Patent Description:
Polymers prepared from benzoxazines with a cationic polymerization catalyst are known. Indeed, <CIT>) is directed to and claims a polymer comprising the reaction product of reacting at least one <NUM>-<NUM>,<NUM>,-dihydrobenzoxazine monomer with a cationic polymerization initiator, where the cationic polymerization initiator compris PCl<NUM>, PCl<NUM>, POCl<NUM>, TiCl<NUM>, (C<NUM>H<NUM>)<NUM>C+(SbCl<NUM>)-, SbCl<NUM>, methyl triflat methyl tosylate, triflic acid, or aluminum phthalocyanine chloride or combinations thereof. In addition, <CIT> describes adducts of glycidylesters of α,α-branched carboxylic acids and carboxylic acids, to poly (ortho ester) as intermediate for their preparation and to a process for the preparation of solid poly (ortho ester) intermediates. The adducts are used as constituent for binders in two component curable coating compositions for clear coat or coloured top coat for automotives or general metal coatings or industrial coatings. <CIT> describes a polymer electrolyte containing lithium hexafluorophosphate and a polymer.

Notwithstanding the above, it has been a long felt, yet unmet, desire to improve the polymerization conversion percent of cationically polymerizable benzoxazine compositions.

In one aspect the present invention relates to a curable composition as defined in appended claim <NUM> and comprising: (a) a benzoxazine component; and (b) a catalyst composition; wherein the catalyst composition comprises: (i) a lithium salt, an anion of which has a conjugate acid with a pKa of less than <NUM>; and (ii) a carboxylic acid, a sulfonic acid, or a combination thereof; or wherein the catalyst composition comprises: (iii) a lithium salt, an anion of which has a conjugate acid with a pKa of less than <NUM>; and (iv) a salt having as an anion a hexahalogenated Group <NUM> element.

In another aspect the present invention relates to a curable composition as defined in appended claim <NUM> and comprising: (a) a benzoxazine component; and (b) a catalyst composition comprising: (i) a cationic catalyst that is either comprised of a lithium cation and an anion comprising a hexahalogenated Group <NUM> element; or selected from lithium trifluoromethane sulfate, lithium palmitate, lithium tetrafluoroborate and lithium perchlorate; and (ii) a co-catalyst selected from tetrabutyl ammonium hexafluorophosphate and adipic acid.

As noted above, a curable composition is provided as defined in the appended claims.

Specific examples of the cationic catalyst include lithium hexafluorophosphate and lithium hexafluoroantimonate.

And of course the cationic catalysts should be used in catalytic amounts, such as about <NUM> to about <NUM> percent by weight.

It is desirable to include a co-catalyst with the so-defined cationic catalysts and other cationic catalysts. Here, and as further illustrated in the examples, a cationic catalyst that itself does not confer a polymerization conversion greater than <NUM>% (such as lithium trifluoromethane sulfate, lithium palmitate, lithium tetrafluoroborate and lithium perchlorate), together with one or more co-catalysts, such as tetrabutyl ammonium hexafluorophosphate and adipic acid, is suitable to achieve a polymerization conversion greater than <NUM>% polymerization conversion. Polymerization conversion is determined by the following formula: percent conversion = ((I<NUM>-I<NUM>)/I<NUM>) * <NUM>, where I<NUM> is the integration (enthalpy) of the DSC cure peak of the uncured formulation and I120 is the integration of the DSC cure peak after a period of time of <NUM> minutes at a temperature of <NUM>.

The benzoxazine component comprises one or more of
<CHM>
where o is <NUM>-<NUM>, X is selected from a direct bond (when o is <NUM>), alkyl (when o is <NUM>), alkylene (when o is <NUM>-<NUM>), carbonyl (when o is <NUM>), thiol (when o is <NUM>), thioether (when o is <NUM>), sulfoxide (when o is <NUM>), and sulfone (when o is <NUM>), R<NUM> is selected from hydrogen, alkyl, and aryl, and R<NUM> is selected from hydrogen, halogen, alkyl, and alkenyl, or
<CHM>
where p is <NUM>-<NUM>, Y is selected from biphenyl (when p is <NUM>), diphenyl methane (when p is <NUM>) and derivatives thereof, diphenyl isopropane (when p is <NUM>), diphenyl sulfide (when p is <NUM>), diphenyl sulfoxide (when p is <NUM>), diphenyl sulfone (when p is <NUM>), and diphenyl ketone (when p is <NUM>), and R<NUM> is selected from hydrogen, halogen, alkyl and alkenyl.

