MXPA06005442A - Pultrusion systems and process - Google Patents

Abstract

Polyisocyanate-based reaction systems, a pultrusion process employing those systems to produce reinforced matrix composites, and to composites produced thereby. The polyisocyanate-based systems are mixing activated reaction systems that include a polyol composition, a catalyst composition which comprises a combination of at least two different metals in effective amounts, an optional chain extender or crosslinker, and a polyisocyanate. The polyisocyanate-based systems facilitate the practical use of higher line speeds in the manufacture of fiber reinforced thermoset composites via reactive pultrusion.

Description

SYSTEMS AND PROCEDURES OF EXTRUSION BY STRETCHING FIELD OF THE INVENTION The invention relates to reaction systems based on polyisocyanate, extrusion by stretching of these systems to produce reinforced matrix composite materials, and with composite materials produced by them.

BACKGROUND OF THE INVENTION Stretch extrusion is a highly cost-effective method for producing composite materials of fiber-reinforced resin materials. The primary raw materials used in stretch extrusion are resin and reinforcement. Fillers and additives such as, but not limited to calcium carbonate, clay, mica, pigments and UV stabilizers, can be added to the resin to improve the physical, chemical and mechanical properties of the product subjected to extrusion by stretching. Stretch extrusion is typically performed by an injection die or an open bath process. The open bath procedure is more common. However, the injection die process is becoming increasingly important due to environmental concerns about the large amounts of volatile contaminants released in the open bath process. In a typical open bath process, the reinforcing material in the form of fibers, mat or wick is continuously pulled through an open resin bath to produce an impregnated reinforcement. The impregnated reinforcement is rolled through plates to remove excess resin and then through a cure die to cure the resin and provide a finished product. In the extrusion process by injection die stretching, the reinforcing material is passed through a closed injection die having resin injection holes. The resin is injected under pressure through the holes to impregnate the reinforcing material. The impregnated reinforcement is pulled through the injection die to make the shaped product. Resins have been used in the open bath and die methods by stretch extrusion injection and include thermosetting resins, such as unsaturated polyesters, epoxies, phenolic materials, methacrylates and the like, as well as thermoplastic resins such as PPS, ABS, Nylon 6. Blocked polyurethane prepolymers have also been used. Polyester and epoxy resins generally react more slowly compared to thermoset materials based on polyisocyanate, such as polyurethanes and polyisocyanurates. Furthermore, the use of polyurethane resins blocked in extrusion by drawing has the disadvantage that it requires unblocking of the isocyanate to form a volatile by-product. This generates environmental concerns and can cause unwanted plasticization of the cured resin. One of the constitutive resin systems used in stretch extrusion includes thermosetting resins which cure through ethylenic unsaturation, such as unsaturated polyesters, vinyl esters, (meth) acrylic materials and the like. These types of resin generally require the use of volatile unsaturated monomers such as styrene and / or methyl methacrylate. As such, resins of this type emit volatile organic compounds (VOC) during processing. Engineering solutions for the concern of VOCs, such as the use of closed injection dies, have only limited success in controlling these emissions and the odors they produce. The monomers used in the production of isocyanate-based resins are usually much less volatile than the unsaturated monomers. Accordingly, polyisocyanate-based resin systems have certain inherent advantages. However, isocyanate-based formulations have had difficulties due to their reactivity, relatively high, at room temperature. Activation of direct mixing has also been used to form isocyanate-based matrix polymers in the stretch extrusion process. Mixed activated systems of this type generally consist of a polyisocyanate component and an isocyanate reactive component (see, for example, WO 00/29459). The mixing activated systems described in the prior art generally have a limited processability range. This is due to the highly reactive nature of the free isocyanate-based chemistry activated by mixing. A careful balance needs to be established between the demands of suitable mixing and fiber wetting, the obtaining of economically efficient line speeds and the physical properties required in the composite article subjected to extrusion by final stretching. The ideal mixed activated resin system has a prolonged open time (or receptacle life) during (and after) mixing at a relatively low temperature, but is characterized by rapid and uniform curing at higher temperatures used for curing "resin in an extrusion curing die by stretching.

In an ideal mixed activated resin system, it also provides extrusion processing by stretching at high line speeds. A significant drawback of isocyanate-based resin systems blended by prior art for use in stretch extrusion processing have been limited line speeds. "Prior art systems of this type show surface and surface defects. processing device failures when processing at line speeds that are economically more interesting The effects seen at these higher line speeds are sometimes referred to in the art as "spraying" or "slippage." These phenomena, as a function of line speed, vary with the geometric complexity of the profiles subjected to stretch extrusion that occur.It is not possible to mention a particular line speed at which these undesirable phenomena always appear. It should be noted that the more complex profiles are usually more demanding in their. ocessing at high line speeds compared to simple (flat) profiles. For any given profile, the ability to process at a higher line speed without surface defects or faults is an advantage in terms of the overall economy of the process. Therefore, there is a need to mix batch-activated isocyanate-based resin systems, such as polyisocyanurate and polyurethane resin systems that can be used in stretch extrusion, especially diecast extrusion, which provide better combination of extended receptacle life and fast cure and which can be processed at higher line speeds compared to prior art systems without spraying or slippage.

BRIEF DESCRIPTION OF THE INVENTION The invention provides a reaction system for the preparation of a fiber reinforced composite material, according to the stretch extrusion process comprising: (a) a reaction mixture formed by combining an isocyanate-reactive composition and a polyisocyanate composition, (b) a continuous fiber reinforcing material, and (c) a catalyst composition; wherein the catalyst composition contains at least two different metals in effective amounts and wherein the combination of the reaction mixture and the catalyst composition (in the following the "catalyzed reaction mixture") initially contains both free isocyanate groups and free alcohol -OH groups, has a gel time greater than 768 seconds at 25 ° C and a gel time not greater than 120 seconds at 175 ° C. The invention further provides an improved stretch extrusion process for preparing a cured fiber reinforced polymeric composite material, comprising the steps of: (a) pulling continuous fibers through an impregnation die, (b) supplying a reactive composition of isocyanate, a catalyst composition and a polyisocyanate composition to produce a catalyzed reaction mixture and feed the catalyzed reaction mixture to the impregnation die, (c) contact the continuous fibers with the reaction mixture catalyzed in the impregnation die for a period of time and at a temperature sufficient to cause substantial polymerization of the catalyzed reaction mixture within the impregnation die to produce a composite of fibers coated by the reaction mixture, (d) direct the fiber composite coated by the reaction mixture through a curing die heated to at least partially advance the curing of the catalyzed reaction mixture so as to produce a polymer matrix reinforced with solid fiber, and (e) pulling the solid composite material from the cure die, wherein the catalyst composition contains a combination of at least two different metals in effective amounts and wherein the mixture of the catalyst composition with the polyisocyanate composition and an isocyanate-reactive composition (hereinafter the "catalyzed reaction mixture") initially contains both free alcohol -OH groups and free isocyanate groups (-NCO), has a gel time greater than 768 seconds at 25 ° C and a time of gelation not greater than 120 seconds at 175 ° C. The extrusion reaction system and method according to the invention are suitable for operation at higher line speeds, without spraying or slippage, and are similar to systems / methods that do not use the catalyst composition based on metal containing a combination of at least two different metals in effective amounts. When a comparison of the same extrusion line is made by stretching and with the same profile geometry - - (curing die geometry), the system and reaction method of stretch extrusion described herein surprisingly provides operation at higher line speeds (prior to the onset of substantially increased part surface defects or problems of failure in the line) when shown "in the prior art The invention further provides a fiber reinforced solid composite material prepared according to the improved extrusion method by stretching In preferred embodiments, the catalyzed reaction mixture has a time of gelation at 25 ° C greater than 900 seconds In more preferred embodiments, the catalyzed reaction mixture has a gel time at 25 ° C of 1000 seconds or more.In still more preferred embodiments, the catalyzed reaction mixture has a time of gelation, at 25 ° C, in the range of 1000 to 4000 seconds. , the catalyzed reaction mixture has a gel time, at 25 ° C, in the range of 1000 seconds to 3900 seconds and a gel time, at 175 ° C, less than 120 seconds. In other preferred embodiments, the catalyzed reaction mixture is always "substantially free of styrene or methyl methacrylate." In further preferred embodiments, the catalyzed reaction mixture is substantially free of organic species other than carbon dioxide, exhibits a lower boiling 200 ° C and a pressure of 1 atmosphere In highly preferred embodiments, the catalyzed reaction mixture remains in a liquid and flowable state, even if partial reaction has occurred, after it has been applied to reinforcing fibers until it reaches the die of curing. In a particularly preferred embodiment, the improved reaction system is free of tertiary amine catalysts. Preferred metal-based catalyst compositions comprise effective amounts of at least two different metals in organically bound form. The different metals may be present in the catalyzed reaction mixture together within a single organometallic compound, in separate organometallic compounds or both. The metals themselves may be present in any or all of their available oxidation states, with the proviso that they are effective for the catalysis of the curing of the reaction system under the conditions used for the stretch extrusion process. The individual metals may be present as coordination complexes, such as covalent compounds, such as ionic compounds or any combination thereof, provided they are effective for the catalysis of the curing of the reaction system. Preferred organometallic compounds are those which have sufficient solubility in the polymer-forming reaction mixture, under the conditions used for extrusion processing by stretching, to be effective in the curing catalyst of the reaction system. In the preferred embodiments, at least two of the metals present in the metal-based catalyst composition are selected from the group consisting of any of the metals of groups IIIB, IVB, VB, VIB, VIIB, VIIIB, IB, IA , IIA, IIIA, IVA, VA, VIA, of the series of the lanthanides and the series of actinides of the Periodic Table of the Elements. In further preferred embodiments, at least two of the metals used in the catalyst composition are selected from the group consisting of metals of groups IIIA, VA and VA. In even more preferred embodiments, at least "two of the metals used in the catalyst composition are selected from the group consisting of Al, Ga, In, Ge, Sn, Sb and Bi. In the most preferred embodiments, at least two of the metals used in the catalyst composition are selected from the group consisting of Al, Sn and Bi.

