DE3305356A1 - COLD-HARDENING COMPONENT SILICONE RUBBER MATERIALS OF LOW MODULES AND METHOD FOR THE PRODUCTION THEREOF - Google Patents

Description

"9O7'4-6ÖSI-64O

ti General Electric Company

Cold-curing one-component silicone rubber compounds are low Module and process for their production

The invention relates to cold-curing one-component silicone rubber compositions and methods of making them, and more particularly, the present invention relates to such compositions with a low modulus and alkoxy functional groups.

The first type of cold-curing one-component silicone rubber compound was one in which a crosslinking agent was an acyloxy functional silane as in the U.S. Patents 3 133 891 and 3 035 016. U.S. Patents 3,296,161, 3,296,195 and 3,438,930 refer to the use of certain self-binding additives to make such masses self-binding. While the masses with the functional acyloxy groups cured rapidly and had other useful properties, they had two disadvantages. One was that during hardening they gave off the somewhat corrosive acetic acid and further this gave off acetic acid an objectionable odor, so that it was somewhat difficult to deal with this mass in an enclosed area work.

It has therefore been highly desirable to have a non-corrosive, one-part, room-temperature quick-curing silicone rubber composition to have.

It is true that US Pat. No. 3,127,363 does not contain corrosive cold-setting ones Silicone rubber compounds described, but these are two-component compounds that are packed in two separate containers and must be mixed immediately before use, because after mixing they within a short time must be consumed, otherwise they would not harden sufficiently quickly. Although it is therefore not corrosive cold

H*

curing silicone rubber compounds exist, but require them additional work during application ^ and after mixing, the mass has a very short shelf life.

An early example of an alkoxy-functional composition in the one-part form can be found in U.S. Patent 3,065,194. This mass, however, suffered from the fact that very thorough drying had to be carried out in the preparation of the mass, and that the composition also had a short shelf life.

Other one-component alkoxy-functional cold-curing silicone compounds are in U.S. Patents 3,122,522 and 3,161,614 and US Pat reissued U.S. Patent RE-29,760. However, these compositions did not cure quickly enough; H. if at all hardened, then they hardened very slowly, especially after being stored for some time, which is a storage period meant of a week or more.

It was found that it was the normal condensation catalyst were for the acyloxy-functional mass that did not cure quickly enough.

Accordingly, various titanium chelate catalysts have been used for such cold-curing one-component silicone rubber compositions created with functional alkoxy groups. Examples of such Titanium chelate catalysts for such compositions are described in U.S. Patents 3,334,067, 3,542,901, 3,689,454 and 3,779,986.

Another example of such a mass that has come on the market with various types of additives is in U.S. Patent 4,100,129. This last-named US patent describes a cold-curing one-component silicone rubber compound with alkoxy functional groups, which is commercially available and which is particularly dependent on a specific one Kind of chelate catalyst to give the mass a sufficient hardening speed after it has been used for a longer period

Has been in storage for 6 months or more. In this USHPS 4 100 129 it is also stated that the mass is a polysiloxane liquid with trifunctional units and a linear dimethylpolysiloxane liquid with trimethylsiloxy units as well as various types of liability intermediaries. With regard to the latter, it is stated that different types of adhesion promoters for such cold-setting ones One-component silicone rubber compounds with functional alkoxy groups can be used, such as SiIylisocyanurate and other connections.

However, as stated above, these masses also suffer still think that they do not have a sufficient shelf life and do not cure quickly enough.

Another example of a somewhat non-corrosive cold-setting One-component silicone rubber composition is described in US Pat. No. 4,257,932, in which one functional acyloxy groups containing crosslinking agent, preferably methyl-tris-2-ethylhexanoxysilane is used. In this last-mentioned US-PS it is further stated that various additives in such Masses can be used, such as a liquid polysiloxane with a high degree of tri- or tetra-functionality, which is similar to that in US-PS 4,001,129, - as well as a Dimethylpolysiloxane liquid. Furthermore, US Pat. No. 4,257,932 discloses various additives, such as adhesion promoters. '

Although the composition of US Pat. No. 4,257,932 was less corrosive, it did release an acid, albeit one of higher molecular weight which is still somewhat corrosivey and in addition, the composition did not harden as quickly as desired.

In addition, the type of corrosion caused by the bulk of U.S. Patent 4,257,932 was _y . such that it caused discoloration of various substrates and, moreover, this composition was somewhat difficult to bond to substrates even after adding various kinds of self-bonding additives.

Examples of various self-binding additives which can be used in such a composition are given in the above US Pat. No. 4,257,932 and further described in US Pat. No. 4,273,698, which discloses the use of various silyl fumarates, Silyl maleates, silyl succinates and other compounds as an adhesion promoter for such masses as well as for cold-curing one-component silicone rubber masses with functional Disclosed alkoxy groups.

U.S. Patent 4,247,445 deals with the use of large size Amounts of potassium carbonate as a filler in such masses to make them paintable.

U.S. Patent No. 4,308,372 relates to the pre-reacted reaction product the adhesion promoter and the crosslinking agent in order to give the mass further storage stability. But even using such a pre-converted product of crosslinking agent and adhesion promoter, the Mass still insufficient shelf life.

U.S. Patent 4,261,758 discloses the use of polyethers as dimensional stability control agents or agents to make the mass thixotropic, described by incorporating small amounts of the polyether into the mass.

In European patent publication 69 256 a stable, essentially acid-free, moisture-curable one-component organopolysiloxane composition with polyalkoxy end groups described, in which a tin compound is preferably used as the condensation catalyst. the Additives of the present invention can be used with any of the cold-setting compositions of the aforesaid European patent publication to be used.

Essentially, the use of certain compounds in cold-curing one-component silicone rubber compounds is a factor functional alkoxy groups, most hydroxy groups

remove the uncured mass, to a mass with good Shelf life and a good cure rate even with a tin soap as a catalyst. Besides, this is Mass not corrosive.

It is also desirable to produce masses with a low modulus, d. H. Compounds that have a low tensile strength and a high elasticity, making them suitable for glazing and sealing can be used especially in tall buildings.

It is also intended to create a mass that is self-binding. The search for self-binding additives is ongoing has been continued, and attempts have been made to produce such masses with the lowest possible modulus, which for the mass described in the above European patent publication does not apply.

The present invention was therefore based on the object of using a cold-curing one-component silicone rubber compound to create functional alkoxy groups, which are made self-binding by the addition of new self-binding additives is. Furthermore, this mass should have a low modulus, i.e. H. low tensile strength and very high elongation. The mass should also be essentially non-corrosive and stable in storage. By incorporating various Ingredients, the mass should also be as cheap as possible.

Another object of the present invention was to provide a method for producing such a mass.

The present invention provides a stable, substantially anhydrous and acid-free, vulcanizable at room temperature One-component organopolysiloxane mass, which under Ambient conditions in the absence of moisture stable and convertible to a tack-free elastomer for an extended period of time, the Composition according to the invention comprises the following components:

-Jg--

(1) an organopolysiloxane in which the silicon atoms at each end of the polymer chain carry at least two alkoxy radicals,

(2) an effective amount of a condensation catalyst,

(3) a stabilizing amount of a silane that eliminates functional hydroxy groups and has the following formula

(1) ^(Ri ° '4- ( _{C +} f) ^{Si (X} »f

wherein R is an aliphatic organic radical having 1 to 8 carbon atoms is selected from alkyl, alkyl ethers, alkyl esters, alkyl ketone and alkylcyan radicals or an aralkyl radical with 7 to 19 carbon atoms,

R is a monovalent, optionally substituted, hydrocarbon radical having 1 to 13 carbon atoms, X is a hydrolyzable removable group selected from amido, amino, carbamato, enoxy, imidato, isocyanato, oximato, thioisocyanato and ureido radicals,
c is an integer from 0 to 3 inclusive, f is an integer from 1 to 4 inclusive and the sum of c + f = 1 to 4 inclusive, and when χ is enoxy or amido,

(4) an effective amount of a curing accelerator selected from substituted guanidines, amines, and mixtures thereof and

(5) 2 to 20% by weight parts per 100 parts by weight of the organo-polysiloxane, a first plasticizer in the form of a liquid polysiloxane with a high degree of trifunctionality

————, —___ or mixtures of

Tri- and tetrafunctionality, this liquid comprising the following units:

(i) 5 to 60 mole percent monoalkylsiloxy-siloxy units

and mixtures of such units (ii) 1 to 6 mol% trialkylsiloxy units and (iii) 34 to 94 mol% of dialkylsiloxy units, this liquid polysiloxane about 0.1 to 2% by weight ar. Contains silicon-bonded hydroxyl groups.

The basic component of such a mass is a diorganopolysiloxane polymer with a large number of functional alkoxy groups, which is preferably obtained by first adding a trialkoxysilane crosslinking agent, such as methyltrimethoxysilane, with a diorganopolysiloxane polymer containing silanol end groups implements. After these two have been implemented, preferably in the presence of a condensation catalyst, such as hexylamine, you add an agent to the whole that eliminates all free hydroxyl groups, such as. B. the methanol, and then such an agent removes all of the silanol groups and hydroxyl groups in the additives that are added to the matrix became. As a result, the mass is stable in storage.

By adding the ingredients disclosed in this application are, you can make the mass self-binding and thixotropic and you can also make them so that they one has a low module.

Alternatively, the basic mass can also be produced by mixing a silanol-containing polymer with a crosslinking agent and an agent for removing the hydroxyl groups together with the other ingredients.

It has been found, however, that a quick-setting, more storage-stable composition is obtained by first the silanol-containing polymer reacts with the crosslinking agent, around the organopolysiloxane with the multitude of functional alkoxy groups and only then is the agent added with the remaining silanol groups, moisture and methanol reacts and only then the other ingredients are added.

However, if optimal storage stability and optimal rapid curing are not required, then the other mixing procedures can be used as described in the above European publication are described.

SH

The basic component of the cold-curing compositions of the present Invention includes a silanol-terminated diorganopolysiloxane polymer and in particular such a polymer of the formula

(2) HO-

R.
SiO.

wherein R is a monovalent, optionally substituted, hydrocarbon radical with 1 to 13 carbon atoms, which is preferably selected from alkyl radicals with 1 to 8 carbon atoms, such as methyl or a mixture of a major amount of methyl and a minor amount of phenyl, cyanoethyl, trifluoropropyl, Vinyl and mixtures of these radicals and η is an integer having a value ranging from about 50 to about 2,500.

Such a silanol polymer can be obtained by various methods are produced, the z. As described in U.S. Patent 4,250,290. Other methods for this are e.g. B. in the U.S. Patent 3,888,815. Since such polymers are known, no further details regarding their production are given here.

Various terms are used in the present application, such as "stable", "essentially acid-free", etc. In this context the term “stable” means in its application to the cold-curing one-component organopolysiloxane compositions with a large number of alkoxy groups according to the present invention a moisture-curable mixture which, with the exclusion of atmospheric Moisture remains essentially unchanged and becomes tack-free even after a long period of storage Elastomer hardens.

In addition, such a "stable" cold-setting silicone rubber composition means also that the freshly made mass is under

atmospheric conditions are essentially the same tack-free Has time, like a mass, after extended storage under ambient conditions, but in a Containers free of moisture content after exposure to atmospheric moisture or such a mass an equivalent duration of accelerated curing with an increased Temperature.

The term "essentially acid-free" with regard to the elastomer produced from the composition according to the invention means that the by-products formed when the mass is exposed to atmospheric moisture have a pKa of 5.5 or more , with 6 or more being preferred and such a value of 10 or more being particularly preferred.

The diorganopolysiloxane polymer having silanol end groups preferably has which is used in the present invention, be it an alkoxy terminated polymer or

mPa-s not, a viscosity in the range of 60,000 to 500,000

at 25 ° C.

The present invention is based on finding the additives for stable, essentially acid-free, moisture-proof Curable at room temperature, containing several alkoxy end groups Organopolysiloxane compositions that can be prepared from polydiorganoiloxanes containing silanol end groups, the consisting essentially of chemically linked diorganosiloxy units of the formula

(3) SiO -

exist, such as polydiorganosiloxane having terminal groups of the formula (2), in which R has the abovementioned meaning, where this siloxane is used together with an effective amount of certain silanes that are capable of chemically bonded hy-

to remove droxy residues.

In the polydxorganosiloxane containing silanol end groups, which consists essentially of chemically bonded units of the Formula (3) consists of the presence of silicon-bonded alkoxy radicals with 1 to 8 carbon atoms, such as the methoxy radical, not excluded.

The hydroxy radicals that can be eliminated by means of the above silane can be found in materials disclosed in mass according to the invention are normally present, such as ζ. Β traces of water, methanol, silanol residues on the silicon dioxide filler, if such is used, the silanol groups of the polymer of the formula (2) or a polymer having units of the above formula (3) which has silanol end groups.

The silane useful for eliminating chemically bonded hydroxy groups in accordance with the present invention preferably has following formula

(R ² ),

(4) 1 ^!

^{(R 0)} 4- (a + b) ^{Si (X)} a

wherein R is an aliphatic organic radical having 1 to 8 carbon atoms is selected from alkyl radicals, alkyl ethers, Alkyl esters, alkyl ketone and alkyl cyan radicals or an aralkyl radical with 7 to 13 carbon atoms,

R is a monovalent organic radical having 1 to 13 carbon atoms, selected from the radicals mentioned for R and is defined in more detail below,

X is a hydrolyzable group that can be split off from amido, amino, carbamato, enoxy, imidato, isocyanato, oximato, thioisocyanato and ureido radicals. The preferred such hydrolyzable radicals are amino, amido and enoxy, such as e.g. B. NC, _{Λ o} > -

(ι-o;

Alkyl; C.Q, acylamido,

a has the value 1 or 2 and is preferably 1 b has the value 0 or 1 and

SI

- vr -

the sum of a + b is equal to 1 or 2.

in the above formula (4), when a is 2, X may be the same or be different. The group X which can be split off preferably reacts before -OR with the available -OH in the group according to the invention Mass and results in a mass which is essentially free of halogenic acid or carboxylic acid.

The silane of the above formula (4) is both suitable for elimination functional hydroxyl groups as well as a crosslinking agent for providing the terminal silicon atom of the organopolysiloxane chain with at least two alkoxy radicals.

Another way of describing the aforesaid invention is in the definition of the basic polyalkoxy polymers, among the ingredients of the composition according to the invention, which as a result the use of the silane of the formula (4) are formed, a silanol-free polydiorganosiloxane, whose chain ends are terminated by 2 or 3 -OR residues.

The silanol-free polydiorganosiloxane can optionally be combined with an effective amount of a crosslinking silane, as will be described in more detail below and this under essentially anhydrous conditions. The crosslinking polyalkoxysilane, which can be used in combination with the silane of the formula (4) has the following formula

⁽ ? ²⁾ b (5) I ^b

(R'0) ₄ _ _b Si

1 2

wherein R, R and b have the abovementioned meaning.

The preferred condensation catalysts in the context of the present invention include metal compounds, selected from tin, zirconium and titanium compounds and mixtures of the compounds mentioned. Other condensation catalysts that can be used are jjr. described in more detail below.

It is not yet fully understood why the polyalkoxy end groups having organopolysiloxane compositions of the present invention in the presence of certain condensation catalysts are stable for an extended period of time in the absence of moisture.

It is believed that the reason why the compositions of the above-mentioned European patent publication are stable is due to the fact that the cleaning silane eliminates the hydroxyl groups in the cold-setting composition so that there are no longer any free hydroxyl groups that would cause the uncured polymer ^ can further crosslink to increase its viscosity and reduce its shelf life. Namely, such hydroxyl groups can affect the alkoxy polymer in various ways during storage.

The use of the hydroxyl-eliminating silane of formula (1) or (4), in which the removable group X is not a halogen radical, essentially eliminates unwanted water from the filler and the silicone polymer as well as residual moisture in the cold-curing composition during storage. When determining the amount of silane of formula (1) or (4) to be used in the composition according to the invention, the total hydroxyl functionality in the composition must be determined. The total hydroxyl functionality of the polymer can be determined by IR analysis. To ensure that an effective or stabilizing amount of the cleaning silane is used to ensure the stability of the composition for extended storage periods of 6 months or more at ambient temperature in a sealed container, an additional amount of this cleaning silane can be used in excess of the amount required to form the alkoxy end groups of the polymer. This excess of cleaning silane can be up to 3% by weight, based on the weight of the polymer. This aforementioned 3 % exceeds the amount required to substantially eliminate the available hydroxy functionality in the polymer as a result of the reaction between the OH groups

and the X residues.

In compositions that also contain fillers and other additives, the additional amount of silane of the formula (1) or (4), that is required is estimated by running a 48 hour stability test at 100 ° C to determine whether the tack-free time remains essentially unchanged compared to the tack-free time of the mass before this aging, determined under essentially the same conditions.

