BLENDS OF POLYCAPROLACTONE POLYOLS AND POLYEPOXIDES

Abstract: Curable blends of cycloaliphatic epoxides and/or diep­ oxides and polycaprolactone polyols having a molecular weight of from about 500 to about 4000 produced by the ring opening reaction of a lactone with a polyfunctional initiator, wherein the minimum percent of lactone hydroxyls, y, in the polyester polyol is a function of the mole ratio, x, of lactone units to active hydrogens in the initiator, and is defined, as y = 52.5 x for x > 0 to 1.5 and y = 2.11 x + 75.6 for x > 1.5 wherein the blends are essentially liquid at 25°C.

Description: BLENDS OF POLYCAPROLACTONE gOLYOLS AND POLYEPOXIDES BACKGROUND OF THE INVENTION This invention relates to liquid blends of polycaprolactone polyols and cycloaliphatic epoxides. Blends of cycloeliphetic epoxides and polycaprolactone polyols have widespread use in the manufacture of insulating components for electrical equipment. These blends are provided in filled and unfilled cured epoxy formulations which are used to impregnate electrical windings, cast or mold electrical insulators, encapsulate conductive metal rods and nonconductive members, and pot various electrical devices. The epoxide components of the blends impart to the cured products good electrical properties, including low dielectric loss, high resistivity and good arc and tracking resistance. The polycaprolactone polyol components of the blends improve the mechanical properties of the cured products. It has been known that polycaprolactone polyols may be used as flexibilizers to enhance the thermal shock resistance of cured epoxide resins. Thermal shock resistance is a measure of a cured resin's ability to withstand rapid temperature fluctuations without cracking. In electrical applications cured epoxide resins are often in contact with metals. With changes in temperature the cured epoxide resins expand and contract. As a result of the difference in the thermal coefficients of expansion between the resins and the metals they contact, stress is produced which causes cracks to develop in the cured resin system. Polycaprolactone polyols impart a degree of elasticity to the epoxides, improving a cured epoxy resin's ability to withstand repeated cycles of high and low temperatures without cracking. Illustrative of prior srt regarding the use of blends of epoxides and polycaprolactone polyols are the following: U.S. Patent No. 3,699,070, which discloses sn epoxy composition flexibilized with polycaprolactone polyols and U.S. Patent No. 4,434,286 which discloses a curable composition comprising o cycloaliphatic epoxide and o polyol having a molecular weight of from about 1,000 to about 4,000, e.g. polycaprolactone polyols (see col.4, line 3 to col. 5, line 16). The cured compositions disclosed by U.S. Patent No. 4,434,286 are described as having high thermal shock resistance values and good combinations of mechanical and electrical properties. Blends of cycloaliphatic epoxides and/or diepoxides with polycaprolactone polyols are commercially available. ERRA > -4090, available from Union Carbide Corporation, and Finelexm.090, available from Fine Polymers, are two such compositions. Both of these blends contain a polycaprolactone polyol having a molecular weight of about 1250, and are waxy solids at 25-C. Polycaprolactone polyols are typically prepared by the ring opening reaction of o caprolactone with an organic polyfunctional initiator. It has been determined that the percentage of caprolactone derived hydroxyl groups as opposed to initiator derived hydroxyl groups tn a given polycaprolactone polyol product (reported as the percent lactone hydroxyl value or PLH) determines whether the polyol will, when used as a flexibilizer in conjunction with a cycloaliphatic epoxide, maximize the contribution of the flexibilizer to the cured expoxide's thermal shock resistance. Also, it has been found that by maximizing the extent of reaction of the lactone with initiator, the resultant lactone polyol is primarily chain capped with lactone derived hydroxyl groups formed by the ring opening addition reaction of the lactone, and that this narrows significantly the molecular weight distribution of the resultant polyol. Polyols of narrow molecular weight distribution tend to have lower melting points than polyols having a broader molecular weight distribution. These polyols are more particularly described in commonly essigned U. S. Patent Application Serial No. 