MXPA06007305A

MXPA06007305A - Non-fugitive catalysts containing imine linkages and tertiary amines, and polyurethane products made therefrom

Info

Publication number: MXPA06007305A
Application number: MXPA/A/2006/007305A
Authority: MX
Inventors: M Casati Francois; E Drumright Ray; Prange Robbyn
Original assignee: M Casati Francois; Dow Global Technologies Inc; E Drumright Ray; Prange Robbyn
Priority date: 2003-12-23
Filing date: 2006-06-23
Publication date: 2006-12-13

Abstract

The present invention pertains to non-fugitive amine catalysts wherein the catalyst contains at least one imine and at least one tertiary amine moiety. Such catalysts are suitable for the production of polyurethane products.

Description

NON-FUGITIVE CATALYSTS CONTAINING IN LACES OF IMINE AND TERCIARY AMINO AND POLYURETHANE PRODUCTS FACTS OF THE SAME The present invention pertains to non-fugitive catalysts containing an imine bond and a tertiary amine, and polyurethane polymer products produced with such catalysts. Polyether polyols based on the polymerization of alkylene oxides and / or polyester polyols are the main components of a system together with the isocyanates. These systems generally contain additional components such as crosslinkers, chain extenders, surfactants, cell regulators, stabilizers, antioxidants, flame retardant additives, optionally fillers and typically catalysts such as tertiary amines and / or organometallic salts. Organometallic catalysts, such as lead or mercury salts, can increase environmental problems due to migration as the polyurethane products age. Others, such as tin salts, are often detrimental to the aging of the polyurethane. The commonly used tertiary amine catalysts give rise to several problems, particularly in flexible, semi-rigid and rigid foam applications. Freshly prepared foams using these catalysts often exhibit the typical smell of amines and give rise to increased vapors (emission of products volatile). The presence, or formation, of tertiary amine catalyst vapors in polyurethane products having vinyl or polycarbonate films or polyester / polyether elastomer such as sheets of Hytrel * thermoplastic polyester elastomer (DuPont Trade Mark) exposed thereto It can be disadvantageous. Such products commonly appear in automotive applications as well as in many domestic ones. Specifically, the tertiary amine catalysts present in the polyurethane foams have been related to the staining of the vinyl film and the degradation of the polycarbonate or Hytrel sheets. This staining of PVC and the problems of decomposition of polycarbonate or Hytrel are especially frequent in environments where there are high temperatures for long periods of time, such as in car interiors when left in sunlight. Several solutions have been proposed to the above problems. One is the use of amine catalysts containing an isocyanate reactive group, i.e., a hydroxylamine or a primary and / or secondary amine. Such a compound is described in the publication of EP 747,407. Other types of reactive monol catalysts are described in U.S. Patent Nos. 4, 122, 038, 4,368,278 and 4,510,269. Since monools are monofunctional, these reactive amines act as chain stoppers and have a detrimental effect on the construction of the polymer and affect the physical characteristics of the polymer. polyurethane product. The use of specific polyols initiated with amine is proposed in EP 539,819, in the U.S. Patent. No. 5,672,636 and in WO 01 / 58,976. Several other publications have reported polyols that have autocatalytic activity and can replace all or a portion of the conventional amine catalysts. See, for example, U.S. Patent No. 5,672,636; European Patent Publications 0 047371, 1 268 598 and 1 319 034; and Publication WO 03/016372, 03/029320 and 03/055930. Topping of the conventional polyether polyols with N, N-dialkylglycidylamine is claimed in the U.S. Patent. No. 3,428,708. Although this process gives polyols with autocatalytic activity, it is restricted to dialkylamino groups which are active primarily to catalyze the water-isocyanate reaction and much less the polyol-isocyanate reaction. Despite the advances made in the art, it remains a need to improve the catalysts to produce polyurethane products and / or catalysts that can reduce or eliminate the amount of fugitive amine catalysts and / or organometallic salts used in the manufacture of polyurethanes. It is also desirable to have an industrial process for manufacturing polyols having autocatalytic properties where the autocatalytic polyols do not interfere with the conventional polyol production or polyurethane production processes and characteristics.

It is an object of the present invention to manufacture polyurethane products containing a reduced level of conventional tertiary amine catalysts, a reduced level of reactive amine catalysts or polyurethane products produced without the need for such amine catalysts. It is another object of the present invention to produce polyurethane products that contain a reduced level of organometallic catalyst or to produce such products in the absence of organometallic catalysts. It is another object of the invention to have a process for adjusting the manufacturing conditions, or the reactivity of polyurethane products using non-fugitive catalysts of the present invention.

It is a further object of the present invention to increase productivity by combining non-fugitive catalysts with conventional catalysts to obtain faster processes in the manufacture of polyurethane products. It is a further object of the present invention to provide non-fugitive catalysts possessing an imine bond and a tertiary amine so that the industrial manufacturing processes of the polyurethane product using these compounds and the physical characteristics of the polyurethane products made to from them are not adversely affected and can be further improved by reducing the amount of conventional catalysts or reactive amine or elimination of the amine catalyst, and / or by reducing or eliminating organometallic catalysts.

The present invention is a catalyst composition wherein the catalyst has at least one imine bond and at least one tertiary amine group. In another embodiment, the present invention is a polyol composition containing from 99.9 to 50 weight percent of a polyol compound having a functionality of 2 to 8 and a hydroxyl number of from 20 to 800 and from 0.1 to 50 per 100 of a catalyst composition wherein the catalyst has at least one imine bond and at least one tertiary amine group. Preferably, the amount of catalyst is present from 0.5 to 10 parts by weight of the polyol. In a further embodiment, the present invention is a process for the production of a polyurethane product by reacting a mixture of: (a) at least one organic polyisocyanate with (b) a composition of polyols with the polyols having a functionality nominally calculated between 2 and 8 and a hydroxyl number from 20 to 800 mg KOH / g and (c) at least one non-fugitive catalyst containing at least one imine bond and at least one tertiary amine group (d) optionally in the presence of another catalyst and / or a blowing agent; and (e) optionally additives or auxiliary agents known per se for the production of polyurethane foams, elastomers or coatings.

