MXPA98005496A - Catalysts of organoestaño sulfonato and its manufacturer - Google Patents

Abstract

The present invention relates to: A strong organic acid-based polyesternoxane salt having multiple catalytic activity, comprising compound of the formula: wherein each R is independently selected from the group consisting of C 1 -C 20 alkyl, aryl and aralkyl; each R1 is independently selected from the group consisting of OR, OH, OOCR, halogen and a strong organic acid derivative having a pKa of less than 1 when at least one selection for R¹es OSO "R, with each R²that is independently selected from the same group as R and R¹; n is an integer that has an average value from 0 to "0; and, X is from 0 to infinity when the catalyst is a water solution

Description

CATALYZED RES OF S ORGANISTA NON-TESTING AND ITS HAND MANUFACTURING BACKGROUND OF THE INVENTION Field of the Invention The invention is directed to organotin sulfonate catalysts, polymers produced with organotin catalysts and organotin catalyst manufacturing. Description of the Related Art Catalysts are commonly used in the polymerization and entanglement reactions of monomeric or resinous materials to form polymers. The catalysts, polymerizable components and other additives can take the form of coatings, particles, articles, solutions or dispersions. The compositions can be handled and polymerized as "pure" compositions, ie, in the absence of solvents or vehicles, as organic solutions or as compositions dispersed or emulsified in water. Each composition has its own resistance and weakness. The chemistry of polymerizable components is the main factor in selecting a specific catalyst to be used. However, it is difficult to predict whether a catalyst is suitable without experimental verification. Frequently, a catalyst that is effective to catalyze a type of reaction, ie, polyurethane polymer formation, is well suited to catalyze a different type of reaction, i.e. polymerization of butylated melamine. Accordingly, when the polyurethane forming and polyamine forming reagents (e.g., melamine) are combined, they are combined in a single formulation, two different catalysts are added, one for the polyurethane formation reaction and one for the polyurethane formation reaction. Melamine formation reaction so that the two different reactions can proceed simultaneously at reasonably comparable reaction regimes. Some poliestanoexanos are known and have been shown to have catalytic activity for certain reactions; see for example: "Distannoxane as reverse micelle type catalyst; novel solvent effect on reaction rate of transesterification" Junzo Otera, Shingi loka; and Hitosi Nozaki, Journal of Organic Chemistry, 1989, 54, 4013-4014. "Novel témplate effect de distannoxane catalysts en highly efficient transesterification and esterification", Juno Otera, Nobuhisa Dan-oh and Hitosi Noaki, Journal of Organic Chemistry, 1991, 56, 5307-531 1. While polysanoxanes have been described, their sulfonate derivatives do not appear in the prior art. For example, the Patent of E. U.A. No. 2,720,507 discloses a wide variety of classes of organotin compounds which are such that they are useful as catalysts in the preparation of polyesters. However, polyestoxane sulfonates are not disclosed. The Patent of E. U.A. No. 3,681, 271, discloses the use of triestanoxanes as catalysts in the preparation of urethane foams. Organotin sulfonates are not disclosed.

Patent of E.U.A. number 3,676,402. This patent describes the use of octa-alkylatanoxanes as catalysts in urethane systems comprising blocked isocyanates. Organotin sulfonates are not disclosed. The Patent of E.U.A. No. 3,194,770, describes the use of a wide variety of classes of organotin compounds useful as catalysts for curing compositions, particularly foams. Stanoxanes are described but polyesternoxanes sulfonates are not described. Mononuclear organotin sulphonates (monomer) have been described as a composition of matter and their use as polyurethane foam catalysts have also been described. For example: The Patent of E.U.A. No. 3,095,434 discloses a wide variety of di and tri-organotin sulphonates and describes their use as pesticides. The utility of catalysts for polyurethane foams is also described. The Patent of E.U.A. No. 4,286,073 claims di and trialkitin sulfonates as catalysts for forming urethane. The Patent of E.U.A. number 4,611,049, describes a process for producing aromatic polyesters. The catalyst may be an organotin compound used with a sulfonic acid promoter but the catalyst and promoter do not constitute an organotin sulfonate. The ability of mononuclear organotin sulphonates to effectively catalyze several different polymerization reactions has not been simultaneously described. SUMMARY OF THE INVENTION The invention provides an organotin sulfonate catalyst capable of effectively catalyzing polymerization, esterification, transesterification and condensation reactions individually or more than one of said reactions simultaneously.

