MXPA01009378A - Internal mold release compositions - Google Patents

Abstract

Internal mold release systems which include an internal mold release agent that includes any one of fatty acids, fatty acid esters and metal carboxylates, and employ a poly(dimethylsiloxane) surfactant of Formula (I):where R is H, C1 to C20 alkyl, or C6 to C25 aryl;x is about 1 to about 24;y is 0 to about 10;m is about 1 to about 25;n is about 0 to about 100 are disclosed. Isocyanate compositions, isocyanate reactive compositions and polyurethane reaction systems which employ the surfactant also are disclosed.

Description

COMPOSITIONS OF RELEASE OF INTERNAL MOLDING TECHNICAL FIELD The present invention relates to internal molding release agents and surfactants, and to polyurethane reaction mixtures employing internal molding release agents and surfactants.

BACKGROUND OF THE ART Developments in the chemistry of the polymer systems used in the SRIM processes have resulted in urethane and urethane-urea polymers that cure to be demolded within approximately 50-90 seconds after injection into a mold. Urethane polymers, however, bind tenaciously to the metal surface of the mold. This makes it necessary to use a release agent so that the urethane polymer products can be quickly and easily removed from the metal mold without damaging those products. For the simplified removal of the unpurified urethane polymer products, the external molding release agents have been applied directly to the metal surfaces of the mold. The application of the external molding release agent requires a minimum of 30-60 seconds and must be repeated at least after the manufacture of each of the five parts. This increases the part where the parts cycle time as much as 50%. Additionally, this repeated application of the molding release agent sometimes causes excessive increase in the areas surrounding the surface of the mold or on the surface of the mold itself. The mold therefore must periodically be cleaned. This is the time consumed and expensive to manufacture the part. The molding release agents that are contained in the reaction systems, i.e., internal molding release agents are advantageous in eliminating such difficulties. Several internal molding release agents have been proposed. For example, polysiloxane release agents such as those in U.S. Patent No. 4,546,154 have been employed. However, such polysiloxane agents do not produce a sufficient number of releases to be commercially acceptable.

Fatty acids and their esters are also known to be used as molding release agents. For example, U.S. Patent No. 4,098,731 describes the use of saturated or unsaturated aliphatic or cycloaliphatic carboxylic acid salts having at least eight carbon atoms with tertiary amines that does not contain amide or ester groups as release agents for foam production of polyurethane. The reaction products of esterification of polysiloxanes and monocarboxylic or polycarboxylic acids, as shown in U.S. 4,024,090, have also been used as molding release agents. In addition, carboxylic acids and their derivatives have been employed as molding release agents. See US Patents Nos. 5,128,807, 4,058,492, 3,993,606 and 3,726,952. The fatty acid esters such as glycerol trioleate, olive oil and peanut oil as a processing aid, as shown in U.S. 4,130,698 has also been used. Such systems, however, produce only a minor improvement in the release embodiment in the SRIM systems. U.S. Patent No. 5,389,696 describes a process for producing a molded foam portion using an internal molding release agent comprising (a) 1-10% mixed esters comprising the reaction product of i) aliphatic dicarboxylic acids, ii ) aliphatic polyols, and iii) monocarboxylic acids. The lubricant compositions have also been used to produce a release effect. For example, U.S. Patent No. 3,875,069 describes lubricant compositions for use in thermoplastic forming materials. These lubricating compositions include: (A) mixed esters of (a) aliphatic, cycloaliphatic and / or aromatic dicarboxylic acids, (b) aliphatic polyols and (c) aliphatic monocarboxylic acids with (B) d &l esters; "(1) dicarboxylic acids and long chain aliphatic monohydric alcohols, (2) long chain aliphatic monohydric alcohols and long chain monocarboxylic acids and (3) full or partial estof aliphatic polyols and long chain aliphatic monocarboxylic acids. However, as with other internal release agents, the release materials described in this patent have not demonstrated the ability to achieve consistently good results.

DESCRIPTION OF THE INVENTION The invention relates to internal molding release systems employing an internal molding release agent that includes any of the fatty acids, fatty acid esters and metal carboxylates, and a poly (dimethyl) surfactant. loxane) of Formula I: wherein R is H, Ci to C2o alkyl, or C6 to C25 aryl; x is about 1 to about 24; and is 0 to about 10; m is about 1 to about 25; n is 0 to about 100. Isocyanate compositions employing the internal molding release agents and / or the surfactant, and the isocyanate reagent compositions employing the internal molding release agents and the surfactant are also described. The reaction systems employing the isocyanate reactive compositions are also described. The invention is especially useful in the manufacture of resin components formed by the process of injection molding of structural reaction (SRIM).