In another embodiment, the present invention is a process as described above wherein the catalyst (c) contains at least one hydrogen reactive of the isocyanate. In another embodiment, the catalyst (c) is a gelation catalyst, that is, it catalyzes the reaction between the polyol and the isocyanate. In another embodiment, the catalyst (c) is a liquid polymer with a molecular weight above 500. In another embodiment, the catalyst (c) contains more than one portion of the catalytically active tertiary amine. In another embodiment, the catalyst (c) contains some portions of aldehyde and / or ketone. In another embodiment, the catalyst (c) is stable against hydrolysis at room temperature. In another embodiment, the catalyst (c) is combined with a polyol having autocatalytic properties when it produces a polyurethane product. In another embodiment, the present invention is a process as described above wherein the catalyst (c) contains at least a reactive hydrogen of the isocyanate. In another embodiment, the present invention is a process as described above wherein the catalyst (c) contains at least one hydrogen reactive of the isocyanate and the polyisocyanate (a) contains at least one polyisocyanate which is a reaction product of an excess of polyisocyanate with the catalyst (c). In a further embodiment, the present invention is a process as described above wherein the catalyst (c) contains at least one reactive hydrogen of the isocyanate and the polyol (b) contains a prepolymer obtained by the reaction of an excess of the catalyst (c) with a polyisocyanate. The invention further provides polyurethane products produced by any of the above processes. The non-fugitive catalysts (c) accelerate the addition reaction of organic polyisocyanates with polyhydroxyl or polyamino compounds and the reaction between the isocyanate and the blowing agent, such as water, or a carboxylic acid or its salts. The addition of these catalysts (c) a polyurethane reaction mixture reduces or eliminates the need to include a conventional tertiary amine catalyst within the mixture or an organometallic catalyst. In combination with conventional amine catalysts and / or autocatalytic polyols, the catalysts (c) present can also reduce the residence time in the mold in the production of molded foams or improve some properties of the polyurethane products. The use of such catalysts (c) reduces the need for conventional fugitive amine catalysts and the associated disadvantages of vinyl staining or polycarbonate degradation of Hytrel elastomer sheets. The advantages of the catalysts (c) present are achieved by including in the reaction mixture for polyurethane products either non-fugitive catalysts (c) containing imine bonds and tertiary amines, or including such catalysts (c) containing reactive hydrogens in existence in the preparation of SAN, PIPA or PHD copolymer polyols or by adding them to the polyurethane reaction mixture or using such catalysts (c) in a prepolymer with a polyisocyanate alone or with isocyanate and a second polyol. As used herein, the term "polyols" are those materials that have at least one group containing an active hydrogen atom capable of undergoing reaction with an isocyanate. Preferred among such compounds are materials having at least two hydroxyls, primary or secondary, or at least two amines, primary or secondary, carboxylic acid, or thiol groups per molecule. Compounds having at least two hydroxyl groups or at least two amine groups per molecule are especially preferred because of their desirable reactivity with polyisocyanates. Suitable polyols that can be used to produce polyurethane materials with the non-fugitive catalysts (c) of the present invention are well known in the art and include those described herein and any other commercially available polyol and / or copolymer polyols SAN, PIPA or PHD. Such polyols are described in "Polyurethane Handbook", by G. Oertel, Hanser publisher. Mixtures of one or more polyols and / or one or more copolymer polyols can also be used to produce polyurethane products according to the present invention. Representative polyols include polyether polyols, polyester polyols, acetal resins terminated in polyhydroxy, amines and polyamines terminated in hydroxyl. Examples of these and other suitable reactive isocyanate materials are more fully described in U.S. Patent No. 4,394,491. Alternative polyols that can be used include polyalkylene polyols with a carbonate base and polyols based on polyphosphate. Preferred polyols are prepared by adding an alkylene oxide, such as ethylene oxide, propylene oxide, butylene oxide or a combination thereof, to an initiator having 2 to 8, preferably 2 to 6, hydrogen atoms assets. The catalysis for this polymerization can be either anionic or cationic, with catalysts such as KOH, CsOH, boron trifluoride, or a complex catalyst of double metal cyanide (DMC) such as zinc hexacyanocobaltate or a quaternary phosphasenium compound. Its instauration is between 0.001 and 0.1 meq / g. After produced, the catalyst is eliminated when it is alkaline. The polyol can be neutralized by the addition of an inorganic or organic acid, such as a carboxylic acid or hydroxyl carboxylic acid. The polyol or mixtures thereof used depend on the final use of the polyurethane product to be produced. The molecular weight or hydroxyl number of the base polyol can thus be selected to result in flexible, semi-flexible, integral-coated or rigid foams, elastomers or coatings, or adhesives when the polymer / polyol produced from the The base polyol is converted into a polyurethane product by reaction with an isocyanate, and depending on the final product in the presence of a blowing agent. The hydroxyl number and the molecular weight of the polyol or polyols used can vary accordingly in a wide range. In general, the hydroxyl number of the polyols used can range from 20 to 800. The selection of a polyol with the appropriate hydroxyl number, level of ethylene oxide, propylene oxide and butylene oxide, functionality and equivalent weight are normal known to those skilled in the art. For example, polyols with a high level of ethylene oxide will be hydrophilic, while polyols with a large amount of propylene oxide or butylene oxide will be more hydrophobic. In the production of a flexible polyurethane foam, the polyol is preferably a polyether polyol and / or a polyester polyol. The polyol generally has an average functionality ranging from 2 to 5, preferably from 2 to 4 and an average hydroxyl number ranging from 20 to 100 mg KOH / g, preferably from 20 to 70 mg KOH / g. As an additional refinement, the application of specific foam will influence the selection of the base polyol in the same way. As an example, for molded foam, the hydroxyl number of the base polyol may be in the order of 20 to 60 with ethylene oxide (EO) cap, and for block foams the number of hydroxyl may be in the order of 25 to 75 and either EO / PO mixed (propylene oxide) is fed or only lightly topped with EO or is 100 percent based on PO. For elastomer applications, it will be it is generally desirable to use relatively high molecular weight base polyols of from 2,000 to 8,000 having relatively low hydroxyl numbers, for example, from 20 to 50. For the production of visco-elastic foams, i.e., flexible foams with very low capacity of recovery (resilience), a combination of polyols with different hydroxyl numbers, up to 300, and functionalities between 1 and 4 are used. Polyols typically suitable for preparing rigid polyurethanes include those having an average molecular weight of 100 to 10,000 and preferably from 200 to 7,000. Such polyols also advantageously have a functionality of at least 2, preferably 3, and up to 8, preferably 6, active hydrogen atoms per molecule. The polyols used for rigid foams generally have a hydroxyl number of 200 to 1, 200 and more preferably 300 to 800. For the production of semi-rigid foams, it is preferable to use a trifunctional polyol with a hydroxyl number of 30 to 80 The initiators for the production of polyols generally have 2 to 8 functional groups which will react with the alkylene oxide. Examples of suitable initiator molecules are: water, organic dicarboxylic acids, such as succinic acid, adipic acid, phthalic acid and terephthalic and polyhydric acid, in particular, the dihydric to octahydric alcohols or dialkylene glycols, for example, ethanediol, 1, 2 and 1,3-propanediol, diethylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, glycerol, trimethylolpropane, pentaerythritol, sorbitol and sucrose or mixtures thereof. Other initiators include linear or cyclic amine compounds such as ethanolamine, triethanolamine and various isomers of toluene diamine. Polyols which have autocatalytic activity can also be used as the polyol or in combination with the polyols described above. In general, such autocatalytic polyols contain a readily accessible tertiary amine moiety. The description of such autocatalytic polyols can be found in the E-Patent. OR . 