the mixture was stirred using a wooden applicator bar. To the resulting catalyst solution was added 2.0 g of the desired concentrated solution, followed by complete mixing, manually, using a wood applicator bar. For the comparative example, 0.02 g of CpFeXylSbFβ were weighed on an aluminum disk, followed by the addition of 0.04 g of propylene carbonate solvent. To aid dissolution of the initiator in the solvent, the mixture was stirred using a wooden applicator bar. To the resulting catalyst solution is added 2.0 g of a mixture of EPON 828/1, 6-hexanediol / CHDM (88: 6: 6 w / w) (prepared in the same manner as described in Comparative Example Cl), followed by by complete mixing, manually, using a wooden applicator bar. The resulting solutions for the examples and the comparative example were subjected to light, then heat, according to the DPC and DSC test methods described herein, with the results shown in Table 7. The CPD tests were run. at 40 ° C. No exothermic was observed either for one or the other of the examples or the comparative examples in the DPC; however, the effect of the accelerator additive can be seen from the subsequent DSC tests. The data in Table 7 show that the exothermic peak temperature is displaced at lower temperatures after the addition of 1% propyl gallate and is displaced at even lower temperatures when 2% propyl gallate is incorporated into the formulation of epoxy. The data are graphically illustrated in Figure 1. The exothermic energy of DSC was determined by integrating the energy under the curve between 43 ° C and 200 ° C. The amount of exothermic energy integrated both above and below the maximum peak temperature of the comparative example CIO (115.3 ° C) was then calculated. The greater the area of exothermic energy of total DSC below the peak temperature of the comparative example, the higher the degree of curing. It can be seen from Table 7 that after the addition of increased amounts of accelerator additive, a significantly higher degree of cure is obtained when larger amounts of additive are present.

TABLE 7 DSC experiments with various amounts of Propyl Gallate Example 34 The gelling time for a photo-initiated epoxy composition containing a Class 2 accelerator additive was examined. A 1% concentrated solution of a Class 2 accelerator additive, 2, 4-pentanedione, was prepared by combining 0.1 g of 2,4-pentanedione with 10 g of a mixture of EPON 828/1, 6-hexanediol / CHDM (88: 6: 6 w / w) and complete stirring manually , using a wooden applicator bar. This produces a 1% w / w solution of the additive in the epoxy. For this example, 0.02 g of CpFeXylSbFe were weighed into an aluminum disk, followed by the addition of 0.04 g of propylene carbonate solvent. To aid dissolution of the initiator in the solvent, the mixture was stirred using a wooden applicator bar. To the resulting catalyst solution is added 2.0 g of the accelerator / epoxy solution, followed by complete mixing, manually, using a wooden applicator bar. The gelation times were determined following the procedure described in comparative example 9. For this example, a gel time of 5:46 (minutes: seconds) is obtained. When the gelling time of this example is compared to the result of Comparative Example 9, it can be seen that a 1% solution of this Class 2 accelerator additive was not particularly useful for accelerating the gelling times of cured formulations using the catalyst of CpFeXylSbF6. Various modifications and alterations of this invention will become apparent to those skilled in the art without departing from the scope and spirit thereof and it should be understood that this invention is not unduly limited to the illustrative embodiments summarized herein. It is noted that, with regard to this date, the best method known to the applicant to carry out the aforementioned invention is that which is clear from the present description of the invention.

Claims (21)

