HEAT-CURABLE EPOXY COMPOSITIONS AND THEIR USE IN PREPARING FORMED ARTICLES

Abstract: Heat-curable epoxy compositions comprise: (1) an epoxy compound having an average more than one epoxy group per molecule, (2) at least one unsaturated monomer selected from the group consisting of esters of ethylenically unsaturated mono­ carboxylic acids, cyano-containing compounds, allyl com­ pounds, olefins and diolefins, (3) a carboxyl-containing compound, (4) at least one epoxy curing accelerator, and (5) a free-radical curing agent. An unsaturated aromatic monomer, such as styrene, may additionally be present. The compositions may be moulded and cured by application of heat to produce formed articles.

Description: HEAT-CURABLE EPOXY CQI!D?OSITIONS AND TEE19 USE IN PREPARING FORMED ia:s This invention relates to heat-curable epoxy compositions and their use in preparing formed articles. Curable compositions comprising polyester resins and styrene are knawn and have been described in, for example, U.S. Patents Nos. 2,691,007, 3,574,157 and 3,634,542. Compositions based on polyether resin and styrene blends are also known. These blends generally exhibit poor processability, short pot life, high viscosity and cure with conventional curing agents to produce products which do not exhibit good physical properties, such as high heat deflection temperatures and retention of physical properties at elevated temperatures. For example, in U.S. Patent No. 2,939,859 there are disclosed compositions based on polyexpoxide/ styrene blends cured with peroxides and/or amines. Although these compositions do exhibit a reduction of viscosity over a corresponding epoxy composition which does not contain styrene, the resulting products do not exhibit high heat deflection temperatures. Other polyepoxide/styrene compositions are described in U.S. Patents Nos. 3,009,638 and 3,099,898, which are directed to the use of anhydride curing agents, optionally in the presence of a peroxide and/or tertiary amine accelerator. Epcxy/styrene blends which can be cured with a special curing agent/curing accelerator blend, e.g., an acid anhydride in cam- bination with an onium salt, to yield products which exhibit improved physical properties, especially increased heat deflection temperatures and excellent retention of physical properties at elevated temperatures are disclosed in U.S. Patent No. 4,284,753. It has now been discovered that heat-curable compositions having excellent chemical and physical properties may be prepared in similar compositions to those referred to above but wherein the unsaturated aromatic monomer, e.g. styrene, is partially or entirely replaced by one or more comonomers. According to the present invention there is provided a heatcurable composition comprising: (1) an epoxy compound having on average more than one epoxy group per molecule, (2) at least one unsaturated monomer selected from the group con sisting of esters of ethylenically unsaturated monocarboxylic acids, cyano-containing compounds, allyl compounds, olefins and diolefins, (3) a carboxyl-containing compound, (4) at least one epoxy curing accelerator, and (5) a free-radical curing agent. A composition of the invention may additionally include an unsaturated aromatic monomer. Examples of unsaturated aromatic monomers include the vinyl aromatic nonamers such as styrene; alpha methyl styrene; halo- and nitro-substituted styrenes such as vinyl toluene, chlorostyrene, bramostyrene, nitrostyrene; divinylbenzene, tertiary-butyistyrene; 2-vinylpyridine; and vinyl naphthalene. Preferably the unsaturated aromatic monomer is styrene or a substituted styrene. Mixtures of unsaturated aromatic monsters may be employed. A preferred mixture comprises styrene and divinylbenzene. Suitable epoxy compounds for inclusion in compositions of the present invention comprise those compounds containing on average morse than one vicinal epoxy group per molecule i.e., nore than one EMI2.1 group. These epoxy compounds may be saturated or unsaturated, aliphatic, cycloaliphatic, aromatic or heterocyclic and may be substituted if desired with non-interfering substituents such as halogen atans, hydroxyl groups and ether radicals. They may also be monomeric or polymeric. Various examples of liquid epoxy compounds which may be used in the compositions of the invention are given in U.S. Patent No. 2,633,458. Other suitable epoxy compounds are disclosed in U.S. Patents Nos. 3,356,624, 3,408,219, 3,446,762 and 3,637,618. Preferred epoxy compounds are the glycidyl polyethers of polyhydric phenols and polyhydric alcohols, especially the glycidyl polyethers of 2,2-bis (4-hydroxyphenyl) propane having an average molecular weight in the range from 300 to 3,000 and an epoxide equivalent weight in the range fram 140 to 2,000 and morse preferably an average molecular weight in the range from 300 to 1000 and an epoxide equivalent weight from 140 to 650. Other suitable epoxy compounds include those compounds derived fran polyhydric phenols and having at least one vicinal epoxy group wherein the carbon-to-carbon bonds within the six-irertered ring are saturated. Examples of such epoxy compounds are described in U.S. Patent No. 3,336,241. Preferred saturated epoxy compounds are the hydrogenated glycidyl ethers of 2, 2-bis (4-hydroxyphenol) propane, sometimes called the diglycidyl ethers of 2,2-bis(4-cyclohexanol)propane. Other examples of suitable epoxy compounds include the glycidyl ethers of novolac resins, e.g. those described in U.S. Patent No. 2,658,885. For nost applications it is desirable to utilize an epoxy