DETAILED DESCRIPTION OF THE INVENTION The invention provides a reaction system for the preparation of a fiber-reinforced composite material according to the stretch extrusion process, comprising: (a) a reaction mixture comprising an isocyanate-reactive composition and a polyisocyanate composition, (b) a continuous fiber reinforcing material, and (c) a catalyst composition; wherein the catalyst composition contains a combination of at least two different metals in effective amounts, and wherein the combination of the reaction mixture and the catalyst composition (in the following "catalyzed reaction mixture") initially contains both groups Free isocyanate as free alcohol -OH groups, has a gel time greater than 768 seconds at 25 ° C and a gel time of less than 120 seconds at 175 ° C. The invention further provides an improved stretch extrusion process for preparing a cured fiber reinforced polymeric composite material, comprising the steps of: (a) pulling continuous fibers through an impregnation die while the fibers are in contact with a mixture of A catalyzed reaction comprising an isocyanate-reactive composition, a polyisocyanate composition and a catalyst composition sufficient to cause substantial polymerization of the catalyzed reaction mixture within the "impregnation die to produce a composite of fibers coated by the mixture of catalyzed reaction, which is not fully cured, (b) directing the composite material of coated fibers by the catalyzed reaction mixture through a heated curing die to further advance the cure of the catalyzed reaction mixture so as to produce a fiber reinforced composite material solid, and (c) removing the solid fiber reinforced composite from the curing die; wherein the catalyst composition contains a combination of at least two different metals in effective amounts, and wherein the initially catalyzed reaction mixture contains both free alcohol -OH groups and free (-NC0) isocyanate groups, has a gel time greater than 768 seconds at 25 ° C and a gel time of less than 120 seconds at 175 ° C. The terms "impregnation die", "injection die", "impregnation box" or "injection box" are synonyms within the context of the specification. The invention further provides an improved fiber-reinforced composite material that is prepared according to the stretch extrusion process. In preferred embodiments, the catalyzed reaction mixture has a gel time at 25 ° C of more than 900 seconds. In more preferred embodiments, the catalyzed reaction mixture has a gel time, at 25 ° C, of 1000 seconds or more. In still more preferred embodiments, the catalyzed reaction mixture has a gel time at 25 ° C in the range of 1000 seconds to 4000 seconds. In still more preferred embodiments, the catalyzed reaction mixture has a gel time at 25 ° C in the range of 1000 seconds to 3900 seconds and a gel time at 175 ° C of less than 120 seconds. In other preferred embodiments, the catalyzed reaction mixture is always substantially free of styrene or methyl methacrylate. In further preferred embodiments, the catalyzed reaction mixture is substantially free of organic species, - different from carbon dioxide, with a boiling point of less than 180 ° C, more preferably free of species with a lower boiling point of 200 ° C at a pressure of 1 atmosphere (760 mmHg). In highly preferred embodiments, the catalyzed reaction mixture remains in a liquid and flowable state, although partial reaction has occurred, after it has been applied to the reinforcing fibers until it reaches the curing die. WO 00/29459 provides background information regarding extrusion processing by stretching with closed impregnation dies, and is incorporated herein completely as a reference. The application of E.U.A. Copendent Serial No. 10 / 626,983, filed July 25, 2003, provides additional information and working examples of prior art reagent-based isocyanate-based extrusion reaction systems and methods utilizing these systems. This copending application is also incorporated herein by reference in its entirety. Suitable isocyanate reactive compositions include compositions containing a plurality of active hydrogen groups that are reactive toward organic isocyanate groups under the processing conditions. The most preferred isocyanate reactive compositions are organic compounds, liquid-organic polymers or mixtures of said species in such a way that each individually contains a plurality of primary or secondary organically bound alcoholic hydroxyl groups. These functional organic polyhydroxy (polyols) species can optionally be used in combination with other classes of "polyfunctional organic isocyanate reactive species" to formulate the isocyanate reactive composition.The preferred examples of the latter are polyamines, which contain primary or secondary amine groups However, it is within the scope of the invention to use polyfunctional organic active hydrogen species that are isocyanate-reactive other than polyols if they provide the desired reaction profile in polymer-forming reaction systems activated by mixing derivatives. of the invention use active hydrogen species, which contain more than one class of an isocyanate-reactive active hydrogen functional group.Preferred examples of the latter include aminoalcohols, which contain both isocyanate-reactive hydroxyl groups as amino groups reactive with isocyanate. Mixtures of different classes of molecular species reactive with polyfunctional isocyanate can, of course, be used in the formulation of the isocyanate reactive composition, if desired. The isocyanate reactive functional groups present are preferably of the active hydrogen type. The isocyanate reactive compositions are all preferably liquid at 25 ° C. All polyfunctional isocyanate reactive molecular species present in the reaction system (which are reactive towards organic isocyanate groups under the processing conditions and which themselves are not isocyanates) are by definition part of the isocyanate reactive composition. It is to be understood that the term "polyfunctional" encompasses molecular species having two or more isocyanate-reactive functional groups (which are reactive towards organic isocyanates under the processing conditions and which themselves are not isocyanate groups.) The isocyanate-reactive composition consists essentially of of one or a combination of these polyfunctional isocyanate reactive molecular species Preferably, the isocyanate reactive composition contains less than 10% by weight, more preferably less than 5% by weight, still more preferably less than 2% by weight. weight and much more preferably less than 1% by weight (of the total weight of the isocyanate-reactive composition) of monofunctional isocyanate reactive molecular species present as impurities Ideally, it is lacking in such monofunctional species The monofunctional isocyanate reactive species can be added to the reaction system deliberately, as optimal dits. However, by definition, they are outside the definition of the isocyanate reactive composition (and within the definition of optional additives, as further defined in the following). Preferably, this isocyanate-reactive composition comprises at least one organic polyol, wherein the organic polyol has an average functionality number of organically linked primary or secondary alcohol groups of at least 1.8. The average polyol functionality number is preferably from 1.8 to 10, more preferably from 1.9 to 8, still more preferably from 2 to 6 and much more preferably from 2.3 to 4. Most preferably, the composition The isocyanate reactant consists predominantly, on a weight basis, of a polyol or a mixture of polyols. Most preferably, the isocyanate reactive composition consists essentially of one or more polyols. In some embodiments, the isocyanate reactive composition will preferably comprise a mixture of two or more organic polyols. The individual polyols in the mixture will differ mainly with respect to the functionality of the hydroxyl group and the molecular weight. In one embodiment of the invention, the organic polyols used in the isocyanate-reactive composition t are selected from the group consisting of soft block polyols, rigid polyols, chain extenders, crosslinkers and combinations of these different types of polyols. Polyols which provide soft block segments are known to those skilled in the art as soft block polyols or as flexible polyols. Such polyols generally have an average number of molecular weight of at least about 1500 (preferably about 1750 to about 8000), an average number of equivalent weight of about 400 to about 4000 (preferably about 750 to 2500) and an average number of functionality of isocyanate-reactive organic OH groups of from about 1.8 to about 10 (preferably from about 2 to about 4). Such compounds include, for example, aliphatic polyether or aliphatic polyester polyols comprising primary or secondary hydroxyl groups. It is preferred that these soft block polyols comprise from about 0 to about 30% by weight and more preferably from about 0 to about 20% by weight of the isocyanate reactive species present in the active hydrogen composition.you.