If polymer containing several alkoxy end groups is prepared without using the silane of the formula (4), then in the present case Invention, a silane can be used to eliminate functional hydroxyl groups in which less than 2 OR radicals the silicon are bound, as the following formula shows

(6) < ^Ri °> 4 (c + a) ^stx a

1 2
wherein R, R and X are as defined above, c is an integer from 0 to 3 inclusive, d is an integer from 1 to 4 inclusive and the sum of c + d is 3 or 4. In such cases, the cleaning silanes of the formula (6) can be used in an amount which is sufficient to stabilize the cold-curing composition, as described in more detail above for the silane of the formula (4). In addition, at least 0.01 and up to 10 parts of the crosslinking silane of the formula (5) can be used together with the silanes of the formulas (4) or (6).

The polyalkoxy-terminated organopolysiloxanes used in the present invention have the formula

° f ²⁾

I.
SiO

(R ² )

1 2
wherein R, R, R, X, η and b have the abovementioned meanings and e has the value 0 or 1 and the sum of b + e is 0 or 1.

The organopolysiloxanes of the formula (7) can be prepared by various processes. One of these is in the U.S. PS 3,542,901 and it includes the implementation of a polyalkoxysilane with a polydiorganosiloxane containing silanol end groups in the presence of an amine catalyst.

Another process not described in this US patent is / consists in the use of the silane of the formula (4) as a chain terminator in the reaction with the silanol end groups comprising polydiorganosiloxane.

The additives of the present invention are preferably employed when the diorganopolysiloxane of formula (7) first is made and then the additives are added.

In the formulas (1) to (7), R is preferably selected from "- · monovalent hydrocarbon radicals, which may optionally be substituted by halogen _; and cyano-substituted alkyl radicals, the radicals each containing 1 to 13 carbon atoms. R is preferred an alkyl radical with 1 to 8 carbon atoms or an aralkyl radical with 7 to 13 carbon atoms

2
material atoms. R is preferably methyl, phenyl or vinyl.

The preferred radicals for X in the above formulas (3), (5) and (6) are amido, amino and enoxy, and most preferred is amido.

It was further found that improved cure rates can be achieved if you have minor amounts of amines, substituted guanidines or mixtures thereof

-ri-

Cure accelerators are employed in the compositions of the present invention. These cure accelerators also catalyze the ability of the enoxy group to remove hydroxyl groups. 0.1 to 5 parts and preferably about 0.3 to 1 part of curing accelerator can be used, in each case for 100 parts of the silanol-terminated polymer of the formula (2) or of a polymer which consists of chemically bonded units of the formula (3) or of the polyalkoxy-terminated polymer of the formula (7) in order to considerably reduce the tack-free time of the composition according to the invention. This improved hardening rate continues even after the mass has been stored for a longer period of time, for example 6 months or more, at ambient temperatures or for a comparable period of time under accelerated aging conditions, ie at elevated temperature. The properties of the composition according to the invention to cure are, after prolonged storage, essentially similar to the initial hardening properties, as z. B. applies to the tack-free time, which can be determined both shortly after manufacture and after extended storage, the mass being exposed to atmospheric moisture in both cases.

It appears that those described in the present application Hardening accelerator, in addition to shortening the tack-free time of the composition according to the invention, is also a surprising one stabilizing effect for certain masses result, which catalyzes with certain condensation catalysts and which show a marked increase in tack-free time after accelerated aging. For this class of condensation catalysts, the addition of amines, substituted guanidines and mixtures thereof results stable, cold-hardening compounds which initially undergo a very rapid hardening process, d. H. less than 30 minutes, and which remains essentially unchanged after accelerated aging.

The compositions according to the invention can cure to a depth of about 3 mm within 24 hours. The durometer hardness

(Shore A) can then be determined and it is used to evaluate the hardening of the masses, as shown in the examples.

A general way of describing the polymer mass according to the above European patent publication is that it is a substantially anhydrous, vulcanizable at room temperature One-component organopolysiloxane composition is that in the absence of moisture under ambient conditions is stable over an extended "period of time and which is in an im essential acid-free and tack-free elastomer is convertible, this mass comprising the following components:

(1) an organopolysiloxane in which the silicon atom on each End of the polymer chain has at least / alkoxy radicals,

(2) an effective amount of a condensation catalyst and

(3) a stabilizing amount of a hydroxyl-removing silane represented by the following formula

, t-

^{(R 0)} 4- (c ₊ f) ^SiX f

1 2
wherein R, R, X and c have the aforementioned meaning and f is an integer from 1 to 4 inclusive, the sum of c + f is 1 to 4 inclusive. In addition, an effective amount of a cure accelerator selected from substituted guanidines, amines and mixtures thereof is used.

According to a further aspect of the present invention there is a stable, room temperature vulcanizable, polyalkoxy end group having organopolysiloxane mass created, which under ambient conditions to a tack-free ^ is curable substantially acid-free elastomer and comprises the following ingredients:

(A) 100 parts of a polyalkoxy-terminated organopolysiloxane of formula (7),

(B) 0 to 10 parts of a crosslinking silane of the formula (5),

- yi -

(C) an effective amount of a condensation catalyst and

(D) a stabilizing amount of a functional hydroxyl group-removing silane of formula (1).

The present invention also includes a method of making a cold-curing organopolysiloxane composition under substantially anhydrous conditions in which an effective Amount of a condensation catalyst together with a silanol-terminated organopolysiloxane and a Polyalkoxysilane is used as a crosslinking agent, the improvement according to the invention being that: (1) To the silanol-terminated polysiloxane, add a stabilizing amount of a polyalkoxysilane which is both a silane for removing functional hydroxyl groups and a crosslinking agent and is of the following formula Has

^(R0) 4- (b ₊ a) ^{Si (x)} a

1 2
wherein R, R, X, a and b have the abovementioned meaning and an effective amount of a condensation catalyst is then added, as a result of which cold-curing polysiloxane compositions of improved stability are obtained.

Another method according to the invention for producing a cold-curing organopolysiloxane composition essentially below anhydrous conditions using an effective amount of a condensation catalyst together with an organopolysiloxane, in which the silicon atom has at least two alkoxy groups at each end of the chain, consists in that one leads to the polyalkoxy-terminated organopolysiloxane

(1) adding a stabilizing amount of a hydroxy group-removing silane represented by the following formula

^iR °> 4- (e ₊ f) ^{Si (X)} f

2
wherein R, R, X ₁ c and f have the aforementioned meaning and

(2) an effective amount of a catalyst catalyst, whereby a cold-curing organopolysiloxane composition with improved stability is obtained.

In a further aspect of the present invention, a method for producing a stable, cold-curing, polyalkoxy-terminated one-component organopolysiloxane composition is provided in which a material which is vulcanizable at room temperature is stirred under substantially anhydrous conditions and is selected from:
(i) a mixture of

(a) 100 parts by weight of a silanol-terminated polydiorganosiloxane which is essentially consists of chemically linked units of the formula (3),

(b) an amount of the silane of the formula (4) which is sufficient to contain available -OH groups in the cold-curing Eliminate bulk and one up

to form a 3% excess, based on the weight of the total cold-curing mass,

(c) 0 to 10 parts of the crosslinking silane of the formula (5),

(d) an effective amount of a condensation catalyst and

(e) 0 to 5 parts of a curing accelerator selected from substituted guanidines, Amines and their mixtures,

wherein the condensation catalyst is added after the silanol terminated Polydiorganosiloxane and the functional hydroxyl group eliminating silane mixed together are and

-Vi-

Il »<·

(ii) a mixture of

(a) 100 parts of a polyalkoxy group-containing polysiloxane of the formula (7),

(b) 0 to 10 parts of the crosslinking silane of formula (5)

(c) an effective amount of a condensation catalyst,

(d) a stabilizing amount of the hydroxyl-removing silane of the formula (1) and

(e) 0 to 5 parts of the curing accelerator selected from substituted guanidines, amines and mixtures thereof.

The remains that z. B. for R in the above formulas (2), (3) and (7) are the following:

If necessary, halogen-substituted aryl radicals, such as phenyl, tolyl, chlorophenyl, Naphthyl; aliphatic ^ and cycloaliphatic radicals such as cyclohexyl, cyclobutyl; Alkyl and alkenyl radicals, such as methyl, Propyl, chloropropyl, vinyl, allyl, trifluoropropyl; and cyanoalkyl radicals such as cyanoethyl, cyanopropyl and cyanobutyl.

Preferred radicals for R are e.g. B. alkyl radicals having 1 to 8 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl; Aralkyl radicals having 7 to 13 carbon atoms, such as benzyl, phenylethyl; Alkyl ether radicals such as 2-methoxyethyl; Alkyl ester residues, such as 2-acetoxyethyl; Alkyl ketone radicals such as 1-butan-3-onyl; Cyan alkyl radicals, such as 2-cyanoethyl.

2
Residues that can stand for R are at the top of the remainders

named for R, where the radicals for R can be identical or different. In general, formulas 1 to 7,

1 2

where R, R and R occur more than once, these radicals may be the same or different.

Some of the silanes of formulas (4), (6) and (1) above useful for removing chemically bonded hydroxyl groups are z. B.

$ 6

- 26 -

Oximatosilanes, like

Methyldimethoxy (ethylmethylketoximo) sllanr Methyl methoxy bis (ethyl methyl ketoximo) silane;

Methyldimethoxy (acetaldoximo) silane. Carbamatosilanes like

Methyldimethoxy (N-methylcarbamato) silane;

Ethyldimethoxy (N-methylcarbamato) silane. Enoxysilanes, such as

Methyldimethoxyisopropenoxysilane; Trimethoxyisopropenoxysilane; Methyltri-iso-propenoxysilane; Methyldimethoxy (but-2-ene-2-oxy) silane; Methyldimethoxy (1-phenylethhenoxy) silane;

Methyldimethoxy-2 (1-carboethoxypropenoxy) silane; Aminosilanes like

Methyl methoxydi-N-methylaminosilane; Vinyldimethoxymethylaminosilane; Tetra-NjN-diethylaminosilanemethyldimethoxymethylaminosilane;

Methyltricyclohexylaminosilane; Methyldimethoxyethylaminosilane; Dimethyldi-N, N-dimethylaminosilane; Methyldimethoxyisopropylaminosilane dimethyldi-N ^ -di-

ethylaminosilane.
Amidosilanes, like

Ethyldimethoxy (N-ethylpropionamido) silane; Methyldimethoxy (N-methylacetamido) silane; Methyltri (N-methylacetamido) silane; Methyltri (N-methylbenzamido) silane; Ethyldimethoxy (N-methylacetamido) silane; Methyltri (N-methylbenzamido) silane; Methyl methoxy bis (N-methylacetamido) silane; Methyldimethoxy (caprolactamo) silane; Trimethoxy (N-methylacetamido) silane.

Imidatosilanes, such as,

Methyldimethoxyethylacetimidatosilane;

Methyldimethoxypropylacetimidatosilane. Ureidosilanes, like

Methyldimethoxy (N, N ¹ , N'-trimethylureido) silane; Methyldimethoxy (N-allyl-N ¹ , N'-dimethylureido) silane;

Methyldimethoxy (N-phenyl-N, N'-dimethylureidosilane. Isocyanatosilanes, such as,

Methyldimethoxyisocyanatosilane;

Dimethoxydiisocyanatosilane.
Thioisocyanatosilanes, such as,

Methyldimethoxythioisocyanatosilane; Methyl methoxydithioisocyanatosilane.

In addition, the functional hydroxyl-removing silanes of formula (6) include such silanes as methyltris (N-methylacetamido) silane and tetra (isopropenoxy) silane. Silanes with different cleavable groups such as diethylamino (N-methylcarbamato) isopropenoxy (N-allyl-N ¹ , N'-dimethylureido) silane are also included.

Some of the crosslinking polyalkoxysilanes of formula (5) are e.g. B. Methyltrimethoxysilane, Methyltriäthoxysilan, Äthyltrimethoxysilan, Tet2: aäthoxysilan and vinyl trimethoxysilane.

Cure accelerators which can be used in the context of the present invention include the silyl-substituted ones Guanidines of the following formula

(8) (Z) _g Si (OR ¹ ) ₄ _ _g

where R has the above meaning and Z is a guanidine residue of the following formula,

(R ⁴ ) N
(9) ^l ^ C = NR-

fa0

wherein R is a divalent alkylene radical having 2 to 8 carbon

4 5
atoms, R and R are selected from hydrogen and alkyl radicals having 1 to 8 carbon atoms and g is an integer from 1 to 3 inclusive.

Further, alkyl-substituted guanidines of the following can also be used Formula can be used

(R ⁴ ), N

^X6

C = N-R

(R ⁵ ) ^

4 5 6

wherein R and R have the abovementioned meaning and R is an alkyl radical having 1 to 8 carbon atoms.

Some of the silyl substituted guanidines within Formula (8) above are described in U.S. Patents 4,180,642 and 4,248,993.

In addition to the substituted gunanidines mentioned above, various amines can also be used, such as di-n-hexyl amine, dichlorohexylamine, di-n-octylamine, hexamethoxymethylmelamine and silylated amines such as ^ -aminopropyltrimethoxysilane and methyldimethoxydi-n-hexylaminosilane. The latter Compound acts both as a silane to eliminate more functional Hydroxyl groups as well as hardening accelerators. The primary, secondary, and silylated secondary amines are preferred, the two secondary amine types being particularly preferred. Silylated secondary amines such as alkyldialkoxy-n-dialkylaminosilanes and guanidines, such as alkyldialkoxyalkylguanidylsilanes, which are useful as curing accelerators also act as silanes to remove functional hydroxyl groups and, in certain cases, as stabilizers for the compositions of the invention.

Effective amounts of the condensation catalyst in the context of the present invention to facilitate the curing of the cold-setting compositions include, for. B. 0.001 to 1 part by weight, based on 100 parts by weight of the silanol end groups Polydiorganosiloxane of the formula (2, examples of such

Condensation catalysts are tin compounds such as dibutyltin dilaurate Dibutyltin diacetate, dibutyltin dimethoxide, carbomethoxyphenyltin trisuberate, Tin octoate, isobutyl tin triceroate, dimethyl tin dibutyrate, dimethyl tin dineodecanoate, triethyl tin tartrate, Dibutyltin dibenzoate, tin oleate, tin naphthenate, butyltin tri-2-ethylhexoate and tin butyrate. The preferred Condensation catalysts are tin compounds, of which dibutyltin diacetate is particularly preferred.

Titanium compounds that can be used are e.g. B. 1,3-propanedioxytitanium bis (ethyl acetoacetate), 1,3-propanedioxytitanium bis (acetylacetonate), diisopropoxytitanium bis (acetylacetonate), Titanium naphthenate, tetrabutyl titanate, tetra-2-ethylhexyl titanate, Tetraphenyl titanate, tetraoctadecyl titanate and ethyl triethanolamine titanate. In addition, the beta-dicarbonyl titanium compounds described in U.S. Patent 3,334,067 can be found in US Pat Can be used in the context of the present invention as condensation catalysts.

Zirconium compounds can also be used, such as zirconium octoate.

Further examples of useful condensation catalysts are lead-2-ethyloctoate, iron-2-ethylhexoate, cobalt-2-ethylhexoate, Manganese-2-ethylhexoate, zinc-2-ethylhexoate, antimony octoate, Bismuth naphthenate, zinc naphthenate and zinc stearate.

Examples of non-metallic condensation catalysts are hexylammonium acetate and benzyltrimethylaminonium acetate.

Albeit the preferred catalyst for the invention If the bulk is dibutyltin diacetate, other tin soaps can be used with almost the same effectiveness.

The Asudrücke used in the present application "moist. activity-free conditions "and" substantially anhydrous conditions "with regard to the preparation of the invention Bulking means mixing in a drying container

or a sealed container that has been evacuated to remove the air and then placed in a dry one Has filled inert gas such as nitrogen.

Experience has shown that a sufficient amount of the silane of formula (1) should be used.

The temperatures used in the mixing can vary in the range of about 0 to about 180 ° C, depending on the grade mixing, the type and amount of filler, etc.

A preferred method of making the cold-setting Compositions according to the present invention consists in a mixture of the under substantially anhydrous conditions Polydiorganosiloxane containing silanol end groups, the filler and to stir an effective amount of the silane of the formula (4) which is sufficient to eliminate the functional Hydroxyl radicals essentially cause and end groups to form the polymer. This formation of the end groups and the removal of the functional hydroxyl groups can be several Minutes, hours or even days, depending on the nature of the group X to be split off, the number of -OR radicals on the silane of the formula (4) etc. Following this, one can then proceed to the essentially silanol-free mixture add the condensation catalyst, the crosslinking silane or a mixture thereof along with other ingredients, z. B. with the curing accelerator and pigments. If desired, a stabilizing excess of the hydroxy functional silane is added in the initial or final stages of the mixing process in the specified quantities.

In those cases in which the polyalkoxy end groups Organopolysiloxane of the formula (7) is prepared by a process in which the use of the silane of the formula (4) Not needed, then stabilizing amounts of the functional hydroxyl-eliminating silane can be added together with or after the addition of the condensation catalyst

to be added.

Alternative methods of making polyalkoxy end groups Organopolysiloxanes comprising organopolysiloxanes are disclosed in US Pat. No. 3,542,901.

