DE3529567A1 - AT ROOM TEMPERATURE, VULCANIZABLE ORGANOPOLYSILOXANES, THEIR PRODUCTION AND ORGANOZIN COMPOUNDS - Google Patents

Description

description

The present invention relates to room temperature vulcanizable (RTV) organopolysiloxane compositions, which improves storage stability and corrosion resistance to have. The invention relates in particular to RTV organopolysiloxane compositions in which an effective Amount of a particular tin condensation catalyst used by carbon-tin bonds Tin has bound organic residues and the remaining valences are saturated by dicarboxylate residues. Di-n-butyltin diethyl malonate can e.g. be used in conjunction with an amine hardening accelerator, namely di-N-butylamine will.

Prior to the present invention, attempts were made to terminate polyalkoxy groups in RTV organopolysiloxane compositions having diorganopolysiloxane and a monocarboxylic acid metal salt catalyst, such as dibutyltin dilaurate to be used as shown in US-S 3,161,614. These Masses did not harden satisfactorily. Improved Results were obtained according to US-S 41 00 129, in which a silanol-reactive organometallic ester, which by Metal-oxygen-carbon bonds bound to metal Has organic residues, is used as a condensation catalyst. Tests have shown that on occasions where silanol-reactive organotin compounds act as RTV condensation catalysts through tin-oxygen-carbon bonds Organo residues bound to tin can be used, the resulting moisture hardenable Crowds are often unstable.

The term "stable" used in the following, as used in the case of the one having a polyalkoxy end group One-component organopolysiloxane RTV mass of the present

Invention applied relates to a moisture-curable composition which is essentially unchanged remains if it is excluded from the humidity and after a relatively long storage period hardens to a tack-free elastomer. Furthermore, a stable RTV mass also means that the tack-free time, the newly mixed RTV ingredients exhibit under atmospheric conditions is essentially the same as that of the mixture of ingredients, which has been exposed to humidity after being in a moisture-proof and moisture-free Container has been kept in ambient conditions for a relatively long period of time, or the accelerated aging at an elevated temperature for an equivalent period of time.

Further progress in terms of RTV stability, were achieved through the use of silane cleaners to remove chemically bound hydroxy residues, of water or methanol, as described in US Pat. No. 4,395,526, which is incorporated herein by reference. The production these silane cleaners, such as methyldimethoxy- (N-methylacetamide) silane however, often requires special procedures and during curing can be undesirable Products are created. Further improvements for cleaners for one-component alkoxy-functional RTV compounds and method, is shown in U.S. Patent 4,417,042, incorporated herein by reference.

Although the above-described methods to improve the stability of vulcanizable at room temperature Organopolysiloxane compositions in which a tin condensation catalyst is used, stable, im essentially acid-free, curable organopolysiloxanes were obtained, a separate organic, inorganic

scissors or organic silicone cleaner for the functional parts Hydroxy residues required. It would be desirable to have stable organopolysiloxane compounds vulcanizable at room temperature produce, in which a silanol end groups or alkoxy end groups comprising polydiorganosiloxane and a tin condensation catalyst is used, which in one further combination with an alkoxysilane crosslinking agent and optionally an amine accelerator without additional Substances such as detergents for functional hydroxyl groups can be used.

The present invention is based on the discovery that stable, fast-curing RTV compounds by using a tin condensation catalyst of formula 15

(1) (R) ₂ Sn [Y]

in which Y is a dicarboxylate group of the formula

O O

Il 1 Il

-0-C (R) C-O-

is, R is made up of monovalent C. ,, ".- hydrocarbon radicals and substituted C ,, _, g »monovalent hydrocarbon radicals , R is derived from divalent C ,,,, - hydrocarbons residues and substituted divalent ones

C / T ι ο χ hydrocarbon radicals is selected, and a ν -L-iö;

is an integer with the value 0 or 1.

Some of the silanol-terminated polydiorganosiloxanes that are used to produce stable, essentially acid-free, moisture-curable organopolysiloxane compositions of the present invention can be used have the formula

(2) HO-

-H

wherein R ^ is a monovalent C., ..- hydrocarbon radical or substituted monovalent hydrocarbon radical, preferred Methyl 'or a mixture of a main amount of methyl and a smaller amount of phenyl, cyanoethyl, trifluoropropyl, Vinyl, hydrogen, and mixtures thereof, and m is an integer having a value between about 5 to about 5000.