469,433, filed on February 24, 1983 in the names of Linda Ann Domeier and Edward Shi Ping Hsi. The lower melting points of the above described polyols allows them to be easily and conveniently blended with cycloaliphatic epoxides at relatively convenient temperatures. These blends are further characterized by their ebility to remain essentially liquid (as hereinafter defined) at temperatures of about 250C. Additionally, it has been determined that the use in an epoxy resin system of a narrower molecular weight caprolactone polyol, having less of higher end lower molecular weight polyols, contributes to increasing 8 cured resin's thermal shock resistance. Without wishing to be bound to theory, it is postulated that lower molecular weight polyols provide shorter, less flexible cross linkages than higher molecular weight polyols. The greater number of shorter linkages provided by a polyol having a broader molecular weight distribution contributes to an uneven distribution of stress in a cured resin making the cured resin more susceptible to reduced thermal shock resistance. THE INVENTION This invention is directed to a curable composition which comprises a blend of a cycloaliphatic epoxide and a polycaprolactone polyol having 8 molecular weight of from about 500 to about 4,000, produced by the ring opening reaction of a lactone with a polyfunctional initiator, wherein the minimum percent of lactone hydroxyls, defined as y, in the polycaprolactone polyol is a function of the mole ratio, x, of lactone units to active hydrogens in the initiator, and is defined as y = 52.5x for x > 0 to 1.5 and y = 2.llx + 75.6 for x > 1.5, wherein the composition is essentially liquid (i.e. forms a slurry-like composition having suspended therein soft, finely divided low melting precipitate which lack a definite particulate structure) at 250C. The solids which precipitate from the composition are easily returned to uniform suspension by mixing, or to solution by very mild heating. In many cases the thermal shock resistance provided by the blends of this invention is superior to that provided by compositions which contain the same epoxide component and an otherwise identical polycaprolactone polyol of the same molecular weight, having fewer lactone hydroxyls incorporated therein. Suitable cycloaliphatic epoxides for purposes of this invention are those having an average of more than one vicinal epoxy group per molecule. The epoxy groups can be terminal epoxy groups or internal epoxy groups as exemplified by the cycloaliphatic epoxides which are subsequently described. Particularly desirable cycloaliphatic epoxides are the cyclohexane diepoxides, that is epoxides having at least one vicinal epoxy group. Illustrative of suitable cycloaliphatic epoxides are the following: FORMULA r Diepoxides of cycloaliphatic esters of dicarboxylic acids having the formula: EMI5.1 wherein R1 through Rg, which can be the same or different are hydrogen or alkyl radicals generally containing one to nine carbon atoms inclusive and preferably containing one to three carbon atoms inclusive as for example methyl, ethyl, n-propyl. n-butyl, n-hexyl, 2-ethylhexyl, n-octyl, n-nonyl and the like; R is a valence bond or a divalent hydrocarbon radical generally containing one to nine carbon stoms inclusive and preferably containing four to six carbon atoms inclusive, as for example, alkylene radicals, such as trimethylene, tetramethylene, pentamethylene, hexamethylene, 2-ethylhexamethylene, octamethylene, nonamethylene, and the like; cycloaliphatic radicals, such as 1,4-cyclohexane, 1,3-cyclohexane, 1,2-cyclohexane, and the like. Particularly desirable epoxides, falling within the scope of Formula I, are those wherein R1 through R9 are hydrogen and R is alkylene containing four to six carbon atoms. Among specific diepoxides of cycloaliphatic esters of dicarboxylic acids are the following: bis(3,4-epoxycyclohexylmethyl )oxalate, bis(3,4-epoxycyclohexylmethyl)adipate, bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate, bis(3,4-epoxycyclohexylmethyl)pimelate, and the like. Other suitable compounds are described in U.S. Pat. No. 2,750,395 to B. Phillips et al. FORMULA II A 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate having the formula: EMI7.1 wherein R1 through Rg which can be the same or different are as defined for R1 in formula I. Particularly desirable compounds are those wherein R1 through Rg are hydrogen. Among specific compounds