MXPA04003069A - Autocatalytic polyols with gelling characteristics and polyurethane products made therefrom. - Google Patents

Abstract

The present invention discloses a process for producing a polyurethane product with autocatalytic polyols with gelling characteristics. These auto-catalytic polyols are reacted with a polyisocyanate in the presence of other additives and/or auxiliary agents known per se to produce polyurethane products.

Description

AUTOCATALYTIC POLYOLS WITH GELIFICATION CHARACTERISTICS AND POLYURETHANE PRODUCTS MADE OF THEMSELVES The present invention pertains to polyurethane polymer products made from autocatalytic polyols with gelling characteristics and to the process for their manufacture. Polyether polyols based on the polymerization of alkylene oxides, and / or polyester polyols, together with isocyanates are the main components of a polyurethane system. The reaction rate between the polyols and the isocyanates and the level of termination of these reactions with time are a measure of the gelation profile of the polyurethane systems. In case of foams, a blowing agent is usually added and in most cases it is water. The reaction between the isocyanate and the water is referred to as the blowing reaction. Additionally these systems generally contain other 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. The degree of gelation and eventually the blowing speeds of polyurethane systems are highly dependent on the type and level of catalysts used in the process. Organometallic catalysts, such as mercury or lead salts, can cause environmental issues due to leaching in the aging of polyurethane products. Others, such as tin salts, are often harmful 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 the amines and give rise to the increase in haze (emission of volatile products). The presence or formation of uniform traces of vapors of the tertiary amine catalyst in polyurethane products having vinyl films or polycarbonate sheets exposed thereto can be disadvantageous. Such products commonly appear in automotive interiors such as seats, arm rests, dashboards or instrument panels, sun visors, door linings, noise insulation parts either under the carpet or in other parts of the interior of the car or on the engine compartment, as well as in many domestic applications such as shoe soles, clothing, appliances, furniture and bedding. Although these materials are excellently developed in these applications, they have a deficiency that has been widely recognized. Specifically, the tertiary amine catalysts present in polyurethane foams have been linked to the staining of the vinyl film or skin and degradation of the polycarbonate sheets. This PVC staining and polycarbonate decomposition problems are especially prevalent in environments where there are elevated temperatures for long periods of time, such as in the ether. automobiles, which favor the emission of amine vapors. Several solutions to this issue problem have been proposed. For example, U.S. Pat. No. 4,517,313, discloses the use of the reaction product of dimethylaminopropylamine and carbonic acid as a catalyst for use in the manufacture of polyurethane. The use of this catalyst is stated to reduce odor and vinyl staining relative to the use of the triethylene diamine catalyst. Triethylene diamine is considered the standard gelation catalyst for urethane reactions as confirmed by literature from suppliers such as Air Products, from the Urethane Additives 1 20-747 bulletin in Dabco glass (trademark of APCI), while bis (2-dimethylaminoethyl) ) ether is considered as the standard blowing catalyst, as confirmed by the product literature in Niax ™ A-99 (trademark of Crompton Corporation). The amine catalyst described in US 4,51 7, 313, can not match the performance of triethylenediamine in the cure of polyurethane since it is a much weaker catalyst, EP 1 75.01 3 reveals the use of specific aminoalkylurea catalysts in the manufacture of polyurethanes. The use of these catalysts is also to reduce the odor and staining of vinyl through the use of high molecular weight amine catalysts. Due to their high molecular weight, these amine catalysts are not able to migrate easily through a polyurethane foam and thus their propensity to produce odors and stain on vinyl films is reduced. Either way, when subjected to elevated temperatures as commonly found in automobile interiors, these compounds migrate within a foam to some degree. Again, these rtQ products can be compared in the gelation performance with triethylene diamine. The use of amine catalysts which contain an isocyanate hydrogen reactive group such as a hydroxyl or a primary and / or secondary amine is proposed by the catalyst suppliers. Such a compound is disclosed in EP 747, 407. Other types of reactive catalysts are described in US 4, 122,038 and in EP 677,540. Reactive amine catalysts with gelling characteristics are claimed in US 3,448, 065; in US 5, 143,944; in US 5,71 0, 1 91 and in US 5,233,039. A reported advantage of the catalyst composition is that they are incorporated into the polyurethane product. In any case, these catalysts have to be used at higher levels in the polyurethane formulation than conventional fugitive tertiary amines to compensate for their lack of mobility during the reactions and obtain normal processing conditions. Furthermore, once they react with isocyanate during the manufacturing process of the polyurethane, they lose activity and can not sufficiently strongly catalyze the urethane reaction support which is the most important for the gelation of the polyurethane systems. The prepolymerization of amine catalysts reactive with a polyisocyanate and a polyol is reported in PCT WO 94/02525. These isocyanate-modified amines exhibit comparable or enhanced catalytic activity compared to the corresponding unmodified amine catalysts. Either way, these amine-based prepolymers provide handling difficulties such as gel formation and poor storage stability, In US Pat. 4,963,399 specific degradants are proposed to produce polyurethane foams that exhibit a reduced tendency to stain vinyl films. These degradants can not be used at sufficient levels to obtain the desired catalytic activity since they negatively affect foam processing and foam properties due to their degradation effect. Such disadvantages would also occur in light chain tertiary aminoalcohol degraders as disclosed in EP 488,219. The modification of polyols by partial amination has been disclosed in U.S. Pat. 3,838,076. Although this gives additional reactivity to the polyol, this does not allow the adjustment of the processing conditions since these aminated functions are quickly bound in the polymer upon reaction with the isocyanate. Therefore, they will give a rapid initiation of reactions but subsequently lose most of their catalytic activity. The process for the production of tertiary amines exhibiting carbonate and urethane groups, and optionally hydroxyl groups is described in EP 696,580. The use of specific amine initiated polyols is proposed in EP 539,819 and in US 5,476,969 where a "spacer bridge" technology is developed to give more catalytic activity to the amine initiator of the claimed polyols. In any case, there is no mention of the gelling activity of these polyols. A polyol technology initiated by polyamine is described in U.S. Pat. 5, 672, 636 and is applied to rigid and semi-rigid polyurethane productions which are based on highly functional isocyanate. The gelation is mainly provided by the isocyanate. Amine-based polyols are described in WO 01 / 58,976 and mention is made of polyols with gelling and blowing characteristics. However, these are obtained by playing with functionalities, equivalent weights and the ratio between EO (ethylene oxide), and PO (propylene oxide). It is well known that increasing the level of primary hydroxyls of a polyol by adding more EO layer provides improved gelation, but this does not allow a significant reduction in amine and / or organometallic catalysts. Acid-modified polyoxypropyleneamines are used as catalysts in US 5,308,882 but still require the use of an organometallic co-catalyst. Thus, it continues to be a need to control the vinyl or skin staining and the decomposition of polycarbonate by the polyurethane compositions and to improve the aging of the polyurethane by means of the elimination or reduction of the amount of amine catalysts and / or organometallic salts through of the use of autocatalytic polyols with gelling characteristics in the production of polyurethane products. There is also a need to obtain autocatalytic polyols with gelling characteristics for efficient urethane processes. There is also a need for autocatalytic polyols with selected characteristics with blowing when making polyurethane foams. It is an object of the present invention to produce polyurethane products containing a reduced level of tertiary gelation amine catalysts or polyurethane products produced in the absence of such amine catalysts It is another object of the present invention to produce polyurethane products containing a reduced level of organometallic catalyst or producing such products in the absence of organometallic catalysts With the reduction of the amount of organometallic and / or gelling amine catalysts needed or the elimination of such catalysts, the disadvantages associated with such catalysts as those given above can be minimized or avoided. It is a further object of the present invention to provide polyols containing autocatalytic activity with gelling characteristics so that the industrial manufacturing process of the polyurethane product is not adversely affected and can even be improved by the reduction in the amount of amine gelling catalysts. or by the removal of the amine catalysts, and / or by the reduction or elimination of organometallic catalysts. It is a further object of the present invention to provide, in the case of foams, autocatalytic polyols with gelling characteristics which can be used in conjunction with autocatalytic polyols having blowing characteristics in various proportions to adjust the reaction perfumes with or without the addition of small amounts of organometallic and / or amine catalysts. In another aspect, the use of autocatalytic polyols of the present invention could reduce the level of amine catalysts to which workers would be exposed in the atmosphere in a manufacturing plant. * The present invention is a process for the production of a polyurethane product by the reaction of a mixture of (a) at least one organic polyisocyanate with (b) a polyol composition comprising (b 1) from 0 to 99 percent by weight of a polyol compound having a functionality of 2 to 8 and a hydroxyl number of from 20 to 800 and (b2) from 100 to 1 weight percent of at least one autocatalytic polyol with gelling characteristics, having a functionality from 1 to 8 and a hydroxyl number from 15 to 800, wherein the percentage by weight is based on the total amount of the polyol component (b), and (b2), is obtained by alkoxylation of at least one initiator molecule of (b2a), (b2b), (b2c), (b2d), (b2e), (b2f), or (b2g), wherein (b2a) is a compound of formula I (CH2) n-NH- ( CH2) n-NR2 (Formula I) where n in each occurrence is independently an integer from 1 to 12, and R in each occurrence is independently an alkyl group Ci to C3; (b2b) is a compound of Formula I I R '- (CH- (CH2) m-NH) q- (CH2) n -NH- (CH2) s- CH-R' Z-NR2 (Formula II) wherein R and n are as previously defined, R 'in each occurrence is independently hydrogen, a linear or branched C12 alkyl, OH or NH2, m in each occurrence is independently an integer from 0 to 12, q and s are independently integers from 0 to 12, with the proviso that s is less than 3 when q is 0 and R 'is NH2; and Z in each occurrence is independently a direct bond or a straight or branched C1 to C12 alkyl; (2bc) is a compound of formula II I. p (E) -A [(CE2) "- N (E) - (CE2)"] jA- (E) p (Formula III) wherein E in each occurrence is independently hydrogen, linear or branched alkyl, -RNR2 or -ROH; where n in each occurrence is independently an integer from 1 to 12; R in each occurrence is independently a Ci to C3 alkyl group; j is from 1 to 6; A is oxygen or nitrogen, and p is 1 when A is oxygen and 2 when A is nitrogen, with the conditions that n is at least 3 when each A is nitrogen and the molecule contains at least one NR2 group: (b2d) is a compound IV formula.