Novel organotin sulfonate catalysts are provided which comprise polysanoxane salts containing an organosulfonate group and corresponding to the following formula: R2 R R2 I I R - Sn O [-Sn-0] n - Sn - R x (H20) R! 11 R 22 R! Wherein each R is independently selected from the group consisting of alkyl having from 1 to 20 carbon atoms, aryl and aralkyl; each R1 is independently selected from the group consisting of OR, OH, OOCR, halogen and a strong organic acid derivative having a pKa of less than 1 as long as at least one selection for R1 is OSO2R, each R having the same meaning as before; each R2 being selected independently from the same groups as R and R1; n is an integer that has an average value of 0 to 20, and, x indicates the amount of water of hydration that can be as low as 0 and reach infinity when the compound is in an aqueous solution. The above formula is sometimes referred to herein as "Formula 1." Good catalytic activity and double curing capacities have also been discovered for an expanded Formula 1 and for monomeric organotins of the formula: R 1 I R - Sn - R 2 (H 20) R2 wherein R, R2 and x have the same values as above for Formula 1 and R1 is independently selected from the group consisting of OR, OH, OOCR, halogen and a strong organic acid derivative having a pKa of less than 1, with R having the same meaning as before, provided that at least one R1 is derived from an organic acid having a pKa less than 1, (hereinafter referred to as Formula 2). The expanded version of Formula 1 for which the uses of catalytic and double cure have been discovered is: R 'R - Sn O [-Sn-0] n - Sn - R x (HzO) R 1 R2 R 1 wherein each R is independently selected from the group consisting of alkyl having from 1 to 20 carbon atoms, aryl and aralkyl; each R1 is independently selected from the group consisting of OR, OH, OOCR, halogen and a strong organic acid derivative having a pKa of less than 1 with R having the same meaning as before; as long as an R1 is derived from an organic acid having a pKa less than 1; each R2 being selected independently from the same groups as R and R1; n is an integer that has an average value of 0 to 20; and, x indicates the amount of water of hydration that can be as low as 0 and reach infinity when the compound is in an aqueous solution. The above formula is sometimes referred to herein as "Expanded Formula 1". The difference between Formula 1 and Expanded Formula 1 is in the definition of R1. In Expanded Formula 1, at least one value of R1 should be derived from an acidic organ having a pKa value less than 1 while in Formula 1 the strong acidic organ derivative is limited to OSO2R. Therefore, Expanded Formula 1 does not include all compounds of Formula 1 plus those compounds having R1 values other than OS02R. It has also been found that the organotin compounds of Formula 1, Expanded Formula 1 and Formula 2 are capable of simultaneously catalyzing more than one polymerization reaction to produce urethane, urea, silicone or amino polymers. The simultaneous catalysis of more than one such reaction is referred to herein as "double cure". A novel process is also provided for the production of the compounds of Formula 1, Expanded Formula 1 and Formula 2 using water and at least one additional polar solvent. The process produces organotins that have novel physical properties. DETAILED DESCRIPTION The novel organotin sulphonates are salts of polysanophenes of a strong organic acid described in Formula 1. It has been found that the organotin compounds described by Formula 1, Expanded Formula 1 and Formula 2, are excellent catalysts for esterification or transesterification reactions or polymerization reactions to produce urethane, urea, silicone and amino polymers. While the organotin catalysts of the present invention can be described by the above formulas, when they are produced, a mixture of organotin compounds is obtained that can be analyzed and theorized to conform to the above structural formulas, the values for n and x being average values . While the analyzes of the compounds of the present invention are consistent with the structure described by Formula 1, Expanded Formula 1 or Formula 2, the analyzes also agree with the description of the compounds by comparable empirical formulas given below. Structural formulas and empirical formulas are considered equivalent for the purposes of the present invention. The values for x in Formula 1, Expanded Formula 1 or Formula 2 can vary significantly, for example x, can have an average value of 0 to 250 and for water soluble species of Formula 1, Expanded Formula 1 and Formula 2, the upper limit of x can be much larger than 250 and reach infinity in an aqueous solution. In a water solution, the equivalent formulas are the formulas without the "x (H2O)." Preferably, at least one selection of R1 in Formula 1, Expanded Formula 1 and Formula 2 is from the group consisting of: (a) , OS02R, wherein R is independently selected from the group consisting of alkyl having from 1 to 20 carbon atoms, aryl and aralkyl; (b), R COO wherein R is an alkyl or aryl group in which the carbon atom attached to the COO group contains at least one F, Cl, Br, I, CN attached