5,672, 636; European Patent Publications 0 047 371, 1 268 598 and 1 31 9 034; and Publications WO 03/016372, 03/029320 and 03/055930, the disclosures of which are incorporated herein by reference. The structural properties of the autocatalytic polyols in relation to the final use of the polyurethane products are generally the same as for the polyols described above. Generally the tertiary amine of such autocatalytic polyols can be part of the initiator, part of the polyol chain and / or part of the end-capped polyol. These tertiary amine groups give autocatalytic characteristics to such polyols. The limitations described above with respect to the characteristics of the polyols are not intended to be restrictive, but are merely illustrative of the large number of possible combinations for the polyol or polyols used. Non-fugitive catalysts (c) containing at least one imine bond and a tertiary amine group are based on the reaction between an aldehyde, or a ketone and a molecule containing both primary amine and tertiary amine groups. It is believed that the non-fugitive aspect of catalyst (c) is due to either its bulky molecular mass which is at least 150 g / mol or its reactive isocyanate moieties, or both. Alternatively, the imino group can react with isocyanate during the reactions of the polyurethane product as described in EP 363,008, although it is true that without catalytic effect in the latter document. An additional advantage of the non-fugitive catalyst (c) is the formed imine linkage which is stable to hydrolysis at room temperature. Various chemistries are possible to obtain non-fugitive catalysts (c) as will be explained hereafter under (d), (c2), (c3), (c4), (c5), (cß), (c7), ( c8), or (c9). The catalysts (d) are obtained by reacting a molecule containing either at least one aldehyde group or a ketone group with a primary amine portion of a molecule containing a primary amine and at least one tertiary amine group. The final compound has a molecular weight greater than 150. Ketones and aldehydes for use in the present invention are defined, as is generally known in the art, by RC (O) -R1 and RC (O) -H, where respectively R and R1 are portions that do not react with the primary amine under conditions necessary to form an imine. Typically R and R1 are independently an alkyl of 1 to 20 carbon atoms, preferably 1 to 15 carbon atoms, substituted or unsubstituted, linear or branched, a cyclic, heterocyclic or aromatic compound containing from 4 to 20 atoms, preferably from 5 to 15 atoms in the ring, or R and R1 may be attached to each other to form a structure of ring containing 5 to 20 atoms in the ring. The ring structures can also be substituted. The variation of substituted ring structures is exemplified by the compounds listed herein. Non-limiting substitutes include hydroxyl, amines, carboxylic acids, alkyl or alkyl oxide moieties. The term "ring structure" as used herein includes compounds that contain more than one ring, such as naphthalene for an aromatic ring structure. Examples of aldehydes are salicylaldehyde, vanillin, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, 4-dimethylamino-benzaldehyde, benzaldehyde, furfural, anisaldehyde, tolualdehyde, isophthalaldehyde, phthalic dicarboxyaldehyde, terephthaldicarboxaldehyde, 4- (dimethylamino) benzaldehyde, 4- (diethylamino) benzaldehyde 4- (dibutyl-amino) benzaldehyde, 4- [3- (dimethylamino) propoxy] benzaldehyde, nitro-benzaldehyde, chlorobenzaldehyde, 2-carboxybenzaldehyde, phenyl-1,3-dicarboxyaldehyde, dihydroxybenzaldehydes, trihydroxybenzaldehydes, piperonal, beta-hydroxybutyric aldehyde (aldol), omega-hydroxy-methylfurfural, hydroxy-acetaldehyde, 5-hydroxy-pentanal, acetaldol, 2,5-dimethyl-2-hydroxyadipaldehyde, 3- (beta-hydroxyethoxy) -propanal, beta-hydroxyacetaldehyde. Preferred compounds are aldehydes with aromatic base such as salicylaldehyde, 4-dimethyl- aminobenzaldehyde, 4-hydroxybenzaldehyde or vanillin. Examples of ketones are cyclohexanone, methylcyclohexanone, cyclopentanone, methyl isobutyl ketone, tropolone, tropona, 2'-hydroxyacetophenone, 4'-hydroxyacetophenone, 3'-hydroxyacetophenone, 3-acetyl-1-propanol, 4-hydroxy-3-methyl-2-butanone. , 4-hydroxy-4-methyl-2-pentanone, 4'-hydroxivalerophenone, dihydroxyacetophenone, benzyl-4-hydroxyphenyl ketone, acetovainillone, aminobenzophenone, aminobenzoquinone. Examples of amines carrying both primary and tertiary amine groups are 3- (dimethylamino) -propylamine, 1- (3-aminopropyl) -i mid-azole, 1- (3-aminopropyl) -2-methylimidazoI, N, N-dimethyldipropylene -triamine, N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N-dibutylethylenediamine, 3- (diethylamino) propylamine, 3- (dibutylamino) -propylamine, N, N, 2,2-tetramethyl-1,3-propanediamine, 2-amino-5-diethylaminopentane, N-methyl- (N'-aminoethyl) -piperazine, 1,4-bis (3-am i not prop I) piperazine, 3-my nuci id i na, 4- (2-aminoethyl) morpholine, 4- (3-aminopropyl) morpholine, N, N-dimethyl-1,4-phenylenediamine, 5-amino-1 - ethylpyrazole, 2-aminopyridine, 2- (aminomethyl) pyridine, 2- (aminoetiI) -pyridine, 4-aminopyridine, 3-amino? iridine, 3- (aminomethyl) pyridine, N-aminopropyl pyrrolidine 2-aminopicolines, diaminopyridines, 2- aminopyrimidine, 4-aminopyrimidine, aminopyrazine, 3-amino-1, 2,4-triazine, aminoquinolines, N, N-dimethyldipropylenetriamine and 3,3'-diamino-N-methyl dipropylamine, N-methyl-1,3-propyldiamine. The catalysts (c2) are obtained by reacting a molecule, which contains at least one aldehyde group or a group ketone and at least one tertiary amine, with one molecule containing a primary amine and optionally other portions of amine and / or alcohol. Ketones and aldehydes containing a tertiary amine can generally be represented by (R2) 2N-R3-C (O) -R and (R2) 2N-R3-C (O) H wherein R is as defined above , R 2 is an alkyl of 1 to 6 straight or branched carbon atoms and R 3 is a linear or branched alkyl of 1 to 12 carbon atoms, an aromatic or aromatic alkyl portion having 6 to 20, preferably 6 to 15 carbon atoms substituted with at least one tertiary amine or R3 and R can be linked to each other to form a ring structure having from 5 to 20 atoms, preferably from 5 to 15 atoms in the ring. R3 can also be a cyclic or bicyclic portion having from 5 to 20 atoms wherein at least one nitrogen is included in the ring structure. The alkyl and the ring portions can be substituted with several portions as described above. Examples of aldehydes and ketones containing a tertiary nitrogen are quinuclidinone, tropinone, 1-methyl-4-piperidinone, 4- (dimethylamino) benzaldehyde, 4- (diethylamino) benzaldehyde, 4- (dibutyl-amino) benzaldehyde, 4- [3 - (dimethylamino) propoxy] benzaldehyde. Compounds containing primary amines are well known in the art. Representative examples of preferred compounds containing one or more primary amines are ethylenediamine, 1,6-hexanediamine, aniline, N, N-dimethyldipropylenetriamine, 3,3'-diamino-N-methyl-dipropylamine, 3-aminopropyl-N-methyl-ethanolamine and 3- (dimethylamino) propylamine, monoethanolamine, 2-amino-1-butanol. The catalysts (c3) are catalysts obtained by modifying functional epoxy molecules with compounds carrying both an aldehyde or ketone and a reactive portion of epoxy such as an alcohol, an amine, a thiol or a carboxylic acid, followed by a subsequent reaction with a primary amine molecule that carries tertiary amine to form an imine bond. The catalysts (c3) preferably contain more than one imine bond and more than one tertiary amine group per molecule. For the present invention, the compounds having aldehyde functionality and reactive functionality of epoxide (alcohol, amine, thiol, or carboxylic acid) are aliphatic, aromatic or polyaromatic compounds of 3 to 30 carbon atoms, preferably of 5 to 18 carbon atoms. carbon and ring structures containing a heteroatom, where the aldehyde portion is directly attached to the ring and the reactive portion of epoxide is attached directly to the ring or by means of an alkyl portion of 1 to 6 carbon atoms, linear or branched Such compounds may contain more than one reactive portion of epoxide or more than one portion of aldehyde. The constituents of the ring may be substituted with groups that do not react with an epoxy, such as an alkyl or alkoxy moiety. Examples of alcohols carrying aldehyde functionality are salicylaldehyde, vanillin, 5- (hydroxymethyl) -furfural, 3-hydroxy-benzaldehyde, 4-hydroxybenzaldehyde, dihydroxybenzaldehydes and trihydroxy benzaldehyde two. Examples of carboxylic acids carrying aldehyde functionality are 2-carboxybenzaldehyde and 3-carboxybenzaldehyde. For the present invention, the compounds having ketone functionality and reactive functionality of epoxide (alcohol, amine, thiol or carboxylic acid) are aliphatic, aromatic or polyaromatic compounds of 3 to 30 carbon atoms, preferably 5 to 18 carbon atoms. carbon and ring structures containing a heteroatom, wherein the reactive portion of epoxide is attached directly to the ring or by means of an alkyl portion of 1 to 6 carbon atoms, linear or branched. The ketone can also be part of the ring structure. Such compounds may contain more than one reactive portion of epoxide or more than one ketone portion. The constituted rings can be further substituted with groups that do not react with an epoxy, such as an alkyl or alkoxy moiety. Examples of alcohols carrying ketone functionality are 2'-hydroxyacetophenone, 4'-hydroxyacetophenone, 3'-hydroxyacetophenone, 3-acetyl-1-propanol, 4-hydroxy-3-methyl-2-butanone, 4-hydroxy-4-methyl -2-pentanone, 4'-hydroxivalerophenone, dihydroxyacetophenone, benzyl-4-hydroxyphenyl ketone and acetovainillone. Examples of amine-bearing ketones are 3'-aminoacetophenone, 4'-aminoacetophenone and aminobenzophenone. Examples of carboxylic acid containing ketones are 4-acetylbenzoic acid and 2-benzoylbenzoic acid.