Formula IV where Z, A, p, are as previously defined, and v in each occurrence is independently an integer from 0 to 6, t is an integer from 2 to 6, f is 1 to 2, and U in each occurrence is independently a linear or branched C1 to C3 alkyl, hydrogen, or NR2 wherein R is as previously defined. (b2e) is a compound W being selected from an aliphatic or cyclic molecule containing an amidine group, a quinuclidine group, a triazaadamantane group, an N-methyl-piperazine group, an imidazole group, a pyridine group or a pyrrolidino group with one or more reactive hydrogens and optionally being substituted with one or more methyl groups, (b2f) is a compound containing W with or without reactive hydrogens as represented in the formula V W - ((CH2) m-AHp) v (Formula V) Where W, A, m, v and p are defined previously, g ^ $ ^ n the condition that when W is a group, the hydroxyl number of (b2) is 48 or less when W is a quinuclidine the hydroxyl number of (b2) is 200 or less; (b2g) is a compound that contains a group W as represented by formula VI. (W- (CH2) m) and - B - (R3 - AHp) e (Formula VI) wherein W, A, m, and p are as previously defined, B is carbon, oxygen or nitrogen, R4 is hydrogen or a straight or branched C1 to C2 alkyl, R3 is straight or branched C ^ to C12 alkyl, and y are 1 and d is 0 when B is oxygen, y and y are 1 and d is 2 when B is carbon, when B is nitrogen e, y and y are 1 o y is 2, d is 0 and is 1; or (b2) is either (b2e), (b2f), or (b2g) formed with a metal salt; or (b2) is (b2h) a prepolymer with hydroxyl tip obtained from the reaction of an ex of (b2a), (b2b), (b2c), (b2d), (b2e), (b2f), or (b2g) with a polyisocyanate; or (b2) is (b2i) a selected mixture of (b2a), (b2b), (b2c), (b2d), (b2e), (b2f), (b2g), or (b2h); (c) optionally in the presence of a blowing agent; and (d) optionally additives or auxiliary agents known per se. -tii I know for the production of polyurethane foams, elastóro íl¾ Jo coatings. In another embodiment the above polyol formulation contains a autocatalytic polyol (b3) wherein the autocatalytic polyol contains at least one N-methyl amino group in the initiator molecule or in the polyol chain and preferably does not contain dimethylamino groups. In another embodiment, the present invention is a pro as disclosed above wherein (b1) and / or (b2) and / or (b3) are copolymer polyols with at least 1 percent and up to 60 percent solids SAN, PIPA or PHD and preferably 10 to 20 percent solids In another embodiment, the present invention is a pro as disclosed above wherein the polyisocyanate (a) contains at least one polyisocyanate which is a reaction product of an ex of polyisocyanate with a polyol as defined by (b2a), a (b2g) above, or a mixture thereof. In an additional mode, the present invention is a process as disclosed above wherein the polyisocyanate contains a polyol-terminated prepolymer obtained by the reaction of an excess of polyol with a polyisocyanate wherein the polyol is a polyol as defined by (b2a) a (b2g) ) above, or a mixture thereof. The invention further provides polyurethane products produced by any of the processes above. In yet another embodiment, the present invention is an isocyanate-terminated prepolymer based on the reaction of a polyol as defined by (b2a) to (b2g), or a mixture thereof, with an exe or a polyisocyanate. In yet another polyol-terminated prepolymer based on the reaction of a polyisocyanate with an excess of polyol as defined by (b2a) to (b2g) or a mixture thereof. The polyols containing linked tertiary amine groups as disclosed in the present invention are catalytically active and accelerate the addition reaction of organic polyisocyanates with polyamino or polyhydroxy compounds and the reaction between the isocyanate and the blowing agent such as water or a carboxylic acid or its salts. They are especially effective in catalyzing the gelation reaction. The addition of these polyols to a polyurethane reaction mixture reduces or eliminates the need to include a tertiary gelation amine catalyst within the mixture or an organometallic catalyst. According to the present invention, there is provided a process for the production of polyurethane products, by means of which polyurethane products of relatively low odor and low emission of amine catalyst are produced. Additionally, the polyurethane products produced according to the invention exhibit a reduced tendency to stain vinyl and skin films or degrade polycarbonate sheets with which they are exposed, exhibit excellent adhesion properties (in appropriate formulations), have a reduced tendency to produce "blue vapor" which is associated with the use of certain tertiary amine catalysts, and are more environmentally friendly through the reduction / elimination of organometallic catalysts. These advantages are achieved by including ¾¾ the reaction mixture either a &; ¾ÉÉjf (b2) in selected concentrations by including a polyol (b2) as a feed stock in the preparation of a polyol of SAN (styrene-acrylonitrile) copolymer, P IPA (poly-polyisocyanate addition) or PHD ( polyarnstoff dispersion) or by adding: (b2) to conventional copolymer polyols or by using (b2) in a prepolymer with a polyisocyanate alone or with an isocyanate and a second polyol which may be optionally (b1) and / or ( b3). The combination of polyols used in the present invention will be a combination of (b1) and (b2) as described above and optionally with polyol optionally (b3). As used herein, the terms "polyol" are those filled or unfilled materials having at least one group containing an active hydrogen atom capable of undergoing reaction with an isocyanate. Preferred 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 per molecule are especially preferred because of their desirable reactivity with polyisocyanates. Suitable polyols (b 1) which can be used to produce polyurethane materials with the autocatalytic polyols (b2) of the present invention are well known in the art and include those described herein and other commercially available polyols and / or SAN, PIPA or PHD copolymer polyols. Such polyols are described in the book Poliu retano, by G. Oertel, Hanser Publishers. Mixtures of one or more polyols and / or urium or more polyols used to produce inventive foams. Representative polyols include polyether polyols, polyester polyols, acetal resins terminated in polyhydroxy, polyamines and hydroxyl-terminated amines. Examples of them and other suitable isocyanate reactive materials are described more fully in U.S. Pat. 4,394,491, the disclosure of which is incorporated herein for reference. Alternate polyols that may be used include polyols based on polyalkylene carbonate and polyols of polyphosphate base. Preferred are polyols prepared by adding an alkylene oxide, such as ethylene oxide (EO), propylene oxide (PO), butylene oxide (BO) or a combination thereof, to an initiator having from 2 to 8, preferably from 2 to 6 active hydrogen atoms. The catalysts for this polymerization can be either anionic or cationic, with catalysts such as KOH, CsOH, boron trifluoride, or a double cyanide complex catalyst (DMC) such as zinc hexacyanocobaltate or phosphazenium. The polyol or the 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 rigid, flexible, semi-flexible, integral to the skin foams, elastomers or coatings, or adhesives when the polymer / polyol produced from the base polyol is converted to a product of polyurethane by reaction with an isocyanate, and depending on the final product in the presence of a blowing agent. The hydroxyl number and weight of the polyol or polyols employed Pwd vary according to the above from a wide range. In generating the hydroxyl number of the polyols employed it can vary from 20 to 800. In the production of a flexible polyurethane sfume 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 2 to 4, and an average hydroxyl number ranging from 20 to 100 mg KOH / g, preferably from 20 to 70 mg OH / g. As an additional refinement, the application of the specific foam will in the same way influence the choice of the base polyol. As an example, for molded foam, the hydroxyl number of the base polyol may be in the order of 20 to 60 with EO layer, and for slab reserve foams, the hydroxyl number may be in the order of 25 to 75 and is either mixed with EO / PO or is only covered with EO. For elastomer applications, it will generally be desirable to use a relatively high molecular weight base, from 2,000 to 8,000, having relatively low hydroxyl numbers, for example, 20 to 50. Polyols typically suitable for preparing rigid polyurethanes include those having a weight molecular average from 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 up to 6, hydrogen active atoms per molecule. The polyols used for rigid foams generally have a hydroxyl number of 200 to 1, 200 and more preferably from 300 to 800. For the production of semi-rigid foams, it is preferred to use a trifunctional polyol with a hydroxyl number of 30 to 80. The initiators for the production of polyols (b1) they generally have 2 to 8 functional groups that will react with the polyol. Examples of suitable initiator molecules are water, organic dicarboxylic acids, such as succinic acid, adipic acid, eftalic acid and terephthalic and polyhydric acid, in particular, 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, pentaerythriol, sorbitol and sucrose or mixtures thereof. Other initiators include linear and cyclic compounds containing a tertiary amine such as ethanoldiamine, triethanoxy diamine, and various isomers of diamine toluene. The autocatalytic polyols having gelling catalytic activity (b2) are those described by (b2a), (b2b), (b2c), (b2d), (b2e), (b2f), (b2g) or (b2h). The polyol (b2b) with gelling characteristics is defined as an autocatalytic polyol which can be substituted by at least 1 0 percent and up to 100 percent of a gelation amine catalyst, such as triethylene diamine, with the formulation maintaining the Same reaction profile. The properties of the autocatalytic polyols can vary widely as described above for the polyol (b1) and such parameters as average molecular weight, hydroxyl number, functionality, etc. , will generally be selected based on the end-use application of the formulation, that is, what type of polyurethane product. The selection of a polyol with the appropriate hydroxyl number, level of EO, PO and / or BO, functionality and equivalent weight for a particular application is known to those skilled in the art. For example, polyols with a high level of EO will be hydrophilic, while polyols with a high amount of PO or BO will be more hydrophobic. The production of the polyols containing the initiators (b2a), (b2b), (b2c), (b2d), (b2e), (b2f), or (b2g) can be made by procedures well known in the art as disclosed by (b1) The addition of the first moles of alkaline oxide in the products of the formula (b2a) to (b2g) can be done autocatalytically, that is, without the addition of catalyst. In general, a polyol (b2) is made by the addition of an alkylene oxide (EO, PO, or BO), or a combination of alkali oxides to the initiator by anionic or cationic reaction, KOH or CsOH or use of a DMC catalyst or BF3 or phosphazenium catalyst as described in EP 897,940. For some applications only one alkylene oxide monomer is used, for other applications a mixture of monomers is used and in some cases a sequential addition of monomers is preferred, such as PO followed by an EO feed, EO followed by a PO etc. Processing conditions such as reactor temperature and pressure, feed rates and catalyst level are adjusted to optimize production and minimize color. Usually, the conditions are selected to produce a polyol with an unsaturation below 1 meq / g.