compound which is liquid or sgni-liquid under the conditions of application. Accordingly, a blend of a liquid and a solid epoxy compound may be employed. Liquid epoxy compounds, particularly liquid glycidyl ethers of 2, 2-bis (4-hydroxyphenyl) propane, having an average molecular weight in the range 380 to 400 and an epoxide equivalent weight in the range 180 to 210 have been found to be very suitable. Compositions of the invention contain at least one unsaturated moncrru3r selected fram the group consisting of esters of ethylenically unsaturated nonocarboxylic acids, cyano-containing compounds, allylcontaining compounds, olefins and diolefins. Suitable unsaturated nonocarboxylic acid esters include the alkyl and haloalkyl esters of ethylenically unsaturated acids such as acrylic acid, methacrylic acid, crotonic acid, alpha-phenylacrylic acid, alpha-cyclohexylacrylic acid, maleic acid, cyanoacrylic acid and irethoxyacrylic acid. Very preferred esters are those of acrylic acid and methacrylic acid. Accordingly, suitable such esters include methyl methacrylate, ethyl acrylate, butyl acrylate, butyl methacrylate, isobutyl methacrylate, 2, 3-dibronopropyl acrylate, 2-chloro-ethyl methacrylate and pentachlorophenyl methacrylate. Very preferred unsaturated monomers include the polyacrylate and polymethacrylate esters of polyols containing more than one terminal acrylate or methacrylate group. These esters are the acrylic and methacrylic acid esters of aliphatic polyhydric alcohols such as, for example, the di- and polyacrylates and the di- and polymethacrylates of alkylene glycols, polyoxyalxylene glycols, alicyclic glycols and higher polyols, such as ethylene glycol, triethylene glycol, tetraethylene glycol, tetrairethylene glycol, hexanediol, trimethylolethane, trimethylo lpropane, pentaerythritol, dipentaerythritol and tripentaerythritol. Typical such esters include trimethylolpropane triacrylate, trimethylolethane triacrylate, trimethylolpropane, trimethacrylate, trimethylolethane trimethacrylate, tetranrethylene glycol dimethacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, 1,6hexanediol diacrylate, 1,6-hexanediol dimethacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, tri methylolpropane triacrylate, pentaerythritol triacrylate, and 1,3-butylene dimethacrylate. Other acrylate or methacrylate esters of polyols include the acrylate or methacrylate esters of epoxy compounds, e.g. those described in U.S. Patent No. 3,377,406. Suitable cyano-containing compounds include acrylonitrile, methacrylonitrile, and halogenated acrylonitrile. Suitable allyl compounds include diallyl phthalate, diallyl isophthalate, allyl diglycol carbonate, and triallyl trimellitate. Examples of olefins and diolefins include ethylene, propylene, butylene, amylene, butadiene and isoprene. It will be appreciated that since these nonomers are normally gases at ambient temperatures and pressures, compositions containing them must be formulated and cured under elevated pressure conditions. Accordingly, their use is nore especially applicable in the so-called reaction injection moulding (RIM) techniques. In especially preferred compositions of the invention, said at least one unsaturated monomer is selected from a polyacrylate or polymethacrylate ester of a polyol, an alkyl ester of an ethylenically unsaturated monocarboxylic acid, and acrylonitrile, and is more preferably selected from pentaerythritol triacrylate, trimethylolpropane trimethacrylate, n-butyl methacrylate, isobutyl methacrylate and acrylonitri le. Trimethylolpropane trimethacrylate and pentaerythritol triacrylate are particularly preferred. Blends of the polyepoxide and unsaturated nonomers suitably contain from 30% to 99% epoxy compound and from 1% to about 70% other monomers on a weight basis. An especially preferred range is from about 50% to 85% epoxy compound and from 15% to 50% unsaturated monomers. In the case of compositions containing an unsaturated aromatic monomer, the total unsaturated monomer present suitably ccmprises a blend of from 5% to 70% by weight of aromatic monomer and frcm 30% to 95% by weight of other unsaturated monomer(s). The carboxyl-containing compound may conveniently be a polycarbcxylic acid or acid anhydride e.g. a saturated or unsaturated aliphatic, aromatic and cycloaliphatic polycarboxylic acid or polycarboxylic acid anhydride, which may be substituted, for example, with halogen atoms. Typical such carboxyl-containing compounds are trimellitic anhydride, maleic acid, maleic anhydride, crotonic acid, itaconic acid, itaconic anhydride, tetrahydrophthalic acid, fumaric acid, phthalic anhydride, isophthalic acid, terephthalic acid, hexahydrophthalic anhydride, dianhydride ester of trimellitic anhydride with ethylene glycol, dodecenyl succinic anhydride, dichloromaleic anhydride, tetrachlorophthalic anhydride, chlorendic anhydride, pyromellitic dianhydride, dimethylmaleic anhydride, n-butylmaleic anhydride, phenylmaleic anhydride, bromophenylmaleic anhydride, chlorendic anhydride and 3,3', 4,4'-benzophenone tetracarboxylic dianhydride. Preferred polycarboxylic acids and anhydrides comprise the normally solid acids and anhydrides having a relating point between about 1500C and 2500C. Preferably the carboxyl-containing compound is an acid anhydride. Preferred anhydrides include chlorendic anhydride, thiodisuccinic anhydride, and more preferably trimellitic anhydride and 3,3', 4,4'-benzophenone tetracarboxylic dianhydride. Outstanding results are obtained when trimellitic anhydride is employed as the epoxy curing agent, particularly