thereto; (c), RPO3H wherein R is independently selected from! a group consisting of alkyl having 1 to 20 carbon atoms, aryl and alkyl; (d) RCr04H wherein R is independently selected from the group consisting of alkyl having from 1 to 20 carbon atoms, aryl and alkyl; and, (e) F; N03; CI04; and (NO) 2C6H2OH. When a selection for R1 in Expanded Formula 1 or Formula 2 of this preferred group, the requirement of the formula which is at least one value for R1 is derived from a strong organic acid having a pKa less than 1 has been fulfilled except when the selection is F, NO3 or CI0. The most preferred selections for R1 is methyl p-toluene sulphonate sulfonate. The preferred selections for R and R2 are butyl. Preferred values for n is from 0 to 3 in Formula 1 and Expanded Formula 1. SYNTHESIS The synthesis of sulfonates of mono-stano-venes of Formula 2 is described in the U.S. Pat. No. 3,095,434 whose description is incorporated herein by reference. Polyestoexan sulfonates of Formula 1 and Formula Expanded 1 have been synthesized in several different forms, such as: 1. 130.0 grams (0.52 moles) of dibutyltin oxide (DBTO), 99.34 grams (0.52 moles) of paratoluene sulfonic acid hydrate and heptane were added to a flask of a 1 liter adapted with a thermometer, paddle stirrer, Dean and Stark separator and a condenser. The mixture was heated to reflux while stirring. The water produced by the reaction and the water of hydration of the paratoluensulfonic acid was removed by distillation. The condensed vapors were recovered in the Dean and Stark separator, in which the lower aqueous phase was removed and the upper organic phase was returned to the reaction flask. After 3 hours of reflux, the heat was removed and the mixture allowed to cool to room temperature. The solids were filtered and dried under vacuum at 60 ° C for 12 hours. The solid product had a "sticky" consistency. The analyzes of the product were: Analysis: Found% Sn 28.8 Number of Acid 134 (mg KOH / g)% HzO 2.74 (Karl-Fisher)% LOD 0.59 (100 ° C, 75 torr, 2hrs) This produced a polysanoxane that can be described by Formula I in which R and R2 are butyl, R1 is p-toluene sulfonate, n is between 0 and 0.1 and x is between 0 and 0.3. Likewise, the analysis of the reaction product agrees with a polyaneoexan of the empirical formula R2SnA0- [R2Sn0] - SnR2A (H20) "in which all the selections for R are butyl, A is p-toluene sulfonate, the derivative of a strong organic acid, x is between 0 and 0.1 and n is approximately 0.3. If a product such as that produced by this synthesis and identified by the above analysis, is described by the empirical formula or by Formula 1, they are considered equivalent for the purposes of this invention. 2. 124.45 grams (0.50 moles) of butyltin oxide, 95.11 grams (0.50 moles) of paratoluenesulfonic acid hydrate, 150.0 grams of 2-propanol, and 150 grams of deionized water were added to 1 one-liter flask adapted with a thermometer, paddle stirrer and condenser. The mixture was refluxed while stirring and refluxed for 1 hour. The heating was stopped and the reaction mixture was allowed to cool to about 25 ° C. The solid product was filtered and dried at 50 ° C under 50 torr of vacuum for 2.5 hours. In contrast to the product of synthesis 1, the product produced in the mixed solvent system of water and an organic polar solvent produced a product that was easily filtered and easily dried to a granular crystalline solid which was not "tacky". Analysis: Found% Sn 27.3 Acid Number 128 (mg KOH / g)% H20 8.46 (Karl-Fisher)% LOD 5.64 (100 ° C, 75 torr, 2hrs) The analysis confirms that the reaction product is a polysanoxane of Formula 1 wherein each R is butyl and each R1 is paratoluen sulfonate, n has an average value between 0 and 0.1, and x has a value of 3.1. to themselves, the analyzes agree with a polysanoxane reaction product of the empirical formula R2SnAO- [R2SnO] x-SnR2A (H20) n in which all selections for R are butyl, A is the derivative of a strong organic acid and is p -tolue sulfonate, x is between 0 and 0.2 and n is approximately 0.3. 3. 124.44 grams (0.50 moles) of dibutyltin oxide, 95.11 grams (0.50 moles) of paratoluenesulfonic acid hydrate, 150.0 grams of 2-propanol and 150 grams of deionized water were added to a one liter flask fitted with a thermometer , paddle stirrer and a condenser. The mixture was refluxed while stirring and refluxed for 1 hour. The heating was stopped and the reaction mixture was allowed to cool to approximately 25 ° C. The solid product was filtered and dried at 80 ° C under 50 torr of vacuum for 8 hours. The solid was easily filtered and easily dried to a granular crystalline solid which was not "tacky". Analysis: Found% Sn 28.3 Number of Acid 131 (mg KOH / g)% H20 4.28 (Karl-Fisher)% LOD 1.87 (100 ° C, 75 torr, 2hrs) This produces a poliestanoexano of the Formula 1 where each R is butyl and each R1 is p-toluene sulfonate, n has an average value between 0 and 0.1 and x has a value of about 1.0. Likewise, the analyzes of the reaction product agree with a polysanoxane of the empirical formula R SnAO- [R2SnOj? -SnR2A (H20) n in which all the selections for R are butyl, A is e! derivative for strong organic acid and is