Optionally the polyol (b2) j is used as a total or partial feedstock for fabrtó j HFolles of copolymer The use of polyols (b2) include conditions wherein the polyol reacts with a polyisocyanate to form a prepolymer and is subsequently added 6¾ > nally polyol to such a prepolymer Thus the polyols can be obtained having a higher functionality than that based on initiators (2ba) - (2bh) For example, a diisocyanate such as 4,4'-diphenylmethane diisocyanate, it can react with an excess of initiator to match it and the initiator-terminated polyisocyanate prepolymer can subsequently react with an alkylene oxide The higher functional compounds can also be prepared by matching the initiators by reaction with a diepoxide compound such as ERL 4221 made by Union Carbide Corporation The use of glycidol also gives polyols with increased functionalities. to polyol start functionality (b2) is to use compounds containing tertiary amine and acetone, to condense with malonate-like compounds and then reduce or transfer for the production of the appropriate initiator. For example, quinuclidinone, 1-methyl-piperidinone, tropinone or (dimethylamino) -acetone can be used with malonitrile or malonate esters to prepare initiators with different functionalities, giving with malonate esters a functionality of 2, with cyanoacetate a functionality of 3 and with malonitrile a functionality of 4. Higher functionalities can be obtained through transesterification / amidation. Similarly, amino alcohols which can be used as polyol initiators can produce cyanide molecules prepared from molecules supporting tertiary mines and ketones or aldehydes. The polyester polyols can be prepared by the reaction of (b2) with diacid. These can be used in combination with conventional polyester polyols as used today in slab stock or in elastomers, such as shoe soles or can be used in combination with polyether polyols (b1) and / or (b3). The polyol (b3) having blowing characteristics is described for example in WO 01/58, 976. More specifically the polyol (b3) is that with blowing characteristics which is defined as a selfcatalytic polyol which can be substituted with at least 10 percent and up to 1 00 percent of a blowing amine catalyst such as bis (2-dimethylaminoethyl) ether while maintaining the same reaction profile. The limitations described with respect to the characteristics of the polyols (b1), (b2), and (b3) above are not intended to be restrictive but are merely illustrative of the large number of possible combinations for the polyol or polyols used. The initiators (b2a) to (b2g) are commercially available or can be prepared by methods known in the art. In one embodiment of Formula I, R is methyl. Preferably n in Formula I is an integer from 2 to 4. In a preferred embodiment, R is methyl and n is an integer from 2 to 4. An example of the commercially available compounds of Formula I is bis (N, N-dimethyl-3-aminopropyl) -amine. - 21 - · * $ t Similarly for the compounds of the preferably methyl and R 'n each fcurrency is hydrogen an alkyl with the same number of carbon atoms. When R 'is an alkyl it is preferably methyl. Z is preferably a direct bond or a Ci alkyl. , and s are preferably whole phtimers from 2 to 6. Preferably q is from 0 to 6. A representative example of formula II is N, N-dimethyl-N'-ethylethylenediamine. For compounds of formula III, in a preferred embodiment A in each occurrence is nitrogen. In another embodiment, at least one of A is oxygen. When A in each occurrence is nitrogen, then n in each occurrence is at least 3. Preferably j is 1 to 3. For appropriate catalytic activity, the initiators of the formula III, contain at least one group -NR2, preferably wherein R is hydrogen. A representative example of Formula III is N, N, 2,2-tetramethyl-1,3-propanediamine. For compounds of formula IV, f for each group of (CHf) is independently 1 or 2 which can be provided for a ring structure with double bonds. For this double bond, it is apparent that f must be 1 for two adjacent groups, ie -CH = CH. Representative examples of formula IV are Cyclen, and 5-amino-1,3-diisopropyl-5-hydroxymethylhexahydropyrimidine. Examples of compounds of (b2e) containing an amidine are disclosed in U.S. Pat. 4,006,124, the disclosure of which is incorporated herein for reference. Examples of compounds W in (b2e) include imidazole, 2,2-bis- (4,5-dimethylimidazole), 2-ethyl 4-methyl imidazole, 2-phenyl imidazole, 1, 5,7-triazabicyclo (4.4.0) dec-5-ene, dicll ^ ^ Ki a, 1, 1, 3,3-tetramil guanidine, 2-amine-pyrimidine and 3-pyrrolidinol. For compounds of Formula V, the value for v will depend on the number of bonds available in the central molecule W. Preferably v is 1 or 2. Representative examples of the formula are 1-amino-4-methyl-p-piperazine; 2,4-diamino-6-hydroxypyrimidine; 2-aminopyrimidine; 1- (3-aminopropyl) -imidazole; 3-quin clidinol; 3-hydroxymethyl quinuclline; 7-amino-1, 3,5-triazadamantane. Preferably R3 and R4 in Formula VI are straight or branched alkyl d to C8. Representative examples of Formula VI include 1-methyl-4- (N-methyl-N- (2-amino-2-methylpropyl) amino] piperidine, and 7- (N- (2-nitroisobutylamino)) - 1, 3 , 5-triazadamantane The polyols (b2f), (b2g) or (b2h) or (b2i) can be complexes with a metal salt A metal salt can be represented generally by the formula MeXfYg where Me, represents a metal valente (f + g), X represents an aliphatic hydrocarbon radical with 1 to 18 carbon atoms, an aliphatic hydrocarbon radical with 6 to 10 carbon atoms, or an araliphatic hydrocarbon radical with 7 to 15 carbon atoms, and represents an aliphatic C2-C18 carboxylate anion with a single negative charge and optionally containing olefinic double bonds and / or alcoholic hydroxyl groups, or a C3-C18 enolate anion carrying a single negative charge f = 0 to 2 g = 0 to 4 with the condition that n + m together = 2 to 4- The weight ratio of (b1) to (b2) will vary depending on the amount of catalyst added. onal and / or the amount of autocatalytic polyol (b3) that one may wish to add to the reaction mixture and the reaction profile required by the specific application. Generally if a mixture of a reaction with a base level of the catalyst having a specific cure time, (b2) is added in an amount such that the cure time is equivalent where the reaction mixture contains at least 10 percent in less catalyst weight. Preferably the addition of (b2) is added to give a reaction mixture containing 20 percent less catalyst than the base level. More preferably the addition of (b2) will reduce the amount of catalyst required by 30 percent above the base level. For some applications, the most preferred addition level (b2) is where the need for volatile reactive or tertiary amine catalysts or organometallic salt is totally eliminated. The combination of two or more autocatalytic gelling polyols of type (b2) and / or autocatalytic blowing polyol types (b3) can also be used with satisfactory results in a single polyurethane formulation when one wants to for example adjust the gelation reactions and blown by varying the ratio between the autocatalytic polyols (b2) and the autocatalytic blowing polyol (b3). The acid neutralization of the polyol (b2) can also be considered when, for example, the delayed action is required. The acids used may be carboxylic acids such as formic, acetic, salicylic, oxalic or acrylic, an amino acid or such as phosphoric or sulfuric acid! The polyols pre-reacted with polyisocyanates and polyol (b2) without isocyanate-free functions can also be used in the polyurethane formulation. Isocyanate prepolymers based on polyol (b2) can be prepared with standard equipment, using conventional methods, such as heating the polyol (b2) in a reactor and slowly adding the isocyanate under agitation and then adding a second polyol, or pre-reacting a first polyol with a diisocyanate and then add the polyol (b2). The isocyanates, which can be used with the autocatalytic polyols of the present invention, include aliphatic isocyanates, arylaliphatic and aromatic cycloaliphatics. Aromatic isocyanates, especially aromatic polyisocyanates, are preferred. Examples of suitable aromatic isocyanates include 4,4'-, 2,4 'and 2,2'-isomers of diphenylmethane diisocyanate (MDI), mixtures thereof and polymeric and monomeric MDI mixtures toluene-2,4- and 2,6-diisocyanates (TDI), m- and p-phenylene diisocyanate , chlorophenylene-2,4-diisocyanate, diphenylene-4,4'-diisocyanate, 4,4'-diisocyanato-3,3'-dimethyldiphenyl, 3-methydephenyl-methane-4,4'-diisocyanate and diphenyletherdiisocyanate and 2, 4 , 6-triisocyanatotoluene and 2,4,4'-triisocyanatodiphenylether. Mixtures of isocyanates can be used, such as the commercially available mixtures of 2,4- and 2,6-isomers of toluene diisocyanates. A crude polyisocyanate may also be crude obtained by the phosgenation of lina diamine dlP mixture or the crude diphenylmethane diisocyanate obtained by the phosgenation of crude methylene diphenylamine. Mixtures of TDI / M D I can also be used. Prepolymers based on M DI or TD I can also be used, made with either polyol (b1), polyol (b2) or any other polyol as described herein. The isocyanate-terminated prepolymers are prepared by reacting an excess of polyisocyanate with polyols, including the amine 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 isocyanates a romatics and mixtures thereof. Preferred polyisocyanates for the production of rigid or semi-rigid foams are polyphenylene polymethylene isolates, 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 thereof. The isocyanate-based prepolymer based on polyol (b2) can also be used in the formulation of polyurethane. It is thought that using such autocatalytic polyol in an isocyanate polyol reaction mixture will reduce / eliminate the presence of If there is an unreacted isocyanate, especially of interest with volatile isocyanates and / or aliphatic isocyanates in adhesive and coating applications as they improve handling conditions and safety of the product. For rigid foam, organic polyisocyanates and isocyanate reactive compounds are fractionated in such quantities as the isocyanate index, defined as the number or equivalents of groups NCO divided by the total number of isocyanate reactive hydrogen atom equivalents multiplied by 1 00, varies 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 the combination of polyurethane-polyisocyanurate foams. For flexible foams, this isocyanate index is generally between 50 and 120 and preferably between 75 and 1 10. For elastomers, coating and adhesives the isocyanate index is generally between 80 and 125, preferably between 100 to 1 1 0. For the production of a polyurethane-based foam, a blowing agent is generally required. In the production of flexible polyurethane foams, water is preferred as a blowing agent. The amount of water is preferred in the range of 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. Carboxylic acids or salts are also used as blowing agents and polyols such as (b2), are especially effective for this application.