Preferred soft block polyols are liquids at 25 ° C. Polyols that provide structural rigidity in the polymer derivative are referred to in the art as rigid polyols and are a preferred class of polyols. Such polyols generally have an average number of molecular weights from 250 to about 3000, preferably from 250 to less than 1500; an averaged number of equivalent weights from 80 to about 750, preferably from 85 to about 300; and an averaged number of functionalities of isocyanate reactive groups from 2 to 10, preferably 2 to 4, and more preferably 2 to 3. Such compounds include, for example, polyether or polyester polyols comprising primary or secondary hydroxyl groups. Preferred rigid polyols are liquids at 25 ° C. Polyols referred to in the art as chain extenders or crosslinkers are another preferred class of polyols. These have molecular weights between 60 to less than 250 (preferably 60 to about 150), equivalent weights of 30 to less than 100 (preferably 30 to 70), and isocyanate reactive group functionalities of 2 to 4 (preferably 2 to 3) . Examples of suitable chain extenders / crosslinkers are simple glycols and triols such as ethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-butanediol, triethanolamine, triisopropanolamine, tripropylene glycol, diethylene glycol, triethylene glycol, glycerol, mixtures, of these and similar. The most preferred chain extenders / crosslinkers are liquids at '25 ° C. Although compounds with aliphatic -OH functionality such as those just mentioned, are the most preferred chain extenders / crosslinkers, it is acceptable to use certain polyamines reactive with isocyanate, polyamine derivatives or polyphenols. Examples of suitable isocyanate-reactive amines known in the art include diisopropanolamine, diethanolamine and 3,5-diethyl-2,4-diaminotoluene, 3,5-diethyl-2,6-diaminotoluene, mixtures thereof and the like. Examples of suitable isocyanate-reactive amine derivatives include certain compounds with imino functionality such as those described in European Patent Applications Nos. 284,253 and 359,456, and certain compounds with enamino functionality such as those described in European Patent Application No. 359,456 having two or more isocyanate-reactive groups per molecule. Reactive amines, especially primary aliphatic amines, are less preferred because of their extremely high reactivity with polyisocyanates, but optionally they can be used if desired, in minor amounts. It is also acceptable, although less preferred, to include within the polyol composition minor amounts of other types of isocyanate reactive species which may not be adapted to the types described in the foregoing. - - - -_ - --___.- ... .. . .... - The term "chain extender" is used in the art to refer to isocyanate reactive species with a dysfunctional low molecular weight, while the term "crosslinker" is limited to isocyanate reactive species with a low molecular weight having a low molecular weight functionality. 3 or more In one embodiment, a preferred isocyanate reactive composition comprises a mixture of: (a) about 0 to 20% by weight of at least one polyol having a molecular weight of 1500 or greater and a functionality of 2 to 4, (b) ) about 60 to 100% by weight of at least one polyol having a molecular weight between 250 and 750 and a functionality of about 3 to about 4, more preferably about 3 and (c) about 2 to about 30% in weight of at least one polyol having a functionality of about 2 to about -3 and a molecular weight of less than 200, more preferably less than 150. The weights of (a) + (b) + (c ) total 100% of the isocyanate reactive composition in this preferred isocyanate reactive composition for extrusion by stretching activated by mixing two components. All of the polyol species in this preferred mixed isocyanate-reactive composition contain essentially all of the primary or secondary organic linked -OH-linked groups. In another modality, the isocyanate reactive composition comprises a total of at least 10% by weight, relative to the total weight of the isocyanate-reactive composition of at least one hydrophobic polyol selected from the group consisting of polyols with the main structure of hydrocarbon, an average number of molecular weight greater than 500, fatty ester polyols with an averaged number of molecular weight greater than 500, and fatty polyester polyols with an average number of molecular weight greater than 500. A particularly preferred class of polyols of fatty polyester are those having an average number of functionalities of organo-linked, isocyanate-reactive hydroxyl groups greater than 2. A particularly preferred, but not limiting, example of this class of fatty polyester polyols is castor oil. All of the polyol species in these preferred isocyanate reactive compositions, according to this embodiment, contain essentially all of the organic -OH groups bonded aliphatically primary or secondary. The fatty ester (and fatty polyester) polyols are further defined, in greater detail, in the present. In a further embodiment, the polyisocyanate composition can contain isocyanate-terminated polymers of one or more hydrophobic polyols mentioned in the foregoing. In the most preferred modes of this embodiment, the polyisocyanate composition comprises a total of at least 5% by weight, relative to the total weight of the polyisocyanate composition of at least one isocyanate-terminated prepolymer of a hydrophobic polyol. In the most preferred modes of this prepolymer embodiment, the polyisocyanate composition additionally contains some monomeric polyisocyanate species that have not reacted. Polyisocyanate compositions comprising isocyanate-terminated castor oil prepolymers are especially preferred in this embodiment. • The incorporation of hydrophobic polyols, as indicated above, either in the isocyanate reactive composition, the polyisocyanate composition (as isocyanate-terminated prepolymers) or both, has the effect of reducing or eliminating unwanted foaming during the processing of the reaction system in composite articles. This provides a means, although not the only one, to reduce skimming during processing. Another technique for inhibiting foaming during processing is to eliminate the use of tertiary amine species from the reaction-system. Aliphatic tertiary amines are particularly problematic in this respect. It should be understood that, unless. to be indicated otherwise, all functionalities, molecular weights and equivalent weights described herein with respect to polymeric materials are averaged numbers, and that all functionalities, molecular weights and equivalent weights described with respect to pure compounds, are absolute. Some preferred types of polyols include polyether polyols and polyester polyols. Suitable polyester polyols which can be used in the reaction systems of the invention include those which are prepared by reacting an alkylene oxide, a substituted halogen or an aromatic substituted alkylene oxide or mixtures thereof, with an active hydrogen which contains a starter compound. Suitable oxides include, for example, ethylene oxide, propylene oxide, 1,2-butylene oxide, styrene oxide, epichlorohydrin, epibromohydrin, mixtures thereof and the like. The propylene oxide and the ethylene oxide are. particularly preferred alkylene oxides. Suitable initiator compounds include water, ethylene glycol, propylene glycol, butanediols, hexanediols, ~ -. glycerin, - • -.-: -.trimethylolpropane, trimethylolethane, pentaerythritol, hexanotrioles, sucrose, hydroquinone, resorcinol, catechol, bisphenols, novolac resins, phosphoric acid and mixtures of these. Additional examples of suitable initiators include ammonia, ethylenediamine, diaminopropanes, diaminobutanes, diaminopentanes, diaminohexanes, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentamethylenehexamine, ethanolamine, aminoethylethanolamine, aniline, 2,4-toluenediamine, 2,6-toluenediamine, 2,4'- diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 1,3-phenylenediamine, 1,4-phenylenediamine, naphthylene-1, 5-diamine, triphenylmethane-4,4 ', 4"-triamine, 4,4'-di- (methylamino) ) -diphenylmethane, 1,3-diethyl-2,4-diaminobenzene, 2,4-diaminomesitylene, l-methyl-3,5-diethyl-2,4-diaminobenzene, l-methyl-1,3-diethyl-2, 6-diaminobenzene, 1, -3,5-triethyl-2,6-diaminobenzene, 3, 5,3 ', 5'-tetraethyl-, 4'-dialdyphenylmethane and condensation products of amine and aldehyde such as polyamine mixtures and polyphenylenepolymethylene crude from aniline and formaldehyde, and mixtures thereof - Suitable polyester polyols include, for example, those stopped by reacting a polycarboxylic acid or anhydride with a polyhydric alcohol. The polycarboxylic acids can be aliphatic, cycloaliphatic, - araliphatic, aromatic or heterocyclic and can be substituted (for example with halogen atoms) or unsaturated. Examples of suitable carboxylic acids and anhydrides include succinic acid; adipic acid; suberic acid; azelaic acid; sebasic acid; phthalic acid, isophthalic acid; terephthalic acid; trimellitic acid; phthalic anhydride; tetrahydrophthalic anhydride; hexahydrophthalic anhydride; tetrachlorophthalic anhydride; endomethylenetetrahydrophthalic anhydride; glutaric acid anhydride; maleic acid; maleic anhydride; fumaric acid, dimeric and trimeric fatty acids such as those obtained from oleic acid, which can be mixed with monomeric fatty acids. Simple esters of polycarboxylic acids can also be used to prepare polyester polyols. For example, the dimethyl ester of terephthalic acid, the bis-glycol esters of terephthalic acid and mixtures thereof. Examples of suitable polyhydric alcohols for use in the preparation of polyester polyols include ethylene glycol; 1,3-, 1,4-, 1,2- and 2,3-butanediols; 1,6-hexanediol; 1,8-octanediol; neopentyl glycol; cyclohexanedimethanol (1,4-bis-hydroxymethylcyclohexane); 2-methyl-1,3-propanediol; glycerol; manitiol; sorbitol; methylglucoside; diethylene glycol; trimethylolpropane; 1, 2, 6-hexanotriol; 1, 2, 4-butanetriol; trimethylolethane; pentaerythritol; triethylene glycol; tetraethylene glycol; polyethylene glycols; dipropylene glycol; tripropylene glycol, - polypropylene glycols; dibutylene glycol; polybutylene glycols; mixtures of these and similar. The polyester polyols optionally may contain some terminal carboxy groups, although preferably they are completely hydroxyl terminated. It is also possible to use polyesters derived from lactones such as caprolactone; or from hydroxycarboxylic acids such as hydroxycaproic acid or hydroxyacetic acid. A particularly preferred class of polyester polyols are fatty polyester polyols derived from natural sources such as castor oil and the like. A non-limiting example of a preferred isocyanate reactive polyol suitable for use in the invention is a glycerol propylene oxide adduct having a nominal functionality of 3 and an average hydroxyl equivalent weight number of 86. This triol with functionality -OH predominantly secondary is an example of a rigid polyol, based on the description provided in the above. It is commercially available from Huntsman Petrochemical Corporation as JEFFOLMR G 30-650 polyol. Another preferred isocyanate reactive polyol suitable for use in the invention is a glycerol propylene oxide adduct having a nominal functionality of 3 and an average hydroxyl equivalent weight number of about 23. This triol with functional group -OH predominantly secondary is another example of a rigid polyol, as in the description of the above. This polyol is also available from Huntsman Petrochemical Corporation as a polyol JEFF0LMR G 30-240. The combinations of the polyol JEFF0LMR G 30-650 with the polyol JEFFOLMR G 30-240 are examples of a preferred polyol mixture. The preferred weight ratios of these two polyols in these preferred combinations are from about 1: 2 to about 2: 1. Examples of particularly preferred crosslinkers suitable for use in the isocyanate reactive composition include glycerol, trimethylolpropane and mixtures thereof. Glycerol is especially preferred. Examples of particularly preferred chain extenders suitable for use in the isocyanate reactive composition include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol and mixtures thereof. Dipropylene glycol, diethylene glycol and mixtures of these two glycols are especially preferred. If desired, combinations of both chain aligners and crosslinkers can be used in the same isocyanate reactive composition. The examples of preferred optional flexible polyols that can be used in isocyanate reactive compositions include polyester polyols of molecular weight 2000 or greater.An example of a preferred flexible polyether polyol suitable for use is JEFFOL1411 G 31-55 which is a nominal polyether triol commercially available from Huntsman Petrochemical Corporation JEFFOLMR G 31-55 polyol has a hydroxyl equivalent weight of about 1000, and is prepared from a combination of propylene oxide and ethylene oxide. An example of another preferred flexible polyol that can be used in polyol compositions suitable for the invention is the polyol JEFFOLMR G 31-35. This polyol, which is also prepared from propylene oxide and ethylene oxide, is a nominal polyether triol commercially available from Huntsman Petrochemical Corporation. The polyol JEFFOLMR G 31-35 has a hydroxyl equivalent weight of about 1,600. A preferred class of flexible polyols contain predominantly primary -OH groups. The flexible polyols are preferably used in concentrations of 20% by weight or less of the total isocyanate reactive composition, but can be used at higher concentrations, if desired. It is within the scope thereof to produce composite materials subjected to extrusion - by relatively flexible stretching - by the use of predominantly flexible polyols in the isocyanate reactive composition. However, it is much more typical to produce composite materials subjected to rigid extrusion by the predominant or exclusive use of rigid polyols or combinations of rigid polyols with chain extenders and / or crosslinkers, in an isocyanate-reactive composition. Other examples of rigid polyols suitable for use include rigid polyether polyols produced from an initiator composition comprising one or more sugars. A specific example of a suitable rigid polyol of this type is the polyol JEFFOLMR SD-441, which is commercially available from Huntsman Petrochemical Corporation. The polyol JEFF0LMR SD 441 is prepared by propoxylation of a mixture of sucrose and a glycol and has an average weight number '' equivalent to about 128.

