NL8300604A - PACKED RTV MATERIALS WITH LOW MODULUS AND METHODS FOR PREPARING THE SAME. - Google Patents

Description

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Short indication; One package low modulus RTV materials and processes for their preparation.

The invention relates to one-pack, room temperature vulcanizable (RTV) materials and methods of preparing the same; more particularly, the invention relates to alkoxy functions containing low-modulus one-pack RTV materials and processes for their preparation.

In the first single-package RTV materials, a silane with acyloxy function was used as a cross-linking agent, as described in U.S. Pat. Nos. 3,133,891 and 3,035,016. Furthermore, U.S. Pat. Nos. 3,296,161, 3,296,195, and 3,438,930 relate to the use of certain additives that render these materials self-adhesive. Although these acyloxy-functional materials have fast curing properties and other desirable properties, they nevertheless have two drawbacks. One of the drawbacks is that acetic acid is liberated from this during curing, which is somewhat corrosive. Furthermore, this acetic acid 15 has an unpleasant odor, so that it is somewhat difficult to work with this system in a closed space.

It was therefore highly desirable at an early stage to have a non-corrosive, fast-curing, one-package RTV system. The two-pack RTV systems, for example, those described in U.S. Pat. No. 3,127,363, are non-corrosive. However, these compositions should be prepared in two packages and mixed immediately prior to application of the system, and once mixed should be used within a short period of time, otherwise the composition will not cure sufficiently quickly.

Thus, although these compositions are non-corrosive, they still require further labor costs in operating the system, and after mixing, the system has a very short shelf life.

An early example of such an alkoxy functions-containing composition in the form of one package is described in U.S. Pat. No. 3,065,194. However, this material has the drawbacks that it has to be dried vigorously during its preparation and that the composition also has a short shelf life. Other single-package alkoxy groups containing RTV compositions are described in U.S. Pat. Nos. 3,122,522 and 3,161,614 and in U.S. "Reissue" Patent 29760. These materials do not cure sufficiently rapidly, i.e. curing, this curing proceeds very slowly, especially after these materials have been stored for some time, i.e., 8300604-2 -V1 * flfl for a period of a week or more. It has been found that these materials do not cure sufficiently quickly when using the normal condensation catalysts used in acyloxy systems.

Thus, for these one-pack RTV systems with alkoxy functions, several titanium chelate catalysts were used. Examples of titanium chelate catalysts in alkoxy-containing, single-package RTV systems are described in U.S. Pat. Nos. 3,334,067, 3,542,901, 3,689,454 and 3,779,986 - the latter two being U.S. Patents.

A further example of these systems made suitable for commercial use in one form or another, particularly with various types of additives, is described in U.S. Patent 4,100,129. This latter patent describes an alkoxy-containing, one-pack RTV system as mentioned above, which has been made suitable for commercial purposes and in particular depends on the use of a particular type of chelate as a catalyst, that the composition is sufficiently cure speed imparted after the composition has been stored for a period of 6 months or more. United States Patent 4,100,129 discloses that alkoxy-containing, one-pack RTV systems, in particular, a liquid, tri-functional polysiloxane and a liquid, trimethylsiloxy-dimethylpolysiloxane, and various types of adhesion promoters can contain. This patent further states that various types of adhesion promoters can be used in combination with these alkoxy-containing, single-package RTV systems, such as silyl isocyanurates and other compounds. However, these materials still have the above-mentioned drawbacks, namely that they are not sufficiently stable in storage and not sufficiently fast. harden.

Another example of a somewhat non-corrosive, single-package RTV system is described in U.S. Patent 4,257,932. This U.S. Patent discloses an acyloxy, one-pack RTV system in which the acyloxy-functional crosslinking agent is preferably methyltris-2-ethylhexanoxysilane. It is stated that various additives can be used in these systems, such as, for example, a liquid silicone having a high degree of tri or tetra functionality, a similar liquid as described in U.S. Patent 4,100,129, as well as a liquid dimethyl polysiloxane. Furthermore, the presence of various additives, such as adhesion promoters and other additives, is reported.

8300604 'i N- \ \ - 3 -

While the system of U.S. Pat. No. 4,257,932 is somewhat non-corrosive, an acid is nevertheless released which, although high molecular weight, is still corrosive and does not set as quickly as desired. Furthermore, it should be noted in particular that the nature of the corrosion is such that this system causes discoloration of various substrates and is even somewhat more difficult to adhere to substrates with various types of self-adhesive additives. Examples of various self-adhesive additives that can be used with such a material are described, for example, in the aforementioned U.S. Patent 4,257,932, as well as in U.S. Patent 4,273,698, which teaches the use of various silyl fumarates, silyl maleates, silyl succinates, and others. compounds as adhesion promoters for these compositions as well as for one-pack alkoxy function RTV systems. A publication 15 which relates to the use in these materials of large amounts of calcium carbonate as a filler in order to be able to use these materials as a paint, is US patent 4,247,445. Another publication in this field is US Patent 4,308,372, which relates to the pre-reacted reaction product of the adhesion promoter and the cross-linking agent, thereby imparting further storage stability to the system.

However, even with these preconverted crosslinking and adhesion promoter systems, storage stability difficulties still arise. Another relevant publication is U.S. Patent 4,261,758 which relates to the use of polyethers as sag inhibitors or as thixotropic compositions by incorporating small amounts of polyethers into the composition.

Recently, a stable, practically acid-free, one-pack, moisture-hardened, terminal polyalkoxy-containing organo-polysiloxane system, preferably having a tin compound as the condensation catalyst, has been developed, as described in U.S. Patent Applications 277,524 and 277,525. . Also relevant are US patent application 338,578, which relates to the use of a particular "scavenger", these systems, and US patent application ..... {Lucas), which relates to the the use of various types of adhesion promoters in these systems and in the preferred system of the present application US Patent Application ..... (Diazarket relates to the use of certain silazanes and silyl nitrogen polymers 8300604 Λ u I Eliminating OH groups as agents for the combination with a polyalkoxy-containing organopolysiloxane base polymer, which materials for eliminating OH groups are not described in the above-mentioned U.S. Patent Application 277,524. US patent application ---- (Dziarklis filed. On \ d <a> pf -ority date of the present application. The RTV system of US l (Dziark) patent application .... preferably cured with the additives of the present application, although the present additives may be used with any of the RTV systems of the aforementioned U.S. Patent Application 277,524. The use of certain agents for hetrin "alkoxy-containing one-pack RTV systems to remove or convert most of the hydroxy groups in the uncured polymer materials results in a composition with good storage stability and good cure speed, even with a tin soap as a catalyst • The system is also non-corrosive.

It is also desirable that these materials have a low modulus, i.e., that these materials have low tensile strength and high extensibility so that they can be used for glazing and sealing applications, especially in high-rise structures. It is also desirable that these compositions be self-adhesive, as described in the above-cited U.S. Patent Application .... (Lucas Meir has been too constantly searching for additional additives for imparting self-adhesion and has also attempted compositions to provide the least modulus possible, which was not the case with the cash base system described in the above-mentioned U.S. Patent Application 277,524.

The present invention therefore provides one-package, alkoxy-functional containing RTV systems that are self-adhesive by using new additives to impart self-adhesion.

Furthermore, the invention provides an alkoxy functions. containing one-package RTV system which has a low modulus, ie, a lower tensile strength. and a very large rack. ". The invention also provides "one cc package" existing RTV systems ..... i. ^ · '' ÏH '' - which are practically · non-corrosive and storage stable and have a low i- · .. ί - ^ νί -! ; "· ·. ]. \ T £ j ·. possess modulus.

Also, the invention provides an inexpensive, single-pack RTV composition with a low modulus due to various components in the formulation. record composition.

Furthermore, the invention provides a method for preparing a one-pack RVTV system which is non-corrosive, inexpensive and stable in storage and has a low modulus. ;. I

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The invention provides a stable, one-pack, practically anhydrous and practically acid-free, room temperature vulcanizable, organopolysiloxane containing composition that is stable for a long time under ambient conditions in the absence of moisture and can be converted to an adhesive free elastomer, which is characterized by composition. . :( 1) an organopolysiloxane in which the silicon atom carries at least 2 alkoxy groups at each end of a polymer chain; (2) an effective amount of a condensation catalyst; (3) a stabilizing amount of a silane as an agent for eliminating functional hydroxy groups, which silane has the formula (1) of the formula sheet, in which formula R is an organic aliphatic group of 1-8 carbon atoms selected from alkyl- alkyl ether, alkyl ester, alkyl ketone and alkyl cyano groups, or an aralkyl group with 7-13 carbon atoms, R represents a monovalent substituted or unsubstituted hydrocarbon group with 1-13 carbon atoms, X is a hydrolyzable cleavable group, selected from amido, amino, carbamato, enoxy, imidato, isocyanato, oximato, thioisocyanato and ureido, and c an integer with a value of 0 - 3 and f a number with a value of 1-4 if desired, ihb

is, where c + f is 1 - 4; and in case X represents an enoxy or amido group, (4) an effective amount of a curing accelerator selected from substituted guanidines, amines and mixtures thereof, and (5) 2 to 20 parts by weight. (per 100 parts by weight of the organopolysiloxane) of a flowable polysiloxane as the first plasticizer, which and / or a high degree of trifunctionality * has a combination of tri- and tetra-functionality, and contains: (i 5-60 mole% monoalkylsiloxy or siloxy units or a mixture of these units; (ii) 1-6 mol% trialkylsiloxy units, and (iii) 34-94 mol% dialkylsiloxy units, which polysiloxane contains about 0.1 -30% by weight silicon bonded hydroxyl groups.

The base constituent in these compositions is a polyalkoxy (ie containing a number of functional alkoxy groups) diorganopolysiloxane polymer, which is preferably prepared by first reacting a trialkoxysilane crosslinking agent such as methyl trimethoxysilane with a di-organopolysiloxane polymer with terminal silanol. Then after conversion of these 2 materials, which conversion preferably takes place in the presence of a condensation catalyst, such as hexylamine, an agent for eliminating all free hydroxy groups ("scavenger" or "scavenger"), for example methanol, is added, and these agents react 8300604.-6-t. * with all the silanol and hydroxy groups in the additives added to the base material, thereby making the composition stable upon storage.

By adding the ingredients listed here, the composition can further be made self-adhesive as well as thixotropic and can be imparted to a low modulus. Alternatively, this system can be prepared by simultaneously mixing a silanol polymer with a cross-linking agent and an hydroxy eliminator, along with other ingredients. However, it has been found that a faster-curing, more stable system is obtained by first reacting the silanol polymer with the cross-linking agent to obtain the polyalkoxysilane-organopolysiloxane and then the hydroxy-group eliminating agent containing residual silanol groups, moisture and methanol react, and then add the other ingredients. If optimum storage stability and optimum rapid curing are not desired, the other mixing methods described in U.S. Patent Application 277,524 may be used.

Preferred embodiment

The basic component in the RTV compositions of the present application (the abbreviation RTV means vulcanizable at room temperature) is a diorganopolysiloxane polymer with silanol terminal, which polymer preferably has the formula (2) of the formula sheet, in which formula R a monovalent substituted or unsubstituted hydrocarbon group having 1 to 13 carbon atoms, which is preferably selected from alkyl groups having 1 to 8 carbon atoms, such as methyl or a combination of a major amount of methyl and a minor amount of phenyl, cyanoethyl, trifluoropropyl or vinyl or combinations thereof, and n is a number with a value of about 50 - 2500. This silanol polymer can be prepared by various methods, for example, by the method described in U.S. Patent 4,250,290. Other methods are described, for example, in U.S. Pat. No. 3,888,815. Since these polymers are known, no further details regarding their preparation are given here.

Various definitions are used in the present application, such as stable, practically acid-free, etc.

The term "stable" as used herein for the one-pack organopolysiloxane with polyalkoxy-terminated RTV materials of the present invention refers to a moisture-hard hair mixture which remains practically unchanged at atmospheric moisture and which after a long storage period until a tack free 8300604 \ - 7 - i \ - hardens. Furthermore, a stable RTV material also means that the time until freshly mixed RTV components are tack free under atmospheric conditions is practically the same as the time until. 1 the same mixture of ingredients which has been exposed to atmospheric moisture after being kept in a moisture-resistant and moisture-free container for a long period of storage at ambient conditions, is tack-free or an equivalent period based on accelerated aging at increased temperature.

The term "practically acid-free" as used herein to define the elastomer obtained from the RTV composition of the present invention upon exposure to atmospheric moisture means that by-products are formed with a pKa of 5.5 or more and preferably from 6 or more and especially preferably from 10 or more.

Preferably, the silanol-terminated diorganopolysiloxane polymer used in the present invention, whether or not it is a polymer with alkoxy-terminated groups, has a viscosity ranging from 60,000 to 500,000 centipoise at 25 ° C.

The invention is based on the discovery of additives for stable, practically acid-free, one-pack moisture-curable organo-polysiloxane with terminal polyalkoxy-containing RTV compositions, which can be prepared by using a terminal silanol-containing polydiorganosiloxane which is at least in mainly consists of chemically bonded diorganosiloxy units of formula (3) of the formula sheet, for example, terminal silanol-containing polydiorganosiloxane of formula (2), wherein R has the above definition, with an effective amount of certain silanes as "scavengers". agents "for chemically bound hydroxy groups. In the silanol-terminated polydiorganosiloxane, which consists at least substantially of chemically bonded units of formula (3), the presence of alkoxy groups of 1 to 8 carbon atoms, such as a methoxy group, which are bonded to silicon is not excluded. The hydroxy groups that can be removed by the silane can be found in materials normally present in the RTW composition of the present invention, for example, trace amounts of water, methanol, silanol groups in the filler silica ( if used), the silanol polymer of formula (2), or a terminal silanol-containing polymer of units of formula (-3). The silane suitable for removing chemically bound hydroxy groups preferably has 8300604 of the formula (4) of the formula sheet, wherein R is an organic aliphatic group of 1-8 carbon atoms selected from alkyl groups, alkyl ether green - represents pen, alkyl ester groups, alkyl ketone groups, and alkyl cyano groups, or a 2 aralkyl group having 7-13 carbon atoms; R represents a monovalent organic group having 1 to 13 carbon atoms selected from the groups R defined above, which groups are further defined below; X is a hydrolyzable cleavable group selected from amido, amino, carbamato, enoxy, imidato, isocyanato, oximato, thioisocyanato and ureido, X preferably being amino, amido or enoxy, for example 10 N-C 1 -C 8 alkyl C 4 -Cg acylamido; a is an integer with a value of 1 or 2 and preferably 1 and b is an integer with a value of 0 or 1, the sum a + b being 1 or 2. When in formula (4) a is 2, the groups X may be the same or different. The group X to be cleaved reacts preferentially before -OR with available -OH in the RTV composition and provides an RTV composition which is practically free from halogen or carboxylic acid. The silane of formula (4) is both a "scavenger" for hydroxy functional groups and a cross-linking agent which introduces at least 2 alkoxy groups to the silicon atoms at each end of the organopolysiloxane chain.