when used as finely ground powder, preferably having an average particle size below 50 wm, more preferably about 30 wm. The amount of carboxyl-containing compound necessary for eventual curing of the composition may vary over a wide range, depending upon the epoxy compound employed, the particular acid or anhydride used and end use considerations. A useful range is from about 0.25 to about 2.0 chemical equivalents of acid or anhydride per chemical equivalent of epoxy compound. An especially suitable range when trirrellitic anhydride is employed with glycidyl polyethers of 2,2'-bis(4-hydroxyphenyl)propane is fran 0.75 to 1.5 equivalents. The epoxy curing accelerator may be one or more known epoxy curing accelerators. Onium compounds represent one class of preferred such accelerators. Useful onium compounds include the onium salts utilized as esterification catalysts, and preferably those containing phosphorus, sulphur or nitrogen, such as, for example, the phosphonium, sulphonium, iodonium and ammonium salts of inorganic acids. Examples of these include, among others, ethyl triphenyl phosphonium iodide, tetrabutyl ammonium bromide, benzyltrimethylaitrnoniuin sulphate, tetramethylammonium chloride, benzyltrimethylammonium nitrate, diphenyldimethylanrronium chloride, benzyltrimethylammonium chloride, diphenyldimethylammonium nitrate, diphenylinethylsulphonium chloride, tricyclohexylsulphonium bromide; ; triphenylmethylphosphonium iodide, diethyldibutylphosphonium nitrate, trimethylsulphonium chloride, dicyclohexyldialkylphosphonium iodide, benzyltrimethylanronium thiocyanate, choline chloride, and ethyl triphenylphosphonium acetate, and mixtures thereof, and commercial catalysts such as "BARQUAT MB-80" (trademark) and "ADOGEN 464" (trademark). Especially preferred onium salts are the alkyl triphenylphosphonium halides such as ethyl triphenyl phosphonium icdide and quarternary ammonium halides such as tetrabutyl ammonium bromide, C14-16 alkyl dimethylbenzyl ammonium chloride and methyl tri (C8-10 alkyl) ammonium chloride. As noted hereinbefore, the anount of onium salt can vary over a wide range, i.e., from about 0.001 to about 10.0 parts by weight per 100 parts by weight of the polyepoxide (phr). A very useful range is fran about 0.005 to about 2.0 phr. Suitable other accelerators which may be used alone or in carbination with onium salts or other accelerators include the stannous salts of monocarboxylic acids, having at least 2 carbon atoms, and more preferably from about 6 to 12 carbon atoms. Examples of operable stannous salts include, stannous caproate, stannous octoate, stannous laurate, stannous palpitate, stannous stearate, stannous oleate and stannous naphthenate. Stannous octoate is particularly preferred. Other suitable curing accelerators include alkali metal salts such as sodium benzoate, lithium benzoate, lithium octoate, lithium naphthenate, lithium stearate, lithium neodecanoate, lithium iodide, potassium iodide and lithium bromide. Still other suitable curing accelerators (catalysts) include the hydroxides and alkoxides and carboxylates of the alkaline earth and alkali metals such as sodium hydroxide, potassium hydroxide, calcium hydroxide and sodium methoxide. The amount of said other accelerator may vary within wide limits e.g. from 0.01 to 10 parts per hundred by weight of polyepoxide (phr), and preferably from 0.05 to 5.0 phr. Preferably the epoxy curing accelerator comprises a phosphonium or ammonium halide or a stannous salt of a tronocarboxylic acid, suitably ethyl triphenylphosphonium iodide or stannous octoate. The free-radical curing agent may conveniently be a known epoxide or azo free-radical curing agent. Examples of such compounds include the peroxides, such as benzoyl peroxide, tertiary butyl hydroperoxide, ditertiary butyl peroxide, hydrogen peroxide, potassium persulphate, methyl cyclohexyl peroxide, current hydroperoxide, acetyl benzoyl peroxide, hydroperoxide of 1,2,3, 4-tetrahydro-naphthalene , phenylcyclohexane hydroperoxide, tertiary butyl peracetate, dicumyl peroxide, tertiary butyl perbenzoate, ditertiary amyl perphthalate, ditertiary butyl peradipate, tertiary amyl percabbonate, and mixtures thereof; and azo compounds such as 2,2'-azobisisobutyronitrile, dimethyl 2,2 '-azobisisobutyrate, 2,2' -azobis (2, 4diinethylvaleronitrile), and 2,2' -azobisisobutyramide . Particularly preferred catalysts include the dialkyl peroxides, tertiary alkyl hydroperoxides, alkyl esters of peroxycarboxylic acids and particularly those which contain no more than 18 carbon atoms per molecule and which have a half-life of at least one hour at 125 C. An especially useful peroxide is 2,5-dimethyl-2,5-bis (tertiarybutylperoxy) hexane. It will be appreciated that the amount of free-radical curing agent will vary over a broad range depending upon the amount of the particular vinyl monomer used, type of peroxide or other free-radical curing agent and end-use properties desired. An effective or curing amount of free-radical curing agent may readily be assessed by one skilled in the art, who would simply adjust the amounts of a particular peroxide to suit his process conditions. Such adjustments are made in one or two trial runs knowing pararreters such as temperatures and half-lives. A particularly preferred heat-curable composition of the invention comprises: (1) fran 30 to 99 parts by weight of a glycidyl polyether of 2,2-bis-(4-hydroxyphenyl)propane, (2) from 1 to 70 parts by weight of a polyacrylate or polymethacrylate ester of a polyol, or of a blend of polyacrylate or polymethacrylate