JPH0543803A - Low modulous one component rtv composition and preparation thereof - Google Patents

Abstract

PURPOSE: To obtain a room temp. curable compsn. low in modulus and excellent in fast curability, storage stability and thixotropicity by compounding silanol terminated polydiorganosiloxzane, a silane sweeping agent, crosslinking silane and a condensation catalyst.

CONSTITUTION: The title compsn. is obtained by mixing 100 pts.wt. of silanol terminated polydiorganosilane substantially composed only of a chemical bonding unit represented by formula I (wherein R is a 1-13C hgydrocarbon group) (A), a silane sweeping agent for a hydroxy functional group represented by formula II (wherein R¹ is a 1-8C aliphatic org, group selected form a group consisting of specific groups such as an alkyl group and the like or a 7-13C alkaryl group; R² is a 1-13C hydrocarbon group; X is a hydrolyzable elimination group selected from a group consisting of specific groups such as an amide group and the like; a is 1 or 2; b is 0 or 1 and a+b is 1 or 2) contained in an amt. within a stabilizing action exerting range (B), 0-10 pts.wt. of crosslinking silane represented by formula III (wherein marks are same to those of the formula II) (C), an effective amt. of a condensation catalyst (e.g.; dibutyltin diacetate) (D) and 0-5 pts.wt. of a curing accelerator (e.g.; substd. guanine) (E).

COPYRIGHT: (C)1993,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to one-component RTV compositions and methods of making the same, and more particularly to low modulus alkoxy functional one-component RTV compositions and methods of making the same.

The earliest types of one-component RTV compositions were found to contain a crosslinker as disclosed in Ceyzeriat US Pat. No. 3,133,891 and Bruner US Pat. No. 3,035,016. It was an acyloxy-functional silane. In addition, Kulpa US Pat. No. 3,296,1
61, Goossens U.S. Pat. No. 3,296,195 and Beers U.S. Pat. No. 3,438,930 disclose the use of certain tackifying additives to render such compositions tacky. Regarding things. While such acyloxy-functional compositions were fast setting and had other desirable properties, there were nevertheless two drawbacks. One disadvantage is that these compositions liberate some corrosive acetic acid upon curing. In addition, the acetic acid gives off an unpleasant odor and thus working with the composition in a closed environment was somewhat difficult.

Therefore, since the early days, it is non-corrosive and fast-hardening 1.
It has been strongly desired to obtain a component type RTV system. Nitzsc
The two-component RTV system as shown in US Pat. No. 3,127,363 to he et al. was non-corrosive. But,
These compositions must be manufactured in two packages and mixed immediately before use of the system and once mixed they must be used in a short period of time otherwise the composition will not be adequate. Does not cure at a fast rate. Therefore, although these compositions are non-corrosive, they require extra labor costs to apply or use the system and, once mixed, have a very short shelf life.

Early examples of one-component alkoxy-functional compositions are found in Nitzsche et al., US Pat. No. 3,065,194. However, these compositions had the drawback that they had to be dried strictly when they were prepared and that they also had a short shelf life. Other alkoxy-functional one-component RTV compositions have been described by Brown et al., U.S. Pat. No. 3,122,522 and Brown et al., U.S. Pat. No. 3,161,614 or U.S. Pat. No. RE-29760.
No. These compositions are not sufficiently fast setting. That is, even if the composition cures, it cures at a very slow rate, especially after the composition has been stored for a period of time, that is, for a week or more. It has been determined that such compositions do not cure at a sufficiently fast rate with the common condensation catalysts used in acyloxy systems.

Therefore, various titanium chelate catalysts have been proposed for such alkoxy-functional one-component RTV systems. Examples of titanium chelate catalysts for alkoxy-functional one-component RTV systems are found in Weyenberg, US Pat.
334,067, U.S. Pat. No. 3,542, Cooper et al.
901, and Smith et al., U.S. Pat. No. 3,689,4.
54 and 3,779,986 (the last two patents are assigned to the applicant).