The invention can also be described by defining the basic polyalkoxy polymers. Among the components of the present RTV compositions, which are formed as a result of the use of the "scavenger" of formula (4) for hydroxy groups, include silanol-free polyiorganosiloxane which at the ends of the chain 2 or 3 - OR * contains groups 25. The silanol-free polydiorganosiloxane may optionally be combined with an effective amount of a crosslinking silane, as defined below, under substantially anhydrous conditions. The crosslinking polyalkoxy silane which can be used in combination with the silane of formula (4) is a compound of formula (5) of the formula sheet wherein R R and b have the definitions given above. The preferred condensation catalysts which can be used in accordance with the invention include metal compounds selected from zirconium tin compounds. compounds and titanium compounds or mixtures thereof. Other condensation catalysts to be used are listed below.

It is not entirely clear why the organopolysiloxane with polyalkoxy-terminated compositions of the present invention are long-term stable in the presence of certain condensation catalysts and in the absence of moisture.

8300604 'w% * - 9 -

It is believed that the reason that the compositions of US patent application 277,524 are stable is that the "scavenger" reacts with all the hydroxy groups in the RTV system so that there are no more free hydroxy groups in the system that are the uncured polymer can further cross-link, at which further cross-linking the viscosity will be increased and the shelf life will be shortened. Furthermore, these free hydroxy groups can degrade and degrade the alkoxy polymer in various ways during storage.

The use of the silane of formula (1) or (4), in which the cif to be cleaved group X is not a halogen, as a means of removing hydroxy groups, eliminates unwanted water in the filler and the siloxane polymer, as well as residual moisture in the RTV composition during the storage period. To determine the amount of silane of formula (1) or (4) to be used as a "scavenger" according to the invention for hydroxy groups, the total hydroxy functionality of the RTV composition can be determined. The total hydroxy functionality of the polymer can be determined by infrared analysis. In order to ensure that an effective or stabilizing amount of hydroxy group removing agent is used to maintain the stability of the composition for a long period of storage of 6 months or longer at ambient temperature in a sealed container, a further use amount of hydroxy group eliminator in excess of the amount needed to introduce terminal groups into the polymer. This excess hydroxy group eliminator may be up to about 3% by weight (based on the weight of the polymer). The above amount of 3 wt% hydroxy group eliminator is greater than the amount needed to eliminate the available hydroxy functionality in the polymer by reaction between functional OH groups and X groups. In compositions 30 which also contain a filler and other additives, the further amount of the agent of formula (1) or (4) required to remove hydroxy groups is determined by performing a 48 hour stability check at 100 ° C in order to determine whether the time until the material is tack-free remains practically unchanged compared to the time before the composition is tack-free, determined under the same conditions.

When the polyalkoxy-terminated polymer is prepared without using a silane of formula (4) as a hydroxy removal agent, a silane having less than 40 2 silicon-bonded -OR1 groups can be used according to the invention, i.e. silane 8300604: ο -ΙΟΙ 2 according to formula (6) of the formula sheet, wherein R, R and X have the definitions given above and c an integer with a value of 0 - 3 and d an integer with a value of 1 - Is 4, where the sum c + d equals 3 or 4. In these cases, the silanes of formula (6) can be used in an amount sufficient to stabilize the RTV composition, as defined above for the silane of formula (4). Furthermore, in combination with "scavengers" of formula (4) or (6), 0.01-10 parts of the crosslinking silane of formula (5) can be used.

The terminal polyalkoxy-containing organopolysiloxane of the present invention has the formula (7) of the formula sheet wherein R, R *, 2 R, X, n and b have the above definitions and e is 0 or 1, wherein the sum b + e equals 0 or 1. The polyalkoxy-organopolysiloxane of formula (7) can be prepared by various methods. One of these methods is described in U.S. Patent 3,542,901; a polyalkoxy silane with a silanol-containing polydiorganosiloxane in the presence of an amine as a catalyst, as discussed above, is used. A method not described in US Pat. No. 3,542,901 is the use of the silane of formula (4) as a terminal group introduction agent, in combination with the polydiorganosiloxane of the terminal silanol used in the invention. The additives of the invention are preferably used when the polyalkoxy-diorganopolysiloxane of formula (7) is first formed and then the additives are added.

In formulas (1 - 7), R is preferably selected from C 1 -C 4 monovalent hydrocarbon groups, halogenated hydrocarbon groups and cyanoalkyl-1 groups, R is preferably an alkyl group of 1-8 carbon atoms or 2 an aralkyl group of 7-13 carbon atoms and R is preferably methyl, phenyl or vinyl.

The preferred groups X in formulas (3), (5) and (6) are amido, amino and enoxy; most preferred is an amido group.

It has further been found that an improved cure rate can be achieved when small amounts of amines, substituted guanidines or mixtures thereof are used as cure accelerators in the polyalkoxy polymer containing compositions of the present invention. These curing accelerators also serve to catalyze the cleavage of the enoxy group which acts as a hydroxy scavenging agent 8300604

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v - (- - 11 - functions. 0.1-5 parts and preferably about 0.3-1 part of the curing accelerator can be added to 100 parts of the terminal silanol-containing polymer of formula (2) or it can be chemically treated with Use interconnected units of formula (3) polymer or per 100 parts of the terminal polyalkoxy-containing polymer of formula (7) to free up time, - ... until the RTV composition of the invention is tack free (TFT), important to reduce This increased cure rate is maintained after aging of the material for a long period of storage, for example 6 months or longer, at the ambient temperature, or a comparable period under accelerated aging conditions. long-term storage periods are practically equal to the original curing properties, for example, the time until the RTV compositions are tack free (TFT) after freshly mixed and immediately visible to the moisture in the atmosphere exposed.

It has been found that the curing accelerators described herein not only reduce the TFT of the RTV compositions of the invention but also provide a surprising stabilizing effect for certain RTV compositions containing certain condensation catalysts, which compositions significantly accelerate TFT elongation after For this group of condensation catalysts, the addition of amines, substituted guanidines and mixtures thereof provides stable RTV compositions that initially exhibit rapid cure, ie, less than about 30 minutes, which cure rate remains substantially unchanged after accelerated aging.

The RTV compositions of the invention can cure for 24 hours to a depth of about 0.32 cm. One can then use the. Determine and use durometer hardness (Shore A) to determine the cure of the compositions, as described in the examples.

Generally, the polymer system of the aforementioned U.S. Patent Application 277,524 can be described as a one-pack, practically anhydrous, room temperature vulcanizable, organopolysiloxane-containing composition that is stable for a long time under ambient conditions in the absence of moisture and can be converted into a practically acid-free, tack-free elastomer, the composition characterized by: (1) an organopolysiloxane in which the silicon atom carries at least 2 alkoxy groups at each end of a polymer chain; (2) an effective amount of a condensation catalyst; and (3) a stabilizing amount of a hydroxy group scavenging silane 1 2 of formula (1), wherein R, R, Xencde have meanings 40 given above and f is an integer value of 1 - 4 , where the sum 8300604 * \ · - 12 - c + f equals 1-4. Furthermore, an effective amount of a curing accelerator selected from substituted guanidines, amines and mixtures thereof is used.

According to a further aspect of the present invention, a stable, room temperature vulcanizable, organopolysiloxane having polyalkoxy-terminated composition, which under the environmental conditions, is hard-coated to provide an tack-free, practically acid-free elastomer, containing: (A) 100 parts of a polyalkoxy-organopolysiloxane according to formula (7); (B) 0-10 parts of a cross-linking silane of formula (5); (C) an effective amount of a condensation catalyst; and (D) a stabilizing amount of a silane of formula (1) as an agent for eliminating hydroxy groups.

The invention also provides a method for preparing a room temperature vulcanizable organopolysiloxane-containing composition under practically anhydrous conditions, using an effective amount of a condensation catalyst with a silanol-containing organopolysiloxane and a polyalkoxy silane crosslinking agent; the improvement provided by the invention consists in adding (1) to the organopolysiloxane with terminal silanol a stabilizing amount of a polyalkoxy silane which is both a "scavenger" for functional hydroxy groups and a cross-linking agent, the compound having the formula (4) wherein R, R, x, a and 25b have the definitions given above, and thereafter add an effective amount of a condensation catalyst, whereby the resulting organopolysiloxane-containing compositions, vulcanizable at room temperature, obtain improved stability .

According to another method of the invention, a room temperature vulcanizable organopolysiloxane-containing composition is prepared under practically anhydrous conditions using an effective amount of a condensation catalyst and an organopolysiloxane in which the silicon atom carries at least 2 alkoxy groups at each end of the polymer chain ; the improvement provided consists in adding to the polyalkoxy-organopolysiloxane: (1) a stabilizing amount of a silane of formula (1), wherein R, R, x, and cf have the above definitions, as "scavenger" for functional hydroxy groups, and (2) an effective amount of a condensation catalyst, whereby the resulting organopolysiloxane-containing composition, vulcanizable at room temperature, obtains an improved stability.

In accordance with a further aspect of the invention there is provided a process for preparing a stable one-pack, polyalkoxy (terminal) organopolysiloxane vulcanizable at room temperature, according to which process a vulcanizable at room temperature is practically anhydrous material stirs, which material is selected from (i) a mixture containing 10 (a) 200 parts by weight. of a terminal silanol-containing polydiorganosiloxane consisting at least substantially of chemically bonded units of formula (3); (b) an amount of silane of formula (4) that is sufficient to react with available -OH in the STV composition and can be up to 3% by weight (excess) based on the weight of the RTV composition? (c) 0-10 parts by weight. of a cross-linking silane of formula (5)? (d) an effective amount of a condensation catalyst, and (e) 0-5 parts by weight. curing accelerator selected from substituted guanidines, amines and mixtures thereof, wherein the condensation catalyst 20 is added after the polydiorganosiloxane has been mixed with silanol terminal and the silane-eliminating agent for hydroxy groups? and (ii) a mixture containing (a) 100 parts by weight. of the polyalkoxy organopolysiloxane of formula 25 (7); (b) 0-10 parts by weight. of the cross-linking silane of formula (5)? (c) an effective amount of a condensation catalyst; (d) a stabilizing amount as an agent for eliminating hydroxy groups serving silane of formula (1) and 30 '(e) from 0 to 5 parts by weight. of a curing accelerator selected from substituted guanidines, amines and mixtures thereof.

* 8300604 - 14 -

Examples of groups represented by R in formula (2), (3) and (7) are aryl groups and halogenated aryl groups such as phenyl, tolyl, chlorophenyl and naphthyl; aliphatic and cycloaliphatic groups, such as cyclohexyl and cyclobutyl; alkyl and alkenyl groups, such as methyl, ethyl, propyl, chloropropyl, vinyl, allyl and trifluoropropyl; and cyanoalkyl groups, such as cyanoethyl, cyanopropyl and cyanobutyl. Examples of preferred groups represented by R 1 are alkyl groups of 1-8 carbon atoms, e.g., methyl, ethyl, propyl, butyl, pentyl; aralkyl groups of 7-13 carbon atoms, e.g. benzyl, phenethyl; alkyl ether groups such as 2-methoxyethyl; alkyl ester groups such as 2-acetoxyethyl; alkyl ketone groups such as 1-2 butan-3-onyl; alkyl cyano groups such as 2-cyanoethyl. The groups represented by R include the groups represented by R and may be the same or different. In formulas (1-7), where more than 1 group can be represented by R, R and R, these groups can be the same or different. Some examples of the agents for eliminating chemically bound hydroxy groups, which fall under formulas (4), (6) and (1) are; Oximato silanes such as methyl dimethoxy (ethyl methyl ketoximo) silane; methyl methoxy bis (ethyl methyl ketoximo) silane; Methyl dimethoxy (acetaldoximo) silane.

Carbamatosilanes such as methyl dimethoxy (N-methyl carbamato) silane; ethyl dimethoxy (N-methylcarbamato) silane.

Enoxysilanes such as methyl dimethoxyisopropenoxysilane; trimethoxyisopropenoxysilane; methyl triisopropenoxysilane; methyl dimethoxy (but-2-and-2-oxy) silane; methyl dimethoxy (1-phenylethenoxy) silane; Methyl dimethoxy-2 (1-carboethoxypropenoxy) silane.

Aminosilanes such as methyl methoxydi-N-methylamino silane; vinyl dimethoxymethylamino silane; tetra-N, N-diethylaminosilane methyldimethoxymethylaminosilane; Methyl tricyclohexylaminosilane; methyl dimethoxyethylamino silane; dimethyldi-N, N-dimethylaminosilane; methyl dimethoxyisopropylamino silane dimethyl di-N, N-diethylamino silane.

8300304 ·· *: ·: · •? »· -» - -4 * \ - 15 -

Amido silanes such as ethyl dimethoxy (n. Ethyl propionamido) silane; methyl dimethoxy (N-methylacetamido) silane; methyl tri (N-methylacetamido) silane; 5 methyl tri (N-methylbenzamido) silane? ethyl dimethoxy (N-methylacetamido) silane; methyltri (N-methylbenzamido) silane? methylmethoxybis (N-methylacetamido) silane? methyl dimethoxy (caproactamo) silane? Trimethoxy (N-methylacetamido) silane.

Imidatosilanes such as methyl dimethoxyethylacetimidatosilane? methyl dimethoxypropylacetimidatosilane. uridosilanes such as methyldimethoxy (N, N ', Ν'-trimethylureido) silane? methyl dimethoxy (N-allyl-N ', N'-dimethylureido) silane; methyl dimethoxy (N-phenyl-N ', N' -dimethylureidosilane.

Isocyanatosilanes such as methyl dimethoxy isocyanatosilane? Dimethyoxydiisocyanatosilane.

Thioisocyanatosilanes such as methyl dimethoxythioisocyanatosilane? methyl methoxydithioisocyanatosilane.

Furthermore, as agents for eliminating hydroxy groups, silanes of formula (6) include compounds such as methyltris (N-methylacetamido) silane and tetra (isopropenoxy) silane. Other examples of silanes are those with different cleavable groups, such as diethylamini (N-methylcarbamato) isopropenoxy (N-allyl-N ', N'-dimethylureido) silane.

Some examples of the crosslinking polyalkoxy silanes of formula (5) are methyl trimethoxy silane, methyl triethoxy silane, ethyl trimoxy silane, tetraethoxy silane, vinyl trimethoxy silane, etc.

Examples of curing accelerators that can be used according to the invention are silyl-substituted guanidines according to the formula (8) of the formula sheet, wherein R 1 has the above definition, Z a guanidine group according to the formula (9) of the formula sheet wherein R represents a divalent alkylene group of 2-8 carbon atoms and R and R are hydrogen or an alkyl group of 1-8 carbon atoms, and g is a number 1-3. Furthermore, alkyl-substituted guanidines of the formula (10) of the 8300604 Λ, 4 5-16 formula sheet, wherein R and R have the above definitions and g R is an alkyl group of 1-8 carbon atoms, may also be used. Some silyl-substituted guanidines of formula (8) are described in U.S. Pat. Nos. 4,180,642 and 4,248,993.