MODES FOR CARRYING OUT THE INVENTION Glossary of Chemicals As used herein, the following brand materials are understood to have the following meanings: 1. Carbowax PEG 600 is a polyoxyethylene glycol of the formula H- (OCH 2 CH 2) n-0H where n is a number average of 13. Carbowax 600 is available from Union Carbide Chemical and Plastic, MW = 600. 2. DABCO®8800 is a delayed action amine type catalyst from Air Products. 3. Plasticolor 205 is a dye available from Plasticolors Corp. KEMESTER®5721 is a tridecyl stearate available from Witco Chemicals. LH-1 is a paste wax that is commercially available from Che-Trend. Loxiol G71S is the reaction product of adipic acid, pentaerythritol, and oleic acid, having an acid number of less than 15 and a hydroxyl number of less than 15, available from Henkel; Niax L-6980 is a poly (dimethylsiloxane) surfactant available from Osi Chemicals; POLYCAT®8 is an N, N-dimethyl t 1-cyclohexy amine catalyst available from Air Products; Reactint X95AB is a reactive dye from Milliken Chemical Co .; RUBINOL® R015 is an oxypropyl glycerol that has an OH number of 650 available from Huntsman Poi urethanes; 11. RUBINATE 8700 is a mixture of diphenylmethane diisocyanate isomers with oligomeric polyphenylene polymethylene polyisocyanates and has an NCO content of 31.5% of Huntsman Poiyurethanes; 12. Sylfat FA-1 is a liquid resin fatty acid of about 194, and saponification numbers of about 197, and has an iodine number of about 131 from Arizona Chemical Co., Panama City, FL. It's a mixture of acids linear monoalterns with an average carbon number of 18. 13. Unitol DSR is a liquid resin fatty acid having a number , and an acid number of about 191, and a saponification number of about 193, and having an iodine number of about approximately 130 from Union Camp. Co. Unitol DSR is a mixture of linear monoalphatic acids with an average carbon number of 18. 14. Functionality All the functionalities described herein with respect to polymeric materials are "average number". All the functionalities described with respect to the pure compounds are "absolute". 15. Molecular weights All the molecular weights described herein with respect to the polymeric materials are "average number". All the molecular weights described with respect to the pure compounds are "absolute". The reaction systems present include an A side and a B side. The A side includes an isocyanate. Side A may also include an internal molding release agent, a pol i surfactant (dime t i 1 s i loxane), as well as one or more additives. Side B includes an isocyanate reactive material. Side B can also include an internal molding release agent, and a pol i surfactant (dime ti 1 s i loxane). The B side may further include chain extenders and / or crosslinking agents, blowing agents, catalysts, as well as optional additives. Preferably, side A includes an isocyanate and, preferably side B includes an isocyanate reactive material together with chain extenders and / or crosslinking agents, blowing agents, catalysts as well as other additives. The isocyanate reactive material used on the b side has a plurality of isocyanate reactive groups and can be a combination of at least two isocyanate-reactive compounds. One of these isocyanate-reactive compounds can finally be a soft block segment. The term "soft block" is well known to those in the art. It is the flexible segment of a polyurethane, which takes into account that the polyurethane can include rings of a soci anur a, urea or other bonds. The soft block segments useful in the present reaction system include those conventionally used in the art.