falling with the scope of Formula II are the following: 3 ,4-epoxycyclohexylmethyl-3,4-epoxycyclo- hexanecarboxylate, 3,4-epoxy-1-methylcyclohexylmethyl-3,4-epoxy-1 methylcyclohexanecarboxylate, 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4 epoxycyclohexanecarboxylate, 3,4 -epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3- methylcyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5- methylcyclohexanecarboxylate; 3,4-epoxycyclohexylmethyl-3,4-epoxycyclo hexanecarboxylate being particularly desirable. Other suitable compounds are described in U.S. Pet. No. 2,890,194 to B. Phillips et al. FORMULA III diepoxides having the formula: EMI8.1 wherein the R single and double primes, which can be the same or different, are monovalent substituents such as hydrogen, halogen, i.e. chlorine, bromine, iodine or fluorine, or monovalent hydrocarbon radicals, or radicals as further defined in U.S. Pat No. 3,318,822 to Hans Batzer et al. issued May 9, 1967. Particularly desirable compounds are those wherein all the R's are hydrogen. Other suitable cycloaliphatic epoxides are the following: EMI8.2 EMI8.3 and the like. The preferred cycloaliphatic epoxides are the following: 3,4-Epoxycyclohexylmethyl-3,4-Epoxy-cyclohexane carboxylate EMI9.1 Bis-(3,4-Epoxycyclohexylmethyl)Adipate EMI9.2 2-(3,4-Epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-meta-dioxane EMI9.3 vinyl cyclohexene dioxide EMI10.1 or mixtures thereof. Epoxides with six membered ting structures may also be used, such as diglycidyl esters of phthalic acid, partially hydrogenated phthalic acid or fully hydrogenated phthalic acid. Diglycidyl esters of hexahydrophthalic acids being preferred. The polyester polyols suitable for use in the this invention are those polyols hereinafter termed "Kinetic" polyols more particularly described in commonly assigned U.S. Patent Application, Serial No. 469,433, incorporated by reference herein, which produce essentially liquid blends with cycloaliphatic epoxides. The polyols are produced by the ring opening reaction of a caprolactone with an organic polyfunctional initiator. The reaction is preferably conducted in the presence of from about 0.1 to 50 parts per million by weight, based on the total weight of the lactone, of a ring opening catalyst such as stannous octanoate, diethylene dilaurate, tetraisopropyl titanate and butyl titanate, etc. The reaction is conducted at a temperature of from about 100 to about 200-C, preferably from about 140 to about 1700C for a period of from about 1 to about 24 hours. preferably from about 3 to about 8 hours. It is important to avoid extended reaction times and excessive reaction temperatures which lead to a gradual decrease in the percent of lactone hydroxyl groups. Preparation of the polyols requires control of the reaction conditions and termination of the reaction when the level of unreacted lactone monomer initially reaches about 1 mole percent or less of the original lactone charge. The lactones suitable for producing the polyols used herein are caprolactones having the formula: EMI11.1 wherein n is four and wherein the R's are independently selected from hydrogen, elkyl, cycloalkyl, alkoxy. halogen or single ring aromatic hydrocarbon radicals. Preferably the caprolactone is epsilon caprolactone, or e methyl epsilon-caprolactone. or a mixture of isomeric methyl epsilon-caprolactones. or a mixture of one or more isomeric methyl epsilon-caprolactones with epsilon ceprolactone. Table I below lists the compositions and various properties of e number of commercially available polycaprolactone polyols as well as the above described Kinetic polyols. The CapaE polyols are available from Interox Chemicals Ltd. and the Tones polyols are available from Union Carbide Corporation. Table 1 Caprolactone Polyol Compositions Mole Ration of Average Lectone Units to Molecular Initiator Mole Active Hydrogens % Lacton Measured Weights Polyol Initiator Percents* in the Initiator Hydroxyls Melting Point C unsub- monosub- disubstituted stituted stituted ToneR 0210 830 Diethylene Glycol 14 45 41 3.2 64 44 - 49 CapaR 205 830 Diethylene Glycol 4 32 64 3.2 80 -- Kinetic I 830 Diethylene Glycol 0 20 80 3.2 90 31 - 36 CapaR 210 1000 Neopentyl Glycol 7 49 45 3.9 68 -- ToneR 0230 1250 Diethylene Glycol 6 39 55 10.0 75 50 - 55 CapaR 215 1250 Diethylene Glycol 0 33 67 10.0 83 39 - 45 Kinetic II 1250 Diethylene Glycol 0 9 91 10.0 96 39 - 44 * Values were determined by analysis of NMR spectra