CN1204553A - Organotin sulfonate catalyst and its production method - Google Patents

Abstract

The present invention provides dual cure organotin salts of strong organic acids, the use of these salts as catalysts and improved methods for preparing these catalysts. These catalysts are effective in catalyzing esterification and transesterification reactions and urethane, silicone, melamine, ester and acrylate forming reactions, and can simultaneously catalyze the reaction of more than one of a mixture of urethane, silicone, amino, ester and acrylate polymer forming reactants to produce a polymer mixture.

Description

Organotin sulfonate catalyst and its production method

The invention relates to an organotin sulfonate catalyst, a polymer prepared by using the organotin catalyst and a preparation method of the organotin catalyst.

Catalysts are often used in polymerization or crosslinking reactions of monomers or resinous substances to form polymers. Catalysts, polymerizable components and other additives may be in the form of coatings, granules, preparations, solutions or dispersions. These compositions can be handled and polymerized in "pure" compositions, ie without the presence of solvents or carriers, in organic solutions or in water-dispersed or water-emulsified compositions. Each composition has its advantages and disadvantages.

The chemical nature of the polymerizable components is a major factor in selecting the particular catalyst used. However, without experimental confirmation, it is difficult to predict the suitability of catalysts. Often catalysts that are effective in catalyzing one reaction (eg, polyurethane polymer formation) are not well suited to catalyze a different type of reaction (eg, butylated melamine polymerization). Therefore, when polyurethane forming reactants and polyamine (such as melamine) forming reactants are mixed in one formulation, two different catalysts need to be added, one catalyzing the polyurethane forming reaction and the other catalyzing the melamine forming reaction , allowing two different reactions to proceed simultaneously at reasonably comparable reaction rates.

Some polystannoxanes are known and have been shown to be catalytically active for certain reactions, see for example:

"Distannoxane reverse micellar catalysts, a novel solvent effect on transesterification reaction rate" JunzoOtera, Shingi Ioka; and Hitosi Nozaki, Journal of Organic Chemistry, 1989, 54, 4013-4014.

"Novel templating effect of distannoxane catalysts in efficient transesterification and esterification reactions", JunoOtera, Nobuhisa Dan-oh and Hitosi Noaki, Journal of Organic Chemistry, 1991, 56, 5307-5311.

Although polystannoxanes have been disclosed, their sulfonate derivatives have not appeared in the prior art. For example, U.S. Patent 2,720,507 discloses a variety of organotin compounds which are said to be useful as catalysts for the preparation of polyesters. However, polystannoxane sulfonates are not disclosed.

U.S. Patent 3,681,271 discloses the use of tristannoxanes as catalysts in the preparation of polyurethane foams. However, organotin sulfonates are not disclosed.

U.S. Patent No. 3,676,402 discloses the use of octaalkylstannoxanes as catalysts in polyurethane systems containing blocked isocyanates. However, organotin sulfonates are not disclosed.

U.S. Patent 3,194,770 discloses the use of various organotin compounds as catalysts in curing compositions, especially foams. Stannoxanes are disclosed but not polystannoxane sulfonates.

Mononuclear (monomeric) organotin sulfonate compositions have now been disclosed, and their use as polyurethane foam catalysts has also been disclosed. For example:

U.S. Patent 3,095,434 discloses a number of di- and triorganotin sulfonates and describes their use as insecticides. The use of the catalyst for polyurethane foam is also disclosed.

U.S. Patent 4,286,073 claims di- and trialkyltin sulfonates as polyurethane foam catalysts.

U.S. Patent 4,611,049 discloses a process for the manufacture of aromatic polyesters. The catalyst may be an organotin compound used with a sulfonic acid cocatalyst, but the catalyst and cocatalyst do not constitute an organotin sulfonate. The ability of mononuclear organotinsulfonates to efficiently catalyze several different polymerization reactions simultaneously is not revealed.

The invention provides an organic tin sulfonate catalyst capable of effectively catalyzing more than one reaction in polymerization reaction, esterification reaction, transesterification reaction and condensation reaction separately or simultaneously. Novel organotinsulfonate catalysts are provided, which include polysiloxane salts containing organosulfonic acid groups, corresponding to the general formula:

In the formula, each R is selected from alkyl, aryl and alkaryl containing 1-20 carbon atoms respectively;

Each ^R is independently selected from OR, OH, OOCR, halogen, and a derivative of a strong organic acid with a pKa less than ¹ , provided that at least one choice of R is OSO _R , and R in the formula has the same meaning as above;

Each R ² is independently selected from the same groups as R and R ¹ ;

n is an integer with an average value of 0-20;

x represents the amount of bound water, x can be as low as 0, and x approaches infinity when the catalyst is in aqueous solution.

The above general formula is sometimes referred to as "general formula 1".

式中R、R²和x具有与上述通式1相同的含义，每个R¹分别选自OR、OH、OOCR、卤素、和pKa小于1的有机强酸的衍生物，式中的R具有上述相同的含义，条件是至少一个R¹衍生自pKa小于1的有机酸(以后称作通式2)。The above-mentioned extended general formula 1 and the catalytic activity and dual curing ability of the monomer organotin represented by the following general formula are also disclosed:

In the formula, R, R ² and x have the same meaning as the above-mentioned general formula 1, and each R ¹ is selected from OR, OH, OOCR, halogen, and a derivative of a strong organic acid with pKa less than 1, and R in the formula has the above-mentioned Same meaning, provided that at least one R ¹ is derived from an organic acid with a pKa of less than 1 (hereinafter referred to as general formula 2).

