CA1246285A

CA1246285A - Room temperature vulcanizable organopolysiloxane compositions and method for making

Info

Publication number: CA1246285A
Application number: CA000484889A
Authority: CA
Inventors: Thomas P. Lockhart; Jeffrey H. Wengrovius
Original assignee: General Electric Co
Current assignee: General Electric Co
Priority date: 1984-08-27
Filing date: 1985-06-21
Publication date: 1988-12-06
Also published as: FR2569415B1; GB2163765B; JPH055261B2; DE3529567A1; GB2163765A; JPS6183254A; FR2569415A1; GB8514485D0

Abstract

ROOM TEMPERATURE VULCANIZABLE ORGANOPOLYSILOXANE
COMPOSITIONS AND METHOD FOR MAKING

ABSTRACT OF THE DISCLOSURE

Room temperature vulcanizable organopolysiloxane compositions are provided based on the use of a silanol or alkoxy terminated organopolysiloxane and an effective amount of a diorganotin dicarboxylate and an amine accelerator.

Description

lZ'-~6Z85 ROOM TEMPERATURE VULCANI ZAsLE ORGANOPOLYSILOXANE
COMPOSITIONS AND METHOD FOR MAKING

Background of the I_vention The present invention relates to room temperature vulcanizable (~TV) organopolysiloxane compositions having improved shelf stability and corrosion resistance~ More particularly, the present invention relates to RTV organopolysiloxane compositions using an effective amount of a particular tin condensation catalyst having organo radicals attached to ti by carbon-tin linkages and whose remaining valences are satisfied by a dicarboxylate radical.
For example, di-n-butyltin-diethylmalonate can be used in combination with an amine cure accelerator, . ~ r,, di-~-butylamine.
Prior to the present invention, as shown by Brown et al., U.S. Patent 3,161,614, attempts were made to make RTV organopolysiloxane compositions employing a polyalkoxy end blocked diorganopolysiloxane and a monocarboxylic acid metal salt catalyst, such as dibutyltindilaurate. These compositions did not cure satisfactorily. Improved results were obtained by Beers, U.S. Pat. 4,100,129, assigned to the same assignee as the present invention, utilizing as a ;~J

1~6Z~5 RD-15891 condensa~ion catalyst, a silanol reactive organometallic ester having organo radicals attached to metal through metal-oxygen-carbon linkages. Experience has shown tha. in instances where silanol reactive organo tin compounds are used as RTV condensation catalysts which have organo ra&i-cals attached to tin by tin-oxygen-carbon linkages the resulting moisture curable compositions are often unstable.
As utilized hereinafter, the term "stable" as applied to the one package polyalkoxy-terminated organopoly-siloxane RTV's of the present invention, means a moisturecurable mixture capable of remaining substantially unchanged while excluded from atmospheric moisture and which cures to a tack-free elastomer after an extended shelf period. In addition, a stable RTV also means that the tack-free time exhibited by freshly mixed RTV ingredients under atmospheric conditions will be substantially the same as that exhibited by the same mixture of ingredients exposed to atmospheric moisture after having been held in a moisture resistant and moisture-free container for an extended shelf period at ambient conditions, or an equivalent period based on accel-erated aging at an elevated temperature.
Further advances in RTV stability have been achieved with the employment of silane scavengers for eliminating chemically combined hydroxy radicals, water, or methanol, as shown by White et al., United States Patent number 4,395,526 which patent is assigned to the same assignee as the present invention. However, the preparation of these silane scavengers, such as methyldimethoxy-(N-methylacetamide)silane often require special techniques and undesirable by-products can be generated during cure.
Further improvements are shown by Dziark for scavengers for one component alkoxy functional RTV compositions and pro-cess, U.S. Patent 4,417,042, assigned to the same assignee as the present invention.
Organic scavengers for the removal of trace amounts of water, methanol and silanol are shown by White et al, United States Patent No. 4,472,551 for One Package, Stable, Moisture Curable Alkoxy Terminated Organopolysiloxane Compositions issued September 18, 1984, assigned to the same assignee as the present invention.
Additional scavenging techniques for chemically combined hydroxy functional radicals are shown by Lockhart in United States Patent Number 4,467,063 issued August 21, 1984.
Although the above discussed techniques for improving the stability of room temperature vulcanizable organopolysiloxane compositions employing a tine condensation catalyst have been found to provide stable, substantially acid-free, curabel organopol,vsiloxanes, a separate organic, inorganic, or organosilicon scavenger for hydroxy functional radicals is required. It would be desirable to make stable room temperature vulcanizalbe organopolysiloxane compositions utilizing a silanol terminated, or alkoxy terminated polydiorganosiloxane and a tin condensation catalyst which can be used in further combination with an alkoxy silane cross-linking agent and optionally an amine accelerator without the employment of additional materials such as scavengers for hydroxy functional materials.
The present invention is based on a discovery that stable fast curing RTV compositions can be made by utilizing a tin condensation catalyst having the formula (1) (R)2Sn[Y3 where Y is a dicarboyxlate group having the formula, 12~6Z85 RD-15891 - O O
-O-C ( Rl ) aC~O~

