MXPA96000890A - Structural product of molding by injection with reaction (rim) resistant to the ca - Google Patents

Abstract

The present invention relates to a heat resistant product prepared by the reaction of a) a mixture of i) an organic polyisocyanate, ii) a compound containing an epoxide group, and iii), optionally, an organic compound containing an active methylene group and which contains at least one electron-withdrawing group adjacent to the methylene carbon, and b) at least one polyalcohol which is free of tertiary amine groups, the reaction being carried out at an equivalents ratio of 2: 1 to 5: 1. The reaction is carried out in the presence of a tertiary amine free isocyanurate catalyst selected from the group consisting of alkali metal, alkaline earth metal, transition metal and quaternary ammonium oxides, alkoxides, hydroxides and carboxylates.

Description

STRUCTURAL PRODUCT OF MOLDING BY INJECTION WITH REACTION (RIM? HEAT RESISTANT REFERENCE TO RELATED APPLICATION This application is a continuation of part of the application serial number 08 / 399,792, filed on March 7, 1995. BACKGROUND OF THE INVENTION Reaction injection molding (RIM) has become an important process in the manufacture of a wide variety of moldings. The RIM process is a process consisting of the intimate mixing of a polyisocyanate component and an isocyanate-reactive component followed by injection of the mixture (generally under high pressure) into a mold with subsequent rapid curing. In the automotive industry, RIM technology has been mainly applied to produce vertical parts (for example bumpers and protection boards) and has not been typically used in the production of horizontal body parts (eg trunks, hoods, roofs) . For the molded product to be useful for the production of horizontal body parts, it must have: 1) high tenacity, 2) a high quality surface, and 3) it must be able to withstand the heat generated during the subsequent treatment of the piece (for example, painting and curing the paint). Typically, this part must have a flexural modulus of 750,000 psi (510,000 kPa) or higher. The products to be used in many automotive applications and in particular the so-called RIM structural parts ("SRIM") must be able to withstand the extreme conditions of the known electrodeposition process used to paint (or prime) and render corrosion resistant parts Of automobiles. Typically, the pieces must be able to withstand two hours in a stove at 400 ° F (ie approximately 204 ° C) without blistering or internal fractures. The structural RIM pieces found in the trade are not able to withstand these conditions. Systems of thermosetting resins based on isocyanates, epoxides and suitable catalysts are known. US Patent 4,070,416 describes the preparation of resins by mixing a polyfunctional isocyanate with a polyfunctional epoxide, and then carrying out a polymerization reaction in the presence of an isocyanurate catalyst containing nitrogen. U.S. Patent 4,728,676 discloses a thermosettable reactive mixture of resins of an organic polyisocyanate, a polyepoxide, and a heat activatable catalyst. U.S. Patent 4,788,224 describes a two-step process for preparing a molded product. In the first step, an organic polyisocyanate is reacted with an organic compound containing at least two epoxide groups in the presence of a tertiary amine catalyst. The reaction is stopped by adding a latent heat activatable catalyst to the product. The mixture is then heated in a mold to complete the crosslinking reaction. U.S. Patent 5,084,544 describes a reactive mixture of a polyisocyanate, an epoxide and a specific amine catalyst. U.S. Patent 5,021,536 discloses a storage stable reaction mixture of an organic polyisocyanate, a polyepoxide and an alkylating agent that inhibits the reaction of the polyisocyanate and polyepoxide. The '536 patent states that hydroxyl compounds having molecular weights of 62 to 2000 can also be added. US Patent 4,129,554 discloses a heat-set composition comprising a polyepoxide and a polyisocyanate stabilized by the incorporation of a quinone or an organic compound that it contains an active methylene group and contains at least one electron-withdrawing group adjacent to the methylene carbon. U.S. Patents 5,071,939 and 5,073,576 describe SRIM (ie, structural molding by injection with reaction) based on isocyanurate formation. Patent '939 describes a product prepared from an organic polyisocyanate, a polyalcohol of OH number 40 to 400 and a trimerization catalyst (ie isocyanurate). The described catalyst is a co-catalyst of a tertiary amine and an epoxide compound. From the examples, it is deduced that the cocatalyst can be prepared by mixing the isocyanate with the epoxide and reacting the mixture with a mixture of polyalcohol catalyst / amine. Patent '576 describes an SRIM system prepared from an isocyanate, an isocyanate-reactive component (which must contain at least 50% by weight of a tertiary amine polyalcohol) and an isocyanurate catalyst. U.S. Patent 5,223,598 discloses a heat curing system based on i) a polyisocyanate and ii) a mixture of a polyalcohol, a polyepoxide and a curing agent. Among the listed curing agents are tertiary amines, sodium methoxide, lead naphthenate and quaternary ammonium halides. The preferred curing agents are tertiary amines. Finally, it is known that mixtures of methylenebis (phenyl isocyanate) and epoxy resins are stable for more than 200 days at 60 ° C when 0.01 percent 2,4-pentanedione is added, compared to 15 days that last only in the absence of dione (see page 15 of the trade bulletin entitled "2,4-PENTANODIONA" by Union Carbide, Specialty Chemical Division). The present invention relates to an improved composition for the production of SRIM castings. In general, the molded parts are produced by placing a reinforcing mat inside the mold cavity, closing the mold, introducing the reaction mixture into the mold, allowing the components to react and removing the product from the mold.

