WO2001058976A1

WO2001058976A1 - Low emission polyurethane polymers made with autocatalytic polyols

Info

Publication number: WO2001058976A1
Application number: PCT/US2001/003484
Authority: WO
Inventors: Simon Waddington; Jean-Marie L. Sonney; Richard J. Elwell; Francois M. Casati; Antoine Storione
Original assignee: Dow Global Technologies Inc.
Priority date: 2000-02-10
Filing date: 2001-02-02
Publication date: 2001-08-16
Also published as: CN1404492A; DE60134394D1; JP2003522261A; BR0108384B1; BR0108384A; PL357131A1; AR029039A1; CA2399835A1; AU2001234776B2; ZA200206102B; KR20020075405A; ATE398147T1; KR100743734B1; AU3477601A; CA2399835C; TR200201955T2; CN1288185C; MXPA02007758A; EP1268598B1; EP1268598A1

Abstract

The present invention discloses a process for producing a polyurethane product with autocatalytic polyols. These auto-catalytic polyols are based on an initiator of the formula (I): HmA-(CH2)n-N(R)-(CH2)p-AHm where n and p are independently integers from 2 to 6, A at each occurrence is independently oxygen, nitrogen or hydrogen, with the proviso that only one of A can be hydrogen at one time, R is a C1 to C3 alkyl group, m is equal to 0 when A is hydrogen, is 1 when A B is oxygen and is 2 when A is nitrogen; or are polyols which contain an alkyl amine of within the polyol chain or a dialkylylamino group pendant to the polyol chain wherein the polyol chain is obtained by copolymerization of at least one monomer containing an alkyl aziridine or N, N-dialkyl glycidylamine with at least one alkylene oxide. 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

LOW EMISSION POLYURETHANE POLYMERS MADE WITH AUTOCATALYTIC POLYOLS

The present invention pertains to low emission polyurethane polymer products based on autocatalytic polyols and to the process for their manufacture.

BACKGROUND OF THE INVENTION

Polyether polyols based on the polymerization of alkylene oxides, and/or polyester polyols, are the major components of a polyurethane system together with isocyanates. These systems generally contain additional components such as cross-linkers, chain extenders, surfactants, cell regulators, stabilizers, antioxidants, flame retardant additives, eventually fillers, and typically catalysts such as tertiary amines and/or organometallic salts.

Organometallic catalysts, such as lead or mercury salts, can raise environmental issues due to leaching upon aging of the polyurethane products. Others, such as tin salts, are often detrimental to polyurethane aging. 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 odor of the amines and give rise to increased fogging (emission of volatile products) . The presence, or formation, of even traces of tertiary amme catalyst vapors m polyurethane products having vinyl films or polycarbonate sheets exposed thereto can be disadvantageous. Such products commonly appear in automotive interiors as seats, armrests, dashboards or instrument panels, sun visors, door linings, noise insulation parts either under the carpet or m other parts of the car interior or in the engine compartment, as well as m many domestic applications such as shoe soles, cloth mterlmers, appliance, furniture and bedding. While these materials perform excellently in these applications, they possess a deficiency that has been widely recognized. Specifically, the tertiary amme catalysts present in polyurethane foams have been linked to the staining of the vinyl film and degradation of polycarbonate sheets. This PVC staining and polycarbonate decomposition problems are especially prevalent in environments wherein elevated temperatures exist for long periods of time, such as in automobile interiors, which favor emission of amine vapors.

Various solutions to this problem have been proposed. For instance, U.S. Patent 4,517,313 discloses the use of the reaction product of dimethylaminopropyla ine 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 standard triethylenediamine catalysts. However this amine catalyst cannot match the performance of a standard catalyst such as triethylenediamine in polyurethane curing since it is a much weaker catalyst. EP 176,013 discloses the use of specific aminoalkylurea catalysts in the manufacture of polyurethanes . Use of these catalysts is also said to reduce odor and vinyl staining through the use of relatively high molecular weight amine catalysts. Due to their high molecular weight, these amine catalysts are unable to readily migrate through a polyurethane foam and thus their propensity to produce odors and stain vinyl films is reduced. However, when subjected to elevated temperatures as are commonly encountered in automobile interiors parked outside during summer time, these compounds migrate withm a foam to some degree.

Use of amine catalysts which contain a hydrogen isocyanate reactive group such as a hydroxyl or a primary and/or a secondary amine are proposed by catalyst suppliers. One such compound is disclosed in EP 747,407. A reported advantage of the catalyst composition is that they are incorporated into the polyurethane product. However those catalysts usually have to be used at high levels in the polyurethane formulation to compensate for their lack of mobility during the reactions to get normal processing conditions. As a result generally not all of these molecules have time to react with isocyanates and some traces of free amine are typically present in the final product, especially in the case of fast gelling and fast curing systems. Pre-polymerization of reactive amme catalysts with a polyisocyanate and a polyol is reported in PCT WO 94/02525. These isocyanate-modifled amines show comparable or enhanced catalytic activity compared with the corresponding non-modified am e catalysts. However, this process gives handling difficulties such as gel formation and poor storage stability.

Specific crossl kers are proposed U.S. Patent 4,963,399 to produce polyurethane foams that exhibit a reduced tendency to stain vinyl films. These crosslmkers cannot be used at levels sufficient to get the desired catalytic activity, since they negatively affect foam processing, due to too fast gelling, and foam properties such as tear strength and elongation at break are detrimentally affected due to a level of crosslmkmg density which is too high. Such disadvantages would also be present for long chain tertiary ammoalcohol crosslmkers as disclosed m EP 488,219.

Modification of polyols by partial animation has been disclosed in U.S. Patent 3,838,076. While this gives additional reactivity to the polyol, this does not allow adjustment of processing conditions since these ammated functions are rapidly tied in the polymer by reacting with the isocyanate. Hence they give fast initiation of the reactions but subsequently loose most of their catalytic activity and do not provide proper final curing . Use of specific amme- itiated polyols is proposed in EP 539,819 and in U.S. Patent 5,672,636 as applied in semirigid and rigid polyurethane foam applications.

Acid modified polyoxypropyleneamme are used as catalysts m U.S. Patent 5,308,882 but still require the use of an organometallic co-catalyst.

Therefore, there continues to be a need for alternative means to control vinyl staining and polycarbonate decomposition by polyurethane compositions.