p-toluene sulfonate, x is between 0 and 0.2 and n is approximately 1. The preferred synthesis is with at least two polar solvents as exemplified in syntheses 2 and 3. Preferably one solvent is water and another polar solvent is an alcohol, particularly aliphatic alcohols of Ci to C5, especially methanol, ethanol, propanol and butanol (including isomers). Synthesis in a mixture of water solvents and at least one additional polar organic solvent produces a crystalline form of the organotin compounds of Formula 1, Expanded Formula 1 and Formula 2 having unique properties that allow the compounds to dry easily. in a crystalline non-sticky powder. Preferably, the water constitutes at least about 25% of the polar solvent mixture, with 50% being particularly preferred. ESTER I FI CATION AND TRANSESTERI FICATION When at least one of the values of R1 in Formula 1, Expanded Formula 1 or Formula 2 is OS02R, the resulting organotin sulphonate, whether it is polysanoxane, monomeric stanoxane or organotin sulphonate, is surprisingly effective as a catalyst for esterification and transesterification reactions in addition to the polymerization or condensation reactions of urethane, silicone and amino. DOUBLE CURE Good catalytic activity and double cure abilities have also been discovered for organotin catalysts of Formula 1, Expanded Formula 1 and Formula 2. The catalysts of the Expanded Formula and Formula 2 have the amazing ability to simultaneously catalyze two or more reactions of formation of urethane, ester, silicone and amino when the reagents for more than one reaction of formation of urethane, silicone, amino and ester are present in a single composition. Said simultaneous catalysts are referred to herein as "double curing" catalysts. In order for a catalyst to simultaneously catalyze two different reactions in a mixture of reactants for each reaction, the catalyst must catalyze each reaction at reasonably equivalent reaction rates so that no reaction reaches the substantial term significantly before the other reaction. In other words, if a reaction reaches a desired degree of cure or termination in a certain amount of time with a specific catalyst, then the other desired reaction should reach a comparable degree of cure in an amount of time that is in the order of magnitude and preferably within + or - 50% of the first reaction time with the same concentration of the same catalyst. This can be determined by testing each desired reaction separately from the white catalyst. In contrast, the current commercial standard is to use at least two different catalysts to catalyze each reaction while a single organotin catalyst of the present invention can perform as different commercial normal catalysts for each reaction. Therefore, a single catalyst of Formula 1, Expanded Formula 1 or Formula 2, can effectively catalyze more than one of said reactions simultaneously. A particular advantage of the double curing capabilities of a catalyst is in coatings of two or more layers. Typically, coatings such as automotive paints are applied in various tai layers as a pigmented bottom layer and a clear topcoat layer. The coating formulation used for the lower layer is a pigmented composition containing urethane-forming reagents, silicone and / or melamine and the upper transparent cover often contains polyurethane and / or melamine-free reagents without pigments. With a double curing catalyst of the present invention, the catalyst can be added to the coating formulation for the first layer or the lower layer with a second layer or the top coating being applied on the upper part of the lower layer and before Curing the lower layer, the upper coating containing or not containing relatively small catalyst. When cured, the lower layer tends to heal faster due to the presence of a larger effective amount of catalyst. During the healing of the lower layer, the catalyst migration in the upper layer occurs but moving the healing of the upper layer. This also promotes the bonding of the strong inner layer and allows the release of volatiles released during the healing of the lower layer which will be released through the top layer not yet cured. While it is preferred that the upper layer does not contain catalyst, it is sufficient that the upper layer contains relatively less catalyst and the lower layer. Relatively less catalyst is an amount of catalyst that results in longer cure time for the upper layer such as more than twice the cure time of the lower layer. A multi-layer coating system using the catalysts of the present invention and a gradation in catalyst concentration between the layers has the advantage of a single cure step after several layers have been applied together with the migration of the catalysts towards up between the layers during the cure to increase the effective catalyst concentration for higher layers. USE OF CATALYST The catalyst is employed in a catalytically effective amount usually from about 0.01% to about 5% and especially from about 0.05% to about 2% based on the weight of the metal in the catalyst and based on the total weight of the catalyst. polymerizable solids. All percentages or other proportions given herein are