R is selected from C(l 18) monovalent hydrocarbon radicals and substituted ~(1-18) monovalent hydrocarbon radicals, is selected rom C(l 18) divalent hydrocarbon radicals and substituted C(l 18) divalent hydrocarbon radicals, and a is a whole number having a value of O or 1.
Some of the silanol terminated polydiorgano-siloxanes which can be used to make the stable, substantial-ly acid~free, moisture curable organopolysiloxane composi-tions of the present invention have the formula,

(2) HO - ~ iO- I II
~2 m where R is a C(1-13) monovalent hydrocarbon radical or substituted monovalent hydrocarbon radical, which is prefer-ably methyl, or a mixture of a major amount of methyl and a minor amount of phenyl, cyanoethyl, trifluoropropyl, vinyl, hydrogen and mixtures thereof, and m is an integer having a value of from about 5 to about 5000.
Polyalkoxy terminated organopolysiloxane which can be used to make the RTV compositions of the present inven-tion has the formula, (IR )a ~ (~3)a 25 (3) (R40)3 a~iO - (~iO ~ i~ OR )3-a ~2 where R2 and m are as previously defined, R3 is a monovalent radical selected from C(l 13) hydrocarbon radicals and ~246Z8~ ~D-15891 substituted C(1_13) hydrocarbon radicals, R4 is a C(l aliphatic organic radical selected from alkyl ~adicals, alkylether radicals, alkylester radicals, alkylketone radicals and alkylcyano or a C(7 13) aralkyl radical and a S is as previously defined.
The RTV compositions of the present invention also can contain a cross-linking polyalkoxysilane having the formula, (R3) I a 10(4) (R )4 a~i

3 4 where ~ , R and a are as prev1ously deflned.

