MXPA97002462A - Amina reagent catalysts for use in polyuretry polymers - Google Patents

Abstract

The present invention relates to the supply of amine / amide catalysts for use in catalyzing the formation of p (C 1 -C 4) olyurethane. These amine / amide catalysts, which have a low fugitivity, due to their reactivity with isocyanates, and good catalytic activity, have the structure: (See Formula) where Q is CnH2n + 1 or (CH2) nN (R3) kT, T is a monovalent (C 1 -C 4) alkyl, amino (C 1 -C 4) alkyl, (C 1 -C 4) -alkylamino (C 1 -C 4) alkyl or (C 1 -C 4) alkyl-amino-alkyl group ( C1-C4) or T is a divalent alkyl group, alkyl substituted with amino, alkylaminoalkyl or alkoxy-alkyl, which forms with the nitrogen atom shown in structure (I) to which T is attached, a cyclic structure, which incorporates up to 6 carbon atoms in the ring, like the nitrogen atom shown in structure (I) 2, this cyclic structure can be substituted with C1 to C4 alkyl. k = 0ó1, where 1 is a monovalent group and 0 if T is a divalent group, R2 = HóCnHzn + 1, R3 CnHzn + 1, R4 = H R5 = HóCH3, n = 2 to 6 and x is = 1 to 4"n" is preferably 2 to 3 and x is preferably 1. Each R3 and T may be the same or different, depending on each value of n and K. Another preferred specific range of structures is that in which Q is CnH2n

Description

AMINA REAGENT CATALYSTS FOR USE IN POLYURETHANE POLYMERS This application claims the priority of the US Provisional Patent Application, No. 60 / 014,843, filed on April 4, 1996. Background of the Invention Certain amine catalysts are known in the polyurethane industry, such as propanamide, N , N-dimethyl-3- [dimethylamino] (DDFA, Structure 1), which is the simplest of a series of catalysts, which do not have reactive functional groups for the formation of polyurethane, described in US Pat. No. 4,011,223 .