An expanded form of Formula I which has found utility in catalysis and dual cure is:

In the formula, each R is selected from alkyl, aryl and alkaryl containing 1-20 carbon atoms respectively;

^Each R is independently selected from OR, OH, OOCR, halogen, and a derivative of a strong organic acid with a pKa of less than 1, wherein R in the formula has the same meaning as above provided that at least one R is derived from an organic acid with a pKa of less than 1;

Each R ² is independently selected from the same groups as R and R ¹ ;

n is an integer with an average value of 0-20;

x represents the amount of bound water, and x can be as low as 0, and when the catalyst is dissolved in an aqueous solution, x approaches infinity.

The above formula is sometimes referred to as "Extended Formula 1". The difference between general formula 1 and extended general formula 1 lies in the definition of R ¹ . In extended formula 1, at least one ^R must be derived from an organic acid with a pKa less than 1, while the derivatives of strong organic acids in formula 1 are limited to OSO ₂ R. Thus, the general formula 1 is extended to include all compounds of the general formula 1 as well as compounds having a value of ^R1 different from _OSO2R .

It has also been found that organotin compounds of formula 1, extended formula 1 and formula 2 can simultaneously catalyze more than one polymerization reaction for the preparation of polyurethane, polyurea, polysiloxane or amino polymer. Simultaneous catalysis of more than one such reaction is referred to herein as "dual cure".

Also provided are novel methods of preparing compounds of Formula 1, Extended Formula 1 and Formula 2 using water and at least one other polar solvent.

The novel organic tin sulfonates are polystannoxane salts of strong organic acids represented by general formula 1. It has now been found that organotin compounds represented by general formula 1, extended general formula 1 and general formula 2 are excellent candidates for esterification reactions, transesterification reactions or polymerization reactions for the preparation of polyurethanes, polyureas, polysiloxanes and amino polymers. catalyst. Although the organotin catalyst of the present invention can be represented by the above general formula, a mixture of organotin compounds is obtained during preparation. This mixture has been analyzed and deduced to conform to the above formula, where n and x are average values. The analytical results of the compounds of the present invention are consistent with the structures represented by the general formula 1, the extended general formula 1 or the general formula 2, and the analytical results are also consistent with the compounds represented by the following comparable empirical formulas. The above structural and empirical formulas are considered equivalent for the purposes of the present invention. The value of x in general formula 1, extended general formula 1 and general formula 2 can change significantly, for example, the average value of x can be 0-250, for the water-soluble substance of general formula 1, extended general formula 1 and general formula 2, The upper limit of x can be much larger than 250, and it approaches infinity in aqueous solution. In aqueous solution, the equivalent general formula is the general formula without "x( _H2O )".

At least one ^R in general formula 1, extended general formula 1 and general formula 2 is preferably selected from the following group:

(a) OSO ₂ R, wherein R is respectively selected from alkyl, aryl and alkaryl groups containing 1-20 carbon atoms;

(b) RCOO, where R is an alkyl or aryl group, and the carbon atom connected to the COO group contains at least one F, Cl, Br, I, CN bonded thereto;

(c) RPO ₃ H, where R is selected from alkyl, aryl and alkaryl groups containing 1-20 carbon atoms;

(d) RCrO ₄ H, where R is selected from alkyl, aryl and alkaryl groups containing 1-20 carbon atoms;

(e) _F ; _NO3 ; _ClO4 ; and ( _NO ) _2C6H2OH .

When one ^R in the extended formula 1 or 2 is selected from the preferred group, except when the choice is F, NO ₃ or ClO ₄ , at least one ^R in the general formula is derived from a pKa less than 1 organic acid requirements. The most preferred choice for ^R1 is p-toluenesulfonate or mesylate. A preferred choice for R and ^R2 is butyl. Preferred values of n in Formula 1 and Extended Formula 1 are 0-3.

synthesis

U.S. Patent No. 3,094,434 discloses a method for synthesizing monostannoxane sulfonates represented by the general formula 2. This patent reference is incorporated herein.

Polystannoxane sulfonates represented by Formula 1 and extended Formula 1 have been synthesized in several different ways, for example:

1. Add 130.0 g (0.52 mol) of dibutyltin oxide (DBTO), 99.34 g (0.52 mol) of hydrated p-toluenesulfonic acid and heptane to the Ann-Stark separator and condenser in a 1 L flask. The mixture was heated to reflux with stirring. The water produced by the reaction and the bound water in p-toluenesulfonic acid were removed by distillation. The condensed vapor is collected in a Dean-Stark separator, the water in the lower layer is removed, and the upper organic phase is returned to the reaction flask.