Another example of this type of RTV system, which has been commercialized in several forms, especially in combination with various additives, is Beer.
S., U.S. Pat. No. 4,100,129. All patents mentioned in the specification are reference materials for the present invention. This last patent discloses an alkoxy-functional one-component RTV system as described above.
The system has been commercialized, and particularly by relying on a particular type of chelating catalyst, the composition exhibits a sufficiently fast cure rate even after storage for a long period of time, i.e. 6 months or more. U.S. Pat. No. 4,1
According to the disclosure of US Pat. No. 00,129, the alkoxy-functional, one-component RTV system may in particular contain a trifunctional-containing polysiloxane fluid and a linear trimethylsiloxydimethylpolysiloxane fluid and various adhesion promoters. it can. Further, the specification discloses that various adhesion promoters such as silyl isocyanurate and other compounds can be used with such alkoxy-functional one-component RTV systems. However, as pointed out earlier, these compositions still have the drawback of not being sufficiently storage-stable and not being sufficiently fast-curing.

Another example of a relatively non-corrosive, one-component RTV system is disclosed, for example, in Beers, US Pat. No. 4,257,932. This patent discloses an acyloxy-functional one-component RTV system in which the acyloxy-functional cross-linking agent is preferably methyltris-2-ethylhexanoxysilane. Various additives are used in this system, such as polysiloxane fluids having a high degree of tri- or tetra-functionality, polysiloxane fluids and dimethylpolysiloxane fluids similar to those disclosed in US Pat. No. 4,100,129. It is disclosed that this can be done. Besides that,
The presence of various additives such as adhesion promoters and other additives is disclosed. Although the system of US Pat. No. 4,257,932 is relatively non-corrosive, it nevertheless is of high molecular weight but liberates acid, so it is also corrosive. Also, it was not as fast as desired. Furthermore, it should be noted that the corrosive nature is such that it causes discoloration of various substrates,
Also, this system was a little too stiff to bond to the substrate with various tackifying additives. Some examples of tackifying additives that can be used with such compositions are described, for example, in the aforementioned US Pat.
7,932 and Mitchell et al., U.S. Pat. No. 4,27.
No. 3,698, the latter using various silyl fumarate, silyl maleate, silyl succinate and other compounds as adhesion promoters for this type of composition as well as alkoxy functional one component RTV systems. It is disclosed. Another disclosure dealing with the use of large amounts of calcium carbonate as a filler in compositions of this type to render the compositions smearable is US Pat.
It is found in No. 47,445. Yet another disclosure in this field is found in U.S. Pat. No. 4,308,372 to Dziark et al., Which uses a pre-reacted reaction product of an adhesion promoter and a crosslinker, It also gives the system storage stability. However, the use of pre-reacted products of such cross-linking agents and adhesion promoters still leaves the system free of storage stability problems. Another related disclosure is Wright et al., U.S. Pat. No. 4,261,758.
In this patent, a polyether is used as a sag inhibitor or thixotropic agent, and a thixotropic property is imparted to the composition by kneading a small amount of the polyether into the composition.

More recently, White et al., US Patent Application No. 277,524 (filed June 26, 1981) and
Halgren, US Patent Application No. 277,525 (1981)
Stable, substantially acid-free, one-component (one-package) moisture-curing polyalkoxy terminations, preferably containing tin compounds as condensation catalysts, Organopolysiloxane systems have been proposed. Chun as another related patent application in this field
g., US Patent Application No. 338,578 (filed Jan. 11, 1982), which relates to the use of certain scavengers (scavengers) in such systems and also Lucas
U.S. patent application (filed on the same date as the U.S. patent application on which this application claims priority) relates to the use of various adhesion promoters in such systems and in the preferred systems of the present invention. Is. Dziark's U.S. patent application (filed on the same date as the U.S. patent application on which the present application claims priority) incorporates certain silazane and silyl-nitrogen polymers as scavengers with polyalkoxy-based organopolysiloxane polymers. Regarding to use. These are some of the scavenging systems that were not included in the White et al. Patent application. Dziark
RTV systems containing the scavenger of the present patent application are preferably cured with the additives of the present invention. However, the additive of the present invention is
It should be understood that it can be used with any of the RTV systems of White et al. US patent application. In short, storage stability is good by removing or restraining most of the hydroxyl groups in the uncured polymer composition with some scavenger in the alkoxy-functional one-component RTV system,
Even with a tin soap catalyst, a composition exhibiting a good curing rate can be obtained. Furthermore, this system is non-corrosive.