More specific examples of benzoxazines include one or more of the representative structures
<CHM>
<CHM>
<CHM>
<CHM>
where X is selected from a direct bond, CH<NUM>, C(CH<NUM>)<NUM>, C=O, S, S=O and O=S=O, and R<NUM>, R<NUM>, R<NUM> and R<NUM> are the same or different and are selected from hydrogen, alkyl, alkenyl and aryl.

Specific examples of the benzoxazine include one or more of
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>.

Monofunctional benzoxazines include those represented by following structure:
<CHM>
where R is alkyl, such as methyl, ethyl, propyls and butyls, or aryl with or without substitution on one, some or all of the available substitutable sites, and R<NUM> is selected from hydrogen, halogen, alkyl and alkenyl.

For instance, monofunctional benzoxazines may be embraced by the structure
<CHM>
where in this case R is selected from alkyl, alkenyl, each of which being optionally substituted or interupted by one or more O, N, S, C=O, COO, and NHC=O, and aryl; m is <NUM>-<NUM>; and R<NUM>-R5 are independently selected from hydrogen, alkyl, alkenyl, each of which being optionally substituted or interupted by one or more <NUM>, N, S, C=O, COOH, and NHC=O, and aryl.

Specific examples of such a monofunctional benzoxazine
<CHM>
where R is as defined above; or
<CHM>.

Benzoxazines are presently available commercially from several sources, including Huntsman Advanced Materials; Georgia-Pacific Resins, Inc. ; and Shikoku Chemicals Corporation, Chiba, Japan, the last of which offers among others B-a, B-m, F-a, C-a, Pd and F-a benzoxazine resins.

If desired, however, instead of using commercially available sources, the benzoxazine may typically be prepared by reacting a phenolic compound, such as a bisphenol A, bisphenol F, bisphenol S or thiodiphenol, with an aldehyde and an alkyl or aryl amine. <CIT> describes a method of forming benzoxazines, where the reaction time can vary from a few minutes to a few hours, depending on reactant concentration, reactivity and temperature. See also <NPL>); see generally <CIT>), <CIT>), <CIT>) and <CIT>).

The benzoxazine should be present in the inventive composition in an amount in the range of about <NUM> to about <NUM> percent by weight, such as about <NUM> to about <NUM> percent by weight, desirably about <NUM> to about <NUM> percent by weight, based on the total weight of the composition.

The composition may also include one or more of epoxy, episulfide, oxetane, (meth)acrylate, maleimide, and cyanate ester as a coreactant.

The epoxy may be selected from glycidylated bisphenols (such as bisphenol A diglycidyl ether, bisphenol F diglycidyl ether, bisphenol S diglycidyl ether, bisphenol E diglycidyl ether), glycidylated biphenyls, and hydrogenated versions thereof; cycloaliphatic epoxy resins; glycidylated anilines and glycidylated hydroxyanilines.

The episulfides may be chosen from the sulfur analogues of any one or more of the epoxies noted in the previous paragraph.

The oxetanes may be chosen from the four membered oxygen-containing rings of any one or more of the epoxies noted.

The (meth)acrylate may be selected from a wide variety of materials, such as those represented by H<NUM>C=CGCO<NUM>R<NUM>, where G may be hydrogen, halogen or alkyl groups having from <NUM> to about <NUM> carbon atoms, and R<NUM> may be selected from alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkaryl, aralkyl, or aryl groups having from <NUM> to about <NUM> carbon atoms, any of which may be optionally substituted or interrupted as the case may be with silane, silicon, oxygen, halogen, carbonyl, hydroxyl, ester, carboxylic acid, urea, urethane, carbonate, amine, amide, sulfur, sulfonate, sulfone, and the like.

Additional (meth)acrylate monomers suitable for use herein include polyfunctional (meth)acrylate monomers, for example, di-or tri-functional (meth)acrylates such as polyethylene glycol di(meth)acrylates, tetrahydrofuran (meth)acrylates and di(meth)acrylates, hydroxypropyl (meth)acrylate ("HPMA"), hexanediol di(meth) acrylate, trimethylol propane tri(meth)acrylates ("TMPTMA"), diethylene glycol dimethacrylate, triethylene glycol dimethacrylates ("TRIEGMA"), tetraethylene glycol di(meth)acrylates, dipropylene glycol di(meth)acrylates, di-(pentamethylene glycol) di (meth)acrylates, tetraethylene diglycol di(meth)acrylates, diglycerol tetra(meth)acrylates, tetramethylene di(meth)acrylates, ethylene di(meth)acrylates, neopentyl glycol di(meth)acrylates, and bisphenol-A mono and di(meth)acrylates, such as ethoxylated bisphenol-A (meth)acrylate ("EBIPMA"), and bisphenol-F mono and di(meth)acrylates, such as ethoxylated bisphenol-A (meth)acrylate.