After refluxing for 3 hours, the heat was removed and the mixture was allowed to cool to room temperature. The solid was filtered off and allowed to dry under vacuum at 60°C for 12 hours. The solid product had a "sticky" consistency. The analytical results of the product are as follows:

Analysis: measured value

%Sn 28.8

Acid value 134 (mgKOH/g)

% _H2O 2.74 (Karl-Fisher)

%LOD 0.59 (100°C, 75 Torr, 2 hours)

This produces polystannoxanes that can be represented by general formula I, wherein R and ^R are butyl, ^R is p-toluenesulfonate, n is 0-0.1, and x is 0-0.3. Similarly, the reaction The analysis result of the product is consistent with the polystannoxane whose empirical formula is R ₂ SnAO-[R ₂ SnO] _x -SnR ₂ A(H ₂ O) _n , in which all R are butyl groups and A is p-toluenesulfonate Acid radicals, derivatives of organic strong acids, x is 0-0.1, n is about 0.3. Regardless of whether the product (eg, as prepared by the synthetic methods described above and identified by the analytical methods described above) is represented by the empirical formula or by the general formula 1, they are equivalent for the purposes of the present invention.

2. Add 124.45 grams (0.50 moles) of dibutyltin oxide, 95.11 grams (0.50 moles) of p-toluenesulfonic acid hydrate, 150.0 grams of 2-propanol and 150 grams of deionized water into a 1 L flask with thermometer, paddle stirrer and cooler. The mixture was heated to reflux with stirring and maintained at reflux for 1 hour. Heating was discontinued, the reaction mixture was allowed to cool to about 25°C, and the solid product was filtered and allowed to dry at 50°C under vacuum at 50 Torr for 2.5 hours. In contrast to the product of Synthesis 1, the product produced in a mixed solvent system of water and organic polar solvent was easily filtered and dried to a non-"sticky" granular crystalline solid.

Analysis: measured value

%Sn 27.3

Acid Value 128 (mgKOH/g)

% _H2O 8.46 (Karl-Fisher)

%LOD 5.64 (100°C, 75 Torr, 2 hours)

Analysis results confirmed that the reaction product is polystannoxane represented by general formula 1, all R are butyl, all ^R1 are p-toluenesulfonate, the average value of n is 0-0.1, and the value of x is 3. 1. Likewise, the analytical results are consistent with the reaction products of polystannoxanes with the empirical formula R ₂ SnAO-[R ₂ SnO] _x -SnR ₂ A(H ₂ O) _n , where all R are butyl groups and A is organic Derivatives of strong acids and p-toluenesulfonate, x is 0-0.2, n is about 3.

3. Add 124.44 grams (0.50 moles) of dibutyltin oxide, 95.11 grams (0.50 moles) of p-toluenesulfonic acid hydrate, 150.0 grams of 2-propanol and 150 grams of deionized water into a 1 L flask with thermometer, paddle stirrer and cooler. The mixture was heated to reflux with stirring for 1 hour. Heating was discontinued, the reaction mixture was allowed to cool to about 25°C, the solid product was filtered and allowed to dry at 80°C under vacuum at 50 Torr for 8 hours. The product was readily filtered and dried to a non-"sticky" granular crystalline solid.

Analysis: measured value

%Sn 28.3

Acid Value 131 (mg KOH/g)

% _H2O 4.28 (Karl-Fisher)

%LOD 1.87 (100°C, 75 Torr, 2 hours)

This produces a polystannoxane represented by the general formula 1, all R are butyl, all ^R1 are p-toluenesulfonate, n has an average value of 0-0.1, and x has a value of 1.0. Likewise, the analytical results of this reaction product are consistent with polystannoxanes of the empirical formula R ₂ SnAO-[R ₂ SnO] _x -SnR ₂ A(H ₂ O) _n , where all R are butyl groups, A It is a derivative of strong organic acid, and it is p-toluenesulfonate, x is 0-0.2, and n is about 1.

As shown in Syntheses 2 and 3, preferred syntheses use at least two polar solvents. One solvent is preferably water and the other polar solvent is an alcohol, especially a C ₁ -C ₅ aliphatic alcohol, in particular methanol, ethanol, propanol and butanol (including isomers). Synthesis in a solvent mixture of water and at least one other organic polar solvent yields crystalline organotin compounds represented by general formula 1, extended general formula 1 and general formula 2, which have properties such that the compound Unique property of being easy to dry to a non-sticky crystalline powder. Water preferably comprises at least about 25%, most preferably 50%, of the polar solvent mixture.

Esterification and Transesterification

When at least one R ¹ in formula 1, extended formula 1 or formula 2 is OSO ₂ R, the resulting organotin sulfonate (polystannoxane, monomeric stannoxane or organotin sulfonate ) are surprisingly effective catalysts for esterification and transesterification reactions in addition to polyurethane, siloxane and amino polymerization or condensation reactions.

