Curative composition and a resin composition containing the curative composition

Abstract

This invention relates to a curative composition and its use in curing epoxy resins and prepregs, adhesives and moulded materials derived therefrom. The curative composition comprises a clathrate comprising a host component and a guest component, the host comprising a carboxylic acid or ester compounds as defined or phenolphthalin and the guest comprising an imidazole or imidazoline component.

Claims

1. A clathrate composition containing a host component (A) and a guest component (B), i. the host component (A) being defined by a. the formula (I): ##STR00011## where n is 1 Ar is a substituted or unsubstituted aryl group X is independently selected from H, OH, a substituted or unsubstituted alkyl group and a substituted or unsubstituted aryl group; Y is independently selected from H, OH, an aryl group, a substituted or unsubstituted alkyl group, and a substituted or unsubstituted aryl group; wherein two or more of X, Y and Ar are an aryl group with a hydroxyl sub stituent; wherein R is a divalent substituted or unsubstituted aliphatic hydrocarbyl group and wherein Z is COOH; and b. the guest component (B) is selected from at least one compound selected from the group consisting of compounds represented by formula (II): ##STR00012## in which R.sub.1 each independently represents a hydrogen atom, a C.sub.10-C.sub.10 alkyl group, an aryl group, an arylalkyl group, or a cyanoethyl group, and R.sub.2 to R.sub.4 each independently represent a hydrogen atom, a nitro group, a halogen atom, a C.sub.1-C.sub.20 alkyl group, a C.sub.1-C.sub.20 alkyl group substituted with a hydroxy group, an aryl group, an arylalkyl group, or a C.sub.1-C.sub.20 acyl group; and a part with a dashed line represents a single bond or a double bond.

2. The composition according to claim 1 in which the guest component has a triggered release from the host component.

3. The composition according to claim 2, wherein the host component (A) contains a single carboxylic acid or carboxylic acid ester group.

4. The composition according to claim 3 in which the host compound is 4,4′-bis(p-hydroxyphenyl)valeric acid (BHPVA).

5. A clathrate composition containing a host component (A), comprising 2,2′-bis(p-hydroxyphenyl) propionic acid (BHPPA); and a guest component (B), the guest component (B) is selected from at least one compound selected from the group consisting of compounds represented by formula (II): ##STR00013## in which R.sub.1 each independently represents a hydrogen atom, a C.sub.1-C.sub.10 alkyl group, an aryl group, an arylalkyl group, or a cyanoethyl group, and R.sub.2 to R.sub.4 each independently represent a hydrogen atom, a nitro group, a halogen atom, a C.sub.1-C.sub.20 alkyl group, a C.sub.1-C.sub.20 alkyl group substituted with a hydroxy group, an aryl group, an arylalkyl group, or a C.sub.1-C.sub.20 acyl group; and a part with a dashed line represents a single bond or a double bond.

Description

Specific Description

(1) Various embodiments of the inventions will now be discussed.

(2) The present invention is based on the finding that a clathrate can be formed from blending in an organic solvent a specific host component (A) such as a carboxylic acid compound represented by

(3) ##STR00004## where n is 0 or 1 Ar is an optionally substituted aryl group X is independently selected from H, OH, an optionally substituted alkyl group and an optionally substituted aryl group; Y is independently selected from H, OH, an aryl group, an optionally substituted alkyl group, an optionally substituted aryl group; R is a divalent optionally substituted hydrocarbyl group and

(4) Z is selected from: 1) C(═O)O—R′ wherein R′ is selected from hydrogen, an optionally substituted hydrocarbyl group; and 2) a ring structure including Y and C or the host component (A) is a phenolphthalin

(5) and a curative compound having an amino group. Imidazole based and imidazoline based curative compounds are particularly suited.

(6) In a further embodiment there is provided a curable epoxy resin composition containing at least the following component (1.) and component (2.):

(7) (1.) an epoxy resin; and

(8) (2.) a clathrate containing the following: i. the host component (A) being defined by a) formula (I):

(9) ##STR00005## where n is 0 or 1 Ar is an optionally substituted aryl group X is independently selected from H, OH, an optionally substituted alkyl group and an optionally substituted aryl group; Y is independently selected from H, OH, an aryl group, an optionally substituted alkyl group, an optionally substituted aryl group; R is a divalent optionally substituted hydrocarbyl group and Z is selected from: 1) C(═O)O—R′ wherein R′ is selected from hydrogen, an optionally substituted hydrocarbyl group; and 2) a ring structure including Y and C or b) a phenolphthalin ii. the guest component (B) comprising a curative.

(10) The average particle size D50 of the clathrate as measured by laser diffraction (ASTM D4464) is, but not particularly limited to, the range of about 0.01 to 100 μm, preferably in the range of about 0.1 to 100 μm, more preferably from 1 to 50 μm and even more preferably from 5 to 40 μm or from 10 to 30 μm and/or combinations of the aforesaid ranges.

(11) Epoxy Resin Component (1.)

(12) The epoxy component may be mono-functional or multifunctional, preferably at least difunctional. In an embodiment, the epoxy resin component (A) may be selected from various conventionally-known polyepoxy compounds. Examples thereof include: aromatic glycidyl ether compounds such as bis(4-hydroxyphenyl)propane diglycidyl ether, bis(4-hydroxy-3,5-dibromophenyl)propane diglycidyl ether, bis(4-hydroxyphenyl)ethane diglycidyl ether, bis(4-hydroxyphenyl)methane diglycidyl ether, resorcinol diglycidyl ether, phloroglucinol triglycidyl ether, trihydroxy biphenyl triglycidyl ether, tetraglycidyl benzophenone, bisresorcinol tetraglycidyl ether, tetramethyl bisphenol A diglycidyl ether, bisphenol C diglycidyl ether, bisphenol hexafluoropropane diglycidyl ether, 1,3-bis[1-(2,3-epoxypropoxy)-1-trifluoromethyl-2,2,2-trifluoroethyl]benzene, 1,4-bis[1-(2,3-epoxypropoxy)-1-trifluoromethyl-2,2,2-trifluoromethyl]benzene, 4,4′-bis(2,3-epoxypropoxy)octafluorobiphenyl, and phenolic novolac type bisepoxy compounds; alicyclic polyepoxy compounds such as alicyclic diepoxy acetal, alicyclic diepoxy adipate, alicyclic diepoxy carboxylate, and vinylcyclohexene dioxide; glycidyl ester compounds such as diglycidyl phthalate, diglycidyl tetrahydrophthalate, diglycidyl hexahydrophthalate, dimethylglycidyl phthalate, dimethylglycidyl hexahydrophthalate, diglycidyl-p-oxybenzoate, diglycidylcyclopentane-1,3-dicarboxylate, and dimer acid glycidyl ester; glycidyl amine compounds such as diglycidyl aniline, diglycidyl toluidine, triglycidyl aminophenol, tetraglycidyl diaminodiphenyl methane, and diglycidyl tribromoaniline; and heterocyclic epoxy compounds such as diglycidylhydantoin, glycidyl glycidoxyalkylhydantoin, and triglycidyl isocyanurate; and oligomer compounds thereof.