There also remains a need to eliminate or reduce the amount of amme catalysts and/or organometallic salts m producing polyurethane products. It is an ob ect of the present invention to produce polyurethane products containing a reduced level of conventional tertiary amme catalysts, a reduced level of reactive amme catalysts or polyurethane products produced in the absence of such amme catalyst. It an another objective of the present mvention to produce polyurethane products containing a reduced level of organometallic catalyst or to produce such products the absence of organometallic catalysts. With the reduction of the amount of amme and/or organometallic catalysts needed or elimination of such catalysts, the disadvantages associated with such catalysts as given above can be minimized or avoided.

It is a further object of the present invention to provide polyols containing autocatalytic activity so that the industrial manufacturing process of the polyurethane product is not adversely affected and may even be improved by the reduction the amount of conventional or reactive amme catalysts or in elimination of the amme catalyst, and/or by reduction or elimination of organometallic catalysts.

In another aspect, the use of the autocatalytic polyols of the present invention could reduce the level of amme catalysts to which workers would be exposed the atmosphere in a manufacturing plant.

SUMMARY OF THE INVENTION

The present invention is a process for the production of a polyurethane product by reaction of a mixture of

(a) at least one organic polyisocyanate with

(b) a polyol composition comprising

(bl) from 0 to 95 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 5 to 100 percent by weight of at least one polyol compound having a functionality of 1 to 8 and a hydroxyl number of from 20 to 800 wherein the weight percent is based on the total amount of polyol component (b) , and (b2) is

(b2a) obtained by alkoxylation of at least one initiator molecule of the formula H_π,A-(CH;)_n-N(R)- (CH₂)_p-AH_m Formula (I) where n and p are independently integers from 2 to 6,

A at each occurrence is independently oxygen, nitrogen or hydrogen, with the proviso that only one of A can be hydrogen at one time, R is a Ci to C₃ alkyl group, m is equal to 0 when A is hydrogen, is 1 when A is oxygen and is 2 when A is nitrogen; or (b2b) a compound which contains an alkyl amine within the polyol chain or a di-alkyl amino group pendant to the polyol chain wherein the polyol chain is obtained by copolymerization of at least one monomer containing an alkylaziridine or N,N-dialkyl glycidylamine with at least one alkylene oxide, wherein the alkyl or di-alkyl moiety of the amine is a Ci to C₃ alkyl; or (b2c) a hydroxyl-tipped prepolymer obtained from the reaction of an excess of (b2a) or (b2b) with a polyisocyanate; or (b2d) is a blend selected from (b2a) , (b2b) or (b2c) ; (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. In another embodiment, the present invention is a process as disclosed above wherein the polyisocyanate (a) contains at least one polyisocyanate that is a reaction product of a excess of polyisocyanate with a polyol as defined by (b2a) or (b2b) above, or a mixture thereof.

In a further embodiment, the present invention is a process as disclosed above where the polyisocyanate contains a polyol-termmated prepolymer obtained by the reaction of an excess of polyol with a polyisocyanate wherem the polyol is a polyol as defined by (b2a) or (b2b) above, or a mixture thereof.

The invention further provides for polyurethane products produced by any of the above processes. In still another embodiment, the present invention is an lsocyanate-termmated prepolymer based on the reaction of a polyol as defined by (b2a), (b2b) or a mixture thereof with an excess of a polyisocyanate.

In yet another embodiment, the present invention is a polyol-termmated prepolymer based on the reaction of a polyisocyanate with an excess of polyol as defined by (b2a) , (b2b) or a mixture thereof.

The polyols containing bonded alkyl amme groups as disclosed m the present invention are catalytically active and accelerate the addition reaction of organic polyisocyanates with polyhydroxyl or polyammo 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 polyols to a polyurethane reaction mixture reduces or eliminates the need to include a conventional tertiary amme catalyst withm the mixture or an organometallic catalyst. Their addition to polyurethane reaction mixtures can also reduce the mold dwell time m the production of molded foams or improve some polyurethane product properties. As the disclosed polyols have an autocatalytic activity, these polyols require less capping with primary hydroxyls, that is, less ethylene oxide capping to obtain the same performance m flexible molded foam (curing time) than conventional polyols when used under the same conditions. Detailed Description

In accordance with the present mvention, a process for the production of polyurethane products is provided, whereby polyurethane products of relatively low odor and emission are produced. Furthermore, the polyurethane products produced in accordance with the invention exhibit a reduced tendency to stain vinyl films or to degrade polycarbonate sheets with which they are exposed, display excellent adhesion properties (m appropriate formulations), have a reduced tendency to produce 'blue haze' which is associated with the use of certain tertiary amme catalysts, are more environmental friendly through the reduction/elimination of organometallic catalysts and these new polyurethane products should be easier to recycle by chemolysis since they possess an inherent basicity. These advantages are achieved by including m the reaction mixture either a polyol containing a tertiary alkyl amme of Formula I as an initiator or a polyol containing an alkyl amme as part of the polyol chain, or a di-alkylammo group pendant to the polyol chain or by including such polyols as feedstock in the preparation of a SAN, PIPA or PHD copolymer polyol and adding them to the reaction mixture or by using such polyols in a prepolymer with a polyisocyanate alone or with an isocyanate and a second polyol.

The combination of polyols used m the present invention will be a combination of (bl) and (b2) as described above. As used herein the term polyols are those materials having 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 ammes, primary or secondary, carboxylic acid, or thiol groups per molecule.

Compounds having at least two hydroxyl groups per molecule are especially preferred due to their desirable reactivity with polyisocyanates .

Suitable polyols (bl) that can be used to produce polyurethane materials with the autocatalytic polyols (b2) of the present invention are well known n the art and include those described herein and any other commercially available polyol and/or SAN, PIPA or PHD copolymer polyols. Such polyols are described in Polyurethane handbook, by G. Oertel, Hanser publishers. Mixtures of one or more polyols and/or one or more copolymer polyols may also be used to produce polyurethane foams according to the present invention.