dual cure

The organotin catalysts represented by Formula 1, Extended Formula 1 and Formula 2 have also now been found to have good catalytic activity and dual cure capability. When a composition contains more than one polyurethane, siloxane, amino group and ester forming reaction reactant, the catalyst represented by extended general formula 1 and general formula 2 has the ability to simultaneously catalyze two or more polyurethanes, esters, The surprising ability of siloxanes and amino groups to form reactions. This simultaneous catalysis is referred to hereinafter as "dual cure" catalysis. In order for a catalyst to catalyze two different reactions simultaneously in a mixture of various reactants, the catalyst must catalyze the various reactions at reasonably equivalent reaction rates such that no one reaction appears to be substantially complete before the other. In other words, if one reaction achieves the desired degree of cure or completeness in a certain amount of time with a particular catalyst, another desired reaction with the same catalyst at the same concentration should achieve the same order of magnitude in time and preferably within A comparable degree of cure is achieved within + or -50% of the reaction time. This can be determined by separately testing the desired reaction with the catalyst of interest. In contrast, the current commercial standard uses at least two different catalysts to catalyze various reactions, whereas the single organotin catalyst of the present invention can catalyze all reactions as well as different commercial standard catalysts. Thus, a single catalyst represented by Formula 1, Extended Formula 1, or Formula 2 can effectively catalyze more than one such reaction simultaneously. A particular advantage of the catalyst's dual cure capability is in two or more layered coatings. Coatings such as automotive paint are typically applied in several layers, such as a pigmented base coat and a clear top coat. Coating formulations for primers are pigmented compositions containing polyurethane, silicone and/or melamine-forming reactants, while clear topcoats typically contain polyurethane and/or melamine-forming reactants and are free of pigments. For the dual curing catalyst of the present invention, the catalyst can be added to the coating formulation of the first layer (i.e. the bottom layer), the second layer (i.e. the surface coating) is coated on the bottom layer, and before the bottom layer is cured, The surface coating contains no or less catalyst. When cured, the bottom layer may cure more quickly due to the presence of a more effective amount of catalyst. During the curing process of the bottom layer, the catalyst migrates to the surface layer (ie, the upper layer) to promote the curing of the surface layer. This also results in a strong bond between the layers and also allows volatile components to evaporate through the as yet uncured upper layer during the curing of the bottom layer. Although the upper layer is preferably catalyst-free, the upper layer may contain less catalyst than the bottom layer. Less catalyst is the amount of catalyst that cures the top layer over a longer period of time (eg, more than twice as long as the bottom layer cures). The multi-layer coating system using the catalyst of the present invention and the catalyst concentration gradient between the layers has the advantage of a single curing step after each layer is coated, and the catalyst gradually migrates upwards between the layers during the curing process, improving the effective catalyst of the upper layer. concentration.

Catalyst application

The catalytically effective amount of the catalyst is usually about 0.01-5%, especially about 0.05-2%, based on the weight of metal in the catalyst and the total weight of polymerizable solids. All percentages or other parts in this application are by weight unless otherwise stated. The catalysts of general formula 1, extended general formula 1 and general formula 2 can be used in combination with other catalysts, especially catalysts containing tin and zinc, such as dibutyltin dilaurate, dibutyltin oxide and zinc neononanoate.

Reactant

Reactants for transesterification and esterification:

The reactants for transesterification and esterification are well known to those skilled in the art. For example, reactants for transesterification reactions include monomeric and polymeric esters of carboxylic acids capable of reacting with monomeric or polymeric alcohols. The reactants of the esterification reaction include monocarboxylic or polycarboxylic acids capable of reacting with monomeric alcohols or polymeric alcohols.

polymer forming reactants

The reactants used to form polymers such as polyurethanes, polyureas, polysiloxanes and aminopolymers are well known to those skilled in the polymer art. The reactants used to form polyurethanes are generally aromatic and aliphatic isocyanates and blocked isocyanates capable of reacting with polyols and polyamino compounds.

The reactants used to form polysiloxanes are generally alkoxysilanes (and alkoxyacryloylsilanes) capable of reacting with polymeric hydroxyl compounds. Conventional reaction products for the preparation of amino resins such as melamine polymers include condensations of urea, melamine, carbamoylated melamine, glycolurils, benzoguanamines, etc., usually reactive with formaldehyde or buranol product reactants. Acrylic carbamate can also react with melamine as a reactant.

other (optional) ingredients

Other components typically added to coating or polymer compositions such as co-catalysts, pigments, fillers, extenders and polymer modifiers can be added to the compositions shown in this application.

Example

Example A

A conventional formulation for the simple urethane reaction with polyol (neophenyl alcohol) and isocyanate (cyclohexyl isocyanate) to form urethane. Since neither the above-mentioned isocyanates nor alcohols are polyfunctional, urethanes are formed instead of polyurethanes. This straight forward reaction was used to screen catalysts with urethane catalytic activity. The catalytic activity of several catalysts of the present invention listed in Table A (Formula 1 and Formula 2) was compared with the industry standard catalyst (dibutyltin dilaurate) used for this urethane reaction. The comparison is made on the basis of equal weight of tin to calculate the amount of catalyst added to the formulation. After adding the catalyst to the formulation, the reaction was allowed to proceed at room temperature. The degree of consumption of isocyanate (formation of urethane) over time was monitored by FTIR. Relative reaction rates were determined from first order kinetics. The higher the reaction rate, the faster the urethane is formed. In contrast to the well-known urethane catalysts (dibutyltin dilaurate), none of the catalysts of the present invention are effective urethane catalysts for the reaction of alcohols with isocyanates. This confirms the common understanding in the art that acid groups slow the urethane reaction and leads one to conclude that the catalysts of the present invention are not effective catalysts for urethane formation reactions. The following examples illustrate the invention and its preferred embodiments.