In addition to the above-mentioned substituted guanidines, various amines can be used, eg, di-n -hexylamine, dicyclohexylamine, di-n, bctylamine, hexamethoxymethylmelamine and silylated amines such as "X-aminopropylmethoxysilane and methyl-dimethoxy-di-n -hexylamin. Di-n-hexyl aminosilane acts both as an agent for eliminating hydroxy groups and as a curing accelerator. The primary amines, secondary amines, and silylated secondary amines are preferred, and secondary amines and silylated secondary amines are particularly preferred. Silylated secondary amines, such as alkyl dialkoxyl dialkyl amino silanes, and guanidines, such as alkyl dialkoxy-alkyl guanidyl silanes which are useful herein as curing accelerators, also act as agents for eliminating hydroxy groups, and in some cases as stabilizers in the compositions of the present invention.

Effective amounts of the condensation catalysts which can be used according to the present invention to facilitate the curing of the RTV compositions are, for example, 0.001-1 parts by weight. per 100 parts by weight. of the silanol-containing polydiorganisiloxane of formula (1). This includes tin compounds, eg! dilaurate; dibutyltin diacetate; dibutyltin dimethoxide; carbomethoxyphenyltin trisuberate; 25 tin octoate? isobutyltin triceroate; dimethyl tin dibutyrate; dimethyltin dinodeconoate; triethyltartartrate; dibutyltin dibenzoate; tin oleate; tin naphthenate; butyltintri-2-ethylhexoate; tin butyrate. The preferred condensation catalysts are tin compounds, and dibutyltin diacetate is particularly preferred.

Titanium compounds that can be used are, for example, 1,3-propanedioxy titanium bis (ethyl acetoacetate; 1,3-propanedioxy titanium bis (acetyl acetonate); diisopropoxy titanium bis (acetylacetonate); titanium naphthenate; tetrabutyl titanate; tetra-2-ethyl-hexyltitan tetraphenyl titanate, tetra-octadecyl titanate, ethyl triethanolamine titanate Furthermore, the β-dicarbonyl titanium compounds of the present invention disclosed in U.S. Patent 3,334,067 can be used as condensation catalysts.

Zirconium compounds, e.g. zirconium octoate, can also be used.

83 0 0 60 4 - 17 - V 'Tl

Further examples of metal-containing condensation catalysts are lead 2-ethyl octoate; iron 2-ethylhexoate; cobalt 2-ethyl-hexoate; manganese 2-ethylhexoate; zinc 2-ethylhexoate; antimony octoate; bismuth naphthenate; zinc naphthenate; and zinc stearate.

Examples of non-metallic condensation catalysts are hexyl ammonium acetate and benzyl trimethyl ammonium acetate.

The preferred catalyst for the present compositions is dibutyltin diacetate. However, other tin soaps with almost the same activity can be used.

The terms "anhydrous conditions" and "practically anhydrous conditions" used herein in connection with the preparation of the RTV compositions of the invention refer to mixing in a dry vessel or in a closed container from which the air has been removed, which air it was then replaced by a dry inert gas such as nitrogen. It has been found that a sufficient amount of silane of formula (1), as mentioned above, must be used. The temperature can range from about 0 ° C to about 180 ° C, depending on the degree of mixing, the type and amount of filler, a mixture of the terminal silanol containing polydiorganosiloxane, filler and an effective amount of 2Q of the silane of formula (4) sufficient to eliminate the functional hydroxy groups and introduce terminal groups into the polymer. This introduction of terminal groups into the polymer and elimination of hydroxy groups may require several minutes, hours or even days, depending on factors such as the nature of the group X to be cleaved, the number of -OR * groups on the silane, etc. the practically silanol-free mixture can then be added with the condensation catalyst, the crosslinking silane or a mixture thereof, together with other ingredients, e.g., the curing catalyst and pigments.

According to a preferred method of preparing the RTV composition of the invention, a mixture of the polydiorganosiloxane with terminal silanol, filler and an effective amount of the silane of formula (4) sufficient to remove the functional hydroxy groups is stirred under practically anhydrous conditions. eliminate and introduce terminal groups into the polymer. This introduction of terminal groups and elimination of functional hydroxy groups may require several minutes, hours or even days, depending on factors such as the nature of the group X to be cleaved, the number of -OR * groups on the silane, etc. Then one can the practically silanol-free mixture, the condensation catalyst, the cross-linking silane or a mixture here- 8300604

V

\, - 18 - r.

of, along with other ingredients, e.g., the curing catalyst and pigments. In the first or last stages of mixing, a stabilizing excess of the silane solvent for the elimination of hydroxy groups can optionally be used in the above amounts.

When the polyalkoxy-organopolysiloxane of formula (7) is prepared by a method that does not require the use of a silane of formula (4) to eliminate hydroxy groups, stabilized amounts of silane to eliminate hydroxy groups may occur before, during or after the addition of the condensation catalyst. Alternative methods for preparing polyalkoxy-organopolysiloxane are described in U.S. Pat. No. 3,542,901.

According to the preferred methods of preparing the RTV compositions of the invention, ie a non-corrosive, fast-curing, and storage stable, low modulus composition, a terminal polyalkoxy-containing diorganopolysiloxane polymer is used, the polyalkoxydiorganopolysiloxane first being formed, the hydroxy groups in the composition are removed and then the other ingredients are added as desired. This process can be carried out by adding the silanol polymer of formula (1) to the cross-linking agent of formula (5), ie the silanol polymer is previously reacted with a cross-linking agent, preferably in the presence of a catalyst, preferably an amine such as hexylamine, to form the desired polymer with 2 terminal alkoxy groups, and then add to the polymer with 2 or 3 terminal alkoxy groups a "scavenger" that reacts with the silanol groups. Then, the other ingredients can be added to the composition under practically anhydrous conditions to prepare a one-pack RTV material which is stable in storage and hard at a sufficient rate, i.e.

30 cures quickly even with tin soap as a catalyst in the composition. The first basic component of the invention to be added to the above RTV system after it has been prepared, ie the polyalkoxy material, the -OH group eliminator and the condensation catalyst, is 2-20 wt. parts. (per 100 parts by weight of diorgano-35 silicone base polymer, i.e., per 100 parts by weight of the silanol polymer of formula (2) or per 100 parts of the polyalkoxy organo-polysiloxane polymer of formula (2) 7)) of a flowable silicone as the first plasticizer, which silicone has a high degree of tri functionality or a combination of tri and tetra functionality, 8300604

V

- 19 - and contains: (i) 5-60 mol% of monoalkoxysiloxy or siloxy units or a mixture of these units; (ii) 1-6 mol% trialkylsiloxy units; and 5 (iii) 34-94 mol% dialkylsiloxy units, which plasticizing polysloxan contains about 0.1-2% by weight silicon bonded hydroxyl groups.

It should be noted that this first plasticizer, which is a flowable polysiloxane, can generally be added in a concentration of 2-20 parts by weight. and preferably in a concentration of 10 to 15 parts by weight. per 100 parts by weight. base polymer. Such a silicone acts as a plasticizer and adhesion promoter in the present composition and more particularly as a plasticizer. Too much of this material cannot be added to plasticize the composition, since due to its tri functionality, this material cross-links on its own and increases the viscosity of the system too much. An amount of more than 20 parts by weight. per 100 parts by weight. base polymer is undesirable. Therefore, this material should generally not be used in an amount of less than 20 parts by weight, while an amount of less than 2 parts by weight. doesn't have much effect.

The highly trifunctional silicone used as a component can be prepared by known methods. For example, a mixture of (i) monoalkyltrichlorosilane, (ii) dialkyldichlorosilane, and (iii) alkyltrichlorosilane, silicon tetrachloride or a mixture thereof may be added in a suitable molar ratio of toluene and water to hydrolyze these materials together.

The mixture can then be heated, for example at about 60 ° C, for a period sufficient to ensure completion of the reaction (for example 3 hours). The oil phase is separated and neutralized, for example, by washing with an aqueous solution of sodium carbonate or bicarbonate. After filtration to remove insoluble material and evaporation, for example by heating to about 140 ° C under reduced pressure, for example about 2 mm Hg, the flowable silicone remains as a residue. For economic reasons, it is preferable to keep the content of hydroxyl bonded to silicon to less than 0.6% by weight in order to minimize the viscosity of the final composition and to reduce the crosslinker content to keep it to a minimum. This is done by heating the product at 110 ° C in the presence of about 1% sodium carbonate. The water 8300604-20 of the silanol condensation can be conveniently removed by azeotropic distillation, for example with toluene. After removal of the toluene by distillation, the product is filtered before being used. Reference is made in this regard to U.S. Pat. No. 3,382,205.

The liquid silicone preferably has a viscosity of 15-300 cp at 25 ° C. Further, the alkyl groups present as substituents in the plasticizing, flowable polysiloxane are at least 50% methyl groups, and the liquid silicone contains 0.2-0.6 wt% silanol. Especially preferred are the monoalkylsiloxy units, siloxy units or a combination of these units at about 10-30 mol%, the trialkylsiloxy units at 3-5 mol% and the dialkylsiloxy units at 65-87 mol%, and the silanol content is about 0.2 - 0.6% by weight.

Although this trifunctional liquid material plasticizes the base composition and thus gives it a low modulus, this material per se does not in itself always provide a sufficiently low modulus and a sufficiently low vicosity. Therefore, it is highly desirable to add 10 to 50 parts by weight in addition to the trifunctional liquid material. of a second week per 100 parts by weight. of the basic organopolysiloxane polymer.

As mentioned above, base organopolysiloxane polymer is understood to mean the terminal silanol-containing diorganopolysiloxane polymer of formula (2) or the terminal polyalkoxy-containing diorganopolysiloxane polymer of formula (7) or a mixture of both materials.

Since the alkoxy groups contribute little to the molecular weight of the polymer, the concentrations of the various additives present in addition to the trifunctional liquid material are practically the same in both polymer systems.

Per 100 parts by weight. from the basic organopolysiloxane polymer, 5 to 60 parts by weight can be added. of a second plasticizer, namely a linear diorganopolysiloxane polymer with triorganosiloxy terminal groups, which polymer has a viscosity of 10-20,000 cp at 25 ° C and wherein the organic groups are monovalent hydrocarbon groups of 1-8 carbon atoms. The second plasticizer preferably has the formula (11) of the formula sheet, wherein R represents a monovalent hydrocarbon group, preferably an alkyl group with 1-8 carbon atoms or an aryl group, for example a phenyl group, and t varies such that the viscosity of the polymefer ranges from 10 to 20. OQQ-ientipoisé At <RTI ID = 0.0> S </RTI> C.-Most preferably, the group R is methyl and the polymer has a viscosity of 8300604 * -Η - 21 - 10 - 10,000 centipoise at 25 ° C; even more preferably, the viscosity is from 10 to 1,000 centipoise at 25 ° C. Generally, as a result of the preparation method, these polymers contain 500 to 1500 parts of silanol (as OH) per million. According to the general method for preparing such a plasticizer of formula (11), suitable chlorosilanes are hydrolyzed. For example, triorganochlorosilane is hydrolyzed with diorganodichlorosilane in water, and then the hydrolyzate is removed and purified by decantation and other methods to obtain the desired linear diorganopolysiloxane polymer of formula (11).

By this hydrolysis method, such a polymer usually has 500-1,500 parts silanol (as OH) per million; the resulting polymer can be further purified by other methods. However, this is normally not done for cost reasons. Furthermore, these island groups or hydroxy groups do not cause difficulties if an agent is present which eliminates or "captures" virtually all of these hydroxy groups present in the polymer. As mentioned above, such an agent should be used in the present system which reacts with all the free hydroxy groups in this plasticizer. As mentioned above, 2 plasticizers should be used to obtain a desired low modulus of the composition, since the trifunctional liquid material alone does not give a maximum decrease in both viscosity and modulus. When obtaining the lowest modulus, maximum adhesion and minimum viscosity. to increase the ease of application of the sealant, it is necessary to use both plasticizers. Thus, the most preferred low-modulus one-pack RTV systems are prepared using the 2 plasticizers of the invention in the above amounts. It is noted that within the above-mentioned wide range of 50-60 parts by weight. for the second plasticizer, preferably a concentration of 20-45 parts by weight. is applied.

Another aspect of the present composition is the low cost. The composition can be made inexpensive by adding 50-300 or more parts by weight. of a filler serving as an extender per 100 parts by weight. of the basic organopolysiloxane. Preferably, in the composition, a filler serving as an extender is present, since this filler lowers the cost of the composition and contributes to the strength of the composition without compromising the low modulus. Most preferably, calcium carbonate is used as a filler.

The most desirable calcium carbonate is stearic acid-treated calcium 8300604-22 - carbonate. This gives the best flow properties to the uncured composition of the invention and the above mentioned best low modulus. Other filler additives in the present composition are also incorporated into the concentrations mentioned above for calcium carbonate. Examples of other extenders and reinforcing fillers that can be used in various concentrations are titanium dioxide, zirconium silicate, silica airgel, iron oxide, diatomaceous earth, gas phase silica, carbon black, precipitated silica, glass fibers, polyvinyl chloride, ground quartz , Etc. The amount of filler used can of course be varied within wide limits according to the intended application. For example, in some sealing applications, curable compositions can be used which even have 700 parts by weight. or more filler per 100 parts by weight. contain organopolysiloxane. In these applications, the filler may consist of a predominant amount of adjuvant materials, such as ground quartz, polyvinyl chloride or mixtures thereof, preferably with an average particle size in the range of about 1-10 microns.

The compositions of the present invention can also be used as sealing and caulking materials for construction purposes. The exact amount of filler therefore depends on factors such as the application for which the organopolysiloxane-containing composition is intended, and the type of filler used (i.e. the density of the filler and its particle size). Preferably, an amount of 1 to 300 parts by weight is used. filler, of which up to about 20 parts by weight. can be formed by a reinforcing filler, such as gas phase silica, per 100 parts by weight. silanol-containing organopolysiloxane.

The in a concentration of 50-300 parts by weight. fillers used, however, should be adjuvant fillers (e.g., calcium carbonate) for the present low modulus compositions. In addition to the filler serving as a lengthening agent, 1-50 parts by weight can be added. and preferably 1-10 parts by weight. 100% by weight of a reinforcing filler. of the basic organopolysiloxane. The reinforcing filler may be precipitated silica or gas phase silica, and is preferably gas phase silica. Preferably, a gas oxide obtained from the gas phase is used, which has been treated with cyclopolysiloxanes, as described in US patent 2,938,009, or with silazanes, as described in US patent 3,635,743.

In particular, 1-10 parts by weight are preferably used. of the gaseous phase treated silica with cyclopolysiloxanes. This 8300604% gaseous silica obtained from the gas phase acts as an anti-sagging agent, which makes the composition thixotropic. Thixotropic means that the composition, when applied to a vertical surface in uncured state, does not flow or only flows minimally. Another method of making the composition thixotropic is described in U.S. Patent 4,261,758.