In the production of rigid polyurethane eaux, the blowing agent includes water, and mixtures of water with a hydrocarbon, or a halogenated aliphatic hydrocarbon wy or partially. The amount of water is preferred in the range of ¾ |N |) .5 to 15 parts by weight, more preferably from 2 to 10 parts by weight based on 100 parts of the polyol. With an excessive amount of water, the rate of cure 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 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 based on 1 00 parts of the polyol. When water is present as an additional blowing agent, it is generally present in an amount from 0.5 to 10, preferably from 0.8 to 6 and more preferably from 1 to 4 and more preferably from 1 to 3 parts by total weight of the total composition of polyol. The hydrocarbon blowing agents are volatile hydrocarbons Ci to C5. The use of hydrocarbons is known in the art as disclosed in EP 421 269 and EP 695 322, the disclosures of which are incorporated herein by reference. 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, 2-tetrafluoroS no (HFC-1 34a), pentafluoroethane , difluoromethane, perfluoroethane, 2,2-difluoropropane, 1, 1, 1-trifluoropropane, perfluorobutane, chlorofluorocarbons for use in this invention include methyl chloride, methylene chloride, ethyl chloride, 1,1-trichloroethane, 1,1-dichloro-1-fluoroethane (FCFC-141 b), 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). Fully halogenated chlorofluorocarbons include trichloromonofluoromethane (CFC-1) dichlorodifluoromethane (CFC-12), trichlorotrifluoroethane (CFC-13), 1,1-trifluoroethane, pentafluoroethane, dichlorotetrafluoroethane (CFC-14), 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 blowing agent is especially of interest when water is present with the present technology. In addition to the above critical components, it is often desirable to employ other certain ingredients in the preparation of polyurethane polymers. Among these additional ingredients are surfactants, preservatives, flame retardants, dyes, antioxidants, reinforcing agents, stabilizers and fillers.