Example 1

Evaluation of the catalytic activity of conventional automotive polyurethane resurfacing. Based on the results of Example A, the catalysts of the present invention (Formula 1, Extended Formula 1 and Formula 2) were not expected to be effective when compared to the current industry standard catalyst (Dibutyltin Dilaurate, DBTDL). Aliquots of formulations of acrylate-based polyester polyols and hexamethylene diisocyanate were prepared in xylene and ketones, each containing sufficient catalyst, calculated on the weight of tin and total weight of solids in the formulation, to account for 0.14%. After adding the catalyst, the formulation was kept at 25°C and the time (in hours) for the formulation to form a gel was recorded as an indicator of "pot life". In addition, prepare the coating with each formulation, and record the time (in hours) for the coating to reach the drying parameter of the sol-gel transition at room temperature and use B. K． The drying recorder records the surface drying time. The results are listed in Table 1. The performance of the catalyst of the present invention is as good as the industry standard of DBTDL.

Example 2

Evaluation of the catalytic effect of blocked isocyanates for the preparation of polyurethane coatings. The catalysts of the present invention (Formula 1, Extended Formula 1 and Formula 2) were compared with the current industry standard catalyst (dibutyltin dilaurate, DBTDL). Aliquots of MEKO terminated HDI, acrylate based polyol formulations were prepared in MAK (2-heptanone) and MIBK (methyl isobutyl ketone) solvents. Each sample contained sufficient catalyst to represent 0.14% catalyst based on the weight of tin and the total weight of solids in the formulation. The formulation is preheated to 70-80°C so that the selected catalyst can dissolve in the formulation. After the catalyst was added to the preheated formulation, the temperature of the formulation was raised to 130°C and the time (in minutes) required for the formulation to reach the gel point (2500 centipoise) was recorded with a Brookfield viscometer. The stated gel point indicates substantially complete reaction. The results are listed in Table 2. The performance of the catalyst of the present invention is better than the industry standard of DBTDL.

Example 3

In combination with a zinc-containing cocatalyst (zinc neodecanoate), the catalytic effect of blocked isocyanates for the preparation of polyurethane coatings was evaluated as described in Example 2. The inventive catalysts (Formula 1, Extended Formula 1 and Formula 2) with and without co-catalysts were compared to current industry standard catalysts (dibutyltin dilaurate, DBTDL) and zinc neodecanoate. Aliquots of formulations containing acrylate-based polyols, oxime-terminated isocyanates, MAK, and MIBK were prepared, each containing the amount of catalyst shown in Table 3 (by weight of tin, for zinc neodecanoate, by weight of zinc). If necessary, the formulation is preheated to allow the selected catalyst to dissolve in the formulation. After the catalyst was added to the preheated formulation, the temperature of the formulation was raised to 120°C and the time required for the formulation to reach the gel point (2500 centipoise) was recorded. This gel point indicated that the reaction was essentially complete. The results are listed in Table 3. The performance of the catalyst of the present invention is better than the industry standard of DBTDL, and the addition of zinc neodecanoate co-catalyst improves the performance of the catalyst of the present invention.

Example 4

Compared with DBTDL, this example evaluates the effect of the catalyst concentration on the catalytic performance of the catalyst represented by the extended formula 1 in the reaction of blocked isocyanate and polyol for the preparation of polyurethane coating. The catalyst of the present invention was compared to the current industry standard catalyst, dibutyltin dilaurate (DBTDL). The catalyst used is polystannoxane represented by extended general formula 1, in which R is butyl, R ¹ is OCOCF ₃ , n is 0, and x is 0. It is consistent with polystannoxanes represented by the empirical formula R ₂ SnAO-[R ₂ SnO] _x -SnR ₂ A(HxO)n, where all R are butyl, A is a derivative of a strong organic acid, and is OCOCF ₃ , x is 0, and n is about 0. Aliquots of formulations containing Desmophen A565 (an acrylic polyol available from Bayer), Desmodur BI3175A (an oxime-terminated isocyanate available from Bayer), MAK, and MIBK were prepared, each containing Table 4 Sufficient amounts of different catalysts shown (% catalyst calculated on weight of tin and total weight of solids in the formulation). After the catalyst was added to the preheated formulation, the formulation was raised to the temperature shown in Table 4 and the time (in minutes) required for the formulation to reach the gel point (2500 centipoise) was recorded. This gel point indicated that the reaction was essentially complete. The results are listed in Table 4. Even when the concentration of DBTDL is 250% higher, the performance of the catalyst of the present invention is better than the industry standard of DBTDL.

Example 5

The catalysts of the present invention were evaluated for their ability to catalyze the polymerization of siloxanes compared to DBTDL. The reactant is tetrapropyl silicate crosslinker for silanol terminated polydimethylsiloxane oil. The formulation containing the desired catalyst was heated to 140°C in a stirred plastic beaker. The time (in minutes) required to reach the gel point was recorded. Excellent performance is obtained with the catalysts of the present invention except in cases where the catalyst is insoluble in the reaction mixture. The results are listed in Table 5.

Example 6

Compared with DBTDL and Nacure 5626 (available from King Industries, an amine-terminated dodecylbenzenesulfonic acid), the ability of the catalyst of the present invention to catalyze the crosslinking reaction of melamine formaldehyde with acrylic polyols was evaluated. The reactants used for formulation in each test were 60.2 g of hexamethoxymelamine (Cymel 303) and 140.71 g of acrylic polyol (Joncryl 500) dissolved in 100 g of butanone (MEK). The formulation containing the desired catalyst was heated to 140°C in a stirred plastic beaker. The time (in minutes) required to reach the gel point was recorded. Superior performance is obtained with the catalyst of the present invention compared to the comparative tin-based catalyst (DBTDL). The results are listed in Table 6.