The preferred method of making the compositions of the invention; H. a non-corrosive, rapidly setting compound low modulus, which is stable in storage, consists in using a diorganopolysiloxane containing polyalkoxy end groups, d. H. to form it first, to remove the hydroxyl groups in the mass and then the other ingredients as desired, to be added. This can be done by adding the silanol polymer of the formula (2) to the crosslinking agent of Formula (5) is added, i.e. H. that the silanol polymer is reacted with a crosslinking agent, preferably in the presence a catalyst and particularly preferably an amine catalyst, such as hexylamine, to the desired dialkoxy end groups having polymer and then adding a functional hydroxyl group-eliminating silane to this, to convert the silanol groups. Thereafter, the other ingredients can be used under essentially anhydrous conditions add to the mass to form a cold-setting one-component mass produce which is stable in storage and hardens sufficiently quickly, d. H. .the one with a catalytic converter a tin soap hardens quickly.

The first basic ingredient to the above cold-curing. Mass should be added after it has been made; d. H. the organopolysiloxane containing polyalkoxy end groups, the functional hydroxyl-eliminating silane and the condensation catalyst are 2 to 20 parts by weight to 100 parts by weight of the diorganopolysiloxane as the base polymer

(i.e. either based on 100 parts by weight of the silanol endgroup having polymer of the formula (2) or 100 parts by weight. of the alkoxy-terminated organopolysiloxane of the formula el (7)), a first plasticizer in the form of a liquid polysiloxane, which has a high degree of trifunctionality

or a mixture of tri- and tetra-functionality and comprises the following units:

(i) 5 to 60 mole percent monoalkylsiloxy, siloxy units

or a mixture of such units, (ii) 1 to 6 mole percent trialkylsiloxy units and (iii) 34 to 94 mole percent dialkylsiloxy units, this liquid polysiloxane being from about 0.1 to about 2% by weight of silicon-bonded hydroxyl groups.

A preferred amount of this liquid polysiloxane is in the range of 5 to 15 parts by weight per 100 parts by weight of the base polymer .

Such a liquid polysiloxane acts as a plasticizer and adhesion promoter in the composition according to the invention. Too much of This plasticizer must not be added, since the plasticizer crosslinks the compound due to its trifunctionality and their viscosity inappropriately increased. More than 20 parts by weight of the first plasticizer per 100 parts by weight of the base polymer are therefore undesirable. Less than 2 parts by weight of it, however, have little effect.

The liquid polysiloxane of high trifunctionality can according to known Process are produced. So you can z. B. a mixture of

(i) monoalkyltrichlorosilane, (ii) dialkyldichlorosilane and

(iii) alkyltrichlorosilane and silicon tetrachloride ■■ - ■ ——— in the appropriate one Hydrolyze or cohydrolyze molar ratio in toluene and water.

The mixture obtained can then be heated, i. H. to about 60 C for a period of about 3 hours, which is sufficient to keep the Complete hydrolysis. The oil phase is then separated off and neutralized, e.g. B. by washing with an aqueous Solution of sodium carbonate or bicarbonate. After your filtering for removing insoluble constituents and after removing volatile constituents by heating to about 140 ° C in a vacuum

9S

from ζ. B. 2 mm Hg, the liquid polysiloxane remains as a remainder. For economic reasons, it is preferred to keep the hydroxyl content bonded to silicon at less than 0.6% by weight. in order to keep the viscosity of the finished mass as low as possible and also the required amount of crosslinking agent as possible to keep it low. This is achieved by heating the product to 1T0 C in the presence of about 1% sodium carbonate. The water formed in the silanol condensation can be prepared in a suitable manner by azeotropic distillation, for. B. with toluene removed. After the toluene has been removed by distillation, the product is filtered before use (cf. US Pat 3 382 205).

The liquid polysiloxane preferably has a viscosity in

rnPa · S _o

Range from 15 to 300 at 25 C. Preferred are at least 50% of the alkyl substituents of this first plasticizer are methyl groups and the liquid comprises 0.2 to 0.6 Wt% silanol. It is particularly preferred that the monoalkylsiloxy units, the siloxy units or a mixture of these Units comprise about 10 to 30 mole percent that the trialkylsiloxy units comprise about 3 to 5 mole percent and the dialkylsiloxy units comprise 65 to 87 mole percent and the silanol content ranges from 0.2 to 0.6 wt%.

Although such a trifunctional liquid serves as a plasticizer for the base mass and gives it a low modulus, after all, it does not always ensure a sufficiently low modulus and a sufficiently low viscosity. Therefore, it is highly desirable that for 100 parts of the base polymer in addition to the trifunctional Liquid 10 to 50 parts by weight of a second plasticizer can be used.

The base polymer is either the one having terminal silanol groups Diorganopolysiloxane of the formula (2) or the diorganopolysiloxane polymer containing polyalkoxy end groups Understood formula (7) or a mixture of both. Since the alkoxy groups contributes very little to the molecular weight of the polymer

ft

- 38 -

wear, the concentration of the various additives is additional to the trifunctional liquid, which will be discussed in more detail below, essentially in both masses the same.

It can therefore per 100 parts by weight of the organopolysiloxane base polymer 5 to 60 parts by weight of a second plasticizer which is a linear triorganosiloxy end group can be used comprising diorganopolysiloxane polymer in one viscosity

20 O00 mP «-s _o

is in the range from 10 to / at 25 C and in which the organic groups are selected from monovalent hydrocarbons rest with 1 to 8 carbon atoms. More preferably, these monovalent hydrocarbon radicals are alkyl radicals with the carbon number mentioned. The second plasticizer therefore preferably has the following formula

R ²⁰ R ²⁰

^20th

, 20

where R is a monovalent hydrocarbon radical, preferably an alkyl radical with 1 to 8 carbon atoms or a vinyl radical or generally an alkyl or aryl radical with 1 to 8 carbon atoms and t varies such that the viscosity of the polymer is in the range of 10 to 20,000 m is at 25 ° C. Most preferably R is methyl and the polymer has a viscosity in the range of

mPa-s _o

10 to 10,000 at 25 C and more preferably im

mPcys ο Range from 10 to 1000 at 25 C. In general, such polymers contain due to their production method 500 to 15,000 ppm of silanol as OH.

The general process for making such a plasticizer of formula (11) consists in the appropriate chlorosilanes to hydrolyze. Triorganochlorosilane is so composed

Diorganodichlorosilane hydrolyzed in water, then the hydrolyzate removed and purified by decanting or otherwise and gives the desired linear diorganopolysiloxane of formula (11) which is further purified by other methods can be. However, because of the cost involved, this is usually not done. In addition, the mentioned No silanol or hydroxyl groups in the present case Cause difficulties because the hydroxy group-eliminating silane is used, which is essentially all in the Removed mass of existing hydroxyl groups.

In order to have the modulus of the composition according to the invention as low as possible, two plasticizers are used, as the polysiloxane liquid with a high trifunctional content alone not the required reduction in viscosity and Module results. Therefore, if you want to get the lowest possible modulus, maximum adhesion and minimum viscosity to To facilitate the application of the sealant consisting of the composition according to the invention, both plasticizers must be used. The second plasticizer is preferably used from 20 to 45 parts.

Another aspect of the inventive composition is cost. The mass is cheaply made by adding 50 to 300 parts or more of an extending filler to 100 parts of the Organopolysiloxane base polymer is used. Such an extending filler not only lowers the cost but also improves it also the strength of the mass without impairing the desired low modulus. Most preferred is the stretching one Calcium carbonate filler, especially one made with stearic acid has been treated. Such an extending filler gives the uncured composition of the present invention the best flow properties and the lowest modulus.

Other extending fillers can also be used in quantities as specified for calcium carbonate.

- 30 -

Other stretching and reinforcing fillers that come in various Concentrations can be used are, for. B. titanium dioxide, zirconium silicate, silicon dioxide "airgel, iron oxide, Diatomaceous earth, fumed silicon dioxide, carbon black, precipitated silicon dioxide, glass fibers, polyvinyl chloride, ground quartz etc.

Depending on the intended use, the amount of filler can be varied within wide limits. In some sealing applications, the curable compositions for producing a binding material can therefore contain up to 700 parts by weight or more of filler per 100 parts by weight of the organopolysiloxane. In such applications, the filler can consist of a major proportion stretch fillers such as ground quartz, polyvinylchloride, or mixtures thereof consist said filler preferably has an average particle size in the range of 1 to 10 microns has.

The compositions according to the invention can also be used as sealants for buildings and for ships. The exact amount the filler used therefore depends on the intended one Intended use also depends on the type of filler used, d. H. the density of the filler and its particle size away.

Preferably, an amount of 1 to 300 parts of filler containing up to 20 parts of a reinforcing filler such as pyrogenic Can include silicon dioxide, used per 100 parts by weight of silanol-terminated polysiloxane. In the an amount of 50 to 300 parts by weight of fillers used

however, should be an elongating filler, like calcium ini t

carbonate to the masses according to the invention / a low modulus to obtain. In addition to the extending filler, 1 to 50 parts, and preferably 1 to 10 parts per 100 Parts of the organopolysiloxane base polymer, a reinforcing Filler used. This reinforcing filler can be selected from precipitated silica and fumed silica, the latter being preferred. Even more preferred

a fumed silicon dioxide is used, which is either with Cyclopolysiloxanes is treated as described in US Pat. No. 2,938 or with silazanes as described in US Pat. No. 3,635,743 described. Of the two, the former is preferred in an amount of 1 to 10 parts by weight.

Such fumed silica acts as a deformation control agent and makes the mass thioxotropic. Thixotropy means that the mass applied to a vertical plane either not at all or in the uncured state very little flows.

Another way of making the composition of the invention thixotropic is described in US Pat. No. 4,261,758.

To 100 parts of the organopolysiloxane base polymer, the reinforcing Pyrogenic silicon dioxide and the extending filler can be added to the composition according to the invention from 0.1 to 2 parts by weight a second deformation controlling agent which is a polyether selected from compounds the formula

, 3, /> - Ο— (C _x H ₂ x O) _n -3-O ₂

wherein A and B represent radicals selected from Hydrogen, alkyl radicals with 1 to 12 carbon atoms, Cycloalkyl radicals with 5 to 7 carbon atoms in the ring, one and dinuclear aryl radicals and mononuclear aryl radicals, the are substituted by lower alkyl radicals, the alkyl radicals , which are bonded to the aromatic nucleus, contain no more than 5 carbon atoms in total A and B can be the following grouping

where R is an alkyl radical with 1 to 11 carbon atoms, Q is a radical of a polyhydric initiator radical which is at least contains two hydroxyl groups selected from ethylene glycol, Glycerine, trimethylolpropane and other polyhydric alcohols with 2 to 6 hydroxyl groups, η is an integer from 2 to 4, y has a value from 2 to 10 and ζ has a value from 1 to 5, the polyether having a molecular weight of has about 300 to about 200,000.

The polyether used as a means for controlling the deformation can be used in addition to or instead of the pyrogenic silicon dioxide be used to give the uncured mass thixotropic properties, which are desirable when the mass is used as a sealant.

The preferred composition of the present invention, i. H. the non-corrosive, rapidly hardening, storage-stable one Low modulus mass is used as a sealant in buildings, for glazing purposes and for other sealing purposes very welcome. It is essential that such a sealant be thixotropic so that it can be used in a gap after it has been inserted does not flow. This thixotropy is due to the incorporation of fumed silicon dioxide in small amounts in combination obtainable with the above polyethers in the composition according to the invention. The polyethers are preferably in an amount from 0.1 to 1 part by weight present in combination with the fumed silica. Although the fumed silica only the deformation of the mass reduces these properties considerably promoted by the incorporation of the polyester. Regarding the use of the polyethers as For means of controlling deformation, reference is made to U.S. Patent 4,261,758.

Examples of commercially available polyethers which can be used in the present invention are Pluracol V-7's
Wyandotte Chemicals Corporation and Ucon LB-1145 from Union Carbide Corporation.

Instead of these two aforementioned means for controlling the deformation, or in addition, 0.2 to 2 parts by weight or per 100 parts by weight of the organopolysiloxane base polymer can be used
more preferably 0.2 to 1.5 parts by weight of a hydrogenated

Use castor oil. A commercial product of this type is available under the name Thixcin from NL Chemicals,
Heightstown, New Jersey available.

Therefore, when such hydrogenated castor oil is used as a means of controlling deformation, neither is needed Fumed silicon dioxide nor the polyether. However, if this hydrogenated castor oil is not used, then one should use the fumed silica together with the polyether, with the alternative of using pyrogenic Silicon dioxide or polyether exist alone.

It should be pointed out that a reinforcing filler is neither necessary nor desirable in the composition according to the invention, since the composition should have a low modulus. A reinforcing filler in large quantities will increase the modulus of the
Increase mass in an undesirable manner. If fumed silica is used at all, it is in addition to that
stretching filler, such as calcium carbonate, especially the calcium carbonate treated with stearic acid, whereby the
Reduced cost of bulk, viscosity and modulus
the uncured mass can be kept low.

Other types of additives can be added to the composition according to the invention, provided they are available or ' to be invented.

In the composition according to the invention, 100 parts of the organic

polysiloxane base polymer 0.1 to 10 parts by weight of an adhesion promoter are incorporated, without the inventive Ground does not bond very well to substrates. It is therefore desirable to have a primer for such a mass or a To use adhesion promoters in bulk. The primers are undesirable as they add labor costs cause the application of the sealant. It is highly desirable to have a self-binding additive in the mass to incorporate.

So z. B. Compounds of the following formula

R ³¹ 0 R ³³ R ³⁴ R ³⁸

. Si-R ³² -0-C-CHCH ₂ -NR ³⁶ - N-R ⁴ °

are incorporated as self-binding additives in an amount of 0.1 to 10 parts by weight into the composition according to the invention, where in the above formula R and R are selected from monovalent hydrocarbon radicals having 1 to 8 carbon

32 3fi

atoms, R and R are selected from divalent Hydrocarbon radicals with 1 to 12 carbon atoms, R

40
and R are selected from hydrogen and monovalent carbon

34

Hydrogen radicals with 1 to 8 carbon atoms, R is selected from hydrogen and alkyl radicals with 1 to 3 carbon atoms and R is selected from hydrogen and methyl and ρ is an integer from 0 to 3, inclusive. Preferably R and R are selected from alkyl radicals having 1 to 8 carbon atoms and most preferably from methyl, however, they can be any of the radicals given for R above. Besides hydrogen, R and R can be any of the for R and R are monovalent hydrocarbon radicals having 1 to 8 carbon atoms. They prefer to be off Alkyl radicals with 1 to 8 carbon atoms, phenyl radicals and

33 34 £ 3 vinyl scraps selected. Most preferred are R, R, R

40
and R is selected from hydrogen and alkyl radicals such as methyl.

ti

The specific compound of the above formula (14) preferred in the present invention is the compound of the following formula

NH ² -CH _O -CH _O -N-CH ₀ -CH-C-O (CH-KSi (OCH,) _ 2 2 ι 2 ι 2 3 3 3

H CH ₃

Such compounds can be made by taking ethylenediamine Reacts with the appropriate silyl acrylate. Such silyl acrylates are known and can be prepared by reacting the appropriate olefinic methacrylate with hydrogen trialkoxysilane in the presence of a platinum catalyst. The hydrogen of a silane attaches itself to the olefin group of the Acrylates and forms a silyl acrylate compound. Such an addition takes place in the presence of a platinum catalyst at a temperature in the range from room temperature to 150 ° C with or without a solvent and preferably below Ambient pressure. After the acrylate silane has been obtained, it can with the appropriate amine in the presence of a solvent are reacted without a catalyst and gives the amine acrylate adduct of the formula (14) for use as an adhesion promoter in the composition according to the invention. For the latter No catalyst is required for conversion and temperatures from room temperature up to 100 ° C can be used.

at

Preferably / ambient pressure is used. The amine acrylate adduct occurs in high yields.

This adhesion promoter is one of the adhesion promoters disclosed in the above-mentioned European patent publication is usable.

Other adhesion promoters still to be developed may also be useful in the composition according to the invention.

To the storage-stable _; To prepare the fast setting composition of the present invention having a low modulus, it is desirable to end the polyalkoxy terminated first

Il

Prepare diorganopolysiloxane base polymer. this happens by reacting the silanol-terminated base polymer with a crosslinking agent of the formula (5) in the presence an amine catalyst, preferably of hexylamine, as disclosed in the above-mentioned European patent publication and then the silane for eliminating the functional hydroxyl groups is added to this product. This silane is preferably an amine or silazane. Then add the various additives, as in the following examples is explained in more detail. In this way, a cold-curing one-component silicone rubber compound is obtained with little Module that is cheap, thixotropic and self-bonding. The mass is also storage-stable and hardens quickly like that in of the above-mentioned European patent publication.