based on weight unless otherwise stated. The catalysts of Formula 1, Expanded Formula 1 and Formula 2 can be used in combination with other catalysts especially tin and zinc containing catalyst such as dibutyltin dilaurate, dibutyltin oxide and zinc neodecanoate. REACT IVOS TRANSESTER REAGENTS I F ICAC ION AND ESTER I FICAC ION Reagents that undergo esterification and transesterification are well known to those skilled in the art. For example, reagents for transesterification include monomeric esters and polymeric esters of carboxylic acid reacted with monomeric or polymeric alcohols. Reagents for esterification include mono and polycarboxylic acids reacted with monomeric or polymeric alcohols. POLYMER FORMATION REAGENTS Reagents for forming polymers such as urethane, urea, silicone and amino polymers are well known to those skilled in the polymer arts. Reagents for urethane polymers are usually aromatic and diphatic isocyanates and blocked isocyanates reacted with polyhydroxy and amino compounds. For silicone polymers, the reactants are usually alkoxy silane (and alkoxy acrylosilane) reacted with a polymeric hydroxy compound. For amino resins such as melamine polymers, the normal reagents for producing amino resins consist of condensation product reagents such as urea, melamine, methylated carbamyl melamines, glycoluril or benzoguanamine usually reacted with formaldehyde or buranol. Also acrylic carbamates reacted with melamine forming reagents. I NG R ADDITIONAL (OPTIONAL) ENTREPRENEURS Additional ingredients can be added to the compositions described herein of the type usually used for coating or polymer compositions such as cocatalysts, pigments, fillers, extenders and polymer modifiers. EXAMPLES Example A A normal formulation for a single urethane reaction was prepared using a polyol (neophenyl alcohol) and an isocyanate (Cyclohexyl isocyanate) to form a urethane. Neither isocyanate nor alcohol are multifunctional and consequently a urethane is formed instead of a polyurethane. Said forward reaction is used to screen catalysts for urethane catalytic activity. The catalytic activity of various catalysts of the present invention (Formula 1 and Formula 2) as identified in Table A were compared to dibutyltin dilaurate, a commercial normal catalyst for said urethane reaction. Comparisons were on an equal weight of tin base to calculate the amount of catalyst added to the formulation. After the addition of catalyst in the formulation, the reaction was allowed to proceed at room temperature. The degree of isocyanate consumption (urethane formation) was monitored by FTIR as a function of time. From the kinetics of the first order, e! relative reaction regime. The higher the rate, the faster the formation of urethane. None of the catalysts of the present invention were effective as urethane catalysts for the reaction with an alcohol with an isocyanate compared to a well-known urethane catalyst, dibutyltin dilaurate. This confirms the general belief in the art that acid groups tend to retard the urethane reaction and could lead one to conclude that the catalysts of the present invention were not effective catalysts for urethane formation reactions. The following examples illustrate the invention and preferred embodiments. Example 1 The catalytic activity for a normal automotive polyurethane finish was evaluated. In view of the results of Example A, the catalysts of the present invention (Formula 1, Expanded Formula 1 and Formula 2) could not be expected to be effective when compared to a normal industrial catalyst present, dibutyltin dilaurate (DBTDL) ( for its acronym in English) . Aliquots for a formulation of an acrylic-based polyester polyol and hexane diisocyanate were prepared with xylene and ketones as solvents each containing enough catalyst to constitute 0.14% catalyst based on the weight of tin and based on the total weight of the catalyst. the solids in the formulation. After the addition of catalyst, the formulation was kept at 25 ° C and the time in hours was recorded for the formulation to form a gel as an indication of "packaging life". In addition, the coatings were made with each formulation and the time in hours at room temperature was recorded so that the coating achieved parameters of Sol-Gel transition drying and Surface Drying time measured by a B.K. The results are given in Table 1. The catalysts of the present invention performed as well as the normal industrial DBTDL. Example 2 Blocked isocyanate catalysts were evaluated for the production of polyurethane coatings. The catalysts of the present invention (Formula 1, Expanded Formula 1 and Formula 2) were compared with a normal industrial catalyst present, dibutyltin dilaurate (DBTDL). Aliquots of an MDI formulation blocked with MECO, an acrylic-based polyol, were prepared in MAC (methyl amyl ketone) solvents and MIBC (methyl isobutyl ketone), each containing enough catalyst to make 0.14% catalyst based on weight of tin and based on the total weight of solids in the formulation. The formulations were preheated to between 70 and 80 degrees C. so that the selected catalyst could be soluble in the formulation. After the addition of the catalyst in the