It is also desirable to have compositions of this type having a low modulus. That is, it is desirable that compositions of this type have low tensile strength and high elasticity, and that they can be used in flat glass and sealant applications, especially in high rise construction operations. As described in the aforementioned Lucas et al. U.S. patent application,
It is also desirable to make compositions of this type tacky. Research into other tackifying additives has been ongoing, and attempts have been made to make such compositions as low modulus as possible. US Patent Application No. 277 to White et al.
This is because the low modulus has not been achieved in the basic system disclosed in No. 524.

Accordingly, one object of the present invention is to provide a one-component alkoxy-functional RTV system which becomes tacky through the use of a novel tackifying additive.

Another object of the invention is to provide an alkoxy-functional one-component RTV which has a low modulus, ie low tensile strength and very high elongation.

Another object of the invention is a one-component RT which is substantially non-corrosive, storage stable and has a low modulus.
It is to manufacture V system.

Yet another object of the present invention is the incorporation of various ingredients into the composition to provide a low modulus one-component R
It is to produce TV compositions at low cost.

Still another object of the present invention is a one-component type R which is non-corrosive, has low modulus, low cost and storage stability.
It is to provide a method for manufacturing a TV system.

These and other objects of the invention include:
It is achieved by the present invention described below.

[0016]

According to the present invention, in accordance with the above objects, (1) an organopolysiloxane in which each polymer chain terminal silicon atom is terminated by at least two alkoxy groups, (2) an effective amount of a condensation catalyst (3) The following formula of a stabilizing amount:

[0017]

[Chemical formula 23] (In the formula, R ¹ is a C _(1-8) aliphatic organic group or C selected from the group consisting of alkyl, alkyl ether, alkyl ester, alkyl ketone and alkyl cyano groups.
_(7-13) aralkyl group, R ² is a monovalent substituted or unsubstituted C _(1-13) hydrocarbon group, X is amide, amino,
A hydrolyzable leaving group selected from the group consisting of carbamato, enoxy, imidate, isocyanato, oximato, thioisocyanato and ureido groups, where c is an integer equal to 0-3, f is an integer equal to 1-4, sum of c + f Is 1
A silane scavenger for a hydroxy functional group having a value equal to 4) and, where X is an enoxy or amide, (4) an effective amount of a cure accelerator selected from the group consisting of substituted guanidines, amines and mixtures thereof And (5) 2 per 100 parts by weight of the organopolysiloxane.
˜20 parts by weight of a polysiloxane first plasticizer fluid, having a high degree of tri-functionality or a combination of tri- and tetra-functionality, (i) 5-60 mol% monoalkylsiloxy units A siloxy unit or a mixture of these units, (ii) 1 to 6 mol% of a trialkylsiloxy unit, and (iii) 34 to 94 mol% of a dialkylsiloxy unit. A polysiloxane primary plasticizer fluid containing 2% by weight of silicon-bonded hydroxyl groups, stable and capable of being converted to a tack-free elastomer over long periods of time under ambient conditions substantially free of moisture, Provided is a one-component, substantially anhydrous and substantially acid free, room temperature curable organopolysiloxane composition.