Examples of epoxies, or epoxy resins, to produce the catalysts (c3) are known in the art. See for example the U.S. Patent 4,609,685, the description of which is incorporated by reference. The epoxy materials can be monomeric or polymeric, saturated or unsaturated, aliphatic, cycloaliphatic, aromatic or heterocyclic and can be substituted if desired with other substituents in addition to the epoxy groups, for example, hydroxyl groups, ether radicals and halogen atoms . A preferred family of polyepoxides can be represented by the formula: wherein R 4 is an aromatic, aliphatic, cycloaliphatic or substituted or unsubstituted heterocyclic group and n has an average value from 1 to 8. Example of preferred epoxies are phenyl glycidyl ether, aromatic epoxy resins of bisphenol A, bisphenol F and resorcinol and hydrogenated versions from the same; aliphatic polyether with epoxy bases such as D.E. R. 736, D. E. R. 732 and ERL-4221 (cyclic aliphatic epoxide) all available from The Dow Chemical Company. Other preferred epoxies include epoxidized oils such as epoxidized soy bean oil and epoxidized linseed oil. A mixture of any two or more epoxides may be used in the practice of the present invention. Preferably the epoxy resin has an average equivalent weight of 90 to 1000. More preferably the epoxy resin has an average equivalent weight of 150 to 500.

Preferred epoxides are aliphatic or cycloaliphatic polyepoxides, more preferably diepoxides such as D.R. 732 or D.E. R. 736 or epoxy resins with little chlorine with similar structures.

Example of amines carrying both primary and tertiary amine groups are described above under section (d). The catalysts (c4) are produced analogously as the catalysts (c3), with the exception that part of the aldehyde or ketone carrying reactive epoxide functionality that is reacted with polyepoxide is replaced by a reagent carrying only reactive epoxide functionality. This substitution allows the average molecular weight of the final catalyst (c4) to be adjusted upward, by extending the polyepoxide chain using polyfunctional compounds, or down by stopping the polyepoxide chain using monofunctional compounds, to adapt the product for a specific application. Examples of suitable molecules for replacing a fraction of the aldehyde or ketone carrying reactive functionality of epoxy include phenol, cresol, bisphenol A, bisphenol F, novolak polyols, resorcinol, ethylenediamine, 3,3'-diamino-N-methyl-dipropylamine, monoethanolamine, acetic acid, adipic acid, succinic acid, isophthalic acid, phthalic acid and terephthalic acid. The catalysts (c5) are produced analogously to the catalysts (c3), with the exception that some of the primary amines substituted with tertiary amine are replaced by a multifunctional primary amine. This substitution allows the average molecular weight of the final catalyst (c5) to be adjusted upwards or down to adapt the product for a specific application. Examples of suitable molecules for this substitution include monoethenolamine, 2-am i no-1-butanol, 2-amino-2-ethyl-1,3-propanediol, ethylenediamine, butanediamine, hexanediamine, polyoxyalkyleneamines JEFFAM INE® (registered trademark of Huntsman Chemical Corporation), methylenedianiline and diaminobenzene. Another option for producing non-fugitive catalysts with multiple active sites is (c6), based on the reaction of polyols capped with primary amines, such as polyoxyalkyleneamine JEFFAM I NE, with a molecule containing an aldehyde or ketone group and a tertiary amine, such as those described under (c2). The general structures of the polyoxyalkyleneamine JEFFAM INE polyoxyalkyleneamines are known, as per the technical bulletin of Huntsman 1008-1002. The catalysts (c7) are identical to (c3) and / or to (c4), but part of the epoxy resin has been reacted with a compound containing a reactive portion of epoxide, such as an amine, before the addition of the aldehyde or the ketone carrying reactive epoxide functionality. For example, the epoxy is reacted with a secondary amine carrying tertiary amine functionality (such as imidazole) or a primary amine such as monoethanolamine, or aniline which allows adjustment of the functionality and molecular weight of the final product. The chain extension compounds are those listed under (c3). Preferably, the compound that is pre-reacted with the poly-epoxide contains also a portion of tertiary amine. Generally, 1 to 50 percent of the epoxy groups will react in this step. In general, the secondary amines can be represented by H NR25 and the primary amines by H2N R5 wherein each R5 is independently a compound having 1 to 20 carbon atoms or can be linked together with the nitrogen atom and optionally other heteroatoms and heteroatoms of substituted alkyl to form a saturated heterocyclic ring. Examples of reactive epoxy amines which are commercially available and which can be used to make the catalyst (c7) are methylamine, dimethylamine, diethylamine, N, N-dimethylethanolamine, N, N-dimethylethylenediamine, N, N-dimethyl-N '- ethylenediamine, 3-dimethylamino-1-propanol, 1-dimethylamino-2-propanol, 3- (dimethylamino) propylamine, dicyclohexylamine, 4,6-dihydroxy pyrimidine, 1- (3-aminopropyl) -imidazo I, 3 -hydroxymethyl quinuclidine, 2-methyl imidazole, 1- (2-aminoethyl) -piperazine, 1-methyl-piperazine, 3-quinuclidinol, 2,4-diamino-6-h idroxy-pyrimidine, 2,4-diamino-6- methyl-1, 3,5-triazine, 3-aminopyridine, 2,4-diamino-pyrimidine, 2-phenylimino-3- (2-hydroxyethyl) -oxazalodyne, N - (2-hydroxyethyl) -2-methyl-tetrahydropyrimidine, N- (2-hydroxyethyl) -imidazoline, 2,4-bis- (N-methyl-2-hydroxyethylamino) -6-phenyl-1,3,5-triazine, bis- (dimethylaminopropyl) -amino-2-propanol, tetramethylamino-bis-propylamine, 2- (2-aminoethoxy) -ethanol, N, N-dimethylaminoethyl-N'-methyl ethanolamine, 2- (me tilamino) -ethanol, 2- (2-methylaminoethyl) -pyridine, 2- (methylamino) -pyridine, 2-methylaminomethyl-1,3-dioxane, dimethylaminopropyl urea. Compounds containing at least one tertiary nitrogen and at least one hydrogen molecule reactive for an epoxide can be represented by ((H) x-A-R6) z-M- (R7) and where A is nitrogen or oxygen; x is 2 when A is nitrogen and 1 when A is oxygen, R6 and R7 are linear or branched alkyl groups having from 1 to 20 carbon atoms; M is an amine or polyamine, linear or cyclic with at least one tertiary amine group; and is an integer from 0 to 6; and z is an integer from 1 to 6. Compounds containing both tertiary nitrogen and primary amine may be represented by the formula: H 2 N - R 8 - N (R 9) 2 wherein R 8 is an aliphatic or cyclic chain having from 1 to 20 carbon atoms and R9 is an alkyl group of 1 to 3 carbon atoms. The catalyst (c8) is obtained by reaction of an isocyanate with a. alcohol carrying aldehyde or ketone functionalities, followed by a subsequent reaction with a primary amine carrying a tertiary amine to form an imine bond with the polyol. Examples of isocyanates are toluene diisocyanate, isophorone diisocyanate, phenyl isocyanate, meilyldiphenylisocyanate, mixtures or prepolymers thereof. Preferred isocyanates are polyisocyanates, more preferably diisocyanates. Examples of alcohols carrying aldehyde ketone functionality and amines carrying both a primary and a tertiary amine are described above. The catalyst (c9) is based on the combination of the chemical described under (c3) and (cd), that is, mixing epoxy and isocyanate-based catalysts. The starting materials for the production of the catalyst (c) are commercially available or can be made by methods known to those skilled in the art, such as the reaction conditions for producing the catalyst (c). In general, the proportion of compounds in a particular reaction step is such that there is a closeness for a molar stoichiometric equivalent of reactive portions, ie from 0.9: 1, preferably from 0.95: 1 to 1: 1. For example, in the production of the catalyst (c3), when the reaction is between the epoxy functionality, such as a portion of aldehyde, and primary amine, the molar equivalents of aldehyde to primary amine is about 1: 1. However, it can be increased up to 1 .2: 1 when it is desired to minimize the amount of free amine in the catalyst (c). With the catalysts (c4) and (c5) this ratio can be adjusted to have a molar excess of one of the reactive groups to increase the molecular weight. The weight ratio of the non-fugitive catalyst (c) relative to the polyol will vary depending on the amount of additional catalyst that may be desired to be added to the reaction mixture and the reaction profile required by the specific application. Generally if a reaction mixture with a base level of catalyst that has a specific cure time, non-fugitive catalyst (c) is added in an amount such that the time Curing is equivalent in that the reaction mixture contains at least 10 weight percent less catalyst. Preferably, the addition of (c) is added to give a reaction mixture containing 20 percent less catalyst than the base level. More preferably the addition of (c) will reduce the required amount of catalyst by 30 percent above the base level. For some applications, the most preferred level of addition of (c) is where the need for a volatile or reactive tertiary amine catalyst or organometallic salt is eliminated. In some other applications, such as to decrease the demolding time, it is desirable to maintain the normal amount of conventional organometallic amine or catalyst and to add the catalyst (c) present in an amount to improve the demolding time. For this latter application, 0.1 to 10 parts or more of catalyst (c) per 100 parts by weight of polyol are generally added. The adjustment of the level of catalyst (c), to be used alone or in combination with polyurethane catalysts or conventional polyols containing aukanoalytic activity, for a particular application is well known to those skilled in the art. The combination of two or more non-fugitive catalysts of type (c) can also be used with satisfactory results in a simple polyurethane formulation when, for example, adjusting the blowing and gelation reactions by modifying the catalyst structure (c) with different tertiary amines, functionalities, equivalent weights, ratio of EO / PO, etc., and their respective quantities in the formulations. The non-fugitive catalysts (c) being any of the types (d), (c2), (c3), (c4), (c5), (cß), (c7), (c8), and (c9) can also be made with combinations of tertiary amines, for example, by making reacting an aldehyde or a ketone with more than one primary amine containing a tertiary amine group as listed below (c1). Conversely, catalyst (c) can be made from different types of groups of aldehydes and / or ketones capable of reacting with one or more primary amines bearing tertiary amine groups. The acid neutralization of the catalyst (c) can also be considered when, for example, a delayed action is required.