DESCRIPTION OF THE INVENTION The present invention is directed to a heat-resistant SRIM product that is capable of resisting two hours in an oven at 400 ° F (ie, approximately 204 ° C) without forming blisters or internal fractures. The product is prepared by reaction of: a) a mixture of i) an organic polyisocyanate, ii) an organic compound containing at least one epoxide group, the weight ratio of component a) i) to a) ii) being 80: 20 to 99: 1, and iü) from 0 to 0.5, and preferably from 0.01 to 0.5 percent by weight, based on the total weight of component a) of an organic compound containing an active methylene group and containing at least one electron-withdrawing group adjacent to the methylene carbon, and b) at least one polyol with 3 to 8 hydroxyl functions having an OH number of 90 to 1850, and being free of tertiary amines, the reaction being carried out at an NCO: OH equivalent ratio of 2: 1 to 5: 1 in the presence of c) a catalytic amount of a tertiary amine free isocyanurate catalyst selected from the group consisting of alkali metal oxides, alkoxides, hydroxides and carboxylates, alkaline earth metals, transition metals and quaternary ammonium rnario The present invention requires the use of four specific components: 1) an organic polyisocyanate, 2) an organic compound containing at least one epoxide group, 3) a free tertiary amine polyalcohol, and 4) a tertiary amine free isocyanurate catalyst. . a) i) Organic polyisocyanates The organic starting polyisocyanate components used in the present invention are known and include aliphatic, siloaliphatic, araliphatic, aromatic and heterocyclic polyisocyanates of the type described, for example, by W. Siefken in Justus Liebi Annalen der Chemie, 562, pages 72 to 136. Specific examples of useful isocyanates include ethylene diisocyanate; 1,4-tetraethylene diisocyanate; 1, 6-hexa-methylene diisocyanate, 1,12-dodecane diisocyanate; Cyclobutane-1,3-diisocyanate; cyclohexane-1,3- and 1,4-diisocyanate and mixtures of these isomers. Additional examples are l-isocyanato-3, 3,5-trimethyl-5-isocyanatomethyl cyclohexane (German Auslegenschrift 1,202,785, US Patent 3,401,190), 2,4- and 2,6-hexahydrotolylene diisocyanate and mixtures of these isomers Also suitable in the present invention are hexa-hydro-1,3- and / or -1,4-phenylene diisocyanate; perhydro-2, 4 '- and / or -4,4 * -diphenylmethane diisocyanate; 1,3- and 1,4-phenylene diisocyanate; 2,4- and 2,6-tolylene diisocyanate, and mixtures of these isomers. Diphenylmethane-2 ', 4'- and / or -4,4-diisocyanate can also be used in the present invention; naphthylene-1, 5-diisocyanate; triphenylmethane-4,4-, 4"-triisocyanate; polyphenyl polymethylene polyisocyanates of the type obtained by condensation of aniline with formaldehyde, followed by phosgenation and described in, for example, British Patents 874,430 and 848,671; m- and p-isocyanate; phenylsulfonyl isocyanates according to US Pat. No. 3,454,606; aryl perchlorinated polyisocyanates of the type described, for example, in German Auslegeschrift 1,157,601 (US Patent 3,277,138); polyisocyanates containing carbodiimide groups of the type described in German Patent 1,902,007 (US Pat. U.S. Patent 3,152,162), diisocyanates of the type described in U.S. Patent 3,492,330, and polyisocyanates containing allophanate groups of the type described, for example, in British Patent 993,890, in Belgian Patent 761,626, and in Dutch Patent Application 7,102. 524 are other examples of suitable isocyanates, and polyisocyanates containing isocyanate group are also suitable. a time of the type described, for example, in U.S. Patent 3,001,973; in German Patents 1,022,789; 1,222,067 and 1,027,394 and in the German Offenlegungsschriften 1,929,034 and 2,004,408; polyisocyanates containing urethane groups of the type described, for example, in Belgian Patent 752,261 or in US Patent 3,394,164; polyisocyanates containing acrylated urea groups according to German Patent 1,230,778 and polyisocyanates containing biuret groups of the type described, for example, in German Patent 1,101,394 (US Patent 3,124,605 and 3,201,372) and British