Thus, in the BTV composition, in addition to the filler serving as an extender, one can use per 100 parts by weight. of the basic organopolysiloxane with the reinforcing silica from the glass phase, 0.1-2.0 parts by weight. of a second anti-sagging agent, namely a polyether selected from compounds of formulas (12) and (13) of the formula sheet, wherein A and B represent groups selected from hydrogen, alkyl groups of 1- 12 carbon atoms, cycloalkyl groups with 5-7 carbon atoms. in the ring, aryl groups with 1 and 2 aromatic rings and single-core aryl-lower alkyl groups, in which the alkyl groups bonded to the aromatic core contain a total of at most 5 carbon atoms, and the groups according to the formula (14) of the formula sheet, wherein R an alkyl group with 1-11 carbon atoms? Q is a residue of a polyhydric initiator containing at least 2 hydroxyl groups and is selected from ethylene glycol, glycerol, trimethylol propane and other polyhydric alcohols with 2-6 hydroxyl groups; n represents a number with a value of 2-4; y has a value of 2-10; and z has a value of 1-5? the polyether has a molecular weight of about 300-200,000.

8300604

V

λ '- 24 -

The polyether serving as a sagging agent can be used in addition to or instead of the gas phase silica to impart thixotropic properties to the uncured RTV composition, which properties are used in a sealant. It is noted that the preferred RTV composition of the present invention, ie the composition which is non-corrosive and stable in storage, cures quickly and has a low modulus, is highly desirable as a sealant in building construction, in glazing applications and in other applications where sealants are used. It is therefore highly desirable that such a sealant be thixotropic, i.e. that it does not flow into a crack or crevice when applied in uncured condition. This thixotropy can be imparted to the present composition by using gas phase silica in small amounts in combination with the above polyethers. Furthermore, the polyethers in combination with the silica obtained from the gas phase are preferably present in an amount of 0.1-1.0 parts by weight. Although the silica obtained from the gaseous phase prevents the sagging of the composition, this counteracting the sagging is greatly improved by the incorporation of the polyether. For further information regarding the use of the polyethers as anti-sag agents, reference is made to U.S. Patent 4,261,758.

Examples of commercially available polyethers that can be used in accordance with the invention include polyethers such as "Pluracol V-7" marketed by Wyandotte Chemicals Corporation, and "UCON LB-1146" marketed by Union Carbide Corporation.

Instead of or in addition to both of these anti-settling agents, 0.2-2.0 parts by weight. and preferably 0.2-1.5 parts by weight. hydrogenated castor oil per 100 parts by weight. of the basic organopolysiloxane.

An example of hydrogenated castor oil that can be used as a sagging agent is "Thixcin" (a trademark of NL Chemicals).

When using hydrogenated castor oil as a sagging agent, neither the gas phase silica nor the polyether need be used. However, when the hydrogenated castor oil is not used as a sagging agent, the silica obtained from the gas phase with the polyether should be used. Instead, only the gas phase silica obtained from the polyether can be used. It is expressly noted that a reinforcing filler in the present composition is neither necessary nor desirable, 8300604

W.

Since it is desired to prepare a low modulus composition.

A large amount of reinforcing filler gives an undesirable increase in the modulus of the present composition. Most preferably, the silica obtained from the gas phase (if used) is used in addition to the admixture filler, such as calcium carbonate and, in particular, calcium carbonate treated with stearic acid, thereby reducing the price of the composition, the viscosity of the uncured composition is maintained and the modulus of the uncured composition is kept low. Several other types of available additives can be added to the composition.

Thus, in the present composition, 0.1-10 parts by weight. of adhesion promoter per 100 parts by weight. of the organopolysiloxane. The present compositions, i.e., the compositions of the above-mentioned US patent application 277,524 do not adhere very well to substrates. It is therefore desirable to use a primer or adhesion promoter in combination with these compositions. Primers are undesirable because they involve additional labor costs for applying the sealant. Therefore, it is highly desirable to use an additive for self-adhering the composition. For these additives, reference is made to the aforementioned U.S. Patent Application ...... (Lucas), the filing date of which coincides with the priority date of the present application.

A further additive for imparting self-adhesion, which may be present in the compositions of the invention in an amount of 0.1-10 parts by weight, is an adhesion promoter which contains the formula ( 15) of the formula sheet, in which formulas R and 31 R are selected from monovalent hydrocarbon groups of 1 to 8 carbon atoms, 32 36 R and R are selected from divalent hydrocarbon groups of 1-12 30 atoms, R 3 and are selected from hydrogen and monovalent hydrocarbon radicals having 1-8 carbon atoms, R selected from hydrogen and 33 alkyl radicals having 1-3 carbon atoms, R selected from hydrogen and methyl, 8300604

1 * V

V * * i - 26 - 33 34 38 40

Most preferably, R and R, R and R are selected from hydrogen x and alkyl groups such as methyl. The most preferred compound of the invention according to the above formula is the compound of the formula (16) of the formula sheet.

These compounds can be prepared by reacting ethylene diamine with the appropriate silyl acrylate. These silyl acrylates are known and can be prepared by reacting the appropriate olefinic methacrylate compound with a hydrotrialkoxy silane in the presence of a platinum-containing catalyst. The hydrogen of the silane is added to the olefinic group of the acrylate to form an acrylate silyl compound, as described, for example, in Dutch patent application 8100008. This reaction takes place in the presence of a platinum-containing catalyst at a temperature between room temperature and 150 ° C, with or without solvent and preferably at the pressure of the environment. When the acrylate silane compound is formed, this compound can then be reacted with a suitable amine without a catalyst in the presence of a solvent to form the desired amine acrylate adduct of formula (15) which can be used according to the invention as a promoter of the bonding. No catalyst is required for this reaction and temperatures between room temperature and 100 ° C can be used. Preferably, the reaction is carried out at ambient pressure. The desired amine acrylate additive is obtained in high yields.

This adhesion promoter is one of the adhesion promoters that can be used in conjunction with the composition of U.S. Patent Application 277,524. For further information regarding the preparation of this adhesion promoter, reference is made to U.S. Patent Application ... (Mitchell) filed on the priority date of the present application.

In addition to the adhesion promoters described in the above-mentioned U.S. Patent Application (Lucas), filed on the priority date of the present application, other adhesion promoters may also be used.

It is noted that the present composition has, in addition to its other properties, a low modulus, fast curing and storage stability, and that the low modulus of the composition is imparted by the plasticizers.

Also, the composition is thixotropic by the addition of a thixotropic agent mentioned above and inexpensive if the preferred filler filler according to the invention is 8300604 -% - 27.

Any of the other adhesion promoters described in the aforementioned U.S. Patent Application ... (Lucas) or in the present specification may be used. Furthermore, other additives can also be included in the compositions of the invention.

To prepare the present storage stable, low modulus, fast curing composition, it is desirable to first form the polyalkoxy diorganopoly lysiloxane polymer. This formation can be effected by reacting the silanol polymer with a cross-linking agent of formula (5) in the presence of an amine as a catalyst, preferably hexyl amine, as described in the above-mentioned US patent application 277,524, and then the agent for the eliminate the hydroxy groups to add to the product. Preferably, this hydroxy group eliminator is an amine or a silazan. The various additives are added thereto, as described in the examples below. This method provides a low-modulus, one-pack RTV system that is inexpensive, thixotropic and self-adhesive. Furthermore, the composition 20 is stable in storage and fast-curing, as described in the above-mentioned U.S. Patent Application 277,524.

The following non-limiting examples further illustrate the invention. All parts are parts by weight.

EXAMPLE I

A base composition containing 100 parts by weight was prepared. of a dimethylpolysiloxane polymer with terminal methyl dimethoxy, which polymer had a viscosity of 150,000 centipoise, 0.5 part by weight of di-n-hexyl amine, 35 parts by weight. of a trimethylsiloxy-containing dimethylpolysiloxane polymer having a viscosity of 100 centipoise at 25 ° C, 10 parts by weight. of a polymer with 3 mol% monofunctional trimethylsiloxy units, 20 mol% tri-functional methylsiloxy units and 77 mol% bi-functional dimethylsiloxy units, which polymer had a viscosity of 50 centipoise at 25 ° C and 0.5 wt. % silanol. 130 parts by weight were also included in this composition. stearic acid treated calcium carbonate, which is supplied by OMZA, Ine. is marketed under the name "Hydrocarb 95T", 3 parts by weight. Octamethylcytlotetrasiloxane treated gas phase silica, 0.2 parts by weight of a polyether marketed by Union Carbide Corporation under the name "UCON LB-1145" and 4.2 parts by weight. methyl dimethoxy N-methylacetamido-8300604-28-silane. This composition, which was prepared under practically anhydrous conditions, was further mixed with a catalyst at practically anhydrous conditions at the concentrations listed in Table A below.

Table A lists the flow properties, the time until the material is tack free, the yield rate, and certain physical properties that these RTV compositions exhibited after curing. The flow properties were determined according to the Boeing test, which is carried out as follows: a vertical device with a cylindrical cavity on the top containing a plunger is used. The cavity is filled with sealant.

The plunger is then slid to the surface level of the above device. After this, the instrument is placed in a vertical position with this sealant protruding about 1.3 cm above the surface. Subsidence is then measured in tenths of centimeters. The cavity has a depth of about 1.3 cm and a diameter of about 3.9 cm.

The time until the material is tack-free is determined by smearing the sealant with dimensions of about 2.54 cm by about 12.7 cm by about 0.32 cm and then determining the time when the surface feels dry when touched with the finger.

The yield rate is determined by filling a Semco tube of approximately 177.4 cm, to which a nozzle with a diameter of approximately 0.32 cm is attached. The application takes place under an air pressure of about 720.5 kPa and the air is provided by an air-filled cylinder. The application rate is expressed in grams of applied sealant per minute. The results of the test are shown in Table A below.

TABLE · A

: s; ...... ·. . I.r '... A B "

Basic composition 100 100

Dibutyltin diacetate 0.4 0.4 30 Methyldimethoxy N-methylacetamidosilane --- 1.0

Flow, cm 1.3 0.13

Time to tack free, minutes 23 20

Application speed, g / min. 14 360

Shore A, hardness 15 18

Tensile strength, kPa 1848 1896

Elongation,% 990 925 EXAMPLE II,

A base composition containing 100 parts by weight was prepared. of a terminal methyl dimethoxy-containing dimethylpolysiloxane polymer having a 8300 60 4 - 29 viscosity of 15,000 centipoise at 25 ° C, 0.5 part by weight dihydric lamin, 35 parts by weight. liquid terminal trimethylsiloxy containing dimethylpolysiloxane with a viscosity of 100 centipoise at 25 ° C, 10 parts by weight. of the same trifunctional liquid material as in Example 1, 130 parts by weight.

5 of the same calcium carbonate as in Example 1, 0.2 part by weight "UCQN LB-1145" and 3.0 part by weight. octamethylcyclotetrasiloxane-treated gas-phase silica having a surface area of about 200 m / g. To this base composition, various amounts of methyl dimethoxy N-methylacetamidosilane and dibutyltin acetate, as well as a standard amount of an adhesion promoter, which are listed in Table B below, were added. The adhesion promoter had the formula (16).

The time until the samples were tack free was examined, which test was described in Example I. The results for the different formulations are shown in Table B below.

TABLE · B

Basic composition A B C D E F

_100 100 100 100 100 100

Methyldimethoxy-N-methyl 2.0 2.5 3.0 3.5 4.0 4.5 acetamidosilane 20

Dibutyltin diacetate 0.3 0.3 0.3 0.3 0.3 0.3

Agent for promoting adhesion 1.0 1.0 1.0 1.0 1.0 1.0

Initial Durometer Hardness 23 24 24 25 27 24 __ 48 Hours / 100 ° C. Durometer Hardness 0 0 22 28 27 28

Initial time to tack free (min.) 24 24 25 25 29 43

Time to tack free (min.) None none after 48 hours / 100 ° C cure cure 20 18 22 31

EXAMPLE III

In this example, the same basic composition as in Example II was used. To this composition were added the hydroxy group eliminator, the catalyst system and the adhesion promoter; times until the materials were tack free 22 are given in Table C below.

------: ___________ Γ1 8300604 - 30 -

TABLE C

A - B C. D E F G H * Basic composition 100 100 100 100 100 100 100 100

Hexamethyldisiliazan 1.7 --- --- --- --- - --- --- 2 t.butoxydimethylisopropyl aminosilane --- 3.0 --- --- --- --- --- ---

Bis- (dimethylamina) dimethylsilane ---- ---- 1.7 --- --- --- --- 1.7

Bis- (diethylamino) dimethylsilane ---- --- --- 1.7 ---- --- —- -

Bis- (dimethylamino) diphenylsilane --- --- --- --- 2.0 - --- ---

Bis- (monoethylamino) -dimethylsilane --- --- ---- --- --- 1.7 -— ---

Bis- (mono-n-butylamino) -dimethylsilane --- --- --- --- --- --- 1.7, _ Adhesion promoter (ethylenediamine methacryloxypropyl trimethoxysilane adduct) ) 1.0 1.0 1.0 1.0 1.0 1.0 1.0

Dibutyltin diacetate 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3

Methyl trimethoxysilane 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 ^ Initial durometer hardness 25 25 25 26 26 20 (1) 25 18 1} 48>; Ureö / 100 ° C Aging durometer hardness 27 23 24 27 0 23 26 0

Initial TFT - 25 minutes 26 16 20 21 15 14 14 30

48 Hours / 100 ° C

Aging TFT 15 14 14 13? EeJ. 14 13? Ee ^.

3 cure cure (1) Air was included in these samples during the addition of the catalyst.

From the results of the above experiment, it was concluded that the adhesion promoter (the ethylene-diamine-methacryloxypropyl trimethoxysilane adduct) contributed to the stabilization of the composition and that the bis (dimethylamino) diphenylsilane was poor means for eliminating hydroxy groups. The other materials have been found to function efficiently as hydroxy group eliminators.

EXAMPLE IV

A base composition containing 100 parts by weight was prepared. of a terminal methyl dimethoxysiloxy containing dimethylpolysiloxane polymer 8300604 4 t - 31 - with a viscosity of 150,000 centipoise at 25 ° C, in which 0.5 part by weight of di-n-hexyl amine was present and with which 35 parts by weight. 10 parts by weight of the same terminal dimethylsiloxy containing polydimethylsiloxane polymer as in Example 1 were mixed. of the same trifunctional liquid material as in Example 1, 180 parts. of the same stearic acid treated carbonate as in. Example I, and 0.2 part by weight "UCON LB 1145".

Xn this base composition were considered as. catalyst system included various amounts of ethylenediamine-methacryloxypropyl dimethoxysilane adduct and dibutyltin diacetate and various means for "scavenging" 10 hydroxy groups. The initial physical properties of the samples as well as the TFT (time to tack-free) of the aged samples of the composition are given in Table D below. The difference in TFT between the initial sample and the sample subject to accelerated aging is a measure of the stabilities of the material on storage. If the TFT does not noticeably change after accelerated aging, the material has good storage stability.

The results are given in Table D below.