Representative polyols include polyether polyols, polyester polyols, polyhydroxy-termmated acetal resins, hydroxyl-termmated am es and polyammes. Examples of these and other suitable isocyanate-reactive materials are described more fully in U.S. Patent 4,394,491, the disclosure of which is incorporated herein by reference. Alternative polyols that may be used include polyalkylene carbonate-based polyols and polyphosphate-based polyols. Preferred are polyols prepared by adding an alkylene oxide, such as ethylene oxide, propylene oxide, butylene oxide, or a combination thereof, to an initiator having from 2 to 8 , preferably 2 to 6 active hydrogen atoms. Catalysis for this polymerization can be either anionic or cationic, with catalysts such as KOH, CsOH, boron trifluoπde, or a double cyanide complex (DMC) catalyst such as zinc hexacyanocobaltate .

The polyol or blends thereof employed depends upon the end use of the polyurethane product to be produced. The molecular weight or hydroxyl number of the base polyol may thus be selected so as to result n flexible, semi-flexible, mtegral-s m or rigid foams, RIM, elastomers or coatings, or adhesives when the polymer/polyol produced from the base polyol is converted to a polyurethane product by reaction with an isocyanate, and depending on the end product in the presence or not of a blowing agent. The hydroxyl number and molecular weight of the polyol or polyols employed can vary accordingly over a wide range. In general, the hydroxyl number of the polyols employed may range from about 20 to about 800.

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 rangmg 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 mgKOH/g. As a further refinement, the specific foam application will likewise influence the choice of base polyol. As an example, for molded foam, the hydroxyl number of the base polyol may be on the order of about 20 to about 60 with ethylene oxide (EO) capping, and for slabstock foams the hydroxyl number may be on the order of about 25 to about 75 and is either mixed feed EO/PO (propylene oxide) or is only slightly capped with EO. For elastomer applications, it will generally be desirable to utilize relatively high molecular weight base polyols, from about 2,000 to 8,000, having relatively low hydroxyl numbers, that is, about 20 to about 50.

Typically polyols suitable for preparing rigid polyurethanes include those having an average molecular weight of 100 to 10,000 and preferably 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, active hydrogen atoms per molecule. The polyols used for rigid foams generally have a hydroxyl number of about 200 to about 1,200 and more preferably from about 300 to about 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 (bl) generally have 2 to 8 functional groups, that will react with alkylene oxides. Examples of suitable initiator molecules are water, organic dicarboxylic acids, such as succmic acid, adipic acid, phthalic acid and terephthalic acid and polyhydric, m particular dihydπc to octahydπc alcohols or dialkylene glycols, for example, ethanediol, 1,2- and 1, 3-propanedιol, diethylene glycol, dipropylene glycol, 1, 4-butanedιol, 1,6- hexanediol, glycerol, trimethylolpropane, pentaerythritol, sorbitol and sucrose or blends thereof. Other initiators include compounds linear and cyclic compounds containing a tertiary amme such as ethanoldiamme, tπethanoldiamme, and various isomers of toluene diamine . The autocatalytic polyols (b2) are those initiated with an alkyl amme as given by Formula I or containing an alkyl amme as part of the polyol chain. As part of the polyol chain means that this alkyl amme group can be introduced m the chain by using N-alkylaziπdme or N,N-dιalkyl glycidylamine as a co- monomer with ethylene oxide and/or propylene oxide in the production of an autocatalytic polyether polyol. The term alkyl as used herem with the alkylaziridme or N,N-dιalkyl glycidylamine means a C_x to C₃ alkyl. In a preferred embodiment the alkyl group is methyl. Processes for making such compounds are known in the art.

The properties of the autocatalytic polyols can vary widely as described above for polyol b(l) 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. Selection of a polyol with the appropriate hydroxyl number, level of ethylene oxide, propylene oxide and butylene oxide, functionality and equivalent weight are standard procedures known to those skilled m the art. For example, polyols with a high level of ethylene oxide will be hydrophilic and may be more prone to catalyze the water-isocyanate or urea reaction, while polyols with a high amount of propylene oxide or butylene oxide will be more hydrophobic and will favor the urethane reaction. It is also clear that the type of molecule based on Formula I will also influence the type of catalytic activity. For instance, when A is oxygen the hydrophilicity of (b2) will be higher than when A is nitrogen and/or hydrogen.

The production of polyols containing the compounds of Formula I as an initiator can be done by procedures well known m the art as disclosed for b(l) . In general, a polyol (b2a) is made by the addition of an alkylene oxide (EO, PO, BO or glycidol), or a combination of alkylene oxides to the initiator by anionic or cationic reaction, use of KOH, CsOH, DMC catalyst, or tertiary oxonium salts as described in FR 2,053,045. The addition of the first alkylene oxide moles onto the product of formula I can be done auto-catalytically, that is, without addition of catalyst. Processing conditions such a reactor temperature and pressure, feeding rates are adjusted to optimize production yield. Of particular importance is the polyol unsaturation which is below 0.1 meq/g. For some applications only one alkylene oxide monomer is used, for other applications a blend of monomers is used and some cases a sequential addition of monomers is preferred, such as PO followed by an EO feed, EO followed by PO, etc. Use of glycidol gives polyols with increased functionalities. Other possibilities to get polyols with functionalities higher than the starter molecules is coupling of these starters with a dnsocyanate or use of a diepoxide compound such as ERL 4221 made by Union Carbide.

The polyols of (b2a) and (b2b) include conditions where the polyol is reacted with a polyisocyanate to form a prepolymer and subsequently polyol is adαed to such a prepolymer .

Monols based on the definition of Formula I can also be used m polyurethane systems, either as softening additives or as viscosity reducers .

Polyester polyols can be prepared by the reaction of (b2a) or (b2b) with a diacid. These can be used in combination with conventional polyester polyols as used today m slabstock or in elastomers, such as shoe soles. The limitations described with respect to the characteristics of the polyols b(l) and b(2) above are not intended to be restrictive but are merely illustrative of the large number of possible combinations for the polyol or polyols used. In a preferred embodiment of Formula I, R is methyl.