Patent 889,050 . Polyisocyanates produced by telomerization reactions of the type described, for example, in U.S. Patent 3,654,106; polyisocyanates containing ester groups of the type described, for example, in British Patents 965,474 and 1,072,956, in U.S. Patent 3,567,763 and in German Patent 1,231,688; reaction products of the aforementioned isocyanates with acetals according to German Patent 1,072,385 and polyisocyanates containing polymeric fatty acid radicals, according to US patent 3,455,883 are also other examples of suitable isocyanates. Aromatic polyisocyanates which are liquid at the treatment temperature are preferably used. Preferred starting polyisocyanates in particular include 4,4'-diisocyanato-diphenylmethane derivatives which are liquid at room temperature, for example, liquid polyisocyanates containing urethane groups of the type obtainable according to US patent 3,644,457. These can be produced, for example, by reacting 1 mole of 4,4'-diisocyanato-diphenylmethane with 0.05 to 0.3 mole of low molecular weight diols or triols, preferably polypropylene glycols having a molecular weight below 700. Diisocyanates based on diphenylmethane diisocyanate containing carbodiimide and / or uretone imine groups of the type obtainable, for example, following US Pat. No. 3,152,162, are also useful. Mixtures of these preferred polyisocyanates can also be used. In general, aliphatic or cycloaliphatic isocyanates are less suitable for the purposes of the present invention. Among the preferred ones are also the polyphenylenepolymethylene polyisocyanates obtained by phosgenation of an aniline / formaldehyde condensate. a) ii) Organic epoxies Useful compounds containing epoxide group (which may be liquids) include aliphatic, cycloaliphatic, aromatic or heterocyclic compounds having at least one epoxide group, preferably at least one 1,2-epoxide group. Preferred epoxides have from about 1 to 4, and preferably about 2, epoxide groups per mole and an epoxide equivalent weight from about 90 to about 500, and preferably from about 170 to about 220. Specific examples of suitable polyepoxides include : Polyglycidyl ethers of polyhydric phenols such as pyrocatechol, resorcinol, hydroquinone, 4,4'-dihydroxydiphenyl ethane, 4,4'-dihydroxy-3, 3'-dimethyl-diphenylmethane, bisphenol A, 4,4'-dihydroxydiphenyl-cyclohexane, 4, 4'-dihydroxy-3, 3 '-di-ethyldiphenyl-propane, 4,4'-dihydroxydiphenyl, 4,4'-dihydroxydiphenylsulfone, tris- (4-hydroxyphenyl) -methane, the chlorination and bromination products of the diphenols set forth above , novolacs (that is, the reaction products of mono- or poly-hydroxylic phenols with aldehydes, in particular formaldehyde, in the presence of acid catalysts), diphenols obtained by esterification of 2 m oles of the sodium salt of an aromatic oxycarboxylic acid with one mole of a dihaloalkane or dihaloalkyl ether (see British Patent 1,017,612) and polyphenols obtained by the condensation of long chain phenols and haloparaffins containing at least two halogen atoms ( see British Patent 1,024,288). Other epoxies useful in the practice of the present invention are glycidyl esters of aromatic, aliphatic and cycloaliphatic polybasic carboxylic acids such as diglycidyl esters of italic acid and diglycidyl esters of adipic acid, glycidyl esters of the reaction products of 1 mole of anhydride aromatic or cycloaliphatic dicarboxylic acid with 1/2 mol of 1 diol or 1 / n moles of a polyalcohol having n hydroxyl groups; and diglycidyl hexahydrophthalic acid ester which may be optionally substituted with methyl groups. Glycidyl ethers of polyhydric alcohols such as 1,4-butanediol, glycerin, trimethylolpropane, pentaerythritol and polyethylene glycols can also be used. Also useful in the practice of the present invention are triglycidyl isocyanurate, N, N'-diepoxypropyl oxamide, polyglycidyl thioethers prepared from polyhydric thiols (for example, bis-mercaptomethylbenzene or diglycidyltrimethylene sulfone), and polyglycidyl ethers based on hydantoins. In the practice of the present invention, the epoxidation products of polyunsaturated compounds such