8300604 * \ * '- 32 -

TABLE D

A B_ C D E F G Η I

Basic composition 100 100 100 100 100 100 100 100 100

Ethylenediamine-methacryloxypropyl-5 trimethoxysilane adduct 1.0 --- 1.0 --- --- --- --- --- ---

Dibutyltin diacetate 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3

Methyltrimethoxysilane - 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 10 Bis- (dimethylamino) dimethylsilane - 1.7 1.7 2.2 2 , 7 3.2 3.2 - ---

Bis- (monoethyl-aminodimethyl-lysane --- --- --- --- --- --- --- --- 3.2 3.7

Initial properties

Time to tack free / 33 25 26 20 23 22 22 23 21 15 minutes

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

Tensile strength, kPa 1462 1082 951 1013 917 882 800 724 710

Elongation,% 280 390 350 390 390 360 350 380 340 20 48 Hours / 1QQ ° C. Accelerated aging

Time to tack free, minutes none none 23 no none semi semi 20 20

Shore A, har-. 18 har- har- har- har- 23 hardness thing thing thing thing thing thing The above data shows that compositions with low modulus were obtained which had good storage stability.

The above data also shows that bis (dimethylamino) -dimethylsilane is a poor agent for the elimination of hydroxy groups, while the ethylenediamine-methacryloxypropyltrimethoxysilane additive per se is not a storage stability additive but in combination with a malfunctioning agent for the elimination of hydroxy groups, such as bis (dimethylamino) dimethylsilane, does promote storage stability.

Bis (monoethylamino) dimethylsilane is an excellent agent for eliminating hydroxy groups.

EXAMPLE V

A base composition as in Example 1 was prepared, in which the methyl dimethyl polysiloxane polymer was the same polymer as in Example I, and 0.5 parts by weight of di-n-hexyl amine was included; to this poly 8300604 v • s. * t - 33 - more were added 15 parts by weight. of the same trifunctional liquid material as in Example 1, 35 parts by weight. of the same trimethylsilyl-containing polydimethylsiloxane terminal as in Example 1, 185 parts by weight. of the same stearic acid-treated calcium carbonate as in Example 15 and 0.2 part by weight of "Pluracol V-7", a polyether anti-sagging polyether marketed by Wyandotte Chemicals Corporation. As in all examples, 100 parts by weight. of the base composition, various amounts of "scavenger" for the hydroxy groups, cross-linking agent, condensation catalyst and additives for imparting self-adhesion under substantially anhydrous conditions are added. In all cases, mixing was preferably carried out in a Semco pressure mixer under anhydrous conditions. The concentration of the ingredients mixed with the base composition as well as the physical properties of the compositions are given in Table E below.

TABLE · E

A B C D

Basic composition 100 100 100 100

Hexamethyldisilazane 2.0 2.0 3.2 2.0 20 Methyltrimethoxysilane --- -1 --- 4.0

Dibutyltin diacetate 0.075 0.075 0.075 0.1

Aminoethylaminopropyltrimethoxysilane 1.0 1.0 1.0 1.0

Properties 22 Shore A, hardness 12 25 10 30

Tensile strength, kPa 820 1427 710 1055

Eek,% 650 410 640 230

Application rate, g / min.

Time to tack free, minutes (initial) 11 12 10 19 30 (20 hours / 100 ° C accelerated) 13 13 8 18

Bond strength at peel off, N / cm,% breaking of cohesion ...

(Concrete) 12.2 / 1 (7 14/10 49/90 98/100 ï) Semi-hardened at interface.

8300604 V / '1 - 34 -

The results of Table E show that the composition has good low modulus, good self-adhesive properties and good storage stability. Another conclusion that can be drawn from the data is that the trimethylmethoxysilane content in the product had a very marked effect on the crosslinking density, as evidenced by the difference in Durometer hardness ranging from 0 to 1 to 4 parts by weight; the Durometer hardness is then resp. 12, 15 and 30. It has also been found that the highest values for the adhesion strength when concrete is pulled out are 4 parts by weight of methyl trimethoxysilane.

EXAMPLE VI

A base composition containing 100 parts of the same dimethoxymethylsiloxy-containing dimethylsiloxane polymer of Example I was prepared, 0.5 parts by weight of part-n -hexylamine, 35 parts of the trimethylsiloxy used in Example 1 Containing polydimethyl-15 siloxane with a viscosity of 100 centipoise at 25 ° C, 10 parts by weight of the same trifunctional liquid material as in Example I, 145 parts by weight of the stearic acid-treated calcium carbonate of Example I and 3 parts by weight of the treated gaseous oxide obtained in Example I used. To 100 parts of this base composition were added 20 different amounts of hydroxy group eliminator listed in Table F below, cross-linking agent, catalyst and self-adhering additive. Table F below lists the physical properties of these samples, as well as the aging properties in storage, ie the TFT of these samples, and the adhesive strength when peeled.

8300604 t - 35 - λ:

TABLE · F

A B C

Basic composition (see above) 100 100 100

Hexamethyldisilazan 2.5 2.5 3.0 5 Methyltrimethoxysilane 0.5 0.25 0.5

Dibutyltin diacetate 0.075 0.075 0.075

Aminoethylaminopropyltrimethoxysilane 1.0 1.0 1.0

Characteristics

Shore A, hardness 16 15 20 10 Tensile strength, kPa 1593 965 1338

Elongation,% 630 630 570

Application rate, g / min. 269 241 313

Time to tack free, minutes 11 5 6

Adhesion strength at peel off, N / cm 15% Breaking cohesion (10 days hardening at 50% / 25eC relative humidity) (1) Anodized aluminum 75/100 73.5 / 100 82/100 (2) Lexan 8.8 / 5 73.5 / 100 84/95 20 (3) PVC 89/100 77/100 87.5 / 100 (4) Glass (5) Polyacrylate 10.5 / 1 12/3 7/0 (6) Concrete '23 / 90 19/95 23/93 (7) Andersen Terrastone PVC 94.5 / 100 77/100 87.5 / 100 25 1) All concrete samples were semi-cured at the substrate interface.

EXAMPLE VII

A basic composition of 100 parts of the same dimethoxymethylsiloxy-dimethylsiloxane polymer of Example I, 0.5 parts of di-n.hexylamine, 35 parts of the trimethylsiloxy-dimethylpolysiloxane of Example I, 10 parts of the mixture was prepared. of the trifunctional liquid material of. Example I, 140 parts by weight of the stearic acid treated calcium carbonate of Example I, 3 parts by weight of the treated gaseous silica of Example I and 0.2 parts by weight of Wyandotte Chemicals Corporation under name "Pluracol V-7" marketed polyether. To 100 parts of this composition were added various amounts of hydroxy group eliminator, crosslinker, condensation catalyst, and self-adhering additive. The physical properties as well as the concentration of the constituents and the adhesive strength on peel are given in Table G below.

8300604 Μ. * - 36 -

TABLE G

A B C

Basic composition 100 100 100

Hexamethyldisilazan 2.5 2.5 3.0 5 Methyl trimethoxysolane 0.5 0.25 0.5

Dibutyltin diacetate 0.075 0.075 0.075

Aminoethylethylaminopropyltrimethoxysilane 1.0 1.0 1.0

Characteristics

Shore A, hardness 17 12 16 10 Tensile strength, kPa 1372 1193 1289

Elongation,% 600 680 600

Application rate, g / min. 294 290 314

Time to tack free, minutes 575

Bond strength at peel off, N / cm, 15% breaking of cohesion (10 days cured at 50% / 25 ° C relative humidity) (1) Anodized aluminum 84/100 82/100 89/100 (2) Lexan 8.8 / 0 17.5 / 22 5.2 / 1 (3) PVC 89/100 82/100 89/100 20 (4) Glass 84/93 73/93 87.5 / 95 (5) Polyacrylate 7/0 8.8 / 0 5.2 / 0 (6) Concrete 26/93 26/97 21/95 (7) Andersen Terrastone PVC 79/100 72/100 82/100

Andersen Terrastone PVC consists of thin layers of PVC and is extruded over wood 25 to be used as window frames.

The above data shows that the compositions have good self-adhesive properties on most substrates and also exhibit low modulus.

EXAMPLE VIII

A base composition was prepared containing 100 parts by weight of the.

methyl dimethoxydimethylpolysiloxane polymer of Example I, 0.5 parts by weight of di-n-hexyl amine, 35 parts by weight of the trimethylsiloxy-containing dimethylpolysiloxane of Example I, 10 parts by weight of the trifunctional liquid material of Example I, 160 parts by weight of the stearic acid-treated calcium carbonate of Example I, 3 parts by weight of the octa-methylcyclotetrasiloxane-treated gas-phase silica of Example I and 0.2 parts by weight "Pluracol V-7" of Example VI. To this base composition was added an agent for eliminating hydroxy groups, a crosslinking agent, a condensation catalyst and an additive for self-adhesion in a Semco pressure mixer in substantially anhydrous conditions in the same manner as in the other examples. The physical data obtained from the samples, the concentrations of the constituents added to the base composition, as well as the adhesive strength on peel-off are shown in Table H below.

8300604 V ^ '* 5 - 37 -

TABLE H

A B C

Parts

Basic composition 100 100 100 5 Hexamethyldisilazan 2.5 2.5 2.5

Methyltrimethoxysilane 0.25 0.70 0.70

Dibutyltin diacetate 0.075 0.025 0.075

Aminoethylaminopropyltrimethoxysilane 1.5 1.0 1.0

Properties 10 Shore A, hardness 10 13 24

Tensile strength, kPa 751 1186 2193

Elongation,% 535 470 360

Application rate, g / min. -

Time to tack free, minutes 22 27 11 15 Adhesion strength at peel off, N / cm, (% cohesive cohesion (10 days cured at 50% / 25 ° C relative humidity) (1) "Alclad" aluminum 21/50 54 / 80 70/80 (2) Lexan 26/100 72/88 77/100 20 (3) PVC 24.5 / 100 73.5 / 80 80.5 / 100 (4) Glass 24.5 / 45 73.5 / 75 82/80 (5) Polyacrylate 37/93 .. 38.5 / 35 7/0 (6) Concrete 19/80; 16/3 24.5 / 3 1) Semi-cured sealant observed at substrate interface.

EXAMPLE IX

A base composition containing 100 parts by weight of the methyl dimethoxypolysiloxane polymer of Example I was prepared, 0.5 parts by weight of di-n-hexyl amine, 10 parts by weight of the same trifunctional liquid material as in Example X, 35 parts by weight. parts of the trimethylsilyl-containing poly-30-dimethylsiloxane of Example I, 220 parts of the stearic acid-treated calcium carbonate "Hydrocarb 95 T" used in Example I and 3 parts of the treated gaseous oxide of Example I. To this base composition, 2.5 parts by weight of hexamethyldisilazan, 0.5 parts by weight of methyl trimethoxysilane, 1.0 parts by weight of aminoethyl amino-35-propyl trimethoxysilane and 0.07 parts by weight of dibutyltin diacetate. The preparation of the base composition and the addition thereto of catalyst and other additives was carried out under practically anhydrous conditions in a continuously operating Wemer-Pfleiderer twin screw extruder. The physical data of several samples of the compositions is given in Table I below. Table I below also lists the adhesive strength when the samples are peeled off. The results show that most samples had good self-adhesive properties for a number of substrates, were stable and had the low modulus desired according to the invention.

8300604

"V

- 38 -%, l V «

TABLE I

Monster No. 5 24 44

Application rate, g / min. 258 234 210

Flow, cm 0.38 0.51 0.38 5 Density 1.52 1.52 1.53

Time to tack free, minutes 30 30 30

Shore A, hardness 16 16 16

Tensile strength, kPa 1289 1269 1338

Elongation,% 555 565 540 10 Adhesion, N / cm Samples Samples Samples (peel off) 5, 6, 7 24,25,26 44,45,46

Concrete 30/0 17.5 / 0 14/0

Glass 105/100 96/90 96/80 PVC (rigid) 100/100 91/100 94.5 / 100 15 Lexan 91/100 84/100 89/100 "Marviplate” 15 102/100 93/100 102/100

1) a rigid PVC from Australia

"Zincalume" 61/30 Not studied 54/100

Anodized aluminum 96/100 96/100 91/100 20 Polyacrylate 70/100 66.5 / 30 65/100 - 72 hours / 100 ° C accelerated aging (Samples 24, 25, 26)

Physical properties (Sample 25) (Shore A, tensile strength and elongation) 2) 2) Samples 24, 25, 26 Time to tack free (minutes) 20,20,20 25 Shore A, hardness 27

Tensile strength, 2068 kPa

Elongation,% 450 2) During test with Werner-Pfleiderermenger, numbered samples were taken.

EXAMPLE X

A base composition containing 100 parts by weight of a dimethoxy-methylsiloxy-containing polydimethylsiloxane polymer having a viscosity of 150,000 centipoise at 25 ° C, 0.5 parts by weight of di-n-hexyl amine, 180 parts by weight of stearic acid-treated calcium carbonate, 35 parts by weight of a liquid trimethylsiloxy-containing polydimethylsiloxane having a viscosity of 100 centipoise at 25 ° C, 10 parts by weight of the same trifunctional liquid material as used in the other examples; and 5.68 parts by weight of "Thixcin R" (hydrogenated castor oil). To 100 parts by weight of the base composition, 2.5 parts by weight of hexamethyldisilazan, 0.5 parts by weight of methyl trimethoxysilane, 1 part, under practically anhydrous conditions. 0 parts by weight of aminoethylaminopropyltrimethoxysilane and 0.05 parts by weight of 8300604 4.

% - 39 - dibutyl in diacetate. The results of the determination of the physical properties are given in Table J below.

TABLE J

Time to tack free, minutes 25 5 Flow, cm 0.20

Application rate, g / min. 164

Shore A Durometer 22

Elongation,% 435

Tensile strength, kPa 1710 10 50% Modulus, kPa 352 75% Modulus, kPa 427 100% Modulus, kPa 517

Bond strength at peel off (10 days cure), N / cm -% breaking of cohesion 15 (1) Anodized aluminum 82/100 (2) Lexan (polycarbonate) 80.5 / 100 (3) Rigid PVC (polyvinyl chloride) 77/100 ( 4) Glass 80.5 / 100

The additives of the invention are preferably used in combination with the RTV compositions of the above-mentioned US patent application ... (Dziark). This US patent application describes certain preferred silazan compounds as means for eliminating hydroxy groups for the RTV systems of US patent application 277,524. Preferred systems of US patent application ....... (Dziark) are prepared by first forming a polyalkoxydiorganopolysiloxane polymer and then a compound to eliminate hydroxy groups - a silazan monomer or polymer or certain polymeric amino compounds to be used separately from the cross-linking agent. It should be noted that the hydroxy group eliminators in U.S. Patent Application ... (Dziark) are separate compounds in addition to the cross-linking agent. The RTV systems that do not contain the hydroxy group eliminators of U.S. Patent Application ....... (Dziark) are described in the

U.S. patent application 277,524 in addition to other RTV systems with functional alkoxy groups. A brief overview of the system according to US patent application ....... (Dziark) is described below; for further information regarding these hydroxy group eliminators and RTV systems, reference is made to this U.S. patent application. According to United States Patent Application ....... (Dziark), the present 8300604 -40-U additives can be used in a stable, one-pack, practically water-free and practically acid-free vulcanization at room temperature. sable, organopolysiloxane-containing composition which is long-term stable under ambient conditions in the absence of moisture and can be converted into a tack-free elastomer, which material contains: (1) an organopolysiloxane in which the silicon atom has a polymer chain at least 2 at each end carries alkoxy groups; (2) an effective amount of a condensation catalyst; (3) a stabilizing amount of a silane as an agent for the elimination of functional hydroxy groups, namely a silicon nitrogen compound selected from: (A) a silicon nitrogen compound of the formula (17) of the formula sheet, wherein Y is selected from R 1 "and R 1 N-, and (B) is a silicon nitrogen polymer containing (i) 3 - 100 mol% of chemical bonded units selected from units of formulas 15 (18), (19), 20 ), (21), (22) and (23) of the formula sheet, and (ii) 0-97 mol% of chemically bonded units of the formula (24) of the formula sheet, and mixtures thereof, wherein the silicon atoms of the silicon nitrogen polymer bonded to each other via a SiOSi bridging group or a SiNR "Si bridging group, the free valencies of the silicon atoms other than those which form to form a siloxy unit. and nitrogen. lower fenfenasilazy unit, .. ·. ..... to bind an R "group and / or an (R") ^ N group, the ratio between the sum of the R "1 groups and the (R") 2N groups and the silicon atoms of the silicon nitrogen polymer 1 , Is 5-3, and R "is selected from hydrogen, monovalent hydrocarbon groups and fluoroalkyl groups, R1" is selected from hydrogen, monovalent hydrocarbon groups and fluoroalkyl groups, and c is an integer of 0-3, and ( iii) optionally an effective amount of a curing accelerator selected from substituted guanidines, amines and mixtures thereof.