Still other (meth)acrylate monomers that may be used herein include silicone (meth)acrylate moieties ("SiMA"), such as those taught by and claimed in <CIT>).

Other suitable monomers include polyacrylate esters represented by the formula
<CHM>
where R<NUM> is a radical selected from hydrogen, halogen, and alkyl of from <NUM> to about <NUM> carbon atoms; q is an integer equal to at least <NUM>, and preferably equal to from <NUM> to about <NUM>; and X is an organic radical containing at least two carbon atoms and having a total bonding capacity of q plus <NUM>. With regard to the upper limit for the number of carbon atoms in X, workable monomers exist at essentially any value. As a practical matter, however, a general upper limit is about <NUM> carbon atoms, preferably <NUM>, and most preferably about <NUM>.

For example, X can be an organic radical of the formula:
<CHM>
where each of Y<NUM> and Y<NUM> is an organic radical, preferably a hydrocarbon group, containing at least <NUM> carbon atoms, and preferably from <NUM> to about <NUM> carbon atoms, and Z is an organic radical, preferably a hydrocarbon group, containing at least <NUM> carbon atom, and preferably from <NUM> to about <NUM> carbon atoms. Other classes of useful monomers are the reaction products of di- or tri-alkylolamines (e.g., ethanolamines or propanolamines) with acrylic acids, such as are disclosed in <CIT>.

Non-limiting examples of useful acrylic ester oligomers include those having the following general formula
<CHM>
where R<NUM> represents a radical selected from hydrogen, lower alkyl of from <NUM> to about <NUM> carbon atoms, hydroxyalkyl of from <NUM> to about <NUM> carbon atoms, and
<CHM>
where R<NUM> is a radical selected from hydrogen, halogen, and lower alkyl of from <NUM> to about <NUM> carbon atoms; R<NUM> is a radical selected from hydrogen, hydroxyl, and
<CHM>
m is an integer equal to at least <NUM>, e.g., from <NUM> to about <NUM> or higher, and preferably from <NUM> to about <NUM>; n is an integer equal to at least <NUM>, e.g., <NUM> to about <NUM> or more, and preferably between about <NUM> and about <NUM>; and p is <NUM> or <NUM>.

Typical examples of acrylic ester oligomers corresponding to the above general formula include di-, tri- and tetraethyleneglycol dimethacrylate; di (pentamethyleneglycol)dimethacrylate; tetraethyleneglycol diacrylate; tetraethyleneglycol di(chloroacrylate); diglycerol diacrylate; diglycerol tetramethacrylate; butyleneglycol dimethacrylate; neopentylglycol diacrylate; and trimethylolpropane triacrylate.

While di- and other polyacrylate esters, and particularly the polyacrylate esters described in the preceding paragraphs, can be desirable, monofunctional acrylate esters (esters containing one acrylate group) also may be used. When dealing with monofunctional acrylate esters, it is highly preferable to use an ester which has a relatively polar alcoholic moiety. Such materials are less volatile than low molecular weight alkyl esters and, more important, the polar group tends to provide intermolecular attraction during and after cure, thus producing more desirable cure properties, as well as a more durable sealant or adhesive. Most preferably, the polar group is selected from labile hydrogen, heterocyclic ring, hydroxy, amino, cyano, and halo polar groups. Typical examples of compounds within this category are cyclohexyl methacrylate, tetrahydrofurfuryl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate ("HPMA"), t-butylaminoethyl methacrylate, cyanoethylacrylate, and chloroethyl methacrylate.

The malemide has the general structure:
<CHM>.

The maleimide may be in liquid or solid form.

Alternatively, while mention is made of maleimides, itaconamides or nadimides may likewise be used. Thus, the maleimides, nadimides, and itaconimides include compounds having, respectively, the following structures:
<CHM>
<CHM>
where m = <NUM>-<NUM>, p = <NUM>-<NUM>, each R<NUM> is independently selected from hydrogen or lower alkyl, and J is a monovalent or a polyvalent moiety comprising organic or organosiloxane radicals, and combinations of two or more thereof.