- yf -

In the following the invention will be explained with reference to the examples explained in more detail, which are not intended to limit the invention in any way. The parts given are parts by weight.

example 1

A matrix was prepared from 100 parts of a methyldimethoxy-terminated dimethylpolysiloxane

P4

P _o

with a viscosity of 150,000 at 25 C, 0.5 parts Di-n-hexylamine, 35 parts of a trimethylsiloxy-terminated dimethylpolysiloxane with a viscosity of 100 centipoise at 25 ° C and 10 parts of a polysiloxane with 3 mol% of monofunctional trimethylsiloxy units, 20 mol% trifunctional methylsiloxy units and 77 mol% difunctional Dimethylsiloxy units with a viscosity of 50 centipoise at 25 ° C and 0.5% by weight of silanol groups. In the Bulk was also mixed in with 130 parts of stearic acid treated calcium carbonate, sold under the trade name Hydrocarb 95T, available from OMYA Inc., Vermont, 3 parts octamethylcyclotetrasiloxane treated fumed Silicon dioxide, 0.2 part of a polyether sold under the tradename UCON LB-1145 from Union Carbide Corporation available, and 4.2 parts of methyldir.ethoxy-N-methylacetamidosilane.

This mass was made in a substantially anhydrous environment and then poured in with the exclusion of water Add catalyst, the amount of which is given in Table I below. This table also shows the Flow properties, tack-free time, application speed and certain physical properties, which were determined after hardening. The flow properties were examined using the Boeing test and was made as follows: a vertical device with a cylindrical above A cavity containing a piston was used. The cavity was filled with sealant and so was the piston then printed so far that it touches the surface of the device just was. Then the device was brought into vertical position

SH

-imposition and left the sealant about 1.25 cm above protrude from the surface. The change in shape was determined in tenths of an inch. The cavity has a depth of about 1.25 cm and a diameter of about 3.7 cm.

The tack-free time was determined by taking an approximately 2.5 χ approximately 12.5 χ approximately 0.3 cm spread from the Made sealant and determined the time after which the surface on the finger touching it was dry was.

The rate of application was determined by placing an approximately 175 g Semco tube with the sealant filled, which had an opening with a diameter of about 3 mm. The pushing out was done under a pressure of

2
about 6.3 kg / cm supplied from an air tank. The application rate was measured in grams per minute.

The test results are shown in Table I below.

Tabel Basic mass I. 100 A. 4th 100 B. 4th Dibutyl tin diacetate 0, 0, 0 Methyldimethoxy-N-methyl-
acetamidosilane 5 1, 05 Flow (inch) 0, 0, tack-free time (min) 23 20th Application speed
(g / min) 14th 360 Shore A hardness 15th 75 (268) 18th 25 (275) 2
Tensile Strength (kg / cm) (psi) 18 19 Strain % 990 925

ts

Example 2

A matrix was prepared from 100 parts of a methyldimethoxy-terminated dimethy / polysiloxane

■ mPe \ -s ο

with a viscosity of 150,000 at 25 ° C., 0.5 part of di-n-hexylamine, 35 parts of a trimethylsiloxy end group having dimethylpolysiloxane liquid with a

mi ⁵ «· * ο

Viscosity of 100 - at 25 C, 10 parts of the same trifunctional liquid as in Example 1, 130 parts of the same calcium carbonate as in Example 1, 0.2 parts of the polyether as in Example 1 and 3 parts of pyrogenic silicon dioxide treated with octamethylcyclotetrasiloxane

with a surface area of about 200 m / g.

Various amounts of methyldimethoxy-N-methylacetamidosilane were added to this base material and dibutyltin acetate and a standard amount of the adhesion promoter as in the following Table II given. This adhesion promoter had the following formula:

NH ₀ -CH _o -CH "-N-CH _o -CH-C- _{O (CH o} ), Si (O-CH-.) _.

²²² I ² I ^{2 3 3 3}

The samples were tested for tack free time in the same manner as described in Example 1. the The results are shown in Table II below.

Table II

Basic mass

ABCDEF 100 100 100 100 100

Methyldimethoxy-N-methylacetamidosilane

Dibutyltin diacetate adhesion promoter Initial hardness Hardness after 48 h / 100 ° C

Initial tack-free time (min)

tack-free time after 48 h / 100 C (min)

2.0 2.5 3.0 3.5 4.0 4.5

0.3 0.3 0.3 0.3 0.3 0.3 1.0 1.0 1.0 1.0 1.0 1.0 24 24 25 27 24 0 0 22 28 27 28

24 25 25 29 43 A + B none

Hardening 20 18 22 31

Example 3

In this example the same basic material as in example 2 was used. This basic mass was with the according to the invention used silane catalyst system catalyzed, and an adhesion promoter was added, whereupon the tack-free times were determined, which are summarized in the following Table III.

egg

Basic mass

Table III

ABCDEFGH 100 100 100 100 100 100 100 100

Hexamethyldisilazane

t-butoxydimethylisopropylaminosilane

Bis (dimethylamine) diroethylsilane

Bis (diethylamino) dimethylsilane

Bis (hazy ethylamino) diphenylsilane

Bis (nonoethylamino) dimethylsilane

Bis- (itDno-n-butylamino) dimethylsilane

Adhesion promoter (ethylenediamine / methacryloxypropyltriinsthoxysilane

3.0

1.7

1.7

2.0

1.7

1.7

Adduct) 1.0 1.0 1.0 1, 0 1.0 1.0 1, 0 Dibutyl tin diacetate 0.3 0.3 0.3 0, 3 0.3 0.3 0, 3 0.3 ffethyltrimethoxysilane 2.5 2.5 2.5 2, 5 2.5 2.5 2, 5 2.5 Initial hardness 25th 25th 26th 26th 26th 20 ⁽¹⁾ 25th 18 ^{1) Hardness after 48 h / 100 ° C 27 23 24 27 0 23 26th 0 Initial tackiness
free time (min) 26th 16 20th 21 15th 14th 14th 30th Tack-free time after
48 h / 10O ° C (min) 15th 14th 14th 13th no
Hardening14 13th no
Hardening

(D

Air had become trapped in these samples during the catalyst incorporation.

Based on the results obtained, it was found that the ethylene diamine / methacryloxypropyltrimethoxysilane adduct used as an adhesion promoter helped stabilize the mass and that bis (dimethylamino) diphenylsilane was of little use was to eliminate the hydroxyl groups. The other silanes appear to be effective in removing the hydroxyl groups be.

Example 4

A matrix was prepared from 100 parts of methyldimethoxysiloxy end groups containing dimethylpropylsiloxane with a viscosity of 150,000 at 25 ° C., 0.5 parts Di-n-hexylamine and 35 parts of the same trimethylsiloxy end groups comprising polydimethylsiloxane used in Example 1, 10 parts of the same trifunctional liquid of Example 1, 180 parts of the same stearic acid treated calcium carbonate as in Example 1 and 0.2 Share the same polyether as in Example 1.

These bases were made with various amounts of ethylenediamine / methacryloxypropyltrimethoxysilane adduct and dibutyltin diacetate catalyzed to produce various silanes added to eliminate the hydroxyl groups. The physical properties of both the original samples and those of the aged samples of the mass were also determined and are summarized in Table IV below. The difference in the tack-free time between the original sample and the sample, which is subject to accelerated aging is subject to is a measure of the storage stability of the mass. Does the tack-free time change after accelerated aging is not measurable, then the mass has a good storage stability. The results are in the following Table IV summarized.

A.
100 B.
100 - S3
■ 43- D.
100 E.
100 m * » G
100 H
100 I.
100 1.0 Table IV Basic mass 0.3 0.3 C.
100 0.3 0.3 F.
100 0.3 0.3 0.3 Ethylenediamine /
Msthacryloxypropyl
trimethoxysilane
Adduct 2.5 2.5 1.0 2.5 2.5 2.5 2.5 2.5 Dibutyl tin
diacetate 1.7 0.3 2.2 2.7 0.3 3.2 .__ Me1 ± yltrimethoxy-
silane 2.5 2.5 Bis (diirethylamino) -
diethylsilane 1.7 3.2

Bis (monoethyl

aininodinethylsilane - ■ 3.2 3.7

Initial physical properties

Tack free

Time (min) 33 25 26 20 23 22 22 23 21

Shore A hardness 34 22 26 21 21 21 20 23 20

Tensile strength 14.84 11.0 9.66 10.29 9.31 8.96 8.12 7.55 7.21

kg / cm2 (psi) (212) (157) (138) (147) (133) (128) (116) (105) (103)

Elongation,% 280 390 350 390 390 360 350 380 340 Properties after 48 h / 100 ° C accelerated aging

Non-tacky A + B none EH-E none P + G half-time (min) hardening 23 hardening hardening 20 20

Shore A hardness dto. 18 dto. Dto. 23 25

The results of the above table show that compositions with a low modulus were obtained which had good storage stability exhibited. The above results also show that bis (dimethylamino) dimethylsilane is more functional for eliminating Hydroxyl groups is not very suitable, while the ethylenediamine / methacryloxypropyltrimethoxysilane adduct is not a means to to give a storage stability, but that it is this storage stability together with one to eliminate the Hydroxyl-less effective silane, such as bis- (dimethylamino) -dimethylsilane, promotes.

Bis- (monoäthy1amino) -dimethylsilan is an excellent one Agent for removing functional hydroxyl groups.

β ν

Example 5

A base was prepared as in Example 1, wherein the methyldimethylpolysiloxane used as the base polymer was the same as in Example 1. Further, the base material 0.5 part of di-n-hexylamine, 15 parts of the same trifunctional liquid as in Example 1, 35 parts of the same Trimethylsilyl-terminated dimethyl polysiloxane as in Example 1, 185 parts of the same stearic acid treated calcium carbonate as in Example 1 and 0.2 parts of a polyether as a deformation control agent (Pluracol V-7 from Wyandotte Chemicals Corporation).

As in all examples, 100 parts of this matrix were made with various amounts of hydroxyl removing agent Crosslinking agent, condensation catalyst and self-binding additives in a substantially anhydrous manner catalyzed. Preferably in all cases the mixing was carried out in a Semco pressure mixer in an anhydrous manner. The amounts of ingredients mixed into the matrix and the physical properties the masses obtained are summarized in Table V below.

d JUJvJvJU

Basic mass

Hexamethyldisilazane methyltrimethoxysilane Dibutyl tin diacetate

Aminoethylaminopropyltrimethoxysilane

properties

Shore A hardness

2 tensile strength kg / cm

(psi)
Strain, %

Initial tack-free time (min)

Tack-free time after accelerated aging 20 h / 100 ° C

Peel strength (kg / cm) (lbs./in.),% Cohesion failure (concrete)

semi-hardened at the interface

Tabel V A.
100 B.
100 C.
100 100 , 0 2.0 2.0 3.2 2 , 0 1 4th ,1 0.075 0.075 0.075 0

1.0

12th

1.0

25th

1.0

1.0

30th

8.33
(119) 14.49
(207) 7.21
(103) 10.71
(153) 650 410 640 230 11th 12th 10 19th 13th 13th 8th 18th 7/10 ⁺ 8/10 28/90 56/100

As the results in Table V above show, the compositions have a low modulus and good self-bonding properties and good storage stability. It can also be concluded from the above results that the amount of trimethylmethoxysilane in bulk one very large has a pronounced effect on the crosslink density, as the difference in hardness shows when the said silane is between zero and 4 parts is used, because the hardness increases from 10 to 30. The table above also shows that the strongest peel adhesion of concrete substrates is obtained with a mass which contains 4 parts of methyltrimethoxysilane.

Example 6

A matrix was prepared comprising 100 parts of the same dimethoxymethylsiloxy-terminated dimethylsiloxane polymer of Example 1 contained further 0.5 part

Bl

Di-n-hexylamine, 35 parts of trimethylsiloxy end groups of the polydimethylsiloxane with a viscosity of 100 at 25 ° C as in Example 1, 10 parts of the same trifunctional Liquid as in Example 1, 145 parts of the same stearic acid treated calcium carbonate from Example 1 and 3 parts of the same treated fumed silica as in Example 1.

Each 100 parts of this base material were mixed with various amounts of silane to remove functional hydroxyl groups, Crosslinking agent, catalyst, and self-bonding additives are catalyzed as indicated in Table VI below. the physical properties of the compositions thus obtained are summarized in Table VI below.

Table VI A. B. C. 100 100 100 Base mass (above) 2.5 2.5 3.0 Hexamethyldisilazane 0.5 0.25 0.5 Methyltrimethoxysilane 0.075 0.075 0.075 Dibutyl tin diacetate

16.17
(231) 9.8
(140) 13.58
(194) 630 630 570 269 241 313 11th 5 6th

Aminoethylaminopropyl

trimethoxysilane 1.0 1.0 1.0

properties

Shore A - hardness 16 15 .20

Tensile strength kg / cm (psi)

Strain, %

Application rate g / min

Tack Free Time (min) Peel Adhesion kg / cm (lbs./in.)

% Cohesive failure (cure 10 days at 50% relative

Humidity / 25 ° C (77 ° F)

(1) anodized aluminum 43/100 42/100 47/100

(2) Lexan 5/5 42/100 48/95

(3) PVC 51/100 44/100 50/100

(4) glass

(5) polyacrylate 6/1 7/3 4/0

(6) Concrete + 13/90 11/95 13/93

(7) Andersen Terrestone PVC 54/100 44/100 50/100

All samples adhering to concrete were semi-cured at the interface with the substrate.

Example 7

A base was prepared from 100 parts of the same Dimethylpolysiloxane having dimethoxymethylsiloxy end groups according to Example 1, the base composition further containing 0.5 parts of di-n-hexylamine, 35 parts of the same trimethylsiloxy end groups containing dimethy! polysiloxane according to Example 1, 10 parts of the same trifunctional liquid of Example 1, 140 parts of the same calcium carbonate treated with stearic acid according to Example 1, 3 parts of the same treated fumed silicon dioxide according to Example 1 and 0.2 parts of the same polyether as in Example 5,

Different amounts of silane were added to each 100 parts of the base material to remove functional hydroxyl groups, Crosslinking agent, condensation catalyst and self-binding additive added - The physical properties the masses obtained and the amounts of the ingredients added are shown in Table VII below summarized.

Table VII A. ltd C. 100 100 100 Base mass II 2.5 2.5 3.0 Hexamethyldisilazane 0.5 0.25 0.5 Methyltrimethoxysilane 0.075 0.075 0.075 Dibutyl tin diacetate

Aminoethylaminopropyl

trimethoxysilane 1.0 1.0 1.0

properties

Shore A hardness 17 12 16

Tensile strength kg / cm ² 13.93 12.11. 13.09

(psi) (199) (173 (187)

Elongation,% 600 680 600

Application speed (g / min) 294 290 314

Tack free time (min) 5 7 5

47/100 51/100 10/22 3/1 47/100 51/100 42/93 50/95 5/0 3/0 15/97 12/95 41/100 47/100

Table VII (continued)

ABC

Deduction bond kg / cm (lbs./in.)

% Cohesive Failure (cured for 10 days at 50% relative

Humidity / 25 ° C (77 ° F)

(1) Anodized aluminum 48/100

(2) Lexan 5/0

(3) PVC 51/100

(4) glass 48/93

(5) polyacrylate 4/0

(6) Concrete 15/93

(7) Andersen Terrastone PVC 45/100

Andersen Terrastone PVC is made up of thin layers of PVC that are extruded over wood for use as window frames became.

The results in the table above show that the compositions have good self-binding properties on most substrates and had a low modulus.

Example 8

A base material was prepared from 100 parts of the methyldimethoxy-terminated dimethylpolysiloxane according to Example 1, 0.5 parts of di-n-hexylamine, 35 parts of the trimethylsiloxy-terminated dimethylpolysiloxane according to Example 1, 10 parts of the trifunctional liquid of Example 1, 160 parts of stearic acid treated calcium carbonate ^ according to example 1, 3 parts of octamethylcyclotetrasiloxane treated fumed silica of example 1 and 0.2 parts of the polyether according to example 5. Fig.

This matrix was catalyzed in a substantially anhydrous manner in a Semco pressure mixer with a silane to remove functional hydroxyl groups, crosslinking agents, condensation catalysts and self-binding additives, as in the other examples. The physical properties of the masses obtained as well as those used to catalyze the The amounts of the various ingredients used in the base mass are summarized in Table VIII below.

JS

Table VIII Basic mass A. B. C. Hexamethyldisilazane 100 100 100 Methyltrimethoxysilane 2.5 2.5 2.5 Dibutyl tin diacetate 0.25 0.70 0.70 0.075 0.025 0.075

Aminoethylaminopropyl

trimethoxysilane 1.5 1.0 1.0

properties

Shore A hardness 10 13th 24 2
Tensile strength kg / cm 7.63 12.04 22.26 (psi) (109 (172) (318) Strain, % 535 470 360 Application rate g / min Tack Free Time (min) 22nd 27 11th

Peel adhesion kg / cm (lbs./in.)

% Cohesive Failure (cured for 10 days at 50% relative

Humidity / 25oc (77 ° F)

(1) Alclad Aliminium 12/50 31/80 40/80

(2) Lexan 15/100 41/88 44/100

(3) PVC 14/100 42/80 46/100

(4) Glass 14/45 42/75 47/80

(5) polyacrylate 21/93 22/35 4/0

(6) Concrete 11/80 9/3 14/3

semi-cured sealant observed at the interface with the substrate.