The term "nominal functionality" applied to polyols, as used in the context of this invention, indicates the expected functionality of the polyol based on the raw materials used in its synthesis. The nominal functionality may differ slightly from the actual functionality, but the difference can currently be ignored in the context of this invention. The nominal functionality of a polyoxyalkylene polyether polyol is the functionality of the initiator. This is particularly true for polyether polyols, which are predominantly based on EO or PO (such as, for example, the JEFFOLMR G 30-650 polyol described above). Of course, the nominal functionality of a pure compound is the same as its absolute functionality. If a mixed initiator is used, then the nominal functionality of the polyol is the averaged number of functionality of the mixed initiator. One class of ester group containing polyols suitable for use in the isocyanate reactive composition are the fatty ester (and fatty polyester) polyols. The fatty ester (and fatty polyester) polyols comprise at least one alkyl or alkenyl (hydrocarbon) side chain of 4 to about 50 carbon atoms, preferably 5 to 25 carbon atoms, most preferably 6 to 25 carbon atoms. 20 carbon atoms, and much more preferably from 6 to less than 15 carbon atoms. Alkyl side chains are most preferred. The fatty ester (and fatty polyester) polyols also comprise at least two primary or secondary aliphatic tOH groups per molecule and preferably more than 2 to 4 of said -OH groups. The fatty ester polyols contain one carboxylic ester link per molecule. Fatty polyester polyols contain at least two carboxylic ester bonds per molecule. Fatty polyester polyols are most preferred. Preferred examples of fatty polyester polyols are those which contain at least one triglyceride structure and which are liquid at 25 ° C. The fatty ester (and fatty polyester) polyols should preferably be free of aromatic rings, although it is within the scope of the invention to use fatty ester (and fatty polyester) polyols containing said rings. The polyol of (poly) fatty ester optionally contains ether linkages. A particularly preferred but non-limiting example of a triglyceride based fatty polyester polyol is castor oil. Mixtures of different poly (fatty) ester polyols can be used if desired. The polyol of (poly) fatty ester can be used by themselves, but preferably they are used in combination with at least one other type of polyol. The poly (fatty) ester polyol is most preferably used in combination with one or more polyether polyols. A preferred range of weight proportions of poly (fatty) ester polyols relative to polyether polyols in the isocyanate reactive composition is from about 1: 9 to about 9: 1, and most preferably from 1: 4 to 4. :1. The poly (ester) fatty polyols have the desired effect of reducing the foaming of the catalyzed reaction mixture during processing and curing, although this is not the only means to reduce foaming. Poly (fatty ester) polyols and castor oils in particular appear surprisingly more effective at reducing foaming compared to conventional drying agents (such as molecular sieves) or conventional defoaming agents (such as silicone-based antifoaming additives). Although it is not desired to join any theory, it is considered that the beneficial effects of the polyols of (poly) fatty ester in reducing unwanted foaming (when foaming is present) it is due to its hydrophobic nature. Other hydrophobic polyols or optional additives that can be utilized for this beneficial effect "(antifoam), when needed, include polyols with the hydrocarbon backbone such as polybutadiene-based polyols, polyisoprene-based polyols, hydrogenation products thereof as well as simple aromatic or aliphatic oils.

Optional, but preferred, hydrophobic polyols can also be incorporated into the polyisocyanate composition. For example, it is possible to include poly (fatty) ester prepolymers or polybutadiene polyols in the polyisocyanate composition. The isocyanate reactive composition is the predominant isocyanate reactive material (other than the organic polyisocyanate itself) in the chemical formulation activated by blending used in the invention. This isocyanate reactive composition, more preferably, is a polyol or a combination of polyols. Preferably, this isocyanate-reactive composition constitutes at least 90% by weight, more preferably at least 95% by weight and much more preferably at least 98% by weight of the combined isocyanate reactive species (different from the organic polyisocyanate itself) present in the chemical formulation used in the present invention. Preferably, isocyanate-reactive resins with non-active hydrogen functionality, such as epoxy resins, are substantially absent from the chemical formulation. By the term "substantially free" is meant that the reaction mixture contains less than 10% by weight of all such isocyanate-reactive resins, with non-active hydrogen-combined functionality, relative to the total weight of the reaction mixture catalyzed (which includes all catalysts and optional additives that may be present). More preferably, the catalyzed reaction mixture contains less than 5% by weight of all such combined species, relative to the total weight of the catalyzed reaction system; Even more preferably, the catalyzed reaction mixture contains less than 2% by weight of said species, even more preferably less than 1%, much more preferably less than 0.5% and ideally less than 0.1% by weight. to the total weight of the catalyzed reaction mixture. In an alternative embodiment, the isocyanate reactive composition can be mixed with smaller amounts of water by weight. When water is used, it functions as a foaming agent. In the most preferred embodiments, the chemical formulation used in the process (which includes the isocyanate-reactive composition, the polyisocyanate composition, catalysts and any optional additive that may be present) is essentially free of water or any other species that generates foam. . Preferably, the chemical formulation (which includes the isocyanate reactive composition, polyisocyanate composition, the required catalyst composition and any optional additive that may be present) contains less than 0.2 wt% of water or other foam generating species. , in relation to the total weight of the formulation. Even more preferably, this chemical formulation contains less than 0.1% by weight and still more preferably less than 0.05% by weight of water or other foam generating species, relative to the total weight of the formulation. Ideally, both the chemical formulation used to form the catalyzed reaction mixture and the entire reaction system (which includes the fibrous reinforcing material) should be free from water and from another foam generating species. It is understood that the phrase "foam generating species" encompasses both chemical blowing agents, which produce a volatile blowing agent under the processing conditions by means of a chemical reaction, as well as physical blowing agents (i.e., atmospheric gases). entrained or volatile organic or inorganic compounds that simply boil under the processing conditions). Composite articles subjected to stretch extrusion reinforced with fibers made from the reaction system and more preferably according to the methods of the invention are solid, and not foamed or cellular. The "polyisocyanate" composition preferably consists of organic polyisocyanates having an average number of isocyanate functionality (-NCO) from at least 1.8 to about 4.0 .., In the most preferred embodiments, the average isocyanate functionality number of the polyisocyanate composition is preferably from 2.0 to about 3.0, more preferably from 2.3 to 2.9. The polyisocyanate composition preferably has a free isocyanate group content (content of -NCO) in the range of 5% to 50% by weight, but more preferably in the range of 7% to 45%, even more preferably in the range of 8% to 40%, so. even more preferable in the range of 9% to 35% and much more preferably in the range of 10% to 33.6% by weight. It will be understood that the term "organic polyisocyanate" encompasses isocyanate molecular species having a plurality of isocyanate groups (organically bound free). This definition includes organic isocyanates, triisocyanates, higher functionality polyisocyanates and mixtures thereof. The polyisocyanates that can be used in the polyisocyanate composition in the preferred embodiments of the present invention include any of the aliphatic, cycloaliphatic, araliphatic or aromatic polyisocyanates known to those skilled in the art.