Example 7

Compared with dibutyltin oxide (DBTO) and butylstannoic acid (BSA), this example evaluates the ability of the catalyst of the present invention to catalyze esterification and transesterification. The reactants are phthalic anhydride and 2-ethylhexanol, the reaction temperature is 220°C, and the alcohol excess is 5%. The formulation containing the desired catalyst was maintained at 220°C and the decrease in acid value over time (hours) was monitored. The catalyst was added in the same weight as tin and in a ratio of 100 mg tin/100 g phthalic anhydride. The reaction was considered complete when the acid number was below about 3. Excellent performance is obtained with the catalysts of the present invention. The results are listed in Table 7.

Table A

Catalyst Relative Rate

                                     

Bu ₂ Sn(OSO ₂ CH ₃ ) ₂ ⁽¹⁾ insoluble

Bu ₂ Sn(pTSA) ₂ ⁽²⁾ 0.17

[Bu ₂ Sn(pTSA)] ₂ O ⁽³⁾ 0.07

1. General formula 2, R and ^R2 are butyl, ^R1 is mesylate

2. General formula 2, R and ^R2 are butyl, ^R1 is p-toluenesulfonate

3. General formula 1, R and R ² are butyl, R ¹ is p-toluenesulfonate, n=0, x is about 0.

Table 1

Catalyst Performance in Polyurethane Coatings Catalyst Sol-Gel Transition Surface Drying Time Pot Life (Hours)

(hour) (hour) dibutyltin dilaurate 3.0 3.8 6.0Bu ₂ Sn(OSO ₂ CH ₃ ) ₂ ⁽¹⁾ 5.0 8.0 7.8Bu ₂ Sn(pTSA) ₂ ⁽²⁾ 3.0 6.5 6.0 [ _Bu2Sn (pTSA)] _2O ⁽³⁾ 3.0 4.0 5.0

1. General formula 2, R and ^R2 are butyl, ^R1 is mesylate

2. General formula 2, R and ^R2 are butyl, ^R1 is p-toluenesulfonate

3. General formula 1, R and R ² are butyl, R ¹ is p-toluenesulfonate, n=0, x is about 0.

Table 2 catalyst %tin gel time@130 gel time@125 DBTDL 0.14 23.4 Bu ₂ Sn(OCOCCl ₃ ) ₂ ⁽¹⁾ 0.14 25.2 {Bu ₂ Sn(OCOCCl ₃ )} ₂ O ⁽²⁾ 0.14 14.9 {Bu ₂ Sn(OCOCF ₃ )} ₂ O ⁽³⁾ 0.14 15.1 Bu ₂ Sn(OSO ₂ CH ₃ ) ₂ ⁽⁴⁾ 0.14 15.7 {Bu ₂ Sn(OSO ₂ CH ₃ )} ₂ O ⁽⁵⁾ 0.14 15.2 {Bu ₂ Sn(OSO ₂ CH ₃ )} ₂ O ⁽⁵⁾ 0.14 22.6 {Bu ₂ Sn(OSO ₂ CH ₃ )} ₂ O ⁽⁵⁾ 0.11 26.2 {Bu ₂ Sn(OSO ₂ CH ₃ )} ₂ O ⁽⁵⁾ 0.095 30.4 {Bu ₂ Sn(OSO ₂ CH ₃ )} ₂ O ⁽⁵⁾ 0.082 33.4

1. General formula 2, R and ^R2 are butyl, ^R1 is trichloroacetate

2. Extending formula 1, R and ^R2 are butyl, ^R1 is trichloroacetate, n=0 and x is about 0

3. Extending formula 1, R and ^R2 are butyl, ^R1 is trifluoroacetate, n=0 and x is about 0

4. General formula 2, R and ^R2 are butyl, ^R1 is mesylate

5. General formula 1, R and R ² are butyl, R ¹ is mesylate, n=0 and x is about 0

table 3 catalyst %Metal Gel time @120C note Dibutyltin dilaurate 0.2% Sn 48.7 Zinc neodecanoate 0.35% Zn >40 Bu ₂ Sn(OSO ₂ CH ₃ ) ₂ (1) 0.2% Sn 26.4 Dissolve at 70°C Bu ₂ Sn(OSO ₂ CH3) ₂ ⁽¹⁾ + Zinc neodecanoate 0.2%Sn0.07%Zn 22.1 Dissolve at 70°C {Bu ₂ Sn(OCOCF ₃ )} ₂ O ⁽²⁾ 0.2% Sn 27.3 Dissolve at 70°C {Bu ₂ Sn(OCOCF ₃ )} ₂ O ⁽²⁾ + Zinc neodecanoate 0.2%Sn0.07%Zn 20.4 Dissolve at 7O℃ Bu ₂ Sn(OCOCCl ₃ )} ₂ ⁽³⁾ 0.2% Sn 27.2 Dissolve at 40°C Bu ₂ Sn(OCOCCl ₃ ) ₂ ⁽³⁾ + Zinc neodecanoate 0.2% Sn 13.4 Dissolve at 40°C {Bu ₂ Sn(OCOCCl ₃ )} ₂ O ⁽⁴⁾ 0.2% Sn 25.5 Dissolve at 25°C {Bu ₂ Sn(OCOCCl ₃ )} ₂ O ⁽⁴⁾ + Zinc neodecanoate 0.2%Sn0.07%Zn 12.7 Dissolve at 25°C