Example 9

A matrix was prepared from 100 parts of the same methyldimethoxy-terminated polydimethylsiloxane according to Example 1 and 0.5 parts of di-n-hexylamine as in Example 1, 10 parts of the same trifunctional liquid as in Example 1, 35 parts of the same trimethylsilyl end groups containing polydimethylsiloxane as in Example 1, 220 parts of the same treated with stearic acid Calcium carbonate as in Example 1 and 3 parts of the treated fumed silica as in Example 1.

2.5 parts of hexamethyldisilazane, 0.5 part of methyltriniethoxysilane and 1 part of aminoethylaminopropyltrimethoxysilane were added to this base material and 0.07 part of dibutyltin diacetate was added.

-YS-

The preparation of the base material and its catalyzing with the aforementioned ingredients took place in one essential step anhydrous way in a continuous twin-screw extruder from Werner & Pfleiderer.

The physical properties of the compositions so produced are summarized in Table IX below, with the Peel adhesion results show that most compositions have good self-bonding properties over a range of Substrates, and further the results in Table IX show that the compositions were stable and low Module had.

Sample no.

Application rate g / min flow (inches) Specific weight Tack-free time (min) Shore A hardness

2 tensile strength kg / ση (psi) elongation,%

Peel adhesion kg / cm (lbs./in.)

concrete

Glass

PVC (rigid) Lexan

Marviplate

a hard PVC from Australia zinc alum

Anodized aluminum polyacrylate

- Accelerated aging 72 h / 100 ° C (samples 24, 25, 26)

Physical Properties

Table IX 24 44 _5 234 210 in 258 0.20 0.15 0.15 1.52 1.53 1.52 30th 30th 30th 16 16 16

13.09 (187) 12.88 (184) 13.58 (194)

555 565

540

rehearse rehearse rehearse 5, 6, 7 24.25.26 44.45.46 17/0 10/0 8/0 60/100 50/90 55/80 57/100 52/100 54/100 52/100 48/100 51/100 58/100 53/100 58/100 35/30 not 31/100 tested 55/100 55/100 52/100 40/30 38/30 37/30

Samples 24, 25, 26 Tack Free Time (min)

Shore A - hardness tensile strength kg / cm (psi) elongation,% -H-

20, 20,

27 21 (300)

450

The numbered samples were on a mixer during the trials unfortunately taken by Werner & Pf.

Example 10

A matrix was prepared from 100 parts of a Polydimethylsiloxane polymer having dimethoxymethylsiloxy end groups with a viscosity of 150,000 at 25 ° C, 0.5 part of di-n-hexylamine, 180 parts with stearic acid treated calcium carbonate, 35 parts trimethylsiloxy end groups comprising polydimethylsiloxane fluid having a viscosity of 100 centipoise at 25 ° C, 10 parts of the same liquid with a high trifunctional content as in the other examples and 5.68 parts hydrogenated Castor Oil (Thixcin R). In each case 100 parts of the base mass were added under essentially anhydrous conditions Parts of hexamethyldisilazane, 0.5 part of methyltrimethoxysilane, 1 part of aminoethylaminopropyltrimethoxysilane and 0.05 part Dibutyl tin diacetate. The physical properties of the resulting composition are summarized in Table X below.

Table X Tack free time 25th Flow (inch) 0.08 Application speed (g / min) 164 Shore A hardness 22nd Strain, % 435 2
Tensile strength kg / cm (psi) 17.36 (248) 50% modulus, kg / cm (psi) 3.57 (51) 75% modulus, kg / cm (psi) 4.34 (.62) 100% module, kg / cm ² (psi) 5.25 (75) Peel-off adhesion (daily hardening) kg / cm (lbs./in.) -% cohesive failure (1) Anodized aluminum 47/100 (2) Lexan (polycarbonate) 46/100 (3) Rigid PVC (polyvinyl chloride) 44/100 (4) glass 46/100

The additives according to the invention can be used for a stable, essentially anhydrous and acid-free, at room temperature One-component vulcanizable organopolysiloxane composition that can be used under ambient conditions in the absence of moisture stable over an extended period of time and in a sticky

$ 3

non-slip elastomer is convertible, this mass comprising the following components:

1. an organopolysiloxane in which the silicon atom on each Chain end has at least 2 alkoxy radicals,

2. an effective amount of a condensation catalyst,

3. a stabilizing amount of a silane for removing functional hydroxyl groups, said silane being a Silicon Nitrogen Compound is selected from:

(A) a silicon nitrogen compound of the formula

R "
I.

(Y) (R ¹ '") ₂ Si N Si (R ¹ ") ₂ Y,

wherein Y is selected from R ¹ "and R ~ N-, and

(B) a silicon nitrogen polymer

(i) 3 to 100 mol% of chemically linked structural units, selected from the following units:

R "· R" 'R "R"

I I / I

(R ") ₂ NSi0—, (R-) ₂ NSiN— , {R"')

R ¹ "R" R " ¹ R ^M R '

I / I / Il

SiN- , -SiN-, -SiN-

and

(ii) 0 to 97 mol% of chemically linked structural units of the formula

as well as their mixtures,

ac -

wherein the silicon atoms of the silicon nitrogen polymer are connected to one another by a grouping which is selected from -SiOSi- and -SiNR ¹¹ Si-, the free valences of the silicon atoms that do not form a siloxy unit with oxygen or with the formation of a silazyl unit connected to nitrogen, with a

Grouping are connected, which is selected from R "residues and (R") ₂ N residues and

wherein the ratio of the sum of said R ¹ ″ radicals and said (R ”) ₂ N radicals to the silicon atoms of the silicon nitrogen polymer has a value in the range from 1.5 to 3 inclusive and

R "is selected from hydrogen, monovalent hydrocarbon radicals and fluoroalkyl radicals, R" ^{1 is} selected from hydrogen, monovalent hydrocarbon radicals and fluoroalkyl radicals, and c is an integer from 0 to 3 inclusive and

(iii) optionally an effective amount of a curing accelerator, which is selected from substituted guanidines, amines and mixtures thereof.

From the silane to the elimination of functional hydroxyl groups 0.1 to 10 parts by weight per 100 parts by weight of the organopolysiloxane are present.

The silazane polymers can be cyclic silazanes chemically with one another include bonded units of the following formula:

R ¹ "R"

I /

—SiN-

wherein R ", R ' ¹ ' have the aforementioned meaning, forming a ratio of 1.5 to 3 for the sum of R ^'11 and (R") -N radicals per silicon atom in the said silazane polymer.

The silazane polymer can comprise linear polymers that are at least have a unit selected from the following units:

R "

(RN) (R ¹¹ M ₂ SiN- and

R "(R ¹¹¹ J ₂ SiN-

* >>. wherein R "and R ¹¹¹ are as defined above, forming a ratio of 1.5 to 3 of the sum of the radicals R ¹¹¹ and (R") ₂ N per silicon atom in the silazane polymer.

The silazane polymers can furthermore comprise linear polymers which essentially consist of the following units:

wherein R "and R" ¹ are as defined above, forming a ratio of 1.5 to 3 of the sum of the radicals R ^'11 and (R ") -N per silicon atom in the silazane polymer.

The silazane polymers can also comprise polymers having at least one unit selected from

ρ ,,, _R »

I /

(R ") ₂ —SiN-

and

(R ¹ ") 3 SiN-

wherein R "and R ¹ " are as defined above, forming a ratio of 1.5 to 3 of the sum of the radicals R ' ¹ ' and (R ") ₂ N per silicon atom in the silazane polymer.

ή92

The silazane polymers further comprise polymers with a sufficient amount of units selected from

_R , " _R ". ρ IM _R « _R »

I / I / M

SiN—, —SiH—, - SiN-1 ! l

where R "and R" ^{1 have} the meaning given above and a ratio of 1.5 to 3 of the sum of the radicals R ¹ V 'and (R ¹¹ K per silicon atom is present in the silazane polymer.

The Si la2, an / siloxane compounds are copolymers with up to 97 of units of the formula

where most of the units have the following formulas:

R "

(R-) _c SiN ₄ _ _c

_R ..i R "R"

I I i

(R ") ₂ N SiO- (Tl") ₂ N Sl-N-

Rl »R-

where R "and R"'and c have the meaning given above and the ratio of the sum of the radicals R " ¹ + (R ¹¹ KN per silicon atom in the silazane / siloxane copolymer is in the range from 1.5 to 3.

The silazane / siloxane compounds can also be cyclic compounds consisting of chemically linked (R ¹ '') _SiO units and units of the following formula:

R '"R"

-SiN - R " ¹

where R "and R" 'have the meaning given above.

Furthermore, the silicon-nitrogen compounds can be linear and be cyclic silazanes of the following formula:

R "
(R "'L SiN-

R ¹ "R"

-Si-N-

■ Si

wherein R "and R ¹ " have the abovementioned meaning, η is an integer with a value of preferably 0 to 20 inclusive and

d has the value 0 or T and, when d = 0, η is preferably equals 3 to 7 inclusive.

The silicon-nitrogen compounds can also be polysiloxanes be of the following formula:

R "

ZN—

"SiO-

R ··· R "

I /

-SiN- Z

η R '

where R ", R ¹¹¹ and η have the abovementioned meaning and Z is selected from R" and -Si (R ¹¹¹ Jo *

Preferred silicon-nitrogen compounds are selected from Hexamethyldisilazane, hexamethylcyclotrisilazane, octamethyl-

one
cyclotetrasilazane and silicon-nitrogen compounds represented by the following formula

[(CF ₃ -CH ₂ -CH ₂ -) (CH ₃ ) ₂ Si] ₂ NH

a silicon-nitrogen compound of the formula

; QCF ₃ -CT ₂ -CH ₂ -) (CH ₃ J ₂ Si] ₃ N

and a silicon-nitrogen compound of the formula

[(CF ₃ -CH ₂ -CH ₂ -)

Claims (1)