Organopolysiloxanes containing polyalkoxy end groups, which are used to produce the RTV compositions of the present Invention can be used have the formula

^ (R ³ ) _a R ² (R ³ ) _a

4i (OR ⁴ ) ₃ . _a

2
wherein R and m have the meaning given above, R is a monovalent, from C., _, ^ v-hydrocarbon radicals and substituted C _M _, ~. -Carbon radicals selected radical, R is an aliphatic organic C _{1 _, g, radical, which is selected from alkyl radicals, alkyl ether radicals, alkyl ester radicals, alkyl ketone radicals and alkyl cyan or a C / -7_, ₃ \ -aralkyl radical, and has a the meaning described above.

The RTV compositions of the present invention can also be a crosslinking polyalkoxysilane of the formula

⁽ ? ^{3) β}

3 4

contain, in which R, R and a have the meaning given above.

The present invention provides vulcanizable compositions at room temperature which

(A) 100 parts of organopolysiloxane, consisting mainly of chemically bonded diorganosiloxy units and polyalkoxysiloxy end groups consists,

(B) 0 to 10 parts of a polyalkoxysilane of the formula (4),

(C) 0 to 5 parts of an amine accelerator, and

(D) an effective amount of a tin condensation catalyst of formula (1),

contained in parts by weight.

The invention further relates to a method for the production of organopolysiloxane compositions vulcanizable at room temperature, which can be mixed together under im essential anhydrous conditions, the following ingredients in parts by weight, namely

(a) 100 parts of an alkoxy end group organopolysiloxane of the formula (3),

(b) 0 to 10 parts of a polyalkoxysilane of the formula (4),

(c) 0 to 5 parts of an amine accelerator, and

(d) an effective amount of a tin condensation catalyst of formula (1),
includes.

In a further version of the present

Finding a process for the preparation of at room temperature vulcanizable organopolysiloxane compositions created that

(1) Stirring under essentially anhydrous conditions from

(A) 100 parts of silanol-terminated polydiorganosiloxane of the formula (2),

(b) 0.1 to 10 parts of an alkoxysilane of the formula (4),

(c) 0 to 5 parts of an amine accelerator, and (d) 0 to 700 parts of a filler,

(2) Allowing the mixture of (1) to equilibrate to produce polyalkoxy-terminated polydiorganosiloxanes and

(3) further stirring the mixture of (2) under substantially anhydrous conditions with an effective Amount of a tin condensation catalyst of formula (1).

To the R of the formula include (1) included radicals, for example C ₍₆ _, _3-beta-aryl radicals, halogenated aryl radicals and alkylaryl radicals such as phenyl, tolyl, chlorophenyl, ethylphenyl, and naphthyl; C ,, _, _g aliphatic, cycloaliphatic Residues and their halogenated derivatives, for example cyclohexyl, cyclobutyl; alkyl and alkenyl radicals, such as methyl, ethyl, propyl, chloropropyl, butyl, pentyl, hexyl, heptyl, octyl, vinyl, allyl and trifluoropropyl , e.g. methylene, dimethylene, trimethylene, tetramethylene, alkyl-substituted dialkylene radical, such as dimethylmethylene, diethylmethylene, alpha-dimethylethylene, 2,2-dimethylpropylene, etc .; cycloaliphatic radicals, e.g. cyclobutylene, cyclopentylene, cyclohexylene, cyclooctylene, etc .; C , ₆ , ₃ ) -arylene radicals, such as phenylene, tolylene, xylene, naphthylene, etc., in which the

The aforementioned R radicals can be further substituted by monovalent radicals such as halogen, cyano, ester, amino, silyl and hydroxyl. The radicals encompassed by R include all of the monovalent ^c m _n r ^radicals specified for R in which R and R can be the same or different. The radicals encompassed by R can be especially methyl, ethyl, propyl, butyl, etc., benzyl, phenylethyl, 2-methoxyethyl, 2-acetoxyethyl, 1-butan-3-onyl, 2-cyanoethyl.