ester of a polyol with styrene or a mixture of styrene and divinyl benzene containing up to 50% by weight of divinyl benzene, (3) fram 0.25 to 2.0 stoichiometric equivalents based on the glycidyl polyether of a polycarboxylic acid anhydride, (4) an accelerating amount of at least one epoxy curing accelerator, and (5) a curing amount of an organic peroxide. The invention also provides a process for preparing a formed article which comprises bringing a heat-curable composition according to the invention into a mould and curing by application of heat. The present compositions may be prepared by various techniques. If, for example, the instant compositions are to be utilized within a short time, they can be prepared by simply mixing all the components, adding any customary additives such as fillers, reinforcement fibres, pigments, and/or flame retardant agents, and then moulding and curing the resulting composition. Under certain conditions, it may be desirable to utilize a tsc-package system wherein an epcxy/unsaturated monomer blend is one package and the other package comprises the curing agents and accelerators. Under other conditions, it may be desirable to mix the epoxy curing agent-accelerators blend into the unsaturated monomer(s) for subsequent reaction with the polyepoxide in the presence of the peroxide. Another method comprises a two-package system wherein the unsaturated monomer(s), accelerator, and curing agent are in one package and the epoxy-peroxide mixture is in another package, the two packages being blended prior to use. Various other modifications will be apparent to one skilled in the art. One special modification comprises mixing and dispersing the finely powdered anhydride into the unsaturated corronorrer to form a paste, thereby reducing dust generation by handling of loose anhydride powder. As noted hereinbefore, other materials may be mixed or added to compositions of the invention, including plasticizers, stabilizers, extenders, oils, resins, tars, asphalts, pigments, reinforcing agents, thixotropic agents and/or antioxidants. The present compositions may be utilized in many applications such as for coatings and impregnating compositions, in the preparation of adhesives for mentals, wood or cement, and in the preparation of reinforced composite Products, such as laminated products, filament windings, sheet moulding compounds (SMC), electrical laminates, moulding powders, fluidized bed powders and potting compounds. A very suitable application is in the preparation of reinforced products and laminates wherein the compositions are applied to fibrous products such as glass fibres or sheets and the material formed into the desired object and cured. In particular, the compositions are especially suitable for use in sheet moulding compositions (sic), in structural applications such as automotive springs, bumpers and drive shafts, and in reaction injection moulding (RIM) applications. The invention will be further understood from the following examples thereof, in which, unless otherwise indicated, parts and percentages are parts and percentages by weight. Epoxy Resin A is a liquid glycidyl polyether of 2,2-bis (4-hydroxyphenyl)propane having an epoxide equivalent weight of 180195 and an average molecular weight of about 380. Epoxy Resin B is a liquid glycidyl polyether of 2,2-bis (4-hydroxyphenyl) propane having an epoxide equivalent weight of 190210 and an average molecular weight of about 400. BIDA is 3,3',4,4'-benzophenone tetracarboxylic dianhydride. "LUPERSOL 101" (trademark) is 2,5-dimethyl-2,5-bis(t-butyl- peroxy) hexane. TMR is trimellitic anhydride. ETPPI is ethyl triphenyl phosphonium iodide. DICUP is dicuryl peroxide. TBPB is tertiary butyl peroxybenzoate. TBAB is tetrabutyl ammonium brarride. "BARQUAT MB-80" (trademark) is a long chain (C14-C16) alkyl dimethyl benzyl ammonium chloride, 80% in alcohol. PETA is pentaerythritol triacrylate. TMPTMA is trimethylolpropane trimethacrylate. BOMA is is 1,3-butylene dimethacrylate. BMk is n-butyl methacrylate. IBMA is isobutyl methacrylate. TTECDMA is tetraethylene glycol direthacrylate. A464 is "ADOGEN 464" (trademark), a methyltrialkylammonium chloride such that the three alkyl groups have eight to ten carbon atoms each. S is styrene. S0 is stannous octoate. Example I Trimellitic anhydride (150 grams) was combined in a 1 quart (946 ml) metal paint can with 1,3-butylene dimethacrylate (300 grams) and "BARQUAT MB-80" (3 grams). This mixture (component B) was mixed with a rotary agitator for approximately 5 minutes until a pourable suspension was obtained. The suspension was allowed to stand overnight and then was combined with a mixture (component A) of 300 grams of Epoxy Resin B and 2 grams of "LUPERSOL 101". This mixture was mixed for approximately 5 minutes and then poured into a mould of glass sheets separated by a Teflon spacer 1/8" (0.32 cm) thick. Another portion was poured into aluminium moulds containing a linear cavity 1/2" (1.25 cm) square to form a bar. The sheet and bar moulds were placed in an oven at 1500C for two hours. The sheets and bars were then removed from the moulds, allowed to cool to ambient temperature (200C), and tested for mechanical properties at ambient temperature (R.T.) and at 1490C. This procedure was essentially repeated wherein varying amounts of BOMA were used. The mechanical properties for five representative experiments are tabulated in Table I wherein the base formulations were as follows: Component A Component B Epoxy Resin B 300 grams TMA 150 grams "LUPERSOL 101" 2 grams BDMA variable "BAROURT