as vegetable oils and their transformation products can also be used; epoxidization products of di- and polyolefins, such as butadiene, vinylcyclohexene, 1,5-cyclooctadiene, and 1,5,9-cyclododecatriene; polymers and copolymers containing still epoxidizable double bonds such as those based on polybutadiene, polyisoprene, butadiene / styrene copolymers, divinylbenzene, cyclopentadiene, unsaturated polyesters; epoxidation products of defines which can be obtained by addition of Diels-Alder and then converted into polyepoxides, or of compounds containing two rings of cyclopentene and cyclohexene joined by atoms or groups of bridging atoms. Polymers of unsaturated monoepoxides such as those prepared from glycidyl ester of methacrylic acid or allyl glycidyl ether can also be used. In the practice of the present invention, the following polyepoxide compounds or mixtures thereof are preferably used: polyglycidyl ethers of polyhydric phenols, in particular bisphenol A; polyglycidyl esters prepared from cycloaliphatic dicarboxylic acids, in particular di-glycidyl ester of hexahydrophthalic acid, and 3,4-epoxycyclohexylmethane-3-j 4-epoxycyclohexane carboxylate. Examples of suitable monoepoxides are phenoxypropylene oxide, styrene oxide and glycidyl alcohol. a) iii) Organic compound containing active methylene group Organic compounds containing active methylene group and containing at least one electron-withdrawing group adjacent to methylenic carbon are known and are described, for example, in US Patent 4,129,554, whose description is incorporated herein by reference. Specific useful compounds include cyanoacetic acid, methyl cyanoacetate ester, ethyl cyanoacetate ester, propyl cyanoacetate ester, butyl cyanoacetate ester, cyanoaceta ida, cyanoacetanilide, malononitrile, nitroacetic acid, methyl nitroacetate ester, ester. ethyl nitroacetate, propyl nitroacetate ester, butyl nitroacetate ester, dinitromethane, nitroacetone, nitrochloromethane, formyl acetic acid, formyl acetate ethyl ester, formyl acetone, acetyl acetone (ie 2,4-pentane dione), malonate ester dimethyl, diethyl malonate ester, dipropyl malonate ester, dibutyl malonate ester, methyl acetoacetate ester, ethyl acetoacetate ester, propyl acetoacetate ester and butyl acetoacetate ester. 2,4-pentane dione is preferred. b) Polyalcohols The polyalcohols useful in the present invention have from 3 to 8 hydroxyl functions, OH numbers of 90 to 1850, and are free of tertiary amines. Examples of suitable compounds include hydroxy functional compounds of relatively low molecular weight (ie having number average molecular weights of about 90 to about 1850), polyesters, polyethers, polythioethers, polyacetals and polycarbonates containing from 3 to 8 and more preferably 3 or 4 hydroxyl groups of the type known for production of polyurethanes. Castor oil is preferred. Polyalcohols containing less than two moles of alkylene oxide (ether) per hydroxyl group are also preferred. Polyethers suitable for use in the invention are known and can be obtained, for example, by polymerization of epoxides such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or epichlorohydrin in the presence of BF3 or potassium hydroxide. , or by chemical addition of these epoxides, preferably ethylene oxide and propylene oxide, in admixture or successively to compounds containing at least three and not more than eight hydroxyl groups. Examples of these compounds include glycerin, trimethylolpropane, sorbitol, pentaerythritol, sucrose and the like. The compounds themselves (ie, without modification of alkylene oxide) can be used as long as they have the required OH numbers. Suitable examples of useful polyesters include the reaction products of polyhydric alcohols with polyvalent carboxylic acids. Instead of using the free carboxylic acids, the corresponding polycarboxylic acid anhydrides or the corresponding polycarboxylic acid esters of lower alcohols or their mixtures can also be used to produce the polyesters. The polycarboxylic acids can be aliphatic, cycloaliphatic, aromatic, and / or heterocyclic and can be unsaturated or