In making polyurethane foam, it is generally preferred to employ a quantity of a suture to stabilize the foam reaction mixture until it is cured. Such surfactants advantageously comprise a liquid or solid organosilicone surfactant. 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 sufficient amounts to stabilize the foaming reaction mixture against collapse and the formation of large, uneven 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 for the reaction of the polyol (and water, if present) can be used with the polyisocyanate. Any suitable urethane catalyst can be used, including tertiary amine compounds, amines with isocyanate reactive groups and organometallic compounds. Preferably the reaction is carried out in the absence of an amine or an organometallic catalyst or a reduced amount as described above. Exemplary tertiary amine compounds include triethylene diamine, N-methylmorphine, N, N-dimethylcyclohexylamine, pentamethyl ethylenediamine, tetramethylethylenediamine, bis (dimethylaminoethyl) ether, 1-methyl-4-dimethylaminoethyl-piperazine, 3-methoxy-N-dimethylpropylamine, N-ethylmorpholine, dimethylethanolamine, N-co-morpholine, N, N-dimethyl-N'-N '~ dimetH isopropylenediamine, N, N-diethyl-3-diethylamino-propylamine and dimethylbenzylamine. Catalyzed organometallic examples include organomercury, organolead, organophthalmic and as well as other organometallic compounds such as disclosed in U.S. Pat. UU 2,846,408. A catalyst for the trimerization of polyisocyanates, resulting in a polyisocyanurate, such as an alkali metal alkoxide may optionally be employed herein. The amount of amine catalysts can vary from 0.02 to 5 percent in the formulation or organometallic catalysts from 0.001 to 1 percent can be used in the formulation. A degradation agent or chain extender can be added, if necessary. The degradation agent or chain extender includes low molecular polyhydric alcohols such as ethylene glycol, diethylene glycol, 1,4-butanediol, and glycerin, low molecular weight amine polyol such as diethylamine and triethanolamine; polyamines such as ethylene diamine, xylenediamine, and methylene-bis (o-chloroaniline). The use of such degradation agents or chain extenders is known in the art as disclosed in U.S. Pat. UU 4,863,979 and 4,963,399 and EP 549, 1 20, the disclosure of which is incorporated herein by reference. When rigid foams are prepared for use in construction, a flame retardant is generally included as an additive. Any known liquid or solid flame retardant can be used with the autocatalytic polyols of the present invention.