A similar, non-reactive analog, which has been found useful as a polyurethane catalyst, is propanamide, 3- [bis (3-dimethylamino] propyl] amino-N, N-dimethyl, as described in the US patent, No. 4,049,591 Additionally, tertiary amine polyurethane catalysts, containing a certain number of hydroxyl and primary / secondary amine, are described in the article Factors Affecting the Discoloration of Vinyl That Has Been Molded Against Urethane Foam, PL Zimmerman and TK Austin, World Congress of Polyurethane 1987, September 29 to October 2, 1987, pages 693-697 However, all these catalysts have deficiencies in their activity in substituted hydroxy cases or with volatility in non-substituted cases. No. 4,384,950 describes the use of a substituted form of DDPA, as a demulsifier, to break oil-in-water emulsions from the recovery of bitumen and tar sands. ia does not describe the use of this compound as a catalyst for urethane systems. The reaction used in the preparation of the substituted compound involves the addition / condensation of methacrylic or acrylic acid with the dimethylaminopropylamine. Methods for the manufacture of this compound are described in the patents of E. U. A., Nos. 4,256,665 and 4,250,259. SUMMARY OF THE INVENTION The present invention provides amine / amide catalysts for use in catalyzing the formation of polyurethane. These amine / amide catalysts have low volatility in the resulting polyurethane (i.e. under fogging) and the reactivity is at least as good as the best reactive component in the system [see Priester, RD, Jr., RD Pefley and RB Turner, High Resiliency Polyurea Foam - An Improved Flexible Foam Matrix, Journal of Cellular Plastics. 30 (2) 1944, pages 147, which is incorporated herein by reference]. These compounds are amine / tertiary amides having base structures similar to DDPA, but contain secondary amine groups to react in the polymer matrix. Unexpectedly, these highly reactive compounds have a catalytic activity that is very close to that of the completely insubstituted catalyst, DDPA. The structure of the tertiary amine / amides of the present invention is: where Q is CnH2n +? or (CH2) nN (R3) kT 't is a divalent cyclic group, by which is meant a group that binds at both ends to nitrogen to form a cyclic group, or T is a monovalent alkyl group, a group aminoalkyl or alkylaminoalkyl, k = 0 or 1, where 1 if T is a monovalent group and 0 if T is a divalent group; R2 = H or CnH2n + l? each occurrence of R3 = CnH2n + ?; R4 = H; R5 = H or CH3, n = 2 to 6; and each occurrence of z = 1 to 4. "n" is preferably 2 or 3 and z is preferably 1. T, when monovalent, may be an alkyl group of one to four carbon atoms, which may have on it one or more amines (for example an amino-C 1 -C 4 alkyl) or in (for example, mono or dialkyl C 1 -C ^ amino-C 1 -Ce-alkyl) T, when it is divalent, it can be alkyl, alkyl substituted by amine, alkylaminoalkyl or alkoxyalkyl, which forms with the nitrogen atom, shown in structure (2), to which T is attached, a cyclic structure incorporating up to 6 carbon atoms in the ring, as well as the nitrogen atom shown in FIG. structure (2) and optionally a second nitrogen atom or an oxygen atom in the ring, for example morpholino, piperazine. These cyclic structures may include C ^ to C? Alkyl substitutions. in the ring. Another aspect of the present invention relates to methods for forming a polyurethane, by combining the polyol and polyisocyanate reagents, in the presence of an effective amount of one or more of a compound of the formula (2), to catalyze the reaction of the reagents. Detailed Description of the Invention A preferred subset of the amine / amides of the present invention is: or more particularly: where R1 = (R3) 2N (CH2) n or C2H2n + ?; R2, R3, R4, R5, T, k, n and z are as defined above, "n" is preferably 2 or 3 and z is preferably 1. Each R + 3 may be the same or different, depending on each value of n and z. A specific preferred range of structures 2A and 2B is that in which R1 is c2 2n + l. Preferred specific compounds are: or) An example of each completed cyclic structure is: These compounds can be manufactured as is known in the amine / amide manufacturing art. In general, the catalyst is prepared from the direct reaction of: dimethylaminopropylamine (DMAPA) or other similar amines, with methyl acrylate (MA), dimethyl acrylamide (DMAA) or similar unsaturated materials. The products of these reactions are substantially the aminopropionamides of the present invention, which contain minor amounts of unreacted raw material and other adducts, such as: Methods for the manufacture of the compounds of the Structure 4 is specifically described in the patents of U. U.A., Nos. 4,256,665 and 4,259,259, which are incorporated herein by reference. These amine / amide catalysts are used for the catalysis of the reaction to form the polyurethane, ie they catalyze the reaction of the isocyanate / water and / or isocyanate / alcohol. These polyurethanes may be rigid, flexible sheet material, ester plate material, molded microcellular elastomers or other types of foams, as are known in the art. The amine / amides of the present invention can be used in previous mixtures of amine, ie mixtures with other amine catalysts, surfactants or other additives or polyurethane components, known in the art. Foam formulations with which the compounds of the present invention can be used as catalysts, generally comprise (a) a polyether or polyol containing an average of more than two hydroxyl groups per molecule; (b) an organic polyisocyanate; (c) at least one catalyst for the production of the polyurethane foam; (d) water; (e) a surfactant, preferably any of the silicone / polyether copolymers known in the art for this purpose; and (f) an inert gas. The polyols have an average number of hydroxyl groups per molecule of at least slightly above 2 and typically from 2.1 to 3.5. In general, the polyol must have an equivalent weight of about 400 to 1500 or even 400 to 3000 grams / equivalent and an ethylene oxide content of less than 20%. Useful polyols include, but are not limited to, polyether polyols, such as alkylene oxide adducts of polyhydroxyalkanes, alkylene oxide adducts of non-reducing sugars and sugar derivatives, alkylene oxide adducts of polyphenols, and alkylene oxide adducts of polyamines and polyhydroxyamines. The alkylene oxides are preferably based on ethylene oxide or propylene oxide. The organic polyisocyanates contain at least two isocyanate groups, for example toluene diisocyanate, and the indicium of the foam is typically 60 to 130. The water generally comprises in the range of 1 to 12 pbw (parts by weight per one hundred parts of polyol). Other additives may be added to the polyurethane foam to impart foam-specific properties, including, but not limited to, color agents, flame retardants and foam additives GEOLITE® Modifier (available from Organ Silicones Group of Witco Corporation, Greenwich, CT). The inert gas is one which is soluble in the foam formulation at elevated pressures, but leaves the solution (i.e. blows) at atmospheric pressure. One example of such gases is C02, but nitrogen, air or other common gases, which include hydrocarbon gases, such as methane and ethane, can also be used. The inert gas may also comprise a volatile organic compound, such as an isomer of pentane or a hydrochlorocarbon with a boiling point above ambient temperature, but having a sufficiently high vapor pressure at room temperature, since its vapor represents a substantial component of the gas in the foam cells . The surfactants of the silicone copolymer should be able to assist in forming a stable foam and should be present in an amount effective to stabilize the polyurethane foam, ie, an amount which is generally 0.05 to 5% by weight of the total reaction mixture, preferably 0.2 to 1.5% by weight. The foam is made by mixing the ingredients (ie, the ingredients (a) to (f)) together, so that the by-product gas generated during the reaction foams the polyurethane. The foam can also be obtained by injecting an inert gas, whereby the reactants are placed under high pressure (ie, at least greater than atmospheric pressure), so that the inert gas is dissolved in the reaction mixture. Then the mixture evaporates, releasing the pressure, which causes the gas to form bubbles at the nucleation sites in the foam system and thus acts as a blowing agent. This produces a reduced density foam. For a more complete description of this process and the required equipment, see European Patent Publication No. 0 645 226 A2, which is incorporated herein by reference. The compounds of the present invention can also be used in non-foam polyurethane reactions, such as the formation of polyurethane elastomers. In such polyurethanes, the water in the formulation is often replaced with a chain extender, which is a compound containing low molecular weight active hydrogen (>400), which contains a compound with at least two reactive groups. Examples are 1,4-butanediol, ethylene glycol, diethylene glycol and ethylene diamine. The conditions and formulations of these reactions are shown in the art, for example in the Polyurethane Handbook, 2 Ed. Gunter Ortel, Ed., Hanser Publishiers, Cincinnati, 1994, which is incorporated herein by reference. In general, these catalysts are used in a catalytically effective amount, ie in an amount to effectively catalyze the reaction and form the polyurethane. In general, this effective amount is about 0.02-5.0 parts per hundred parts of the polyol in the reaction formulation. In flexible molded foam, which is described in the following examples, these catalysts produce a cream and slightly faster exit times than for the DDPA and the loading properties (ILD) and curing characteristics of the foams, were at least as good as for the DDPA.