of the various polyols Polyfunctional initiators used to produce kinetic polyols are represented by the General formula: : R'(YH)8 in which R' is an organic radical selected from the group consisting of aliphatic, cycloaliphatic, aromatic and heterocyclic radicals, a is a number equal to the functionality of the initiator, and the Y is selected from -O-, -NH-, NR2 (R2 is selected from alkyl, acryl, aralkyl or cycloalkyl), -S-, and -C(O)0. Organic polyols in which the YH groups are hydroxyl groups, include the following: ethylene glycol, diethylene glycol, 2,2,4-trimethyl-1,3-pentanediol, dipropylene glycol, propylene glycol, triethylene glycol, 1,4-cyclohexane dimethanol, neopentyl glycol, 2, 2-dimethyl-3-hydroxypropyl 2,2-dimethyl-3-hydroxy-propionate, the ethylene and propylene oxide adducts of 2,2-dimethyl-3-hydroxypropyl 2,2-dimethyl-3-hydroxypropionate, triethanolamine, 1,3-butanediol, tetraethylene glycol, 2,2-bis(4-hydroxyphenyl) propane and the ethylene and propylene oxide edducts of 2,2-bis(4-hydroxyphenyl)propane, low molecular weight polymeric polyols derived from ethylene oxide or propylene oxide or tetrahydrofursn (e.g., polytetramethylene glycols such ss Polymeg 650), pentaerythritol, erythritol, glycerine, trimethylolpropane, 1,4-butanedlol, 1,6-hexanediol, It has been found that not all kinetic polyols produce liquid blends with cycloaliphatic epoxides. For example, a polyollepoxide blend containing 70 weight percent of a polycaprolectone polyol having a molecular weight of about 1250 initiated by diethylene glycol may be a liquid at 25 C whereas, a polyollepoxide blend having the same epoxide component and containing equal amounts of an otherwise identical polycaprolactone polyol initiated by 1,4 butane diol may be a waxy solid. It is, therefore, critical that the initiator chosen produce a polyol which may be blended with a cycloaliphatic epoxide to form 8 liquid composition at a desired concentration. It is not precisely known what effect all of the above cited initiators have on the polyols produced thereby. For purposes of this invention, particularly preferred initiators are diethylene glycol and neopentyl glycol. The polyols particularly well suited for use herein are low melting polycaprolactone polyols having a molecular weight of from about 800 to about 2,000, preferably from about 1,200 to 1,300 produced by the reaction of diethylene glycol with caprolactone. A polycaprolactone polyol having e PLH value of at least about 96, produced by the ring opening reaction of ceprolectone with diethylene glycol, is especially desired. It should also be noted that the concentration of the polyol component in a polycaprolactonelcycloaliphatic epoxide blend affects the melting point and thus the physical state of the blend. As a general rule, polyols of higher molecular weight form solids with cycloaliphatic epoxides at lower polyol concentrations than polyols having lower molecular weights. It is required that the blends of this invention be essentially liquid at 25-C. In one embodiment, the compositions of this invention are suitable for use as modifiers, which are commercially provided as concentrates to be further blended with cycloaliphatic epoxides. These compositions contain a minimum of about 30 percent by weight of polycaprolactone polyol, based on the total weight of the polyol and epoxide components. A composition containing from about 30 to about 50 percent by weight0 based on the total weight of the polyol and epoxide components, of cycloaliphatic epoxide and from about 50 to about 70 percent by weight, based on the total weight of the polyol and epoxide components, of polycaprolactone polyol is preferred; compositions containing about 30 to about 35 percent by weight of a cycloaliphatic epoxide and about 70 to about 65 percent by weight of a polycaprolactone polyol are especially preferred. In another embodiment, the compositions of this invention are suitable for use in molding compositions. Molding compositions typically contain from about 5 to about 55 percent by weight, based on the total weight of the polyol and epoxide components, of polycaprolactone and from about 45 to about 95 percent, based on the total weight of the polyol and epoxide components, of cycloaliphatic epoxides. Compositions containing from about 10 to about 40 percent by weight of polycaprolactone and from about 60 to about 90 percent by weight of polycaprolactone are particularly desirable. The