1. General formula 2, R and ^R2 are butyl, ^R1 is mesylate

2. Extending the general formula 1, R and ^R2 are butyl, ^R1 is trifluoroacetate, n=0, x is about 0

3. General formula 2, R and ^R2 are butyl, ^R1 is trichloroacetate

4. Expand the general formula 1, R and ^R2 are butyl, ^R1 is trichloroacetate, n=0, x is about 0

Table 4

Effect of increasing catalyst concentration on performance catalyst %Sn Min@130℃ Min@125℃ Min@120℃ Dibutyltin dilaurate 0.20 18.6 48.7 Dibutyltin dilaurate 0.50 17.3 33.5 {Bu ₂ Sn(OCOCF ₃ )} ₂ }O ⁽¹⁾ 0.20 13.0 18.6 27.3 {Bu ₂ Sn(OCOCF ₃ )} ₂ }O ⁽¹⁾ 0.5 11.8 16.2 24.0 1. Extending the general formula 1, R and ^R2 are butyl, ^R1 is trifluoroacetate, n=0, x is about 0

table 5

Curing temperature °C catalyst g Gel time (minutes) 140 Dibutyltin dilaurate 0.63 149.9 140 Bu ₂ Sn(OAc) ₂ ⁽¹⁾ 0.35 96.4 140 Bu ₂ OAcSnOSnOAcBu ₂ ⁽²⁾ 0.44 >130.0 (insoluble) 140 Bu ₂ Sn(OCOCCl ₃ ) ₂ ⁽³⁾ 0.56 11.5 140 [Bu ₂ (OCOCCl ₃ )Sn] ₂ O ⁽⁴⁾ 0.40 12.4 140 [Bu ₂ (OCOCF ₃ )Sn] ₂ O ⁽⁵⁾ 0.35 10.7 140 Bu ₂ Sn(OCOCF ₃ ) ₂ ⁽⁶⁾ 0.46 8.8

1. General formula 2, R and ^R2 are butyl, ^R1 is acetate

2. Expand the general formula 1, R and ^R2 are butyl, ^R1 is acetate, n=0, x is about 0

3. General formula 2, R and ^R2 are butyl, ^R1 is trichloroacetate

4. Expand the general formula 1, R and ^R2 are butyl, ^R1 is trichloroacetate, n=0, x is about 0

5. Extending the general formula 1, R and ^R2 are butyl, ^R1 is trifluoroacetate, n=0, x is about 0

6. General formula 2, R and ^R2 are butyl, ^R1 is trifluoroacetate

Table 6

Melamine Crosslinking

catalyst Solubility at room temperature Gel time@115℃(min) Bu ₂ Sn(OSO ₂ CH ₃ ) ₂ ⁽¹⁾ partially dissolved 6.1 {Bu ₂ Sn(OSO ₂ CH ₃ )} ₂ O ⁽²⁾ partially dissolved 5.9 Nacure 5625 (amine-terminated sulfonic acid) to dissolve 6.4 Dibutyltin dilaurate to dissolve >100 Dibutyltin oxide to dissolve >100

1. General formula 2, R and ^R2 are butyl, ^R1 is mesylate

2. General formula 1, R and R ² are butyl, R ¹ is mesylate, n=0, x is about 0

Equimolar addition of catalyst

Catalyst concentration = 0.18 mmol, based on the total weight of solids

Gel time measurements (Brookfield viscometer) were performed at 115°C

Measure the rate of viscosity increase to the gel point (2500 centipoise)

Table 7

The relationship between acid value and time

time (hours) DBTO ⁽¹⁾ BSA ⁽²⁾ BuSn(MSA) ₃ ⁽³⁾ Bu ₂ Sn(MSA) ₂ ⁽⁴⁾ (Bu ₂ SnMSA) ₂ O ⁽⁵⁾ (Bu ₂ SnpTSA) ₂ O ⁽⁶⁾ 0.5 63.9 60.5 27.5 32.2 41.8 43.6 1.0 40.5 69.1 10.5 15.8 23.2 22.6 1.5 29.2 23.0 5.3 9.1 14.2 14.2 2.0 22.4 12.1 3.3 5.6 9.2 9.3 2.5 17.5 7.6 3.8 6.5 5.9 3.0 13.4 4.7 3.9 3.8 3.5 10.1 4.0 7.2 4.5 5.3 5.0 3.8

1. Dibutyltin oxide

2. Butylstannoic acid

3. General formula 2, R is butyl, R ¹ and R ² are mesylate

4. General formula 2, R and ^R2 are butyl, ^R1 is mesylate

5. General formula 1, R and R ² are butyl, R ¹ is mesylate, n=0, x is about 0

6. General formula 1, R and R ² are butyl, R ¹ is p-toluenesulfonate, n=0, x is about 0

Claims (15)

1. have the poly-tin oxygen alkane salt of the organic acid of multiple catalytic activity, it is characterized in that it contains the compound that useful following general formula is represented:

Each R is selected from alkyl, aryl and the alkaryl that contains 1-20 carbon atom respectively in the formula; Each R ¹Be selected from OR, OH, OOCR, halogen and the pKa derivative less than 1 organic acid respectively, condition is R ¹At least a selection be OSO ₂R, the R in the formula have above-mentioned identical implication; Each R ²Be selected from respectively and R and R ¹Identical group; N is that mean value is the integer of 0-20; X is 0 to convergence infinity when this catalyst is in the aqueous solution.