EXAMPLES Glossary: pep Parts of the product per 100 pairs of polyol in the formulation Polyol 1 A polyether of ethylene / oxide or propylene oxide, sold by ARCO Chemical as ARCOL Poiyol E-656 Polyol 2: A polyether of ethylene oxide / oxide of propylene, sold by ARCO Chemical as ARCOL Poiyol E-698. Polyol 3: A polyether of propylene oxide, sold by Dow Chemical as VORANOL 490. Polyol 4: A polyether of propylene oxide, sold by Dow Chemical as VORANOL 800. Polyol 5: A polyester polyol, sold by Stepan Chemical as PS-3152. Polyol 6: A polyester polyol, sold by Witco as FOMREZ 53. Silicone 1: A silicone surfactant sold by Witco as NIAX Surfactant L-3001. Silicone 2: A silicone surfactant, sold by Witco as NIAX Surfactant Y-10829. Silicone 3: A silicone surfactant sold by Witco as NIAX Surfactant 1-6900.

Silicone 4: A silicone surfactant, sold by Witco as L-532. Surfactant 1: An organic surfactant sold by Union Carbide Corp. as NP-9. Catalyst 1: An amine catalyst, brought by Witco as NIAX Catalyst A-1. Catalyst 2: An amine catalyst, sold by Witco as NIAX Catalyst A-33. Catalyst 3: An amine catalyst, sold by Witco as MIAX Catalyst A-99. Isocyanate 1: A variant of diphenylethylene diisocyanate (MDI), sold by Dow Chemical as ISONATE 143. L. Isocyanate 2: The standard commercial mixture of 80% 2,4- and 20% 2,6-toluene. diisocyanate Isocyanate 3: A variant of MDI, sold commercially by Dow Chemical as PAPI 27. IFD: Foam load values, as determined by ASTM D-3574, Test Bl.