Some of the tin condensation catalysts encompassed by formula (1) are e.g. di-N-butyltin diethyl malonate, Di-N-octyltin succinate, di-N-octyltin oxalate, di-N-butyltin hexahydrophthalate, Dimethyltin adipate, di-N-butyltin glutamate, di-N-propyltin (2-cyanglutarate), di-sec-butyltin adipate and di-N-pentyltin phthalate.

The crosslinking polyalkoxysilanes of the formula (4) include, for example, methyltrimethoxysilane, methyltriethoxysilane, Ethyltrimethoxysilane, tetraethoxysilane, vinyltrimethoxysilane, etc.

Among the amine hardening accelerators that are used in the The present invention can be practically applied include silyl-substituted guanidines of the formula

(5) (Z) _g Si (OR ⁴ ) ₄ _ _g ,

wherein R has the meaning described above, Z is a guanidine residue of the formula

-14-

where R is a divalent C _{/ oo} . Is alkylene. R and R are made up of hydrogen and C ,, _o , alkyl radicals

t l-ö;

selected and g is an integer from 1 up to and including 3. In addition, alkyl-substituted guanidines of the formula

are used, where R and R have the meaning given above and R is a Cq_o \ alkyl-

rest. Some of the silyl-substituted guanidines in the formula (5) are given in US-Sen 41 80 642 and 42 48 993.

In addition to the substituted guanidines mentioned above, various amines can be used, e.g. di-n-hexylamine, dicyclohexylamine, di-n-octylamine, Hexamethoxymethylmelamine and silylated amines, e.g., S-aminopropyltrimethoxysilane and methyldimethoxy-d-n-hexylaminosilane. Methyldimethoxy-di-n-hexylaminosilane acts as a crosslinker and hardening accelerator. Primary amines, secondary amines, and silylated secondary amines are preferred, and secondary amines and silylated secondary amines are particularly preferred. Silylated secondary Amines such as alkyldialkoxy-n-dialkylamine silanes and Guanidines such as alkyldialkoxyalkylguanidylsilanes are useful as hardening accelerators.

In addition to the amine accelerators described above Certain sterically hindered diamines can also be put to practical use in the present invention

as they rapidly harden the RTV masses of the present Invention when used in effective amounts as previously described. to These nitrogen bases include e.g. di-t-butylethylenediamine (DBEDA), 1,5-diazabicyclo [4,3,0] non-5-ene (DBN) and 1,8-diazabicyclot5,4,0] undec-7-ene (DBU).

Polydiorganosiloxanes of the formula (2) containing silanol end groups are known and preferably have a viscosity in the range of about 100 to about 400,000 centipoise, and more particularly from about 1,000 to about 250,000 Centipoise when measured at a temperature of around 25C. These liquids containing silanol end groups can be prepared by treating higher molecular weight organopolysiloxanes such as dimethylpolysiloxane with water in the presence of a mineral acid or basic catalyst to increase the viscosity of the polymer set to the desired area. Process for the production of such higher molecular weight organopolysiloxanes, those in the manufacture of silane-terminated polydiorganosilxanes of the formula (2) are also known. For example, by hydrolyzing a diorganohalosilane, such as dimethyldichlorosilane, diphenyldichlorosilane, methylvinyldichlorosilane or mixtures thereof, the production of low molecular weight hydrolysates are made possible. The equilibration of the cyclopolysiloxanes, such as octamethylcyclotetrasiloxane, octaphenylcyclotetrasiloxane or mixtures thereof also gives higher molecular weight polymers. The equilibration catalyst is preferably applied to such polymers by conventional methods withdrawn before use, as shown in ÜS-S 31 53 007.

Organopolysiloxanes containing silanol end groups and having viscosities below 1200 centipoise can through

Treatment of organopolysiloxanes, which essentially consist of chemically bonded diorganosiloxy units, can be produced with steam under pressure. Other Processes Used in Making Silanol Endgrouped Polydiorganosiloxanes which can be used are described in more detail in US-S 26 07 792 and GB-PS 835 790.

To facilitate curing of the RTV compositions of the present invention, 0.1 to 10 parts of the can Tin catalyst of the formula (1) to 100 parts of the polydiorganosiloxanes containing silanol end groups or alkoxy end groups and very particularly 0.1 to 1.0 part per 100 parts of the polydiorganosiloxanes can be used.