Generally such agents are substituted phosphates flame hhaallóóggeennoo ooff tthhee yy aaggeenntteess aa pprruueebbaa iinnoorrggáánniiccooss ffllaammaa .. FFoossffaattooss ssuussttiittuuiiddooss ooff hhaallóóggeennoo ccoommuunneess ssoonn ffoossffaattoo ttrriiss ,, ((22 ,, 33 - ddiibbrroommoopprrooppiill)) 5 5 rreettaarrddaanntteess ooff tthhee ddiiffoossffaattoo .. hhiiddrraattoo ooff aalluummiinniioo óóxxiiddoo ,, ooff ggrraaffiittoo eexxppaannddiibbllee uurreeaa ,, oo oo mmeellaammiinnaa cciiaannuurraattoo ooff tthhee mmeezzccllaass ppoorr lloo mmeennooss ddooss rreettaarrddaanntteess ooff ffllaammaa ddiiffeerreenntteess .. IInn ggeenneerraall ,, I ,, tthhee ccuuaannddoo eessttáánn pprreesseenntteess rreettaarrddaanntteess ooff aa ffllaammaa ssee aaggrreeggaann uunn nniivveell ddeessddee ooff aa 55 5500 1100 ppaarrtteess eenn ppeessoo ,, pprreeffeerreenntteemmeennttee ddeessddee 55 aa 2255 ppaarrtteess eenn ppeessoo ddeell rreettaarrddaannttee dde ffllaammaa ppoorr 110000 ppaarr tteess eenn ppeessoo ddeell ppoolliiooll ttoottaall pprreesseennttee .. 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 15 for appliances and refrigerators. Flexible foams and elastomers find use in applications such as furniture, shoe soles, car seats, sun visors, steering wheels, arm rests, door panels, noise insulation parts and instrument panels. 0 Processing for the production of polyurethane products are well known in the art. In general, the components of the polyurethane-forming reaction mixture can be mixed together in any convenient manner, for example using any mixing equipment described in the prior art for the purpose as described in Polyurethane Handbook, by G. Oertel , Hanser Publisher.

The products of ^^^ urethane are * produced either continuously or discontinuously, by injection, pouring, spraying, smelting, calendering, etc .; those are made under free molding or rinsing conditions, with or i; * release agents, in mold coating, or any ffering or placement of skin in the mold. In case of flexible foams, those can be of single or dual hardness. To produce rigid foams, the known single-shot prepolymer or semi-prepolymer techniques can be used together with conventional mixing methods including collision mixing. The rigid foam can also be produced in the form of slab reserve, molds, cavity filler, sprayed foam, laminates or foams with other materials such as paper, metal, plastics or wooden boards. Flexible foams are either free-rinsing and molded while microcellular elastomers are usually molded. The following examples are given to illustrate the invention and should not be construed as limiting in any way. Unless stated otherwise, all parts and percentages are given by weight. A description of the raw materials used in the examples is as follows. DEOA LFG 85 percent Is 85 percent diethanolamine in water Tegostab B8715 LF It is a silicone-based surfactant available from Goldschmidt AG.