General Synthesis: Uncatalyzed reaction of certain tertiary amines containing primary amine, with acrylates or methacrylates The synthesis of the following tertiary amine / amides was conducted in a 500 ml round bottom flask. The flask is equipped with a pressure equalizing addition funnel, mechanical stirrer, nitrogen purge, thermometer and heating mantle. Any one mole of the amine of interest or one mole of MA and two moles of amine were used. If the amine is primary, it was charged into the flask and the DMAA or MA was loaded into the addition funnel. If the amine is not primary, the order was reversed (ie, the amine was placed in the addition funnel and the DMAA or MA in the flask). Specific details of the reactions are shown below. Example 1 - Synthesis of the Amines / Amides of the Present Invention Propanamide. 3- [3-dimethylaminopropylamino-N.N-dimethyl] - One mole of DMPA (dimethylaminopropylamine, 102.21 g) was charged to the flask. The system was purged with nitrogen for several minutes. The DMAA was added (6 ml / min) to the flask, while the mixture was stirred and the temperature monitored. The initial temperature was 24se and did not change during the addition. Once the addition of the DMAA was complete, the flask was heated to 100dC and held for two hours, with agitation. Structure # 3 above was obtained with a conversion greater than 90%. Propanamide 3 [3-dimethylaminopropyl) amino-Nf 3-dimethylamino-propylol - The synthesis of the MA / MAP version of the amine was conducted by the above procedure, using two moles of DMAPA (204.42 g) and one mole of the MA (80.10). g). During the addition of the MA, the temperature increased from the initial temperature of 24dC to the final temperature of 75SC. The temperature was maintained at 752C for two hours. The sample was then separated on a rotary evaporator for four hours at 70 ° C, 5 mm Hg, to remove the methanol. Structure # 4 above was obtained with a conversion of more than 92%. Propanamide 3- [3-dimethylaminopropyl] amino-N- [3-dimethylaminopropyl] 2-methyl - The synthesis of methyl methacrylate (MMA) / DMPA, version of the amine, was conducted by the aforementioned procedure, using two moles of the DMPA (204.42 g) and one mole of MMA (86.10 g). During the addition of the MMA, the temperature did not change from the initial temperature of 24 sec. The temperature was increased to -1220 ° C for a total of twenty-four hours. The sample was separated on a rotary evaporator for two hours, at 70 ° C, 5 mm Hg, to remove the methanol. The following structure was obtained with a conversion of approximately 80%: Example 2 - Synthesis of Comparative Catalysts Propanamide, 3- [dimethyl] amino-N, N-dimethyl, was obtained starting from the DMAA (one mole) which was added to a stirred reactor, under nitrogen. Dimethylamine (one mole) was added at a rate to keep the reactor temperature at less than 35dc. When all the dimethylamine was added, the reactor was maintained between 35 and 45dC for about two hours. After that time, the temperature was increased to 60dC for 5 more hours. After cooling to 25 C, the reaction was complete and the product was analyzed. The analysis confirmed the anticipated structure of the DDPA at a conversion of more than 99%. Similarly, propanamide, 3- [3-methyl-3-hydroxyethyl] amino-N, N-dimethyl (9) was obtained from DMAA and MEOA (N-methylethanolamine).

Additionally, propanamide, 3- [bis (2-hydroxyethyl) amino] -N, N-dimethyl (10) was obtained from DMAA and DEOA (diethanolamine).

Propanamide, 3- [3-methyl-3-hydroxyethyl] amino-N-methyl-N-hydroxyethyl (11) was obtained from MA and MEOA.

Propanamide, 3- [bis (2-hydroxyethyl) amino] -N, N- [bis (2-hydroxyethyl)] (12), was obtained from MA and DEOA.

Example 3 - Evaluation of a Single Urethane Foam, Blown with Water. Each of the reactive DDPA catalysts were evaluated in terms of their blowing and gel capabilities relative to DDPA. To obtain the blowing capabilities of a simple system of 97.22 pep (0.049 eq.) Of Polyol 1, 1.79 pep (0.195 eq.) Of water, 1 pb of surfactant 1 and isocyanate 1 of index 103, were used. A total of 50 grams of the previously obtained polyol mixture, water and surfactant, obtained previously, were loaded into a half-liter lined paper cup. The catalysts were evaluated by adding 0.25 g (0.5 pb) or 0.5 g (1.0 pb) to this mixture. The isocyanate was added and the mixture was stirred in a drill press for 5 seconds. Blowing capacities were determined by measuring the top of the cup and the blow and exhaust times, compared to the DDPA. The data are presented in Table 1.