Statement of the Invention There is provided by the present invention, room temperature vulcanizable compositions comprising by weight, (A) 100 parts of organopolysiloxane consisting essentially of chemically combined diorganosiloxy units and terminated with polyalkoxy siloxy units, (B) Q to 10 parts of a polyalkoxy silane of formula (4), (C) 0 to 5 parts of amine accelerator, and (D) an effective amount of a tin condensation catalyst of formula (1).
Also included within the scope of the present invention is a method for making room temperature vulcaniz-able organopolysiloxane compositions which comprises, mixingtogether under substantially anhydrous conditions, the following ingredients by weight, (i) 100 parts of alkoxy terminated organopoly-siloxane of formula (3), _5_ ~Z46~85 R~-15891 - (ii) 0 to lO parts of polyalkoxysilane of formula (4) (iii) 0 to 5 parts of amine accelerator, ~nd (iv) an effective amount of tin condensation catalyst of formula (l).
In a further aspect of the present invention, there is provided a method for making a room temperature vulcanizable organopolysiloxane composition which comprises, (l) agitating under substantially anhydrous conditions (i) lO0 parts of silanol terminated polydiorganosiloxane of formula (2), (ii) O.l to lO parts of alkoxy silane of formula (4), (iii). 0 to 5 parts of amine accelerator, and (iv) 0 to 700 parts of filler (2) allowing the mixture of (l) to equilibrate to produce polyalkoxy terminated polydiorganosiloxane, and (3) further agitating the mixture of (2) under substantially anhydrous conditions with an effective amount of a tin condensation catalyst of formula (l).
Radicals included within R of formula (l) are, for example, C(6 13) aryl radicals, halogenated aryl radicals, and alkylaryl radicals such as phenyl, tolyl, chlorophenyl, ethylphenyl and naphthyl; C(l 18) aliphatic, cycloaliphatic radicals, and halogenated derivatives thereof, for example, cyclohexyl, cyclobutyl; alkyl and alkenyl radicals, such as methyl, ethyl, propyl, chloropropyl, butyl, pentyl, hexyl, heptyl, octyl, vinyl, allyl, and trifluoropropyl. Radicals included within Rl are, for example, methylene, dimethylene, trimethylene, tetramethylene, alkyl substituted dialkylene radical, such as dimethylmethylene, diethylmethylene, alphadimethylethylene, 2,2-dimethylpropylene; etc.;

:~246Z~35 cycloaliphatic radicals, for example, cyclobutylene, cyclopentylene, cyclohexylene, cyclooctylene, etc.;
C(6 13) arylene radicals such as phenylene, tolylene, xylene, naphthylene, etc. where the aforesaid R
radicals can be further substituted with monovalent radicals such as halogen, cyano, ester, amino, silyl and hydroxyl. Radicals included within R3 are all of the C(l 13) monovalent radicals shown for R, where R and R can be the same or different. Radicals included within R4 can be more particularly methyl, ethyl, propyl, butyl, etc. benzyl, phenylethyl, 2-methoxyethyl, 2-acetoxyethyl, l-butan-3-onyl, 2-cyanoethyl.
Some of the tin condensation catalysts included within formula (1) are, Eor example, di-n-butyltindeiethylmalonate, di-n-octyltinsuccinate, di-n-octyltinoxalate, di-n-butyltinhexahydrophthalate, dimethyltinadipate, di-n-butyltin glutamate, di-n-propyltin(2-cyanoglutarate), di-sec-butyltin adipate, and di-n-pentyltinphthalate.
Included within the cross-linking polyalkoxysilanes of formula (4) are, for example, methyltrimethoxysilane; methyltriethoxysilane;
ethyltrimethoxysilane; tetraethoxysilane;
vinyltrimethoxysilane; etc.
Among the amine curing accelerators which can be used in the practice of the present invention are silyl substituted guanidines having the formula, (5) (Z)gSi(OR ~4 g where R4 is a previously defined, Z is a guanidine radical of the formula, ~Z46285 RD-15~91 ~5) ~
~ =N-R7 (R6)2N~

where R7 is divalent C(2 8) alkylene radical, R5 and R6 are selected from hydrogen and C(1-8) alkyl radicals and g is an integer equal to 1 to 3 inclusive. In addition, alkyl substituted guanidines having the formula, (R5) ~
~C=N- R8 (R )2N