substituted, for example with halogen atoms. The polycarboxylic acids and polyalcohols used to prepare the polyesters are known and are described, for example, in U.S. Patents 4,098,731 and 3,726,952, incorporated herein by reference in their entirety. In the above-mentioned US patents polyethylether, polyacetals, polycarbonates and other suitable polyhydroxy compounds are also described. Finally, representative examples of the many and varied compounds that can be used according to the invention can be found in, for example, High Polymers, Volume XVI, "Polyuretanes, Chemistry and Technology", by Saunders-Frisch, Interscience Publishers, New York, London, Vol. I, 1962, pages 32-42 and 44-54, and Volume II, 1964, pages 5-6 and 198-199; and in Kunststoff Handbuch, Vol. VII, Vieweg-Hochtlen, Cari Hanser Verlag, Munich, 1966, pages 45-71. The amount of polyalcohol and isocyanate used is such that the ratio of NCO: OH equivalents is from 2: 1 to 5: 1. c) Tertiary amine free isocyanurate catalyst The reaction mixture should also contain a tertiary amine free isocyanurate catalyst selected from the group consisting of oxides, alkoxides, hydroxides and carboxylates of alkali metals, alkaline earth metals, transition metals and quaternary ammonium. The amount of catalyst used is generally from about 0.1 to about 10% by weight, and preferably from about 0.5 to about 5% by weight, based on the total weight of the hydroxyl functional components of the reaction mixture. Free tertiary amine isocyanurate catalysts (ie, catalysts that drive the polymerization reaction of isocyanate groups) are known in the art. The catalysts used in the present invention are oxides, alkoxides, hydroxides and carboxylates of alkali metals (i.e., Group I metals), alkaline earth metals (i.e. Group II metals), transition metals (i.e., Fe , Hg, Ni, Pb, Co, Zn, Cr and Ti) and quaternary ammonium. Specific suitable catalysts are sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, potassium t-butoxide, calcium oxide, magnesium oxide and benzyl trimethylammonium hydroxide. Preferred catalysts are carboxylates such as potassium octoate, potassium acetate, sodium acetate, potassium adipate, sodium benzoate, trimethyl-N-hydroxypropyl ammonium octoate and trimethyl-N-hydroxypropyl ammonium formate. Examples of commercial trimerization catalysts include the organic potassium salt catalysts sold as Dabco K-15 and Dabco T-45 from Air Products, Hexchem 977 from Hexchem, Polycat 46 from Air Products and Pel-Cat 9540A from Ele, Dabco TMR (N-hydroxypropyl trimethyl ammonium octoate) and Dabco TMR 2 (N-hydroxypropyl trimethyl ammonium formate) from Air Products. The reaction mixtures are generally prepared by pre-mixing the isocyanate (component a) i)), the epoxy compound (component a) ii) and component a) iii) to form a "part A". The polyalcohol (s) (component (b) and the catalysts (component c) are then mixed to form "part B." Then the two parts are mixed and reacted.The molded parts are usually produced by placing a reinforcing mat inside the mold cavity, closing the mold, introducing the reaction mixture into the mold, allowing the components to react and removing the product from the mold.The amount of glass reinforcing mat can vary between very wide limits and is typically used in an amount of about 10 to about 60% by weight based on the total weight of the reaction mixture Glass mats useful in the present invention are known in the art and include sectioned strand mats, mats continuous thread and surface mats (for example glass veils) In addition, other additives that are typically used in the urethane technique can be added. two include flame retardants, plasticizers (such as, for example, dioctyl phthalate), colorants, fillers (such as, for example, calcium carbonate and talc), internal mold release agents (such as, for example, zinc carboxylates). and silicone release agents), silicone surfactants and the like. The invention is illustrated below with the following examples which are not to be construed as limiting and in which all parts and percentages are by weight unless otherwise specified.