preheated formulation, the formulation was raised to 130 ° C and the time in minutes was recorded for the formulation to reach the gel point (2,500 Centipoises) indicating the substantial completion of the reaction using a Brookfield Checker. The results are given in Table 2. The catalysts of the present invention performed better than the normal industrial DBTDL. Example 3 Blocked isocyanate catalysts were evaluated for the production of polyurethane coatings as in Example 2 in combination with a cocatalyst containing zinc (zinc neodecanoate). The catalysts of the present invention (Formula 1, Expanded Formula 1 and Formula 2) with and without the cocatalyst were compared with a current normal industrial catalyst, DBTDL and with zinc neo decanoate. Aliquots of a formulation of an acrylic-based polyol, an isocyanate blocked with Oxy, MAC and M I BC were prepared, each containing a quantity of catalyst indicated in Table 3 based on the weight of tin (zinc for zinc neodecanoate). The formulations were preheated when necessary so that the selected catalyst could be soluble in the formulation. After the addition of the catalyst in the preheated formulation, the formulation was raised to 120 ° C and the time recorded for the formulation to reach the gel point (2,500 Centipoises) indicating the substantial completion of the reaction using. The results are given in Table 3. The catalysts of the present invention performed better than the normal industrial DBTDL and their performance was improved by the addition of the zinc neodecanoate cocatalyst. Example 4 This example evaluates the effect of the catalyst concentration on the unemployment of catalysts for catalysts of Expanded Formula 1 compared to DBTDL for the reaction of blocked isocyanates with polyol for the production of polyurethane coatings. A catalyst of the present invention was compared with a normal industrial catalyst present, dibutyltin dilaurate (DBTDL). The catalyst used was a poliestanoexano of the expanded Formula 1 wherein each R is butyl and each R1 is OCOCF, n is 0 and x is 0 which agrees with a poliestanoexano of the empirical formula R2SnAO- [R2SnO] x-SnR2A (H20) n in which all selections for R are butyl, A is the derivative of a strong organic acid and is OCOCF3, x is 0 and n is about 0. Aliquots of a formulation of Desmofen A565, an acrylic polyol available from Bayer, were prepared, Desmodur Bl 3175A of an isocyanate blocked with oxime available from Bayer, MAC and MI BC, each containing several sufficient amounts of catalyst as set forth in Table 4 (% catalyst based on tin weight and total weight of solids in the formulation). After the addition of the catalyst in the preheated formulation, the formulation was raised to the temperature set forth in Table 4 and the time in minutes recorded for the formulation to reach the gel point (2,500 Centipoises) which indicates the substantial term. of the reaction. The results are given in Table 4. The catalysts of the present invention performed better than the normal industrial DBTDL even though the concentration of DBTDL was 250% higher. Example 5 The ability of the catalysts of the present invention to catalyze silicone polymerization was evaluated in comparison to DBTDL. The reagents were tetrapropyl silicate as an interlayer for a silanol-terminated polydimethylsilicone oil. The formulation with the desired catalyst was heated to 140 ° C in a stirred plastic blender and the time in minutes was recorded to reach the gel point. Higher performance was obtained with the catalysts of the present invention except when the catalyst was not soluble in the reaction mixture. The results are given in Table 5. EXAMPLE 6 The ability of the catalysts of the present invention to catalyze entanglement of formaldehyde from melamine with acrylic polyol was evaluated in comparison to DBTDL and Nacure 5626 available from King Industries and is a docetylbenzenesulfonic acid blocked with amine. The formulation for each test used as reagents 60.2 grams of hexametoxy melamine (Cymel 303) and 140.71 grams of an acrylic polyol (Juncryl 500) in 100 grams of methylethyl ketone (MEC). The formulation with the desired catalyst was heated to 140 ° C in a stirred plastic blender and the time in minutes was recorded to reach the gel point. Higher performance was obtained with the catalysts of the present invention compared to the comparative tin-based catalyst, DBTDL. The results are given in Table 6. Example 7 The ability of the catalysts of the present invention to catalyze esterification and transesterification reactions are evaluated in comparison with dibutyltin oxide (DBTO) and butyl-istanoic acid (BSA). The reagents were phthalic anhydride and 2-ethylhexanol at a reaction temperature of 220 ° C and with 5% excess alcohol. The formulation with the desired catalyst was maintained at 220 ° C and the decrease in acid number was monitored with time (hours). The addition of catalyst was on a basis of equal weight of tin at the rate of 100 milligrams of tin per 100 grams of phthalic anhydride. The termination is considered at an acid number below about 3. Higher performance was obtained with the catalysts of the present invention.