where R5 and R6 are as previously defined and R8 is a C(l 8) alkyl radical, also can be employed. Some of the silyl substituted quanidines included within formula (5) are shown by Takago U.S. Patents 4,180,64~ and 4,248,993.
In addition to the above substituted guanidines, there can be used various amines, for example, di-n-hexyl-amine, dicyclohexylamine, di-n-octylamine, hexamethoxy-methylmelamine, and silylated amines, for example, ~-amino-propyltrimethoxysilane and methyldimethoxy-d-n-hexylamino-silane. Methyldimethoxy-di-n-hexylaminosilane acts as both a cross-linker and curing accelerator. Th primary amines, secondary amines, silylated secondary amines are preferred and secondary amines, and silylated secondary amines are particularly preferred. Silylated secondary amine such as 25 alkyldialkoxy-n-dialkylaminosilanes and guanidines such as alkyldialkoxyalkylguanidylsilanes which are useful as cure accelerators.
In addition to the above-described amine accelera-tors, there is also included in the practice of the present ~246Z85 RD-15891 invention the use of certain sterically hindered diamines which have been found to effect rapid cures of the RTV
compositions of the present invention when utilized in effective amounts as previously defined. These nitrogen bases include, for example, di-t-~utylethylene diamine (DBEDA), l,5-diazabicyclo[4.3.0]non-5-ene ~DBN), and 1,8-di-azabicyclo[5.4.0]undec-7-ene (DBU).
Silanol-terminated polydiorganosiloxanes of formula (2) are well known and preferably have a viscosity in the range of from about lO0 to about 400,000 centipoise and more preferably from about lO00 to about 250,000 centi-poise when measured at about 25C. These silanol-terminated fluids can be made by treating a higher molecular weight organopolysiloxane, such as dimethylpolysiloxane with water in the presence of a mineral acid, or base catalyst, to tailor the viscosity of the polymer to the desired range.
Methods for making such higher molecular weight organopoly-siloxane utilized in the production of silanol-terminated polydiorganosiloxane of formula (2) aiso are well known.
For example, hydrolysis of a diorganohalosilane such as dimethyldichlorosilane, diphenyldichlorosilane, ~ethylvinyl-dichlorosilane, or mixtures thereof, can provide for the production of low molecular weight hydrolyzate. Equilibra-tion thereafter can provide for higher molecular weight organopolysiloxane. Equilibration of cyclopolysiloxane such as octamethylcyclotetrasiloxane, octaphenylcyclotetra-siloxane, or mixtures thereof, will also provide for higher molecular weight polymers. Preferably, such polymers are decatalyzed of equilibration catalyst by standard procedures prior to use, such as shown by Boot U.S. Patent 3,153,007, assigned to the same assignee as the present invention.
Silanol-terminated organopolysiloxanes having viscosities below 1200 centipoises can be made by treating _g_ ~246Z85 RD-15891 organopolysiloxanes consisting essentially of chemically combined diorganosiloxy units with steam under pressure.
Other methods that can be employed to make silanol-termin-ated polydiorganosiloxanes are more particularly described in U.S. Patent 2,607,792 to Warrick and U.K. Patent 835,790.
In order to facilitate the cure of the RTV compo-sitions of the present invention, the tin condensation catalyst of formula (l) can be utilized at from 0.1 to 10 parts of tin catalyst, per lOO parts of the silanol terminated or alkoxy terminated polydiorganosiloxane, and preferably from O.l to l.O part, per lOO parts of the polydiorganosiloxane.
Various fillers, pigments, adhesion promoters, etc., can be incorporated in the silanol or alkoxy-termin-ated organopolysiloxane, such as for example, titaniumdioxide, zirconium silicate, silica aerogel, iron oxide, diactomaceous earth, fumed silica, carbon black, precipitat-ed silica, glass fibers, polyvinyl chloride, ground quartz, calcium carbonate, ~-cyanoethyltrimethoxysilane, etc. The amounts of filler used can obviously be varied within wide limits in accordance with the intended use. For example, in some sealant applications, the curable compositions of the present invention can be used free of filler. In other applications, such as the employment of the curable composi-tions for making binding material on a weight basis, as muchas 700 parts or more of filler, per 100 parts of organopoly-siloxane can be employed. In such applications, the filler can consist of a major amount of extending materials, such as ground quartz, polyvinylchloride, or mixtures thereof, preferably having an average particle size in the range of from about l to lO microns.
The compositions of the present invention also can be employed as construction sealants and caulking compounds.