(13) Examples of the liquid epoxy resin include polyalkylene ether type epoxy compounds such as (poly)ethylene glycol diglycidyl ether, (poly)propylene glycol diglycidyl ether, and trimethylolpropane triglycidyl ether; glycidyl ester type epoxy compounds such as dimer acid diglycidyl ester, phthalic acid diglycidyl ester, and tetrahydrophtalic acid diglycidyl ester; and homopolymers of glycidyl (meth)acrylate, allyl glycidyl ether and the like or copolymers of these monomers with other soft unsaturated monomers. In this context, soft unsaturated monomer refers to a monomer which contains a homopolymer which has a glass transition temperature of less than 60° C. Examples of soft unsaturated monomers include methyl acrylate, ethyl acrylate, butyl(meth)acrylate, isobutyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, and lauryl methacrylate.

(14) Clathrate Component (2.)

(15) In the present invention, the term “clathrate” refers to a compound in which two or more molecules are bound via a bond other than a covalent bond, and more preferably, it refers to a crystalline compound in which two or more molecules are bound via their molecular interaction. For Example in a clathrate formed between a host containing a carboxyl or carboxylic acid ester group such as phenolphthalin and a guest component containing nitrogen such as an imidazoline the molecules may be bound by one of the hydrogens on the nitrogen forming a hydrogen bond with the oxygen of the carboxylate functionality.

(16) A compound which includes is referred to as the host compound and the compound which is included in the host compound is referred to as the guest compound. The host compound and the guest compound form the clathrate compound or structure.

(17) Instead of a single guest compound, two or more different guest compounds may be present in the clathrate. The guest compounds are preferably amino based curatives such as imidazole compounds or imidazoline compounds as defined above under formula (II). The guest compounds may also include accelerators or a combination of curatives and accelerators.

(18) Host Compound (A)

(19) The host compound (A) is at least one compound selected from the group consisting of a carboxylic acid compound represented by a phenolphthalin or the formula (I): i. the host component (A) being defined by the formula (I):

(20) ##STR00006## where n is 0 or 1 Ar is an optionally substituted aryl group X is independently selected from H, OH, an optionally substituted alkyl group and an optionally substituted aryl group; Y is independently selected from H, OH, an aryl group, an optionally substituted alkyl group, an optionally substituted aryl group; R is a divalent optionally substituted hydrocarbyl group and Z is selected from 1) C(═O)O—R′ wherein R′ is selected from hydrogen, an optionally substituted hydrocarbyl group; and 2) a ring structure formed including Y and C in formula I;

(21) R and R′ may be independently a linear or branched substituted or unsubstituted, saturated or unsaturated C.sub.1-C.sub.9 alkyl or aryl hydrocarbyl group and when it is an alkyl group it may be cyclic or heterocyclic.

(22) The “optional substituent” of R and/or R′ may be a halogen atom, a C.sub.1-C.sub.6 alkyl group, an aryl group, a C.sub.1-C.sub.6 alkoxy group, a hydroxy group, a carboxy group, a nitro group, an amino group, and an acyl group.

(23) In preferred embodiments the carboxylic acid or carboxylic ester compound may be selected from phenylacetic acid, 4-aminophenylacetic acid (APAA), phenolphthalin ® (PhPh), benzilic acid (BA), 2,2-bis(p-hydroxyphenyl)propionic acid (BHPPA), or 4,4-bis(p-hydroxyphenyl)valeric acid (BHPVA) or 2,2-bis(p-hyroxyphenyl) acetic acid (BHPAA) and their alkyl esters preferably C.sub.1 to C.sub.9 alkyl ester.

(24) Guest Compound (B)

(25) The guest component (B) preferably comprises an accelerator or curative compound having an amino group. Imidazole-based and/or imidazoline based curative compounds are particularly suitable.

(26) The guest component (B) may be selected from at least one compound selected from the group consisting of a compound represented by formula (II) and/or DBCA.

(27) In the formula (II), R.sub.1 represents a hydrogen atom, a C.sub.1-C.sub.10 alkyl group, an aryl group, an arylalkyl group, or a cyanoethyl group, and preferably represents a hydrogen atom.

(28) The C.sub.1-C.sub.10 alkyl group is preferably a C.sub.1-C.sub.6 alkyl group, and optionally has a substituent. Specific examples of the C.sub.1-C.sub.10 alkyl group can include a methyl group, an ethyl group, a n-propyl group, an i-propyl group, a n-butyl group, a s-butyl group, an i-butyl group, a t-butyl group, a n-pentyl group, a n-hexyl group, a nonyl group, an i-nonyl group, and a decyl group.

(29) The aryl group means a monocyclic or polycyclic aryl group. Here, in the case of a polycyclic aryl group, the aryl group also encompasses a partially saturated group in addition to a fully unsaturated group. Examples thereof include a phenyl group, a naphthyl group, an azulenyl group, an indenyl group, an indanyl group, and a tetralinyl group. Among these groups, a C.sub.6-C.sub.10 aryl group is preferred. Further, the aryl group optionally has a substituent.

(30) The arylalkyl group is a group in which the aryl group and the alkyl group are combined with each other. Examples thereof include a benzyl group, a phenethyl group, a 3-phenyl-n-propyl group, a 1-phenyl-n-hexyl group, a naphthalen-1-ylmethyl group, a naphthalen-2-ylethyl group, a 1-naphthalen-2-yl-n-propyl group, and an inden-1-ylmethyl group. Among these groups, a C.sub.6-C.sub.10 aryl/C.sub.1-C.sub.6 alkyl group are preferred. Further, the arylalkyl group optionally has a substituent.

(31) R.sub.2 to R.sub.4 each independently represent a hydrogen atom, a nitro group, a halogen atom, a C.sub.1-C.sub.20 alkyl group, a C.sub.1-C.sub.20 alkyl group substituted with a hydroxy group, an aryl group, an arylalkyl group, or a C.sub.1-C.sub.20 acyl group.