However, this can be detrimental to the catalyst composition since it has to be stable when added to the master batches of polyol, ie, water, surfactant, interlacer, etc. , preferably for at least one week at room temperature. Preferably, the catalyst (c) is stable in a polyol premix for at least 6 months. Preferred acids are carboxylic acids, more preferably carboxylic acids with an OH group and / or a halogen moiety. The catalysts (c) reacted previously with polyisocyanates and polyol (b1) with non-free isocyanate functions can also be used in the polyurethane formulation. The isocyanate prepolymers based on the catalyst (c) can be prepare with normal equipment, using conventional methods, such as heating the catalyst (c) in a reactor and slowly adding the isocyanate under stirring and then eventually adding a polyol, or pre-reacting a first polyol with a diisocyanate and then adding the catalyst (c). The isocyanates that can be used with the autocatalytic polyols of the present invention include aliphatic, cycloaliphatic, arylaliphatic and aromatic isocyanates. Aromatic isocyanates, especially aromatic polyisocyanates, are preferred. Examples of suitable aromatic isotionates include the 4,4'-, 2,4'- and 2,2'-isomers of diphenylmethane diisocyanate (MDI), mixtures thereof and polymeric and monomeric mixtures of M DI of toluene-2,4- and 2,6-diisocyanates (TDl), m - and p-phenylene diisocyanate, chlorophenylene-2,4-diisocyanate, diphenylene-4, 4'-diisocyanate, 4,4'-diisocyanato-3,3'-dimethyldiphenyl, 3-methyldiphenyl-methane-4,4'-diisocyanate and diphenylether-diisocyanate and 2,4,6-triisocyanatoioluene and 2,4,4 '-isoisocyanatodiphenyl-ether. Isocyanate mixtures can be used, such as commercially available mixtures of 2,4- and 2,6- isomers of toluene diisocyanates. A crude polyisocyanate can also be used in the practice of this invention, such as crude toluene diisocyanate obtained by the phosgenation of a mixture of toluenediamine or the crude diphenylmethane diisocyanate obtained by the phosgenation of crude methylenediphenylamine. TDI / MDI mixtures can also be used. The prepolymers based on MDI or TDl can also be use, made with either polyol (b1), polyol (b2) or any other polyol as described so far. The isocyanate terminated prepolymers are prepared by reacting an excess of polyisocyanate with polyols, including aminated polyols or imines / enamines thereof, or polyamines. Examples of aliphatic polyisocyanates include ethylene-diisocyanate, 1,6-hexamethylene diisocyanate, isophorone diisocyanate, cyclohexane-1,4-diisocyanate, 4,4'-dicyclohexylmethane-diisocyanate, saturated analogs of the aforementioned aromatic isocyanates and mixtures thereof. Preferred polyisocyanates for the production of rigid or semi-rigid foams are the polymethylene polyphenylene isocyanates, the 2,2 ', 2,4' and 4,4 'isomers of diphenylmethylene diisocyanate and mixtures thereof. For the production of flexible foams, the preferred polyisocyanates are toluene-2-4- and 2,6-diisocyanates or MDI or combinations of TDI / MDI or prepolymers made therefrom. The isocyanate-terminated prepolymers based on non-fugitive catalyst (c) can also be used in the polyurethane formulation. It is thought that using such an autocatalytic socianate in a polyol isocyanate reaction mixture will reduce / eliminate the presence of unreacted isocyanate monomers. This is of special interest with volatile isocyanates such as TDl and / or aliphatic socianates in coating and adhesive applications since it improves the handling conditions and the safety of the workers. For rigid foam, the organic polyisocyanates and the isocyanate reactive compounds are reacted in such amounts as the isocyanate index, defined as the number or equivalents of NCO groups divided by the total number of equivalents of reactive hydrogen atoms of the isocyanate multiplied by 100, ranges from 80 to less than 500, preferably from 90 to 100 in the case of polyurethane foams, and from 100 to 300 in the case of polyurethane-polyisocyanurate foams in combination. For flexible foams, this isocyanate index is generally between 50 and 120 and preferably between 75 and 1 10. For elastomers, coatings and adhesives the isocyanate index is generally between 80 and 125, preferably between 100 and 1 1 0. For To produce a polyurethane-based foam, a blowing agent is usually required. In the production of flexible polyurethane foams, water is preferred as a blowing agent. The amount of water is preferably in the range from 0.5 to 10 parts by weight, more preferably from 2 to 7 parts by weight based on 100 parts by weight of the polyol. The carboxylic acids or salts are also used as reactive blowing agents. In the production of rigid polyurethane foams, the blowing agent includes water and mixtures of water with a hydrocarbon, or a Total or partially halogenated aliphatic hydrocarbon. The amount of water is preferably in the range of 2 to 15 parts by weight, more preferably 2 to 10 parts by weight based on 100 parts of the polyol. With an excessive amount of water, the cure rate becomes lower, the range of the blowing process becomes narrower, the density of the foam becomes lower or the moldability becomes worse. The amount of hydrocarbon, hydrochlorofluorocarbon or hydrofluorocarbon to be combined with the water is suitably selected depending on the desired density of the foam, and is preferably not more than 40 parts by weight, more preferably not more than 30 parts by weight. weight based on 100 parts by weight of the polyol. When the water is present as an additional blowing agent, it is generally present in a quantity from 0.5 to 10, preferably from 0.8 to 6 and more preferably from 1 to 4 and most preferably from 1 to 3 parts by total weight of the total polyol composition. The hydrocarbon blowing agents are volatile hydrocarbons of 1 to 5 carbon atoms. The use of hydrocarbons is known in the art as described in EP 421 269 and EP 695 322. Preferred hydrocarbon blowing agents are butane and isomers thereof, pentane and isomers thereof (including cyclopentane) and combinations thereof. Examples of fluorocarbons include methyl fluoride, perfluoromethane, ethyl fluoride, 1,1-difluoroethane, 1,1-trifluoroethane (HFC-143a), 1,1,1-tetrafluoroethane (HFC-134a), 1, 1,1,3,3-pentafluoropropane (HFC-245fa), 1,1,1,3,3-pentafluorobutane (HFC-365mfc), heptafluoropropane (HFC-227ea), penta-fluoroethane, difluoromethane, perfluoroethane , 2,2-difluoropropane, 1,1, 1-trifluoropropane, perfluoropropane, dichloropropane, difluoropropane, perfluorobutane, perfluorocyclobutane or mixtures thereof. Preferred combinations are those which contain a combination of two or more blowing agents 245, 265 and 227. The partially halogenated chlorocarbons and the chlorofluorocarbons for use in this invention include methyl chloride, methylene chloride, ethyl chloride, 1,1 , 1-tricloethane, 1,1-dichloro-1-fluoroean (FCFC-141b), 1-chloro-1,1-difluoroethane (HCFC-142b), 1,1-dichloro-2,2,2-trifluoroethane (HCHC -123) and 1-chloro-1, 2,2,2-tetrafluoroethane (HCFC-124). Halogenated chlorofluorocarbons totally include trichloromonofluoromethane (CFC-11) dichlorodifluoromethane (CFC-12), trichlorotrifluoroethane (CFC-113), 1,1-trifluoroethane, penfafluoroethane, dichlorotetrafluoroethane (CFC-114), chlorheptafluoropropane and dichlorohexafluoropropane. Halocarbon blowing agents can be used in conjunction with low-boiling hydrocarbons, such as butane, pentane (including isomers thereof), hexane, or cyclohexane or with water. The use of carbon dioxide, either as a gas or as a liquid, as an auxiliary or complete blowing agent is of particular interest with current technology. The use of atmospheric pressure artificially reduced or increased can also be applied to current technology. In addition to the above critical components, it is often desirable to employ certain other ingredients in the preparation of polyurethane polymers. Among these additional ingredients are surfactants, preservatives, flame retardants, colorants, antioxidants, reinforcing agents, stabilizers and fillers. In the manufacture of polyurethane foam, it is generally preferred to use an amount of a surfactant to stabilize the foaming reaction mixture until it cures. Such surfactants advantageously comprise a liquid or solid organosilicon tensoacivo. Other surfactants include polyethylene glycol ethers of long chain alcohols, tertiary amine or alkanolamine salts of long chain alkyl acid sulfate esters, alkyl sulfonic esters and alkyl arylsulfonic acids. Such surfactants are used in amounts sufficient to stabilize the foaming reaction mixture against collapse and the formation of large, non-uniform cells. Typically, 0.2 to 3 parts of the surfactant per 100 parts by weight of total polyol (b) are sufficient for this purpose. One or more catalysts can be used for the reaction of the polyol (and water, if present) with the polyisocyanate. Any suitable urethane catalyst can be used, including tertiary amine compounds, amine reactive groups with isocyanate and organometallic compounds. Preferably the reaction is carried out performed in the absence of a fugitive amine or an organometallic catalyst or a reduced amount as described above. Exemplary tertiary amine compounds include triethylenediamine, N-methylmorpholine, N, N, -dimethylcyclohexylamine, pentamethyldietilenthamine, tetramethylethylenediamine, bis (dimethylaminoethyl) ether, 1-methyl-4-dimethylaminoethyl piperazine, 3-methoxy-N-dimethyl-propylamine. , N-ethylmorpholine, dimethylethanolamine, N-co-morpholine, N, Nd i methyl-N ', N' -dimethyl isopropylpropylenediamine, NN-diethyl-3-dieylamino-propylamine and dimethylbenzylamine. Exemplary organometallic catalysts include organomercury, organolead, organoferric and organotin catalysts, with organotin catalysts being preferred among these. Suitable tin catalysts include stannous chloride, tin salts of carboxylic acids such as dibutyltin di-laurate, as well as other organometallic compounds such as are described in US Pat.846,408. A catalyst for the trimerization of polyisocyanates, which results in a polyisocyanurate, such as an alkali metal alkoxide may also be optionally employed herein. The amount of amine catalysts can vary from 0.02 to 5 percent in the formulation or organometallic catalysts can be used from 0.001 to 1 percent. Preferably, none of these catalysts is necessary when non-fugitive catalyst (c) is used. An interlacing agent or chain extender can be added if necessary. The interlacing agent or the chain extender includes low molecular weight polyhydric alcohols such as ethylene glycol, diethylene glycol, 1,4-butanediol and glycerin; low molecular weight amine polyol such as diethanolamine and triethanolamine; polyamines such as ethylenediamine, xylylenediamine and mutilen-bis (o-chloroaniline). The use of such chain crosslinkers or extensors is known in the art as described in US Patents 4,863,979 and 4,963,399 and in EP 549, 120. When rigid foams are prepared for use in construction, a flame retardant is generally included. Flame as an additive. Any known liquid or solid flame retardant can be used with the autocatalytic polyols of the present invention. Generally such flame retardants are halogen-substituted phosphates and inorganic flame-proofing agents. Common halogen-sushioid phosphates are iricresyl phosphate, fris (1,3-dichloropropyl) phosphate, tris (2,3-dibromopropyl) phosphate and tetrakis (2-chloroethyl) ethylene diphosphate. Inorganic flame retardants include red phosphorus, aluminum oxide hydrate, antimony trioxide, ammonium sulfate, expandable graphite, urea or melamine cyanurate or mixtures of at least two flame retardants. In general, when present, the flame retardants are added at a level of from 5 to 50 parts by weight, preferably from 5 to 25 parts by weight of the flame reikator per 100 parts by weight of the total weight of polyol present. The fillers include, for example, barium sulfate, calcium carbonate, recycled foam powder, such as those described in EP 71 1, 221 or GB 922,306. The applications for foams produced by the present invention are those known in the industry. For example, rigid foams are used in the construction industry and for insulation of appliances and refrigerators. Flexible foams and elastomers find use in applications such as furniture, mattresses, shoe soles, car seats, sun visors, steering wheels, arm rests, door panels, noise insulating panels and parts. The process for producing polyurethane products is well known in the art. In general, the components of the reaction mixture for polyurethane formation can be mixed together in any convenient manner, for example, using any of the mixing equipment described in the prior art for the purpose as described in "Polyurethane Handbook" , by G. Oerlel, Hanser publisher. Polyurethane products are produced in either continuous or discontinuous form, by means of injection, pouring, spraying, molding, calendering, etc .; These are made under free-standing or in-mold conditions, with or without release agents, mold-coating, or any inserts or skin placed in the mold. In the case of flexible foams, those may be of single or double hardness. To produce rigid foams, known techniques of prepolymer or semi-prepolymer can be used in one shot along with conventional mixing methods including impact mixing. The rigid foam can also be produced in the form of blocks, moldings, cavity filling, sprayed foam, foamed foam or laminated with other material such as paper, metal, plastics or wooden board. The flexible foams are either by free lifting and molding while the microcellular elastomers are molded in the usual way. The following examples are given to illustrate the invention and should not be construed as limiting in any way. Unless otherwise indicated, all parts and percentages are given by weight. The abbreviation mol is used for mol or moles. A description of the raw materials used in the examples is as follows: DEOA is pure diethanolamine. DMAPA is 3-dimethylamino-1-propylamine. API is 1- (3-aminopropyl) -imidazole, a tertiary amine with a primary amine available from Aldrich. D. E. R. * 736 P is an aliphatic diepoxide resin with an EEW (epoxy equivalent weight) of 190 available from The Dow Chemical Company. D. E. R. 732 is an aliphatic diepoxide resin with an EEW of 320 available from The Down Chemical Company. D. E. R. 383 is a liquid aromatic epoxy resin with an EEW of 180.4 available from The Down Chemical Company. D. E. N. 438 is a liquid aromatic epoxy Novolak resin with a EEW of 190 available from The Down Chemical Company. Epoxy resin A is an aliphatic diepoxide resin with an EEW of 300 and contains less than 2% chlorine. Dabco DC 5169 is a silicone-based surfactant available from Air Products and Chemical Inc. Niax Y-10184 is a silicone-based surfactant available from G.E. Dabco 33 LV is a tertiary amine catalyst available from Air Products and Chemical Inc. Niax A-1 is a tertiary amine catalyst available from Crompton Corporation. Polyol A is a propoxylated tetrol with an equivalent weight of 1, 700 initiated with 3,3'-diamino-N-methyl dipropylamine and topped with 15% ethylene oxide. Polyol B is identical to Polyol A but topped with 20% ethylene oxide. SPECFLEX NC 632 is a polyoxypropylene polyoxyethylene polyol with an EW 1, 700 initiated with a mixture of glycerol and sorbitol available from The Down Chemical Company. SPECFLEX NC-630 is a polyol similar to Specflex NC-632 which has lower functionality and is available from The Down Chemical Company. Polyol C is a polyol similar to Specflex NC-630 except because the content of ethylene oxide is increased up to 17%. SPECFLEX NC-700 is a copolymer polyol based on 40% SAN with an average hydroxyl number of 20 available from The Down Chemical Company.