PATENT CLAIMS 1. Stable, essentially anhydrous and acid-free, cold-curing one-component organopolysiloxane composition, which in the absence of Moisture stable under ambient conditions for an extended period of time and which is non-tacky Elastomer is convertible, characterized by the following components:
1.) An organopolysiloxane in which the silicon atom on each End of the polymer chain carries at least 2 alkoxy radicals, 2.) an effective amount of a condensation catalyst, 3.) a stabilizing amount of a functional hydroxyl group-removing silane of the following formula ₄ _ _{(c + £)} Si (X) _f where R is an aliphatic organic radical having 1 to 8 carbons is material atoms selected from alkyl, alkyl ethers, alkyl esters, Alkyl ketone and alkyl cyan radicals or an aralkyl radical with 7 to 13 carbon atoms, R is a monovalent, optionally substituted hydrocarbon radical with 1 to 13 carbon atoms, X is a hydrolyzable group from amido, amino, carbamato, Enoxy, Imidato, Isocyanate, Oximato, Thioisocyanato and Ureido residues, c is an integer from 0 to 3 inclusive, ^{V (w} 'f is an integer from 1 to 4 inclusive and the sum of c + f is 1 to 4 inclusive, 4.) an effective amount of a curing catalyst selected is composed of substituted guanidines, amines and their mixtures when X is enoxy or amido and 5.) 2 to 20 parts by weight per 100 parts by weight of the organopolysiloxane, a first liquid polysiloxane as a plasticizer, which has a high degree of trifunctionality or mixtures Contains tri- and tetra-functionality and comprises the following units: (i) 5 to 60 mol% of monoalkylsiloxy, siloxy units or a mixture of such units, (ii) 1 to 6 mole percent trialkylsiloxy units and (iii) 34 to 94 mol% dialkylsiloxy units, this polysiloxane containing from about 0.1 to about 2% by weight of silicon-bonded hydroxyl groups. 2. Mass according to claim 1, characterized in that that the organopolysiloxane has a viscosity in the range from 30,000 to 500,000 at 25 ° C. 3. Mass according to claim 2, characterized in that that it further contains 5 to 60 parts by weight of a second plasticizer per 100 parts of the organopolysiloxane, where 33053S6 this second plasticizer has a linear triorganosiloxy end group having diorganopolysiloxane has a viscosity in the range from 10 to 20,000 at 25 C, the Organogroups are monovalent hydrocarbon radicals. 4. Composition according to claim 3, characterized in that the second plasticizer is a polymer of the following Formula is , 20 R ²⁰
SiO- 20th R ²⁰
I.
• SiO · -R 20th R is a monovalent hydrocarbon radical and t has a value such that the viscosity of the polymer is from Varies 10 to 20,000 centipoise at 25 ° C. 5. mass according to claim 4, characterized 20th net that R is methyl and t varies such that the viscosity of the polymer is in the range from 10 to 10,000 centipoise at 25 ⁰ C and the second plasticizer has a hydroxyl group content from 500 to 1500 ppm. 6. Composition according to claim 4, characterized in that that it contains 100 to 300 parts by weight of an extending filler per 100 parts by weight of the organopolysiloxane. 7. Composition according to claim 6, characterized in that that the extending filler is potassium carbonate. ' 8. Composition according to claim 7, characterized in that that the potassium carbonate is treated with stearic acid. 9. Mass according to claim 7, characterized that it contains 1 to 50 parts by weight of a reinforcing filler per 100 parts by weight of the organopolysiloxane. 10. Composition according to claim 8, characterized in that the reinforcing filler as a change in shape controlling agent acts and is fumed silica, which is present in an amount of 1 to 10 parts by weight 100 parts by weight of the organopolysiloxane is present. 11. Composition according to claim 8, characterized in that that they 0.1 to 2 parts by weight per 100 parts by weight of the organopolysiloxane of a second the change in shape contains controlling agent which is a polyether selected from compounds of the formula and the formula (CH ₀ O) 1 Q χ 2x 'n Jy -z wherein A and B stand for radicals selected from hydrogen, alkyl radicals with 1 to 12 carbon atoms, cyclo alkyl radicals with 5 to 7 carbon atoms in the ring, mononuclear and dinuclear aryl radicals and mononuclear aryl radicals with lower alkyl radicals as substituents, the alkyl radicals, bonded to the aromatic nucleus contain no more than 5 carbon atoms, and A and B also contain the following Rest can be ~ r_JL_O_ where R is an alkyl radical with 1 to 11 carbon atoms, Q is a radical of a polyhydric initiator radical which is at least Contains 2 hydroxy radicals and which is selected from ethylene glycol, glycerine, trimethylolpropane and other polyhydric Alcohols with 2 to 6 hydroxyl groups, a is a number from 2 to 4, y has a value from 2 to 10 and ζ has a value of 1 to 5, the polyester having a molecular weight of about 300 to about 200,000. 12. Composition according to claim 7, characterized in that that they are 0.2 to 2 parts by weight of hydrogenated castor oil as -. deformation controlling agent to 100 Contains parts by weight of the organopolysiloxane. 13. Composition according to claim 2, characterized in that that the reinforcing filler has been treated with cyclopolysiloxane prior to its incorporation into the mass. 14. Composition according to claim 1, characterized in that that it contains 0.1 to 10 parts by weight of an adhesion promoter represented by the following formula r31 OR ³³ R ³⁴ R ³⁸ 30 '32 »
CR ³⁰ O) ₃ Si-R ^J -0-C- wherein R and R are selected from monovalent hydrocarbon radicals having 1 to 8 carbon atoms, R and R are selected from water - substance and monovalent hydrocarbon residues with 1 to 6 34
Carbon atoms, R is selected from hydrogen and 33 alkyl radicals with 1 to 3 carbon atoms and R is selected from hydrogen and methyl, R and R are selected from divalent hydrocarbon radicals having 1 to 12 carbon atoms and ρ is an integer from 0 to 3. 15. Composition according to claim 14, characterized in that the adhesion promoter is the following Formula has Ii NH, -CH, -CH, -N-CH, -CH-C-O (CH-) "Si (OCH,), -t ^. I [ 2 3 3 3 H CH ₃ 16. Composition according to claim 1, characterized that the silane has the following formula ^(Ri0) 4- (b ₊ a) ^{Si (X)} a wherein R is an aliphatic organic radical having 1 to 8 carbon atoms is selected from alkyl, alkyl ether, allyl ester, alkyl ketone and alkylcyan radicals or an aralkyl radical with 7 to , 13 carbon atoms, 2
R is a monovalent, optionally substituted, hydrocarbon radical with 1 to 13 carbon atoms, X is a hydrolyzable group from amido, amino, carbamato, enoxy, imidato, isocyanato, oximato, thioisocyanato and ureido residues, a is an integer from 1 to 2 inclusive, b is an integer from 0 to 1 inclusive and the sum of a + b is 1 or 2 and the silane both eliminates and functional hydroxyl groups is a polyalkoxysilane crosslinking agent for forming terminating groups at the ends of the organopolysiloxane chain so that each terminal Si has at least 2 alkoxy radicals. 17. Stable, essentially anhydrous and acid-free, at room temperature vulcanizable one-component organopolysiloxane composition which, in the absence of moisture, over an extended Stable for a long time and which can be converted into a tack-free elastomer, characterized by the following components: 1.) An organopolxsiloxane in which the silicon atoms at each end of the polymer chain have at least 2 alkoxy radicals, 2.) an effective amount of a condensation catalyst, 3.) a stabilizing amount of a hydroxyl functional group eliminating silane of the following formula (R ² ) 1 ' ^C
(R0) 4- (c ₊ f) ^{Si (X} > f where R is an aliphatic organic radical with 1 to 8 Carbon atoms is selected from alkyl, alkyl ethers, alkyl esters, alkyl ketone and alkyl cyano radicals or one Aralkyl radical with 7 to 13 carbon atoms, 2
R is a monovalent, optionally substituted hydrocarbon radical with 1 to 13 carbon atoms, X is a hydrolyzable residue from amido, amino, carbamato, Enoxy, imidato, isocyanato, oximato, thioisocyanato and ureido residues, c is an integer from 0 to 3 inclusive, f is an integer from 1 to 4 inclusive, and the sum of c + f is equal to 1 up to and including 4, 4.) an effective amount of a curing catalyst selected from substituted guanidines, amines and mixtures the aforementioned compounds and 5.) 2 to 20 parts by weight per 100 parts by weight of the organopolysiloxane a liquid polysiloxane as the first plasticizer with a high degree of trifunctionality and mixtures of tri- and tetrafunctionality, which comprises the following units: (i) 5 to 60 mole percent monoalkylsiloxy, siloxy units and a mixture of such units, (ii) 1 to 6 mole percent trialkylsiloxy units and (iii) 34 to 94 mol% dialkylsiloxy units, said polysiloxane having about 0.1 to about 2% by weight of silicon-bonded hydroxyl groups contains. 18. Composition according to claim 17, characterized in that the organopolysiloxane has a viscosity in the range of 60,000 to 500,000 at 25 ° C. 19. Composition according to claim 18, characterized in that that they further 10 to 50 parts by weight to parts by weight of the organopolysiloxane of a second plasticizer containing a linear triorganosiloxy-terminated diorganopolysiloxane having a viscosity in the range of mPa-s
10 to 20,000 at 25 ^° C. and the organic groups are monovalent hydrocarbon radicals. 20. Composition according to claim 19, characterized in that the second plasticizer is a polymer of the following formula R ²⁰ SiO- B ²⁰
-SiO- 20th • R ' R is a monovalent hydrocarbon radical and t has a value such that the viscosity of the polymer is from Varies 10 to 20,000 centipoise at 25 ° C. 21 .. mass according to claim 20, characterized in that that R is methyl and t varies such that the viscosity of the polymer is in the range from 10 to 10,000 mP «-s is at 25 ° C and the second plasticizer has a hydroxyl group content from 500 to 1,500 ppm. 22. Composition according to claim 20, characterized in that that it contains 100 to 300 parts by weight of an extending filler per 100 parts by weight of the organopolysiloxane. 23. Composition according to claim 22, characterized in that that the extending filler is potassium carbonate. 24. Composition according to claim 23, characterized in that the calciuracarbonate with stearic acid is treated. 25. Composition according to claim 23, characterized in that that it contains 1 to 50 parts by weight of a reinforcing filler per 100 parts by weight of the organopolysiloxane. _ Q - 26. Composition according to claim 23, characterized in that net that the reinforcing filler as a change in shape controlling agent acts and is fumed silica, which is present in an amount of 1 to 1C parts by weight 100 parts by weight of the organopolysiloxane is present. 27. Composition according to claim 24, characterized in that that they 0.1 to 2 parts by weight per 100 parts by weight of the organopolysiloxane of a second the change in shape contains controlling agent which is a polyether selected from compounds of the formula < ^C x ^H 2x ⁰⁾ n - ^B and the formula wherein A and B represent radicals selected from hydrogen, alkyl radicals with 1 to 12 carbon atoms, cycloalkyl radicals with 5 to 7 carbon atoms in the ring, mononuclear and binuclear aryl radicals and mononuclear aryl radicals with lower alkyl radicals as substituents, the alkyl radicals attached to the aromatic nucleus, contain no more than 5 carbon atoms and A and B can also be the following radical _Q R — C — O— where R is an alkyl radical with 1 to 11 carbon atoms, Q is a radical of a polyhydric initiator radical which contains at least 2 hydroxy radicals and which is selected from Ethylene glycol, glycerin, trimethylolpropane and other polyhydric Alcohols with 2 to 6 hydroxyl groups, a is a number from 2 to 4, y has a value from 2 to 10 and ζ has a value of 1 to 5, the polyester having a molecular weight of about 300 to about 200,000. 28. Composition according to claim 23, characterized in that it contains 0.2 to 2 parts by weight of hydrogenated RiC i nut oil as the deformation controlling agent to 100 Contains parts by weight of the organopolysiloxane. - Composition according to claim 18, characterized in that that the reinforcing filler has been treated with cyclopolysiloxane prior to its incorporation into the mass. 30. Composition according to claim ^, characterized in that that it contains 0.1 to 10 parts by weight of an adhesion promoter represented by the following formula OR ³³ R ³⁴ R ³⁸ LLJ sI-R ³² -o J- wherein R and R are selected from monovalent hydrocarbons residues with 1 to 8 carbon atoms, R and R are selected from water - substance and monovalent hydrocarbon residues with 1 to 6 34
Carbon atoms, R is selected from hydrogen and alkyl radicals with 1 to 3 carbon atoms and R is selected from hydrogen and methyl, R and R are selected from divalent hydrocarbon radicals having 1 to 12 carbon atoms and ρ is an integer from 0 to 3. 31. Composition according to claim 30, characterized in that the adhesion promoter is the following Formula has NH-CH, - CH- N-CH.-CH-C-O (CH,), Si (OCH-), I ί I \ 2 t 2 3 3 3 H CH, 32. organopolysiloxane composition according to claim 1, characterized in that a plurality of Alkoxy-terminated organopolysiloxane has the following formula ^(R0) 3- (b + e) | ^{10 (} | ⁱ⁰⁾ nf ^{1 X} e ^R * _e wherein R is an optionally substituted monovalent hydrocarbon radical having 1 to 13 carbon atoms, R is an aliphatic organic radical having 1 to 8 carbon atoms is selected from alkyl, alkyl ethers, alkyl esters, alkyl ketone and alkyl cyan radicals or an aralkyl radical with 7 up to 13 carbon atoms, 2
R is a monovalent, optionally substituted, hydrocarbon radical with 1 to 13 carbon atoms, X a hydrolyzable removable group is selected from amido, amino, carbamate enoxy, imidato, isocyanato, oximato, Thioisocyanato and üereido residues, b the value 0 or 1, e the value 0 or 1, the sum of b + e has the value 0 or 1 and η is an integer with a value from about 50 to about 2,500. 33. Composition according to claim 1, characterized by an effective amount of a crosslinking silane of the formula (R ² ) _b < ^Ri °> (4-b) ^Si wherein R is an aliphatic organic radical having 1 to 8 carbon atoms is selected from alkyl, alkyl ether * alkyl ester, alkyl ketone and alkylcyan radicals or an aralkyl radical with 7 to 13 carbon atoms, 2
R is a monovalent, optionally substituted, hydrocarbon radical having 1 to 13 carbon atoms and b is 0 or 1. 34. Cold-curing composition according to claim 1, characterized in that the hydroxyl group eliminates Silane is methyldimethoxy (N-methy! Acetamido) silane. 35. Cold-curing composition according to claim 1, characterized in that that they are considered a tin compound Contains condensation catalyst. 36. Composition according to claim 1, characterized 1 2
draws that R, R and R are methyl groups and that the composition contains a tin compound as a condensation catalyst. 37. Composition according to claim 1, characterized in that it contains an effective amount of a curing accelerator selected from substituted Guanidines, amines and mixtures thereof. 38. Composition according to claim 1, characterized in that it has a plurality of methoxy end groups Polydimethylsiloxane, an effective amount of a tin-containing condensation catalyst and a stabilizing Contains amount of a polymethoxy-di-n-hexylaminosilane. 39. Composition according to claim 1, characterized in that that it is a methoxy-terminated polydimethylsiloxane, an effective amount of a tin-containing one Condensation catalyst, an effective amount of a trimethoxysilylpropyl-tetramethylguanidine as a curing accelerator and contains a stabilizing amount of polymethoxyacetamidosilane. 40. Composition according to claim 38, characterized in that that it contains dibutyltin diacetate. 41. Composition according to claim 38, characterized net that it contains polymethoxysilane as a crosslinking agent. 42. Stable and essentially acid-free, one-component polyalkoxy end groups that can be vulcanized at room temperature - <ä & organopolysiloxane composition under ambient conditions is curable to a tack-free elastomer over an extended period of time, characterized by the following components: (i) 100 parts by weight of an essentially silanol free polyalkoxysiloxydiorganopolysiloxane the formula -SiO (R ² ), ■ Si (OR ^X ) / η Χ 3-ib + e) (ii) 0 to 10 parts by weight of a crosslinking polyalkoxysilane the formula 2'b Si (iii) an effective amount of a condensation catalyst and (iv) a stabilizing amount of a functional hydroxyl-removing silane of the formula (R ² ) ^{(E. Si (X)} where R is an optionally substituted hydrocarbon radical having 1 to 13 carbon atoms, R is an aliphatic organic radical with 1 to 8 carbon atoms is selected from alkyl, alkyl ethers, alkyl esters, alky! Ketone and alkyl cyan radicals or an aralkyl radical with 7 to 13 carbon atoms, R is an optionally substituted monovalent hydrocarbon radical with 1 to 13 carbon atoms, X is a hydrolyzable removable group selected from amido-amino, carbamato, enoxy, imidato, isocyanato, oximato, thioisocyanato and ureido radicals,
b the value 0 or 1,
e has the value 0 or 1 and the sum of b + e has the value 0 or 1 and η is an integer with a value from about 50 to is about 2 500, c is an integer from 0 to 3 inclusive, f is an integer from 1 to 4 inclusive and the sum c + f has a value up to and including 4 and (v) when X is the enoxy group, 0.1 to 5 parts by weight of a curing accelerator selected from substituted ones Guanidines, amines and their mixtures and ^ (vi) 2 to 20 parts by weight per 100 parts by weight of the Organopolysiloxane, a first plasticizer in the form of a liquid polysiloxane with a high degree of trifunctionality or mixtures of tri- and tetrafunctionality, this liquid siloxane having the following units: (a) 5 to 60 mol% of monoalkylsiloxy, siloxy units and a mixture of such units, (b) 1 to 6 mol% trialkylsiloxy units and (c) 34 to 94 mole percent dialkylsiloxy units, this liquid polysiloxane about 0.1 contains up to about 2% by weight of hydroxyl groups bonded to silicon. 43. Composition according to claim 42, characterized in that the organopolysiloxane has a viscosity mPa'S in the range of 60,000 to 500,000 at 25 ° C. 44. Composition according to claim 42, characterized in that that they further 5 to 60 parts by weight of a second plasticizer per 100 parts of the organopolysiloxane contains, wherein this second plasticizer contains a linear triorganosiloxy-terminated diorganopolysiloxane one mPci-S Viscosity in the range from 10 to 20,000 - at 25 ° C where the organic groups are monovalent hydrocarbon radicals. 45. Composition according to claim 44, characterized in that the second plasticizer is a polymer of the following formula 20th SiO- 20th R ²⁰ I SiO- 20th • R R is a monovalent hydrocarbon radical and \ t has such a value that the viscosity of the polymer varies from 10 to 20,000 at 25 ° C. 46 ,. Mass according to claim 45, characterized 20th net that R is methyl and t varies such that the viscosity of the polymer in the range from 10 to 10,000 mPa · s is at 25 ° C und.der second plasticizer has a hydroxyl group content from 500 to 1,500 ppm. 47. Composition according to claim 45, characterized in that that it contains 100 to 300 parts by weight of an extending filler per 100 parts by weight of the organopolysiloxane. 48. Composition according to claim 47, characterized in that the stretching filler is calcium carbonate is. 49. Composition according to claim 48, characterized in that the potassium carbonate is treated with stearic acid is. 50. Composition according to claim 48, characterized in that it contains 1 to 50 parts by weight of a reinforcing Contains filler per 100 parts by weight of the organopolysiloxane. 51. Composition according to claim 49, characterized in that that the reinforcing filler acts as a shape change control agent and fumed silica which is present in an amount of 1 to 10 parts by weight per 100 parts by weight of the organopolysiloxane. 52. Composition according to claim 49, characterized in that that they 0.1 to 2 parts by weight per 100 parts by weight of the organopolysiloxane of a second the change in shape contains controlling agent which is a polyether selected from compounds of the formula ^(C x ^H 2x ⁰⁾ _n - ^B and the formula wherein A and B stand for radicals which are selected from hydrogen, alkyl radicals having 1 to 12 carbon atoms, cycloalkyl radicals with 5 to 7 carbon atoms in the ring, mononuclear and binuclear aryl radicals and mononuclear aryl radicals with lower alkyl radicals as substituents, the alkyl radicals, which are bound to the aromatic nucleus, no longer as 5 carbon atoms and A and B can furthermore be the following radical _Q R — c — σ— where R is an alkyl radical with 1 to 11 carbon atoms, Q is a radical of a polyhydric initiator radical which is at least Contains 2 hydroxy radicals and which is selected from ethylene glycol, glycerine, trimethylolpropane and other polyhydric Alcohols with 2 to 6 hydroxyl groups, a is a number from 2 to 4, y has a value from 2 to 10 and ζ has a value of 1 to 5, the polyester having a molecular weight of about 300 to about 200,000. 53. Composition according to claim 48, characterized in that that they add 0.2 to 2 parts by weight of hydrogenated castor oil as the deformation control agent to 100 Contains parts by weight of the organopolysiloxane. 54. Composition according to claim 43, characterized in that that the reinforcing filler has been treated with cyclopolysiloxane prior to its incorporation into the mass. 55. Composition according to claim 42, characterized in that that it contains 0.1 to 10 parts by weight of an adhesion promoter represented by the following formula "31 OK ³³ R ³⁴ P ³⁸ , R ³⁰ O) ₃ _ _p Li-R ³² -OC-CHCH ₂ -iR ³⁶ -iR ⁴ ° wherein R and R are selected from monovalent hydrocarbon radicals having 1 to 8 carbon atoms, R and R are selected from water - - substance and monovalent hydrocarbon residues with 1 to 6 34