(32) Examples of the C.sub.1-C.sub.20 alkyl group include a methyl group, an ethyl group, a n-propyl group, an i-propyl group, a n-butyl group, a s-butyl group, an i-butyl group, a t-butyl group, a n-pentyl group, a n-hexyl group, a nonyl group, an i-nonyl group, a decyl group, a lauryl group, a tridecyl group, a myristyl group, a pentadecyl group, a palmityl group, a heptadecyl group, and a stearyl group. A C.sub.1-C.sub.10 alkyl group is preferred.

(33) The aryl group and the arylalkyl group include the same groups as the groups for R.sub.1.

(34) The C.sub.1-C.sub.20 acyl group means a group in which a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, or the like is combined with a carbonyl group. Examples of the acyl group include a formyl group; alkylcarbonyl groups such as an acetyl group, a propionyl group, a butyroyl group, a pentanoyl group, a hexanoyl group, a heptanoyl group, an octanoyl group, a nonanoyl group, a decanoyl group, a 3-methylnonanoyl group, an 8-methylnonanoyl group, a 3-ethyloctanoyl group, a 3,7-dimethyloctanoyl group, an undecanoyl group, a dodecanoyl group, a tridecanoyl group, a tetradecanoyl group, a pentadecanoyl group, a hexadecanoyl group, a 1-methylpentadecanoyl group, a 14-methylpentadecanoyl group, a 13,13-dimethyltetradecanoyl group, a heptadecanoyl group, a 15-methylhexadecanoyl group, an octadecanoyl group, a 1-methylheptadecanoyl group, a nonadecanoyl group, an eicosanoyl group, and a heneicosanoyl group; alkenylcarbonyl groups such as an acryloyl group, a methacryloyl group, an allylcarbonyl group, and a cinnamoyl group; alkynylcarbonyl groups such as an ethynylcarbonyl group and a propynylcarbonyl group; arylcarbonyl groups such as a benzoyl group, a naphthylcarbonyl group, a biphenylcarbonyl group, and an anthranilcarbonyl group; and heteroarylcarbonyl groups such as a 2-pyridylcarbonyl group and a thienylcarbonyl group. Among these groups, a C.sub.1-C.sub.20 (including a carbonyl group) acyl group is preferred, and a C.sub.1-C.sub.6 acyl group is particularly preferred.

(35) Specific examples of the imidazole compound represented by formula (II) include imidazole, 2-ethyl-4-methylimidazole, 1-methylimidazole, 2-methylimidazole, 4-methylimidazole, 1-benzyl-2-methylimidazole, 2-heptadecylimidazole, 2-undecylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, 1,2-dimethylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, and 2-phenyl-4,5-dihydroxymethylimidazole, and imidazole, 2-ethyl-4-methylimidazole, 1-methylimidazole, 2-methylimidazole, 4-methylimidazole, 1-benzyl-2-methylimidazole, 2-heptadecylimidazole, 2-undecylimidazole, 1,2-dimethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2-phenylimidazole, or 2-phenyl-4,5-dihydroxymethylimidazole is preferred.

(36) Examples of the imidazoline compound represented by formula (II) include 2-methylimidazoline, 2-phenylimidazoline, 2-undecylimidazoline, 2-heptadecylimidazoline, 2-ethylimidazoline, 2-isopropylimidazoline, 2,4-dimethylimidazoline, and 2-phenyl-4-methylimidazoline, and 2-methylimidazoline or 2-phenylimidazoline is preferred.

(37) With respect to the clathrate of the compound of (i) with the imidazole compound or imidazoline compound and/or DBCA of (ii), the combination thereof is not particularly limited as long as these compounds are within the range as described above.

(38) Method for Producing Clathrate

(39) With respect to the method for producing the clathrate, the clathrate can be obtained by directly mixing the compound of (A) with the imidazole compound or imidazoline compound and/or DBCA (B) with all components in their liquid (molten) phase, or by mixing these compounds in a solvent.

(40) When a solvent is used, the clathrate can be obtained by adding the host compound and the guest compound to a solvent, followed by subjecting the resulting mixture to heat treatment or heating and reflux treatment with optional stirring to precipitate the clathrate. It is preferred to use organic solvents such as methanol, acetone, and ethyl acetate as a solvent.

(41) When the imidazole compound or imidazoline compound and/or DBCA of (B) is a substance having a low boiling point or a substance having high vapour pressure, a target clathrate can be obtained by applying the vapour of these substances to the compound of (A).

(42) A clathrate consisting of three components or more can also be obtained by allowing two or more types of compounds of (B) to react with the compound of (A). Furthermore, a target clathrate can be obtained by first producing a clathrate of a compound of (A) with a certain compound (ii) and then allowing the resulting clathrate to react with a different compound of (ii) in the manner as described above.

(43) The structure of the clathrate obtained can be verified by thermal analysis (TGA-DSC, Simultaneous Thermogravimetry & Differential Scanning calorimetry), an infrared absorption spectrum (IR), an X-ray diffraction pattern, a NMR spectrum, or the like, X-ray diffraction being particularly useful. Further, the composition of the clathrate can be verified by thermal analysis, a .sup.1H-NMR spectrum, high performance liquid chromatography (HPLC), elementary analysis, or the like.

(44) Organic Solvent

(45) Organic solvents may be used in the forming of the clathrates. Suitable organic solvents include alcohols such as methanol, ethanol, propanol, and butanol; ethers such as 2-methoxyethanol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol, diethylene glycol monoethyl ether, and diethylene glycol monobutyl ether; ketones such as acetone, methyl ethyl ketone, 2-pentanone, 2-hexanone, methyl isobutyl ketone, isophorone, and cyclohexanone; esters such as methyl acetate, ethyl acetate, propyl acetate, butyl acetate, isobutyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and diethylene glycol monoethyl ether acetate; and aromatics such as toluene and xylene; and any mixture of two or more of the aforesaid solvents.

(46) Curing Agent or Curing Accelerator

(47) When the component (B) is a curing agent, a curing accelerator may be further included, and when the component (B) is a curing accelerator, a curing agent may be further included.