MB-80" 3 grams TABLE I BDMA HDT R.T. R.T. 149 C 149 C R.T. R.T. R.T. 149 C 149 C 149 C (phr)* 1-8 MPa Flex Flex Flex Flex Tensile Tensile Tensile Tensile Tensile Tensile ( C) Strength, Modulus, Strength, Modulus, Strength, Modulus, Elonga- Strength Modulus Elonga MPa MPa MPa MPa MPa MPa tion,MPa MPa MPa tion,% 11.1 166 53 3440 50 1730 18 3480 0.6 26 1640 4.0 25 169 92 3510 50 1740 56 3250 2.1 27 1620 6.2 42.7 164 128 3520 54 1760 47 3910 1.4 29 1770 4.8 66.6 161 105 3520 58 1830 36 3270 1.2 32 1810 3.7 100 158 123 3560 61 1880 61 3330 2.3 28 1604 3.1 * Parts by weight per 100 parts of Epoxy Resin B Example II Trimellitic anhydride (45 grams) was combined in a jar with trimethylolpropane trirrethacrylate (54 grams) and the mixture was blended for approximately 5 minutes with a rotary agitator until a pourable suspension was obtained. To the suspension were added 300g of Epoxy Resin B, 3g of stannous octoate and 1.5g of "LUPERSOL 101". This mixture was mixed for approximately 5 minutes and then poured into moulds as in Example I. The moulds were placed in an oven at 150 0C for 2 hours for curing. The casting samples had a heat deflection temperature (at 1.8 MPa) of 1390C, ambient temperature flexural strength and modulus of 106 MPa and 3390 MPa respectively, and flexural strength and modulus at 1490C of 28 MPa and 870 MPa respectively. Example III The procedures of Examples I and II were essentially repeated using Epoxy Resin A, varying amounts of BMA and I, TBAB as epoxy curing accelerator and as anhydride BTDA. The amounts of BMA and IBMA are in phr (parts per hundred) based on 100 parts of Epoxy Resin A. All samples were cured at 150 0C for two hours. Representative experimental runs are tabulated in Table II. Example IV The procedures of Example III were essentially repeated wherein various amounts of BMA or a blend of BMA and TMETMA were utilized. The results are tabulated in Table III. Example V The procedures of Examples I to IV were repeated using the following base formulation: Epoxy Resin A or B 300 grams Trimellitic Anhydride 150 grams ETPPI or TBAB 1.5 grams Monomers) variable LUPERSOL 101 0.6 grams Epoxy Resin A was used when TBAB was used and Epoxy Resin B was used with ETPPI. Representative laboratory runs are tabulated in Table IV. Example VI The procedures of the Examples I to V were repeated using various miscellaneous monomers according to the following basic formulation: Epoxy Resin B 300 grams 150 150 grams monomer Variable ETPPI 0.75 grams LUPERSOL 101 Variable The cure cycle was 2 hrs. at 1500C. The e results of representative laboratory experiments are tabulated in Table V. Example VII The procedures of Examples I to VI were repeated using various monomers, giving the results tabulated in Table VI. The following basic formulation was used: Epoxy Resin A or B 300 grams Trimellitic Anhydride 150 grams Monomer Variable Quarternary compound Variable LUPERSOL 101 Variable Epoxy Resin A was used when TBAB was employed; in other cases Epoxy Resin B was used. TABLE II BTDA Monomer Catalyst/ Visc. HDT, R.T. R.T. 149 C (phr) (phr) Initiator 20 C 1.8 MPa Flex Flex Flex Experiment (phr) (Pa.s) ( C) Str., Mod., Str., No. MPa MPa MPa 1 70 BMA(30) TBAB(0.5) L101(0.2) 3.03 (a) 28 2820 7 2 75 BMA(30) TBAB(0.5) L101(0.2) 4.25 218 21 1470 10 3 80 BMA(30) TBAB(0.5) L101(0.2) 5.03 210 25 3010 9 4 85.6 IBMA(25) TBAB(0.5) 193,197 L101(0.2) 5 85.6 BMA(30) L101(0.2) TBAB(0.5) 186 43 2950 24b) -cont'd- TABLE II (CONT'D) 149 C R.T. R.T. R.T. 149 C 149 C 149 C Tg, C Flex Ten. Ten. Ten. Ten. Ten. Ten. Rheometrics Experiment Mod., Str., Mod., Elong., Str., Mod., Elong., disp.phase No. MPa MPa MPa (%) MPa MPa (%) (resin phase) 1 1090 14 3140 0.5 5.3 1150 0.5 ( > 230) 2 1280 14 3090 0.5 5.4 1210 0.5 ( > 230) 3 1420 13 2890 0.5 4.5 1270 0.4 ( > 230) 4 5 1360b) 30 2820 1.3 17b) 1330b) 1.6b) a) HDT bars broke during testing; b) Values derermined at 121 C instead of 149 C TABLE III Experiment BTDA Monomer Catalyst/ Visc. HDT, R.T. R.T. No. (phr) (phr) Initiator 20 C 1.8 MPa Flex Flex (phr) (Pa.s) ( C) Str., Mod., MPa MPa 1 85.6 BMA(11.1) TBAB(0.5) 26.0 225,237 48 3590 L101(0.33) 2 85.6 BMA(25) TBAB(0.5) 17.5 218,219 25 2910 L101(0.33) 3 85.6 BMA(42.8) TBAB(0.5) 7.8 208,215 27 2650 L101(0.33) 4 85.6 BMA(66.7) TBAB(0.5) 2.8 176,184 48 1870 L101(0.33) 5 85.6 BMA(100) TBAB(0.5) 1.5 71,74 26 870 L101(0.33) 6 85.6 BMA(50)) TBAB(0.5) 4.85 187 TMPTMA(50) L101(0.33) -cont'd- TABLE III (CONT'D) 149 C 149 C R.T. R.T. R.T. 149 C 149 C 149 C Flex Flex Ten. Ten. Ten. Ten. Ten. Ten. Experiment Str., Mod., Str., Mod., Elong., Str., Mod., Elong., No. MPa MPa MPa MPa (%) MPa MPa (%) 1 21 2030 19 3810 0.5 16 1960 0.9 2 18 1690 14 2770 0.5 7 1560 0.5 3 16 1410 22 2380 0.9 10 1370 0.7 4 20 920 26 1800 1.6 11 970 1.3 5 10 390 15 840 2.3 6 410 1.9 TABLE IV Experiment Monomers Catalysts Initial HDT R.T. R.T. 149 C No. (phr) (phr) Viscosity 1.8 MPA Flex Flex Flex Pa.s ( C) Str., Mod., Str., MPa MPa MPa 1 IBMA(25) ETPPI(0.5),L101(0.2) 158.5,160 2 IBMA(20), TTEGDMA(5) TBAB(1), L101(0.5) 157.4 3 IBMA(20), PETA(5) ETPPI(0.5),L101(0.2) 159,159.5 4 IBMA(15), PETA(10) " " 174.6,178.6 5 IBMA(10), PETA(15) " " 185.1,185.6 6 IBMA(5), PETA(20) " " 177.7,183.6 7 PETA(25) " " 177.8,177.5 8 BMA(25) TBAB(0.5),L101(0.2) 0.85 122 96 2650 42 9 BMA(20), TMPTMA(5) " " 1.04 131 122 3110 43 10 BMA(20), PETA(5) " " 1.11 140 105 2930 52 11 BMA(15), TMPTMA(10) " " 2.5 143 94 3230 56 12 BMA(15), PETA(10) " " 3.8 178 114 3080 63 13 BMA(10), TMPTMA(15) " " 7.3 167 106 3290 67 TABLE IV (CONT'D) 149 C R.T. R.T. R.T. 149 C 149 C 149 C Flex Ten. Ten. Ten. Ten. Ten. Ten. Experiment