compositions of this invention may be further blended with hardeners such as aliphatic, aromatic, and cycloaliphatic polycarboxylic acid anhydrides to effect cure. Especially well suited for use herein are dicarboxylic acid anhydrides, particularly hydrocarbon dicarboxylic acid anhydrides which include the following: phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride, maleic anhydride, chloromaleic anhydride, dichloromaleic anhydride, glutaric anhydride, adipic anhydride, succinc anhydride, itaconic anhydride, heptylsuccinic anhydride, hexylsuccinic anhydride, methylbutylhydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, n-nonenylsuccinic anhydride, octenyl- succinic anhydride, pentenylsuccinic anhydride, propylsuccinic anhydride, citraconic anhydride, 4-nitrophthalic anhydride, l,2-naphthalic anhydride, 2,3-naphthalic anhydride, 1,8-naphthalic anhydride, tetrabromophthalic anhydride, tetraiodophthalic anhydride, and the like. Mixtures of anhydrides, polymeric anhydrides or mixed polymeric anhydrides of sebasic, adipic, pimelic, cyclohexane, 1,4-dicarboxylic, terephthalic and isophthalic acids are also suitable for use herein. Polycarboxylic acid anhydrides, such as l,2,4,5-benzenetetracarboxylic dianhydride and 1,5-dimethyl-2,3,4,6,7,8-hexahydronaphthalene 3,4-7.8-tetracarboxylic dianhydride can also be used. Especially preferred hardeners are hexahydrophthallc anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthelic anhydride and methyl nadic anhydride. The compositions of this invention may also contain curing catalysts such as metal and non-metal halide Lewis acids, tertiary amines, peroxides, ethylene glycol, fatty acids, acrylates of group IV-B metals. organotin compounds having at least one SN-C bond, and carboxylic acid salts of lead and manganese. Especially preferred curing catalysts are (2-hydroxyethyl)trimethyl ammonium hydroxide, benzyl dimethyl amine, and 2-methyl imidazole. In addition, the compositions may also contain modifiers such ss a dimer acid, for example EmpolTM 1022 available from Emery Industries, which is a mixture of 3 percent mono, 75 percent dimer and 22 percent trimer scids made from unsaturated C18 fatty ecids; a carboxyl terminated butadiene acrylonitrile (80-20) random copolymer having a molecular weight of about 3300; fillers such ss clay, silica, alumina, or aluminum trihydrate which may be coated with, for example, silanes, which fillers may be added in amounts of up to about 70 percent by weight; pigments such as carbon black; mold release agents, and the like. Cured compositions are generally prepared by mixing the polycaprolactone polyol, cycloaliphatic epoxide, hardener and other ingredients and heating the resultant mixture to temperatures of about 1000C to about 2000C for a period of about 1 to 6 hours depending on the temperature employed as well as upon the ratio and relative emounts of materials used. The polycaprolactone polyolicycloaliphatic epoxide blends of this invention may also be U.V. radiation cured. U.V. curing processes suitable for use herein are set forth more fully in U.S. Patent Application Serial Nos. 464,571 and 464,564 filed in the names of Joseph Victor Koleske and George Thomas Kwiatkowski on February 7, 1983 and commonly assigned. EXAMPLES The following examples serve to illustrate the specific embodiments of this invention. It is not intended that the scope of the invention shall be limited by these examples. The designations which appear in the Examples and Tables below have the following meanings: Epoxide: 3-4 epoxycyclohexylmethyl-3,4-epoxy cyclohexane carboxylate Polyol I: A diethylene glycol initiated polycaprolactone polyol having a molecular weight of about 1250 and a Percent Lactone Hydroxyl (PLH) value of about 75, obtained under the product designation Tones 0230 Polyol II: A diethylene glycol initiated polycaprolactone polyol having a molecular weight of about 1250 and a PLH value of about 83, obtained under the product designation CapaS 215 Polyol III: A diethylene glycol initiated polycaprolactone polyol having a molecular weight of about 1250 and a PLH value of about 96. Polyol IV: A 1,4-butane diol initiated polycaprolactone polyol having a molecular weight of about 1250 and a PLH value of about 96. Polyol V: An diethylene glycol initiated polycaprolactone polyol having a molecular weight of about 2,000 and 8 PLH value of about 96. HHPA: Hexahydrophthalic anhydride MTHPA: Methyltetrahydrophthalic