EXAMPLES In the examples, the following materials were used POLIALCOHOL A: a glycerin / propylene oxide adduct having an OH number of 1050 POLIALCOHOL B: an adduct of trimethylol propane / propylene oxide having an OH number of 550 POLIALCOHOL C: a monoethanolamine / propylene oxide adduct having an OH number of 700 RICINO OIL DB Oil, a commercially available, refined castor oil from CasChem (having an OH number of 164, an acid number of 0.6 and a saponification coefficient of 180); DB Oil is a triglyceride of a mixture of fatty acids, 90% of the acid mixture is ricinoleic acid and 7% oleic and linoleic acids. BAYLITH L: a composition of potassium sodium aluminosilicate zeolite commercially available from Bayer AG, Germany. EPOXIDE: Epon 828, a diglycidyl ether of bisphenol A commercially available from Shell (epoxy equivalent of 185-192). 2,4-PD: 2,4-pentanedione PCAT 9: Polycat 9, a tris (dimethylaminopropyl) amine commercially available from Air Products. K-15: Dabco K-15, a 70% by weight solution of potassium octoate in diethylene glycol, commercially available from Air Products. TMR: Dabco TMR, N-hydroxypropyl trimethyl ammonium octoate, commercially available from Air Products. : a mixture of 5 parts by weight of tetra-n-butylammonium bromide and 0.1 part of dibutyltin dilaurate (comparison catalyst). ISO: Mondur MR-5, a polymethylene poly (phenyl isocyanate) commercially available from Miles Inc., having an isocyanate group content of 32.5% and a viscosity Brookfield at 25 ° C at 50 mPa.s. The systems were first hand molded in an aluminum mold of 15 cm x 15 cm x 0.3125 cm (6 inches x 6 inches x 1/2 inch) heated to 70 ° C and demoulded after 2 minutes. The castings were either post-cured or post-cured at 120 ° C for 1 hour and then at 150 ° C during 2 hours. As demonstrated, it was found that the post-curing had no effect on the strength of the molded part in the annealing test. Two different mixtures of polyalcohol were prepared by mixing the following ingredients: Mix 1 of polyalcohol Mix 2 of polyalcohol (comparative) Polyalcohol A 10 p.e. • P Polialcohol C 50 p. e.p. Polialcohol B 50 II Castor oil 50 II Castor oil 40 • 1 Baylith L 3 II Baylith L 3 • 1 Isocyanate 1 was ISO, while isocyanate 2 was prepared by mixing 90 parts by weight of ISO, 10 parts by weight of Epoxide and 0.05 parts by weight of 2,4-PD. When using PCAT-9 (comparative) it was added to the particular mixture of polyalcohol in an amount of 4 parts by weight per 100 parts by weight of polyol mixture. When using K-15, it was added to the particular mixture of polyalcohol in an amount of 4 parts by weight per 100 parts by weight of polyol mixture. When using TMR, this was added to the particular mixture of polyalcohol in an amount of 2 p by weight per 100 parts by weight of polyalcohol mixture. All formulations were tested at an isocyanate index of 300. The various moldings were then kept in an oven at 400 ° F (about 204 ° C) for 2 hours. The pieces that passed had no cracks. The parts that failed had cracks in at least 50% of the surface area. In Table 1 the various formulations and the results are given.