Various fillers, pigments, adhesion promoters, etc., can be added to the silanol or alkoxy-terminated organopolysiloxane, e.g. Titanium dioxide, zirconium silicate, silicon dioxide airgel, iron oxide, diatomaceous earth, fumed silicon dioxide, carbon black, precipitated silicon, glass fibers, polyvinyl chloride, ground quartz, potassium carbonate, cyanoethyltrimethoxysilane, etc. The amount of filler used can of course can be varied widely in accordance with the intended use. In the case of various applications as a sealant, the curable compositions of the present invention can also be used without fillers. For other applications, such as for example, when using the curable compositions to make binding materials, on a weight basis 700 or more parts of filler per 100 parts of organopolysiloxane can be used. In such applications, the Filler consists mainly of stretching materials, such as ground quartz, polyvinyl chloride or theirs Mixtures, with a preferred particle size in the range of about 1 to 10 µm.

The compositions of the present invention can also be used as a sealant in construction will. The exact amount of filler therefore depends on factors such as the application for which the organopolysiloxane compound is used and the type of filler used (i.e. the density of the filler and its Particle size), 10 to 300 parts of filler are preferred, the up to 35 parts of a reinforcing Fillers, such as fumed silicon dioxide, contain organopolysiloxane containing end groups of silanol per 100 parts can, used.

In the practice of the present invention, the room temperature vulcanizable compositions can be, for example by agitation, e.g. stirring a mixture of materials from the tin condensation catalyst and the alkoxy-terminated polydiorganosiloxane can exist under moisture-free conditions. If appropriate, crosslinking polyalkoxysilanes and amine accelerators can be used.

On occasions where silanol-terminated polydiorganosiloxanes instead of the alkoxy-terminated containing polydiorganosiloxanes are used, the mixing of the fillers, e.g. the pyrogenic Silicon dioxide, the silanol-terminated polydiorganosiloxane and the crosslinking polyalkoxysilane in the absence of the tin condensation catalyst is preferred.

The tin condensation catalyst can be most advantageous after agitating the resulting mixture at room temperature for 24 hours.

The expressions used in the following "moisture-free Conditions "and" essentially water

Free Conditions "in relation to the preparation of the RTV compositions of the present invention refer to mixing in an oven or closed container with the air evacuated and replaced with a dry inert gas such as nitrogen. Temperatures can fluctuate between about 0 C and about 180 ⁰ C and depend on the degree of mixing and the type and amount of filler.

A preferred method of making the RTV compositions of the present invention is by stirring essentially anhydrous conditions of a mixture of silanol end groups or alkoxy end groups Polydiorganosiloxanes, filler and an effective amount of the tin condensation catalyst. To the Mixture can include crosslinking silanes or their mixtures and other ingredients, e.g. curing accelerators and Pigments, are added.

The invention is explained in more detail using the following example. All parts given are parts by weight.

example 1

A mixture of 300 g of dibutyltin oxide, 193 g of diethylmalonic acid and 500 ml of toluene was used during a Heated at reflux for an hour. 21 grams of water was collected by azeotropic distillation in a Dean-Stark trap. The reaction mixture was then filtered while hot and cooled to ambient temperature. Removal of the solvent in vacuo gave 460 g (98% yield) of dibutyltin diethyl malonate as a white crystalline solid. The identity of the product was confirmed by NMR, IR and FD-MS analyzes.

An RTV base mixture was prepared by good mixing of all the parts of a Methyldimethylsiloxy-terminated polydimethylsiloxane having a viscosity of about 40,000 centipoise at 25 ⁰ C, 0.3 parts of dibutylamine, 17 parts of fumed silica, 30 parts of a trimethylsiloxy-end-terminated polydimethylsiloxane a viscosity of 100 centipoise at 25 ⁰ C and 1.4 parts / Q -Cyanethyltrimethoxysilan.

0.35 g of dibutyltin diethyl malonate and 0.30 g of methyltrimethoxysilane were added to 100 g of the abovementioned RTV base batch. The resulting RTV batch was mixed in a Semco mixer for 15 minutes under essentially anhydrous conditions. One half of the RTV composition was heat-aged then 48 hours at 100 ⁰ C and the other half of the RTV composition was stored at 25 ⁰ C. The RTV masses were evaluated while in a sealed container under essentially anhydrous conditions. After exposure to ambient humidity, the heat-aged RTV mass and the unaged RTV mass cured to a tack-free state within 30 minutes.