i246285 The exact amount of filler, therefore, will depend upon such ~
factors as the application for which the organopolysiloxane composition is intended, the type of filler utilized (that is, the density of the filler and its particle si~e).
Preferably, a proportion of from l0 to 300 parts of filler, which can include up to about 35 parts of a reinforcing filler, such as fumed silica filler, per l00 parts of silanol-terminated organopolysiloxane is utilized.
In the practice of the invention, the room temper-ature vulcanizable compositions can be made by agitating, for example, stirring under moisture-free conditions, a mixture of materials which can consist of the tin condensa-tion catalyst and the alkoxy terminated polydiorganosilox-ane. Optionally, cross-linking polyalkoxysilane and amine accelerator can be used.
In instances where silanol terminated polydi-organosiloxane is used in place of the alkoxy terminated polydiorganosiloxane it i~ preferred that blending of the filler, for example,~fumc silica, the silanol terminated . .~,~
polydiorganosiloxane and the cross-linking polyalkoxysilane be performed ~ in the absence of the tin condensation catalyst. The tin condensation catalyst can be introduced advantageously after the resulting blend has been agitated for a period of about 24 hours at room temperature.
As used hereinafter, the expressions "moisture free conditions" and "substantially anhydrous conditions", with reference to making the RTV compositions of the present invention, mean mixing in a dry box, or in a closed contain-er which has been subjected to vacuum to remove air, which thereafter is replaced with a dry inert gas, such as nitro-gen. Temperatures can vary from about 0C to about 180C
depending upon the degree of blending, the type and amount of filler.

lZ~6285 - A preferred procedure for making the RTV composi- ~
tions of the present invention is to agitate under substan-tially anhydrous conditions a mixture of the silanol termin-ated polydiorganosiloxane or alkoxy terminated polydiorgano-siloxane, filler and an effective amount of the tin conden-sation catalyst. There can be added to the mixture, the cross-linking silane or mixture thereof along with other ingredients, for example, the curing accelerator and pig-ments.
In order that those skilled in the art will be better able to practice the invention, the following example is given by way of illustration and not by way of limita-tion. All parts are by weight.

Example 1 A mixture of 300 grams of dibutyltin oxide, 193 grams of diethylmalonic acid, and 500 ml. of toluene was refluxed for 1 hour. There was collected 21 grams of water in a Dean Stock trap by azeotropic distillation. The reac-tion mixture was then filtered while hot and allowed to cool to ambient temperatures. Removal of the solvent in vacuo provided 460 grams (98% yield) of dibutyltin diethylmalonate as a white crystalline solid. The identity of the product was confirmed by NMR, IR and FD-MS analysis.
A base RTV formulation was prepared by thoroughly mixing all the parts of a methyldimethoxysiloxy terminated polydimethylsiloxane having a viscosity of about 40,000 centipoise at 25C, 0.3 part of dibutylamine, 17 parts of fume silica, 30 parts of a trimethylsiloxy terminated polydimethylsiloxane having a viscosity of 100 centipoise at 25C and 1.4 part of ~-cyanoethyltrimethoxysilane.

lZ~6285 - There was added to 100 grams of the above base RTV -formulation, 0.35 gram of dibutyltindiethylmalonate and 0.30 grams of methyltrimethoxysilane. The resulting RTV formula-tion was blended for 15 minutes under substantially anhy-drous conditions in a Semco mixer. One half of the RTV wasthen heat aged for 48 hours at 100C and the other half of the RTV was stored at 25C. The RTV's were evaluated while under substantially anhydrous conditions in sealed contain-ers. Upon exposure to atmospheric moisture, the heat aged RTV and the unaged RTV cured to a tack-free state in 30 minutes.
The following table summarizes the physical properties of the cured products obtained from the aged and unaged RTV's after 12 days of cure where "H" is hardness (Shore A), "T" is tensile (psi), "E" is elongation ~%), "M"
is modulus (psi).