Dabco DC 5169 Chemicals Inc. Dabco 33 LV in Air Products And Chemicals Inc. Niax A-1 It is a catalyst based on bis (2-dimethylaminoethyl) ether available from Crompton Corp. Polycat 15 It is a catalyst based on bis- (N, N-dimethyl- 3-aminapropyl) amine available from Air Products and Chemicals Inc. VORANOL CP 1421 It is a polyoxyethylene, polyoxypropylene polyol initiated by glycerin having an average hydroxyl number of 32 available from The Dow Chemical Company VORANOL CP 6001 It is a polyoxyethylene, polyoxypropylene polyol initiated by glycerol having an average hydroxyl number of 28 available from The Dow Chemical Company. SPECFLEX NC 632 It is a polyol of polyoxyethylene, polyoxypropylene 1, 700 EW initiated con: with a mixture of glycerol and sorbitol available from The Dow Chemical Company SPECFLEX NC-700 polyol ß - ín 40 percent copolymer | jj flado in SAN with an average hydroxyl number of 20 available from The Dow Chemical Company.

Specflex NE-1 50 is an isocyanate prepolymer based on MDI available from The Dow Chemical Company. VORANATE T-80 It is TDI 80/20 available from The Dow Chemical Cornpany Suprasec 2447 It is an isocyanate MDI available from Huntsman Corporation. Polyol A In a propoxylated monol of 1 000 equivalent weight with 1 5 percent EO initiated with bis (N, N-dimethyl-3-aminopropyl) amine. Polyol A is a polyol with gelling catalytic activity. Polyol B is a propoxylated diol with EW 1, 000 with 15 percent EO coating initiated with N-methyl-diethanolamine. Polyol B is a polyol with catalytic blowing activity.

Polyol C It is an equivalent diol dimethylaminopropylamine. Polyol C polyol with catalytic blowing activity. Propoxylated Polyol D Tetrol of equivalent weight 1, 700 initiated with 3,3'-diamino-N-methyl dipropylamine and covered with 1 5 percent EO. Polyol D is polyol with catalytic blowing activity All foams were made in the laboratory by pre-mixing polyols, surfactants, degradants, catalysts and water, then adding the isocyanates under agitation at 3,000 RPM for 5 seconds. At the end of the mixture, the reagents are poured into an aluminum mold of 30X30X10 cm. heated to 60 ° C which is subsequently closed. The release agent used is Klueber 41 -201 3 available from Klueber Chemie. The curing at specific demold times is evaluated by manual demolding of the part and running an indentation test, first cycle, at 50 percent deflection one minute after demolding (crushing force) and when measuring 50 percent IFD in Newton immediately after the crushing (opening) of all the cells of the part. Hot IFD is a measure of the degree of cure of the foam in the mold. The density of the foam in kg / m3 is measured since it is a critical parameter.

Examples 1 2, 3, v 4 ¾ Molded flexible foams were made according to formulations 1, 2, 3 and 4 based on the polyol of gelation, Polyol A. The comparative foam A was rifo with a blowing Jifftol, Polyol B The foam comparative B was made with poÉÉÉfi which is based on the polyols described in EP 539, 819. The formulations and properties of the foams produced are given in table I. Table I * It is not an example of the present invention. The results show that Polyol A at low levels gives stable foam and can be used to replace conventional gelling catalysts. The ion of only one polyol with catalytic blowing activity gives a collapsed foam. Polyol C does not perform as well as Polyol A since Polyol C requires a much higher level of use. Examples 5-7 The formulations of Examples 5-7 show the production of a foam based on polyol combinations having gelling catalyst activity, Polyo) A, and blown catalytic activity (Polyol B). Comparative C is based solely on a polyol having catalytic blowing activity. The formulations and foam properties are given in Table II. Table II * Comparative, not part of the ijivetion. Examples 5-7 confirm that good, stable foam is obtained with the combination of Polyol A for gelation and a Polyol B for blowing. A foam produced correctly a polyol with collapsed catalytic blowing activity (Comparative C). EXAMPLE 8 A comparison is made between a formulation with Polyol A, against an amine catalyst of conventional fugitive catalysts (comparative F and G), a (comparative E), a polyol with autocatalytic blowing activity (comparative D and E) . The formulations and foam properties are shown in Table II I showing that the comparative foam G was stabilized by the addition of Dabco 33 LV while the foam F with a lower level collapsed. Table III "Comparative examples Hot IFD of example 8 is 260 N while hot IFD of a comparative G is 1 6§? $?, showing G foam catalyzed with triethylene diamine is less cured. These results confirm that Polyol A can replace conventional amine catalysts, including triethylene diamine, with good processing while Folioles B and C give incompletely cured, unstable foams. Examples 9 and 1 0 The foams were made with polyol A at two different levels to confirm their influence on the cure of the foam. These foams were produced together with polyol D, a blowing polyol, based on the teaching of WO 01 / 58,976. Polycat 1 5, the amine used as the initiator for Polyol A was also used for comparative purposes. The formulations and foam properties are given in Table IV. Table IV * Comparative examples.

These results confirm that the gelation of the foaming reaction can be controlled if the level of use of Polycat 15 is injected as the foam was given a strong odor, confirming that all the amines had not reacted with isocyanate in the demoulding. The results also indicate that the foaming mass was very fluid as it was due to the large loss in ventilation holes and the densification of the foam. Polyol D, a blowing polyol, when used alone (comparative H and J) had to be co-catalyzed with a relatively large amount of Dabco 33 LV to give a cured, stable foam. Other embodiments of the invention will be apparent to those skilled in the art from a consideration of this specification or practice of the invention disclosed herein. It is intended that the specification and examples be considered as exemplary only, with the true scope and spirit of the invention being indicated by the following claims.

Claims (10)