The results are given in Table 7. Table A Catalyst Relative Regime Dibutyltin Dilaurate 1.0 Bu2Sn (OS02CH3) 2 (1) Insoluble Bu2Sn (pTSA) 2 (2) 0.17 [Bu2Sn (pTSA)] 20 (3) 0.07 1. Formula 2, R and R2 are butyl and R1 are methylsulphonate 2. Formula 2, R and R2 are butyl and R1 are p-toluene sulfonate 3. Formula 1, R and R2 are butyl, R1 are p-toluene sulfonate, n = 0 and x is approximately 0. Table 1 Catalyst Performance in Polyurethane Coating Catalyst Sun Transition- Drying Time Packing Life Gel (hrs) Surface (hrs) (hrs) Dibutyltin Dilaurate 3.0 3.8 6.0 Bu2Sn (OS02CH3) 2 (1) 5.0 8.0 7.8 Bu2Sn (pTSA) 2 < 2) 3.0 6.5 6.0 [Bu2Sn (pTSA)] 20 (3) 3.0 4.0 5.0 1. Formula 2, R and R2 are butyl and R1 are methylsulphonate 2. Formula 2, R and R2 are butyl and R1 are p-toluenesulfonate 3. Formula 1, R and R2 are butyl, R1 are p-toluenesulfonate, n = 0 and x is approximately 0.

Table 2 1. Formula 2, R and R are butyl and R are trichloroacetate 2. Expanded Formula 1, R and R2 are butyl, R1 is trichloroacetate, n = 0 and x is approximately 0 3. Expanded Formula 1, R and R2 are butyl, R1 are trifluoroacetate , n = 0 and x is approximately 0 4. Formula 2, R and R2 are butyl and R1 are methylisulfonate 5. Formula 1, R and R2 is butyl, R1 is methylisulfonate, n = 0 and x is approximately 0 Table 3 1 . Formula 2, R and R are butyl and R are methylisulfonate 2. Expanded Formula 1, R and R2 are butyl, R1 is trifluoroacetate, n = 0 and x is approximately 0 3. Formula 2, R and R2 are butyl, R1 are trichloroacetate 4 Expanded Formula 1, R and R2 are butyl, R1 is trichloroacetate, n = 0 and x is approximately 0 Table 4 Effect of Increase in Concentration of Catalyst on Performance 1. Expanded Formula 1, R and R are butyl, R is trifluoroacetate, n = 0 and x is approximately 0 Table 5 1. Formula 2, R and R are butyl and R are acetate 2. Expanded Formula 1, R and R 2 are butyl, R 1 is acetate, n = 0 and x is about 0 3. Formula 2, R and R 2 are butyl, R 1 is trichloroacetate 4 Expanded Formula 1, R and R2 are butyl, R1 is trichloroacetate, n = 0 and x is about 0 5. Expanded Formula 1, R and R2 are butyl, R1 is trifluoroacetate, n = 0 and x is about 0 6. Formula 2, R and R2 are butyl and R1 are trifluoroacetate. Table 6 Melamine crosslinking Catalyst Solubility @ Temp. Gel time @ 115 ° C Environment (min) Bu2Sn (OS02CH3) 2? G partially soluble 6.1. { Bu2Sn (OS02CH3)} 2O partially soluble T2T 5.9 Nacure 5625 (soluble sulfonic acid 6.4 blocked with amine) Dibutyltin dilaurate soluble > 100 Soluble dibutyltin oxide > 100 1. Formula 2, R and R2 are butyl and R is methylisulfonate 2. Formula 1, R and R2 are butyl, R1 is methylisulfonate, n = 0 and x is about 0 Catalysts aggregated on equimolar base Conc. Catalysts = 0.18 mmol based on the total weight of solids Gel time measurements (Brookfield Viscometer) at 115 ° C Viscosity measurement regime is increased to reach the gel point (2,500 cps) Table 7 Number of Acid versus Time 2. Butylstanoic acid 3. Formula 2, R is butyl and R and R2 are methylisulfonate 4. Formula 2, R and R2 are butyl and R1 is methylisulfonate 5. Formula 1, R and R2 are butyl, R1 is methylisulfonate, n = 0 and x is approximately 0 6. Formula 1, R and R2 are butyl, R1 is p-toluene sulfonate, n = 0 and x is approximately 0

Claims (15)

1. CLAIMS 1. A salt of poliestanoexano of a strong organic acid that has multiple catalytic activity, comprising a compound of the formula: R 'R R' I I R - Sn O [-Sn-0] n - Sn - R (H20) x R! 11 R 22 R 'i1 wherein each R is independently selected from the group consisting of alkyl having from 1 to 20 carbon atoms, aryl and aralkyl; each R1 is independently selected from the group consisting of OR, OH, OOCR, halogen and a strong organic acid derivative having a pKa of less than 1 as long as at least one selection for R1 is OS02R, each R having the same meaning as before; each R2 being selected independently from the same groups as R and R1; n is an integer that has an average value of 0 to 20; and, x is from 0 until it reaches infinity when the catalyst is in an aqueous solution.