The materials of the reactive material that provide soft block segments are also known in the art. Such materials generally have an average molecular weight number of at least about 1500, preferably from about 1500 to about 8000, an average weight equivalent number from about 400 to about 4000, preferably from about 750 to about 2500, and a average number of functionality of the social-reactive groups i from about 2 to about 10, preferably from about 2 to about 4. Such materials include for example, polyether or polyester polyols having primary or secondary hydroxyl groups. Preferably, the soft block segments are from 0 to about 30% by weight, most preferably from 0 to about 20% by weight of the species of the analyte-reactive agent of the composition containing a plurality of groups and socianat o-react i vo. It is especially preferred that the active compound (s) have (a) 0 to about 20% by weight of at least one polyol having a molecular weight of about 1500 or greater and a functionality of about 2 to approximately 4; (b) about 70% by weight to about 98% by weight% of at least one polyol having a molecular weight of about 200 to about 500 and a functionality of about 2 to about 6; and (c) about 2% to about 15% by weight of at least one polyol having a functionality of about 2 to about 4 and an average molecular weight number of less than about 200. Suitable polyether polyols that can be employed on the B side include those prepared by reacting an alkylene oxide, substituted halogen or substituted aromatic alkylene oxide or mixtures thereof with an initiator compound containing active hydrogen. Suitable alkylene oxides include, for example, ethylene oxide, propylene oxide, 1,2-butyl oxide, styrene oxide, epichlorohydrin, epibromohydrin, and mixtures thereof. Suitable initiator compounds include water, ethylene glycol, propylene glycol, butanediol, hexanediol, glycerin, trimethylolpropane, pentaerythritol, hexantriol, sorbitol, sucrose, hydroquinone, resorcinol, catechol, bisphenols, novolac resins, phosphoric acid, and mixtures of the same. Suitable initiators also include, for example, ammonium, ethylenediamine, di to inopropanes, diaminobut anos, di aminopentones, diaminohexanes, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pent amethylenhexamine, ethanolamine, aminoethyl ethanolamine, aniline, 2,4-toluenediamine. , 2, 6 - 1-l-enediamine, "2,4'-diaminodi phenylamine, 4,4'-diaminodiphenylmethane, 1,3-phenylenediamine, 1,4-phenylenediamine, naphthylene-1,5-diamine, tri-phenylene Imetaño, 4 ', 4' '' - tr iamina, 4, 4 '-di (me ti lamino) di feni ímet ano, 1, 3 -di eti 1 - 2, 4 -diaminobenzene, 2, 4 -di aminomes iti 1-ene, 1-methyl-3,5-diethyl-2, 4-diaminobenzene, 1-methyl-3, 5-diethyl-2, 6-diaminobenzene, 1, 3, 5-triethyl-2, 6-diaminobenzene, 3 , 5, 3 ', 5' -tetra-ethyl-4,4'-diamino-diphenylmethane and amine aldehyde condensation products such as the polyamines of polyphenol 1-ime-1-ene produced from aniline and formaldehyde and mixtures of them. Suitable polyester oils include, for example, those prepared by reacting a polycarboxylic acid or anhydride with a polyhydric alcohol. The polycarboxylic acids can be aliphatic, cycloaliphatic, aromatic and / or heterocyclic and can be substituted (for example, with halogen atoms) and / or unsaturated. Examples of suitable carboxylic acids and anhydrides include succinic acid; adipic acid; suberic acid; azelaic acid; sebacic acid; phthalic acid; isophthalic acid; terephthalic acid; trimellitic acid; phthalic acid anhydride; tetrahydrofetic acid anhydride; hexahydrophthalic acid anhydride; anhydride of tet rae parrot phthalic acid; endomethylene-tetrahydrophthalic acid anhydride; glutaric acid anhydride; maleic acid; maleic acid anhydride; fumaric acid; dimeric and trimeric fatty acids, such as those of oleic acid which can be mixed with monomeric fatty acids. The simple esters of polycarboxylic acids such as terephthalic acid dimethyl ester, bis-glycol ester of terephthalic acid and mixtures thereof can also be used. Examples of suitable polyhydric alcohols include ethylene glycol, 1,2-propylene glycol; 1,3-propylene glycol; 1,3-, 1,4-, 1,2- and 2,3-butylene glycol; 1,6-hexanediol; 1, 8 -oct andio 1; neopent ilgl ico 1; dimethanol cyclohexane (1,4-bis-hydroxylmethyl cyclohexane); 2-methyl-l, 3-propanediol, glycerol; trimethylolpropane; 1,2,6-hexantriol; 1,2,4-butantriol; trimethyloletylene; pentaerythritol; chitinol; mannitol; sorbitol; met i lgl icos ida; diethylene glycol; triethylene glycol; tetraethylene glycol; polyethylene glycols; dipropylene glycol; polypropylene glycols; dibutylene glycol; ilen glycols and the like. The polyesters may contain the same terminal carboxy groups although preferably they are hydroxyl terminated. It is also possible to use lactone polyesters such as caprolactone, or hydroxy carboxylic acids such as hydroxy caproic acid or hydroxy acetic acid. A preferred compound for the use on the B side is a glycerol propylene oxide adduct having a functionality of about 3 and a hydroxyl equivalent weight of about 86 such as RUBINOL® R-015. Mixtures of RUBINOL® R-015 with glycerol are also useful in the present invention. In this aspect, the weight ratio of RUBINOL ^ R-015 to glycerol can be from about 99: 1 to about 50:50, preferably from about 98: 2 to about 90:10, more preferably about 95: 5. at approximately 90:10. These mixtures may be from about 70% to about 98%, preferably from about 80% to about 95% by weight of the one or more compounds reactive in the present reaction systems. Internal molding release agents for use on the A side or B side include one of the fatty acids, fatty acid esters, and metal carboxylates of fatty acids. Examples of release agents that can be employed are shown as follows. U.S. Patent No. 5,529,739 shows the use of aspartic derivatives as release agents. The release agent corresponds to the formula: R2 I R1 - N CH CH2 / i COOR3 COOR * where R2 represents hydrogen, the group R 5 --NH - CO--, or a C 1 to C 24 alkyl or substituted alkyl group, a C 3 to C 24 cycloalkyl group or substituted cycloalkyl, a C 2 to C 4 alkenyl group or substituted alkenyl group, or a group C6 to C24 aryl or substituted aryl, and wherein R1, R3, R4 and R5 can be the same or different and represents an alkyl group of Ci to C24 or substituted alkyl, a C to C24 cycloalkyl or substituted cycloalkyl group, a C2 to C24 alkenyl or substituted alkenyl group, or a C6 to C2 aryl or substituted aryl group, with the proviso that at least one of R1, R2, R3, R4, R5 is a C2 to C24 alkyl or alkyl group substituted, or a C 2 to C 24 alkenyl group or substituted alkenyl, and with the proviso that the substituted groups are inert toward the isocyanate groups at temperatures of 100 ° C or less. As described in U.S. Patent No. 5,529,739, aspartic acid derivatives useful as release agents can be synthesized from dialkyl maleates and primary or secondary fatty chain monoamines in the Michael-type reaction wherein a dialkyl maleate is reacted with and a primary amine). To produce the compounds wherein R 2 is the group R 5 --NH - CO--, the product is reacted with a monoisocyanate. Additional examples of internal molding release agents that may be employed include those shown in U.S. Patent Nos. 5,389,696, 5,500,176, and 5,536,465. U.S. Patent No. 5,389,696 shows an internal molding release agent including a) mixed esters comprised of the reaction product of i) aliphatic dicarboxylic acids, ii) aliphatic polyols, and iii) monocarboxylic acids having 12 to 30 carbon atoms in the molecule. This internal molding release agent may additionally include b) and / or c) wherein: b) represents the reaction product of the N, N-dimethylpropane diamine with a compound selected from the group of liquid resin, monofunctional carboxylic acids of C8-? o, and mixtures of monofunctional carboxylic acids; and c) represents the reaction product of oleic acid, adipic acid, and pentaerythritol; with the proviso that the reaction product of a) is different from the reaction product of c). U.S. Patent No. 5,500,176 shows an internal molding release agent including mixed esters including the reaction product of i) aliphatic dicarboxylic acids, ii) aliphatic polyols, and iii) monocarboxylic acids with 12 to 30 carbon atoms in the 1 écu 1 a.