anhydride MHHPA: Methylhexahydrophthalic anhydride MNA: Methyl nadic anhydride BDMA: Benzyldimethylamine Examples 1 to 10 and Comparative Examples C1 to C6 Various blends of epoxides and polyols were prepared by mixing the various components listed in Table II below. Prior to mixing, the polyol component of each was heated to temperatures of about 800C to achieve liquidity. The physical state of the blends is provided below. Table 2 Formulation Physical State Example Polyol Epoxide (gms) Polyol (gms) After z4 nrs. after 1 month C1 Polyol I 70.0 30.0 liquid solid C2 Polyol I 50.0 50.0 solid solid C3* Polyol I 33.3 66.7 solid C4 Polyol I 30.0 70.0 solid solid C5* Polyol II 33.3 66.7 solid 1 Polyol III 70.0 30.0 liquid liquid 2 Polyol III 50.0 50.0 liquid liquid 3* Polyol III 33.3 66.7 liquid 4 Polyol III 30.0 70.0 liquid liquid C6 Polyol IV 70.0 30.0 solid 5 Polyol V 70.00 30.0 liquid liquid 6 Polyol V 50.00 50.00 liquid liquid 7 Polyol V 30.00 70.00 liquid liquid * It should be noted that four formulations of the 1: :2 blends of epoxide and polyol I, II and III were prepared. The data presented is representative of three of the four formulations. In one formulation, however, blends of all three polyols remained liquid after a period of one week. It is believed that the data presented is representative of typical blend behaviour and that the non-conforming formulation was abberational. Example 8-10 and ComParative Examples C to Cg The thermal shock resistance of a series of ten cured resin discs for each of 6 resin systems, prepared using the epoxide, polyol, snhydride and curing catalyst quantities specified in Table III below, was measured eccording to the following test procedure: Uncured specimens of a given resin system were prepared by mixing the epoxide and polyol components of the system in a first container at a temperature of about 800C; mixing the anhydride and during catalyst components of the system in 8 second container at a temperature of about 800C; combining the contents of the two containers to form a blend; and pouring the resultant blend into 10 aluminum milk test evaporating dishes 5 cm. in diameter by 1 cm. deep, having a common steel washer Positioned in their centers. The washers had 2.5 cm - - 11 mum outside dlameters of EMI22.1 inside diameters of EMI22.2 weighed about 6.6 grams and were supported in the 6.4 mm dishes by rings of filter paper EMI22.3 high cut from a Whatman single thickness cellulose extraction thimble. The uncured specimens were then heated in 8 circulating air oven at a temperature of about 1000C for about 2 hours to form resin discs. The discs were postcured at temperature of about 1600C for a period of about 4 hours. The cured discs were next subjected to a series of hot and cold temperature cycles of increasing severity. The initial upper temperature was 600C and the initial lower temperature was 200C. In succeeding cycles the high temperature limit was increased by 20C and the low temperature limit reduced by 100C. The test was run through 10 cycles1 the final cycle having a high temperature of 2400C and a low temperature of -700C. Each hot temperature cycle ran for a period of 30 minutes in a circulating air oven while each cold temperature cycle ran for a period of 10 minutes in a dry ice-methanol bath. After each series of hot and cold cycles the disc was examined for cracks. Cycling of a specimen was discontinued when cracks were noted. The number of discs failing at a given cycle was recorded. The test was run on each series of ten replicate specimens simultaneously. Thermal shock resistance (TSR) values are reported as an average cycles to fail rating for B series of ten replicate tests. The average cycles to fail rating is calculated by multiplying the cycle number (1 through 10) by the number of specimens that developed cracks at that cycle, adding together the resultant products for each of the 10 cycles, and dividing that sum by 10. Specimens that develop cracks after molding, prior to being subjected to the first temperature cycle, are given failure rating values of zero. For purposes of interpretation, higher average cycles to failure rating values are indicative of systems which provide better thermal shock resistance. TSR values for Examples 8 to 10 and Comparative Examples C7 to C9 are reported in Table III below. TABLE III EXAMPLE C7 C8 C9 8 9 10 Formulation Epoxide (gms) 86.7 73.3 60.0 86.7 73.3 60.0 Polyol I (gms) 13.3 26.7 40.0 Polyol