TABLE 1 Results Mix of Isocyanate Polyalcohol Post-cure catalyst No post-cure 2 1 PCAT - 9 Failed Failed 2 1 K-15 Happened 2 1 TMR Happened Passed 1 1 TMR Failed Failed 2 2 PCAT - 9 Failed Failed 2 2 TMR Failed Failed 1 2 TMR Failed Failed 2 1 TAB Failed Failed The third formulation of Table 1 (ie, Isocyanate 2, Polyalcohol Mixture 1 and TMR) was tested on a KM-245 RIM machine with and without glass reinforcing mat (10 oz / square foot - 280, 34 grams / 9, 29m, 2 of M8610 from Owens Corning). The mold used was a 37.5 cm x 37.5 cm x 0.31 cm (15 x 15 x 0.125 inch) steel mold. The temperature of both the Polyalcohol mixture and the isocyanate was 32 ° C (90 ° F). The feed rate of the reaction mixture was 267 g / second. The temperature of the mold was 79.4 ° C (175 ° F) and the mold was first sprayed with wax CT-2006, commercial product of Chemtrend. The gelling time of the system was 34 seconds and the demolding time was 2 minutes. The properties of the molding products were as follows: Uncoated Reinforced ASTM Test Density 76.5 104.9 D1622 lb / ft3 (1.22 g / cc) (1.68 g / cc) Tensile strength 8.050 30.850 D638 pounds / inch2 (65 N / mm2) (216 N / mm2) Elongation,% 1.9 2.1 D638 Bending module 530,000 2.197.000 D790 pounds / inch2 (3.710 N / mm2) (15.379 N / mm2) HDT, ° F 374 (190 ° C) > 428 (220 ° C) D648 The pieces were reinforced or post-cured for 1 hour at 204 ° C (400 ° F) or not post-cured. The pieces were subjected to annealing at 204 ° C (400 ° F) for 2 hours after 48 hours, 1 week, 2 weeks, 3 weeks and 4 weeks of aging at ambient temperature and humidity. The pieces that did not receive post-cure were filled with blisters after 4 weeks of aging. The post-cured parts showed signs of whitening of the glass fiber on the surface, but no blisters had formed on them. After a post-cure piece was aged for 7 weeks at room temperature and humidity, it was dried at 93 ° C (200 ° F) for two hours and then annealed at 204 ° C (400 ° F) for 2 hours. hours. The piece did not show any signs of fiber whitening or blistering. Although the invention has been described in detail in the foregoing for purposes of illustration, it is to be understood that that detail has only the aforementioned purpose and that variations may be made by those skilled in the art without departing from the spirit and scope of the invention except as limited by the claims.

Claims (8)

1. CLAIMS 1. A heat-resistant product prepared by reaction of: a) a mixture of i) an organic polyisocyanate, ii) an organic compound containing at least one epoxide group, the weight ratio of component a) i) aa) being ii) from 80:20 to 99: 1, and iii) from 0 to 0.5 weight percent based on the total weight of component a) of an organic compound that contains an active methylene group and that contains at least one group electron collector adjacent to methylene carbon, and b) at least one polyalcohol having from 3 to 8 hydroxyl functions, having an OH number of 90 to 1850, and being free of tertiary amine groups, the reaction being carried out at a ratio of equivalents NC0: 0H for 2: 1 to 5: 1 in the presence of c) a catalytic amount of a catalyst free isocyanurate tertiary amine selected from the group consisting of oxides, alkoxides, hydroxides and carboxylates of alkali metals, alkaline earthworks, transition metals and am Quaternary onium. The product according to claim 1, wherein component a) ii) contains from 1 to 4 epoxide groups and has an epoxide equivalent of 90 to 520. 3. The product according to claim 2, wherein component a) ii) it contains from 2 epoxide groups and has an epoxide equivalent of 170 to 220. The product according to claim 1, wherein component a) iii) is present in an amount of 0.01 to 0.5 percent by weight. 5. The product according to claim 4, wherein component a) iii) is 2,4-pentanedione. 6. The product according to claim 5, wherein component b) is castor oil. The product according to claim 1, wherein component c) is present in an amount of 0.1 to 10% by weight based on the weight of component b). The product according to claim 6, wherein component c) is present in an amount of 0.5 to 5% by weight based on the weight of component b). STRUCTURAL PRODUCT OF MOLDING BY INJECTION WITH REACTION fRIM) HEAT RESISTANT SUMMARY OF THE INVENTION The present invention relates to a heat-resistant product prepared by the reaction of a) a mixture of i) an organic polyisocyanate, ii) a compound containing an epoxide group, and iii), optionally, an organic compound containing an active methylene group and containing at least one electron-withdrawing group adjacent to the methylene carbon, and b) at least one polyalcohol that is free from tertiary amine groups, the reaction being carried out at a ratio of equivalents of 2: 1 to 5. :1. The reaction is carried out in the presence of a catalyst free isocyanurate tertiary amine selected from the group consisting of oxides, alkoxides, hydroxides and alkali metal carboxylates, alkaline earth, transition metals and quaternary ammonium.