(48) A curing agent which may be contained in addition to the curing agent accelerator is not particularly limited as long as it is a compound which reacts with an epoxy group in an epoxy resin to cure the epoxy resin. Similarly, a curing accelerator which may be contained in addition to the curing agent is not particularly limited as long as it is a compound which accelerates the above curing reaction. Any one of conventional curing agents or curing accelerators of epoxy resins can be selected and used as such a curing agent or a curing accelerator, respectively. Examples thereof include amine-based compounds such as aliphatic amines, alicyclic and heterocyclic amines, aromatic amines, and modified amines, imidazole-based compounds, imidazoline-based compounds, amide-based compounds, ester-based compounds, phenol-based compounds, alcohol-based compounds, thiol-based compounds, ether-based compounds, thioether-based compounds, urea-based compounds, thiourea-based compounds, Lewis acid-based compounds, phosphorus-based compounds, acid anhydride-based compounds, onium salt-based compounds, and active silica compound-aluminium complexes.

(49) Specific examples of the curing agent or the curing accelerator include the following compounds.

(50) Examples of the aliphatic amines include ethylenediamine, trimethylenediamine, triethylenediamine, tetramethylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenediamine, dimethylaminopropylamine, diethylaminopropylamine, trimethylhexamethylenediamine, pentanediamine, bis(2-dimethylaminoethyl)ether, pentamethyldiethylenetriamine, alkyl-t-monoamine, 1,4-diazabicyclo(2,2,2)octane(triethylenediamine), N,N,N′,N′-tetramethylhexamethylenediamine, N,N,N′,N′-tetramethylpropylenediamine, N,N,N′,N′-tetramethylethylenediamine, N,N-dimethylcyclohexylamine, dibutylaminopropylamine, dimethylaminoethoxyethoxyethanol, triethanolamine, and dimethylaminohexanol.

(51) Examples of the alicyclic and heterocyclic amines include piperidine, piperazine, menthanediamine, isophoronediamine, methylmorpholine, ethylmorpholine, N,N′,N″-tris(dimethylaminopropyl)hexahydro-s-triazine, 3,9-bis(3-aminopropyl)-2,4,8,1 0-tetraoxyspiro(5,5)undecane adduct, N-aminoethylpiperazine, trimethylaminoethylpiperazine, bis(4-aminocyclohexyl)methane, N,N′-dimethylpiperazine, and 1,8-diazabicyclo[4.5.0]undecec-7ene and 1,5 diazabicyclo(4.3.0) non-5-ene.

(52) Examples of the aromatic amines include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, diaminodiphenylmethane, diaminodiphenyl sulfone, benzylmethylamine, dimethylbenzylamine, m-xylenediamine, pyridine, picoline, and a-methylbenzylmethylamine.

(53) Examples of the modified amines include epoxy compound-added polyamine, Michael-added polyamine, Mannich-added polyamine, thiourea-added polyamine, ketone-blocked polyamine, dicyandiamide, guanidine, organic acid hydrazide, diaminomaleonitrile, amine imide, a boron trifluoride-piperidine complex, and a boron trifluoride-monoethylamine complex.

(54) Examples of the imidazole-based compounds include imidazole, 1-methylimidazole, 2-methylimidazole, 3-methylimidazole, 4-methylimidazole, 5-methylimidazole, 1-ethylimidazole, 2-ethylimidazole, 3-ethylimidazole, 4-ethylimidazole, 5-ethylimidazole, 1-n-propylimidazole, 2-n-propylimidazole, 1-isopropylimidazole, 2-isopropylimidazole, 1-n-butylimidazole, 2-n-butylimidazole, 1-isobutylimidazole, 2-isobutylimidazole, 2-undecyl-1 H-imidazole, 2-heptadecyl-1H-imidazole, 1,2-dimethylimidazole, 1,3-dimethylimidazole, 2,4-dimethylimidazole, 2-ethyl-4-methylimidazole, 1-phenylimidazole, 2-phenyl-1 H-imidazole, 4-methyl-2-phenyl-1 H-imidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylim idazole, 1 -cyanoethyl-2-methylim idazole, 1 -cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 2-phenylimidazole-isocyanuric acid adduct, 2-methylimidazole-isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 1-cyanoethyl-2-phenyl-4,5-d i(2-cyanoethoxy)methylimidazole, 1 -dodecyl-2-methyl-3-benzylimidazolium chloride, and 1-benzyl-2-phenylimidazole hydrochloride.

(55) Examples of the imidazoline-based compounds include 2-methylimidazoline and 2-phenylimidazoline.

(56) Examples of the amide-based compounds include a polyamide obtained by condensation of a dimer acid with a polyamine.

(57) Examples of the ester-based compounds include active carbonyl compounds such as an aryl ester and a thioaryl ester of a carboxylic acid.

(58) Examples of the phenol-based compounds, alcohol-based compounds, thiol-based compounds, ether-based compounds, and thioether-based compounds include, as a phenolic resin curing agent, aralkyl type phenolic resins such as a phenol aralkyl resin and a naphthol aralkyl resin, novolac type phenolic resins such as a phenolic novolac resin and a cresol novolac resin, modified resin thereof such as epoxidized or butylated novolac type phenolic resins, dicyclopentadiene-modified phenolic resins, paraxylene-modified phenolic resins, triphenol alkane type phenolic resins, and polyfunctional phenolic resins. Further examples include polyols, polymercaptans, polysulfides, 2-(dimethylaminomethylphenol), 2,4,6-tris(dimethylaminomethyl)phenol, and tri-2-ethylhexyl hydrochloride of 2,4,6-tris(dimethylaminomethyl)phenol.

(59) Examples of the urea-based compounds, thiourea-based compounds, Lewis acid-based compounds include a butylated urea, a butylated melamine, a butylated thiourea, and boron trifluoride.

(60) Examples of the phosphorus-based compounds include organic phosphine compounds, including primary phosphines such as alkylphosphines such as ethylphosphine and butyl phosphine, and phenylphosphine; secondary phosphines such as dialkyl phosphines such as dimethylphosphine and dipropylphosphine, diphenylphosphine, and methylethylphosphine; and tertiary phosphines such as trimethylphosphine, triethylphosphine, and triphenylphosphine.

(61) Examples of the acid anhydride compounds include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, maleic anhydride, tetramethylenemaleic anhydride, trimellitic anhydride, chlorendic anhydride, pyromellitic anhydride, dodecenylsuccinic anhydride, benzophenone tetracarboxylic acid anhydride, ethyleneglycol bis(anhydrotrimellitate), glycerol tris(anhydrotrimellitate), methylcyclohexene tetracarboxylic acid anhydride, and polyazelaic acid anhydride.

(62) Examples of the onium salt-based compounds and active silica compound-aluminum complexes include aryldiazonium salt, diaryliodonium salt, triarylsulfonium salt, a triphenylsilanol-aluminum complex, a triphenylmethoxysilane-aluminum complex, a silyl peroxide-aluminum complex, and a triphenylsilanol-tris(salicylaldehydato)aluminum complex.