III (gms) --- --- --- 13.3 26.7 40.0 HHPA (gms) 87 73 60 87 73 60 BDMA (gms) 1 1 1 1 1 1 Ethylene Glycol (gms) 2 2 --- 2 2 Thermal Shock Resistance (TSR) 0.0 4.3 7.0 0.0 4.3 7.4 Examples 11 to 14 and Comparative Examples C10 to C13 Samples of resin systems were prepared and tested as described for Examples 8 to 10 end comparative examples C7 to C9 using 33.5 grams of polyol; 66.5 grams of epoxide; and various anhydride hardeners. Relatively small quantities of catalyst were also added to the compositions. Resin system formulations and TSR values are summarized in Table IV below. Table IV EXAMPLE C10 11 C11 12 C12 13 C13 14 Formulation Epoxide (gms) 66.5 66.5 66.5 66.5 66.5 66.5 66.5 66.5 Polyol I (gms) 33.5 --- 33.5 --- 33.5 --- 33.5 Polyol III (gms) --- 33.5 --- 33.5 --- 33.5 --- 33.5 HTHPA (gms) 66.6 66.6 HKPA (gr.s) 62.2 62.2 MHHPA (gms) 67.4 67.4 Mh'A (gms) 71.5 71.5 BDMA (gms) .85 .85 .85 .85 .85 .85 .85 .85 TSR 6.1 6.6 5.7 6.8 4.0 4.1 1.1 1.4

Claims: Claims 1. A curable composition essentially liquid at 250C, which comprises a blend of a cycloaliphatic epoxide and/or diepoxide and a polycaprolactone polyol having a molecular weight of from about 500 to about 4,000, preferably from about 1,200 to about 1,300, produced by the ring opening reaction of a lactone with a polyfunctional initiator, preferably in an amount of at least 30 weight percent, based on the total weight of the polyol and epoxide components, wherein the minimum percent of lactone hydroxyls, y; in the polyester polyol is a function of the mole ratio , of lactone units to active hydrogens in the initiator, andis defined, as y = 52.5x for x > 0 to 1.5 and Y = 2.11 x + 75.6 for x > 1.5. 2. A curable composition as defined in claim 1 wherein the polyol has a molecular weight of from about 800 to about 2,000 and is produced by the ring opening reaction of epsilon -caprolactone with a multifunctional initiator, preferably diethylene glycol or neopentyl glycol. 3. A curable composition as defined in anyone of claims 1 or 2 wherein the epoxide is 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexane carboxylat. 4. A curable composition as defined in anyone of claims 1 to 3 wherein the composition further comprises a carboxylic acid or anhydride hardener, preferably selected from the group consisting of hexahydrophthalic anhydride, Inethyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride and methyl nadic anhydride. 5. The curable composition as defined in claim 4 which further comprises a curing catalyst and/or fiber and or filler. 6. A molding composition essentially liquid at 25-C, which comprises a blend of from about 45 to about 95 percent by weight, based on the total weight of the polyol and epoxide components, of a cycloaliphatic epoxide andlor diepoxide and from about 5 to about 55 percent by weight, based on the total weight of the polyol and epoxide components, of a polycaprolactone polyol having a molecular weight of from about 800 to about 2,000 produced by the ring opening reaction of epsilon-ceprolectone with diethylene glycol, wherein the minimum percent of lactone hydroxyls, y, in the polyester polyol is a function of the mole ratio, x, of lactone units to active hydrogens in the initiator, and is defined, as y - 52.5x for x > 0 to 1.5 and y = 2.11 x + 75.6 for x > 1.S. 7. A molding composition as defined in claim 6 which further comprises fiber and/or filler and optionally a carboxylic acid or anhydride hardener and a curing catalyst, if desired. 8. A curable composition, essentially liquid at 250C which comprises a blend of from about 30 to about 50 percent by weight, based on the total weight of the polyol and epoxide components, of 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, and from about 70 to about 50 weight percent by weight, based on the total weight of the polyol and epoxide components, of a polycaprolactone polyol having a molecular weight of about 1250, produced by the ring opening reaction of epsilon-caprolactone with diethylene glycol, wherein the PLH value of the polycaprolactone polyol Is at least about 96. 9. A curable composition as defined in claim 8 which further comprises fiber and/or filler and optionally a carboxylic acid or anhydride hardener. 10. The cured product of anyone of claim 1 to 9.

Inventors: SPURR, ORSON KIRK
Applicants: UNION CARBIDE CORPORATION
Application year: 1986
Main classification: C08L63
IPC codes: C08L63, C08L33, C08L21, C08G59, C08L67, C08K5, C08L7