In one embodiment, J is a monovalent or polyvalent radical selected from the group consisting of hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, hydrocarbylene, substituted hydrocarbylene, heteroatom-containing hydrocarbylene, substituted heteroatom-containing hydrocarbylene, polysiloxane, polysiloxane-polyurethane block copolymer, and combinations of two or more thereof, optionally containing one or more linkers selected from a covalent bond, -O-, -S-, -NR-, -O-C(O)-, -O-C(O)-O-, -O-C(O)-NR-, -NR-C(O)-, -NR-C(O)-O-, -NR-C(O)-NR-, -S-C(O)-, -S-C(O)-O-, -S-C(O)-NR-, -S(O)-, -S(O)<NUM>-, -O-S(O)<NUM>-, -O-S(O)<NUM>-O-, -O-S(O)<NUM>-NR-, -O-S(O)-, -O-S(O)-O-, -O-S(O)-NR-, -O-NR-C(O)-, -O-NR-C(O)-O-, -O-NR-C(O)-NR-, -NR-O-C(O)-, -NR-O-C(O)-O-, -NR-O-C(O)-NR-, -O-NR-C (S)-, -<NUM>-NR-C (S)-O-, -O-NR-C(S)-NR-, -NR-O-C(S)-, -NR-O-C(S)-O-, -NR-O-C(S)-NR-, -O-C(S)-, -O-C(S)-O-, -O-C(S)-NR-, -NR-C(S)-, -NR- C(S)-O-, -NR-C(S)-NR-, -S-S(O)<NUM>-, -S-S(O)<NUM>-O-, -S-S(O)<NUM>-NR-, -NR-O-S (O)-, -NR-O-S(O) -O-, -NR-O-S(O)-NR-, -NR-O-S(O)<NUM>-, -NR-O-S (O)<NUM>-O-, -NR-O-S(O)<NUM>-NR-, -O-NR-S(O)-, -O-NR-S(O)-O-, -O-NR-S(O)-NR-, -O-NR-S(O)<NUM>-O-, -O-NR-S(O)<NUM>-NR-, - O-NR-S(O)<NUM>-, -O-P(O)R<NUM>-, -S-P(O)R<NUM>-, and -NR-P(O)R<NUM>-, where each R is independently hydrogen, alkyl or substituted alkyl, and combinations of any two or more thereof.

When one or more of the above described monovalent or polyvalent groups contain one or more of the above described linkers to form the "J" appendage of a maleimide, nadimide or itaconimide group, as readily recognized by those of skill in the art, a wide variety of linkers can be produced, such as, for example, oxyalkyl, thioalkyl, aminoalkyl, carboxylalkyl, oxyalkenyl, thioalkenyl, aminoalkenyl, carboxyalkenyl, oxyalkynyl, thioalkynyl, aminoalkynyl, carboxyalkynyl, oxycycloalkyl, thiocycloalkyl, aminocycloalkyl, carboxycycloalkyl, oxycloalkenyl, thiocycloalkenyl, aminocycloalkenyl, carboxycycloalkenyl, heterocyclic, oxyheterocyclic, thioheterocyclic, aminoheterocyclic, carboxyheterocyclic, oxyaryl, thioaryl, aminoaryl, carboxyaryl, heteroaryl, oxyheteroaryl, thioheteroaryl, aminoheteroaryl, carboxyheteroaryl, oxyalkylaryl, thioalkylaryl, aminoalkylaryl, carboxyalkylaryl, oxyarylalkyl,thioarylalkyl, aminoarylalkyl, carboxyarylalkyl, oxyarylalkenyl, thioarylalkenyl, aminoarylalkenyl, carboxyarylalkenyl, oxyalkenylaryl, thioalkenylaryl, aminoalkenylaryl, carboxyalkenylaryl, oxyarylalkynyl, thioarylalkynyl, aminoarylalkynyl, carboxyarylalkynyl, oxyalkynylaryl, thioalkynylaryl, aminoalkynylaryl or carboxyalkynylaryl. oxyalkylene, thioalkylene, aminoalkylene, carboxyalkylene, oxyalkenylene, thioalkenylene, aminoalkenylene, carboxyalkenylene, oxyalkynylene, thioalkynylene, aminoalkynylene, carboxyalkynylene, oxycycloalkylene, thiocycloalkylene, aminocycloalkylene, carboxycycloalkylene, oxycycloalkenylene, thiocycloalkenylene, aminocycloalkenylene, carboxycycloalkenylene, oxyarylene, thioarylene, aminoarylene, carboxyarylene, oxyalkylarylene, thioalkylarylene, aminoalkylarylene, carboxyalkylarylene, oxyarylalkylene, thioarylalkylene, aminoarylalkylene, carboxyarylalkylene, oxyarylalkenylene, thioarylalkenylene, aminoarylalkenylene, carboxyarylalkenylene, oxyalkenylarylene, thioalkenylarylene, aminoalkenylarylene, carboxyalkenylarylene, oxyarylalkynylene, thioarylalkynylene, aminoarylalkynylene, carboxy arylalkynylene, oxyalkynylarylene, thioalkynylarylene, aminoalkynylarylene, carboxyalkynylarylene, heteroarylene, oxyheteroarylene, thioheteroarylene, aminoheteroarylene, carboxyheteroarylene, heteroatom-containing di- or polyvalent cyclic moiety, oxyheteroatom-containing di- or polyvalent cyclic moiety, thioheteroatom-containing di- or polyvalent cyclic moiety, aminoheteroatom-containing di- or polyvalent cyclic moiety, carboxyheteroatom-containing di- or polyvalent cyclic moiety, disulfide, sulfonamide, and the like.