M
RTV (48H) H T E ~ 75~ 100%
25C 19 246 375 44.256.0 68.0 20100C 22 262 382 48.461.1 72.9 Those RTV's were also found to pass the vapor phase corro-sion of copper metal test as described in Military Specifi-cation No. 46146A. In addition, the RTV's were found to be non-yellowing.

Exam~le 2 A mixture of 161.4 grams of dibutyltin oxide and 100 grams of hexahydrophthalic anhydride was heated to reflux in 100 ml. of toluene for 2 hours. During this time, the dibutyltin oxide dissolved quickly and formed a yellow homogeneous solution. After cooling, the reaction mixture .~ was filtered. ~ solvent was removed in vacuo and a quanti-~ di~
tative yield of a yellow glassy solid was obtained. Based on method of preparation and its NMR spectra the solid was dibutyltin hexahydrophthalate.
An RTV composition was prepared by mixing together under anhydrous conditions lO0 parts of a dimethoxymethyl-siloxy endcapped polydimethylsiloxane having a viscosity of 20,000 centipoises at 25C, l part of ~-cyanoethyltrimeth-oxysilane, 20 parts of fumed silica, 20 parts of a tri-methylsiloxy terminated polydimethylsiloxane having a viscosity of lO0 centipoises, l part of 1,3,5-tris(tri-methoxysilylpropyl) isocyanurate, 0.08 part of di-~-butyl-amine, 0.25 part of the above di-~-butyltin hexahydrophtha-late condensation catalyst and 0.3 part of methyltrimethoxy-silane.
A portion of the above RTV composition was allowed to cure under atomospheric moisture over ambient conditions.
It had a tack free time of about 20 minutes. Another portion of the RTV composition was heated under sealed conditions for 120 hours at 70C. The tack free time was found to be 25 minutes when allowed to cure under atmos-pheric conditions.

Example 3 A mixture of lO00 grams of dibutyltin oxide, 587.2 grams adipic acid and 500 ml. of toluene were refluxed for 3 hours. There was obtained 72 grams of water by azeotropic distillation. The reaction mixture was then hot filtered and the solvent was removed in vacuo from resulting light yellow filtrate. After drying, there was obtained lS01 grams of a dibutyltin adipate or a 99.1% yield. The product 12gL6~35 had a melting point of 128-130C. The identity of the product was further confirmed by its NMR spectrum.
An RTV formulation was prepared by mixing together under substantially anhydrous conditions 100 parts of a methyldimethoxysiloxy endcapped polydimethylsiloxane of Example 2, 20 parts of fumed silica, 20 parts of the tri-methylsiloxy endcapped silicone oil, 1.4 part of ~-cyano-ethyltrimethoxysilane, 1 part of ~, 1,3,5-tris(trimethoxysilylpropyl) isocyanurate, 0.3 part of dibutyltin adipate, 0.05 part of di-~-butyl amine and 0.3 part of methyltrimethoxysilane. A portion of the RTV
formulation was allowed to cure under atmospheric conditions and it was found to have a tack free time of 15 minutes.
Another portion of the RTV composition was heat aged for 120 hours at 70C. It was found to have a tack free time of 30 minutes.

Exam~le 4 As shown in copending application RD-15866, filed concurrently herewith, the compositions of the present invention can be rendered less corrosive to copper when in contact with copper under ambient conditions over an extended period of time as follows:
An RTV base formulation was prepared by mixing together under substantially anhydrous conditions 100 parts by weight of a methyldimethoxysiloxy terminated polydi-methylsiloxane having a viscosity of 40,000 centipoises at 25C, 0.3 part of dibutylamine, 30 parts of a trimethoxy-siloxy terminated polydimethylsiloxane having a viscosity of 100 centipoise at 25C, 17 parts of fumed silica and 1.4 part of ~-cyanoethyltrimethoxysilane.