Table 1 - Examples of Water Blowing Foams a The time of the upper part of the cup represents the time (seconds) in which the rise of the foam reached the height of the cup. b The Krel DDPA value represents the relative activity of the catalyst and was obtained by dividing the time of the upper part of the cup for the amine-amide by the time of the upper part of the cup for the DDPA at a given use level. For Operation 3, 157 seconds 168 seconds = 0.9 = KREED DDPA at 0.5 pcp. c The blowing time represents the time (seconds) in which the gases visibly escape from the foam.

Table 1 shows this comparison in a simple urethane foam formulation of water blowing. Each catalyst was evaluated at levels of 0.5 and 1.0 pbw and the times of elevation (top of the cup) and blowing and exhaust were noted. It is clear that the candidates are broken down into two families, those with activities reasonably close to the DDPA of control (Operations 2-6) and those with a significantly poorer activity (Operations 7-14). The foams of Operations 3-6 contain the above-mentioned preferred catalysts (Structures 3 and 4), while Operations 7-14 were catalyzed with poorer-performing hydroxyl candidates (Structures 9-12). The difference in overall performance is significant, suggesting a unique catalytic behavior of the preferred structures. Example 4 - Evaluation in a Urethane Elastomer A similar experiment was used to evaluate the gel capacities of the reactive DDPA catalysts with respect to DDPA. The resin mixture consisted of 94 pep (0.047 eq.) Of Polyol 1 and 6 pep (0.193 eq.) Of ethylene glycol. Isocyanate 1 was used in the index 103. A total of 100 grams of the resin mixture was loaded into a half-liter sized paper lined cup. The isocyanate was added and stirred by hand. The catalysts were evaluated at 3 pcp. The gel capacities were determined by measuring the gel time (point at which the mixture was too viscous to be stirred by hand) and the tack release time, as compared to DDPA. The data are presented in table 2. Table 2 - Examples of urethane elastomer All catalysts were evaluated in 3.0 parts. Amine equivalents based on the tertiary amine content @ 3.0 use level part The gel time represents the time at which the mixture is too viscous to be stirred by hand The Krel DDPA value represents the relative activity of the corresponding catalyst in comparison with the DDPA (gel time of the amine-amide of interest DDPA gel time). The tack-free time represents the time in which the mixture is free from stickiness to the touch.

Operations 2 and 3 confirmed that the Structures 3 and 4 have activities reasonably close to those of the DDPA, while all the other candidates are much slower. This significant difference in the elastomer system confirms the unique catalytic character of these compounds and the wide range of their utility.

Example 5 - Evaluation in a Molded Flexible Foam Formulation The catalysts were then evaluated in a molded flexible foam formulation. The control formulation contained 80 pep of Polyol 1, 20 pep of Polyol 2, 1.2 pep of Silicone 2, 1.5 pep of DEOA, 3.56 pep of water, 0.23 pep of Catalyst 2, 0.14 pep of Catalyst 1 and 0.25 pep of the " DDPA mixture "(see table 3). Isocyanate 2 was used at an index of 100. The reactive DDPA catalysts were mixed exactly as the "DDPA mixture", replacing this DDPA with each catalyst to be evaluated. The new mixtures were used in place of the "DDPA mixture" in equal parts in the formulation. The mixture was mixed (drilling press) for 55 seconds, the isocyanate was added and mixed for another 5 seconds after the addition of the isocyanate. The foams were made in an aluminum mold with ventilations of 1.5875 mm. The temperature of the mold was 65.5ßc (heating with warm water) with a demolding time of 3.5 minutes. The foams were compared by measuring the cream and exit times, 50% or 75% of the ILD values and the response to healing. The data are presented in Table 3.

Table 3 - Comparison of the Catalyst in a Molded Foam • Flexible to E! Exit time represents the time at which this first amount of foam was visible in the mold vents. b ILD indicates notch load deviation. c The indicated amine-amide catalyst, 33.5% / TERGITOL 15-S-7, surfactant (Union Carbide Corp), 66.5%. Indian nm that this value was not measured. MB = Very Good The performance of the preferred catalysts is given in Operations 2-5. These catalysts produced slightly higher cream and exit times than those for the DDPA control mixture and the loading properties (ILD) and cure characteristics of the foams were at least as good as the control. This is additional evidence that the typical catalytic activity of these tertiary amide / amide compounds is very close to that of DDPA. The performance of hydroxyl-containing candidates is shown in Operations 6-13. While, like the DDPA, they tend to give somewhat longer times of exit, (that is, they are slower to react) and lower loading properties. Example 6 - Confirmation of amine / amide reactivity with isocyanate Structure 4 (0.315 g, 0.00265 mol) was added to a small reactor, followed by phenyl isocyanate (0.684, 0.00265 mol). Immediately upon mixing, there was a significant exothermic reaction and a marked increase in the viscosity of the mixture, suggesting a rapid reaction. After about three minutes, a sample of the mixture was taken, which confirmed that all the phenyl isocyanate had been consumed. This result confirmed that the compounds react easily with the isocyanate, supporting the concept that they will react in the foam and will not be volatile.