VORANATE T-80 is isocyanate with 80/20 TDl available from The Down Chemical Company. All foams are made in the laboratory by pre-mixing polyols, surfactants, interlayers, cayalisers and water. This master batch is in the machine ichne of a high pressure machine (Krauss-Maffei or Cannon) with the isocyanate side filled with Voranate T-80. The reagents are poured into an aluminum mold of 40x40x10 cm, it is heated to 60 ° C, which closes posioriormenie.

Before using the mold, it is sprayed with a release agent. The curing in the specific demolding times is evaluated by manually demolishing the parle and looking for defects. The minimum demolding time is reached when there are no defects on the surface. Free-lift tests are carried out using a 22.7-liter plastic bucket and verifying from the pressure machine a shot of sufficient size to fill the bucket with a crown of foam about 30 centimeters above the top of the bucket. the bucket. The stability of the foam is then visually removed. BVT reactivity tests are carried out (Brookfield Viscosity Test) as follows: let 100 grams of polyol equilibrate at 25 ° C and then mix with 0.26 grams of Dabco 33 LV. Then Voranate T-80 is added at a concentration corresponding to an index of 1 10. The viscosity accumulated with time is recorded until full gelation is obtained. In the case of the non-fugitive catalysts (c), these are mixed in various proportions with the control polyol and Dabco 33 LV is not used. The time is recorded to reach the final target viscosity of 20,000 mPa.s (corresponding to 100% of torque). Example 1 Salicylaldehyde adduct v 1 - (3-aminopropyl) imidazole A 100 mL two-neck round bottom flask equipped with a magnetic stir bar, an additional funnel and a condenser is charged with 15.0 g (0.123 mol) ) of salicylaldehyde. 1 -3- (aminopropyl) imidazole (15.4g, 0.123 mol) is placed in the additional funnel. The amine is added dropwise while the reaction mixture is stirred under nitrogen. After the addition is complete, a bright, clear yellow oil is poured from the flask into a bottle. Isolated production = 28.5g. After rest, the product solidifies and has the following properties. 1 H NMR (DMSO): 8.55 (singlet, 1 H), 7.65 (singlet, 1 H), 7.45 (doublet, 1 H), 7.3 (triplet, 1 H), 7.2 (singlet, 1 H), 6.9 ( multiplefe, 3H), 4.1 (multiple, 2H), 3.5 (triplet, 2H), 3.3 (broad singlet, ~ 3H), 2.1 (m, 2H); 13C RM N (DMSO-d6) 166.4, 160.5, 137.3, 132.3, 131.7, 128.5, 1 19.3, 1 18.7, 1 18.6, 1 16.4, 55.5, 43.9, 31 .6. The theoretical amount of water in the product is 7.3% by weight. EXAMPLE 2 Salicylaldehyde adduct v 3-dimethylaminopropylamine A 100 ml two-neck round bottom flask equipped with a magnetic stir bar, an additional funnel and a condenser is charged with 15.0 g (0.123 mol) of salicylaldehyde. 3- dimethylaminopropylamine (12.55g, 0.123 mol) is placed in the additional funnel. The amine is added dropwise while the reaction mixture is stirred under nitrogen. After the addition is complete, a clear, bright yellow oil is poured from the flask into a bottle. Isolated production = 26.9g. with the following properties. 1 H NMR (DMSO): 8.55 (singlet, 1H), 7.45 (doublet, 1H), 7.3 (triplet, 1H), 6.9 (multiplet, 2H), 3.6 (triplet, 2H), 3.4 (broad singlet, ~ 3H), 2.25 (triplet, 2 H), 2.15 (singlet, 6H), 1.75 (multiplet, 2H). 13 C NMR (DMSO-d 6) 165.5, 160.6, 131.8, 131.2, 118.2, 118.0, 116.2, 56.2, 55.9, 44.8, 28.0. The theoretical amount of water in the product is 8.0% by weight. Example 3 Resin adduct A Epoxy, salicylaldehyde v 3-dimethylaminopropylamine A 1L two-neck round bottom flask equipped with a mechanical stirrer, a Claissen adapter and a gas inlet adapter connected to a vacuum / nitrogen source is charged with 444.0 g (1.5 mol of epoxy groups) of Epoxy resin A, 183.2 g (1.5 mol) of salicylaldehyde and 5.8 g (3.42 g active, 9.0 mmol) of tetrabutylphosphonium acetate (59% by weight in methanol). The device is evacuated up to 20 mm Hg and then vented with nitrogen. The vacuum / nitrogen is cycled a total of 5 times ending in nitrogen. The apparatus is left under a dynamic atmosphere of nitrogen and immersed in an oil bath maintained at 120 ° C. After 1 hour, the bath temperature is increased to 150 ° C and the reaction mixture is stirred overnight. After 20 hours, the reaction mixture is sampled and analyzed by NMR revealing that all the epoxy has been consumed. The flask is taken out of the oil bath and adapted with a funnel containing 152.3 g (1.49 mol) of 3- (dimethylamino) propylamine. The amine is added dropwise to the warm reaction mixture, stirred for one hour. After the addition is complete, a clear, bright red oil is poured from the flask into a bottle. Isolated production = 775.2 g. with the following properties. 1 H NM N (DMSO): 8.7 (singlet, 1 H), 7.85 (doublet, 1 H), 7.4 (multiplet, 1 H), 7.0 (multiplet, 2H), 5.2 (broad singlet, OH), 4.0 (multiplet , Polyether H's), 3.4 (broad multiplet, polyether + H's amine derivatives), 2.25 (triplet, 2H), 2.1 (singlet, 6H), 1.7 (multiplet, 2H), 1.0 (broad singlet, CH3 of polyether). The theoretical amount of water in the product is 3.4% by weight. The theoretical amount of dimethylamino groups in the sample is 1.9 meq / g. Example 4 Resin adduct A Epoxy, salicylaldehyde and 1- (3-aminopropyl) midazole A 1-liter two-necked round bottom flask equipped with a mechanical stirrer, a Claissen adapter and an adapter gas inlet connected to a vacuum / nitrogen source, charged with 450.3 g (1.54 mole of epoxy groups) of resin E Epoxy, 187.7 g (1.54 mole) of salicylaldehyde and 5.8 g (3.42 g active, 9.0 mmol) of tetrabutylphosphonium acetate (59% by weight in methanol). The apparatus is evacuated to 20 mm Hg and then vented with nitrogen. The vacuum / nitrogen is cyclized for a total of 5 times ending in nitrogen. The apparatus is left under a dynamic atmosphere of nitrogen and immersed in an oil bath maintained at 140 ° C. After 2 hours, the bath temperature is increased to 150 ° C and the reaction mixture is stirred overnight. After 20 hours, the reaction mixture is sampled and analyzed by NMR which reveals that all the epoxy has been consumed. The flask is removed from the oil bath and adapted with an addition funnel containing 188.5 g (1.51 mol) of 1- (3-aminopropyl) imidazole. The amine is added dropwise to the warm reaction mixture, stirred for 30 minutes. After the addition is complete, a clear, orange oil is poured from the flask into a bottle. Isolated production = 816.7 g with the following properties. 1 H NMR (DMSO): 8.7 (singlet, 1 H), 7.85 (doublet, 1 H), 7.6 (singlet, 1 H), 7.4 (multiplet, 1 H), 7.2 (singlet, 1 H), 7.0 (multiplet) , 3H), 5.2 (broad singlet, OH), 4.0 (multiplet, polyether + H's amine derivatives), 3.4 (broad multiplet, polyether + H's amine derivatives), 2.05 (multiplet, 2H), 1.7, 1.0 ( broad singlet, polyether CH3). The theoretical amount of water in the product is 3.3% by weight. The theoretical amount of imidazole groups in the sample is 1.81 meq / g.