U.S. Patent No. 5,536,465 shows internal molding release agents that include a zinc carboxylate containing from 8 to 24 carbon atoms, and a fatty acid. Preferably, the internal molding release agent includes a mixture of (1) a fatty polyester component, (2) a fatty acid ester component, and (3) a fatty acid component. In general, each of these components may be present in an amount of from about 0.5% to about 5.0%, preferably from about 1.5% to about 3.5%, and most preferably about 3% based on the weight of the polymer system total. Suitable fatty polyesters used in the preferred internal molding release agents include polyesters having an average molecular weight number of from about 500 to about 12,000, preferably from about 800 to about 5,000, more preferably from about 1,000 to about 4,000, more preferably from about 2000 to about 3000. Suitable fatty polyesters are mixed esters formed as the reaction product of three monomers: (1) a monofunctional monomer; (2) a difunctional monomer; and (3) a poly functional monomer (i.e., trifunctional or greater). The 'functionality' of these monomers arises from the hydroxyl groups, acid groups, or derivatives thereof. Each of the monomers (1), (2) and (3) can independently comprise from about 2 to about 54 and preferably from about 2 to about 18 carbon atoms. Suitable fatty polyesters include mixed esters formed as the reaction product of (i) aliphatic dicarboxylic acids, (ii) aliphatic polyols and (iii) fatty monocarboxylic acids wherein the monocarboxylic acid comprises about 12 to about 30 carbon atoms, preferably from about 16 to about 20 carbon atoms. The preferred fatty polyester used in the internal molding release agent is the reaction product of (i) adipic acid, (ii) pentaerythritol and (iii) oleic acid. A suitable compound is available as LOXIOL G-71S from Henkel Corporation.