Especially preferred are those polyisocyanates that are liquid at 25 ° C. Examples of suitable polyisocyanates include 1, 6-hexamethylene diisocyanate, isophorone diisocyanate, 1,4-cyclohexane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,4-xylylene diisocyanate, 1,4-phenylene diisocyanate. , 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, 4,4'-diphenylmethane (4,4I-] VIDI) diisocyanate, 2,4'-diphenylmethane diisocyanate (2,4'-MDI) , polymethylene and polyphenylene polyisocyanates (crude or polymeric, MDI) and 1,5-naphne diisocyanate. Mixtures of these polyisocyanates can also be used. In addition, it is also possible to use polyisocyanate variants with isocyanate functionality, for example polyisocyanates which have been modified by the introduction of urethane, allophanate, urea, biuret, carbodiimide, uretonimine, isocyanurate or oxazolidone residues. In general, aromatic polyisocyanates are most preferred. The most preferred aromatic polyisocyanates are 4,4'-MDI, 2,4 '-MDI, polymeric MDI, MDI variants (defined to encompass the isocyanate-terminated prepolymers) and mixtures thereof. This most preferred class of aromatic polyisocyanates will be referred to collectively as the "MDI series" of polyisocyanates. Optionally, isocyanate-terminated prepolymers can be used. Such prepolymers are generally prepared by reacting a molar excess of polymeric or pure polyisocyanate with one or more polyols. The polyols can include aminated polyols, imine or enamine modified polyols, polyether polyols, polyester polyols or polyamines. It is also possible to use pseudoprepolymers (also known as semiprepolymers or quasi-polymers) which are mixtures of an isocyanate-terminated prepolymer and one or more monomeric polyisocyanates. The use of prepolymers and especially pseudoprepolymers is a preferred optional method for modifying the mechanical properties of the matrix resin. The use of polymers and pseudoprepolymers is also a useful technique for controlling the proportions by weight of the reactive components during the extrusion processing by stretching of two components activated by mixing. Although it is within the scope of the invention to incorporate polyisocyanates that are totally or partially blocked, it is much more preferable not to use any species of blocked isocyanate. The free isocyanate groups (-NCO) are strongly preferred. Accordingly, the polyisocyanate must essentially be free of blocked isocyanate groups. Commercially available polyisocyanates useful in the preferred two-component isocyanate-based extrusion process include the branched polymeric isocyanates, RUBINATEM® and SUPRASEC ™ available from Huntsman International LLC. A specific example of a preferred polyisocyanate composition particularly suitable for use in the invention is SUPRASEC polyisocyanate "11 9700. This liquid isocyanate is of the polymeric MDI type and has a free isocyanate group (-NCO) content of 31.5% by weight and a averaged isocyanate group functionality of 2.7 This polyisocyanate is commercially available from Huntsman International LLC Another specific example of a preferred polyisocyanate composition suitable for use in some embodiments of the invention is the polyisocyanate RUBINATEMR 1790. This product, which is commercially available from Huntsman International LLC is a pure, urethane-modified 4,4'-MDI product having an average isocyanate group functionality of about 2.00 and having a free isocyanate group (-NC0) content of about 23. % by weight The catalyzed reaction mixture contains a catalyst composition to catalyze one or more of the polymer forming reactions of the polyisocyanates. One or more of the catalysts are preferably introduced into the reaction mixture - by pre-mixing with the isocyanate-reactive composition (i.e., the combination of polyol). The catalyzed reaction mixture, in this preferred embodiment, results when the preformed mixture of the isocyanate-reactive composition, with the catalyst composition is combined with the polyisocyanate composition. It is a defining feature of the invention that the reaction system must contain a catalyst composition comprising at least two different metals in. catalytically effective amounts. The metals are preferably incorporated into one or more organometallic compounds that are sufficiently soluble in the reaction mixture to provide effective catalytic activity under the extrusion processing conditions by stretching. The catalyst composition preferably contains at least two different metals that are selected from the group consisting of metals of groups IIIA, IVA and VA of the Periodic Table of the Elements. In the most preferred embodiments of the invention, the catalyst composition contains at least two different metals that are selected from the group consisting of aluminum, tin and bismuth. Although not essential, it is acceptable to include additional metals in the catalyst composition. It is also possible to include non-metallic catalysts in the catalyst composition. Examples of suitable non-metallic catalysts for promoting the polymer formation reactions of the polyisocyanates are tertiary amines. It is within the broadest scope of the invention to use tertiary amines as optional additional catalysts. However, in a highly preferred embodiment of the invention, no aliphatic tertiary amine catalysts or "salts" are used in the reaction system. In this preferred embodiment, it is possible to use aromatic tertiary amines such as polyols initiated with aromatic amine. However, it is more preferable to exclude the aliphatic tertiary amine species from the reaction system. In another highly preferred embodiment, the reaction system is free of both aliphatic and aromatic tertiary amine species or salts thereof. For the purposes of this specification, an aliphatic tertiary amine is a tertiary amine in which the tertiary nitrogen atom is bound only to aliphatic carbon atoms. An aromatic tertiary amine is a tertiary amine in which the tertiary nitrogen atom is attached to at least one aromatic carbon atom. Optional additional catalysts for polymerization reactions of organic polyisocyanates are well known. The additional catalyst package may consist of a single catalyst or a mixture of two or more catalysts, which are different from those required herein. Some examples of optional additional catalysts are selected from the group consisting of tertiary amines and salts of tertiary amine acid. Examples of tertiary amine catalysts which may optionally be used in the reaction system include triethylenediamine, N, N-dimethylcyclohexylamine, bis- (dimethylamino) -diethylether, N-ethylmorpholine, N, N, N ', N ", N "-pentamethyldiethylenetriamine, N, N-dimethylaminopropylamine, N-benzyldimethylamine and aliphatic tertiary amine-containing amides of carboxylic acids such as the N, N-dimethylaminopropylamine amides with stearic acid, oleic acid, hydroxystearic acid and dihydroxystéaric acid. Commercially available tertiary amine catalysts include the JEFFCATMR brand catalysts from Huntsman Petrochemical Corporation and the amine catalysts P0LYCATMR and DABCOMR, both available from Air Products and Chemicals Inc. Examples of suitable tertiary amine acid salt catalysts which optionally can be used include those prepared by at least partial neutralization of formic acid, acetic acid, 2-ethylhexanoic acid, oleic acid or oligomerized oleic acid with a tertiary amine such as triethylenediamine, triethanolamine, triisopropanolamine, N-methyldiethanolamine, N, N-dimethylethanolamine, mixtures of these amines or the like. These amine salt catalysts are sometimes referred to as "blocked amine catalysts", due to the delayed onset of catalytic activity that provides improved convenience of resin application. - - - - - - - The catalyst composition must contain at least two different catalytically active metals, in effective amounts. These metals should preferably be selected from the group consisting of metals of groups IIIB, IVB, VB, VIB, VIIB, VIIIB, IB, IA, HA, HA, VAT, VA, VIA, series of lanthanides and series of the actinides of the Periodic Table of the Elements. Optional additional metal catalysts containing metals outside these groups can be used in the catalyst composition if desired, but only in addition to one or more of the required metal catalysts, according to the invention. The most preferred catalyst compositions according to the invention comprise catalytically effective amounts of at least two metals which are selected from the group consisting of aluminum, tin and bismuth. The examples; from •. some optional additional organometallic compounds for possible use as supplemental (optional) catalysts within the catalyst composition of the reaction system include potassium 2-ethyl hexanoate (potassium "octoate"), potassium oleate, potassium acetate, potassium oleate, calcium, potassium hydroxide, zinc neodecanoate, zinc laurate, zinc oleate and zinc stearate. The additional examples of optional additional catalyst suitable for use within the catalyst composition of the reaction system include amido amine compounds derived from the amidation reaction of N, N-dimethylpropanedimine with fatty carboxylic acids. A specific example of such a catalyst is the BUSPERSE 47 catalyst from Buck an Laboratories. Optional tertiary amine salts, optional amine acid salt and optional additional organometallic catalysts may be used within the catalyst composition. Sometimes it is desirable to include in the chemical formulation activated by mixing one or more additional optional catalysts for the trimerization of isocyanate groups. Preferred examples of these optional additional catalysts include alkali metal salts of carboxylic acids. Some specific examples of optional isocyanate trimerisation (isocyanurate) catalysts include 2-ethyl potassium hexanoate, potassium oleate, potassium acetate and potassium hydroxide. These compounds are also effective as optional additional catalysts for the reaction of polyisocyanates with active hydrogen compositions such as polyols. The organometallic compounds used in the composition of. Catalyst - and any - additional catalyst that can also be used in the catalyst composition, regardless of the specific structure or function in the formulation, preferably - must be non-volatile species. Therefore, the most preferred catalysts are those having boiling points above 200 ° C (at a pressure of 1 atmosphere), still more preferably above 250 ° C and much more preferably above 260 ° C. (at a pressure of 1 atmosphere). The most preferred catalyst compositions contain at least two separate organometallic compounds, based on at least two different metals that are selected from the group consisting of aluminum, tin "and bismuth." Organometallic compounds are preferably soluble in the isocyanate-reactive composition. At concentrations necessary for efficient use in a stretch extrusion process, examples of suitable classes of organometallic compounds include metal carboxylates of the three metals mentioned above and acetoacetates of these metals. These examples should not be considered as limiting. concentrations of the preferred catalysts necessary to obtain the reactivity profile necessary for extrusion processing by stretching "They will vary with the composition of the reaction system and must be optimized for each reaction system." Such optimization is well understood by those ordinarily skilled in the polyisocyanate-based polymer chemistry technique.The catalysts preferably have at least certain degree of solubility in the isocyanate-reactive compositions (polyol combinations) used and more preferably are completely soluble in the polyol combination at the required use concentrations. In the preferred embodiments, each of at least two required metals is present in the catalyzed reaction mixture as a soluble organometallic compound and each of these organometallic compounds is present in a concentration greater than 0.0001% by weight, more preferably. preferably at least 0.001% - and still more preferably at least 0.005% by weight, based on the total weight of the catalyzed reaction mixture. In preferred embodiments, each of at least two required metals is present in the form of a separate organometallic compound. , The required metals may be present in any available oxidation state or any desired combination of oxidation state, provided that the selected oxidation states offer catalytic activity - effective for the cure of the reaction system under the conditions selected for processing. by extrusion by stretching. Each of at least two metals optionally required may be present together in a single organometallic compound. In this unusual situation the mixed metal compound must be present in the catalyzed reaction mixture at a concentration higher than 0.0001%, preferably at least 0.001% and more preferably at least 0.005% by weight, relative to the total weight of the catalyzed reaction mixture. The chemical precursors used to form the catalyzed reaction mixture may contain other optional additives, if desired. The catalyst composition and the optional additives are typically added to the isocyanate reactive composition (typically this is a polyol combination) before processing, although it is within the scope of the invention to pre-mix all or any part of the catalysts and the package of optional additives with the polyisocyanate composition provided that it does not cause the polyisocyanate to react with itself or otherwise interfere with the extrusion processing by stretching the reaction system. Non-limiting examples of additional optional additives include particulates or short fiber fill materials, release agents, internal molds, flame retardants, smoke suppressants, dyes, pigments, antistatic agents, antioxidants, UV stabilizers, minor amounts of inert viscosity reducing diluents '(preferably those that boil at about 180 ° C at a pressure of 760 mmHg, most preferably those that boil above 260 ° C at a pressure of 760 mmHg), combinations of these and any other additive known in the art of polyisocyanate-based polymer chemistry. In an alternative embodiment, the additives or portions thereof can be provided to the reinforcing fibers of the reaction system, for example by coating the fibrous reinforcement material with the additive. Suitable fillers include, for example, calcium carbonate, barium sulfate, clays, aluminum trihydrate, antimony oxide, ground glass fibers, wollastonite, talc, mica, flake glass, silica, titanium dioxide, molecular sieves, micronized polyethylene, combinations of these and the like. Internal mold release additives are highly preferred in the extrusion by extrusion of mixed activated isocyanate-based reaction systems in order to avoid adhesion or accumulation in the die. Suitable internal mold release agents can include, for example, fatty amides such as erucamide or stearamide, fatty acids such as oleic acid, oleic acid amides, fatty esters such as the inert polyester LOXIOL G71S (from Henkel), carnuba wax, beeswax (natural esters), butyl stearate, octyl stearate, ethylene glycol monostearate, ethylene glycol distearate, glycerin dioleate, glycerin trioleate and esters of polycarboxylic acids with long chain aliphatic monovalent alcohols such as dioctyl sebacate, mixtures of: (a) mixed esters of aliphatic polyols, dicarboxylic acids and long-chain aliphatic monocarboxylic acids, and (b) esters of the groups: (1) esters of dicarboxylic acids and long-chain aliphatic monofunctional alcohols, (2) esters of long-chain aliphatic monofunctional alcohols and long-chain aliphatic monofunctional carboxylic acids, (3) full or partial esters of aliphatic polyols and acid s long-chain aliphatic monocarboxylates, silicones such as silicones TEGOMR IMR 412T (ex Goldschmidt), ester KEMESTERMR 5721 (a product of fatty acid ester of Witco Corporation), carboxylates of fatty acid metal "such as zinc stearate and stearate - of calcium, waxes such as Montana wax and chlorinated waxes, fluorine-containing compounds such as polytetrafluoroethylene, fatty alkyl phosphates (acid and non-acid type) which are known in the art, chlorinated alkyl phosphates; hydrocarbon oils, combinations of these and the like. Other preferred optional additives for use in the extrusion processing by stretching of mixed activated isocyanate-based polymer systems include moisture scavengers, such as molecular sieves; defoamers such as polydimethylsiloxanes; coupling agents such as trialkoxysilanes with monooxirane functionality or organ amine; combinations of these and similar ones. Coupling agents are particularly preferred for improving the bonding of the matrix resin to the fiber reinforcement in the composite material subjected to extrusion by final stretching. Fine particulate fillers such as clays and fine silicas are often used in ticsotropic additives. Such particulate fillers can also serve as thinners to reduce the use of resin. Sometimes flame retardants are used as additives in composite materials subjected to extrusion by stretching. Examples of preferred optional fire retardant categories include, but are not limited to, triaryl phosphates; trialkyl phosphates, especially those having halogens; melamine (as filler material); melamine resins (in minor amounts); halogenated paraffins; combinations of these and similar. Other optional additives that can be used will be apparent to those skilled in the art. In preferred embodiments, the ratio of the combined weight of all of the optional additives in the complete chemical formulation, of the precursor to the catalyzed reaction mixture, to the combined weights of the isocyanate reactive composition (in isolation of any of the additives) ) and the polyisocyanate composition (in isolation of any of the additives) is less than 1, more preferably less than 0.5, still more preferably less than 0.25, and even more preferably less than 0.1, much more preferably lower of 0.07.