(63) Particularly, amine-based compounds, imidazole-based compounds, and phenol-based compounds are preferably used as the curing agent or the curing accelerator. Among the phenol-based compounds, a phenolic resin curing agent is more preferably used.

(64) Prepreg Matrix Formulation

(65) In a further embodiment a moulding material is provided comprising a reinforcement material and resin formulation containing a clathrate composition according to this invention.

(66) The moulding material may be constructed from a cast resin film which contains the resin formulation and which is combined with a fibrous reinforcement layer. Preferably the resin film impregnates the fibrous reinforcement which may be accomplished by pressing a layer of resin onto the fibrous material or by infusion of the resin into fibrous material within a mould.

(67) A liquid curable epoxy resin composition of the present invention is particularly useful as a prepreg matrix resin formulation comprising epoxy resin component (1.) and clathrate component (2.).

(68) The prepreg resin formulation of the present invention is excellent in both storage stability and curing characteristics although it is a one-component liquid epoxy resin composition. A prepreg resin formulation which is significantly excellent in storage stability and curing characteristics and provides a cured product significantly excellent in characteristics, particularly organic solvent resistance, can be obtained by using, a clathrate which is the component (2.) of the prepreg resin formulation of the present invention.

(69) In the prepreg resin formulation of the present invention, the clathrate component (2.) can be used as a curing agent or as a curing accelerator. The component (2.) contains a host (A) and a guest component (B).

(70) The guest component (B) which may operate as a curing agent or as a curing accelerator. The component (B) is quickly released by heating from a host component (A), and if the component (B) is a curing agent, it will undergo a crosslinking reaction with the resin component (1.). If the component (B) is an accelerator, the released curing accelerator acts as a curing catalyst of the curing agent and the resin component (1.), thereby forming a cured formulated resin matrix. Since the temperature at which the curing agent or the curing accelerator is released is different depending on: the type of the guest component (chemical structure); the type of host component (chemical structure); and the blending ratio of the guest to the host, solubility in the epoxy resin
the conditions for the release of the host component can be controlled by selecting appropriate host and guest components.

(71) In the resin formulations of the present invention, the host compound can react with the resin after releasing the guest compound, thereby having an effect as a crosslinking agent. This is particularly so when the host compound is a carboxylic acid and can result in the cured resin formulation product having improved flexibility and improved impact resistance and adhesion. This is an important advantage over known clathrates which may be used as curatives or accelerators in epoxy resin formulations.

(72) When the epoxy resin composition of the present invention is used as a prepreg resin formulation, known additives such as fillers, viscosity modifiers, tougheners, pigments, thixotropic agents, and fire retardants, or the like can be optionally mixed into the formulation to enhance its mechanical performance and flow behaviour during cure.

(73) A prepreg resin formulation of the present invention can be prepared by uniformly mixing the clathrate of the invention, the resin and other additives using a pot mill, a ball mill, a bead mill, a roll mill, a homogenizer, Supermill, Homodisper, a universal mixer, Banbury mixer, a kneader, or the like.

(74) Since the prepreg resin formulation of the present invention can be a one-component type and has both high storage stability and excellent thermosetting properties, it can be suitably used for applications which require long term storage or storage in unconditioned facilities at room temperature.

(75) We will now disclose a number of preferred clathrate components (2.) which can be used in combination with a suitable resin component (1.).

(76) We have found that clathrates with dicarboxylic acid hosts in which the carboxyl groups are linked totally directly to an aromatic nucleus tend to have good outlife but lack the required reactivity for snap cure. On the other hand, clathrates with tri and di functional phenolic hosts tend to have the desired reactivity for snap cure but tend to have poor outlife.

(77) In a preferred embodiment, the host component (A) contains both phenolic and carboxylic acid or ester functionalities both of which are capable of forming clathrates with imidazoles. For example a preferred host component is 4,4′-bis(4′-hydroxyphenyl)valeric acid (BHPVA) which contain both phenol and carboxylic acid functionalities. Preferably the clathrate is formed with 2-ethyl-4-methylimidazole (2E4MZ). The structures are shown below.

(78) ##STR00007##

(79) This clathrate of BHPVA with 2E4MZ can be prepared by stirring in BHPVA in a refluxing organic solvent and adding in the imidazole guest component (B) in the same solvent. The precipitate of this mixture is the clathrate of BHPVA-2E4MZ.

(80) Other monocarboxylic clathrate compositions according to the invention are now described.

(81) Another preferred host component (A) may be phenolphthalin (PhPh) which contains bis-phenol and mono-carboxylic acid functionalities, both of which are capable of forming clathrates with imidazoles. Preferably the clathrate is formed with 2-ethyl-4-methylimidazole (2E4MZ), 2-methylimidazole (2MZ) or imidazole (IMZ). The structure with 2E4MZ is shown below.

(82) ##STR00008##

(83) In another clathrate, the host component (A) may be benzilic acid (BA) which contains phenyl and mono-carboxylic acid functionalities, which is capable of forming clathrates with imidazoles. Again, preferably the clathrate is formed with 2-ethyl-4-methylimidazole (2E4MZ). The structures are shown below.

(84) ##STR00009##

(85) In another clathrate, the host component (A) may be 4-aminophenylacetic acid (APAA) containing aminophenyl and mono-carboxylic acid functionalities, both of which are capable of forming clathrates with imidazoles. Again, preferably the clathrate is formed with 2-ethyl-4-methylimidazole (2E4MZ). The structures are shown below.

(86) ##STR00010##

(87) The esters of these carboxylic acid based clathrates are also embodiments of the invention.

EXAMPLES

(88) Embodiments of the invention will now be described by way of example only and with reference to the below Examples.

(89) The following constituent components were used in the preparation of the compositions of the Examples.