Particularly desirable maleimides, nadimides, and itaconimides include, for example, maleimides, nadimides, and itaconimides having the following structures:
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
<CHM>
or
<CHM>.

Particularly desirable maleiitiides and nadimides include, but are not limited to,
<CHM>
<CHM>
and
<CHM>
where R<NUM> and R<NUM> here are each selected from alkyl, aryl, aralkyl or alkaryl groups, having from about <NUM> to about <NUM> carbon atoms, with or without substitution or interruption by a member selected from silane, silicon, oxygen, halogen, carbonyl, hydroxyl, ester, carboxylic acid, urea, urethane, carbamate, sulfur, sulfonate and sulfone.

Other desirable maleimides include
<CHM>
<CHM>.

Maleimides should be present in the compositions within the range of from about <NUM> percent by weight to about <NUM> percent by weight, desirably from about <NUM> percent by weight to about <NUM> percent by weight, such as from about <NUM> percent by weight to about <NUM> percent by weight, based on the weight of the total composition.

The cyanate ester may include compounds having the general structure:
<CHM>
where m is from <NUM> to <NUM> and R<NUM> is an aromatic nucleus-containing residue and an (meth)acrylate monomer. The composition is free of added metallic catalyst.

R<NUM> here should contain at least <NUM> carbon atoms and may be derived, for example, from aromatic hydrocarbons, such as benzene, biphenyl, naphthalene, anthracene, pyrene or the like. The aromatic residue may be also be derived from a polynuclear aromatic hydrocarbon in which at least two aromatic rings are attached to each other through a bridging group. In one embodiment, the bridging member has the formula
<CHM>
where Ra and Rb are the same or different and each represents a hydrogen atom or an alkyl group containing <NUM> to <NUM> carbon atoms.

R<NUM> also includes residues derived from novolac-type phenolic resins - i.e., cyanate esters of these phenolic resins. R<NUM> may also contain further ring attached, nonreactive substituents.

Examples of useful cyanate esters include, for instance <NUM>,<NUM>-dicyanatobenzene; <NUM>,<NUM>-dicyanatobenzene; <NUM>,<NUM>,<NUM>-tricyanatobenzene; <NUM>,<NUM>-, <NUM>,<NUM>-, <NUM>,<NUM>-, <NUM>,<NUM>-, <NUM>,<NUM>- or <NUM>,<NUM>-dicyanatonaphthalene; <NUM>,<NUM>,<NUM>-tricyanatonaphthalene; <NUM>,<NUM>'-dicyanato-biphenyl; bis(<NUM>-cyanatophenyl)methane and <NUM>,<NUM>',<NUM>,<NUM>'-tetramethyl, bis(<NUM>-cyanatophenyl)methane; <NUM>,<NUM>-bis(<NUM>,<NUM>-dichloro-<NUM>-cyanatophenyl)propane; <NUM>,<NUM>-bis(<NUM>,<NUM>-dibromo-<NUM>-dicyanatophenyl)propane; bis(<NUM>-cyanatophenyl)ether; bis(<NUM>-cyanatophenyl)sulfide; <NUM>,<NUM>-bis(<NUM>-cyanatophenyl)propane; tris(<NUM>-cyanatophenyl)-phosphite; tris(<NUM>-cyanatophenyl)phosphate; bis(<NUM>-chloro-<NUM>-cyanatophenyl)methane; cyanated novolac; <NUM>,<NUM>-bis[<NUM>-cyanatophenyl-<NUM>-(methylethylidene)]benzene and cyanated, bisphenol-terminated polycarbonate or other thermoplastic oligomer.