Mod., Str., Mod., Elong., Str., Mod., Elong., No. MPa MPa MPa % MPa MPa % 1 2 3 4 5 6 7 8 1280 73 2930 4.7 19 1030 5.5 9 1230 68 3020 3.9 23 1120 6.3 10 1380 43 3120 1.6 26 1590 5.5 11 1600 57 2510 4.6 27 1380 5.5 12 1810 66 2840 4.3 32 1560 4.9 13 1940 54 2860 2.7 33 1660 3.9 TABLE V Experiment Monomer Resin/ LUPERSOL HDT R.T. R.T. 149 C No. Monomer 101 1.8 MPa Flex Flex Flex w/w (g/100g ( C) Str., Mod., Str., Resin) MPa MPa MPa 1 Isoprene 90/10 0.2 171,169 (a) 2 " 80/20 0.2 167,169 (a) 3 Diallyl Phthalate 90/10 0.2 135,140.5 87 3470 24.3 4 " " 80/20 0.2 105,109 82 3440 4.7 5 " " 90/10 0.6 150,152 91 3580 32.8 6 " " 80/20 1.2 136.5,137 129 3620 24.2 7 " " 90/10 1.1 153,154 115 3470 8 " " 80/20 2.5 147,150 121 3490 a) casting not prepared because of volatility of monomer. -cont'd- TABLE V (CONT'D) Experiment 149 C R.T. R.T. R.T. 149 C 149 C 149 C Tg, C Rheometrics No. Flex Ten. Tensile Tensile Tensile Tensile Tensile Disperse Phase Mod., Str., Modulus Elong., Str., Mod., Elong., (Resin Phase) MPa MPa MPa % (MPa) (MPa) % 1 2 3 858 63.5 3440 2.5 13.6 681 8.1 96,162 4 78 61.3 3200 2.9 29 48.3 6.8 70,150 5 1160 53.3 3190 1.9 100,170 6 905 64.4 3320 2.7 13.5 592 13.1 95,170 7 47.0 3330 1.7 8 75.6 3300 3.4 TABLE VI Experiment Monomer Resin/ Catalysts HDT R.T. R.T. 149 C No. Monomer (phr) 1.8 MPa Flex Flex Flex w/w C Str. Mod. Str. MPa MPa MPa 1 Methyl Methacrylate 90/10 ETPPI(0.5), L101(0.2) 167,167 2 Methyl Methacrylate 80/20 ETPPI(0.5), L101(0.2) 165,168 3 Butyl Acrylate 80/20 TBAB(0.5), L101(0.5) 176 82 2440 53 4 Butyl Acrylate 90/10 ETPPI(0.5), L101(0.2) 76 3120 5 Butyl Acrylate 90/10 ETPPI(0.5), L101(0.2) 172,175 6 Butyl Acrylate 80/20 ETPPI(0.5), L101(0.2) 157,159 7 Butyl Acrylate 80/20 ETPPI(0.5), L101(0.2) 173,174 8 Butyl Acrylate 80/20 ETPPI(0.5), L101(0.2) 101 2560 9 Isobutyl Methacrylate 80/20 ETPPI(0.5), L101(0.2) 159,160 10 Isobutyl Methacrylate 80/20 TBAB(0.5), L101(0.5) 155 92 2760 42 11 Isobutyl Methacrylate 80/20 A464(1.0), L101(0.2) 148 94 2580 37 12 Butyl Methacrylate 90/10 TBAB(0.5), L101(0.33) 163,164 107 3080 47 13 Butyl Methacrylate 80/20 TBAB(0.5), L101(0.33) 137,138 98 2880 23 14 Butyl Methacrylate 70/30 TBAB(0.5), L101(0.33) 158,161 80 4040 15 Butyl Methacrylate 60/40 TBAB(0.5), L101(0.33) 152,153 59 1661 22 TABLE VI (cont'd) Experiment Monomer Resin/ Catalysts HDT R.T. R.T. 149 C No. Monomer (phr) 1.8 MPa Flex Flex Flex w/w C Str. Mod. Str. MPa MPa MPa 16 Butyl Methacrylate 50/50 TBAB(0.5), L101(0.33) 142,143 30 1124 15 17 Butyl Methacrylate/ 50/50 TBAB(0.5), L101(0.33) 145,152 93 2640 30 Trimethylolpropane Trimethacrylate (1:) 18 Isodecyl Methacrylate 80/20 ETPPI(0.5), L101(0.2) 147 65 2440 40 19 Isodecyl Methacrylate 80/20 ETPPI(0.5), L101(0.2) 163 55 2700 41 20 Dodedyl Methacrylate 80/20 ETPPI(0.5), L101(0.2) 166 47 2190 35 21 Dodecyl Methacrylate 80/20 ETPPI(0.5), L101(0.2) 170 52 2680 41 22 Acrylonitrile 90/10 ETPPI(0.5), L101(0.2) 163,164 23 Acrylonitrile 80/20 ETPPI(0.5), L101(0.2) 137,138 24 Acrylonitrile 90/10 ETPPI(0.5), L101(1.0) 167,168 25 Acrylonitrile 80/20 ETPPI(0.5), L101(1.0) 161,165 -cont'd- TABLE VI (CONT'D) Experiment 149 C R.T. R.T. R.T. 149 C 149 C 149 C Notched No. Flex Ten., Ten., Ten., Ten., Ten., Ten., Izod., Mod., Str. Mod. Elong. Str. Mod. Elong. J/M MPa MPa MPa % MPa MPa % 1 2 3 1550 42 2420 2.3 26 1430 3.6,3.8 4 43 2900 1.7 5 6 7 8 52 2270 4.2 9 10 1480 54 2770 3.1 20 1200 3.7,5.4 11 1050 39 2430 2.4 17 1040 6.2 12 1430 39 3040 1.5 22 1240 3.5 22 13 657 48 2400 3.3 10 355 7.1 26 14 53 2130 5.0 24 15 601 31 1680 2.5 17 16 459 20 1230 1.9 12 520 7.1 17 TABLE VI (CONT'D) Experiment 149 C R.T. R.T. R.T. 149 C 149 C 149 C Notched No. Flex Ten., Ten., Ten., Ten., Ten., Ten., Izod., Mod., Str. Mod. Elong. Str. Mod. Elong. J/M MPa MPa MPa % MPa MPa % 17 807 43 2500 2.3 7.6 305 5.2 19 18 1340 55 2360 4.8 22 1220 3.5 19 1600 30 2460 1.4 20 1360 13 2070 0.6 17 1150 2.0 21 1590 34 2400 1.6 24 1470 2.2 22 23 24 25 Example VIII Into a 1 quart (946 ml) metal paint can were placed 285 grams of Epoxy Resin B, 150 grams of finely ground TMA powder (average particle size of 30V), 15 grams of a 10%wt solution of TBAB in Epoxy Resin A, 120 grams of styrene, 180 grams of TMPTMA and 1 gram of "LUPERSOL 101". These were thoroughly mixed for 5 to 10 minutes. A portion of the mixture was poured into a mould made of glass sheets separated by a Teflon spacer 1/8" (0.32 cm) thick. Another portion was poured into aluminium moulds containing a linear cavity 1/2" (1.25 cm) square to form a bar. The sheet and bar moulds were placed in an oven at 1500C for two hours. The sheets and bars were then removed from the moulds and tested for mechanical properties. This procedure was essentially repeated wherein various acrylic caronomers were used with varying amounts of styrene. The resulting data is tabulated in Table VII. TABLE VII Experiment Monomers Expony Resin R.T. Init. H.D.T. R.T. Flex R.T.Flex 149 C Flex No. (wt.ratio) Total Monomers Visc. 1.8 MPa Str. MPa Mod. MPa Str. MPa (w/w) MPa's C 1 S:BMA (80:20) 80/20 2000 165,167 100 3340 47 2 S:BMA (60:40) 80/20 1400 159,161 104 3060 39 3 S:IBMA (60:40) 80/20 1240 160,162 87 3030 40 4 S:BMA (40:60) 80/20 688 161,164 116 3280 48 5 S:BMA (20:80) 80/20 608 159,159 112 3070 37 6 S:IBMA (20:80) 80/20 164,165 94 3060 38 7 S:BMA (40:60) 90/10 4250 165,165 72 3150 45 8 S:BMA (40:60) 80/20 668 161,164 116 3280 48 9 S:BMA (40:60) 70/30 225 159,162 95 2540 36 10 S:IBMA (40:60) 70/30 54 144,151 92 2620 23 11 S:TMPTMA (40:60) 50/50 301 183,184 95 3680 60 12 S:BMA:TMPTMA 50/50 63 134 44 2480 38 (40:30:30) -cont'd- TABLE VII (cont'd) Experiment 