In another preferred embodiment R is methyl and n and p are integers of the same value. In a more preferred embodiment n and p are an integer of 2 to 4. Preferably when A is not hydrogen, A at each occurrence will be either oxygen or nitrogen. In a more preferred embodiment one A will be oxygen and the other A will be oxygen, and the final polyol (b2a) will be a triol. The alkyl ammes of Formula I are commercially available or can be made by techniques known m the art, such as U.S. Patent 4,605,772, the disclosure of which is incorporated herein by reference. For example, methylamme is reacted with the appropriate alkylene oxide for producing compounds where A is oxygen. Preferably the alkylene oxide is ethylene oxide, propylene oxide, or butylene oxides, which gives a preferred range of 2 to 4 for n when each A is oxygen. Preferred compounds are N-metnyldiethanolamme, N-methyldipropanolamme, N-methyldibutanol-amme, N-methylethanol-propananol-amme

For producing compounds where each A is nitrogen, methyl amme can be reacted with any known reactive group that reacts with an amme and contains an additional nitrogen. For example, 2 moles of X(CH )_nNR'R'' can be reacted with one mole of methylamme where X represents chlorine, bromine or iodine, and R' and R' ' can be H or an alkyl group. Preferred compounds include 3, 3' -diammo-N-methyldipropylamme, 2, 2' -diammo-N- methyldiethylam e, 2 , 3-dιammo-N-methyl-ethyl-propylamιne .

For producing compounds where one A is nitrogen and one A is oxygen, one can use a process such as the one described in JP 09,012,516, the disclosure of which is incorporated herein by reference.

Examples of commercially availaole compounds of Formula I include N-methyldiethanolamme, 3, 3' -diammo-N- methyldipropylam e and N- (2-hydroxyethyl ) -N-methyl-1 , 3- propanediamme .

The weight ratio of (bl) to (b2) will vary depending on the amount of additional catalyst one may desire to add to the reaction mix and to the reaction profile required by the specific application. Generally if a reaction mixture with a base level of catalyst having specified curing time, (b2) is added m an amount so that the curing time is equivalent where the reaction mix contains at least 10 percent by weight less catalyst. 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 over the base level. For some applications, the most preferred level of (b2) addition is where the need for a volatile tertiary or reactive amme catalysts or organometallic salt is eliminated.

Combination of two or more autocatalytic polyols of (b2) type can also be used with satisfactory results a single polyurethane formulation when one wants for instance to adjust blowing and gelling reactions modifying the two polyol structures with different functionalities, equivalent weights, ratio EO/PO etc, and their respective amounts in the formulations.

Acid neutralization of the polyol (b2) can also be considered when for instance delayed action is required. Acids used can be carboxylic acids such as formic or acetic acids, an ammo acid or a non-organic acid such as sulfuric or phosphoric acid. More preferred options are carboxylic acids having hydroxyl functionality as described in U.S. Patent 5,489,618 or carboxylic acids having halofunctionality and optionally hydroxyl functionality or aryloxy substituted carboxylic acids. Polyols pre-reacted with polyisocyanates and polyol (b2) with no free isocyanate 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 a heatmg the polyol (b2) in a reactor and adding slowly the isocyanate under stirring and then adding eventually a second polyol, or by prereactmg a first polyol with a dnsocyanate and then adding polyol (b2) .

The isocyanates which may 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 isocyantes include the 4,4'-, 2,4' and 2,2'-ιsomers of diphenylmethane dnsocyante (MDI), blends thereof and polymeric and monomeπc MDI blends toluene-2,4- and 2 , 6-dιιsocyanates (TDI), m- and p- phenylenednsocyanate, chlorophenylene-2, 4-dιιsocyanate, dιphenylene-4, 4 ' -dnsocyanate, 4,4' -dιιsocyanate-3, 3 ' - dimehtyldiphenyl, 3-methyldιphenyl-methane-4 , 4 ' -dnsocyanate and diphenyletherdnsocyanate and 2 , 4 , 6-trιιsocyanatotoluene and 2,4,4' -tπisocyanatodiphenylether .

Mixtures of isocyanates may be used, such as the commercially available mixtures of 2,4- and 2,6-ιsomers of toluene dnsocyantes . A crude polyisocyanate may also be used in the practice of this mvention, such as crude toluene dnsocyanate obtamed by the phosgenation of a mixture of toluene diamine or the crude diphenylmethane dnsocyanate obtained by the phosgenation of crude methylene diphenylamme . Especially preferred are methylene-bπdged polyphenyl polyisocyanates and mixtures thereof with crude diphenyl methylene dnsocyanates . TDI/MDI blends may also be used. MDI or TDI based prepolymers can also be used, made either with polyol (bl), polyol (b2) or any other polyol as described heretofore. Isocyanate-termmated prepolymers are prepared by reacting an excess of polyisocyanate with polyols, including ammated polyols or lmmes/enamines thereof, or polyamines. Examples of aliphatic polyisocyanates include ethylene dnsocyanate, 1, 6-hexamethylene dnsocyanate, 1,4- tetramethylene dnsocyanate, isophorone dnsocyanate, cyclohexane 1, -dιιsocyanate, 4 , 4 ' -dicyclohexylmethane dnsocyanate, saturated analogues of the above mentioned aromatic isocyanates and mixtures thereof. The preferred polyisocyantes for the production of rigid or semi-rigid foams are polymethylene polyphenylene isocyanates, the 2,2', 2,4' and 4,4' isomers of diphenylmethylene dnsocyanate and mixtures thereof. For the production of flexible foams, the preferred polyisocyanates are the toluene-2,4- and 2 , 6-dιιsocyanates or MDI or combinations of TDI/MDI or prepolymers made therefrom.

Isocyanate tipped prepolymer based on polyol (b2) can also be used m the polyurethane formulation. It is thought that using such an autocatalytic polyol m a polyol isocyanate reaction mixture will reduce/eliminate the presence of unreacted isocyanate monomers. This is especially of interest with volatile isocyanates such as TDI and/or aliphatic isocyanates in coatmg and adhesive applications since it improves handling conditions and workers safety.

For rigid foam, the organic polyisocyanates and the isocyanate reactive compounds are reacted in such amounts that the isocyanate index, defined as the number or equivalents of NCO groups divided by the total number of isocyanate reactive hydrogen atom equivalents 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 m the case of combination polyurethane-polyisocyanurate foams. For flexible foams, this isocyanate index is generally between 50 and 120 and preferably between 75 and 110.

For elastomers, coatmg and adhesives the isocyanate index is generally between 80 and 125, preferably between 100 to 110.

For producing 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 preferably 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 as described m BE 893,705 are also used as blowing agents and polyols such as (b2) are especially effective for this application since these autocatalytic polyols are less sensitive to acidity than conventional amme catalysts which lose most of their catalytic activity when neutralized.