(90) TABLE-US-00001 Component Description Host BHPVA 4,4′-bis(4′-hydroxyphenyl)valeric acid PhPh phenolphthalin BHPPA 2,2-bis(p-hydroxyphenyl)propionic acid BA benzilic acid APAA 4-aminophenylacetic acid BHPAA 2,2-bis(p-hydroxyphenyl)acetic acid Comparative Host PDCA 2,6-pyridine dicarboxylic acid SA succinic acid Guest C11Z 2-undecylimidazole IMZ imidazole 2MZ 2-methylimidazole 2E4MZ 2-ethyl-4-methylimidazole 2PZL 2-phenylimidazoline DBU 1,8-diazabicyclo(5.4.0)undec-7-ene IPDA isophorone diamine MXDA meta-xylylenediamine BDMA N1N-dimethylbenzylamine DMP30 (2,4,6-trisdimethylaminomethyl)phenol Resin LY1556 bisphenol A epoxy resin (Huntsman) Epikote 828 bisphenol A epoxy resin (Hexion)

(91) The following methods were used to measure various parameters of the cured resin:

(92) Dynamic differential scanning calorimetry (DSC) was performed using a TA Q100 instrument to determine uncured glass transition temperature (Tg) in accordance with ASTM D7028, cure onset temperatures T.sub.c, and reactivity and residual cure using a heating rate of 10° C./min, from −50 to 350° C.

(93) Isothermal differential scanning calorimetry (DSC) was performed using a DSC 1 from Mettler Toledo instrument to determine time to 95% cure at various temperatures and cure schedules.

(94) Dynamic mechanical analysis (DMA) was performed using a Q800 instrument on cured resin to determine glass transition temperatures Tg at a heating rate of 5° C./min and at a frequency of 1 Hz, and at an amplitude of 30 μm. E′ Tg was determined in accordance with ASTM D7028-07 (2015).

(95) All clathrates obtained according to the processes described in the examples were verified as clathrates by means of measuring IR spectra, NMR spectra, and thermal analysis (TGA-DSC).

Comparative Example 1—PDCA-IMZ

(96) 10.0 g of 2,6-pyridine dicarboxylic acid was stirred in 200 ml of refluxing ethyl acetate. 4.1 g of imidazole was added to the solution portion-wise. The mixture was refluxed for 3 hours before allowing to cool to room temperature. The resulting precipitate was collected by filtration and dried in a vacuum oven at room temperature overnight to give 13.8 g of a white powder. The ratio of host to guest in the precipitated clathrate was shown to be approximately 1:1 by 1H NMR which is equal to 28.9 wt. % of imidazole.

Comparative Example 2—PDCA-C11Z

(97) 10.0 g of 2,6-pyridine dicarboxylic acid and 13.3 g of 2-undecylimidazole were stirred in 200 ml of refluxing ethyl acetate. The mixture was refluxed for 3 hours before allowing to cool to room temperature. The resulting precipitate was collected by filtration and dried in a vacuum oven at room temperature overnight to give 22.6 of a white powder. The ratio of host to guest in the precipitated clathrate was shown to be approximately 1:1 by 1H NMR which is equal to 57.1 wt. % of imidazole.

Comparative Example 3—SA-2E4MZ

(98) 10.0 g of succinic acid was stirred in 70 ml of refluxing methanol. A solution of 9.5 g of 2-ethyl-4-methylimidazole in 15 ml of acetone was added to the solution drop-wise. The mixture was refluxed for 3 hours before allowing to cool to room temperature. The resulting precipitate was collected by filtration and dried in a vacuum oven at room temperature overnight to give 16.5 g of a white powder. The ratio of host to guest in the precipitated clathrate was shown to be approximately 1:1 by 1H NMR which is equal to 48.3 wt. % of imidazole.

Example 1—BHPVA-2E4MZ

(99) 10.0 g of 4,4′-bis(4′-hydroxyphenyl)valeric acid was stirred in 150 ml of refluxing acetone. A solution of 3.85 g of 2-ethyl-4-methylimidazole in 15 ml of acetone was added to the solution drop-wise. The mixture was refluxed for 3 hours before allowing to cool to room temperature. The resulting precipitate was collected by filtration and dried in a vacuum oven at room temperature overnight to give 12.3 g of a white powder. The ratio of host to guest in the precipitated clathrate was shown to be approximately 1:1 by 1H NMR which is equal to 27.8 wt. % of imidazole.

Example 2—BHPVA-2MZ

(100) BHPVA-2MZ was prepared using the procedure in example 1 with 10.0 g of 4,4′-bis(4′-hydroxyphenyl)valeric acid and 2.9 g of 2-methylimdazole to give 12.9 g of a white powder. The ratio of host to guest in the precipitated clathrate was shown to be approximately 1:1 by 1H NMR which is equal to 22.3 wt. % of imidazole.

Example 3—PhPh-2E4MZ

(101) PhPh-2E4MZ was prepared using the procedure in example 1 with 10.0 g of phenolphthalin and 3.4 g of 2-ethyl-4-methylimidazole to give 12.2 g of a white powder. The ratio of host to guest in the precipitated clathrate was shown to be approximately 1:1 by 1H NMR which is equal to 25.6 wt. % of imidazole.

Example 4—PhPh-2MZ

(102) PhPh-2MZ was prepared using the procedure in example 1 with 10.0 g of phenolphthalin and 2.9 g of 2-methylimdazole to give 12.3 g of a white powder. The ratio of host to guest in the precipitated clathrate was shown to be approximately 1:1 by 1H NMR which is equal to 22.3 wt. % of imidazole.

(103) X-ray crystallographic studies showed the material to be a salt type clathrate containing hydrogen bonds between phenolic groups, carboxylic groups and the nitrogen atoms of the imidazole.

Example 5—PhPh-IMZ

(104) PhPh-IMZ was prepared using the procedure in example 1 with 10.0 g of phenolphthalin and 2.2 g of imidazole to give 11.5 g of a white powder. The ratio of host to guest in the precipitated clathrate was shown to be approximately 1:1 by 1H NMR which is equal to 17.5 wt. % of imidazole.

(105) X-ray crystallographic studies showed the material to be a salt type clathrate containing hydrogen bonds between phenolic groups, carboxylic groups and the nitrogen atoms of the imidazole.

Example 6 BHPPA-2E4MZ

(106) BHPPA-2E4MZ was prepared using the procedure in example 1 with 16.0 g of 2,2′-bis(4′-hydroxyphenyl)propionic acid and 6.8 g of 2-ethyl-4-methylimdazole to give 15.1 g of an off white powder. The ratio of host to guest in the precipitated clathrate was shown to be approximately 1:1 by 1H NMR which is equal to 22.3 wt. % of imidazole.

Example 7—BA-2E4MZ

(107) BA-2E4MZ was prepared using the procedure in example 1 with 10.0 g of benzilic acid and 4.8 g of 2-ethyl-4-methylimdazole to give 13.3 g of a white powder. The ratio of host to guest in the precipitated clathrate was shown to be approximately 1:1 by 1H NMR which is equal to 32.6 wt. % of imidazole.