1. CLAIMS Having described the invention as above, the content of the following claims is claimed as property: 1. A method characterized in that it comprises the steps of using an accelerator to increase the speed or reduce the curing temperature of a polymerizable composition by energy, in wherein the composition comprises a cationically curable material and at least one salt of an organometallic complex cation wherein said cation contains at least one carbon atom linked to a transition metal atom and wherein such an accelerator or an active portion thereof , comprises at least one compound selected from compounds described by Formula III wherein each R1, independently, may be hydrogen or a radical portion selected from substituted and unsubstituted alkyl, alkenyl, alkynyl and alkoxy groups containing from 1 to 30 carbon atoms or groups from 1 to 4 substituted or unsubstituted aromatic rings in where 2 to 4 rings may be fused or unbound or two R1 taken together may form at least one ring that is saturated or unsaturated and the ring may be substituted or unsubstituted, compounds described by Formula IV wherein each R 2 may be the same or different and, to the exclusion of hydrogen, may be the same as R 1 described for Class 1 accelerators and wherein R 3 may be a substituted or unsubstituted alkyl or aryl group, 2, 4- pentanedione, 3,5-heptanedione, 1,3-diphenyl-1,3-propanedione, 1-phenyl-1,3-butanedione, 1,1-trifluoro-2, -pentanedione, 1, 1, 5 , 5, 5-hexafluoro-2,4-pentanedione and 1- (4-methoxyphenyl) -3- (4-tert-butylphenyl) propan-1,3-dione, esters of gallic acid, tannins, nitrocatechols, 2,3 , 4-trihydroxy-benzophenone and 2, 3, 4-trihydroxyacetophenone.
2. 2. The method of compliance with the claim 1, characterized in that it further comprises adding sufficient energy in the form of at least one of heat and light, in any combination or order, to cure such cationically curable material.
3. 3. An energy polymerizable composition characterized in that it comprises: (a) at least one cationically curable material, (b) a two-component initiator system comprising: (i) at least one salt of an organometallic complex cation, wherein said cation contains at least one carbon atom bonded to a transition metal atom (ii) at least one accelerator or an active portion thereof, as defined in claim 1.
4. 4. The composition according to claim 3, characterized in that it further comprises at least one non-phenolic monoalcohol or polyalcohol.
5. 5. The composition according to claim 3, characterized in that it also comprises at least one additive stabilizer of the useful life.
6. 6. The composition according to claim 3, characterized in that such a salt of an organometallic complex cation has the formula: [(1) and (2) zM] + < l Xn (I) where: M is selected from the group containing Cr, Ni, Mo, W, Mn, Te, Re, Faith, Ru, Os, Co, Rh and Go; L1 represents none, one or two of the same or different ligands contributing with pi electrons that can be selected from aromatic compounds and heterocyclic aromatic compounds and the ligand is able to contribute with six pi electrons to the valence shell of M; L2 represents none, one or two of the same or different ligands contributing with pi electrons that can be selected from anionic groups of cyclopentadienyl and indenyl and the ligand is capable of contributing six pi electrons to the valence shell of M; q is an integer that has a value of 1 or 2, the residual charge of the complex cation; y and z are integers that have a value of zero, one or two, provided that the sum of y and z equals 2; X is an anion selected from tris- (highly fluorinated alkyl) sulfonyl, bis- (highly fluorinated alkyl) sulfonyl imide, tris- (fluorinated aryl) sulfonyl methanide, tetrakis- (fluorinated aryl); organic sulfonate anions and complex anions containing halogen of a metal or metalloid and n is an integer having a value of 1 or 2, the number of complex anions required to neutralize the charge q on the complex cation.
7. The composition according to claim 6, characterized in that said salt is selected from the group consisting of complex cations of bis- (eta6-arene) iron, complex cations of bis (eta-cyclopentadienyl) iron and complex cations of (eta -5-cyclopentadienyl) arene iron.
8. 8. The composition according to claim 3, characterized in that said accelerator is selected from propyl gallate 2,3,4-trihydroxybenzophenone, 2,4-pentanedione or 1- (4-methoxyphenyl) -3- (4-tert- butylphenyl) propan-1,3-dione.
9. 9. The composition according to claim 3, characterized in that said accelerator is a compound of formula III and such salt is selected from the group consisting of complex cations of bis- (eta6-arene) iron, complex cations of bis (eta5-) cyclopentadienyl) iron and complex cations of (eta5-cyclopentadienyl) iron arene.
10. 10. The cured composition according to claim 3-4.
11. 11. A process characterized in that it comprises the steps of: (a) providing the curable composition according to claim 3 and (b) adding sufficient energy to the composition in the form of at least one of heat and light, in any combination and order, to cure such a composition.
12. 12. A process characterized in that it comprises the steps of: (a) coating at least one surface of a substrate with a layer of the curable composition according to claim 3 and (b) supplying sufficient energy to the composition in the form of at least one of heat and light, in any combination and order, for a sufficient time to cure such a composition.
13. An article, characterized in that it comprises a substrate having on at least one surface thereof a layer of the composition according to claim 3. 1.
14. The article according to claim 13, characterized in that it also comprises a thermoplastic resin.
15. 15. The article according to claim 13, characterized in that the composition layer is an adhesive.
16. 16. The article according to claim 15, characterized in that the adhesive is electrically conductive.
17. 17. The article according to claim 13, characterized in that the composition layer is a magnetic medium.
18. 18. An article characterized in that it comprises a substrate having on at least one surface thereof a layer of the composition according to claim 10.
19. 19. The article according to claim 18, characterized in that said layer of composition is a protective coating. .
20. 20. A composition of matter characterized in that it comprises: (i) at least one salt of an organometallic complex cation, wherein said cation contains at least one carbon atom bonded to a transition metal atom and (ii) less an accelerant compound or an active portion thereof as defined in claim 1.
21. 21. The composition of matter according to claim 20, characterized in that said accelerator compound is selected from catechol, propyl gallate, tannic acid, 2, 3, 4-trihydroxybenzophenone, 2,3,4-trihydroxyacetophenone, 2,4-pentanedione, 1,3-diphenyl-1,3-propanedione and 1- (4-methoxyphenyl) -3- (4-tert-butylphenyl) propan -1, 3-dione. ENERGY SUMMARY OF, INVENTION Accelerators are described which may be useful for an energy polymerizable composition, comprising a cationically curable material; energy polymerizable compositions comprising at least one cationically curable material and an initiation system therefor, the initiation system comprises at least one organometallic complex salt and at least one accelerator and a method for curing the compositions. Cured compositions can provide useful articles. The invention also provides compositions of matter comprising an organometallic complex salt and at least one compound selected from the Class 1 and Class 2 compounds disclosed herein.