Fatty acid esters suitable for use in the preferred internal molding release agents contain about 22 carbon atoms or more, and preferably at least about 31 carbon atoms. The maximum number of carbon atoms in the fatty acid ester is limited only where the carbon number causes the material to be of limited solubility by mixing with or in a polyol. Fatty acid esters suitable for use in the present invention include esters of stearic acid, oleic acid, linoleic acid, linolenic acid, adipic acid, behenic acid, aralkydic acid, montanic acids, tartaric acid and acids, polymerized acids and mixtures thereof. Examples of suitable fatty acid esters include butyl stearate, tridecyl stearate, glycerol trioleate, isocetyl stearate, ditridecyl adipate, stearyl stearate, glycerol stearate t r i (12-hydroxy), dioctyl dimerate and ethylene glycol distearate. Preferably, the fatty acid ester is tridecyl stearate. Commercially available fatty acid esters suitable for use in the preferred internal molding release agent include Priolube 1414 from Uniquema and the KEMESTER acid series from Witco Chemical, including KEMESTER 5721, KEMESTER 5822, KEMESTER 3681, KEMESTER 5654 and KEMESTER 1000 Fatty acids suitable for use in preferred internal molding release agents include mixtures of linoleic acid and oleic acid, and other aliphatic carboxylic acids having eight or more carbons. Examples of suitable fatty acids of liquid resin include Sylfat FA-1 and Unitol DSR, preferably Unitol DSR. Preferred internal molding release agents can be prepared by any of the suitable methods known to those skilled in the art. In general, internal molding release agents can be prepared by mixing (a) fatty polyester, the fatty acid ester compound and the fatty acid in the reaction system component containing the "B side" polyol. The fatty acid, the fatty polyester, and the fatty acid ester component are generally not reacted prior to their addition to the B side of the reaction system. The internal molding release agents may be present on the A side or the B side, preferably the B side, in an amount of about 1.0% to about 50.0%, preferably from about 3.0% to about 20.0%, most preferably of about 13.0% by weight based on the total weight of the B side. When the ingredients of the internal molding release agent are placed on the A side, it is preferred that those ingredients be inert toward the isocyanates. The surfactants po 1 i (dime t i 1 s i 1 oxane) suitable for use with internal molding release agents such as those described above can be prepared by the well-known hydrosilation process. In the hydrosolution, an allyl-terminated polyether is coupled with a polydimethyl siloxane which supports the Si-H groups. The result is a polysiloxane-polyether copolymer that supports stable Si-C bonds between the base structure of the polysiloxane and the secondary side chains of polyether. See, for example, any of U.S. 4,857,583; U.S. 5,045,571; U.S. 4,242,466; U.S. 5,856,369; U.S. 5,492,939; U.S. 5,432,206; and U.S. 4,031,042. The poly (dimethylsiloxane) surfactants useful with the internal molding release agents employed in the invention include Niax L6980, Niax L5340, DC 5357, surfactant A, surfactant B, and surfactant C. These surfactants are characterized as having ethylene ("EO") in the polyether side chains. These surfactants are represented by the following Formula I: where R is H, C 1 to C 0 alkyl, or C to C 25 aryl, preferably H; x is from about 1 to about 24, preferably from about 12; and is from 0 to about 10, preferably 0; m is from about 1 to about 25, preferably about 10; and n is from 0 to about 100, preferably from about 29. The product of myx can vary from about 1 to about 600, preferably from about 50 to about 200. In the surfactant A, x = 13, y = 3, m = 5, and n = 45; in Niax L-6980, x-7, y = 0, m = ll, and n = 47; in DC-5357, x = ll, y = 0, m = 2, and n = 16; in surfactant B, x = 12, y = 0, m = 5, and n = 21; in the surfactant C, x = 12, y = 0, m = 10, and n = 29; and in Niax L5340, x = 20, y = 10, m = 7, and n = 63. In the above surfactants, R is H except for Niax L-5340 where R is CH3. In the structure shown in Formula I, EO is attached to a siloxane radical of poly idime. In the structure of Formula (I), the dimethyl groups and the modified dimethyl siloxane groups can be randomly distributed. The surfactant po 1 i (tell me ti 1 if loxane) may be present on the A side or B side, preferably the B side, in an amount sufficient to produce more than about 0.006 moles EO / 100 g of the polymer, preferably about 0.006 to about 0.050 moles EO / 100 g of the polymer, more preferably about 0.006 moles EO / 100 g of the polymer. The surfactant may be present in an amount of from about 0.1% to about 10.0%, preferably from about 0.2% to about 1.0%, most preferably from about 0.85% by weight based on the total weight of the reaction system, inclusive of any re fo rming of fibers used in the reaction system. Chain extenders suitable for use on the B side have a formula weight of less than about 750, preferably from about 62 to about 750, and a functionality of about 2. These chain extenders can be selected from polyols such as ethylene glycol , diethylene glycol, butanediol, dipropylene glycol and tripropylene glycol; aliphatic and aromatic amines such as dianilines 4, 4 '-methyl 1 ene having a lower alkyl substituent placed ortho to each N atom; and certain imino-functional compounds are such as those described in European Patent Applications Nos. 284 253 and 359 456, and certain enamino-functional compounds such as those described in European Patent Application No. 359 456 having 2 groups i socianato- reactive ivo s per molecule. Crosslinking agents suitable for use on the B side include glycerol, glycerol oxyalkyl, pentaerythritol, sucrose, trimethylolpropane, sorbitol, sucrose ox ip ropy, and oxyalkylene polyamines. The functionality of the crosslinking agents can average from about 3 to about 8, preferably from about 3 to about 4, and the molecular weight can vary between the same ranges as described above with respect to the chain extender. A preferred class of crosslinking agents include oxypropyl derivatives of glycerol having an average molecular weight number of about 200 to about 750, glycerol and mixtures thereof. Suitable blowing agents that can be employed include physical blowing agents such as liquid gases such as nitrogen, carbon dioxide, and air; chlorofluorocarbons and hydrocarbons; and chemical blowing agents, such as water, hydroxy functional cyclic ureas, etc. The blowing agents can be used in amounts up to about 10%, preferably from about 0.1 to about 5%, more preferably from about 0.25 to about 4% based on the total weight of side B.