In the production of rigid polyurethane foams, the blowing agent includes water, and mixtures of water with a hydrocarbon, or a fully or partially halogenated aliphatic hydrocarbon. The amount of water is preferably the range of from 2 to 15 parts by weight, more preferably from 2 to 10 parts by weight based on 100 parts of the polyol. With excessive amount of water, the curing rate becomes lower, the blowing process range becomes narrower, the foam density becomes lower, or the moldability becomes worse. The amount of hydrocarbon, the hydrochlorofluorocarbon, or the 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 based on 100 parts by weight 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 most preferably from 1 to 3 parts by total weight of the total polyol composition.

Hydrocarbon blowing agents are volatile Ci to C₅ hydrocarbons. 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, 1,1,1- trifluoroethane (HFC-143a) , 1, 1 , 1, 2-tetrafluoroethane (HFC- 134a), pentafluoroethane, difluoromethane, perfluoroethane, 2,2- difluoropropane, 1 , 1, 1-trifluoropropane, perfluoropropane, dichloropropane, difluoropropane, perfluorobutane, perfluorocyclobutane .

Partially halogenated chlorocarbons and chlorofluorocarbons for use in this invention include methyl chloride, methylene chloride, ethyl chloride, 1,1,1- trichloroethane, 1 , 1-dichloro-l-fluoroethane (FCFC-141b),

1-chloro-l, 1-difluoroethane (HCFC-142b) , 1 , l-dichloro-2, 2 , 2- trifluoroethane (HCHC-123) and 1-chloro-l, 2 , 2, 2- tetrafluoroethane (HCFC-124) .

Fully halogenated chlorofluorocarbons include trichloromonofluoromethane (CFC-11) dichlorodifluoromethane (CFC-12), trichlorotrifluoroethane (CFC-113), 1,1,1- trifluoroethane, pentafluoroethane, dichlorotetrafluoroethane (CFC-114), chloroheptafluoropropane, and dichlorohexafluoropropane . The halocarbon blowing agents may be used in conjunction with low-boiling hydrocarbons such as butane, pentane (including the isomers thereof) , hexane, or cyclohexane or with water. Use of carbon dioxide, either as a gas or as a liquid, as auxiliary blowing agent is especially of interest when water is present with the present technology since polyols (b2) are less sensitive to acidity than conventional ammes. In addition to the foregoing critical components, it is often desirable to employ certain other ingredients m preparing polyurethane polymers. Among these additional ingredients are surfactants, preservatives, flame retardants, colorants, antioxidants, reinforcing agents, stabilizers and fillers.

In making polyurethane foam, it is generally preferred to employ an amount of a surfactant to stabilize the foaming reaction mixture until it cures. Such surfactants advantageously comprise a liquid or solid organosilicone surfactant. Other surfactants include polyethylene glycol ethers of long-chain alcohols, tertiary amme or alkanolamme salts of long-chain alkyl acid sulfate esters, alkyl sulfonic esters and alkyl arylsulfomc acids. Such surfactants are employed in amounts sufficient 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 total polyol (b) are sufficient for this purpose .

Use of (b2) is also of mterest with semi-rigid foams, shock absorbing foams, water dispersible latex, elastomers, integral skin foams, RIM materials, PUR cast systems, paints and coatings, adhesive, binders, all applications described in "Polyurethane Handbook", edited by G. Oertel, Hanser publishers, Munich. For these applications no changes of processing are required when using polyol (b2) of the present invention. Only a reduction or elimination of conventional, migratory catalysts is obtained.

One or more catalysts for the reaction of the polyol (and water, if present) with the polyisocyanate can be used. Any suitable urethane catalyst may be used, including tertiary amme compounds, ammes with isocyanate reactive groups and organometallic compounds. Preferably the reaction is carried out the absence of an amme or an organometallic catalyst or a reduced amount of catalyst as described above. Exemplary tertiary amme compounds include triethylenediamine, N- methylmorphol e, N, N-dimethylcyclohexylamme, pentamethyldiethylenetriamme, tetramethylethylenediamme, bis (dimethylammoethyl ) ether, l-methyl-4-dιmethylammoethyl- piperazme, 3-methoxy-N-dιmethylpropylamme, N-ethylmorpholme, dimethylethanolamme, N-cocomorpholme, N, N-dimethyl-N ' , N ' - dimethyl isopropylpropylenediam e, N, N-dιethyl-3-dιethylammo- propylam e and dimethylbenzylamme . Exemplary organometallic catalysts include organomercury, organolead, organoferπc and organot catalysts, with organotm catalysts being preferred among these. Suitable tin catalysts include stannous chloride, tin salts of carboxylic acids such as dibutylt di-laurate, as well as other organometallic compounds such as are disclosed in U.S. Patent 2,846,408. A catalyst for the trimeπzation of polyisocyanates, resulting in a polyisocyanurate, such as an alkali metal alkoxide or quaternary ammonium carbonylate salts as described in US 4,040,992 and such as Dabco TMR sold by Air Products and Chemicals Inc may also optionally be employed herein. The amount of catalyst can vary from 0.02 to 5 percent m the formulation or organometallic catalysts from 0.001 to 1 percent in the formulation can be used.

A crossl kmg agent or a chain extender may be added, if necessary. The crosslmkmg agent or the chain extender includes low-molecular polyhydric alcohols such as ethylene glycol, diethylene glycol, 1 , 4-butanedιol, and glycerin; low-molecular amme polyol such as diethanolamme and tπethanolamme; polyammes such as ethylene diamine, xlylenediamme, and methylene-bis (o-chloroan line) . The use of such crosslmkmg agents or chain extenders is known in the art as disclosed in U.S. Patents 4,863,979 and 4,963,399 and EP 549,120, the disclosure of which are incorporated herein by reference . When preparing rigid foams 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 flame retardant agents are halogen-substituted phosphates and inorganic flame proofing agents. Common halogen-substituted phosphates are tπcresyl phosphate, tris ( 1, 3-dιchloropropyl phosphate, tris (2 , 3-dιbromopropyl ) phosphate and tetrakis (2- chloroethyl) ethylene diphosphate. Inorganic flame retardants mclude red phosphorous, aluminum oxide hydrate, antimony tπoxide, ammonium sulfate, expandable graphite, urea or melamme cyanurate or mixtures of at least two flame retardants. In general, when present, flame retardants are added at a level of from 5 to 50 parts by weight, preferable from 5 to 25 parts by weight of the flame retardant per 100 parts per weight of the total polyol present.