1 . A polyurethane by reaction of a mixture of (a) by (b) a pp-bearing composition (b 1) from 0 to 99 weight percent of a polyol compound having a functionality of 2 to 8 and a hydroxyl number from 20 to 800 and (b2) from 100 to 1 weight percent of at least one autocatalytic polyol with gelling characteristics, having a functionality of 1 to 8 and a hydroxyl number of from 15 to 800, wherein the percentage by weight is based on the total amount of the polyol component (b), and (b2), is obtained by alkoxylation of at least one initiator molecule of (b2a), (b2b), (b2c), (b2d), ( b2e), (b2f), or (b2g), wherein (b2a) is a compound of the formula I R2N- (CH2) n -NH- (CH2) n-NR2 (Formula I) wherein n in each occurrence is independently an integer from 1 to 12, and R in each occurrence is independently a Ci to C3 alkyl group; (b2b) is a compound of Formula I I R CH- (CH 2) m-NH) p- (CH 2) n -NH- (CH 2) s- CH-R ' Z-NR2 (Formula II) wherein R and n are as previously defined, R 'in each occurrence is independently hydrogen, a straight or branched C1 to C12 alkyl, OH or NH2, m in each occurrence is independently an integer from 0 to 12, q and s are independently integers from 0 to 12, with the proviso that s is less than 3 when q is 0 and R 'is NH2; Y Z in each occurrence is independently a direct link or an alkyl C1 to C 1 2 linear or branched; (2bc) is a compound of formula II I. p (E) -A [(CE2) nN (E) - (CE2) n] jA- (E) p (Formula III) wherein E in each occurrence is independently hydrogen, straight or branched d-C12 alkyl, -RNR2 or -ROH; where n in each occurrence is independently an integer from 1 to 12; R in each occurrence is independently a Ci to C3 alkyl group; j is from 1 to 6; A is oxygen or nitrogen, and p is 1 when A is oxygen and 2 when A is nitrogen, with the conditions that n is at least 3 when each A is nitrogen and the molecule contains at least one NR2 group: (b2d) is a compound I formulated formula IV. Formula IV wherein Z, A, p, are as previously defined, v in each occurrence is independently an integer from 0 to 6, t is an integer from 2 to 6, and U in each occurrence is independently an alkyl Ci to linear or branched C3, hydrogen, or NR2 where R is as previously defined. (b2e) is a compound W being selected from an aliphatic or cyclic molecule containing an amidine group, a quinuclidine group, a triazaadamantane group, an N-methyl-piperazine group, an imidazole group, a pyridine group or a pyrrolidino group with one or more reactive hydrogens, (b2f) is a compound containing W with or without reactive hydrogens as represented in the formula V W - ((CH2) m-AHp) v (Formula V) wherein W, A, m, v and p are as defined previously, group with the proviso that when W is an imidazole group the hydroxyl number of (b2) is 48 or less when W is a quináclidine the hydroxyl number of (b2) is 200 or less; (b2g) is a compound that contains a group W as represented by formula VI. (W- (CH2) m) and - B - (R3 - AHp) e (Formula VI) R4d wherein W, A, m, and p are as previously defined, B is carbon, oxygen or nitrogen, R4 is hydrogen or a straight or branched Ci to C12 alkyl, R3 is straight or branched C1 to C12 alkyl, e and y are 1 and d is 0 when B is oxygen, eyy is 1 and d is 2 when B is carbon, when B is nitrogen e, and d are 1 oy is 2, d is 0 and is 1; or (b2) is either (b2e), (b2f), or (b2g) formed with a metal salt; or (b2) is (b2h) a prepolymer with hydroxyl tip obtained from the reaction of an excess of (b2a), (b2b), (b2c), (b2d), (b2e), (b2f), or (b2g) with a polyisocyanate; or (b2) is (b2i) a selected mixture of (b2a), (b2b), (b2c), (b2d), (b2e), (b2f), (b2g), or (b2h); (c) optionally in the presence of a blowing agent; and (d) optionally additives or auxiliary agents known per se for the production of polyurethane foams., elastomers and / or coatings. 2. The process of claim 1, characterized in that (b2) contains at least one polyol based on a starter molecule of (b2a) wherein n in each occurrence in Formula 1 is an integer from 2 to 4 and R It is methyl. 3. The process of claim 2, characterized in that the initiator is bis- (N, N-dimethyl-3-amino propyl) -amine. The process of claim 1, characterized in that (b2) contains at least one polyol based on a starter molecule of (b2b) wherein R is methyl and R 'in each occurrence is methyl. 5. The process of claim 4, characterized in that the initiator is N, N-dimethyl-N'-ethylenediamine. The process of claim 1, characterized in that (b2) contains at least one polyol based on a starter molecule of (b2c) wherein j is an integer from 1 to 3. The process of claim 6, characterized because A in each occurrence is nitrogen. 8. The process of claim 6, characterized in that the initiator is N, N, 2,2-tetramethyl-1,3-propanediamine. 9. The process of claim 1, characterized in that (b2) contains at least one polyol based on a (b2d) starter molecule. The process of claim 9, characterized in that the initiator molecule is cyclin or 5-amino-1,3-diisopropyl-5-hydroxymethylhexahydropyrimidine. eleven . The process of claim 1, characterized in that (b2) contains at least one polyp J roasted in a starter molecule of (b2e). The process of claim 1, characterized in that the initiator contains at least one initiator selected from imWazoJa, 2,2-bis- (4,5-dimethylamidazole), 2-ethyl-4-methyl imidazole, 2-phenyl imidazole, 1, 5,7-triazabicyclo (4,4,0) dec-5-ene, dicyandiamide , 1, 1, 3,3-tetrameiii 1 guanidine, 2-amine-pyrimidine or 3-pyrrolidinol. The process of claim 1, characterized in that (b2) contains at least one polyol based on an initiator molecule of (b2f) The process of claim 13, characterized in that v is 1 or 2. 15. The process of claim 13, characterized in that the polyol contains at least one initiator selected from 1-amino-4-methyl-piperazine; 2,4-diamino-6-hydroxypyrimidine; 2-aminopyrimidine; 1- (3-aminopropyl) -imidazole; 3-quinuclidinol; 3-hydroxymethyl quinuclidine; or 7-amino-1, 3,5-triazaadamantane. 16. The process of claim 1, characterized in that (b2) contains at least one polyol based on an initiator molecule of (b2g) The process of claim 16, characterized in that the initiator is 1-methyl-4- [N-methyl-N- (2-amino-2-methylpropyl) amino] piperidine, or 7- (N- (2-nitroisobutylamino )) - 1, 3,5-triazaadamantane. 18. The process of claim 1, characterized in that they have an average functionality of 6 and an average hydroxyl number of 200 to 800. 19. The process of claim 1, characterized in that the polyurethane product is a dispersion. Jjf to flexible and the polyols (b1) and (b2) have an average functionality of 2 to 4 and an average hydroxyl number of 20 to 100. The process of claim 1, characterized in that the polyurethane product is an elastomer , a coating or an adhesive. twenty-one . A polyol produced by alkoxylation of any of the initiators of (b2a) to (b2g) as defined in (b2) in claim 1. 22. A prepolymer with hydroxyl tip obtained from the reaction of an excess of either of (b2a) ) - ((b2g) with a polyisocyanate. The present invention describes a process for producing a polyurethane product with autocatalytic polyols with gelling vehicles. These autocatalytic polyols are reacted with a polyisocyanate in the presence of other metals and / or auxiliary agents known per se to produce polyurethane products.