Suitable catalysts that can be used on the B side include tertiary amines, organometallic compounds and saturated or unsaturated C 2 -C 24 fatty acid amides, and di, tri or tetra-aminoalkanes having at least one catalytic amino group and therefore minus a reactive amino group. Fatty amido-amines having hydroxyl substituents may also be useful. The catalysts are useful in amounts necessary for a particular application that will be apparent to one skilled in the art from the present disclosure. Examples of catalysts useful with the internal molding release agents of the invention include tertiary aliphatic amines such as N, N-dimethylethylcyclohexylamina, triaminendiamine, bi-ether (dimethylamino) -diethyl ether , N-et-il-fol folin, N, N, N ', N', N "-pent amet i 1 die ti 1 en-triamine, N, N-dime ti laminoprop i lamina and amides which contain tertiary amine aliphatic carboxylic acids, such as the N, N-dimethylaminopropylamine amides with stearic acid, oleic acid, hydroxystearic acid and dihydroxy acid. Commercially available aliphatic tertiary amines include the POLYCAT® series of amines and the DABCO® series of amine catalysts both available from Air Products Inc. Other suitable additives that may be employed include, for example, conventional additives such as dyes and pyro-retardants. Useful ro-retardants include phosphonates, phosphites, and phosphates such as phosphate tris- (2-chloro-sopropylo) (TCPP), dime thi-methyl phosphonate, ammonium polyphosphate, and various cyclic phosphates and phosphonate esters. known in the art; halogens containing compounds known in the art such as brominated diphenyl ether and other brominated aromatic compounds; melamine; antimony oxides, such as antimony pentoxide and antimony trioxide; zinc compounds such as zinc oxide; alumina trihydrate; and magnesium compounds such as magnesium hydroxide. The tardy pyro-re can be used in any suitable amount that will be apparent to those skilled in the art from the present contradictions. For example, the crosslinker may be used in an amount of from 0 to about 55% based on the total weight of side B. Other conventional additives generally used in the art may also be useful. Examples of these additives include fillers such as calcium carbonate, silica, mica, wollastonite, wood flour, melamine, vitreous or mineral fibers, vitreous spheres, etc .; pigments; surfactants; and plasticidas. Such additives may be used in amounts that will be apparent to one skilled in the art from the present disclosure. Side A can be an organic polyisocyanate having an average isocyanate functionality number of about 1.8 to about 4.0. Preferably, the average isocyanate functionality number is from about 2.3 to about 3.0. Suitable organic polyisocyanates include any of the aliphatic, cycloaliphatic, aral and faceric, or aromatic polyisocyanates known to those skilled in the art, especially those that are liquid at room temperature. Examples of suitable polyisocyanates include 1, 6-hexamethylidene, isocyanate, isophorone diisocyanate, 1,4-cyclohexane diisocyanate, 4,4'-dicyclohexylimisocyanate, 1,4-diisocyanate. xi 1 i log, 1,4-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4 '-di phenylmethane diisocyanate (4,4'-MDI), 2,4,4'-diisocyanate di (2,4'-MDI), polyisocyanates of po 1 i f eni 1 enpo 1 ime t i 1 ene (Unrefined or polymeric MDI) and 1,5-naphthylene diisocyanate. Mixtures of these polyisocyanates can also be used. Polyisocyanate variants, ie, polyisocyanates that have been modified by the introduction of urethane, allophanate, urea, biuret, carbodiimide, uretonimine, isocyanurate and / or oxazolidone residues can also be used on the A side. The finished isocyanate prepolymers can also be used . The prepolymers are generally prepared by reacting an excess of polymeric MDI or pure MDI with polyols, including aminated polyols, modified imine or enamine polyols, polyether polyols, polyester polyols or polyamines. The pre-prepared polymers that are a mixture of prepolymer and one or more di- or monomeric polyisocyanates can also be used. Commercially available polyisocyanates useful in the present reaction systems include the RUBINATE® series of suitable polymeric isocyanates available from Huntsman Poiyurethanes, Inc. Aromatic polyisocyanates are preferred for use on the A side.