149 C R.T. R.T. R.T. 149 C 149 C 149 C Notched No. Flex Ten., Ten., Ten., Ten., Ten., Ten., Izod., Mod., Str. Mod. Elong. Str. Mod. Elong. J/M MPa MPa MPa % MPa MPa % 1 1390 59 2330 2.6 25 1320 4.8 2 1150 62 3080 3.3 21 1120 5.5 29 3 1260 49 3210 1.9 22 1180 4.6 26 4 1350 60 2950 2.9 23 1230 5.9 27 5 1100 53 2860 2.5 19 1040 6.6 27 6 1210 61 3380 2.7 21 1200 6.0 26 7 1490 46 2980 1.7 26 1470 3.6 30 8 1350 60 2950 2.9 23 1230 5.9 27 9 1110 52 2410 3.6 18 943 7.8 25 10 690 52 2670 5.2 6.1 320 6.9 25 11 2230 55 3680 1.7 37 2070 3.7 12 1240 42 3050 1.6 19 1020 4.6 Example IX The procedures of Example VIII were essentially repeated wherein pentaerythritol triacrylate (PETA) is used together with styrene (S). The results are tabulated in Table VIII. TABLE VIII Experi- Monomers Resin/ Peroxide HDT R. T. R. T. R. T. R. T. R. T. Notched Izod, ment No. (wt ratio) Monomer (g/100g 1.8 MPa Flex Flex Tensile Tensile Tensile J/M (w/w) resin) ( C) Str. Mod. Strength Modulus Elonga MPa MPa MPa MPa tion (%) 1 S/PETA 90/10 0.2 171,172 129 3130 68.4 3150 2.9 29.3 2 S/PETA(94.5/5.5) 80/20 0.2 171,170 131 3200 78.1 3170 3.9 30.0 3 S/PETA(91/9) 80/20 0.2 120 3360 75.2 2960 3.9 26.3 Example X The procedures of Example VIII were essentially repeated wherein acrylonitrile (ACN) or acrylonitrile/butyl acrylate (ACN/BA) is blended with styrene. The results are tabulated in Table IX. The basic formulation was as follows: Epoxy Resin B 300 pbw ETPPI 1.5 pbw 150 150 pbw Monomer(s) Variable Peroxide ("LUPERSOL 101") Variable TABLE IX Experiment Monomers Resin/Monomer Peroxide (g/100 g HDT Number. (w/w) resin) (1.8 MPa) ( C) 1 Styrene/Acrylonitrile (76/24) 90/10 0.2 169,170 2 Styrene/Acrylonitrile (76/24) 80/20 0.2 168,168 3 (Styrene/Butyl 90/10 0.2 167,168.5 ( 4 (Acrylate 80/20 0.2 158.5,164 ( 5 (Acrylonitrile 90/10 1.0 171,168 ( 6 ((52/24/24) 80/20 1.0 161,162 Example XI This example illustrates the preparation of a blend of epoxy and styrene-acrylic polymers with the epoxy curing agent and onium compound predispersed in the acrylic monomer. Trimellitic anhydride (150 g) was combined in a l-quart (946 ml) paint can with 1,3-butylene dimethacrylate (BDMA) (105g) and 3g of an 80% (wtt) solution in ethanol of a mixture of alkyl dimethyl benzyl ammonium chlorides (alkyl groups: C12 40%, C14 50%, C16 10%) sold under the trade mark "BARQUAT MB-80". This mixture (component B) was mixed with a rotary agitator for approximately 5 minutes until a pourable suspension was obtained. The suspension was allowed to stand overnight and then was cambined with a mixture (component A) of 300g of Epoxy Resin B, 45g of styrene and 2g of "LUPERSOL 101". This mixture was mixed for approximately 5 minutes; entrained air bubbles were allowed to rise to the top and the viscosity was measured with a Brookfield viscometer. The mixture was then poured into moulds as in Examples I and VIII and the moulds were placed in an oven at 1500C for 2 hours for curing. Further experiments were run with different amounts of BDMA and styrene monomers and cured by the same procedure. Mechanical properties are shown in Table X. TABLE X R.T. R.T. 149 C 149 C R.T. R.T. R.T. 149 C 149 C 149 C Experi- Mono- Init. HDT Flex Flex Flex Flex, Ten. Ten, Ten. Ten. Ten. Ten. ment mers Visc. 1.8MPA Str., Mod., Str., Mod., Str., Mod., Elon., Str., Mod., Elong., No. (phr) Pa's ( C) MPa MPa MPa MPa MPa MPa (%) MPa MPa (%) 1 BDMA(35) Styrene(15) 0.55 163 134 3520 59 2000 52 2900 3.4 23 1680 7.8 2 BDMA(35) Styrene(30) 0.15 164 100 2820 59 1980 47 2890 3.4 24 1630 7.7 3 BDMA(35) Styrene(45) 0.083 156 114 3450 47 1690 49 3150 2.6 19 1290 8.8 TABLE X (cont'd) R.T. R.T. 149 C 149 C R.T. R.T. R.T. 149 C 149 C 149 C Experi- Mono- Init. HDT Flex Flex Flex Flex, Ten. Ten, Ten. Ten. Ten. Ten. ment mers Visc. 1.8MPA Str., Mod., Str., Mod., Str., Mod., Elon., Str., Mod., Elong., No. (phr) Pa's ( C) MPa MPa MPa MPa MPa MPa (%) MPa MPa (%) 4 BDMA(45) Styrene(15) 0.326 168 103 2980 56 2010 62 2930 2.8 28 1680 5.0 5 BDMA(45) Styrene(30) 0.12 116 3450 63 1580 43 3280 1.5 36 2090 2.8 6 BDMA(45) Styrene(45) 0.060 157 114 3430 52 1700 65 3120 3.0 24 1670 9.4 Example XII The procedures of Example XI were followed using trimethylolpropane triacrylate (TMPTA) and triirethylolpropane trimethacrylate (TMPIMA) as the acrylic monomers in which the TMA was suspended. The amount of "LUPERSOL 101" used was raised to 3g. Heat deflection temperatures for bars cast fram the resulting epoxy/styrene-acrylic blends are shown in Table XI. TABLE XI Initial HDT, Experiment Viscosity 1.8 MPa Number Monomers (phr) Pa.s ( C) 1 TMPTMA (83), Styrene (30) 0.19 177 2 TMPTMA (83), Styrene (60) 0.055 177 3 TMPTMA (83), Styrene (90) 0.026 170 4 TMPTMA (60), Styrene (10) 0.14 171 5 TMPTMA (60), Styrene (70) 0.040 171 6 TMPTA (50), Styrene (15) 0.15 170 7 TMPTA (50), Styrene (45) 0.10 171 8 TMPTA (50), Styrene (75) 0.036 162 9 TMPTA (70), Styrene (15) 0.68 176 10 TMPTA (70), Styrene (45) 0.15 171 Example XIII 257g of benzophenonetetracarboxyl Ic dianhydride (BTDA) were mixed with 38.5g butyl methacrylate and 90g styrene to make a wetted powder (component A) which was allowed to stand for two days. The powder was then mixed with a mixture of 300g of Epoxy Resin B, 1.5g of TBAB and ig of "LUPERSOL 101" (car- ponent B); the mixture was stirred for approximately 5 minutes, poured into moulds as in Examples I and VIII, and cured for 2 hours at 1500C. Mechanical properties of this sample and another prepared similarly are shown in Table XII. TABLE XII R.T. R.T. 149 C 149 C R.T. R.T. R.T. 149 C 149 C 149 C Experi- Mono- Init. HDT Flex Flex Flex