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 for appliances and refrigerators. Flexible foams and elastomers find use in applications such as furniture, shoe soles, automobile seats, sun visors, steering wheels, armrests, door panels, noise insulation parts and dashboards. Addition of recycled powder foam mto the polyurethane products object of the invention, as disclosed for example m EP 711,221 or in GB 922,306, can also be practiced with the present invention.

Processing for producing polyurethane products are well known in the art. In general components of the polyurethane-formmg reaction mixture may be mixed together m any convenient manner, for example by using any of the mixing equipment described in the prior art for the purpose such as described in Polyurethane Handbook, by G. Oertel, Hanser publisher.

The polyurethane products are either produced continuously or discontinuously, by injection, pouring, spraying, casting, calendering, etc; these are made under free rise or molded conditions, with or without release agents, m- mold coat g, or any inserts or skin put in the mold. In case of flexible foams, those can be mono- or dual-hardness. For producing rigid foams, the known one-shot prepolymer or semi-prepolymer techniques may be used together with conventional mixing methods including impingement mixing. The rigid foam may also be produced in the form of slabstock, moldings, cavity filling, sprayed foam, frothed foam or laminates with other material such as paper, metal, plastics or wood-board. Flexible foams are either free rise and molded while microcellular elastomers are usually molded.

The following examples are given to illustrate the invention and should not be interpreted as limiting anyway. Unless stated otherwise, all parts and percentages are given by weight .

A description of the raw materials used m the examples is as follows:

DEOA 100 % is pure diethanolamme. Niax L3002 is a silicon surfactant available from CK-Witco-Osi Specialties. Tegostab B8715 LF is a silicon-based surfactant available from Goldschmidt AG.

Tegostab B8719 LF is a silicon-based surfactant available from Goldschmidt AG .

Tegostab B8427 is a silicon-based surfactant available from Goldschmidt AG.

Dabco NE-1060 is a reactive amme catalyst available from Air Products and

Chemical Inc.

Dabco 33 LV is a tertiary amme catalyst available from Air Products and

Chemicals Inc.

Dabco DMEA is a tertiary amme catalyst available from Air Products and

Chemicals Inc. Polycat is a tertiary amme catalyst available from Air Products and

Chemicals Inc. Toyocat RX-20 is a reactive amme catalyst available from Tosoh Corporation,

Niax A-l is a tertiary amine catalyst available from CK-Witco-Osi Specialties Inc.

Niax A-4 is a tertiary amme catalyst available from CK-Witco Osi Specialties Inc.

Niax C-182 is a blend of tertiary amme catalysts available from CK-Witco- Osi Specialties Inc.

VORANOL CP 1421 is glycerine initiated polyoxypropylene polyoxyethylene polyol having an average hydroxyl number of 32 available from The Dow Chemical Company,

VORANOL 9815 is a glycerol initiated polyoxypropylene polyoxyethylene polyol having an average hydroxyl number of 28 available from The Dow Chemical Company,

VORANOL CP 6001 is a glycerol initiated polyoxypropylene polyoxyethylene polyol having an average hydroxyl number of 28 available from The Dow Chemical Company,

VORANOL CP 4702 is a glycerol initiated polyoxypropylene polyoxyethylene polyol having an average hydroxyl number of 32 available from The Dow Chemical Company,

VORANOL CP 3001 is a glycerol initiated polyoxypropylene polyoxyethylene polyol having an average hydroxyl number of 56 available from The Dow Chemical Company,

VORANOL EP 2001 is a dipropylene glycol (DPG) initiated polyoxypropylene, polyoxyethylene diol with an average hydroxyl number of 56 available from The Dow Chemical Company,

1, 4-BDO is 1,4-butane diol dried with Baylith L paste, a molecular sieve,

SPECFLEX NC-700 is a 40% SAN based copolymer polyol with an average hydroxyl number of 20 available from The Dow Chemical Company.

VORANOL RH 360 is a high functional polyol with an average hydroxyl number of 360 available from The Dow Chemical Company. ISONATE M-125 is an MDI based isocyanate available from The Dow Chemical Company,

Isonate M-140 is an MDI based isocyanate available from the Dow Chemical Company,

SPECFLEX NS 540 is an MDI-based isocyanate available from The Dow Chemical Company .

VORANATE T-80 is TDI 80/20 available from The Dow Chemical Company,

VORANATE M-229 is a PMDI available from The Dow Chemical Company,

Polyol A is a 1,000 equivalent weight propoxylated diol with 15% EO capping initiated with N-methyl diethanolamme .

Polyol B is a 1,000 EW propoxylated tetrol with 15% EO capping initiated with 3, 3' -diammo-N- methyldipropylamme .

Polyol C is a prepolymer based on an equal molar reaction between polyol A, Isonate M-125 and VORANOL CP 4702. (Polyol A is reacted at 50°C with VORANOL CP 4702 using isocyanate M-125 in a stoichiometric ratio of polyol A, VORANOL CP 4702 and Isonate M-125. The final polymerization is carried out at 75°C for three hours. Polyol C has a viscosity of 28,000 mPa.s at 25°C) .

Polyol D is a prepolymer based on one mole of polyol A reacted with 2 moles of Isonate M-125 and 2 moles of VORANOL CP 3001 (same procedure for this reaction as with polyol C) .

Polyol E is a 1,000 EW propoxylated tetrol with 16% EO capping initiated with Ethylenediamine.

Polyol F is a 1,700 EW propoxylated tetrol With 15 % EO capping, initiated with 3, 3' -Diamino-N-methyl dipropylamine .

Polyol G is a 200 EW propoxylated tetrol initiated with 3, 3' -Diamino-N- methyl dipropylamine.

Isocyanate H is a prepolymer based on one mole of polyol A reacted with 2 moles of Isonate M-125. Isocyanate I is a prepolymer based on one mole of VORANOL EP 2001 reacted with 2 moles of Isonate M-125.