The most preferred aromatic polyisocyanates are 4,4'-MDI, 2,4 * -MDI, polymeric MDI, MDI variants and mixtures thereof.

Addition of Surfactant The surfactant po 1 i (dimeth ils i loxane) can be added to side A or side B, preferably to side B. When used on side B, the surfactant can first be combined with the molding release agent. internal by any known method suitable by one skilled in the art to produce an internal molding release system. Typically, the pol i surfactant (dime t i 1 i i loxane) is mixed with the internal molding release agent. The resulting mixture is then added to the polyol component used on the B side. Alternatively, the internal molding release agent can be added to the B-side polyol followed by the addition of the pol i surfactant (dimeth ils i loxane). The pol i (dimethylsiloxane) surfactant is from about 1% to about 75% by weight of the internal molding release agent.

Preparation of the Reaction System The reaction systems employing side A and side B can be prepared by any conventional method known in the art. For example, side A can be mixed with side B in conventional high or low pressure shock mixing machines known in the art. In this aspect, side A and side B can be mixed in weight ratios such as the ratio of the number of isocyanate groups to "isocyanate-reactive" groups commonly known as the index) is about 75 to about 150%, with the It should be noted that when the catalysts for the trimerization of isocyanates are used, the index can be extended to about 500% Preferably, the index is from about 90 to about 115, more preferably from about 95 to about 105%. of the internal molding release agent and the pol i surfactant (dimet i 1 if loxane) is from about 0.55% to about 20% by weight, preferably from about 2.0% to about 6% by weight based on the total weight of the system of reaction.

Manufacturing of Molding Products The reaction systems of side A and side B described in the above are especially suitable for use in SRIM processes using closed molds and open molds. Preferably, the products prepared by the SRIM processes are made with a reinforced mat pre-positioned in a closed mold. The reinforced mats may include, for example, vitreous mat, graphite mats, polyester mats, polyaramide mats such as KEVLAR mats, and mats made from fiber materials. Suitable mats include random continuous strand mats made of fiberglass bundles, woven mats and oriented mats such as uniaxial or triaxial mats. During manufacture, the reaction system is injected into the mold with the mat. The resulting product is a reinforced mat compound that is molded after the cures of the reaction system. The SRIM composite products can also be produced including reinforced fibers on the A side or B side, preferably the B side, of the reaction system. Suitable reinforced materials include woven or nonwoven structural fibers such as glass, carbon, metal, graphite, silicon carbide, alumina, titania, boron, cellulosic polyamide, cellulose, aromatic, polyester, polyolefin and mixtures thereof. The final composite can contain about 0.5 to about 95% by weight, preferably about 10 to about 70% by weight of the reinforced material. The diameter of the fibers can vary from about 0.001 mm to about 1.0 mm. The fibers can optionally be pretreated with sized agents, coatings and adhesion promoters and other kinds of surface treatments known in the art. The invention will now be illustrated by reference to the following non-limiting examples. E j ects 1-10 In Examples 1-10, as in the comparative examples i and 2, the B side is prepared by mixing all the components listed for each example in a standard mixing vessel at room temperature. Side B and side A are supplied in a Kraus s -Ma f fe i 'RIM-Star 16' RIM machine equipped with a shock mixing head to prepare a reaction mixture. The pressure of the mixing head used to prepare the reaction mixture is 2200 psi. The resulting reaction mixture arises from the mixing head at room temperature. To evaluate the release properties due to the use of the internal molding release agents in combination with the pol i surfactants (dimet i 1 s i loxane), the molded upper and lower metal surfaces are prepared by removing solid contaminants with m-pyrol. The m-pyrol is then removed with mineral spirits. A wax coating of LH-1 paste is then applied to the molded metal surface. A continuous strand of E fiberglass mat from CertainTeed Corp. having an area density of 1.0 oz / ft2 is then deposited on the lower metal molding surface. The composite products are made by the open pouring process where the reaction system at 30 ° C is poured into a heated mold at 82 ° C having the fiberglass mat. The mold is then closed for 90 seconds to cure the foam. Immediately therefore, the mold is opened and then the resulting composite part is released from the mold. Without cleaning or coating the mold surfaces, the additional composite parts are made until a part of the composite falls to release from the mold surfaces. The number of releases obtained in the consecutive molded parts, ie without additional application of wax, are measured. The reaction systems evaluated and the number of releases obtained as shown in Table 1. All amounts in Table 1 are parts by weight. In Table 1, comparative example 1 shows the use of an EO, PO-contunide surfactant, uncapped. Comparative example 2 illustrates the effect of adding EO to side B in the form of an elevated EO polyol such as Carbowax PEG 600. In comparative example 2, Carbowax PEG 600 contributes to an addition of 0.0037 moles EO per 100 gm of polymer total and the surfactant A contributes 0.0048 moles EO per 100 gm of the total polymer. Examples 1-4, and 6 show the use of a poly (dimethyl s i loxane) surfactant without PO, of high EO. Example 5 shows the use of a poly (dimethyl s i loxane) surfactant without PO, with low EO. Example 7 shows the use of a poly (dimet ilsi loxane) surfactant without very high PO, EO. Example 8 shows the use of a capped methyl polyoxymethylidene (dime t i 1x loxane) surfactant containing high EO PO. Example 9 shows the use of a large amount of uncovered poly (di me t i ls i loxane) surfactant, containing PO, of high EO. Example 10 shows the effect of mixing an internal molding release agent which increases the surfactant with a conventional non-increased surfactant. in n LT) O LO O (NJ or Üi or Cp or 1. Number of parts (of successive molding) produced before releasing the fault 2. Test completed after 323 releases without failure on release 3. Test terminated after 294 releases without failure upon release As can be seen from Table 1, surprising improvements in the release characteristics are obtained when the internal molding release agents, in combination with the poly (dimethylsiloxane) surfactant are employed as described above.