Carbon atoms, R is selected from hydrogen and alkyl radicals with 1 to 3 carbon atoms and R is selected from hydrogen and methyl, 32 36
R and R are selected from divalent hydrocarbon radicals having 1 to 12 carbon atoms and ρ is an integer from 0 to 3. 56. Composition according to claim 55, characterized in that the adhesion promoter is the following Formula has Il NH-- CH, - CH, -N — CH - CH-C — O (CH-), Si (OCH.), H CH ₃ 57. Composition according to claim 42, characterized in that it contains an effective amount of a hardening accelerator selected from substituted Guanidines, amines and mixtures thereof. 58. Composition according to claim 42, characterized 1 2 indicates that R, R and R are methyl groups. 59. Composition according to claim 42, characterized in that the condensation catalyst is a Tin compound is. 60. Composition according to claim 42, characterized in that it has a plurality of methoxy end groups comprising polydimethylsiloxane, a polymethoxysilane, an effective amount of a curing accelerator selected from substituted guanidines, amines and mixtures thereof, an effective amount of a tin compound as a condensation catalyst and a stabilizing amount of a silane that eliminates functional hydroxy groups and at least one has hydrolyzable removable group selected from amido, amino, carbamato, enoxy, imidato, isocyanato, Oximato, thioisocyanato and ureido residues. 61. Composition according to claim 60, characterized in that the polymethoxysilane is methyltrimethoxysilane is. 62. Composition according to claim 60, characterized that the substituted guanidine is butyltetramethylguanidine is. 63. Composition according to claim 60, characterized in that the organic amine is dialkylamine. 64. Composition according to claim 63, characterized in that it has a methyldimethoxysiloxy end group comprising polydimethylsiloxane, a reinforcing amount of an octamethylcyclotetrasiloxane treated pyrogenic Silica as a filler, an effective amount of dibutyltin diacetate as a condensation catalyst, a cure accelerator Amount of TrimethoKysilylpropyltetramethylguanidin and an excess of up to 3% by weight, based on the weight of the polydimethylsiloxane, on methyldimethoxy-N-methylacetamidosilane includes. 65. Composition according to claim 63, characterized in that an excess instead of the acetamidosilane of up to 3% by weight, based on the weight of the polydimethylsiloxane, Methyldimethoxyisopropenoxysilane is present. 66. Composition according to claim 63, characterized in that it contains up to 10 parts of methyltrimethoxysilane contains per 100 parts of polydimethylsiloxane. 67. Composition according to claim 63, characterized in that it contains an effective amount of di-n-hexylamine as a curing accelerator instead of trimethoxysilylpropyltetramethylguanidine contains. 68. Process for producing a substantially acid-free, One-component silicone rubber mass vulcanizable to a solid elastomeric state at room temperature, wherein under substantially anhydrous conditions at a temperature ranging from 0 to 180 ⁰ C a vulcanizable at room temperature material is agitated, which is selected from: (i) a mixture of (a) 100 parts by weight of a silanol terminated Polydiorganosxloxant, which consists essentially of chemical interconnected Units of the following formula -SiO (b) a stabilizing amount of a functional Hydroxy group-eliminating silane of the formula ^(Ri °> 4- (a ₊ b) ^{sl (x)} a (c) 0 to 10 parts by weight of a crosslinking silane of the formula (R ² ) _b (R ¹ O) ₍ 4_ _b) si (d) an effective amount of a condensation catalyst and (e) 0 to 5 parts by weight of a curing accelerator selected from substituted guanidines, Amines and their mixtures and (ii) a mixture of (a) 100 parts by weight of a polyalkoxy-terminated diorganopolysiloxane of the formula - 21 * ^2% R (R ² ) ^r .b 3- (b + e) X. -SiO 1, -Si (OR) 3- (b + e) η Χ. (b) 0 to 10 parts by weight of a crosslinking silane of the formula 1 ⁽ f ²⁾ b ^{(R 0)} (4-b) ^Si (c) an effective amount of a condensation catalyst, (d) a stabilizing amount of a hydroxyl-removing silane of the formula ,? ■ ^{(R 0)} 4- (c ₊ f) ^{Si (X)} f (e) 0 to 5 parts by weight of a curing accelerator selected from substituted guanidines, Amines and their mixtures, wherein R is selected from optionally substituted monovalent hydrocarbon radicals with 1 to 13 carbon atoms, R is an aliphatic organic radical having 1 to 8 carbon atoms selected from alkyl, Alkyl ethers, alkyl esters, alky! Ketone and alkyl cyan radicals or an aralkyl radical with 7 to 13 carbon atoms, R is an optionally substituted monovalent hydrocarbon radical with 1 to 13 carbon atoms is, X is a hydrolyzable removable group selected from amido, amino, carbamato, enoxy, imidato, isocyanato, oximato, thioisocyanato and ureido radicals,
a has the value 1 or 2,
b has the value 0 or 1 and
the sum of a + b has the value 1 or 2, e has the value 0 or 1 and the sum of b + e has the value 0 or 1, η is an integer with a value is from about 50 up to about 2,500, c is an integer from 0 up to and including 3, f is an integer from 1 to 4, inclusive, and the sum of c + f is equal to 1 to, inclusive 4, and in any mixture in which X is enoxy becomes more functional before or with the silane for elimination Hydroxy groups a curing accelerator in an amount of 0.1 to 5 parts selected from substituted guanidines, amines and their mixtures added, further, 2 to 20 parts by weight per 100 parts by weight of the organopolysiloxane are mixed in first plasticizer in the form of a liquid polysiloxane with a high degree of trifunctionality or with mixtures of tri- and tetrafunctionality, said liquid polysiloxane comprising the following units: (i) 5 to 60 mol% of monoalkylsiloxy siloxy units th or a mixture of such units, (ii) 1 to 6 mol% trialkylsiloxy units and (iii) 34 to 94 mol% dialkylsiloxy units, said liquid polysiloxane having about 0.1 to about 2% by weight of silicon-bonded hydroxyl groups contains. 69. The method according to claim 68, characterized in that the organopolysiloxane has a viscosity rvtPci-S in the range of 60,000 to 500,000 at 25 ° C. 70. The method according to claim 69, characterized in that in the mass further 5 to 60 parts by weight of a second plasticizer per 100 parts by weight of the Organopolysiloxane are incorporated. said second plasticizer being a linear triorganosiloxy end group comprising diorganopolysiloxane having a viscosity in the range from 10 to 20,000 at 25 ° C and the organo groups are monovalent hydrocarbon radicals. 71. The method according to claim 70, characterized in that that the second plasticizer has the following formula 20th -SiO- .20 20th
where R is a monovalent hydrocarbon radical and t varies such that the viscosity of the polymer is in the range from 10 to 20,000 at 25 ° C. 72. The method according to claim 71, characterized in 20th
shows that R is a methyl group and t varies such that the viscosity of the polymer is in the range from 10 to 10,000 at 25 ° C. and the second plasticizer has a hydroxyl group content in the range from 500 to 1,500 ppm. 73. The method according to claim 71, characterized that in the mass 100 to 300 parts by weight per 100 parts of the organopolysiloxane of an extending filler be incorporated. 74. The method according to claim 73, characterized in that the extending filler is calcium carbonate is. 75. The method according to claim 73, characterized in that the potassium carbonate with stearic acid is treated. 76. The method according to claim 74, characterized in that further 1 to 50 _{parts by weight per 100 parts by weight of the organopolysiloxane y of} a reinforcing filler are incorporated into the mass. 77. The method according to claim 75, characterized in that the reinforcing filler as Deformation control agent acts and is fumed silica incorporated in an amount of 1 to 10 parts by weight per 100 parts of the organopolysiloxane will. 78. The method according to claim 75, characterized in that that 0.1 to 2 parts by weight per 100 parts by weight of the organopolysiloxane of a second agent for controlling the deformation, this second agent being a polyether selected is made up of compounds of the formula AC- (C _x H _2x O) _n -B and r 1 : —Q wherein A and B represent radicals selected from hydrogen, alkyl radicals having 1 to 12 carbon atoms, Cycloalkyl radicals with 5 to 7 carbon atoms in the ring, mononuclear and binuclear aryl radicals and mononuclear aryl radicals, the Have lower alkyl substituent groups, the alkyl groups bonded to the aromatic nucleus no longer in total than 5 carbon atoms, for A and B also the the following grouping can be R- \ j \ j -ο υ where R is an alkyl radical with 1 to 11 carbon atoms, Q is a polyhydric initiator radical which is at least 2 Contains hydroxyl groups selected from ethylene glycol, glycerol, trimethylolpropane and other polyhydric alcohols with 2 to 6 hydroxyl groups, η is a number from 2 to 4, y has a value from 2 to 10 and ζ has a value from 1 to 5 wherein the polyether has a molecular weight in the range of about 300 to about 200,000. "\ 79. The method according to claim 74, characterized that 0.2 to 2 parts by weight of a deformation controlling agent per 100 parts by weight of the organopolysiloxane may be added, this agent being hydrogenated castor oil. 80. The method according to claim 69, characterized in that the reinforcing filler before his Incorporation into the mass is treated with cyclopolysiloxane. 81. The method according to claim 68, characterized in that 0.1 to 10 parts by weight in the mass an adhesion promoter of the following formula can be incorporated _R 31 _{0 R} 33 _R 34 _R 38 _(B 30 _{0) 3} _ _p li_ _R 32_ ₀ _l! _IHCH ₂ -N-R ³⁶ -i-R ⁴⁰ wherein R and R are selected from monovalent hydrocarbon radicals having 1 to 8 carbon atoms, R and R are selected from divalent hydrocarbon radicals with 1 to 12 carbon atoms, R and R are selected from hydrogen and monovalent hydrocarbon radicals with 34
1 to 6 carbon atoms, R is selected from hydrogen and alkyl radicals having 1 to 3 carbon atoms, R is selected from hydrogen and methyl and ρ is an integer from 0 to 3. 82. The method according to claim 81, characterized in that the incorporated adhesion promoter has the following formula Q- CH, -CH, -N -CH ₂ -CH-fc-O (CH ₂ ) ₃ Si (OCH ₃ ) 3 H CH ₃ 83. The method according to claim 68, characterized in that it includes 2 ei
are. 1 2 records that R, R and R are each methyl groups 84. The method according to claim 68, characterized in that the curing accelerator is selected is made from silylated guanidine and alkylguanidine. 85. The method according to claim 68, characterized in that the silane is functional for eliminating Hydroxyl groups is polymethoxyacetamidosilane. 86. The method according to claim 68, characterized in that the crosslinking silane is methyltrimethoxysilane is. 87. The method according to claim 68, characterized in that the condensation catalyst is a Tin compound is. 88. The method according to claim 87, characterized in that the silane is functional for eliminating Hydroxyl groups is methyldimethoxy (N-methylacetamido) silane. 89. Mix of (a) 100 parts of a silanol-terminated polydiorganosiloxane, which consists essentially of chemically linked units of the following formula -SiC (b) a stabilizing amount of a hydroxy functional group eliminating silane of the formula ι I ^(R °> 4- <a ₊ b) ^{Si (X)} a (c) 0 to 10 parts of a crosslinking silane of the formula (R ² ) _b (d) an effective amount of a condensation catalyst and (e) 0 to 5 parts of a curing accelerator selected from substituted guanidines, amines and their mixtures, where R is selected from monovalent, optionally substituted hydrocarbon radicals having 1 to 13 carbon atoms, R is an aliphatic organic radical with 1 to 8 carbon atoms is selected from alkyl, alkyl ethers, alkyl esters, alkyl ketones and alkylcyan radicals or an aralkyl radical with 7 to 13 carbon atoms, 2
R is an optionally substituted monovalent hydrocarbon radical with 1 to 13 carbon atoms, X is a hydrolyzable removable group is selected from Amido, amino, carbamato, enoxy, imidato, isocyanato, oximato, Thioisocyanato and ureido residues, a has the value 1 or 2, b has the value 0 or 1 and the sum of a + b is 1 or 2 and when X is enoxy, the mixture is also 0.1 to 5 parts des contains the above curing accelerator and 2 to 20 parts by weight per 100 parts of the organopolysiloxane, a first plasticizer in the form of a liquid polysiloxane, which contains a high degree of trifunctionality or mixtures of tri- and tetrafunctionality and the following units includes: (i) 5 to 60 mole percent monoalkylsiloxy, siloxy units and a mixture of such units, (ii) 1 to 6 mole percent trialkylsiloxy units and (iii) 34 to 94 mol% dialkylsiloxy units, said liquid polysiloxane having about 0.1 to about 2% by weight of silicon-bonded hydroxyl groups contains. 90. Mixture according to claim 89, characterized in that the organopolysiloxane has a viscosity in the range of 60,000 to 500,000 at 25 ° C. 91. Mixture according to claim 90, characterized in that it further contains 5 to 60 parts by weight of a second Plasticizer contains per 100 parts of the organopolysiloxane, this second plasticizer having a linear triorganosiloxy end group comprising diorganopolysiloxane having a viscosity in the range from 10 to 20,000 at 25 ° C., the Organogroups are monovalent hydrocarbon radicals. 92. Mixture according to claim 91, characterized in that the second plasticizer is a polymer of the following Formula is R ² - ° - SiO R ²⁰ SiO- 20th -R 20th R is a monovalent hydrocarbon radical and t has a value such that the viscosity of the polymer is from 10 up to 20,000. varies at 25 ° C. 93. Mixture according to claim 92, characterized 20th
net that R is methyl and t varies such that the viscosity of the polymer is in the range from 10 to 10,000 at 25 ° C. and the second plasticizer has a hydroxyl group content of 500 to 1,500 ppm. 94. Mixture according to claim 92, characterized in that that it contains 100 to 300 parts by weight of an extending filler per 100 parts by weight of the organopolysiloxane. 95. Mixture according to claim 94, characterized in that that the extending filler is potassium carbonate. 96. Mixture according to claim 95, characterized in that that the potassium carbonate is treated with stearic acid. 97. Mixture according to claim 95, characterized in that that it contains 1 to 50 parts by weight of a reinforcing filler per 100 parts by weight of the organopolysiloxane. 98. The blend of claim 96, characterized in that the reinforcing filler acts as a shape-controlling agent and ^s Modified fumed silica is present in an amount of 1 to 10 weight parts to 100 weight parts of the organopolysiloxane. 99. Mixture according to claim 96, characterized in that that they 0.1 to 2 parts by weight per 100 parts by weight of the organopolysiloxane of a second the change in shape contains controlling agent which is a polyether selected from compounds of the formula wherein A and B represent radicals selected from hydrogen, alkyl radicals with 1 to 12 carbon atoms, cycloalkyl radicals with 5 to 7 carbon atoms in the ring, mononuclear and binuclear aryl radicals and mononuclear aryl radicals with lower alkyl radicals as substituents, the alkyl radicals attached to the aromatic nucleus, contain no more than 5 carbon atoms and A and B can also be the following radical _Q R — C — O— where R is an alkyl radical with 1 to 11 carbon atoms, Q is a radical of a polyhydric initiator radical which contains at least 2 hydroxy radicals and which is selected from Ethylene glycol, glycerin, trimethylolpropane and other polyhydric Alcohols with 2 to 6 hydroxyl groups, a is a number from 2 to 4, y has a value from 2 to 10 and ζ has a value of 1 to 5, the polyester having a molecular weight of about 300 to about 200,000. 100. Mixture according to claim 95, characterized net that they contain 0.2 to 2 parts by weight of hydrogenated castor oil as the deformation controlling agent for 100 parts by weight of the organopolysiloxane. 101. Mixture according to claim 90, characterized in that the reinforcing filler prior to its incorporation has been treated in the mass with cyclopolysiloxane. 102. Mixture according to claim 89, characterized in that that it contains 0.1 to 10 parts by weight of an adhesion promoter represented by the following formula r31 OR ³³ R ³⁴ R ^{38 P} II ^ 70 I 32 "I I 36 ^ 40 (R ³⁰ O) ₃ Si-ROC-CHCH ₂ - N-R ^Je - N-R * ^ü wherein R and R are selected from monovalent hydrocarbons residues with 1 to 8 carbon atoms, R and R are selected from water - Substance and monovalent hydrocarbon residues with 1 to 6 34
Carbon atoms, R is selected from hydrogen and alkyl radicals with 1 to 3 carbon atoms and R is selected from hydrogen and methyl / R and R are selected from divalent hydrocarbon radicals with 1 to 12 carbon atoms and ρ is an integer from O. to 3. 103 · Mixture according to claim 102, characterized in that that the adhesion promoter is the following Formula has NH-CH-CH, -N-CH, -CH-C-O (CH,) -Si (OCH,), Δ £ t \ i ι 2 3 3 3 H CK ₃ 104. A method for producing a substantially acid-free, room temperature vulcanizable organopolysiloxane composition under substantially anhydrous conditions using an effective amount of a condensation catalyst together with an organopolysiloxane containing silanol end groups and a polyalkoxysilane as a crosslinking agent, characterized in that: "to the organopolysiloxane having terminal silanol groups a adding a stabilizing amount of a polyalkoxysilane that both eliminates the functional hydroxyl groups as also acts as a crosslinking agent and has the following formula f ^{b Si (X} »a wherein R is an aliphatic organic radical with 1 to 8 carbon atoms selected from alkyl, alkyl ethers, alkyl esters, alkyl ketone and alkylcyan radicals or an aralkyl radical with 7 to 13 carbon atoms,