Flex, Ten. Ten, Ten. Ten. Ten. Ten. ment mers Visc. 1.8MPA Str., Mod., Str., Mod., Str., Mod., Elon., Str., Mod., Elong., No. (phr) Pa's ( C) MPa MPa MPa MPa MPa MPa (%) MPa MPa (%) 1 BMA(12.8) Styrene(30) 3.32 196 38 3360 12.6 940 21 3470 0.6 7.0 900 0.8 2 BMA(30) Styrene(76.7) 2.50 124 43 3360 11.2 700 17 3300 0.6 5.8 650 0.8 Example XIV Trimellitic anhydride (45g) was mixed with trimethylolpropene trimethacrylate (54g) to form a pourable suspension (component B). This mixture was then mixed with a mixture of 300g Epoxy Resin B, 45g styrene, 3g stannous octoate and 1.5g 1,LUPEPSOL 101" (component A). Camponents A and B were mixed together for approximately 5 minutes and the resultant mixture was poured into molds as in Examples I and VIII and cured for 2 hours at 150 0C. mechanical properties for cast specimens of this and other compositions made using the above procedure are shown in Table XIII. TABLE XIII R.T. R.T. 149 C 149 C 149 C 149 C 149 C Experi- Mono- Init. HDT Flex Flex Flex Ten. Ten. Ten. Ten. ment mers Visc. 1.8MPA Str., Mod., Str., Mod., Str., Mod., Elong. No. (phr) Pa.s ( C) MPa MPa MPa MPa MPa MPa (%) 1 TMPTMA(18) 4.25 152 34 1150 16 984 6.4 Styrene (5) 2 TMPTMA (18) 132 157 105 3350 52 1650 Styrene(10) 3 TMPTMA(18) 0.65 153 48 1400 24 1550 4.6 ExmpleXV This example iliustrates the use of stannous octoate as the accelerator in an epoxy-styrene/trimethylolpropane trimethacrylate (TMPTMA) blend. The basic formulation is as follows: Componenet A Componenet B Epoxy Resin A 100 pbw TMA - 15 pbw Stannous Octoate (SO) 1 pbw TMPIMA - 18 pbw "LUPERSOL 101" (L101) Variable Styrene Variable The procedures used in Example XII were employed and the results are tabulated in Table XIV. TABLE XIV Init. Gel Time, R.T. R.T. 149 C 149 C 149 C 149 C 149 C Dyn.Mech.Data Experi- Mono- Cata- Mix. 150 C HDT Flex Flex Flex Ten. Ten. Ten. Ten. Tg C Temp. for ment mers lysts, visc. Cure 1.8MPA Str., Mod., Str., Mod., Str., Mod., Elong. (tan G, G' 300) No. (phr) phr R.T.(Pa.s) Plate Sec. ( C) MPa MPa MPa MPa MPa MPa (%) peak, MPa( C) 1 TMPTMA(18) SO(1) 12.72 45 139 106 3390 28 870 16 820 5.7 161 147 L101(0.5) 2 TMPTMA(18) SO(1) 4.25 54 152 34 1150 16 980 6.4 170 152 Styrene(5) L101(0.5) 3 TMPTMA(18) SO(1) 1.32 61 157 105 3350 52 1670 180 169 Styrene(10) L101(0.5) 4 TMPTMA(18) SO(1) 0.645 57 153 48 1400 24 1550 4.6 160 171 Styrene(10) L101(0.5)

Claims: CLAIMS 1. A heat-curable composition comprising: (1) an epoxy compound having on average more than one epoxy group per molecule, (2) at least one unsaturated monomer selected from the group con sisting of esters of ethylenically unsaturated monocarbo xylic acids, cyano-containing compounds, allyl compounds, olefins and diolefins (3) a carboxyl-containing compound, (4) at least one epoxy curing accelerator, and (5) a free-radical curing agent. 2. A composition according to Claim 1, which additionally, includes an unsaturated aromatic monomer. 3. A composition according to Claim 2, wherein the unsaturated aromatic monomer is styrene or a substituted styrene. 4. A composition according to Claim 1, 2 or 3 wherein the epoxy compound is a glycidyl polyether of a polyhydric phenol or a hydrogenated polyhydric phenol. 5. A composition according to Claim 4 wherein the polyhydric phenol is 2, 2-bis (4-hydroxyphenyl) propane. 6. A composition according to any of Claims 1 to 5 wherein said at least one unsaturated monomer is selected fran a polyacrylate or polyrrethacrylate ester of a polyol, an alkyl ester of an ethylenically unsaturated monocabboxylic acid, and acrylonitrile. 7. A composition according to Claim 6 wherein said at least one unsaturated monomer is selected from pentaerythritol triacrylate, trimethyloipropane trimethacrylate, n-butyl methacrylate, isobutyl methacrylate, and acrylonitrile. 8. A composition according to any of Claims 1 to 7 wherein the carboxyl-containing compound is an acid anhydride 9. A composition according to Claim 8 wherein the acid anhydride is trimellitic anhydride or 3,31,4,4'-benzophenone tetracarboxylic dianhydride. 10. A composition accoridng to any of Claims 1 to 9 wherein the epoxy curing accelerator is a phosphonium or ammonium halide or a stannous salt of a monocarboxylic acid. 11. A composition according to Claim 10 wherein the epoxy curing accelerator is ethyl triphenyl phosphonium iodide or stannous octoate. 12. A heat-curable composition according to Claim 1 comprising: (1) from 30 to 99 parts by weight of a glycidyl polyether of 2, 2-bis (4-hydroxyphenyl) propane, (2) from 1 to 70 parts by weight of a polyacrylate or polymetha crylate ester of a polyol or of a blend of polyacrylate or polymethacrylate ester of a polyol with styrene or a mixture of styrene and divinyl benzene containing up to 50% by weight of divinyl benzene, (3) fran 0.25 to 2.0 stoichiametric equivalents based on the glycidyl polyether of a polycarboxylic acid anhydride, (4) an accelerating amount of at least one epoxy curing ac celerator, and (5) a curing amount of an organic peroxide. 13. A composition according to any of Claims 1 to 12 wherein the polyacrylate or polymethacrylate ester is trimethylolpropane trimethacrylate or, pentaerythritol triacrylate. 14. A process for preparing a formed article which comprises bringing a composition according to any of Claims 1 to 13 into a mould and curing by application of heat. 15. A formed article prepared by a process according to Claim 14.

Inventors: CORLEY, LARRY STEVEN
Applicants: SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ B.V.
Application year: 1983
Main classification: C08F283
IPC codes: C08G59, C08F283