2. 2. The stanoxane of claim 1, wherein each R1 is independently selected from the group consisting of OS02R, wherein R has the same meaning as R defined in claim 1; R3COO wherein R3 is an alkyl or aryl group in which the carbon atom bonded to the COO group contains at least one of F, Cl, Br, I, CN attached thereto; RPO3H wherein R has the same qune R defined in claim 1; RCr0 H wherein R has the same meaning as R defined in claim 1; R; N03; CI04; and, (N0) 2C6H20H; as long as at least one selection for R1 is OS02R.
3. 3. An improved curable polymeric coating composition comprising or obtained by combining at least one group of polymer-forming reagents selected from the group consisting of polyurethane-forming reagents, silicone-forming reagents, amino-forming reagents and reagents of formation of esters; wherein the improvement comprises including in said composition an organotin of a strong organic acid as a catalyst for the reaction of said polymer formation reagents, said catalyst being selected from the group of organotin compounds corresponding to the formulas consisting of : R2 R R2 I 1 I Sn 0 [-Sn • 0] "Sn (H20) x 1 1 k < 2 -V R1 I R - Sn - R2 x (H20) wherein each R is independently selected from the group consisting of alkyl having from 1 to 20 carbon atoms, aryl and aralkyl; each R1 is independently selected from the group consisting of OR, OH, OOCR, halogen and a derivative of a strong organic acid having a pKa of less than 1, R having the same meaning as before; provided that at least one selection for R1 is derived from an organic acid having a pKa less than 1; each R2 being selected independently from the same groups as R and R1; n is an integer that has an average value of 0 to 20; and, x is from 0 until it reaches infinity when the catalyst is in an aqueous solution.
4. The composition of claim 3, wherein each R1 is independently selected from the group consisting of OS02R, wherein R has the same meaning as R defined in claim 1; R4COO wherein R4 is an alkyl or aryl group in which the carbon atom bonded to the COO group contains at least one of F, Cl, Br, I, CN attached thereto; RP03H wherein R has the same qune R defined in claim 1; RCr0 H wherein R has the same meaning as R defined in claim 1; R; N03; CI04; and, (NO) 2CßH2OH; as long as at least one selection for R1 is OS02R.
5. The composition of claim 3, wherein said group of polymer forming reagents are polyurethane forming reagents.
6. 6. The composition of I claim 3, wherein said group of polymer forming reagents are silicone polymer forming reagents.
7. The composition of claim 3, further comprising a cocatalyst containing zinc or tin.
8. The composition of claim 3, wherein the group of polymer forming reagents are amino resin forming reagents.
9. The composition of claim 3, wherein two groups of polymer forming reagents are combined in said composition.
10. The composition of claim 9, wherein said two groups of polymer forming reagents are reagents for forming amino polymers and polyurethane forming reagents.
11. The composition of claim 10, wherein said amino-forming reagents are melamine-forming reagents.
12. 12. An improved coating containing at least two layers comprising a first layer containing a coating composition of claim 3 and a second layer at the top and in contact with the first layer containing a coating composition of the claim 3 but without the catalyst component of claim 3 or containing relatively less catalyst than the first layer.
13. 13. An improved process for producing an organotin salt of a strong organic acid of the formula: R I Sn O [-Sn-0] n Sn - R (H20) x R 'i1 R U2 R1 R1 I R - Sn - R x (H20) wherein each R is independently selected from the group consisting of alkyl having from 1 to 20 carbon atoms, aryl and aralkyl; each R1 is independently selected from the group consisting of OR, OH, OOCR, halogen and a derivative of a strong organic acid having a pKa of less than 1, R having the same meaning as before; provided that at least one selection for R1 is derived from an organic acid having a pKa less than 1; each R2 being selected independently from the same groups as R and R1; n is an integer that has an average v of 0 to 20; and, x is from 0 until it reaches infinity when the catalyst is in an aqueous solution; said process comprising reacting the reagents for said organotin salt in a solvent system; wherein the improvement comprises using as the solvent system a mixture of at least two solvents, one solvent being water and the other solvent being an alcohol.
14. The novel process of claim 13, further comprising the steps of: (a) cooling and crystallizing the stannoxane in said mixture of polar solvents; (b) separating the stenoexan from said mixture; and, (c) drying the stanoxane to produce crystalline, granular, non-tacky solid.
15. 15. The crystalline, granular, non-sticky solid produced by the process of claim 12.