- The stoichiometry of the mixed-activated, isocyanate-based polymer-forming formulations containing an organic polyisocyanate composition and a polyfunctional isocyanate-reactive composition are often expressed by an amount known in the art as the index. The index of such activated formulation by simply mixing - is - the ratio of the total number of reactive isocyanate groups (-NCO) present to the total number of isocyanate-reactive groups (which can react with the isocyanate under the conditions used in the process) . This amount is often multiplied by 100 and expressed as a percentage. Typical index values in the mixed-activated formulations, which are suitable for use in the invention, range from about 70 to about 150%, but can be extended to such large amounts, as about 1500% if included in the mixture. Catalyzed reaction an optional catalyst for the trimerization of isocyanate groups. A preferred range of index values is from 90 to 110% A more preferred index range is still from 100 to 110% A much more preferred index range is from 100 to 105% Another preferred range of index values is 200 to 700%, when an optional catalyst for the trimerization of isocyanate groups includes in the mixture in the catalyzed reaction mixture A reinforcing material based on long fiber provides mechanical strength to the composite material subjected to extrusion by stretching and , means for transmitting the pull force in the process The fibers must be at least long enough to pass through both the impregnation and curing dies and be attached to a tension source. can make any fibrous materials or materials that can provide long fibers, which are capable of being wetted at least partially by the reaction mixture ca carved during impregnation. The fibrous reinforcement structure may consist of single chains, braided chains, woven or non-woven mat structures, combinations of these or the like. The mats or veils made of long spheres can be used in single layers or multi-layer structures. Suitable fibrous materials are those known in the stretch extrusion technique and include, but are not limited to, glass fibers, "glass mat, carbon fibers, polyester fibers, natural fibers, aramid fibers, nylon fibers, combinations of these and the like Fibrous reinforcing materials should preferably be dry The preferred reinforcing structures are those made from long glass fibers, In preferred embodiments, fibers and / or fibrous reinforcing structures are formed continuously from one or more feed spools to a stretch extrusion apparatus and are attached to a source of pulling force on the outlet side of the curing die.The reinforcing fibers can optionally be pre-treated with sizing agents or adhesion promoters known in the art The weight percentage of the long fiber reinforcement in the composite articles subject to Final stretch extrusion can vary considerably, depending on the proposed end use application for composite items. Typical reinforcing fillers are from about 30 to 95% by weight, but more typically from 40 to 90% by weight of the final composite. Preferred reinforcing fillers are in the range of 60 to 90%, more preferably 70 to 90% by weight of the final composite. It is within the general scope of the invention to use mixing activated reaction systems comprising more than two components. However, the most preferred systems are activated by mixing two components. In the most preferred modalities, a polyisocyanate component [component A] and an isocyanate reactive component [component B] are the only common components that are fed into the impregnation die of the extrusion-by-extrusion process. The polyisocyanate component contains the polyisocyanate composition and any additives that have been pre-mixed therewith. The isocyanate reactive component contains the isocyanate reactive composition and any additives that are pre-mixed therewith. The term "additive" is understood to encompass both the required catalysts and any optional additive. The impregnation die should provide for the proper mixing of the reactive components and proper impregnation of the fibrous reinforcement material. The impregnation die may preferably be placed with a mixing apparatus, such as a static mixer, which provides mixing of the reactive components before the resulting catalyzed reaction mixture is used to impregnate the fibrous reinforcement structure. Other types of optional mixing devices can be used. These may include, but are not limited to, high pressure incidence mixing devices or low pressure dynamic mixers such as rotating blades. In some cases, suitable mixing is provided in the impregnation die itself, without any additional mixing apparatus. In the most preferred embodiments, the additives, which include the required catalyst composition and any optional additional catalyst, are premixed with the isocyanate reactive composition prior to mixing the latter with the polyisocyanate composition. However, it should be understood that those additives which in themselves are not polyfunctional isocyanate reactive materials should be considered (counted) as separate entities from the isocyanate reactive composition, even when mixed therewith. Likewise, if the additives or any part thereof are premixed with the polyisocyanate composition, these should be considered as separate entities from the polyisocyanate composition, except in the rare case where they themselves are polyfunctional isocyanate species. In a particularly preferred embodiment of the process, the two-component, binder-activated chemical formulation (ie, precursor to the catalyzed reaction mixture) is formulated to provide mixing in a weight ratio of components of about 1: 1. The stretch extrusion apparatus preferably contains at least one impregnating die and at least one curing die. The cure die operates at a higher temperature than the impregnation die. The stretch extrusion apparatus optionally may contain a plurality of dies or curing zones. Different curing zones can be established at different temperatures, if desired, but all of the curing zones of the curing die must be of a higher temperature than the impregnation die. The stretch extrusion apparatus optionally may contain a plurality of impregnation dies. Preferably, there is only one impregnation die, and this is preferably immediately before the first cure die (or zone). The impregnation die is set at a temperature that provides a certain degree of reaction (polymerization) between the polyisocyanate and the polyisocyanate reactive ingredients in the catalyzed reaction mixture before the fibrous reinforcement structure, which has been impregnated at least partially with said reaction mixture, entering the first cure die (or zone). It is highly preferable that the catalyzed reaction mixture retain a certain degree of fluid capacity (liquidity) until it enters the first cure die (or zone). It is highly preferred that the wetting of the fibrous reinforcement structure of the reaction system be complete and that there be no dry spots., which can lead to surface defects or holes in the cured composite material. Further details about the preferred mixing-activated isocyanate-based extrusion-based extrusion processing methods and apparatuses are provided in WO 00/29459. In a highly preferred embodiment, the chemical precursors (used to prepare the catalyzed reaction mixture) are substantially free of organic species other than carbon dioxide, with a boiling point of less than 200 ° C and a pressure of 1 atmosphere. In an even more preferred embodiment, the catalyzed reaction mixture is substantially free of organic species, other than carbon dioxide, with a boiling point of less than 250 ° C at a pressure of 1 atmosphere. In an even more preferred embodiment, the catalyzed reaction mixture is substantially free of other organic species other than carbon dioxide, with a boiling point of less than 260 ° C at a pressure of 1 atmosphere. In another highly preferred embodiment, the catalyzed reaction mixture is substantially free of organic species other than carbon dioxide, which have a vapor pressure greater than or equal to 0.1 mmHg at 25 ° C. In another further highly preferred embodiment, the catalyzed reaction mixture is substantially free of any organic species having a vapor pressure greater than or equal to 0.1 mmHg at 25 ° C. By "substantially free" is meant that the catalyzed reaction mixture contains less than 10% by weight of all such combined organic species, relative to the total weight of the catalyzed reaction mixture (including all optional additives that may be present in it). More preferably, the catalyzed reaction mixture contains less than 5% by weight of all said combined organic species, relative to the total weight of the catalyzed reaction mixture. Even more preferably, the catalyzed reaction mixture contains less than 2% by weight of such organic species, even more preferably less than 1% and much more preferably less than 0.5%, and ideally less than 0.1% in relation to the total weight of the catalyzed reaction mixture. The catalyzed reaction mixture contains less than 0.1% by weight, more preferably less than 0.01% by weight, and much more preferably 0% of styrene or methyl methacrylate. Surprisingly it has been found that a new class of bivalent-activated isocyanate-based two-component liquid precursors containing the requisite combination of metal-based catalysts for extrusion by stretching have resulted in substantially improved processing. Substantially higher line speeds, improved processing efficiency and improved part quality have been obtained. The catalyzed reaction mixtures used in the reaction systems and processes of the invention exhibit certain gel-time intervals under a dry atmosphere. The reaction systems are thermosetting systems which preferably cure by forming a covalently crosslinked organic network polymer structure as the matrix resin of a fiber reinforced composite material. The catalyzed reaction mixture (ie, the chemical precursor mixture that forms the matrix resin), which initially contains both free alcohol -OH groups and groups (-NC0) free isocyanates, has a gel time greater than 768 seconds at 25 ° C and a gel time not greater than 120 seconds at 175 ° C. It should be understood that the catalyzed reaction mixture is the (mixed) reaction system (as defined above) without the reinforcing fibers. In preferred embodiments, the catalyzed reaction mixture has a gel time at 25 ° C of more than 900 seconds. In more preferred embodiments, the catalyzed reaction mixture has a gel time at 25 ° C of 1000 seconds or more. In more highly preferred embodiments, the catalyzed reaction mixture has a gel time at 25 ° C in the range of 1000 seconds to 4000 seconds. In still more highly preferred embodiments, the catalyzed reaction mixture has a gel time at 25 ° C in the range of 1000 seconds to 3900 seconds and a gel time at 175 ° C of less than 120 seconds. In another preferred embodiment, the catalyzed reaction mixture has a gel time at 25 ° C greater than 1000 seconds, but less than 1200 seconds, and a gel time at 175 ° C of less than 60 seconds. In another preferred embodiment, the catalyzed reaction mixture has a gel time at 25 ° C of 2400 seconds at 2700 seconds and a gel time at 175 ° C from 60 seconds to 120 seconds. In still another preferred embodiment, the catalyzed reaction mixture has a gel time at 25 ° C from 3000 seconds to 3300 seconds, and a gel time at 175 ° C from 60 seconds to 120 seconds. In yet another preferred embodiment, the catalyzed reaction mixture has a gel time at 25 ° C from 3600 seconds to 3900 seconds, and a gel time at 175 ° C from 60 seconds to 120 seconds. These gelling time intervals are all determined in a complete formulation (with any other optional additive that may be present) but without the reinforcing fibers present, under mixing conditions similar to those used in the current stretch extrusion apparatus. They are measured according to the following general procedure (in the absence of reinforcing fibers): Procedure to determine the reactivity parameters (at 25 ° C): • Add the required weights of the completely formulated isocyanate component (component A) and the completely formulated polyol component (component B) including all the additives, in the container used for mixing in a DAC 400 FV laboratory mixer. The mixer is known as a Speed Mixer and is manufactured by Hauschild Engineering. The use of this particular type of mixer minimizes entrainment of air into the liquid resin sample. The chemical components and the device are initially all at 25 ° C. It must be ensured that there is at least 100 g of material for the mixer to work properly, but not more than 200 g of material. The objective scale of the reaction should be 120 g of material. The mixing should be carried out under a dry atmosphere (for example dry air or dry nitrogen). The component B is first weighed in the mixing vessel, followed by the component A in the appropriate weight ratio of the components. The mixing container is then closed immediately and inserted into the mixer. • Mix the material for 25 seconds at approximately 2250 rpm. - Start the stopwatch as soon as the mixer starts. • Once the mixer is stopped, pour the material into a small container (approximately 125 ml) to obtain the reactivity. • The material is usually thick, creamy beige and turns a clear brown color as the mixture reacts. • To check the gelling time, lightly touch the surface of the material with a wooden tongue swath (or alternatively, a stainless steel spatula). The material has gelled when a strand is generated from the top surface. The strand resembles a fine spun rib material. Consider that the contact of the wooden tongue swath with the surface can cause frothing. • A hardening time can be obtained in this way. The hardening time can be noticed when the tongue-cutter hits a hard or cured spot on the surface of the material.