The silicon-containing agent for eliminating hydroxy groups is present in an amount of 0.5-10 parts by weight per 100 parts by weight of the organopolysiloxane.

Silazan polymers include cyclic silazanes of chemically bonded units of formula (21), wherein R "and R" "have the definitions given above and the ratio between the sum of R" "and (R" ^ jN) groups and the silicon atoms in the silazan polymer is 1.5-3.0.

The silazan polymer may also be a linear polymer with at least one unit selected from the units of formulas (25) and (26), 8300604%

* V

* - 41 - wherein R "and R" 'have the definitions given above, wherein the ratio between the sum of the R "' and (R") 2N groups and the silicate atoms in the silazan polymer is 1.5-3.0 . Furthermore, the silazan polymers may be linear polymers consisting at least substantially of units of formula (21), wherein R "and R" f have the definitions given herein, the ratio between the sum of R "r and (R" ) 2N groups and the silicon atoms in the silazan polymer is 1.5-3.0.

The silazan polymers may be polymers having at least one unit selected from the units of formulas (27) and (20), wherein R "and R" "have the above definitions, the ratio of the sum of R" and (R ") N groups and the silicon atoms in the silazan polymer is 1.5-3.

Furthermore, the silazan polymers may be polymers having a sufficient amount of units selected from those of the formulas (21), 15 (22) and (23), wherein R "and R" "have the definitions given above, wherein the ratio between the sum of the R "'and (R") 2N groups and the silicon atoms in the silazan polymer is 1.5-3.

The silazan-siloxane compounds are copolymers with up to 97 mol% units according to formula (28) of the formula sheet; most units are selected from the units of formulas (29), (18) and (30) of the formula sheet, wherein R ", R" "and c have the meanings given above and the ratio between the sum of R" * + (R ") 2N groups and the silicon atoms in the silazan-siloxane copolymer are 1.5-3.

The silazan-siloxane compounds may be cyclic compounds consisting of chemically bonded (R "1) 2 SiO units and units of formula (21), wherein R" and R "1 have the above definitions.

Furthermore, the silazan nitrogen compounds may be linear and cyclic silazanes of the formula (31) of the formula sheet, wherein R 1 and R 11 have the definitions given above, n is a positive integer and is preferably 0-20, and d is an integer with a value of 0 or 1, where, when d = 0, n is preferably 3-7.

The silazan nitrogen compounds can be polysiloxanes of the formula (32) of the formula sheet wherein R 1, R 1 and n have the definitions given above and Z is a group R 1 or -Si (R 1).

Preferred silicon nitrogen compounds are hexamethyl disilazan, hexamethylcyclotrisilazan, octamethylcyclotetrasilazan and silicon nitrogen compounds of formulas (33), (34) and (35) of the formula sheet.

8300604

Claims (3)