Example 7 - Evaluation in the Formulation of Rigid Foam The catalyst was evaluated in a rigid foam formulation containing 60 pep of Polyol 3, 15 pep of Polyol 4, 25 pep of Polyol 5, 2 pep of Silicone 3, 1.0 pep of water, 36 pep of HCFC-141b, a blowing agent. Isocyanate 3 was used at an index of 120. Structure 4 was used as the catalyst for the evaluation. All the components, except the isocyanate, were previously mixed in a half-liter sized paper lined cup. The mixture was mixed (drilling press) for 10 seconds, the isocyanate was added and mixed for another 3 seconds. This mixture was then transferred to a lined paper cube and the cream, cord and gel and final lift times were measured. The data shown in Table 4 demonstrate that the catalyst 4 of the present invention supplies a good rigid foam.

Table 4 - Evaluation of the Catalyst in Rigid Foam Example 8 - Evaluation in the Polyester Foam Formulation Structure 5 was also evaluated in a polyester foam formulation. Two foams were obtained: a control and a foam using Structure 4, as a replacement for DDPA at the same amine equivalents. The formulations are listed in the following Table 5. The TDI was added to the polyol and the mixture was mixed by hand until it was clear. Then the polyol / TDI mixture was mixed at 1000 rpm for 8 seconds. The pre-mix of water, amine and surfactant was added with a syringe and mixing was continued for 7 seconds. The mixture was then emptied immediately in a cardboard box (20 x 20x 20 cm.) And the cream and blow times were monitored along with the elevation profile. The foam cream control times and the experimental foam were 13 seconds each. The blowing times for the two foams were 119 seconds and 121 seconds, respectively. No differences were observed in the two foams.

Table 5 - Evaluation of the Catalyst in the Formulation of Polyester Foam Example 9 - Verification of Non Volatility Volatility studies were also conducted in a series of polyester foams, using each of the following catalysts: N-ethyl-morpholine, N-methyl-morpholine, N, N, -dimethyl-benzylamine , n-hexadecyldimethylamine and Structure 4. The following formulations were used: Polyol 6, water, Silicone 4, Surfactant 1, Isocyanate 2 with an index of 103. Each of the catalysts was evaluated at the level of use required to give a blowing time of 41 seconds. The polyol was loaded in a paper cup of 944 cc. The TDI was added to the polyol and the mixture was mixed by hand until clarity. Next, the polyol / TDI mixture was mixed at 100 rpm for 8 seconds. Pre-mixing of water, amine, and surfactant was added with a syringe and mixing was continued for 7 seconds. This mixture was then emptied immediately into a paper cube and the times of the upper part of the cup were recorded. Then, samples of approximately 0.2 grams of each foam were taken from the center of the sample, cut from 5.08 cm. from the bottom of the cube. These samples were placed in glass jars and sealed and analyzed in a DB-1 column (30 m x 0.32 mm) using a Varian 3760 Gas Chromatogram, equipped with a Per in-Elmer HS-40 Headspace Autosampler device. The data is shown below.

TABLE 6 Volatility Data a pep required to give a top cup time of 41 seconds b Less than the detection limit (<1, 000,000) The above data confirm that Structure 4 has an undetectable volatility. Thus, we anticipate that Structure 4 will not be volatile in foam applications.