In the table below are the physical properties of the cured products obtained from the aged and unaged RTV masses obtained after a curing time of 12 days are indicated; "H" means hardness (Shore A), "T" means tensile strength in MPa (psi), "E" means elongation in% and "M" is the modulus in MPa (psi).

RTV (48H) 19th H 1 T 375 25th ⁰ C 22nd 1 . 722 ( 382 100 ° C . 834 ( ; 246) .262)

M.

50% 75% 100%

0.309 (44.2) 0.392 (56.0) 0.476 (68.0) 0.339 (48.4) 0.428 (61.1) 0.510 (72.9)

These RTV masses also passed vapor phase corrosion of the copper metal test, as in the military specification No. 46146A. In addition, it was found that the RTV masses do not yellow.

Example 2

A mixture of 161.4 g of dibutyltin oxide and 100 g of hexahydrophthalic anhydride in 100 ml of toluene 2 Heated at reflux for hours. During this time I solved the dibutyltin oxide developed very quickly and formed a yellow homogeneous solution. After cooling down, the Reagent mixture filtered. The solvent was removed in vacuo and a quantitative yield of a yellow glassy solid was obtained. According to the manufacturing process and its NMR spectrum, the solid was Dibutyltin hexahydrophthalate.

An RTV composition was prepared by mixing together 100 parts of a Dimethoxymethylsiloxy-terminated Polydimetnylsiloxans having a viscosity of 20,000 centipoise at 25 ⁰ C, a part / o-cyanoethyltrimethoxysilane, 20 parts fumed silicon dioxide, 20 parts of a trimethylsiloxy-Ejidgruppen polydimethylsiloxane having a Viscosity of 100 centipoise, one part 1,3,5-tris (trimethoxysilylpropyl) isocyanurate, 0.08

Parts of di-N-butylamine, 0.25 part of the above di-n-butyltin hexahydrophthalate condensation catalyst and 0.3 parts of methyltrimethoxysilane under essentially anhydrous Conditions established.

A portion of the above RTV mass was allowed to cure in ambient humidity and under ambient conditions. It had a tack free time of about 20 minutes. Another part of the RTV mass was sealed and ^{heated to 70 °} C. for 120 hours. The glue-free time was 25 minutes when curing took place under ambient conditions.

Example 3

A mixture of 1000 g of dibutyltin oxide, 587.2 g of adipic acid and 500 ml of toluene was refluxed for 3 hours heated. Azeotropic distillation gave 72 g of water. The reaction mixture was then filtered hot and the solvent was removed from the resulting light yellow filtrate in vacuo. To drying gave 1501 g of dibutyltin adipate, i.e. a yield of 99.1%. The product had one Melting point from 128 to 130 ° C. The identity of the product was also confirmed by its NMR spectrum.

An RTV approach was made by mixing together of 100 parts of methyldimethoxysiloxy-terminated polydimethylsiloxane from Example 2, 20 parts fumed silica, 20 parts trimethylsiloxy end groups exhibiting silicone oil, 1.4 parts / ^ - Cyanethyltrimethoxysilan, 1 part 1,3,5-tris (trimethoxysilylpropyl) isocyanurate, 0.3 part dibutyltin adipate, 0.05 part Di-N-butylamine and 0.3 parts of methyltrimethoxysilane below

essentially anhydrous conditions. Part of the RTV approach was allowed to harden under ambient conditions, with a tack-free time of 15 minutes. Another part of the RTV composition was heat-aged for 120 hours at 70 ⁰ C. It had a tack free time of 30 minutes.

Example 4

As shown in the concurrently filed application with internal file number RD-15866, the Compositions of the present invention can be made less corrosive to copper when under ambient conditions are in contact with copper for an extended period of time, as shown below:

An RTV base mixture was prepared by mixing together 100 parts by weight methyldimethoxysiloxy-terminated polydimethylsiloxane having a viscosity of 40,000 centipoise at 25 ⁰ C, 0.3 parts of dibutyl amine, 30 parts of having trimethoxysiloxy-terminated polydimethylsiloxane having a viscosity of 100 centipoise at 25 ⁰ C , 17 parts of fumed silica and 1.4 parts of A- cyanoethyltrinethoxysilane prepared under essentially anhydrous conditions.