R is an optionally substituted monovalent hydrocarbon radical with 1 to 13 carbon atoms, X is a hydrolyzable removable group is selected from amido, amino, carbamato, enoxy, imidato, isocyanato, oximato, thioisocyanato and ureido radicals,
a has the value 1 or 2,
b has the value 0 or 1 and
the sum of a + b is equal to 1 or 2 and then an effective amount of a condensation catalyst is added, resulting in improved stability in the resulting cold-curing organopolysiloxane composition and when X is enoxy, one before or together with the hydroxyl group-eliminating siloxane is an effective Adds amount of a curing accelerator selected from substituted guanidines, amines and mixtures thereof and 2 to 20 parts by weight per 100 parts by weight of the organopolysiloxane a liquid polysiloxane as the first plasticizer that has a high degree of trifunctionality or mixtures of tri- and tetrafunctionalities and comprises the following units: (i) 5 to 60 mole percent monoalkylsiloxy-siloxy units or a mixture of such units, (ii) 1 to 6 mole percent trialkylsiloxy units and (iii) 34 to 94 mole percent dialkylsiloxy units said liquid polysiloxane having from about 0.1 to about 2 percent by weight silicon-bonded Contains hydroxyl groups. 105. The method according to claim 104, characterized in that an organopolysiloxane is used, which has a viscosity in the range of 60,000 to 500,000 at 25 ° C. 106. The method according to claim 105, characterized that in the mass further 5 to 60 parts by weight of a second plasticizer per 100 parts by weight of the Organopolysiloxane are incorporated, said second plasticizer is a linear triorganosiloxy endblocked diorganopolysiloxane exhibiting a viscosity in the range from 10 to 20,000 at 25 ⁰ C and the organo groups are monovalent hydrocarbon radicals. 107.Verfahren according to claim 106, characterized in that the second plasticizer has the following formula R ²⁰ - 20th
where R is a monovalent hydrocarbon radical and t varies such that the viscosity of the polymer is in the range from 10 to 20,000 at 25 ° C. 108. The method according to claim 107, characterized in that 20th
shows that R is a methyl group and t varies such that the viscosity of the polymer is in the range from 10 to 10,000 at 25 ° C. and the second plasticizer has a hydroxyl group content in the range from 500 to 1,500 ppm. 109. The method according to claim 107, characterized in that 100 to 300 parts by weight per 100 parts of the organopolysiloxane _/ an extending filler are incorporated into the mass. 110.Verfahren according to claim 109, characterized in that the stretching filler is calcium carbonate. ♦ Process according to claim 110, characterized in that the calcium carbonate with stearic acid is treated. 112. The method according to claim 110, characterized in that further 1 to 50 _{parts by weight per 100 parts by weight of the organopolysiloxane /} a reinforcing filler are incorporated into the mass. 113. The method according to claim 111 »characterized in that that the reinforcing filler acts as a deformation control agent and fumed silica is incorporated in an amount of 1 to 10 parts by weight per 100 parts of the organopolysiloxane will. 114. The method according to claim 111 * characterized that 0.1 to 2 parts by weight per 100 parts by weight of the organopolysiloxane ^ of a second agent for controlling the deformation, this second agent being a polyether selected is made up of compounds of the formula ^(C x ^H 2x ⁰⁾ n - ^E and wherein A and B represent radicals selected from hydrogen, alkyl radicals having 1 to 12 carbon atoms, Cycloalkyl radicals with 5 to 7 carbon atoms in the ring, a <and dinuclear aryl radicals and mononuclear aryl radicals which have lower alkyl substituent groups, where the to aromatic nucleus bound alkyl groups contain not more than 5 carbon atoms in total, for A and B also the the following grouping can be where R is an alkyl radical with 1 to 11 carbon atoms, Q is a polyhydric initiator radical which contains at least 2 hydroxyl groups selected from ethylene glycol, glycerine, Trimethylolpropane and other polyhydric alcohols with 2 to 6 hydroxyl groups, η is a number from 2 to 4, y has a value from 2 to 10 and ζ has a value from 1 to 5 wherein the polyether has a molecular weight in the range of about 300 to about 200,000. 115. The method according to claim 110, characterized in that that 0.2 to 2 parts by weight of an agent for controlling the deformation per 100 parts by weight of the organopolysiloxane be added, this agent being hydrogenated castor oil. 116. The method according to claim 105, characterized in that g e> k e η η that the reinforcing filler treated with cyclopolysiloxane before its incorporation into the mass will. 117. The method according to claim 104, characterized in that that incorporated into the mass 0.1 to 10 parts by weight of an adhesion promoter of the following formula will & _{0 R} 33 _R 34 38 where R and R are selected from monovalent hydrocarbons 32 36 hydrogen radicals with 1 to 8 carbon atoms, R and R are selected from divalent hydrocarbon radicals having 1 to 12 carbon atoms, R and R are selected of hydrogen and monovalent hydrocarbon radicals with 1 to 6 carbon atoms, R is selected from hydrogen and alkyl radicals having 1 to 3 carbon atoms, R is selected from hydrogen and methyl and ρ is an integer of Is 0 to 3. 118.Verfahren according to claim 117, characterized draws that the incorporated adhesion promoter has the following formula NH ₂ -CH ₂ -CH ₂ -N-CH ₂ -CH-CO (CH ₂ ) ₃ Si (OCH ₃ ) ₃ CH ₃ 119.Verfahren according to claim 104, characterized in that the silane for eliminating functional hydroxyl groups is methyldimethoxy-N-methylacetamidosilane. 120. The method according to claim 104, characterized in that that the silane for removing functional hydroxyl groups is methyldimethoxyisopropenoxysilane. 121. The method according to claim 104, characterized in that that the silane for removing functional hydroxyl groups is methyltriisopropenoxysilane. 122. The method according to claim 104, characterized in that that one uses an effective amount of dibutyltin diacetate as a condensation catalyst. 123. Process for the preparation of an essentially acid-free, organopolysiloxane composition vulcanizable at room temperature under substantially anhydrous conditions using an effective amount of a condensation catalyst together with an organopolysiloxane in which the silicon atoms at each end of the chain have at least 2 alkoxy radicals, characterized in that this organopolysiloxane containing polyalkoxy end groups (1) a stabilizing amount of a hydroxy functional group f> Λ β - ** « - Add 37 eliminating silane of the following formula ^{S1 (X)} f wherein R is an aliphatic organic radical having 1 to 8 carbon atoms is selected from alkyl, alkyl ethers, alkyl esters, Alkyl ketone and alkyl cyan radicals or an aralkyl radical with 7-13 carbon atoms, 2
R is an optionally substituted monovalent hydrocarbon radical with 1-13 carbon atoms, X a hydrolyzable removable group is selected from amido, amino, carbamato, enoxy, imidato, isocyanato, oximato, Thioisocyanato and ureido residues, c is an integer from 0 to 3 inclusive, f is an integer from 1 to 4 inclusive, and the sum of c + f is equal to 1 up to and including 4 and (2) an effective amount of a condensation catalyst, thereby causing in the resulting cold-setting organopolysiloxane composition improved stability is obtained and (3) when X is enoxy, one before or together with the silane to the Removing functional hydroxyl groups by adding an effective amount of a curing accelerator selected from substituted Guanidines, amines and their mixtures, as well as (4) two to twenty parts by weight per 100 parts by weight of the Organopolysiloxane of a first plasticizer in the form of a liquid polysiloxane with a high degree of trifunctionality or a mixture of trifunctionality and tetrafunctionality, this liquid polysiloxane having the following units includes: (i) 5 to 60 mole percent monoalkylsiloxy, siloxy units or a mixture of such units, (ii) 1 to 6 mole percent trialkylsiloxy units (iii) 34 to 94 mole percent dialkylsiloxy units, this liquid polysiloxane from about 0.1 to has about 2% by weight of hydroxyl groups bonded to silicon. 124. The method of claim 123, characterized in that the organopolysiloxane used has a viscosity in the range from 60,000 to 500,000 - has mP <* · * at 25 ⁰ C. 125. The method according to claim 124, characterized that in the mass further 5 to 60 parts by weight of a second plasticizer per 100 parts by weight of the organopolysiloxane are incorporated, this second plasticizer being a linear triorganosiloxy- Diorganopolysiloxane containing end groups and having a viscosity of ⁵ sity is in the range from 10 to 20,000 at 25 ° C and the organic groups are monovalent hydrocarbon radicals. 126. The method according to claim 125, characterized in that the second plasticizer is the following Formula has .20 "20 R ²⁰ - SiO- F. 20th -SiO- .20 20th
where R is a monovalent hydrocarbon radical and t varies such that the viscosity of the polymer is in the range m? ft «s
from 10 to 20,000 at 25 ° C. 127. The method according to claim 1 26, characterized in 20th
shows that R is a methyl group and t varies in such a way that the viscosity of the polymer is in the range from 10 to 10,000 - at 25 ^° C. and the second plasticizer has a hydroxyl group content in the range from 500 to 1,500 ppm. 128. The method according to claim 126, characterized that 100 to 300 parts by weight per 100 parts of the organopolysiloxane ^, an extending filler, are incorporated into the mass. 129. The method according to claim 128, characterized in that the extending filler is calcium carbonate is. 130. The method according to claim 129, characterized in that that the calcium carbonate is treated with stearic acid. 131. The method according to claim .129, characterized in that in the mass further 1 to 50 parts by weight per 100 parts by weight of the organopolysiloxane, one reinforcing filler can be incorporated. 132. The method according to claim 130, characterized that the reinforcing filler acts as a deformation control agent and fumed silica is incorporated in an amount of 1 to 10 parts by weight per 100 parts of the organopolysiloxane will. 133. The method according to claim 130, characterized that 0.1 to 2 parts by weight per 100 parts by weight of the organopolysiloxane.eineses second agent for controlling the deformation, this second agent being a polyether selected is made up of compounds of the formula and ^iC x ^H 2x ⁰⁾ 4th wherein A and B represent radicals selected from hydrogen, alkyl radicals having 1 to 12 carbon atoms, Cycloalkyl radicals with 5 to 7 carbon atoms in the ring, mononuclear and binuclear aryl radicals and mononuclear aryl radicals, the Have lower alkyl substituent groups, where the aromatic nucleus bound alkyl groups contain not more than 5 carbon atoms in total, for A and B also the the following grouping can be Il where R is an alkyl radical with 1 to 11 carbon atoms, Q is a polyhydric initiator radical which contains at least 2 hydroxyl groups selected from ethylene glycol, glycerine, Trimethylolpropane and other polyhydric alcohols with 2 to 6 hydroxyl groups, η is a number from 2 to 4, y has a value from 2 to 10 and ζ has a value from 1 to 5, the polyether having a molecular weight in the range of has about 300 to about 200,000. 134. The method according to claim 129, characterized in that that 0.2 to 2 parts by weight of an agent for controlling the deformation per 100 parts by weight of the organopolysiloxane be added, this agent being hydrogenated castor oil. 135. The method according to claim 124, characterized in that the reinforcing filler before his Incorporation into the mass is treated with cyclopolysiloxane. 136. The method according to claim 123, characterized in that 0.1 to 10 parts by weight in the mass an adhesion promoter of the following formula can be incorporated «31 ο R ³³ S ³⁴ R ³⁸ _, 32_ ₀ JJ ^ -L ^ -i— where R and R are selected from monovalent hydrocarbons 32 36 hydrogen radicals with 1 to 8 carbon atoms, R and R are selected from divalent hydrocarbon radicals having 1 to 12 carbon atoms, R and R are selected of hydrogen and monovalent hydrocarbon radicals with 1 to 6 carbon atoms, R is selected from hydrogen and alkyl radicals having 1 to 3 carbon atoms, R is selected is made up of hydrogen and methyl and ρ is an integer from 0 to 3. .13 7. The method according to claim 136, characterized draws that the incorporated adhesion promoter has the following formula - CH - CH -. - N - CH, - CH - CC NH ₂ -CH ₂ -CH ₂ -N-CH ₂ -CH-UO (CH ₂ ) 3 S1 (OCB ₃ ) 3 H CH ₃ 138. The method according to claim 123 / characterized by - ^ indicates that the silane is more functional for eliminating Hydroxyl groups methyldimethoxy-N-methylacetamidosilane is. 139. The method according to claim 123, characterized that the silane for removing functional hydroxyl groups is methyldimethoxyisopropenoxysilane. 140.Verfahren according to claim 123, characterized that one has a stabilizing amount of methyltriisopropenoxysilane and an effective amount of methyltrimethoxysilane begins. 141. The method according to claim 123, characterized in that that one uses an effective amount of dibutyltin diacetate as a condensation catalyst. 142. Stable, essentially anhydrous and acid-free, at room temperature One-component vulcanizable organopolysiloxane composition, which under ambient conditions in the absence of Moisture is stable over an extended period of time and which is convertible into a tack-free elastomer, characterized by the following components: (1) an organopolysiloxane in which the silicon atom at each end of the chain bears at least 2 alkoxy radicals, (2) an effective amount of a condensation catalyst, (3) a stabilizing amount of a hydroxyl-removing silane, which is a silicon nitrogen connection is selected from: (A) a silicon-nitrogen compound of the formula R ¹ ' (Y) (R ¹ ' ¹ J ₂ Si N Si (R ^{1 1} M ₃ Y wherein Y is selected from R ¹ "and R ¹ " ₂ N and (B) a silicon-nitrogen polymer that (i) 3 to 100 mole percent chemically bonded structural units which are selected from units of the following formulas I I (R-) -NSiO-, (R ") - NSiN-, ² I ² I R " ¹ R" _R .M _R « R " I / I / 1 1 SiN- - SiN- —SiN- and (ii) 0 to 97 mole percent chemically linked structural Units of the formula as well as their mixtures, wherein the silicon atoms of the silicon-nitrogen polymer are connected to one another by a grouping which is selected from -SiOSi- and -SiNR ¹¹ Si-, being the free valences of these silicon atoms, which do not form a siloxy unit with Are linked to oxygen or to form a silazyl moiety with nitrogen with a moiety which is selected from an R "radical and an (R") ₂ N radical and where the ratio of the sum of said R ¹ "radicals and said (R") ₂ N radicals to the silicon atoms of the silicon-nitrogen polymer has a value in the range from 1.5 to 3 inclusive and R "is selected from hydrogen, monovalent hydrocarbon radicals and fluoroalkyl radicals, R ^{'11 is} selected from hydrogen, monovalent hydrocarbon radicals and fluoroalkyl radicals and c is an integer from 0 to 3 inclusive and (4) 2 to 20 parts by weight per 100 parts by weight of the organopolysiloxane of a liquid polysiloxane as the first plasticizer, the contains a high degree of trifunctionality or a mixture of trifunctionality and tetrafunctionality and comprises the following units: (i) 5 to 60 mole percent monoalkylsiloxy-siloxy units or a mixture of such units, (ii) 1 to 6 mol% trialkylsiloxy units and (iii) 34 to 94 mol% dialkylsiloxy units, this liquid polysiloxane about 0.1 up to about 2% by weight bonded to silicon Contains hydroxyl groups. 143. Composition according to claim 142, characterized in that the organopolysiloxane has a viscosity in the range of 60,000 to 500,000 at 25 ° C. 144. Composition according to claim 142, characterized in that it further contains 5 to 60 parts by weight of a second plasticizer per 100 parts of the organopolysiloxane, this second plasticizer being a linear diorganosiloxy endgroup diorganopolysiloxane having a viscosity in the range from 10 to 20,000 at 25 ⁰ C, where the organic groups are monovalent hydrocarbon radicals. 145.Mass according to claim 144, characterized in that net that the second plasticizer is a polymer of the following Formula is SiO- 20th SiO- 20th 20th
R is a monovalent hydrocarbon radical and t has a value such that the viscosity of the polymer varies from 10 to 20,000 at 25 ° C. 146.Masse according to claim 145, characterized in that R is methyl and t varies such that the viscosity of the polymer is in the range from 10 to 10,000 at 25 ⁰ C and the second plasticizer has a hydroxyl group content of 500 to 1,500 ppm. 147. Composition according to claim 145, characterized in that it contains 100 to 300 parts by weight of an elongating Contains filler per 100 parts by weight of the organopolysiloxane. 148. Composition according to claim 147, characterized in that that the extending filler is calcium carbonate. 149. Composition according to claim 148, characterized in that that the calcium carbonate is treated with stearic acid. 150. Composition according to claim 148, characterized in that that it contains 1 to 50 parts by weight of a reinforcing filler per 100 parts by weight of the organopolysiloxane. ο ο u OO ο υ 151.Masse according to claim 149, characterized in that the reinforcing filler as a change in shape controlling agent acts and is fumed silica, which is present in an amount of 1 to 10 parts by weight 100 parts by weight of the organopolysiloxane is present. 152. Composition according to Claim 149, characterized in that that they 0.1 to 2 parts by weight per 100 parts by weight of the organopolysiloxane of a second the change in shape contains controlling agent which is a polyether selected from compounds of the formula and the formula where A and B stand for radicals selected from hydrogen, alkyl radicals with 1 to 12 carbon atoms, cycloalkyl radicals with 5 to 7 carbon atoms in the ring, mononuclear and binuclear aryl radicals and mononuclear aryl radicals with lower alkyl radicals as substituents, the alkyl radicals which are bonded to the aromatic nucleus, contain no more than 5 carbon atoms and A and B can furthermore be the following radical _Q R — C — O— where R is an alkyl radical with 1 to 11 carbon atoms, Q is a radical of a polyhydric initiator radical which contains at least 2 hydroxy radicals and which is selected from Ethylene glycol, glycerin, trimethylolpropane and other polyhydric Alcohols with 2 to 6 hydroxyl groups, a is a number from 2 to 4, y has a value from 2 to 10 and ζ has a value of 1 to 5, the polyester having a molecular weight of about 300 to about 200,000. 153. Composition according to claim 148, characterized in that it contains 0.2 to 2 parts by weight of hydrogenated Rici- nut oil as - _: the deformation controlling agent to 100 Contains parts by weight of the organopolysiloxane. 154 ,. Composition according to Claim 143, characterized in that the reinforcing filler is incorporated prior to its incorporation has been treated in the mass with cyclopolysiloxane. 155. Composition according to claim 142, characterized in that that they contain 0.1 to 10 parts by weight of an adhesion promoter the formula below _R 31 OR ³³ R ³⁴ R ³⁸ 50 I ^P 32 Nf i 36 I 40 (R 0) _3- Si-R-O-C-CHCH ₂ -N-IT ⁰ -N-R ™ wherein R and R are selected from monovalent hydrocarbon radicals having 1 to 8 carbon atoms, R and R are selected from water - substance and monovalent hydrocarbon residues with 1 to 6 34
Carbon atoms, R is selected from hydrogen and alkyl radicals with 1 to 3 carbon atoms and R is selected from hydrogen and methyl, R and R are selected from divalent hydrocarbon radicals having 1 to 12 carbon atoms and ρ is an integer from 0 to 3. 156. Composition according to claim 155, characterized in that the adhesion promoter is the following Formula has Il NH, -CH-CH, -N-CH. - CH-CO (CH.), Si (OCH,), 2 2 2 ι 2 ι 23 33 H CK ₃