Procedure to determine the reactivity parameters on a hot plate (175 ° C): • As mentioned above, after the material has been poured into a ~ 125 ml container, the reactivity can be checked in a hot plate while the reaction is carried out. For this point, the procedure is exactly as described above (for 25 ° C). • Reactivity should be taken at 175 ° C. Using a temperature probe, find a point on the plate that is at 175 ° C. • A flat steel washer and syringe are used to obtain consistent results. The washer should have an external diameter of 5.7 cm (2.25 inches) and an internal diameter (inner ring diameter) of 2.4 cm (15/16 inches) and a thickness of 3 mm (1/8 inch). The center of the washer ring is placed over the point at 175 ° C. It is left in that place for 5 min and then it is verified that the temperature of the center (orifice) is 175 ° C. This must be a sufficient time for the temperature of the washer to equilibrate with that of the hot plate (175 ° C). There is a second stopwatch ready to record the reactivity. • 2 ce are extracted from the catalyzed reaction mixture of the container, in., The syringe. When the timer to be used to obtain the gel time at 25 ° C shows 3 minutes, simultaneously a second chronometer is started as the material is supplied to the middle part of the ring. The material should fill the circle right up to the edge. • Three times should be noted: 1. The time of cremation - when the entire circle of material has been changed from opaque to transparent. 2. Time of gelation - when the material produces a thin thread from the surface when the wooden tongue-twister is pulled. The gel time is taken from the center of the circle. 3. Hardening time - when the material has fully cured. • The material, once cured, must come out of the circle so that the washer can be reused. Scrape off any remaining residue so that the washer continues to lie flat on the hot plate. The chemical formulations activated by mixing of two preferred components described herein provide a surprising combination of extended open time at relatively low temperature with rapid curing at relatively high temperature. The catalyzed reaction mixtures formed from these compositions generally cure homogeneously and do not form separate solids before entering the first zone cured from the extrusion line by stretching. This homogeneity of curing (without separation of solids) is highly desirable. The catalyst compositions described herein, particularly those having the preferred combination of catalytic metals, have unexpectedly provided reaction systems that are capable of being processed at much higher extrusion line speeds compared to comparable systems in the art. previous. The higher stretch extrusion processing speeds are obtained without unacceptable increases in processing problems such as spraying and slippage. The invention is further illustrated by the following non-limiting examples.

EXAMPLES In the examples that follow; All percentages are given as percentages by weight, unless indicated otherwise. All component proportions (A / B) are proportions, by weight, unless otherwise indicated. The composition of components B is defined for each example. The isocyanate used in each example is component A.

Glossary 1) Polyol JEFFOLMR G 30.650: is an oxypropyl glycerol, nominal triol having a hydroxyl number of about 650, available from Huntsman. 2) Polyol JEFF0Lm G 30-240: is an oxypropyl glycerol, nominal triol that has a hydroxyl number of 240, available from Huntsman. 3) JEFF0LMR G 31-55 Polyol: is an oxyethylated and oxyethylated glycerol, a nominal flexible triol having a hydroxyl number of about 55. It is available from Huntsman. 4) JEFFOLMR G31-35 Polyol: is an oxyethylated and oxyethylated glycerol, a nominal flexible triol having a hydroxyl number of about 35. It is available from Huntsman. 5)) Polyol JEFFOLMR SD-441: is a polyol composition obtained by oxypropylation of a mixture of sucrose and a glycol. This polyol has an average number of hydroxyl functionality of more than 3, a hydroxyl value of about 440. It is available from Huntsman. 6) SUPRASEC ™ 9700 Polyisocyanate: is a liquid polymeric MDI product having a free isocyanate group content of about 31.5% by weight and an average isocyanate group functionality of about 2.7.- This product is available from Huntsman. 7) RUBINATE ™ * 1790 Polyisocyanate: is a liquid 4,4 '- pure MDI derivative containing urethane groups, has an average isocyanate group functionality of about 2.00 and an isocyanate group content of about 23% by weight. This derivative is commercially available from Huntsman. 8) Molecular sieve 3: alternatively sieve BAYLITHMR 3A, BAYLITHMR 4A sieve or any mixture thereof. Both of these molecular sieve moisture scavenger products are available from Bayer Corporation. 9) TECHLUBEMR Lubricant BR 550: is a registered internal mold release agent that contains a complex "of a complex condensation polymer of synthetic resins, glyceride and organic esters manufactured by Technick Products, Rahway NJ. 10) Molecular sieve 4: is A molecular sieve moisture scavenger product having a pore size of 4 Angstroms, such as the BAYLITHMR 4A sieve available from Bayer Corporation 11) COSCATMR BiZn catalyst: is a registered organometallic catalyst composition that is considered to be consisting of bismuth and zinc, commercially available from Caschem Chemical Corporation 12) Catalyst K-KATm 5218: is an aluminum chelate catalyst which is considered to be aluminum acetylacetonate This catalyst product is commercially available from King Industries 13) Mold WizMR INT1938MCH: is an internal mold release additive (IMR) available from Axel Industries. is registered 14) Catalyst F0MREZMR UL29: is an organotin catalyst from Witco Corp.

Extrusion by stretching of polyurethane and polyisocyanurate systems In general, the extrusion by stretching of polyurethane and polyisocyanurate systems with fiber reinforced composites is carried out by supplying the formulated isocyanate and the polyol components to a mixing / dosing machine for the supply in a desired ratio to a mixing apparatus, preferably a static mixer, to produce a reaction mixture. The catalyzed reaction mixture is supplied to an injection die where it can be used to impregnate fibers that are pulled concurrently into the interior of the injection die where partial polymerization and impregnation of the fibrous reinforcement materials occur. The resulting incompletely cured composite material is pulled through the zone heating die, directly attached to the injection die having a desired cross section where it is fully formed and cured. The dynamic forces necessary to pull the composite material through the forming die are supplied by a pulling machine. This machine typically consists of fastening devices that make contact with the cured composite profile (or with the glass fibers therein) and provide the traction necessary to pull the composite profile through the die. The machine also consists of a device that develops a force in the desired pulling direction that provides the impetus necessary to pull the composite profile continuously through the die. The resulting composite profile at the exit of the pulling machine is then cut to the desired length; typically by an abrasive clipping saw.

The examples indicated in the following have been processed in an extrusion line by laboratory stretching. The dosing / mixing machine used to supply the catalyzed reaction mixture to the injection die is Liquid Control Corp., North Canton, OH, Model RPV. It supplies the liquid reaction components in the desired ratio to the static mixer at a rate of approximately 2 g / s. The static mixer is equipped with two static mixing tubes in series with 30 polypropylene elements, each of which combines the reactants to form a homogeneous mixture. The internal diameter of this static mixer is 8 mm and the total length of each unit is 32.26 cm. The static mixer is attached to an injection box that combines the catalyzed reaction mixture with the reinforcement that is pulled concurrently through the injection box. The internal dimensions of the injection box are 20 cm (8 inches) long by 3.8 cm (1.5 inches) wide by 15 mm (0.6 inches) flat to a height of 2 mm (0.1 inches). The injection box is attached to the curing die that has internal measurements of 66 cm (26 inches) long by 3.8 cm (1.5 inches) wide by 3 mm (0.120 inches) high. The curing die has two long 30 cm (12 inch) heated zones equipped with individually controlled electric heating coils to maintain the desired temperatures. - Curing dies with three zones can also be used. The reinforcement used in the preparation of the composite material subjected to extrusion by stretching is in the form of 45 strands of fiberglass supplied by Owens Corning Fiberglass Co., 366AD Type 30, 4400 Tex. A pull machine manufactured by Huntsman International LLC pulls the wicks and composite material. It is a caterpillar type machine in which the fasteners provide the propulsion that drives the process.

Example 1 and Comparative Example A It is evaluated in the laboratory on a stretch extrusion line. The mixed-activated formulation shown in Example 1 (according to the invention) utilizes a commercial catalyst based on aluminum organ (an aluminum acetylacetonate catalyst) which is obtained from King Industries, in combination with an organ-based catalyst. tin. The formulation provides unexpected and surprising improvements in stretch extrusion processing which facilitates obtaining superior practical line speeds compared to the prior art formulations. The improvements are based on the use of the mixed metal catalyst composition. The catalyst composition contains two different metals, aluminum and tin, in effective amounts. The formulation and a description of the observed improvements that result from its use in stretch extrusion are provided in detail in the following, in example 1. The formulation is a reactive formulation activated by mixing two components. A comparative example, Example A, is shown to illustrate the benefits of the invention. The formulation shown in the following for Example 1 should not be considered as limiting the scope of the invention. The stretch extrusion formulation of Example 1 consists of a polyol combination component (see below) and a polyisocyanate component (see below). The proportion of the combination of polyol and the polyisocyanate components, used in example "1, is uniquely defined by its isocyanate index (which is 105%.) The numbers correspond to the amounts of the individual ingredients in the following component B and are expressed in parts by weight (PBW), the filler material (CaC03), the internal mold release and the molecular sieves are optional additive ingredients. use of internal mold release material (IMR) as well as molecular sieves.

Component B Polyol JEFFOLMR G30-650"- -85" ---- - Polyol JEFFOLMR G31-35 7.75 Molecular sieves SIL0SIVMR A3 2.5 Mold-Wiz release mold "11 INT1938MCH 5 Catalyst K-KATMR 5218 0.75 Catalyst FOMREZm UL29 0.25 CaC03 40 The polyisocyanate component (component A) is isocyanate from Huntsman's SUPRASECMR 9700. The system activated by two-component mixing is processed at an isocyanate index of 105% This corresponds to a weight ratio of the two components in a base not filled with 1.4 / 1 A / B (ie, without the calcium carbonate filler shown) With the filler material (as shown above) the proportion by weight of the components, in which it satisfies the ratio of 105% is 1: 1. The combination of polyol with the additives is component B. The polyisocyanate is component A. The composition of the combination of component B (above) is by weight (expressed as PBW The proportions of the component are in weight and correspond to the indicated isocyanate index. The following observations of reactivity are made on the catalyzed reaction system (without the fibrous reinforcement structure): Temperature Hot plate to room 121 ° C (250 ° F) Gelification Hardening time hardening time Extrusion Run by Stretching: The system shown above, with 0.75 pbw of catalyst K-KATMR 5218 and 0.25 pbw of tin catalyst FOMREZ ^ UL29, is run in a stretch extrusion line to produce a flat profile reinforced with fiber of glass. The following observations are made: 7 * The "die temperature" is the surface temperature of the curing die. A stage change in the line speed is shown in the production of flat profiles with a thickness of 3 mm. Purges (ie, surfaces of the composite material during line stops) have a better appearance with the catalyst package according to the invention. The pulverization that is finally observed with the catalyst package according to the invention is much lower than with the BiZn catalyst package (which is not according to the invention). The parts subjected to extrusion by stretching made by the process of the invention cure very well and no reading is observed through glass. No problems are observed when obtaining complete fiber moisture removal, even at 86"/ min., The line speed of -86" / min is the maximum speed which can be obtained in the stretch extrusion line used. The use of the organoaluminum catalyst combination (ie, Al-ac-ac) with the organotin catalyst is a preferred embodiment of the invention.