- RTV formulations were prepared by blending togeth- ~
er under substantially anhydrous conditions 100 parts of the base polymer mixture, 0.35 part of dibutyltin(diethylmalo-nate) and 0.30 part of methyltrimethoxysilane (mixture 1).
A mixture of 100 parts of the base polymer was also blended with 0.30 part of dibutyltindiethylmalonate, 0.13 part of benzotriazole and 0.30 part of methyltrimethoxysilane (mixture 2). A third mixture was prepared employing 100 parts of the base polymer, 0.37 part of dibutyltindiethyl-10 malonate, 0.02 part of Reomet 39, a Ciba-Giegy benzotriazole derivative, and 0.66 part of methyltrimethoxysilane (mixture 3).
The above three formulations were blended under substantially anhydrous conditions and were mixed for 15 minutes in a Semco mixer. Five grams of each of the RTV
formulations were applied to the surface of a 2" x 2"
section of clean copper metal. The RTV's were allowed to cure for 7 days while in contact with the copper metal surface. The samples were then heated to 120F in a 95%
relative humidity environment for 28 days. A portion of the RTV sample was then removed from each of the copper sub-strates and the exposed substrate was visually examined for corrosion. It was found that the RTV made from mixture 1 left a blue film on the copper indicating that corrosion of the copper surface had occurred. There was no evidence of any change in the surface of the copper as shown by a clean metallic appearance of the RTV samples which were formed from mixture 2 and 3.
Although the above examples are directed to only a few of the very many variables which can be utilized in making the room temperature vulcanizable composition of the present invention, it should be understood that the room temperature vulcanizable compositions of the present RD-15~91 ~ 246Z85 invention can be formulated from a much broader variety of tin dicarboxylate salts as shown by formula (l), silanol terminated polydiorganosiloxanes as shown by formula (2), polyalkoxysilanes as shown by formula (3) and all of the other ingredients shown in the description preceding this example.

Claims

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A stable, moisture curable room temperature vulcanizable organopolysiloxane composition substantially free of organic solvent and scavenger for hydroxy functional material which is capable of substantially maintaining the same tack-free time as when freshly mixed after and extended shelf period at ambient conditions in a moisture-resistant moisture free container, comprising by weight:
(A) 100 parts of a polydiorganosiloxane having terminal polyalkoxy siloxy units, (B) 0.1 to 10 parts of a polyalkoxy silane, (C) 0.05 to 5 parts of an amine accelerator selected from the class consisting of primary amines, secondary amines, silyl-substituted alkyl guanidines and alkyl-substituted ]
(D) up to 700 parts of filler, and (E) an effective amount of a tin carboxylate condensation catalyst selected from the class consisting of di-n-butyltindiethylmalonate, di-n-octyltindiethyl-malonate, di-n-octyltinsuccinate, di-n-butyltinglutamate, di-n-butyltin(2-cyanoglutarate), and di-n-pentyltinphthalate.