Claims (19)

1. CLAIMS 1. An amine / amide, of structure (1): wherein: T is a monovalent (Ci-C4) alkyl, aminoalkyl (C? -C4), mono (C? -C4) amino-alkyl (C? -C4) or dialkyl (C? ~ C4) amino group -alkyl (C1-C4), or T is a divalent alkyl group, alkyl substituted by amine, alkylaminoalkyl or alkoxyalkyl, which form with nitrogen, shown in structure (1), to which T is attached, a cyclic structure, which incorporates up to 6 carbon atoms in the ring, like the nitrogen atom shown in structure (1), this cyclic structure can be substituted with (C 1 -C 4) alkyl; = 0 or 1, where 1 is T if it is a monovalent group and 9 if T is a divalent group; R2 = H, or C2H2n + i? each occurrence of R3 = c2H2n + ?. R4 = H; R3 = H or CH3; n = 2 to 6; and each occurrence of z = 1 to 4.
2. 2. An amine / amide, according to claim 1, of the structure:
3. 3. An amine / amide, according to claim 2, wherein R1 is methyl.
4. 4. An amine / amide, according to claim 3, wherein R3 is methyl.
5. 5. An amine / amide, according to claim 2, wherein R3 is methyl
6. 6. An amine / amide, according to claim 3, of the structure:
7. 7. An amine / amide, according to claim 3, wherein n is 2 or 3 and z is l.
8. 8. In the formation of the polyurethane, in which a reaction mixture comprises a polyol component, and a polyisocyanate component is formed and reacted in the presence of an effective amount of a catalyst for the reaction, the improvement in that the reaction mixture also comprises an amine / amide of the structure: where Q is C2H2n +? or (CH2) nN (R3) kT; T is a monovalent (C1-C4) alkyl, amino (C1-C4) alkyl, monoalkyl (^ -04) amino-alkyl (^ -04) or dialkyl (C1-C4) amino-alkyl (C? -C4) group ), or T is a divalent alkyl group, alkyl substituted by amine, alkylaminoalkyl or alkoxyalkyl, which form with nitrogen, shown in structure (1), to which T is attached, a cyclic structure, which incorporates up to 6 carbon atoms. carbon in the ring, like the nitrogen atom shown in structure (1), this cyclic structure can be substituted with (C 1 -C 4) alkyl; k = 0 or 1, where 1 is T if it is a monovalent group and 9 if T is a divalent group; R2 = H, or C2H2n + ?; each occurrence of R3 = C2H2n + i; R4 = H; R3 = H or CH3; n = 2 to 6; and each occurrence of z = 1 to 4.
9. 9. A process, according to claim 8, wherein Q is R1, where R1 is C2H2n +? .
10. 10 # A process, according to claim 8, wherein n is 2 or 3, and z is l.
11. 11. A process, according to claim 10, wherein R * l is methyl.
12. 12. A process, according to claim 8, wherein R3 is methyl.
13. 13. A process, according to claim 8, wherein R4 is hydrogen.
14. 14. A process, according to claim 8, wherein the amine / amide is of the structure:
15. 15. A process, according to claim 8, in which the formed polyurethane is an elastomer.
16. 16. A process, according to claim 8, wherein the formed polyurethane is a polyurethane foam.
17. 17. A process, according to claim 16, wherein the foam is a molded flexible foam.
18. 18. A process, according to claim 16, wherein the foam is a rigid foam.
19. 19. A process, according to claim 8, wherein the amine / amide is present in 0.02 to 5 parts per hundred parts of polyol. SUMMARY OF THE INVENTION The present invention provides amine / amide catalysts for use in catalyzing the formation of p (C? ~ C4) polyurethane. These amine / amide catalysts, which have a low volatility, due to their reactivity with isocyanates, and good catalytic activity, have the structure: where Q is CnH2n +? ° (CH2) nN (R3) t »t is a monovalent (C1-C4) alkyl, amino-alkyl (^ -04), mono (C? -C4) -amino-(C1-C4) alkyl or dialkyl (C-C4) alkyl group ^ -04) -amino-alkyl (C? -C4) or T is a divalent alkyl group, alkyl substituted with amino, alkylaminoalkyl or alkoxyalkyl, which forms with the nitrogen atom shown in structure (I) to which it is attached T, a cyclic structure, which incorporates up to 6 carbon atoms in the ring, like the nitrogen atom shown in structure (I) 2, this cyclic structure can be substituted with C ^ to C4 alkyl. k = 0 or 1, where 1 is if T is a monovalent group and 0 if T is a divalent group. R2 = H or CnH2n + i »R3 = cnH2n + l, R4 = H R5 = H or CH3, n = 2 to 6 and x is = the 4." n "is preferably 2 to 3 and x is preferably 1. Each R3 and T can be the same or different, depending on the value of n and k. Another preferred specific range of structures is that in which Q is CnH n + ?.