Example 8—BHPAA-2E4MZ

(108) BHPAA-2E4MZ was prepared using the procedure in example 1 with 6.5 g of 2,2′-bis(P-hydroxyphenyl)acetic acid and 2.7 g of 2-ethyl-4-methylimdazole to give 8.3 g of a cream powder. The ratio of host to guest in the precipitated clathrate was shown to be approximately 1:1 by 1H NMR which is equal to 31.1 wt. % of imidazole.

Example 9—BHPAA-2MZ

(109) BHPAA-2MZ was prepared using the procedure in example 1 with 10.0 g of 2,2′-bis(P-hydroxyphenyl)acetic acid and 3.0 g of 2-methylimdazole to give 9.9 g of an off white powder. The ratio of host to guest in the precipitated clathrate was shown to be approximately 1:1 by 1H NMR which is equal to 25.1 wt. % of imidazole.

Example 10—APAA-2E4MZ

(110) 10 g of 4-aminophenylacetic acid was stirred in 60 ml of refluxing acetone. To the solution/suspension was added 7.3 g of 2-ethyl-4-methylimidazole drop-wise as a solution in 15 ml of acetone. The mixtures were refluxed for 3 hours before cooling to room temperature. The precipitate was removed by filtration. The solvents from the filtrate were removed by rotary evaporation to yield a liquid. Ethyl acetate was added and the product left to crystallise overnight. The crystals were collected by filtration and then dried in a vacuum oven at room temperature overnight to give 12.8 g of a pale orange powder. The ratio of host to guest in the precipitated clathrate was shown to be approximately 1:1 by 1H NMR which is equal to 42.1 wt. % of imidazole.

Example 11—PhPh-2MZ-IMZ

(111) PhPh-2MZ-IMZ was prepared using the procedure in example 1 with 10.0 g of 4 phenolphthalin 1.3 g of 2-methylimidazole and 1.1 g of imidazole to give 12.1 g of a white powder. The ratio of host to guest in the precipitated clathrate was shown to be approximately 1:1 by 1H NMR. The ratio of 2MZ to IMZ in the clathrate was shown to be 0.58 to 0.42 which is equal to 18.7 wt. % of imidazole.

Example 12—BHPVA-2PZL

(112) BHPVA-2PZL was prepared using the procedure in example 1 with 10.0 g of 4,4′-bis(4′-hydroxyphenyl)valeric acid and 5.1 g of 2-phenylimidazoline to give 14.7 g of a cream powder. The ratio of host to guest in the precipitated clathrate was shown to be approximately 1:1 by 1H NMR which is equal to 33.8 wt. % of imidazoline.

Example 13—PhPh-2PZL

(113) PhPh-2PZL was prepared using the procedure in example 1 with 10.0 g of phenolphthalin and 5.3 g of 2-phenylimidazoline to give 14.3 g of a white powder. The ratio of host to guest in the precipitated clathrate was shown to be approximately 1:1 by 1H NMR which is equal to 31.3 wt. % of imidazoline.

Example 14—BHPVA-DBU

(114) 10 g of the 4,4′-bis(4′-hydroxyphenyl)valeric acid was stirred in 60 ml of refluxing acetone. To the solution/suspension was added 5.3 g of 1,8-diazabicyclo(5.4.0)undec-7-ene either drop-wise as a neat liquid. A small amount of IMS was added until all the oily solid had dissolved. 150-200 ml of additional acetone was then added causing a precipitate to form. The mixtures were refluxed for 3 hours before cooling to room temperature. The precipitate was collected by filtration and then dried in a vacuum oven at 60° C. to give 14.2 g of white powder. The ratio of host to guest in the precipitated clathrate was shown to be approximately 1:1 by 1H NMR which is equal to 34.7 wt. % of DBU.

Example 15—PhPh-DBU

(115) PhPh-DBU was prepared using the procedure in example 1 with 10.0 g of phenolphthalin and 5.3 g of 1,8-diazabicyclo(5.4.0)undec-7-ene to give 13.7 g of a white powder. The ratio of host to guest in the precipitated clathrate was shown to be approximately 1:1 by 1H NMR which is equal to 32.2 wt. % of imidazoline.

Example 16—BHPVA-IPDA

(116) BHPVA-IPDA was prepared using the procedure in example 1 with 10.0 g of 4,4′-bis(4′-hydroxyphenyl)valeric acid and 6.0 g of isophorone diamine to give 11.5 g of a yellow powder. The ratio of host to guest in the precipitated clathrate was shown to be approximately 1:1 by 1H NMR which is equal to 37.3 wt. % of the amine.

Example 17—PhPh-IPDA

(117) PhPh-IPDA was prepared using the procedure in example 1 with 10.0 g of phenolphthalin and 5.3 g of isophorone diamine to give 5.0 g of a cream powder. The ratio of host to guest in the precipitated clathrate was shown to be approximately 1:0.7 by 1H NMR which is equal to 27.1 wt. % of the amine.

Example 18—PhPh-MXDA

(118) PhPh-MXDA was prepared using the procedure in example 1 with 10.0 g of phenolphthalin and 4.3 g of meta-xylylenediamine to give 8.4 g of a yellow powder. The ratio of host to guest in the precipitated clathrate was shown to be approximately 1:0.7 by 1H NMR which is equal to 22.9 wt. % of the amine.

Example 19—BHPVA-BDMA

(119) BHPVA-BDMA was prepared using the procedure in Example 1 with 10.0 g of 4,4′-bis(4′-hydroxyphenyl)valeric acid replacing the 3.85 g of 2ethyl-4-methylinodazole with 4.7 g of N,N-dimethylbenzylamine to give 12.9 g of a white powder. The ratio of host to guest in the precipitated clathrate was shown to be approximately 1:1 by .sup.1H NMR which is equal to 32.1 wt. % of the amine.

Example 20—PhPh-BDMA

(120) PhPh-BDMA was prepared using the procedure in Example 3 with 10.0 g of phenolphthalin and 4.2 g of N,N-dimethylbenzylamine to give 13.6 g of a white powder. The ratio of host to guest in the precipitated clathrate was shown to be approximately 1:1 by .sup.1H NMR which is equal to 29.7 wt. % of the amine.

Example 21—BHPVA-DMP30

(121) 10.0 g of 4,4′-bis(4′-hydroxyphenyl)valeric acid was dissolved in 150 ml of ethyl acetate. A solution of 3.0 g of (2,4,6-trisdimethylaminomethyl)phenol in 50 ml of ethyl acetate was added to the solution drop-wise. The mixture was stirred at room temperature for 2 hours. The resulting precipitate was collected by filtration, washed with ethyl acetate and dried in a vacuum oven at room temperature overnight to give 12.0 g of a white powder. The ratio of host to guest in the precipitated clathrate was shown to be approximately 3:1 by .sup.1H NMR which is equal to 23.6 wt. % of the amine.