Claims (10)

1. Internal molding release system for use in a reaction system for the manufacture of a polymer comprising an internal molding release agent and a pol i surfactant (dimet i lsi loxane), wherein the internal molding release agent it comprises at least fatty acids, fatty acid esters and metal carboxylates derived from fatty acid, and the pol i surfactant (dimet i 1 if loxane) is represented by formula I: where R is H, Ci to C2o alkyl, or aryl of C6 to C25, "x is from about 1 to about 24, and is from 0 to about 10, m is from about 1 to about 25, n is from 0 to about 100, and the surfactant is present in an amount sufficient to produce more than about 0.006 moles EO / 100 g of the polymer.

2. Internal molding release system of claim 1, wherein the internal molding release agent is selected from internal molding release agents (I) to (IV), wherein the molding release agent (I) internal is represented by R2 IR »_ N CH CHz / I COOR3 COOR * where R2 represents H, the group R5 --NH - CO--, or an alkyl group of Ci to C24 or substituted alkyl, a C3 to C24 cycloalkyl group or substituted cycloalkyl, a C2 to C24 alkenyl group or substituted alkenyl, or an aryl group of C6 to C24 or substituted aryl, and wherein R1, R3, R4 and R5 may be the same or different and represent an alkyl group of Ci to C24 or substituted alkyl, a cycloalkyl group of C3 to C24 or substituted cycloalkyl, an alkenyl group of C2 to C24 or substituted alkenyl, or an aryl group of a C2 or substituted aryl, with the proviso that at least one of R1, R2, R3, R4, R5 is a C2 to C24 alkyl group or substituted alkyl, or a C2 to C24 alkenyl group or substituted alkenyl, and with the proviso that the substituent groups are inert towards the isocyanate groups at temperatures of 100 ° C or less; the internal molding release agent (II) includes mixed esters comprised of the reaction product of the aliphatic dicarboxylic acids, aliphatic polyols. and monocarboxylic acids; the internal molding release agent (III) comprises a zinc carboxylate containing from 8 to 24 carbon atoms, and a fatty acid; and an internal molding release agent (IV) comprises a fatty polyester component, a fatty acid ester component and a fatty acid.

3. Internal molding release system of claim 1, wherein the internal molding release agent comprises a fatty polyester component, a fatty acid ester component, and a fatty acid.

4. Internal molding release system of claim 3, wherein the fatty polyester component is a mixed ester which is a reaction product of a monofunctional monomer, a difunctional monomer, and a functional pol monomer, wherein each of the monomers monofunctional, difunctional monomers, and polyfunctional monomers independently have about 2 to about 54 carbon atoms.

5. Internal molding release system of claim 4, wherein the fatty polyester component is a mixed ester formed as a reaction product of (i) aliphatic dicarboxylic acid, (ii) aliphatic polyol and (iii) fatty monocarboxylic acid wherein the The monocarboxylic acid comprises about 12 to about 30 carbon atoms.

6. Internal molding release system of claim 4, wherein the fatty polyester is a reaction product of adipic acid, pentaerythritol and oleic acid.

7. The internal molding release system of claim 3, wherein the fatty acid ester has about 22 carbon atoms.

8. The internal molding release system of claim 6, wherein the fatty acid ester has about 31 carbon atoms.

9. Internal molding release system of claim 8, wherein the fatty acid comprises a mixture of linoleic acid, oleic acid and an aliphatic carboxylic acid having eight or more carbons.

10. The internal molding release system of claim 9, wherein in the surfactant, R is H, x is about 12, and is 0, m is about 10, and n is about 29.