1. Stable, one-pack, practically anhydrous and practically acid-free, room temperature vulcanizable, organopolysiloxane-containing composition which is stable for a long time under the conditions of the environment in the absence of moisture and can be converted into a tack-free elastomer, characterized by : .. "..". " : (1) an organopolysiloxane in which the silicon atom carries at least 2 alkoxy groups at each end of a polymer chain; (2) an effective amount of a condensation catalyst; (3) a stabilizing amount of a silane as an agent for eliminating functional hydroxy groups, which silane has the formula (1) of the formula sheet, in which formula R is an organic aliphatic group of 1-8 carbon atoms selected from alkyl - alkyl ether, alkyl ester, alkyl ketone and alkyl cyano groups, or an aralkyl group with 7-13 2 carbon atoms, R represents a monovalent substituted or unsubstituted hydrocarbon group with 1-13 carbon atoms, X a hydrolyzable cleavable group · Selected from amido, amino, carbamato, enoxy, imidato, isocyanato, oximato, thioisocyanato and ureido, and c is an integer with a value of 0 - 3 and f is a number with a value of Lsyentueel, ihb from 1 to 4, where c + f equals 1-4; and Y in case X is an enoxy or amido group. represents (4) an effective amount of a curing accelerator selected from substituted guanidines, amines and mixtures thereof; and (5) 2-20 parts by weight (per 100 parts by weight of the organopolysiloxane) of a flowable polysiloxane as the first plasticizer having a high degree of tri functionality or a combination of tri and tetra functionality, and contains: (i) 5-60 mol% of monoalkylsiloxy or siloxy units or a mixture of these units; (ii) 1-6 mole% trialkylsiloxy units, and (iii) 34-94% mole dialkylsiloxy units, which polysiloxane contains about 0.1% wt% silicon bonded hydroxyl groups. 2 Rl "R'H- R" f R ". * T ~~~ V V f I I. ,, (31) (R" », - SiH - L — Si — N --— Si (R The composition of claim 1, wherein the organopolysiloxane has a viscosity of 30,000-500,000 centipolse at 25 ° C. The composition of claim 2, wherein the organopolysiloxane has a viscosity of 60,000-500,000 centipoise at 25 ° C. A composition according to claims 1-3, further comprising 5-60 parts by weight of a second plasticizer per 100 parts by weight of the organopolysiloxane, said second plasticizer being a linear, terminal triorganosiloxy containing diorganopolysiloxane having a viscosity of 10-20,000 centipoise at 25 ° C, wherein the organic groups are monovalent hydrocarbon groups 8300604 ♦, - 43 -. The composition of claim 4, wherein the amount of the second plasticizer is 10-50 parts by weight. 6. A composition according to claim 4 or 5, wherein the second plasticizer 20 is a polymer of formula (11), in which formula R represents a monovalent hydrocarbon group and t varies such that. the viscosity of the polymer ranges from 10 to 20,000 centipoise at 25 ° C. 20 The composition of claim 6, wherein R is methyl and t is such that the polymer viscosity is 10-10,000 centipoise at 25 ° C, and the second plasticizer has a hydroxy content of 500-1500 parts per million. A composition according to claims 1-7 containing 100-300 parts by weight of an excipient filler per 100 parts by weight of the organopolysiloxane. The composition of claim 8, wherein the excipient is a calcium carbonate filler. The composition of claim 9, wherein the calcium carbonate is treated with stearic acid. 11. A composition according to claims 1-10, containing 1-50 parts by weight of a reinforcing filler per 100 parts by weight of the organopolysiloxane. The composition of claim 11, wherein the reinforcing filler is an anti-sagging τπ-ίddfti, such as gas phase silica, which is present in a concentration of 1-10 parts by weight per 100 parts by weight of the organopolysiloxane. . 13. Composition according to claims 1-12, containing 0.1-2.0 parts by weight (per 100 parts by weight of the organopolysiloxane) of a (optionally second) anti-sagging agent, namely a polyether according to the formula (12) or (13), wherein A and B represent groups selected from hydrogen, alkyl groups of 1-12 carbon atoms, cycloalkyl groups of 5-7 carbon atoms in the ring, aryl groups of 1 and 2 aromatic rings and mononuclear aryl-low alkyl groups, wherein the alkyl groups bonded to the aromatic core contain a total of at most 5 carbon atoms, and groups of formula (14), wherein R is an alkyl group of 1-11 carbon atoms; Q is a residue of a polyhydric initiator containing at least 35 2 hydroxyl groups and is selected from ethylene glycol, glycerol, trimethylolpropane and other polyhydric alcohols containing 2-6 hydroxyl groups; n represents a number just representing a value of 2-4; y has a value of 2-10; and z has a value from 1-5; which polyether has a molecular weight of about 300-200,000. 83 0 0 SO 4 »* Λ - 44 - A composition according to claims 1-13 containing 0.2-2.0 parts by weight of hydrogenated castor oil as an anti-sagging agent per 100 parts by weight of the organopolysiloxane. 15. A composition according to claims 11-14, wherein the reinforcing filler prior to incorporation into the composition has been treated with cyclopolysiloxane. 16. A composition according to claims 1-15, containing 0.1 to 10 parts by weight of an agent of formula (15) for promoting adhesion, in which formulas R and R are selected from monovalent hydrocarbon groups with 1-8 carbon atoms, R ^ and R ^ are selected from hydrogen and 34 monovalent hydrocarbon radicals with 1-8 carbon atoms. R is selected 33. . from hydrogen and alkyl groups of 1-3 carbon atoms, R is selected from hydrogen and methyl, R and RJ are selected from divalent hydrocarbon groups of 1-12 carbon atoms and p is an integer with a value of 0-3. The composition of claim 16, wherein the adhesion promoter has the formula (16). A composition according to claims 1-17, wherein the silane is a compound of formula (4), wherein R, R and X have the meanings given in claim 1, a a number with a value of 1 or 2 and b represents a number 20 with a value of 0 or 1, the sum b + a = 1 or 2, which silane is both an agent for eliminating functional hydroxy groups and a cross-linking agent for introducing at least 2 alkoxy groups to the silicon atoms at each end of the organopolysiloxane chain. 19. A composition according to claims 1-18, containing an organopoly-siloxane with polyalkoxy-terminated polyalkoxy-containing organopolysiloxane-containing polyalkoxy is a material of formula (7), in which formula R represents a monovalent substituted or unsubstituted hydrocarbon group having 1 to 13 carbon atoms, R * represents an organic aliphatic group of 1-8 carbon atoms selected from alkyl, alkyl ether, alkyl ester, alkyl ketone and alkyl cyano groups, or an aralkyl group having 7-13 carbon atoms, R represents a monovalent substituted or unsubstituted hydrocarbon group with 1-13 carbon atoms represents X is a hydrolyzable cleavage group selected from amido, amino, carbamato, enoxy, imidato, isocyanato, oximato, thioisocyanato and ureido, and is an integer with a value of 0 or 1 and e represents an integer with a value of 0 or 1, where the sum b + e equals 0 or 1, and n a number with a value of approximately 50 - 25 00 represents. A composition according to claims 1-19, containing an effective amount of a cross-linking silane of formula (5), wherein R is an 8300604-45 - organic aliphatic group with 1-8 carbon atoms selected from alkyl, alkyl ether, alkyl ester , alkyl ketone and alkyl cyano groups, or an aralkyl-2 group with 7-13 carbon atoms, R represents a monovalent substituted or unsubstituted hydrocarbon group with 1-13 carbon atoms-5 and b is an integer with a value of 0 or 1 . A composition according to claims 1-20, wherein the silane serving as an elimination agent for hydroxy groups is methyl dimethoxy (N-methyl acetamido) silane. 22. A composition according to claims 1-21, containing a tin compound as a condensation catalyst. The composition of claim 22, wherein the tin compound is dibutyltin diacetate. 1 2 A composition according to claims 1-23, wherein R, R and R are methyl. A composition according to any of the preceding claims comprising a polydimethylsiloxane with polymethoxy terminated, an effective amount of a tin-containing condensation catalyst and a stabilizing amount of a polymethoxy-di-n-hexamino-silane. 26. A composition according to any one or more of the preceding claims, comprising a polydimethylsiloxane with terminal polymethoxy, an effective amount of a tin-containing condensation catalyst, an effective amount of trimethoxysilylpropyltetramethylguanidine as a curing accelerator and a stabilizing amount of a polymethoxyacetamidosilane. 27. A composition according to claims 20-26, containing a polymethoxy-silane crosslinking agent. A composition according to claim 1, characterized by (i) 100 parts by weight of a silanol-free or practically silanol-free polyalkoxy-siloxydiorganopolysiloxane of formula (7), (ii) 0-10 parts of a cross-linking polyalkoxy silane of formula 30 (5) (iii) an effective amount of a condensation catalyst, and (iv) a stabilizing amount of a silane of an agent for the elimination of functional hydroxy groups of formula (1), in which formulas R is a monovalent stabilized or unsubstituted hydrocarbon group with 1-13 carbon atoms, R * represents an organic aliphatic group with 1-8 carbon atoms selected from alkyl, alkyl ether, alkyl ester, alkyl ketone and alkyl cyano groups, or an aralkyl group with 7-13 carbon 2 atoms, R a monovalent substituted or unsubstituted hydrocarbon group with 1-13 carbon atoms, X a hydrolysable cleavage 8300604 - 46% c group, selected from amido, amino, carbamat o, enoxy, imidato, isocyanato, oximato, thioisocyanato and ureido, b an integer with a value of 0 or 1, e an integer with a value of 0 or 1, where the sum b + e is 0 or 1, n a number with a value of about 50 - 2500, c a whole number with a value of 0 - 3 ·, f an integer with a value of 1-4, where the sum c + 'f is 1 - 4 ; and or amido (v) when X represents enoxy, 0.1-5 parts by weight of a curing accelerator selected from substituted guanidines, arnines and mixtures thereof / and 10 (vi) 2-20 parts by weight (per 100 wt. parts of the organopolysiloxane) of a flowable polysiloxane as the first plasticizer, which has a high degree of tri-functionality or a combination of tri- and tetra-functionality, and contains: (a) 5-60 mole% monoalkylsiloxy or siloxy units or a mixture of these units; (b) 1-6 mol% trialkylsiloxy units, and (c) 34-94 mol% dialkylsiloxy units, which polysiloxane contains about 0.1-2% by weight silicon-bonded hydroxyl groups. The composition of claim 28, wherein the organopolysiloxane 20 has a viscosity of 60,000-500,000 centipoise at 25 ° C. A composition according to claim 28 or 29 containing 5-60 parts by weight of a second plasticizer per 100 parts by weight of the organopolysiloxane, said second plasticizer being a linear, terminal triorganosiloxy containing diorgano-polysiloxane having a viscosity of 10-20,000 centipoise at 25 ° C, where the organic groups are monovalent hydrocarbon groups. 31. The composition of claim 30, wherein the second plasticizer is a polymer of formula (11), in which formula R represents a monovalent hydrocarbon group and t varies such that the viscosity of the polymer ranges from 10 to 20,000 centipoise at 25 ° C. 20 The composition of claim 3-1, wherein R is methyl and t is such that the polymer viscosity is from 10 to 10,000 centipoise at 25 ° C, and the second plasticizer has a hydroxy content of from 500 to 1500 parts per million. 33. A composition according to claims 28-32 containing 100-300 parts by weight of an excipient filler per 100 parts by weight of the organopolysiloxane. The composition of claim 33, wherein the excipient serving as a filler is calcium carbonate. The composition of claim 34, wherein the calcium carbonate 8300604-147 has been treated with stearic acid. 36. Composition according to. claims 28-35, containing 1-50 parts by weight of a reinforcing filler per 100 parts by weight of the organopolysiloxane. 37. A composition according to claim 36, wherein the reinforcing filler is an anti-sagging agent, such as gas phase silica, which is present in a concentration of 1-10 parts by weight per 100 parts by weight of the organopolysiloxane. . 38. A composition according to claims 28-37, containing 0.1-2.0 parts by weight (per 100 parts by weight of the organopolysiloxane) of a (optionally second) anti-sagging agent, namely a polyether according to formula (12) - or (13), wherein A and B represent groups selected from hydrogen, alkyl groups of 1-12 carbon atoms, cycloalkyl groups of 5-7 carbon atoms in the ring, aryl groups of 1 and 2 aromatic rings and mononuclear aryl-low alkyl groups, in which the alkyl groups bonded to the aromatic core contain a total of at most 5 carbon atoms, and groups of formula (14), wherein R is an alkyl group with 1-11 carbon atoms? Q is a residue of a polyhydric initiator containing at least two hydroxyl groups and is selected from ethylene glycol, glycerol, trimethylol propane and other polyhydric alcohols with 2-6 hydroxyl-20 groups? n represents a number with a value of 2-4; y has a value of 2-10; and z has a value of 1-5, the polyether having a molecular weight of about 300-200,000. 39. A composition according to claims 28-38 containing 0.2-2.0 parts by weight of hydrogenated castor oil as anti-sagging agent per 100 parts by weight of the organopolysiloxane. The composition of claims 11 to 39, wherein the reinforcing filler prior to incorporation into the composition has been treated with cyclopolysiloxane. A composition according to claims 28-40, containing 0.1-10 parts by weight of an adhesion promoter, a compound 30 of formula (15), wherein R 1 and are selected from monovalent carbon 32 36 hydrogen groups with 1-8 carbon atoms, R and R are selected from two- 38 40 divalent hydrocarbon groups with 1-12 carbon atoms, R and R are selected from hydrogen and monovalent hydrocarbon groups with 1-8 carbon-34 atoms, R is selected from hydrogen and alkyl groups of 1-3 carbon-33 atoms, R represents hydrogen or methyl, and p is an integer of 0-3. The composition of claim 41, wherein the adhesion promoter has the formula (16). 12 A composition according to claims 28-42, wherein R, R and R are methyl 8300604 V-48-v I. The composition of claims 28-43, wherein the condensation catalyst is a tin compound. 45. A composition according to claims 28-44 containing a polydimethyl-5 siloxane with polymethoxy terminal. A composition according to claims 28-45, containing a polymethoxy silane. The composition of claim 46, wherein the polymethoxysilane is methyl trimethoxysilane. A composition according to claims 28-47, containing a tin compound as a condensation catalyst. 49. A composition according to claims 28-48 containing as substituted guanidine butyltetramethylguanidine. 50. A composition according to claims 28-48, containing as organic amine a dialkylamine. 51. A composition according to claim 1 containing polydimethylsiloxane with methyldimethoxysolixy terminated, a reinforcing amount of octamethylcyclotetrasiloxane treated as a filler, an effective amount of dibutyltin diacetate as condensation catalyst, tri-methoxysilylpropyltetramethylguanidin or dimethylnardine-dimethyl-guanidine or dimethyl-guinidine. excess to 3% by weight (based on the weight of the polydimethylsiloxane) of methyl dimethoxy-N-methyl acetamidosylan or methyl dimethoxyisopropenoxysilane. The composition of claim 51, containing 10 parts by weight. methyl trimethoxysilane per 100 parts by weight. of the polydimethylsiloxane. 53. Process for the preparation of a one-pack and practically acid-free, room temperature vulcanizable composition which is hard-bristled to the solid elastomeric state, characterized in that, under practically anhydrous conditions, a temperature in the range of from 0 ° - 180 ° C stirs a material which is vulcanizable at room temperature, which is selected from (i) a mixture containing (a) 100 parts by weight. of a terminal silanol-containing polydiorgano-siloxane, which at least substantially consists of chemically bonded units of formula (3) (b) a stabilizing amount of a silane of formula (1) for the elimination of functional hydroxy groups, (c) 0-10 parts by weight. of a crosslinking silane of formula (5) (d) an effective amount of a condensation catalyst, and 8300604 Λ i J '- 49 - (β) O - 5 parts by weight. of a curing accelerator selected from substituted guanidines, taiines and mixtures thereof; and (ii) a mixture containing (a) 100 parts by weight. of a polyalkoxy-containing polydi-5 organosiloxane of formula (7), (b) 0-10 parts by weight of a crosslinking silane of formula (5), (c) an effective amount of a condensation catalyst, (d ) a stabilizing amount of a silane of formula (1) to eliminate functional hydroxy groups, 10 (e) 0-5 parts by weight. of a curing accelerator selected from substituted guanidines, amines and mixtures thereof,. in which formulas R is selected from monovalent substituted or unsubstituted hydrocarbon groups of 1-13 carbon atoms, R an organic aliphatic group of 1-8 carbon atoms, selected from alkyl, alkyl ether, alkyl ester, alkyl ketone and alkyl cyano groups, or a alkaryl-2 group with 7-13 carbon atoms, R represents a monovalent substituted or unsubstituted hydrocarbon group with 1-13 carbon atoms, X represents a hydrolyzable cleavable group selected from amido, amino, carbamato, enoxy, imidato, isocyanato, oximato, thioiso-20 cyanato and uréido, a is a number with a value of 1 or 2 and b is a number with a value of 0 or 1, where the sum a + b equals 1 or 2, e is a number with a is a value of 0 or 1 and b + requirement equal 0 - 1, n represents a number with a value of approximately 50 - 2500, c is a number with a value of 0 - 3, f represents a number with a value of Is 1 - 4 and the sum of 25 c + f equals 1-4, and = if necessary, in the case When X is enoxy or amido, 0.1-5 parts by weight are also included in both mixtures before or together with the hydroxy group eliminator. of a curing accelerator selected from substituted guanidines, amines and mixtures thereof, and from 2 to 20 parts by weight, per 100 parts by weight. of the organopolysiloxane, of a flowable polysiloxane as the first plasticizer, which polysiloxane has a high degree of tri functionality or a combination of tri and tetra functionality, and contains: (i) 5-60 mol% monoalkylsiloxy or siloxy units or a mixture of these units; (ü) 1-6 mole% trialkylsiloxy units, and (iii) 34-94 mole% dialkylsiloxy units, which polysiloxane contains about 0.1-2% by weight silicon-bonded hydroxy groups. 54. Process according to claim 53, characterized in that the organo-polysiloxane has a viscosity in the range of 60,000 - 500,000 centipoise 8300604 ............ -50 - at 25 ° C. 55. Process according to claim 53 or 54, characterized in that 5 - 60 parts by weight are also used. of a second plasticizer per 100 parts by weight of the organopolysiloxane, the second plasticizer being a linear terminal triorganosiloxy containing diorganopolysiloxane having a viscosity of 10-20,000 centipoise at 25 ° C, wherein the organic groups are monovalent hydrocarbon groups. 56. Process according to claim 55, characterized in that the second plasticizer is a polymer of formula (11), in which formula R represents a monovalent hydrocarbon group and t varies such that the viscosity of the polymer ranges from 10 to 20,000 centipoise Bee. 25 ° C. 20 57. Process according to claim 56, characterized in that R is methyl, t has such a value that the polymer viscosity is 10-15,000 centipoise at 25 ° C and the second plasticizer has a hydroxy content of 500-1,300 parts per million possession. 58. Process according to claims 53-57, characterized in that 100-300 parts by weight are used. of a filler serving as an extender per 100 parts by weight. of the organopolysiloxane. 59. Process according to claim 58, characterized in that calcium carbonate is used as the adjuvant filler. 60. Process according to claim 59, characterized in that calcium carbonate treated with stearic acid is used. 61. Process according to claims 53-60, characterized in that 25-150 parts by weight are used. of a reinforcing filler per 100 parts by weight. of the organo-polysiloxah. 62. Process according to claim 61, characterized in that an anti-settling agent is used as the reinforcing filler, for example silicon oxide obtained from the gas phase, in a concentration of 1-10 parts by weight. per 100 parts by weight. of the organopolysiloxane. 63. Process according to claims 53-62, characterized in that 0.1-2.0 parts by weight, per 100 parts by weight. of the organopolysiloxane, of a (optionally second) anti-sagging agent used, namely a polyether of formula (12) or (13), wherein A and B represent groups selected from hydrogen, alkyl groups of 1-12 . carbon atoms, cycloalkyl groups with 5-7 carbon atoms in the ring, aryl groups with 1 and 2 aromatic rings and single-core aryl-lower alkyl groups in which the alkyl groups bound to the aromatic core contain a total of at most 5 carbon atoms, and groups according to formula (14) 40 wherein R represents an alkyl group of 1-11 carbon atoms; Q is a residue 8300604-51 - of a polyhydric initiator containing at least 2 hydroxyl groups and selected from ethylene glycol, glycerol, trimethylol propane and other polyhydric alcohols with 2-6 hydroxyl groups; n represents a number with a value of 2 - 4, y represents a number with a value of 2 - 10 and z represents a number 5 with a value of 1-5; which polyether has a molecular weight of about 300-200,000. 