All foams were made in the laboratory by preblending polyols, surfactants, crosslinkers, catalysts and water, then by adding the isocyanates under stirring at 3,000 RPM for 5 seconds. At the end of mixing the reactants are poured either in a cardboard box or in a plastic cup for free rise foaming, or are poured in a 30x30x10 cm aluminum mold heated at 55°C which is subsequently closed. The release agent used is Klueber 41- 2013 available from Klueber Chemie. With free rise foams mam reactivity parameters such as cream time, gel time and full rise time are recorded. In the case of molded parts, curing at a specific demoldmg times is assessed by manually demoldmg the part and looking at hand marking defects until the minimum demoldmg time is reached where there is no surface defects. With both free rise and molded foam, density m kg/m³ is measured since it is a critical parameter.

Elastomers were made by mixing 200 grams of polyols (bl) and (b2) or of polyol (bl) by itself with various amounts of Dabco 33 LV to get different curing times, or of polyol (b2) by itself with a reduced amount of Dabco 33 LV, with 5 parts of 1,4-BDO. These polyols (bl) and or (b2) had been first dried under vacuum over night. Isocyanate M-340 was then added with the amounts indicated in the Examples, and the mixture was stirred carefully with a tongue depressor for 10 seconds . After this mixing, 175 grams of these reactants, when still liquid, were poured in a Teflon™ coated cylinder mold (internal diameter 50 mm; height 100 mm) and a thin thermocouple was inserted the middle of the mold at 75 mm depth to record core temperature of these reactants. The values n the Examples for core temperatures (°C) were measured 10 mmutes after mixing and the physical aspect of the elastomers after 40 mmutes.

Example 1

Free rise flexible foams were made according to formulation 1A and IB based on polyols of the invention. For comparison free rise foams were made according to formulations IC and ID, using either a conventional amme-mitiated polyol or the starter of polyol A as a catalyst at the same concentration as it is present in 100 part by weight of polyol A, both foams are not part of the invention (all formulations are in parts by weight) . Data on the formulations and foam properties are given in Table I .

TABLE I

*Not an example of the present invention

Example 2

Two free rise and two molded flexible PU foams were made with the following formulations 2A and 2B, containing no amine catalysts and catalyzed only with polyols of the invention. As a comparison, two foams were produced with amine catalysts as reported in columns 2C (not part of the invention) For all of these foams the demolding time was 5 minutes. Data on the formulations and foam properties are given in Table II TABLE I I

"Not an example of the present invention.

Example 3

Two free rise and two molded flexible PU foams were made with either isocyanate F, a prepolymer based on polyol A or Isocyanate G (comparative) as reported under formulations 3A and 3B respectively. Data on the foam formulations and foam properties are given n Table III. TABLE III

^cNot an example of the present invention. Example 4

Three free rise foams 4A, 4B and 4C and three identical molded foams were produced using three different combinations of polyol A and polyol B and without having any other catalyst in the formulation. These tests confirm that reactivity profiles can be adjusted just by using blends of autocatalytic polyols without the need for conventional catalysis. Data on the formulations and foam properties is given in Table IV.

TABLE IV

Example 5

The addition of the auto-catalytic polyol to a standard NVH (Noise Vibration and Harshness) formulation improves the adhesion of the foam to the EPDM (Ethylene Propylene Diene Monomer Rubber) , PA (Polyamide) , and EVA (Ethylene Vmyl Acetate) heavy layer as shown by the formulation 5A and 5B. Data on the formulations and foam properties are given m Table V.

TABLE V

*Not an example of the present invention.

A piece of PA backed carpet was attached at the bottom of a 3-L polyethylene bucket using double sided tape.

The foaming mixture was poured the bucket. After 3 minutes, the foam was removed from the bucket. The foam from the formulation 5A showed no adhesion to the heavy layer. The foam prepared from formulation 5B showed a cohesive failure of the foam that left a layer of polyurethane sticking onto the PA sheet . Example 6

Accelerated aging tests under heat were carried out in closed containers the presence of a PVC sheet under the following conditions: a foam sample size 50x50x50 mm (about 6 grams of foam) cut from each of the pads' cores produced with the formulations reported hereafter was placed m the bottom of a one-liter glass jar, then a piece of gray PVC skm reference E6025373AO175A obtained from a Benecke-Kaliko was hung with a Chromium-Nickel alloy based string supported by the rim of the ar which was then sealed. All of the jars were then put m an oven heated at 115°C for 72 hours (3 days) . After cooling the PVC sheet was then measured for color changes using a Minolta Chroma Meter CR 210, which is a compact tristimulus color analyzer for measuring reflective colors of surfaces such as cloth or textured surfaces. The higher the reading and calculation of Delta E, the more colored is the sample after aging compared with the control sample of PVC skm which was aged by itself in a ar not containing any foam. The smaller the reading, the closer is the sample to the control PVC. This simple test measures the effect of the amme vapors coming from the foam on PVC dehydrochlormation and hence change m color and texture. For instance, foam 6A which is catalyzed with conventional tertiary ammes and which is not part of the invention gives a strong blackening of the PVC skm as evidenced by the high Minolta rating of over 20. Data on the formulations and foam properties are given in Table VI .

TABLE VI

Examples 7

Elastomers based on polyols A and F and comparative examples based on conventional polyols (EP 2001 and CP 4702) and Dabco 33 LV as the catalysts and were made using the procedure described above. Results are shown in Table VII.

TABLE VII

*Not part of the present invention

The data confirm that a polyol the invention can replace a conventional tertiary amine catalyst in an elastomer formulation . Examples 8

Rigid foams were made by pre-mixing all components except isocyanate according to the following formulations, at room temperature as follows:

Formulation A B

Voranol RH 360 94.1 89.1

Polyol G 0 5.0

Water 1.8 1.8

Dabco DMEA 1.8 1.6

Polycat 8 0.8 0.6

Tegostab B8427 1.5 1.5

Voranate M-229 125 131

Then Voranate M-229 was added to the formulation and mixed at 3,000 RPM for 6 seconds and this mixture was poured in a 2 liter container and allowed to free rise while cream, gel and tack free times were recorded.

Two rigid foams were produced using the formulations A and B and the procedure described above. Reactivity times are reported in Table VIII.