Comparative Example B and Examples 2 and 3: The following is a list of formulations for stretch extrusion systems and some results of stretch extrusion tests. Some of these systems (Example-2 and Example-3, both of which are in accordance with the invention) exhibit unexpected and surprising improvement in processing capacity, specifically, it is possible to process the formulations of the invention consistently at line speeds. higher than expected in a reactive stretch extrusion process using long fiberglass reinforcement. The main factor limiting the line speed in extrusion by stretching for these reactive polyurethane formulations is the slippage of the partially cured resin particles. This phenomenon, known as "spraying" occurs at higher line speeds with the formulations of the invention, ones in relation to. others The improvement seems to be related to the use of a combination of at least two different metal catalysts. Preferred formulations shown in the following - contain an organotin catalyst (UL 29) combined with a catalyst. organism B-iZn). The system with better performance additionally contains an organaluminum catalyst (K-KAT 5218). The two formulations of the invention are the last two on the right side of table I below. The organbismuth catalyst (BiZn) is considered to contain an organozinc compound as well as an organbismuth compound. The improved line speed performance in a conceivable manner can be due to an interaction of an organometallic catalyst with an organic species (such as ligands) of one or more of the other organometallic catalysts. However, it is currently considered that at least two different metals are required in the catalyst composition for better results. The formulations are shown in Table I and run with isocyanate SUPRASEC ™ 9700 as the polyisocyanate. The glass fiber load is approximately 80% by weight "of the weight of the final part subjected to extrusion by stretching.

- - Comparative example B (shown in the following table) is outside the invention. The basic details of the stretch extrusion process, the glossary of the formulation ingredients and other relevant details can be found in the above.

-TABLA I Example Example 2 Comparative Example B Polyol JEFFOL G30-650 85 85 85 Polyol JEFFOL G31-35 7.75 7.75 7.75 Product Techlube BR 550 INT 1938 CH 7.5 7.5 7.5 Sieves Silosiv A3 * 2.5 2.5 2.5 Catalyst Fomrez UL29 0.1 0.1 Product Coscat BiZn 1 Al-ac-ac [catalyst K-KAT 0.05 5218 **] CaCO, 20 20 20 Weight ratio of 1.17 1.17 1.17 ISO / DOIÍO!

Claims (23)

- CLAIMS

1. Reaction system for the preparation of a fiber reinforced composite material, according to the stretch extrusion process, comprising: (a) a reaction mixture comprising an isocyanate-reactive composition and a polyisocyanate composition; (b) a continuous fiber reinforcing material; and (c) a catalyst composition, wherein the catalyst composition contains a combination of at least two different metals that are selected from the group containing any of the metals of groups IIIB, IVB, VB, VIB, VIIB, VIIIB , IB, IA, HA, IIIA, IVA, VA, VIA, the series of the lanthanides and the series of the actinides of the periodic table of the elements, in effective quantities, and where the combination of the reaction mixture and the The catalyst composition initially contains both free isocyanate groups and free alcohol -OH groups, has a gel time greater than 768 seconds at 25 ° C and a gel time of less than 120 seconds at 175 ° C.

2. Reaction system for the preparation of a fiber reinforced composite material, according to the stretch extrusion process, comprising: (a) a reaction mixture comprising an isocyanate reagent composition and a polyisocyanate composition; (b) a continuous fiber reinforcing material; and (c) a catalyst composition, wherein the catalyst composition contains a combination of at least two different metals that are selected from the group consisting of any of the metals of groups IIIB, IVB, VB, VIB, VIIB, VIIIB, IB, IIIA, IVA, VA, - VIA, the series of the lanthanides and the series of the actinides of the periodic table of the elements, in effective quantities, and where the combination of the reaction mixture and the composition The catalyst initially contains both free isocyanate groups and free alcohol -OH groups, has a gel time greater than 768 seconds at 25 ° C and a gel time of less than 120 seconds at 175 ° C.

3. Reaction system as described in claim 2, wherein the reaction system is a thermosetting system activated by mixing that cures to form a covalently crosslinked organic polymer network structure, the organic polymer network structure provides the reagent phase. matrix resin of a fiber-reinforced composite material. Reaction system as described in claim 2, wherein the polyisocyanate composition comprises one or more polyisocyanates of the MDI series, has an average number of isocyanate group functionality in the range of 2.3 to 2.9, and a content of isocyanate group in the range of 10% by weight to 33.6% by weight. Reaction system as described in claim 2, wherein the isocyanate reactive composition comprises a mixture of: (i) from 0 to 20% by weight of at least one polyol having an averaged number of molecular weight of 1500 or greater and an average number of functionality of 2 to 4, (ii) 60 to 100% by weight of at least one polyol having an averaged number of molecular weight between 250 and 750 and an averaged number of functionality from 3 to 4, and (iii) 2 to about 30% by weight of at least one polyol having an average functionality number of 2 to 3 and an average number of molecular weight less than 200; wherein the weights of (i) + (ii) + (iii) total 100% of the isocyanate reactive composition. Reaction system as described in claim 2, wherein the reactive isocyanate composition comprises a total of at least 10% by weight, relative to the total weight of the isocyanate reactive composition, of at least a hydrophobic polyol selected from the group consisting of polyols of hydrocarbon backbone with an average number of molecular weight greater than 500, fatty ester polyols of averaged number of molecular weight greater than 500 and fatty acid polyols of averaged number of molecular weight greater than 500. 7. Reaction system as described in claim 6, wherein at least one hydrophobic polyol is a fatty polyester polyol having an averaged number of functionalities of hydroxy-reactive groups with organically bound isocyanate of more than 2. 8. Reaction system as described in the claim 2, wherein the catalyst composition comprises an organbismuth catalyst and an orotain catalyst. 9. Reaction system as described in claim 2, wherein the catalyst composition comprises an organotin catalyst and an organaluminum catalyst. 10. Reaction system as described in claim 2, wherein the catalyst composition comprises an organbismuth catalyst and an organaluminum catalyst. 11. Reaction system as described in claim 2, wherein the catalyst composition comprises an organotin catalyst, an organaluminum catalyst and an organbismuth catalyst. 12. The reaction system as described in claim 8, wherein the catalyst composition further comprises at least one additional catalyst that contains at least one metal selected from the group consisting of zinc and potassium. 13. Stretch extrusion process for preparing a fiber reinforced composite material, comprising the steps of: (a) pulling - continuous fibers through an impregnation die while contacting the fibers with a mixture of a catalyzed reaction comprising an isocyanate reactive composition, a polyisocyanate composition and a catalyst composition sufficient to cause substantial polymerization of the catalyzed reaction mixture within the impregnation die to produce a composite of coated fibers by the catalyzed reaction mixture, which is not fully cured, (b) directing the composite material of coated fibers by the catalyzed reaction mixture through a heated curing die to further advance the curing of the catalyzed reaction mixture so as to produce a material "Reinforced solid fiber composite, and (c) extract the composite material or reinforced solid fiber curing die; wherein the catalyst composition contains a combination of at least two different metals that are selected from the group consisting of any of the metals of groups IIIB, IVB, VB, VIB, VIIB, VIIIB, IB, IA, HA, HIA, IVA, VA, VIA, the series of the lanthanides and the series of the actinides of the periodic table of the elements, in effective amounts, and where the initially catalyzed reaction mixture contains both free alcohol -OH groups and groups ( -NCO) free isocyanate, has a gel-time greater than 768 seconds at -25 ° C and a gel time of less than 120 seconds at 175 ° C. Stretch extrusion process for preparing a fiber reinforced composite material, comprising the steps of: (a) pulling continuous fibers through an impregnation die while contacting the fibers with a catalyzed reaction mixture that it comprises an isocyanate-reactive composition, a polyisocyanate composition and a catalyst composition sufficient to cause substantial polymerization of the catalyzed reaction mixture within the impregnation die to produce a composite material of fibers coated by the catalyzed reaction mixture, which is not has completely cured, (b) directing the composite material of coated fibers by the catalyzed reaction mixture through a heated curing die to further advance the curing of the catalyzed reaction mixture so as to produce a reinforced composite solid fiber, and (c) extract the reinforced composite material from solid fiber of the curing die; wherein the catalyst composition contains a combination of at least two different metals that are selected from the group consisting of any of the metals of groups IIIB, IVB, VB, VIB, VIIB, VIIIB, IB, HIA, IVA, VA , VIA, the series of the lanthanides and the series of the actinides of the periodic table of the elements, in effective quantities, and where the initially catalyzed reaction mixture contains both free alcohol -OH groups and free (-NCO) isocyanate groups , has a gel time of more than 768 seconds at 25 ° C and a gel time of less than 120 seconds at 175 ° C. 15. Process as described in claim 14, wherein the catalyst composition comprises an organbismuth catalyst and an organotin catalyst. 16. Process as described in claim 14, wherein the catalyst composition comprises an organotin catalyst and an organoaluminium catalyst. 17. Process as described in claim 14, wherein the catalyst composition comprises an organbismuth catalyst and an organaluminum catalyst. 18. Process as described in claim 14, wherein the catalyst composition comprises an organotin catalyst, an organoaluminum catalyst and an organbismuth catalyst. 19. Process as described in claim 15, wherein the catalyst composition further comprises at least one additional catalyst that contains at least one metal that is selected from the group consisting of zinc and potassium. 20. Process as described in claim 14, wherein the polyisocyanate composition comprises one or more polyisocyanates of the MDI series, has an average number of isocyanate group functionality in the range of 2.3 to 2.9, and an isocyanate group content. free in the range of 10% by weight to 33.6% by weight. 21. Process as described in claim 14, wherein the isocyanate reactive composition comprises a mixture of: (i) from 0 to 20% by weight per pound minus a polyol having an average molecular weight number of 1500 or and an averaged number of functionality from 2 to 4, (ii) 60 to 100% by weight of at least one polyol having - "an average number of molecular weight between 250 and 750 and an average number of - functionality of 3". to 4, and (iii) 2 to about 30% by weight of at least one polyol having an average number of functionality of 2 to 3 and an average number of molecular weight less than 200; wherein the weights of (i) + (ii) + (iii) total 100% of the isocyanate-reactive composition. 22. Fiber-reinforced composite material -, - as described in the stretch extrusion process of claim 13. 23. Fiber-reinforced, stretched composite material prepared from the reaction system of claim 1.