Example 5 Adduct of DER 732, salicylaldehyde and 3-dimethylaminopropylamine The procedure of Example 3 is used when the reactor is charged with 450.0 (1.4 millio of epoxy groups) of DER 732 (a liquid aliphatic epoxy resin with an epoxide equivalent weight). of 322), 170.7 g (1.4 mol) of salicylaldehyde and 5.4 g (3.17 g active, 8.4 mol) of tetrabutylphosphonium acetate. After a reaction period of 20 hours, 141.8 (1.39 mol) of 3- (dimethylamino) propylamine are added dropwise during one hour. After the addition is complete, an orange, clear oil is poured from the flask into a bottle. Isolated yield = 760.1 g which has the following properties. 1 H NMR (DMSO): 8.7 (singlet, 1 H), 7.85 (doublet, 1 H), 7.4 (multiplet, 1 H), 7.0 (multiplet, 2H), 5.2 (broad multiplet, OH), 4.0 (multiplet) , Polyethylene H), 3.4 (broad multiplet, polyether + H's amine derivatives), 2.25 (triplet, 2H), 2.1 (singlet, 6H), 1.7 (multiply, 2H), 1.0 (broad singlet, CH3 of polyether). The theoretical amount of water in the product is 3.3% by weight. The theoretical amount of dimethylamino groups in the sample is 1.82 meq / g. Example 6 Adduct of DER 383. salicylaldehyde v 3-dimethylaminopropylamine To the apparatus of Example 3 there are added 30.6 g (169.6 mol of epoxy groups) of DER 383, 20.7 g (169.5 mol) of salicylaldehyde, and 660.2 mg (389.5 mg active, 1 .03 mol) of tetrabutylphosphonium acetate. After a vacuum / nitrogen cycle as in Example 3, the apparatus is left under a dynamic atmosphere of nitrogen and immersed in a oil bath maintained at 85 ° C. After two hours, the bath temperature is increased to 100 ° C and the reaction mixture is stirred overnight. After 20 hours, the reaction mixture is sampled and analyzed by NMR revealing that all the epoxy has been consumed. The oil bath containing the reaction mixture is cooled to 70 ° C and the flask is conditioned with an addition funnel containing 17.0 g (166.4 mol) of 3- (dimethylamino) propylamine. The amine is added dropwise to the stirred reaction mixture, lukewarm for ten minutes. After the addition is complete, a viscous, yellow, clear oil is poured from the flask into a bottle while still lukewarm. Isolated yield = 64 g which has the following properties. 1 H RM N (DMSO): 8.7 (singlet, 1 H), 7.85 (doublet, 1 H), 7.4 (multiplet, 1 H), 7.1 (doublet, 2H), 7.0 (multiplet, 2H), 6.85 (doublet, 2H), 5.5 (broad singlet, OH), 4.1 (multiplet, polyether H's), 3.5 (triplet, H's amine derivatives), 3.4 (broad singiete), 2.25 (triplet, 2H), 2.1 (singlet, 6H), 1.7 (multiplet, 2H), 1.55 (broad singlet, CH3 derived from bisphenol A). The theoretical amount of water in the product is 4.36% by weight. The theoretical amount of dimethylamino groups in the sample is 2.42 meq / g. Example 7 Addition of DER 438, salicylaldehyde and 3-dimethylaminopropylamine. To the apparatus of Example 3 are added 33.6 g (187.5 mole of epoxy groups) of DEN 438 (an epoxide equivalent weight of 179.2), 22.9 g (187.5 mole) of salicylaldehyde and 647.6 mg (382.1 mg active, 1.0 mol) of tetrabutylphosphonium acetate. The device is evacuated to 20 mm Hg and then vented with nitrogen. Vacuum / nitrogen is cycled for a total of tre & sometimes ending in nitrogen. The apparatus is left under a dynamic nitrogen atmosphere and immersed in an oil bath maintained at 90 ° C. After 30 minutes, the bath temperature is increased to 100 ° C and the reaction mixture is stirred overnight. After 20 hours, the reaction mixture is sampled and analyzed by NMR revealing that all the epoxy has been consumed. The oil bath containing the reaction mixture is cooled to 90 ° C and the mary is conditioned with an addition funnel containing 19.0 g (185.9 mol) of 3- (dimethylamino) propylamine. The amine is added dropwise to the stirred reaction mixture, lukewarm for 30 minutes. After the addition is complete, pour a viscous, red, clear syrup from the flask into a bottle while it is still warm. Isolated yield = 68 g. When cooled to ambient temperature the product is a clear, red glass that has the following properties. 1 H NMR (DMSO): 8.7 (singlet, 1 H), 7.85 (doublet, 1 H), 7.4 (multiplet, 1 H), 6.9 (broad multiplet, 5H), 5.6 (broad singlet, OH), 3-4.3 (broad multiplet), 2.25 (muitiplete, 2H), 2.1 (broad singlet, 6H), 1.7 (multiplele, 2H). The theoretical amount of water in the product is 4.41% by weight. The theoretical amount of dimethylamino groups in the sample is 2.45 meq / g. Example 8 Resin adduct A epoxy, vanillin and 3-dimethylaminopropylamine The procedure of Example 3 is used when the apparatus is charged with 30.0 g (101.4 mmol of epoxy groups) of epoxy resin A, 15.4 g (101.2 mmol) of vanillin and 487 mg (287.3 mg of active, 0.76 mmol) of acetate of tetrabutylphosphonium. After overnight reaction, 10.3 g (101.2 mmol) of 3- (dimethylamino) propylamine are added dropwise over ten minutes. After the addition is complete, an orange / light brown oil is obtained. Isolated yield = 50.8 g which has the following properties. 1 H NMR (DMSO): 8.2 (singlet, 1 H), 7.35 (singlet, 1 H), 7.15 (doublet, 1 H), 6.95 (doublet, 2H), 5.1 (broad singlet, OH), 4.0 (multiplet, Polyether's H), 3.8 (singlet, 3H, polyether + amine derivatives), 2.25 (triplet, 2H), 2.1 (singlet, 6H), 1.7 (multiplet, 2H), 1.0 (broad singlet, CH3 of polyether). The theoretical amount of water in the product is 3.25% by weight. The theoretical amount of dimethylamino groups in the sample is 1.8 meq / g. Example 9 Adduct of Epoxidized Soybean Oil, Vanillin and 3-Dimethylaminopropylamine To an apparatus as in Example 3, 30.0 g (127.7 mmol of epoxy groups) of epoxidized soybean oil are added (Paraplex G-62 from CP Hall Co., with an epoxide equivalent weight of 235), 19.4 g (127.5 mol) of vanillin and 491.2 mg (289.8 mg of the active substance, 0.76 mmol) of tetrabutylphosphonium acetate. The device is evacuated to 20 mm Hg and then vented with nitrogen. This cycle is repeated four times and the apparatus is left under a dynamic atmosphere of nitrogen and immersed in an oil bath maintained at 150 ° C. After 30 minutes, the bath temperature is increased to 165 ° C and the reaction mixture is stirred overnight. After 14 hours, the reaction mixture is sampled and analyzed by NMR revealing that all the epoxy has been consumed. The oil bath containing the reaction mixture is cooled to 60 ° C and the flask is conditioned with an addition funnel containing 13.0 g (127.2 mmol) of 3- (dimethylamino) propylamine. The amine is added dropwise over 10 minutes. After the addition is complete, a viscous, warm syrup is obtained. Isolated yield = 57.4 g with the following analysis. 1 H NMR (DMSO): 8.2 (singlet, 1 H), 7.35 (singlet, 1 H), 7.0 (broad multiplet, 2H), 5.2 (broad singlet, OH), 3.2-4.6 (broad multiplet), 2.25 (triplet , 2H), 2.1 (singlet, 6H), 1 .7 (multiplet, 2H), 1 .0-1 .6 (multiplet), 0.8 (broad singlet). The theoretical amount of water in the product is 3.65% by weight. The theoretical amount of dimethylamino groups in the sample is 2.03 meq / g. Examples 10. 1 1 and 12 Reactivity data with BVT tests. Aducío 3 paríes SPECFLEX NC 630 100 paríes VORANATE T-80 index 1 10 Example 10; using the adduct of Example 2; 2200 cps reached after 10 minutes. Example 1 1; using the adduct of Example 3; 20000 cPs reached at 5 minutes, 20 seconds. Example 12; using the adduct of Example 4; 20000 cPs reached at 5 minutes, 45 seconds. These data confirm that the catalyst (c) catalyzes the polyol-isocyanate reaction, hence it is a gelling catalyst. This is confirmed by Comparative Example 12C. Comparative Example 12C. Voramnol NC 630 100 parts Dabco 33 LV 0.26 parts Voranate T-80 index 1 10 The complete gelling (20,000 cPs) is reached after 5 minutes, 40 seconds. Examples 13 and 14 Duplicate experiments are carried out using a high pressure machine equipped with a Krauss-Maffei mixing head with the adduct of Example 3. Specflex formulation NC-632 18.5 Specflex NC-700 30 Polyol A 50 Adducing example 3 1.5 Water 3.6 DEOA 0.7 Dabco DC-5169 0.6 Voranate T-80 index 100 and 105 Free Lifting Foam Example 13 Eiem iplo 14 Cream time (s) 4 4 Gel time (s) 61 60 Lifting time (s) 1 31 133 Density of free lift (kg / m3) 28 ND Molded foam: demolding time 4 ', molding density 38. 4 kg / m3. Examples 13 and 14 show that good, stable foams are obtained when the catalyst (c) is combined with a polyol having catalytic activity (polyol A) and conventional polyols. Other catalysts are not used with examples 13 and 14. No amine odors were detected in the demolding. Examples 15, 16 For example 15, the adduct of example 4 is used instead of the adduct of example 3, with the formulation of examples 13/14; index 100: measured reactivity: cream time 5 s; gel time 70 s; Lifting time 157 s. A good foam with a free lifting density of 28.5 kg / m3 is obtained. For Example 16, the adduct of Example 5 is used in place of the adduct of Example 3, with the formulation of Examples 13/14; index 100: measured reactivity: cream time 4 s; gel time 58 s; Lifting time 126 s. A good foam with a free lifting density of 28 kg / m3 is obtained. Examples 17 and 18 For example 17 the adduct of example 3 is used in the following formulation.

Formulation Polyol C 24.4 Polyol Specflex NC-700 37.5 Polyol B 36.6 Adduct of example 3 1 .5 Water 3.9 DEOA 1 .4 Niax Y-1 01 84 1 .2 VORANATE T-80 index 1 05 Size: 600 grams in cuvette of 1 9 liters. Measured reactivity: cream time 5 s; lifting time 84 s. Good foam was obtained with a free lift density of 28.8 kg / m3. For Example 18, the adduct of Example 5 is used with the formulation of Example 1 7. Size: 600 grams in a 1-liter cuvette. Measured reactivity: cream time 5 s; lifting time 83 s. Good foam was obtained with a free lift density of 28. 4 kg / m3. Example 1 9 The adduct of example 3 is mixed with polyol B and C at several levels and an aging study is carried out by measuring the reactivity by the BVT test and by visual inspection to record any sign of phase separation. After 13 weeks at 60 ° C no loss of reactivity or sign of phase separation was observed with the following mixture: Adduct of example 3 5 parts by weight Polyol B 38 Polyol C 57 Example 20 A mixture of polyols was prepared with the following composition by weight: Specflex NC-632 1 8.5 Specflex NC-700 30 Polyol A 50 Adduct of example 5 1 .5 Water 3.6 DEOA 0.7 Dabco DC-5169 0.6 This mixture was foamed with Voranate T-80 using a Krauss-Maffei mixing head in several days: day 1 day 4 Cream time (s) 5 5 Gel time (s) 69 70 Lifting time (s) 1 41 143 Free lift density (kg / m3) 30 29 These aging data show that the mixture of polyols containing water and catalyst (c) with imine base is stable for several days. Example 21 Addition of DER 732, salicylaldehyde. 1- (3-aminopropyl) imidazole and 3- dimethylaminopropylamine The procedure of Example 3 is followed when the apparatus is charged with 475.0 g (1,498 mol of epoxy groups) of DE R 732, 1 73.8 g (1.424 mol) of salicylaldehyde and 5.8 g (3.42 g active, 9.0 mmol) of tetrabutylphosphonium acetate. The reaction is allowed to proceed for 1 6 hours after which time 72.7 g (0.712 mol) of 3- (dimethylamino) propylamine and 89.1 g (0.71 2 mol) of 1- (3-aminopropyl) are added dropwise. ) imidazole via an addition funnel. The amine is added dropwise to the stirred reaction mixture, lukewarm for one hour. After the addition is complete, an orange, clear oil is obtained. Isolated yield = 805.9 g. The theoretical amount of water in the product is 3.1 5% by weight. The theoretical amount of total amine functionality in the sample is 1.75 meq / g divided equally between dimethylamino groups and imidazole groups. Example 22 The foaming is done with 1.5 parts by weight of adduct of example 21 using the formulation and conditions of examples 14 and 1 5: Cream time (s) 4 Gel time (s) 69 Lifting time ( s) 1 29 This formulation is used to mold parts of foam with molding densities of 38 kg / m3 with good curing time of demolding of 4 minutes.

Examples 23 Epoxy resin A adduct. salicylaldehyde. bisphenol A v 3- dimethylaminopropylamine A 1 L round neck flask equipped with a mechanical stirrer, a Claissen adapter and a gas inlet adapter connected to a vacuum / nitrogen source is charged with 500.0 g (1.69 mol epoxy groups) of resin A Epoxy, 103.0 g (0.845 mol) of salicylaldehyde, 96.45 g (0.4435 mol) of bisphenol A and 6.5 g of tetrabutylphosphonium acetate (59% in methanol). The device is evacuated to 20 mm Hg and then vented with nitrogen. The vacuum / nitrogen is cycled a total of 5 times ending in nitrogen. The apparatus is left under a dynamic atmosphere of nitrogen and immersed in an oil bath maintained at 120 ° C. After 1 hour, the bath temperature is increased to 150 ° C and the reaction mixture is stirred overnight. After 20 hours, the reaction mixture is sampled and analyzed by NMR revealing that all the epoxy has been consumed. The flask is removed from the oil bath and adapted with an addition funnel containing 86.4 g (0.845 mol) of 3- (dimethylamino) propylamine. The amine is added dropwise to the warm reaction mixture, agitated, for one hour. After the addition is complete, a clear, orange oil is poured from the flask into a bottle. Isolated production = 780.4 g. Example 24 Epoxy resin A adduct. 3.3 'diamino-N-methyl-dipropylamine and 3-dimethylaminopropylamine The procedure of Example 23 is followed using 444 g (1.5 mol of epoxy groups) of Epoxy resin A, 183.2 g (1.5 mol) of salicylaldehyde and 5.8 g of tetrabutylphosphonium acetate (59 wt.% In methanol). After reacting overnight at 150 ° C, a mixture of 76.6 g (0.75 mol) of 3-dimethylaminopropylamine and 54.5 g (0.375 mol) of 3,3'-diamino-N-methyldipropylamine was added to the reactants. Isolated yield = 752.9 g. Other embodiments of the invention will be apparent to those skilled in the art from a consideration of this specification or the practice of the invention described herein. It is intended that the specification and examples be considered as exemplary only, the true scope and spirit of the invention being indicated by the following claims.