TABLE VIII

*Not part of the invention

These data confirm that a substitution of 15 percent conventional amine catalysts with 5 parts by weight of polyol G gives a faster reactivity in a rigid foam system. 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

WHAT IS CLAIMED IS

1. A process for the production of a polyurethane product by reaction of a mixture of

(a) at least one organic polyisocyanate with (b) a polyol composition comprising

(b2) from 5 to 100 percent by weight of at least one polyol compound having a functionality of 1 to 8 and a hydroxyl number of from 20 to 800, where the weight percent is based on the total amount of polyol component (b) , and (b2) is

(b2a) obtained by alkoxylation of at least one initiator molecule of the formula

H_mA- (CHι)_r-N(R) - (CH- _p-AH_^ Formula (I) where n and p are independently integers from 2 to 6,

A at each occurrence is independently oxygen, nitrogen or hydrogen, with the proviso that only one of A can be hydrogen at one time,

R is a Ci to C₃ alkyl group, m is equal to 0 when A is hydrogen, is 1 when A is oxygen and is 2 when A is nitrogen; or (b2b) a compound which contains an alkyl amme withm the polyol chain or a dialkylylammo group pendant to the polyol chain wherem the polyol chain is obtamed by copolymeπzation of at least one monomer containing an alkylaziridme or N,N-dιalkyl glycidylamine with at least one alkylene oxide, wherem the alkyl or di-alkyl moiety of the amme is a Ci to CT alkyl; or (b2c) a hydroxyl-tipped prepolymer obtained from the reaction of an excess of (b2a) or (b2b) with a polyisocyanate; or (b2d) is a blend selected from (b2a) , (b2b) or (b2c);

(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 wherem A at each occurrence m Formula I is nitrogen.

3. The process of Claim 2 wherem the compound represented by Formula I is 3, 3' -diammo-N-methyldipropylamine, 3,3' -diammo-N-ethyldipropylamme , 2,2' -diammo-N- methyldiethylamme .

4. The process of Claim 1 wherem A at each occurrence in Formula I is oxygen.

5. The process of Claim 4 wherem the compound represented by Formula I is N-methyldiethanolamme or N- methyldipropanolamme .

6. The process of Claim 1 wherem one A formula I is oxygen and the other A is nitrogen.

7. The process of Claim 6 wherem the compound represented by Formula I is N- (2-hydroxyethyl) -N-methyl-1 , 3- propanediamme, or N- (2-hydroxyethyl) -N-methyl-1 , 2- ethanediamme .

8. The process of Claim 1 wherem (b2b) is derived from an alkylaziridme .

9. The process of Claim 8 wherem the alkylaziridme is methylaziπdme .

10. The process of Claim 1 wherem (b2b) is derived from an N,N-dιalkyl glycidylamine.

11. The process of Claim 10 wherem the N,N-d alkyl glycidylamine is N,N-dιmethyl glycidylamine.

12. The process of any one of Claims 1 to 11 for making a rigid polyurethane foam wherem the polyols (bl) and (b2) have an average functionality of 3 to 6 and an average hydroxyl number of 200 to 800.

13. The process of Claim 12 wnerem the blowing agent is a hydrocarbon, a hydrochlorofluorocarbon, a hydrofluorocarbon a hydrochlorocarbon or a mixture thereof.

14. The process of Claim 13 wherem the blowing agent contains 0.5 to 10 parts by weight water per 100 parts per weight of (b) .

15. The process of Claim 14 where the reaction mixture contains one or more flame retardants.

16. The process of any one of Claims 13 to 15 wherein the polyisocyanate is polymethylene polyphenylene dnsocyanate, or isomers of diphenylmethylene dnsocyanate or mixtures thereof.

17. The process of any one of Claims 1 to 11 for making a flexible polyurethane foam wherem the polyols (bl) and (b2) have an average functionality of 2 to 4 and an average hydroxyl number of 20 to 100.

18. The process of Claim 17 wherem the blowing agent is water m an amount fiom 0.5 to 10 parts by weight of component b.

19. The process of Claim 18 wherem carbon dioxide is used either as a gas or as a liquid the formulation to act as an auxiliary blowing agent.

20. The process of Claim 17 where an acid is used m the polyurethane formulation to act either as a delayed action additive or as a blowing agent m case of carboxylic acids .

21. The process of any one of Claims 17 to 20 wherem the polyisocyanate is toluene dnsocyanate, polymethylene polyphenylene dnsocyanate, isomers of diphenylmethylene dnsocyanate or mixtures thereof.

22. The process of any one of Claims 1 to 11 for producing an elastomer, a coatmg or an adhesive.

23. The process of any one of Claims 1 to 11 for producing a foam containing an integral skin.

24. The process of any one of the preceding Claims wherein the polyisocyanate (a) contains at least one polyisocyanate that is a reaction product of a excess of polyisocyanate with a polyol which contains an alkyl amine group of (b2a) or (b2b) .

25. The process of any one of Claim 1 to 23 wherein the polyol (b) 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 (b2) or is a mixture of (b2) with another polyol.

26. A rigid polyurethane product produced by any one of Claims 1 to 16.

27. A flexible polyurethane product produced by any one of Claims 1 to 11 and 17 to 19.

28. An elastomer, a coating or an adhesive product produced by the process of any one of Claim 1 to 11 or 13.

29. An integral-skin product produced by the process of any one of Claims 1 to 11 or 22.

30. An autocatalytic polyol composition that contains from 5 to 100 percent by weight of a polyol obtained by alkoxylation of at least one initiator molecule of formula

H_mA-(CH₂)_n-N(R) - (CH₂)_p-AH_m Formula (I) where n and p are independently integers from 2 to 6,

A and at each occurrence is independently oxygen, nitrogen or hydrogen, with the proviso that only one of A can be hydrogen at one time, R is a Ci to C₃ alkyl group m is equal to 0 when A is hydrogen, is 1 when A B is oxygen and is 2 when A is nitrogen; with the proviso that the initiator is not N-methyl diethanolamme .

31. A prepolymer formed by reaction of an excess of polyisocyanate with a polyol as defined by (b2a) or (b2b) m Claim 1 or a mixture thereof.

32. A prepolymer formed by reaction of an excess of polyol as defined by (b2a) or (b2b) in Claim 1, or a mixture thereof, with a polyisocyanate.

33. The process of any one of Claims 1 to 21 where the amount of (b2) is present m an amount so that the curing time is substantially equivalent to a similar reaction mixture containing standard polyurethane catalysts, where the reaction mix with b2 contains at least 10 percent by weight less catalyst .