Other cyanate esters include those disclosed in <CIT> and <CIT>, <CIT>, and International Patent Publication No. <CIT>.

Particularly desirable cyanate esters for use herein are available commercially from Ciba Specialty Chemicals, Tarrytown, New York under the tradename "AROCY" [<NUM>,<NUM>-di(<NUM>-cyanatophenylethane)]. The structures of four desirable "AROCY" cyanate esters are
<CHM>
<CHM>
<CHM>
<CHM>.

The coreactant should be used in an amount of about <NUM> to about <NUM> percent by weight, based on the total weight of the composition.

The composition may further include a silica component.

In some instances, the silica component should have a mean particle diameter on the nanoparticle size; that is, having a mean particle diameter on the order of <NUM>-<NUM> meters. The silica nanoparticles can be pre-dispersed in epoxy resins, and may be selected from those commercially available under the tradename NANOPOX, from Hanse Chemie, Germany. NANOPOX is a tradename for a product family of silica nanoparticle reinforced epoxy resins showing an outstanding combination of material properties. The silica phase consists of surface-modified, synthetic SiO<NUM> nanospheres with less than <NUM> diameter and an extremely narrow particle size distribution. The SiO<NUM> nanospheres are agglomerate-free dispersions in the epoxy resin matrix resulting in a low viscosity for resins containing up to <NUM> wt% silica.

Commercially available examples of the NANOPOX products include NANOPOX XP <NUM> (a cycloaliphatic epoxy resin matrix), XP <NUM> (a bisphenol A epoxy resin matrix), and XP <NUM> (a bisphenol F epoxy resin matrix). These NANOPOX products are silica nanoparticle dispersions in the noted epoxy resins, at a level of up to about <NUM>% by weight, though the manufacturer reports <NUM>% by weight for the three noted products. These NANOPOX products are believed to have a particle size of about <NUM> to about <NUM>, though the manufacturer reports less than <NUM>.

The silica component should be present in an amount in the range of about <NUM> to about <NUM> percent by weight, such as about <NUM> to about <NUM> percent by weight, desirably about <NUM> to about <NUM> percent by weight, based on the total weight of the composition.

The composition may further include a toughening agent. Representative toughening agents include a core-shell rubber, a CTBN elastomer, or a block copolymer.

When used, the toughening agent should present in an amount between <NUM> to <NUM> percent by weight, based on the total weight of the composition.

The present invention makes use of a catalyst composition. The catalyst composition comprises a lithium salt, an anion of which has a conjugate acid with a pKa of less than <NUM>; and a carboxylic acid, a sulfonic acid, or a combination thereof. The carboxylic acid or sulfonic acid should have a pKa of <NUM> or less, examples of which include adipic acid.

In some embodiments, the anion of the lithium salt may be a Group <NUM> element, such as P, Sb or As.

In some embodiments, the halogen of the hexahalogenated Group <NUM> element may be selected from F, Cl, Br or I.

More specifically, the lithium salt may be lithium hexafluoroantimonate.

Examples of this catalyst include lithium perchlorate, lithium tetrafluoroborate, lithium perchlorate, lithium carboxylates (such as lithium palmitate), lithium sulfonates (such as lithium trifluoromethanesulfonate), and combinations thereof.

A different catalyst composition can also be used. Here, the catalyst composition comprises a lithium salt, an anion of which has a conjugate acid with a pKa of less than <NUM>; and a salt having as an anion a hexahalogenated Group <NUM> element, an example of which anion is hexafluorophosphate. The salt may have as a cation a tetraalkyl ammonium.

The composition may also include one or more of epoxy, episulfide, oxetane, acrylate, methacrylate, maleimide, and cyanate ester as a coreactant, examples of which are as set forth above.