Claims

CLAIMS 1. A catalyst composition wherein the catalyst has at least one imine bond and at least one tertiary amine moiety, wherein the imine bond is obtained by the reaction mixture comprising (i) a compound having at least one minus one portion of aldehyde or ketone and (ii) a compound having at least one primary amine portion wherein the tertiary amine portion is present in the compound of (i), the compound of (ii) or both compounds of (i) and (ii).
2. The catalyst of claim 1, wherein the compound having a ketone or aldehyde portion further contains a tertiary amine moiety.
3. The catalyst of claim 1, wherein the compound having a primary amine moiety further contains a tertiary amine moiety.
4. The catalyst of claim 1, wherein the ketone is represented by RC (O) -R1 wherein R and R1 are independently an alkyl of 1 to 20 carbon atoms, substituted or unsubstituted, linear or branched, a cyclic compound, heterocyclic or aromatic containing from 4 to 20 carbon atoms or R and R1 are joined to each other to form a ring structure containing from 5 to 20 ring atoms.
The catalyst of claim 1, wherein the aldehyde is represented by R-C (O) -H, wherein R is an alkyl of 1 to 20 carbon atoms, substituted or unsubstituted, linear or branched, a cyclic, heterocyclic or aromatic compound containing from 4 to 20 carbon atoms.
The catalyst of claim 1, wherein the compound having both primary and tertiary amine portions is represented by the formula: H 2 N-R 8 -N (R 9) 2 wherein R 8 is an aliphatic or cyclic chain having from 1 to 20 carbon atoms and R 9 is an alkyl group of 1 to 3 carbon atoms.
The catalyst of claim 1, wherein the compound having both primary and tertiary amine portions is 3- (dimethylamino) -propylamine, 1- (3-aminopropyl) imidazole, 1- (3-aminopropyl) -2- methylimidazole, N, N-dimethyldipropylenetriamine, N, N-dimethylyleylenediamine, N, N-diethylelylenediamine, N, N-di-butyl ethyl-endiamine, 3- (di-eti-lamino) -propylamine, 3- (dibu ti -lamino) -propi-lamine, N, N, 2,2-tetramethyl-1,3-propanediamine, 2-amino-5-diethylaminopentane, N-methyl- (N'-aminoethyl) -piperazine, 1,4-bis (3-aminopropyl) -piperazine , 3-aminoquinuclidine, 4- (2-aminoethyl) morpholine, 4- (3-aminopropyl) morpholine, N, N-dimethyl-1,4-phenylenediamine, 5-amino-1-ethylpyrazole, 2-aminopyridine, 2- ( aminomethyl) pyridine, 2- (aminoetiI) -pyridine, 4-aminopyridine, 3-aminopyridine, 3- (aminomethyl) pyridine, N-aminopropyl pyrrolidine 2-aminopicolines, diaminopyridines, 2-aminopyrimidine, 4-aminopyrimidine, aminopyrazine, 3-amino -1, 2,4-triazine, amino-quinolines, N, N-dimethyldipropylenetriamine and 3 , 3'-diamino-N-methyI dipropylamine, N -methyl-1,3-propyldiamine.
8. The catalyst of claim 1, obtained by the reaction product of a compound containing at least one tertiary amine and at least one group of aldehyde or ketone portion with a compound containing a primary amine.
9. The catalyst of claim 8, wherein the compound containing the ketone and tertiary amine moieties is represented by the formula (R2) 2N-R3-C (O) -R wherein R is an alkyl of 1 to 20 carbon atoms, substituted or unsubstituted, linear or branched, a cyclic, heterocyclic or aromatic compound containing 4 to 20 atoms, R 2 is an alkyl of 1 to 6 straight or branched carbon atoms and R 3 is an alkyl of 1 to 12 linear or branched carbon atoms, an aromatic or aromatic alkyl moiety having from 6 to 20, substituted with at least one tertiary amine; or R3 is a cyclic or bicyclic portion having from 5 to 20 atoms, wherein at least one nitrogen is included in the ring structure; or R3 and R may be attached to each other to form a ring structure having from 5 to 20 atoms.
The catalyst of claim 2, wherein the compound conferring portions of the aldehyde and a tertiary amine is represented by the formula (R2) 2N-R3-C (O) H wherein R2 is an alkyl of 1 to 6 carbon atoms. linear or branched carbon and R3 is an alkyl of 1 to 12 straight or branched carbon atoms, an aromatic or aromatic alkyl portion that ranges from 6 to 20, substituted with at least one tertiary amine; or R3 is a cyclic or bicyclic portion having from 5 to 20 atoms, wherein at least one nitrogen is included in the ring structure; or R3 and R may be linked to one another to form a ring structure having 5 to 20 atoms. eleven .
The catalyst of claim 1, wherein the compound containing a primary amine is N, N-dimethyl dipropylene triamine, 3,3'-diamino-N-methyl-dipropylamine, 3-aminopropyl-N-methyl-ethanolamine and 3- (dimethylamino) propylamine.
The catalyst of claim 1, which is the reaction product of the steps comprising: (a) a mixture of (i) a compound containing at least a portion of epoxy with (ii) a compound containing a reactive portion of epoxy and a portion of aldehyde or ketone and (b) mixing the product of step (a) with a compound containing at least one primary amine and at least one tertiary amine portion.
The catalyst of claim 12, wherein the reactive portion of epoxy is an alcohol, amine, thiol or carboxylic acid.
The catalyst of claim 12, wherein the compound having an aldehyde portion and a reactive portion of epoxide is an aromatic or polyaromatic compound of 3 to 30 carbon atoms or a ring structure containing a heteroatom, with the provided that when the compound having an aldehyde and epoxide moiety contains a ring structure, the aldehyde moiety binds directly to the ring and the reactive portion of epoxide is directly attached to the ring or attached to the ring via an alkyl of to 6 straight or branched carbon atoms.
15. The catalyst of claim 14, wherein the compound having a reactive portion of epoxide and a portion of aldehyde is salicylaldehyde, vanillin, 5- (hydroxymethyl) -furfural, 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, dihydroxybenzaldehydes, trihydroxybenzaldehydes, 2-carboxybenzaldehyde, 3-carboxybenzaldehyde or a mixture thereof.
16. The catalyst of claim 12, wherein the compound having a functional ketone and epoxide moiety is an aromatic or polyaromatic compound of 3 to 30 carbon atoms or a ring structure containing a heteroatom with the proviso that when the compound having ketone and epoxide portions contains a ring structure, the reactive portion of epoxide is attached directly to the ring or linked via an alkyl of 1 to 6 straight or branched carbon atoms.
The catalyst of claim 13, wherein the compound having a ketone and epoxide functionality is 2'-hydroxyacetophenone, 4'-hydroxyacetophenone, 3'-hydroxyacetophenone, 3-acetyl-1-propanol, 4-h id roxi -3-methyl-2-butanone, 4-hydroxy-4-methyl-2-pentanone, 4'-hydroxivalerophenone, dihydroxyacetophenone, bencyl-4-hydroxyphenyl ketone, acetovainillone, 3'-aminoacetophenone, 4'-aminoacetophenone, aminobenzophenone, acid 4-acetylbenzoic acid, 2-benzoylbenzoic acid or a mixture thereof.
The catalyst of claim 12, wherein the compound containing at least one portion of epoxide is represented by the formula: wherein R 4 is an aromatic, aliphatic, cycloaliphatic or heterocyclic group, substituted or unsubstituted and n has an average value from 1 to 8.
The signaling device of claim 12, wherein in step (a) the mixture also contains a phenol, cresol, bisphenol A, bisphenol F, a polyol novolak, ethylenediamine, 3,3'-diamino-N-methyl-dipropylamine, resorcinol, adipic acid, succinic acid, isophthalic acid, phthalic acid , terephthalic acid, acidic acid, or a combination thereof.
20. The catalyst of claim 12, wherein in step (b) the compound containing primary amine and tertiary amine portions contains two or more primary amines. twenty-one .
The catalyst of claim 1, formed by the reaction of an amine-terminated polyol with a compound containing a tertiary amine portion and an aldehyde or ketone moiety.
22. The catalyst of claim 12, wherein 1 to 50 percent of the epoxy moieties present in step (a) are reacted with a compound containing an epoxy reactive group and a tertiary amine moiety.
23. The catalyst of claim 1, which is the reaction product of an isocyanate with a compound having at least one alcohol or amine moiety and at least one moiety of aldehyde or ketone.
24. A polyol composition containing from 99.9 to 50 weight percent of a polyol compound or polyol mixture having a functionality of 2 to 8 and a hydroxyl number of from 20 to 800 and from 0.1 to 50 percent of a catalyst composition wherein the catalyst has at least one imine bond and at least one tertiary amine group.
The polyol composition of claim 24, wherein the polyol or mixture of polyols has an average hydroxyl number from 20 to 1 00.
26. The polyol composition of claim 25, wherein the catalyst composition is a catalyst. of any one of claims 1 to 23.
27. A process for the production of a polyurethane product by reacting a mixture of: (a) at least one organic polyisocyanate with (b) a polyol composition wherein the polyol has a nominal functionality calculated between 2 and 8 and a hydroxyl number from 20 to 800, and (c) at least one non-fugitive catalyst containing at least one imine bond and at least one tertiary amine group, (d) optionally in the presence of another catalyst and / or blowing agent; and (e) optionally additives or auxiliary agents known per se for the production of foams, elastomers or coatings of polyurethane.
The process of claim 27, wherein the catalyst is present in an amount from 0.1 to 50 weight percent of the total weight of (b) and (c).
29. The process of claim 27, wherein the catalyst is a catalyst of any of claims 1 to 23.
30. The process of claim 29, for producing a flexible polyurethane foam wherein the polyol composition has a number of hydroxyl from 20 to 100 and the blowing agent is water in an amount of 0.2 to 10 weight percent of the polyol.
31 A flexible polyurethane foam made by the process of claim 30.
32. The process of claim 29, for producing a rigid polyurethane foam wherein the polyol composition has an average hydroxyl number from 200 to 1000 and the blowing agent It is water in combination with a hydrocarbon or a hydrocarbon.
33. A rigid polyurethane foam made by the process of claim 32.