RTV masses were made by mixing together 100 parts of the basic batch, 0.35 parts of dibutyltin (diethyl malonate) and 30 parts of methyltrimethoxysilane (Mixture 1) were prepared under essentially anhydrous conditions. 100 parts of this batch were also mixed with 0.30 parts of dibutyltin diethyl malonate, 0.13 parts Benzotriazole and 0.30 parts of methyltrimethoxysilane (mixture 2) mixed. A third mixture was made with 100

Parts of the basic batch, 0.37 parts of dibutyltin diethyl malonate, 0.02 part of Reomet 39, a Ciba-Geigy benzotriazole derivative and 0.66 parts of methyltrimethoxysilane (Mixture 3).

The three above-mentioned compositions were mixed under essentially anhydrous conditions for 15 minutes in a Semco mixer. 5 g of each RTV mass was applied to the surface of a 5 × 5 cm section of clean copper metal. The RTV masses cured for 7 days while in contact with the copper metal surface. The samples were then heated for 28 days at about 50 ⁰ C in 95% relative ambient humidity. A portion of the RTV sample was then removed from each copper substrate, and the exposed substrates were visually checked for corrosion. It was found that the RTV composition made from Mixture 1 left a blue film on the copper, indicating that corrosion had occurred on the copper surface. For the RTV samples made from Mixtures 2 and 3, there was no evidence of any change in the copper surface as demonstrated by their clean metallic appearance.

Although the above examples address only a few of the very many variables involved in making at room temperature vulcanizable compositions of the present invention can be used, it is clear that the room temperature vulcanizable compositions of the present invention are made up of a much larger number of tin dicarboxylate salts - as shown by the formula (1) polydiorganosiloxanes containing silanol end groups - such as it shows the formula (2) - polyalkoxysilanes - as shown in the formula (3) - and all other components, as in shown in the description preceding the examples.

Claims (1)