And like above, the coreactant should be used in an amount of about <NUM> to about <NUM> percent by weight, based on the total weight of the composition.

The inventive curable compositions, when exposed to appropriate cure conditions, demonstrates over <NUM> percent polymerization conversion, such as over <NUM> percent polymerization conversion, desirably over <NUM> percent polymerization conversion, and particularly desirably over <NUM> percent polymerization conversion.

The appropriate cure conditions ordinarily are a period of time of <NUM> minutes at a temperature of <NUM>.

The examples below are provided for illustrative purposes.

<NUM> samples of benzoxazine (<NUM>:<NUM> by weight combination of <NUM>,<NUM>'-(methylenedi-<NUM>,<NUM>-phenylene) bis[<NUM>,<NUM>-dihydro-<NUM>-<NUM>,<NUM>-benzoxazine] and <NUM>,<NUM>-dihydro-<NUM>-phenyl-<NUM>-<NUM>,<NUM>-benzoxazine) with <NUM>×<NUM>-<NUM> mol/g of catalyst were prepared by transferring the components into aluminum weighing dishes and mixing vigorously by hand on a hot plate at a temperature of about <NUM> for a period of time of about <NUM> minutes. Small portions (~<NUM>) of each sample were removed from each weighing dish for initial differential scale calorimeter ("DSC") measurements, and the samples were cured in a convection oven at a temperature of about <NUM> for a period of time of about <NUM> minutes. DSC was performed on the cured samples and the percent conversion was calculated from the peak integrations by the following formula: percent conversion = ((I<NUM>-I<NUM>)/I<NUM>) * <NUM>, where I<NUM> is the integration (enthalpy) of the DSC cure peak of the uncured formulation and I<NUM> is the integration of the DSC cure peak after a period of time of <NUM> minutes at a temperature of <NUM>. In all cases the ramp rate was <NUM>/minute and the measurement were taken at <NUM> intervals from <NUM>-<NUM>.

In Table <NUM> below, the catalyst is identified together with the percent conversion.

This example illustrates enhanced cure activity using various lithium salts and combinations with co-catalysts. The procedure of Example <NUM> was followed. All co-catalysts are present at <NUM>×<NUM>-<NUM> mol/g. The percent conversion results shown below in Table <NUM> confirm that higher percent conversions were observed when an acid or a hexafluorophosphate salt co-catalyst was used, even with an unreactive lithium salt. The first two entries in Table <NUM> (sodium and potassium hexafluorophosphate) provide negative controls showing that a percent conversion of <NUM> or greater was not obtained using these two salts with or without a co-catalyst. Examples that do not use a co-catalyst are provided for reference purposes.

This example illustrated high percent conversions in quite short cure times using lithium catalysts, with and without co-catalysts. The procedure of Example <NUM> was followed here, except that cure times of <NUM> and <NUM> minutes were both used at <NUM>. High percent conversion at a short cure time (i.e., <NUM> minutes) were measured for all of the lithium catalyst systems, as can be seen with reference to Table <NUM> below. Examples that do not use a co-catalyst are provided for reference purposes.

This example illustrates use of the lithium catalysts with and without co-catalysts with a single monofunctional benzoxazine. The procedure of Example <NUM> was followed here, except that only a single monofunctional benzoxazine (<NUM>,<NUM>-dihydro-<NUM>-phenyl-<NUM>-<NUM>,<NUM>-benzoxazine) was used instead of the <NUM>:<NUM> benzoxazine combination recited there. Reference to Table <NUM> below shows that these lithium catalysts together with a co-catalyst in each case with a single monofunctional benzoxazine demonstrated a percent conversion of over <NUM>. The lithium hexafluorantimonate catalyst, even without a co-catalyst, demonstrated over a <NUM> percent conversion with a single monofunctional benzoxazine. Examples that do not use a co-catalyst are provided for reference purposes.

Claim 1:
A curable composition comprising:
(a) a benzoxazine component; and
(b) a catalyst composition;
wherein the catalyst composition comprises:
(i) a lithium salt, an anion of which has a conjugate acid with a pKa of less than <NUM>; and
(ii) a carboxylic acid, a sulfonic acid, or a combination thereof;
or wherein the catalyst composition comprises:
(iii) a lithium salt, an anion of which has a conjugate acid with a pKa of less than <NUM>; and
(iv) a salt having as an anion a hexahalogenated Group <NUM> element.