Example 22—PhPh-DMP30

(122) PhPh-DMP30 was prepared using the procedure in Example 21 with 10.0 g of phenolphthalin and 2.7 g of (2,4,6-trisdimethylaminomethyl)phenol to give 9.5 g of a pale yellow powder. The ratio of host to guest in the precipitated clathrate was shown to be approximately 3:1 by .sup.1H NMR which is equal to 21.6 wt. % of the amine.

(123) Various resin compositions were prepared by dispersing the clathrates of the Examples into LY1556/Epikote 828 at room temperature (21° C.) before speedmixing so that the content of the curative in the mixture was 5% by weight based on the weight of the overall mixture. Milling of clathrates was performed using an IKA tube mill for 30 seconds at 5000 rpm followed by 30 seconds at 15000 rpm and finally 30 seconds at 25000 rpm. The mixtures were then evaluated by DSC. The mixture was cured in an oven at 120° C. for 1 hour with a 1° C./min ramp rate. The Tg of the cured resin formulation was determined by DMA in accordance with ASTM D7028-07 (2015).

(124) The cure performance and neat resin properties of the compositions are shown below in Table 1.

(125) TABLE-US-00002 TABLE 1 Cure onset Peak cure temperature temperature Enthalpy E′ Tg Compound (° C.) (° C.) (J/g) (° C.) BHPVA-2E4MZ 138 144 380 110 BHPVA-2MZ 122 133 336 124 PhPh-2E4MZ 142 148 368 128 PhPh-2MZ 150 155 325 132 PhPh-IMZ 127 139 303 136 BHPPA-2E4MZ 137 131 360 133 BA-2E4MZ 115 144 370 129 APAA-2E4MZ 124 132 402 133 PhPh-2MZ-IMZ 139 147 349 132 BHPAA-2E4MZ 143 149 367 121 BHPAA-2MZ 136 145 376 126 BHPVA-2PZL 134 142 125 n/a PhPh-2PZL 154 159 85 n/a BHPVA-DBU 130 139 168 n/a PhPh-DBU 144 154 191 n/a BHPVA-BDMA 119 130 371 n/a PhPh-BDMA 131 138 3409 n/a BHPVA-DMP30 133 156 225 n/a PhPh-DMP30 128 135 265 n/a

(126) Dynamic DSC of the BHPVA-2E4MZ clathrate shows similar reactivity to that of the dicarboxylic acid clathrates. However, Isothermal DSC shows BHPVA-2E4MZ to have a shorter time to 95% cure at 120° C. and 150° C., as shown in Table 2.

(127) TABLE-US-00003 TABLE 2 T to 95% at 120° C. T to 95% at 150° C. Compound (mins) (mins) BHPVA-2E4MZ 7.9 1.2 BHPVA-2MZ 4.7 1.2 PhPh-2E4MZ 9.3 1.3 PhPh-2MZ 16.2 2.0 PhPh-IMZ 5.8 0.6 BHPPA-2E4MZ 5.7 0.7 BA-2E4MZ 6.7 2.2 APAA-2E4MZ 3.6 0.5 PhPh-2MZ-IMZ 11.1 1.3 BHPAA-2E4MZ 10.0 1.8 BHPAA-2MZ 9.9 1.9 BHPVA-2PZL 11.7 2.6 PhPh-2PZL 29.3 4.4 BHPVA-DBU 11.3 3.4 PhPh-DBU 34.1 3.4 Comparative Examples PDCA-IMZ 18.6 3.9 PDCA-C11Z 9.7 4.4 SA-2E4MZ 9.8 3.5

(128) The outlife was tracked by monitoring the uncured Tg of the mixture of the resin and the clathrate-curative and the results are shown in Table 3.

(129) TABLE-US-00004 TABLE 3 Outlife at 23° C., Uncured Tg (° C.) Curative Compound weight % Start 1 week 2 weeks 4 weeks 6 weeks 8 weeks BHPVA-2E4MZ 27.7 −19.2 −19.7 −18.7 −16.3 −12.2 −8.7 PhPh-2E4MZ 25.6 −17.7 −18.1 −17.5 −1.8 16.9 BHPVA-2MZ 22.3 −17.0 −16.8 12.4 PhPh-2MZ 20.4 −17.8 −17.9 −15.0 −13.3 −11.3 −10.7 PhPh-IMZ 17.5 −17.6 −18.2 −11.5 −6.9 −0.7 BHPPA-2E4MZ 29.9 −14.7 −14.1 −7.5 27.5 BA-2E4MZ 32.6 −12.6 −3.8 APAA-2E4MZ 42.2 −18.2 21.0 BHPAA-2E4MZ 31.1 −15.3 −17.7 −18.0 27.4 BHPAA-2MZ 25.1 −18.4 −18.6 −15.7 24.5 PhPh-2MZ-IMZ 18.7 −18.6 −18.4 −17.6 −13.6 −12.7 −11.9 BHPVA-2PZL 33.8 −19.0 −17.7 −16.7 −14.2 −11.9 −8.9 PhPh-2PZL 31.3 −19.2 −19.0 −18.3 −18.0 −17.0 BHPVA-DBU 34.7 −18.7 −18.1 −17.2 −15.9 −14.6 PhPh-DBU 32.2 −18.8 −18.1 −17.8 −17.6 −16.7 BHPVA-BDMA 32.1 −18.5 −16.9 −10.4 11.2 PhPh-BDMA 29.7 −18.3 −17.8 −17.1 −10.2 −9.5 −8.7 BHPVA-DMP30 23.6 −17.8 −17.1 −17.3 −17.2 −16.9 −16.9 PhPh-DMP30 21.6 −17.4 −16.7 −16.6 −14.7 −13.8 −13.8 Comparative Examples PDCA-IMZ −18.7 −18.8 −18.8 n/a −14.4 PDCA-C11Z −19.3 −18.5 −17.4 −16.2 −10.6 SA-2E4MZ −19.2 −18.2 −14.7 −12.4 −6.9

(130) A prepreg can be manufactured by casting the mixture of the above examples on a polyolefin film in a thin sheet of approximately 0.5 mm thickness. The cast film is then combined with a carbon fibre unidirectional fabric of 268 g/m.sup.2 in between a set of compression rollers to produce the prepreg.