Dr. Horst pupil PATENT LAWYER EUROPEAN PATENTATTORNEY NACHQEREIÖHT 6000 Frankfurt / Main 1 Kaiserstrasse 41 0 0 C \ J OD / phone (069) 235555 telex 04-16759 mapat d telegram main patent frankfurt Fax machines (069) 251615 (CCITT group 2 and 3) Bank account 225/0389 Deutsche Bank AG Postal checking account 282420-602 Frankfurt / M. Your reference / Your ref. : P 35 29 567.8 Our sign / Our ref .: 9612.8-RD-15891 Date : September 12, 1985 Dr.Sb:Da GENERAL ELECTRIC COMPANY 1 River Road Schenectady, N.Y./U.S.A. Organopolysiloxane compounds vulcanizable at room temperature, their production and organotin compounds Claims 1. RTV compounds vulcanizable at room temperature, in parts by weight (A) 100 parts of organopolysiloxane, consisting mainly of chemically bonded diorganosiloxy units and Polyalkoxysiloxy units as end groups, consists, (B) 0 to 10 parts of a polyalkoxysilane of the formula 10 (C) 0 to 5 parts of an amine accelerator, and (D) an effective amount of a tin condensation catalyst of the formula 15th (R) ₂ Sn [Y], wherein Y is a dicarboxylate group of Formula 20 is, R from the group of monovalent C _{,,, 0} > -hydrocarbon radicals and substituted monovalent ^C ( ^{1-8) hydrocarbon radicals} , R from divalent C ,, _, gv-hydrocarbon radicals and substituted divalent C ,,., _o .- Hydrocarbon radicals, R is selected from monovalent C _{,,, 3} »-hydrocarbon radicals and substituted monovalent C ,, _,., - hydrocarbon radicals, and R is an aliphatic organic C ,, g. Alkylesterresten, alkylketone and Alkylcyan or C '_ _{7, 3} "aralkyl radicals is selected, and a is an integer having the value 0 or 1 2. RTV composition according to claim 1, in which the tin dicarboxylate Is dibutyltin diethyl malonate. 3. RTV composition according to claim 1, in which the tin dicarboxylate Is dibutyltin hexahydrophthalate. 4 RTV composition according to claim 1, in which the tin dicarboxylate is dibutyltin adipate.
10 5. RTV composition according to claim 1, in which the organopolysiloxane a polydimethylsiloxane liquid with dimethyloxymethylsiloxy end groups is. / ΊΠ) tin dicarboxylate of the formula (R) ₂ Sn [Y]
in which R consists of monovalent C ,. _Ίox hydrocarbon residues \ 1-18 ) and substituted monovalent C, i_io \ hydrocarbon radicals is selected and Y is selected from a malonate group, a hexahydrophthalate group and their substituted Groups selected. 7. tin diethyl malonate according to claim 6. 8. tin hexahydrophthalate according to claim 6. 9. Dibutyl tin diethyl malonate.
30th 10. Dibutyltin Hexahydrophthalate. 11. A process for the preparation of organopolysiloxane compositions vulcanizable at room temperature, the process of missing the following ingredients in parts by weight under im essential anhydrous conditions include: (1) 100 parts of an alkoxy-terminated organopolysiloxane of the formula OK (2) 0 to 10 parts of a polyalkoxysilane of the formula (R ⁴ o) ₄ _ _a k (3) 0 to 5 parts of an amine accelerator, (4) an effective amount of a tin condensation catalyst selected from (R) ₂ Sn [Y] is selected, in which Y is a dicarboxylate group of the formula 0 O -0-U (R ¹ ) JO- Cl is, R is made up of monovalent C ,,,, - hydrocarbon radicals and substituted monovalent C .. _ηo . hydrocarbon -, \ i-iö; Substance radicals, R is selected from divalent C _{1, 8} ) hydrocarbon radicals and substituted divalent C _{,,, Ολ} -Κοη-lenwasserstoffresten, R is a monovalent C ₁₁ ,. ,, hydrocarbon radical or substituted \ l-lj ι 2 monovalent hydrocarbon radical, R is a monovalent radical consisting of C ₍ ,, ^ - hydrocarbon radicals and 35 substituted C , I _- -Hydrocarbon residues- 4th
is selected, R is an aliphatic organic C, ._g. radical, which is selected from alkyl radicals, alkyl ether radicals, alkyl ester radicals, alkyl ketone radicals and alkylcyan or a C ₍₇ _, -.- aralkyl radical) _f m is an integer with a value of about 5 to about 5000 and a is an integer with the value 0 or 1. 12. A process for the preparation of a vulcanizable organopolysiloxane composition at room temperature, the (1) stirring under essentially anhydrous conditions of (a) 100 parts of a silanol-terminated polydiorganosiloxane of the formula HO- OK
2 -H (b) 0.1 to 10 parts of alkoxysilane of the formula (c) 0 to 5 parts of an amine accelerator and (d) 0 to 700 parts of a filler, (2) Equilibrating the mixture of (1) to produce polyalkoxy-terminated polydiorganosiloxanes and (3) further stirring the mixture of (2) under substantially anhydrous conditions with an effective Amount of a tin condensation catalyst of the formula (R) ₂ Sn [Y] in which Y is a dicarboxylate group of the formula Ri? -0-C (R ¹ ) CO- el is, R is made up of monovalent C _{,,, o} > -hydrocarbon radicals ( l-lo; and substituted monovalent C _{,,, Q} , hydrocarbon , (l-lo; Substance remnants is selected, R is from divalent C ,. ...- hydrocarbon radicals and substituted divalent C ,, _, g "hydrocarbyl radicals; R is a monovalent C ,,, _{3-hydrocarbon} radical. Or unsubstituted monovalent hydrocarbon radical, R is a monovalent radical selected from C ,, - ,, »-Calals- 4 1-L- ¹ YY hydrogen radicals is selected, R is an aliphatic organic C / -, _ ■■ ₈ \ radical, which is selected from alkyl radicals, alkyl ether radicals, alkyl ester radicals, alkyl ketone radicals and alkyl cyan or a C, ₇ _ ,, »- aralkyl radical, m is a whole Number with a value from about 5 to about 5000 and a is an integer with the value 0 or 1. 13. Organopolysiloxane mass vulcanizable at room temperature, those in parts by weight (A) 100 parts of silanol terminated polydiorganosiloxane, (B) 0.1 to 10 parts of a polyalkoxysilane, (C) 0 to 5 parts of an amine accelerator, (D) 0 to 700 parts of a filler and (E) an effective amount of a diorganotin dicarboxylate condensation catalyst
contains.