64. Process according to claims 53 -63, characterized in that hydrogenated castor oil in an amount of 0.2-2.0 parts by weight. per 100 parts by weight. of the organopolysiloxane as anti-sagging agent. 65. Process according to claims 61-64, characterized in that an reinforcing filler is used which has been treated with cyclopolysiloxane before incorporation into the composition. 66. Process according to claims 53-65, characterized in that 0.1-10 parts by weight are used. of an adhesion promoter, a compound of formula (15), wherein and selected from monovalent hydrocarbon radicals having 1-8 carbon atoms, 32 36 R and R are selected from divalent hydrocarbon radicals having 1-12 carbon atoms, R ^ and R ^ are selected from hydrogen and monovalent hydrocarbon radicals having 1-8 carbon atoms, R is selected from hydrogen 33 and alkyl radicals having 1-3 carbon atoms and R represents hydrogen or methyl, and p is an integer with is a value from 0 - 3. 67. Process according to claim 66, characterized in that a compound according to formula (16) is used as the adhesion promoter. 68. Process according to claims 53-67, characterized in that R, R 2 and R are methyl. 69. Process according to claims 53-68, characterized in that the hardening accelerator used is silylated guanidine or an alkylguanidine. 70. Process according to claims 53-69, characterized in that the silane used to eliminate hydroxy groups is polymethoxyacetamido-silane. 71. Process according to claims 53-70, characterized in that methyltrimethoxysilane is used as crosslinking silane. 72. Process according to claims 53-71, characterized in that a tin compound is used as the condensation catalyst. 73. Process according to claim 71 or 72, characterized in that methyl dimethoxy (n-methylacetamido) silane is used to eliminate hydroxy groups. 8300604 - 52 - 74. Mixture, characterized by (a) 100 parts by weight. of a terminal silanol-containing polydiorgano-siloxane, at least substantially consisting of chemically bonded units of formula (3), 5 (b) a stabilizing amount of a silane of formula (1) to eliminate functional hydroxy groups (c) 0-10 parts by weight. of a crosslinking silane of formula (5) (d) an effective amount of a condensation catalyst, and (e) 0-5 parts by weight. a curing accelerator selected from substituted guanidines, amines and mixtures thereof, wherein formulas R, R, R, X, a and b have the meanings given in claim 53; optionally, especially when X enoxy qf is amido, 0.1-5 parts by weight. 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 organo-polysiloxane, of a flowable polysiloxane as the first plasticizer, which polysiloxane has a high degree of tri functionality or a combination of tri and tetra functionality, and contains: (i) 5 - 60 mol% monoalkylsiloxy or siloxy -units or a combination of 20 of these units; (ii) 1-6 mol% trialkylsiloxy units, and (iii) 34-94 mol% dialkylsiloxy units, which polysiloxane contains about 0.1-2% by weight silicon-bonded hydroxyl groups. 75. The mixture of claim 74, wherein the organopolysiloxane has a viscosity of 60,000-500,000 centipoise at 25 ° C. 76. Mixture according to claim 74 or 75. containing 50-60 parts by weight. of a second plasticizer per 100 parts by weight. of the organopolysiloxane, which second plasticizer is a linear terminal triorganosiloxy containing diorganopolysiloxane having a viscosity of 10-20,000 centipoise at 25 ° C, wherein the organic groups are monovalent hydrocarbon groups. 77. Mixture according to claims 74-76, characterized in that the second plasticizer is a polymer according to formula (11), wherein R is a monovalent hydrocarbon group and t varies such that the viscosity of the polymer ranges from 10 to 20,000 centipoise at 25 ° C. 20 The mixture according to claim 77, wherein R is methyl, t has such a value that the viscosity of the polymer is from 10 to 10,000 centipoise at 25 ° C, and the polymeric second plasticizer has a hydroxy content of from 500 to 1500 parts per million. 79. Mixture according to claims 74-78, containing 100-300 parts by weight. 83 0 0 6 0 4 «* ί - 53 - of an extenders filler per 100 parts by weight. of the organopolysiloxane. A mixture according to claim 79 / wherein the excipient serving as an extender is calcium carbonate. The mixture of claim 80, containing stearic acid treated calcium carbonate. 82. Mixture according to claims 74-81, containing 1-50 parts by weight. of a reinforcing filler per 100 parts by weight. of the organopolysiloxane. 83. Mixture according to claim 82, wherein the reinforcing filler is an anti-sagging agent, such as gaseous phase silica, and is present in a concentration of 1-10 parts by weight. per 100 parts by weight. of the organopolysiloxane. 84. Mixture according to claims 74-83, containing 0.1-2.0 parts by weight, per 100 parts by weight. of the organopolysiloxane, of a (optionally second) anti-sagging agent, namely a polyether of formula (12) or (13), wherein A, B, Q, n, y and z have the meanings given in claim 13 to own; which polyether has a molecular weight of about 300-200,000. 85. Mixture according to claims 74-84, containing a hydrogenated castor oil as anti-sagging agent in an amount of 0.2 parts by weight per 100 parts by weight. of the organopolysiloxane. A mixture according to claims 82-85, wherein the reinforcing filler is treated with cyclopolysiloxane before incorporation into the composition. 87. Mixture according to claims 74-86, containing 0.1-10 parts by weight. An adhesion promoter, a compound of formula (15), wherein the various symbols have the meanings given in claim 16. A mixture according to claim 87, characterized in that the adhesion promoter is a compound of formula (16). 89. A process for preparing a practically acid-free, room temperature vulcanizable, organopolysiloxane-containing composition under practically anhydrous conditions using a silanol-containing organopolysiloxane and a cross-linking polyalkoxy silane in combination with an effective amount of a condensation catalyst, characterized in that a stabilizing amount of a polyalkoxy silane which is both an agent for eliminating functional hydroxy groups and a crosslinking agent is added to the terminal silanol-containing organopolysiloxane, which poly-1-alkoxy silane is a compound of formula (4), wherein R , R, X, b and a 8300604-54 - e have the meanings given in claim 53, and thereafter add an effective amount of a condensation catalyst, thereby improving the resulting organopolysiloxane-containing composition which is vulcanizable at room temperature stability, and optionally, especially when X enoxy or amido-SnTsT before or together with the agent for eliminating the hydroxy groups, adds an effective amount of a curing accelerator, which curing accelerator is selected from substituted guanidines, amines and mixtures of this, and 2 - 20 parts by weight, per 100 parts by weight. from the organopolysiloxane, from a liquid silicone as the first plasticizer, the poly-siloxane having a high degree of tri functionality or a combination of trien tetra functionality; (i) 5-60 mol% of monoalkylsiloxy or siloxy units or a combination of these units; (ii) 1-6 mol% trialkylsiloxy units, and 15 (iii) 34-94 mol% dialkylsiloxy units, which polysiloxane contains about 0.1-2% by weight silicon bonded hydroxyl groups. 90. Process according to claim 89, characterized in that an organopolysiloxane with a viscosity of 60,000-500,000 centipoise at 25 ° C is used. 91. Process according to claim 89 or 90, characterized in that 5-60 parts by weight are also used. of a second plasticizer per 100 parts by weight. of the organopolysiloxane, which second plasticizer is a linear terminal triorganosiloxy containing diorganopolysiloxane having a viscosity of 10-20,000 centipoise at 25 ° C, wherein the organic groups are monovalent hydrocarbon groups. 92. A process according to claim 91, characterized in that the second plasticizer is a polymer according to formula (11), wherein R and t have the meanings given in claim 6. 20 93. Process according to claim 92, characterized in that R is methyl, 30. has a value such that the viscosity of the polymer is 10 - 10,000 centipoise at 25 ° C, and the second plasticizer has a hydroxy content of 500 - 1500 parts per million. 94. Process according to claims 89 - 93, characterized in that 100 - 300 parts by weight. of a filler serving as an extension agent per 100 wt. 35 parts. of the organopolysiloxane. 95. Process according to claim 94, characterized in that calcium carbonate is used as the adjuvant filler. 96. Process according to claim 95, characterized in that calcium carbonate treated with stearic acid is used. 97. Process according to claims 89 - 96, characterized in that 8300604 - 55 - 1-50 parts by weight. of a reinforcing filler per 100 parts by weight. of the organopolysiloxane. 98. Process according to claim 97, characterized in that as the reinforcing filler an anti-settling agent, for example 5 gaseous oxide obtained from the gas phase, in a concentration of 1-10 wt. parts. per 100 parts by weight. of the organopolysiloxane. 99. Process according to claims 89-98, characterized in that 0.1-2.0 parts by weight. of a polyether as anti-sagging agent per 100 parts by weight. of the organopolysiloxane, which polyether 10 is a compound of formula (12) or (13), wherein A, B, Q, n, y and z have the meanings given in claim 13, and a molecular weight of about 300-200,000 possession. 100. A process according to claims 89-99, characterized in that hydrogenated castor oil is used as an anti-sagging agent in an amount of 0.2-2.0 parts by weight. per 100 parts by weight. of the organopolysiloxane. 101. Process according to claims 97-100, characterized in that an reinforcing filler is used which has been treated with cyclopolysiloxane before incorporation into the composition. 102. Process according to claims 89-101, characterized in that a compound of formula (15) in an amount of 0.1-10 parts by weight is used as an agent for promoting adhesion. includes in the composition in which formula the various symbols have meanings given in claim 16. The process according to claim 102, characterized in that a compound of formula (16) is used as the adhesion promoter. 104. Process according to claims 89-103, characterized in that as means for the elimination of hydroxy groups methyldimethoxy-N-methyl-acetamidosilane is used. 105. Process according to claims 89-103, characterized in that as means for the elimination of hydroxy groups, methyl dimethyl oxyisopropenoxy silane is used. 106. Process according to claims 89-103, characterized in that methyltriisopropehoxysilane is used as agent for the elimination of hydroxy groups. 107. Process according to claims 89-106, characterized in that an effective amount of dibutyltin diacetate is used as condensation catalyst. 8300604> * V *% s' ........- 56 - 108. Process for preparing a practically acid-free, room temperature vulcanizable, organopolysiloxane-containing composition under practically anhydrous conditions, using an organopolysiloxane in which the silicon atom carries at least two alkoxy groups at each end of a polymer chain and a condensation catalyst, with the characterized in that to the terminal polyalkoxy-containing organopolysiloxane is added: (1) a stabilizing amount of a silane of formula (1) to eliminate functional hydroxy groups, in which formula, R, R, X, c and f are as defined in claim 1 given meanings, 10 and (2) an effective amount of a condensation catalyst, thereby providing the resulting room temperature vulcanizable organopolysiloxane-containing composition with improved stability, and (3). when X is enoxy, before or together with it. means for eliminating hydroxy groups an effective amount of a curing accelerator selected from substituted guanidines, amines, and mixtures thereof, and (4) 2-20 parts by weight, per 100 parts by weight. of the organopolysiloxane, of a polysiloxane defined in claim 1 as the first plasticizer. 109. Process according to claim 108, characterized in that an organopolysiloxane with a viscosity of 60,000-500,000 Centipoise 20 is used at 25 ° C. 110. Process according to claim 108 or 109, characterized in that further 5-60 parts by weight are added. of a second plasticizer per 100 parts by weight. of the organopolysiloxane, which second plasticizer is a linear terminal triorganosiloxane containing diorganopolysiloxane having a viscosity of 10-20,000 centipoise at 25 ° C, wherein the organic groups are monovalent hydrocarbon groups. 111. Process according to claim 110, characterized in that the second plasticizer used is a polymer according to formula (11), and which formulas R "and t have the meanings given in claim 6. 20 112. Process according to claim 111, characterized in that R is methyl, t has such a value that the viscosity of the polymer is 10 - 10,000 centipoise at 25 ° C, and the polymer the second plasticizer has a hydroxy content of 500 - 1500 parts per million. 113. Process according to claims 108 - 112, characterized in that 100 - 300 parts by weight are used. of a filler serving as an extension agent per 100 wt. parts. of the organopolysiloxane. 114. Process according to claim 113, characterized in that calcium carbonate is used as the adjunct filler. 115. Process according to claim 114, characterized in that calcium carbonate treated with 8300604 w -57-stearic acid is used. 116. Process according to claims 108-115, characterized in that 1-50 parts by weight are used. of a reinforcing filler per 100 parts by weight. of the organopolysiloxane. 117. Process according to claim 116, characterized in that as the reinforcing filler an anti-settling agent, for example silica obtained from the gas phase, in a concentration of 1-10 wt. parts. per 100 parts by weight. of the organopolysiloxane. 118. Process according to claims 108 - 117, characterized in that 0.1 - 2.0 parts by weight, per 100 parts by weight. of the organopolysiloxane, of a polyether used as (optionally second) anti-sagging agent, said polyether being a compound of formula (12) or (13), wherein the different symbols have the meanings given in claim 13, and a molecular weight from approx. 300-200,000 possessions. 119. Process according to claims 108-118, characterized in that 0.2-2.0 parts by weight. hydrogenated castor oil as anti-settling agent per 100 parts by weight. of the organopolysiloxane. 120. Full-mesh method claims 116 - 119, characterized in that an reinforcing filler is used which has been treated with cyclopolysiloxane before incorporation into the composition. 121. Process according to claims 108-120, characterized in that 0.1-10 parts by weight of an adhesion promoter is used, namely a compound according to formula (15), in which the various symbols have the meanings given in claim 16. 122. Process according to claim 121, characterized in that a compound of formula (16) is used as the adhesion promoter. 123. Process according to claims 108-122, characterized in that as means for the elimination of hydroxy groups methyldimethoxy-N-methyl-acetamidosilane is used. 124. Process according to claims 108-122, characterized in that methyl-dimethoxyisoprope-noxysilane is used as agent for the elimination of hydroxy groups. 125. Process according to claims 108-122, characterized in that a stabilizing amount of methyl triisopropenoxysilane and an effective amount of methyl trimethoxysilane are used. 126. Process according to claims 108-125, characterized in that an effective amount of dibutyltin diacetate is used as condensation catalyst. 8300604 - 58 -. Η * V% 127. Stable, one-pack, practically anhydrous and practically acid-free, room temperature vulcanizable organopolysiloxane-containing composition which is stable for a long time in the absence of moisture under ambient conditions and can be converted into a tack-free elastomer, characterized by: (1 an organopolysiloxane in which the silicon atom carries at least two alkoxy groups at each end of a polymer chain; (2) an effective amount of a condensation catalyst, (3) a stabilizing amount of a silane serving as an agent for eliminating functional hydroxy groups, namely a silicon-nitrogen-10 compound selected from: (A) a silicon nitrogen compound of the formula (17), wherein »Y is selected from R'1 'and R” N-, (B) a silicon nitrogen polymer containing (i), 3 - 100 mol% chemically bonded units selected from units of the formulas (18), (19) ', (29), (21), (22) and (23), and (ii) 0-97 mol% of chemically bonded units of the formula ( 24), and mixtures thereof, wherein the silicon atoms of the silicon nitrogen polymer are bonded together via a SiOSi bridging group or a SiNR '' Si bridging group, the free valencies of the silicon atoms other than those forming a siloxy unit bound to oxygen, and nitrogen to form a silazy unit, an R '' group and / or an (R '' Y ^ N group b inden, wherein the ratio between the sum of the R'11 groups and the (R '') ^ N groups and the silicon atoms of the silicon nitrogen polymer is 1.5-3, and R '' is selected from hydrogen, monovalent hydrocarbon groups and fluoroalkyl groups, R'11 is selected from hydrogen, monovalent hydrocarbon groups and fluoroalkyl groups, and c is an integer value from 0 to 3, and (iii) 2 to 20 parts by weight, per 100 wt. .dln. of the "organopolysiloxane, of a liquid polysiloxane as the first plasticizer, which has a high degree of triphenolality or a combination of tri- and tetra-30 functionality, and contains: (i) 5-60 mol% monoalkylsiloxy or siloxy units or a combination of these units: (ii) 1-6 mole% trialkylsiloxy units, and (iii) 34-94 mole% dialkylsiloxy units, which polysiloxane contains about 0.1-235% by weight silicon bonded hydroxyl groups. The composition of claim 127, wherein the organopolysiloxane has a viscosity of 60,000-500,000 centipoise at 25 ° C. 129. A composition according to claim 127 or 128 containing 5-60 wt. parts. of a second plasticizer per 100 parts by weight. of the organopolysiloxane (8300604 • Λ <* Λ ,, h - 59 - which second plasticizer is a linear terminal triorganosiloxy containing diorganopolysiloxane having a viscosity of 10-20,000 centipoise at 25 ° C, wherein the organic groups are monovalent hydrocarbon groups. 130. The composition of claim 129, wherein the second plasticizer 20 is a polymer of formula (11), wherein R represents a monovalent hydrocarbon group and t varies such that the viscosity of the polymer ranges from 10 to 20,000 centipoise at 25 ° C. 20 131. The composition of claim 130, wherein R is methyl, t has a value such that the viscosity of the polymer is 10 - 10,000 centipoise at 25 ° C, and the polymeric second plasticizer has a hydroxy content of 500 - 1500 parts per million. 132. A composition according to claims 127-131 containing 100-300 parts by weight. filler serving as extension agent per 100 parts by weight. of the organopolysiloxane. 133. The composition of claim 132, wherein the extender filler is calcium carbonate. The composition of claim 133, wherein the calcium carbonate is treated with stearic acid. 135. A composition according to claims 127-134 containing 1-50 wt. 20 parts. of a reinforcing filler per 100 parts by weight. of the organopoysiloxan. The composition of claim 135, wherein the reinforcing filler is an anti-settling agent, for example, gaseous phase silica, which is present in a concentration of 1-10 parts by weight. per 100 parts by weight. of the organopolysiloxane. 137. A composition according to claims 137-136, containing 0.1-2.0 parts by weight, per 100 parts by weight. of the organopolysiloxane, of a polyether as (optionally second) anti-sagging agent, said polyether being a compound of formula (12) or (13), wherein the different symbols have the meanings given in claim 13, and a molecular weight of approx. 300 - 200,000 possession. 138. A composition according to claims 127-137 containing 0.2-2.0 parts by weight. hydrogenated castor oil as anti-sagging agent per 100 parts by weight. of the organopolysiloxane. 139. A composition according to claims 135-138, wherein the reinforcing filler is treated with cyclopolysiloxane before incorporation into the composition. 140. A composition according to claims 127-139, containing 0.1-10 parts by weight. of an adhesion promoter, a compound of formula (15), wherein the various symbols have the meanings given in claim 8300604-60 - claim 16. The composition of claim 140, wherein the adhesion promoter is a compound of formula (16). * 8300604 S 2343-1233 Ned. - Attachment 3 . General Electric Company of Schenectady, New York, United States of America ^ 2? I ,,, I; (2) K0 - sio — 1 — h (R 0.4- (g + £) Sl (X, f ..... yy · "· n. 'T' - - R 2 'i (?> B (3) I10. '-M) (Rl °) 4- (a + b) SifW, · R. - "' <f> = '' · (5) (Rl °> 4-b 81 (6) tRlo) 4-1 = + 3) s ** <j (f> b R (R2) b (7) (Rl °> 3- (b + e) | i0— | i0 - ^? i (0Rl, 3 - (b + e) 'XR η X ·. * · ee (H4) Nn (ZthSUQB · 1 ·), 5 CM-P / - (8) 9 · 4 5 ---------- ( R) 2N <l • V ..... R20 I R20 ίΡ'5 '2 "NmJ-R6 · U)' R20-SiO - Sio - R20 <10> (R> 2N.> Τ! 2 ° (L2) »-« - iy2xoirB. (131 ,; (14) R — I — 0— '' R31 O R33.:. R34 'R38 3 · 32 32 · ii 3δ I 40 (15) (RO) , Si — R - ^ 0 — C — CHCH_ — N —- R —N - ^ - R 3-p 2 8300604 I - - 2 - O II (16) NH2-CH2-CH2-N-CH2-CH-C —0 (CH2) 3Si (OC. ^) 3 Η '. CiI3 R "_' · '(17) I (Y) (R, M) 2Si N Si (Rm) Y * · ..-' Rm Rm R ". 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