2. A composition in accordance with claim 1, where the carboxylate tin catalyst is di-n-butyltindiethyl-malonate.

3. A composition in accordance with claim 1, where the tin catalyst is di-n-octyltindiethylmalonate.

4. A composition in accordance with claim 1, where the tin catalyst is di-n-octyltinsuccinate.

5. A composition in accordance with claim 1, where the tin catalyst is di-n-octyltinoxylate.

6. A composition in accordance with claim 1, where the tin catalyst is di-n-butyltinhexahydrophthalate.

7. A composition in accordance with claim 1, where the tin catalyst is di-n-butyltinglutamate.

8. A composition in accordance with claim 1, where the tin catalyst is di-n-butyltin(2-cyanoglutarate).

9. A composition in accordance with claim 1, where the tin catalyst is di-n-pentyltinphthalate.

10. A stable, moisture curable room temperature vulcanizable organopolysiloxane composition useful as a construction sealant and caulking compound which is substantially free of organic solvent and scavenger for hydroxy functional material consisting essentially of by weight (A) 100 parts of a silanol terminated poly-diorganosiloxane, (B) 0.1 to 10 parts of a polyalkoxy silane, (C) 0.05 to 5 parts of an amine accelerator selected from the Glass consisting of primary amines, secondary amines, silyl-substituted alkyl guanidines and alkyl-substituted guanidines, (D) up to 700 parts of filler, and (E) an effective amount of a tin dicarboxylate condensation catalyst selected from the class consisting of di-n-butyltindiethylmalonate, di-n-octyltindiethyl-malonate, di-n-octyltinsuccinate, di-n-octyltinoxylate, di-n-butyltinhexahydrophthalate, di-n-butyltinglutamate, di-n-butyltin(2-cyanoglutarate), di-n-pentyltinphthalate, and dimethyltinadipate.

11. A composition in accordance with claim 10, where the tin catalyst is di-n-butyltindiethylmalonate.

12. A composition in accordance with claim 10, where the tin catalyst is di-n-octyltindiethylmalonate.

13. A composition in accordance with claim 10, where the tin catalyst is di-n-octyltinsuccinate.

14. A composition in accordance with claim 10, where the tin catalyst is di-n-octyltinoxylate.

15. A composition in accordance with claim 10, where the tin catalyst is di-n-butyltinhexahydrophthalate.

16. A composition in accordance with claim 10, where the tin catalyst is di-n-butyltin-glutamate.

17. A composition in accordance with claim 10, where the tin catalyst is di-n-butyltin(2-cyanoglutarate).

18. A composition in accordance with claim 10, where the tin catalyst is di-n-pentyltinphthalate.

19. A composition in accordance with claim 10, where the tin catalyst is dimethyltinadipate.

20. A stable, moisture curable room temperature vulcanizable organopolysiloxane composition substantially free of organic solvent and scavenger for hydroxy functional material which is capable of substantially maintaining the same tack-free time as when freshly mixed after an extended shelf period at ambient conditions in a moisture-resistant moisture free container, comprising by weight:
(A) 100 parts of a polydiorganosiloxane having terminal polyalkoxy siloxy units, (B) 0.1 to 10 parts of a polyalkoxy silane, (C) 0.05 to 5 parts of an amine accelerator selected from the class consisting of primary amines secondary amines, silyl-substituted alkyl guanidines and alkyl-substituted guanidines, (D) up to 700 parts of filler, and (E) an effective amount of a tin dicarboxylate condensation catalyst having the formula (R)2Sn[Y] , where Y is a dicarboxylate group having the formula, R is selected from C(1-18) monovalent hydro-carbon radicals and substituted C(1-18) monovalent hydro-carbon radicals, R1 is a C(3-9) dialkyl substituted methylene, and a is a whole number having a value of 0 or 1.

21. A stable, moisture curable room temperature vulcanizable organopolysiloxane composition useful as a construction sealant and caulking compound which is substantially free of organic solvent and scavenger for hydroxy functional material consisting essentially of by weight:
(A) 100 parts of a silanol terminated poly-diorganosiloxane, (B) 0.1 to 10 parts of a polyalkoxy silane, (C) 0.05 to 5 parts of an amine accelerator selected from the class consisting of primary amines, secondary amines, silyl-substituted alkyl guanidines and alkyl-substituted guanidines, (D) up to 700 parts of filler, and (E) an effective amount of a tin dicarboxylate condensation catalyst having the formula (R)2Sn[Y]
where Y is a dicarboxylate group having the formula, R is selected from C(1-18) monovalent hydro-carbon radicals and substituted C(1-18) monovalent hydro-carbon radicals, R1 is a C(3-9) dialkyl substituted methylene, and a is a whole number having a value or 0 or 1.