2. tin oxygen alkane as claimed in claim 1 is characterized in that each R ¹Be selected from OSO respectively ₂R, R has the implication identical with R in the claim 1 in the formula; R ³COO, R in the formula ³Be alkyl or aryl, contain at least one F of bonding, Cl, Br, I, CN mutually with it with carbon atom that the COO group connects; RPO ₃H, R has the implication identical with R in the claim 1 in the formula; RCrO ₄H, R has the implication identical with R in the claim 1 in the formula; F; NO ₃ClO ₄(NO) ₂C ₆H ₂OH; Condition is R ¹At least a OSO that is chosen as ₂R.

3. improved curable polymer coating composition is characterized in that its logically mixes at least one group and be selected from polyurethane and form reactant, siloxanes and form reactant, aminoly form polymer that reactant and ester form reactant and form reactant and constitute or make; Its improvement is included in the catalyst of the organic tin salt of adding organic acid in the described composition as described polymer formation reactant reaction, and described catalyst is selected from the organo-tin compound of representing corresponding to following general formula:

With

Each R is selected from alkyl, aryl and the alkaryl that contains 1-20 carbon atom respectively in the formula; Each R ¹Be selected from OR, OH, OOCR, halogen and the pKa derivative less than 1 organic acid respectively, the R in the formula has above-mentioned identical implication; Condition is at least one R ¹Derived from pKa less than 1 organic acid; Each R ²Be selected from respectively and R and R ¹Identical group; N is that mean value is the integer of 0-20; X is 0 to convergence infinity when this catalyst is in the aqueous solution.

4. composition as claimed in claim 3 is characterized in that each R ¹Be selected from OSO respectively ₂R, R has the implication identical with R in the claim 1: R in the formula ⁴COO, R in the formula ⁴Be alkyl or aryl, contain at least one F of bonding, Cl, Br, I, CN mutually with it with carbon atom that the COO group connects; RPO ₃H, R has the implication identical with R in the claim 1 in the formula; RCrO ₄H, R has the implication identical with R in the claim 1 in the formula; F; NO ₃ClO ₄(NO) ₂C ₆H ₂OH; Condition is R ¹At least a OSO that is chosen as ₂R.

5. composition as claimed in claim 3 is characterized in that it is that polyurethane forms reactant that described one group of polymer forms reactant.

6. composition as claimed in claim 3 is characterized in that it is that siloxane polymer forms reactant that described one group of polymer forms reactant.

7. composition as claimed in claim 3 is characterized in that it also comprises the co-catalyst that contains zinc or tin.

8. composition as claimed in claim 3 is characterized in that it is that amino resins forms reactant that described one group of polymer forms reactant.

9. composition as claimed in claim 3 is characterized in that two groups of polymer form reactant and are blended in the described composition.

10. composition as claimed in claim 9 is characterized in that it is that amino polymer forms reactant and polyurethane forms reactant that described two groups of polymer form reactant.

11. composition as claimed in claim 10 is characterized in that it is that melamine forms reactant that described amino polymer forms reactant.

12. improved coating, it is two-layer at least to it is characterized in that it comprises, ground floor contains coating composition as claimed in claim 3, the second layer that also contacts with it above the ground floor contains coating composition as claimed in claim 3, but does not contain catalytic component as claimed in claim 3 or contain the catalyst more less than ground floor.

13. improving one's methods of an organic tin salt for preparing the organic acid of representing with following general formula: Or

Each R is selected from alkyl, aryl and the alkaryl that contains 1-20 carbon atom respectively in the formula; Each R ¹Be selected from OR, OH, OOCR, halogen and the pKa derivative less than 1 organic acid respectively, the R in the formula has above-mentioned identical implication; Condition is at least one R ¹Derived from pKa less than 1 organic acid; Each R ²Be selected from respectively and R and R ¹Identical group; N is that mean value is the integer of 0-20; X is 0 to convergence infinity when this catalyst is in the aqueous solution; It is characterized in that described method is included in the reactant reaction that makes the described organic tin salt of preparation in the dicyandiamide solution; Its improvement comprises that the mixture with at least two kinds of polar solvents is used as dicyandiamide solution, and wherein a kind of solvent is a water, and another kind of solvent is an alcohol.

14. as claimed in claim 13 improving one's methods is characterized in that it also comprises the steps:

(a) the tin oxygen alkane in the above-mentioned polar solvent mixture is cooled off and crystallization;

(b) from described mixture, separate tin oxygen alkane;

(c), produce crystallization, graininess, non-sticky solid with this tin oxygen alkane drying.

15. the crystallization, graininess, the non-sticky solid that make with the described method of claim 12.