The basic component of the composition is a polyalkoxy-functional diorganopolysiloxane polymer, which is preferably prepared first by first adding a trialkoxysilane crosslinker, such as methyltrimethoxysilane, to a silanol-terminated diorganopolymer. React with polysiloxane polymer. After reacting both, preferably in the presence of a condensation catalyst such as hexylamine, a scavenger is added to the reaction system to absorb all free hydroxyl groups such as methanol. Thus, such scavengers act to absorb all silanol and hydroxyl groups in the additives added to the base composition. As a result, the composition is storage stable.

In addition, the composition can be made tacky and low modulus as well as thixotropic by adding the components described herein.
Alternatively, the system can be made by mixing the silanol polymer with other components simultaneously with the crosslinker and scavenger. However, first the silanol polymer should be pre-reacted with the crosslinker to form the polyalkoxysilane organopolysiloxane, then the scavenger should be added to react with residual silanol groups, water and methanol, and then the other ingredients. It was confirmed that, by this, a system having faster curing and higher storage stability was obtained. However, if maximum storage stability and fast hardening are not required, the White
Other mixing procedures disclosed in US patent application Ser. No. 277,524 may be employed.

[0020]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The RTV composition of the present invention (herein, RTV means room temperature vulcanizable).
(meaning e) is a silanol-terminated diorganopolysiloxane polymer, preferably of the formula:

[0021]

[Chemical formula 24] Of a polymer having R in the above formula is a monovalent substituted or unsubstituted C _(1-13) hydrocarbon group, preferably 1 to
Selected from alkyl groups having 8 carbon atoms,
For example, methyl or a large amount of methyl and a small amount of phenyl, cyanoethyl, trifluoropropyl, vinyl or a mixture thereof, and n is an integer having a value of about 50 to 2500. Such silanol polymers can be prepared by various techniques, for example, by Peterson, US Pat.
It can be made by the method of No. 250,290. Other methods are described, for example, in Lampe US Pat. No. 3,888,81.
No. 5 is disclosed. Since such polymers are well known, their production will not be described in further detail.

In the present specification, several limiting terms such as stable and substantially free of acid are used. The term "stable" is that when modifying the one-component polyalkoxy-terminated organopolysiloxane RTV composition of the present invention, it can remain substantially unchanged when excluded from atmospheric moisture. , A moisture-curable mixture which can be cured into a tack-free elastomer after a long storage period. In addition, a "stable RTV composition" is a tack-free time exhibited by RTV components that have been mixed for the first time under atmospheric conditions, but a mixture of the same components may be stored under ambient conditions in a moisture-proof, moisture-free container. It is meant to be substantially the same as the tack-free time that it exhibits when exposed to atmospheric moisture after prolonged storage or storage for a considerable period of time due to accelerated aging at elevated temperatures.

RTV of the present invention exposed to atmospheric humidity
The expression "substantially acid-free" as used in the definition of an elastomer made from a composition means producing a by-product having a pKa of 5.5 or higher, preferably 6 or higher, particularly preferably 10 or higher.

The silanol terminated diorganopolysiloxane polymer used in the present invention, whether or not it is an alkoxy terminated polymer, has a viscosity at 25 ° C. of 60,
It is preferably in the range of 000 to 500,000 centipoise.

The present invention was made with the finding of suitable additives for stable, substantially acid-free, one-component, moisture-curing polyalkoxy-terminated organopolysiloxane RTV compositions, which composition comprises: The thing is substantially the following formula:

[0026]

[Chemical 25] A silanol-terminated polydiorganosiloxane consisting solely of chemically-bonded diorganosiloxy units of the formula (wherein R is as defined above), for example, a silanol-terminated polydiorganosiloxane of formula (2), is provided with an effective amount of chemically-bonded hydroxyl groups. Of the silane scavenger. In silanol-terminated polydiorganosiloxanes consisting essentially of chemically bonded units of formula (3), the presence of silicon-bonded C _(1-8) alkoxy groups, such as methoxy groups, is not excluded. Hydroxyl groups that can be removed by silane scavengers are found in the materials normally present in RTV compositions of the present invention.
For example, trace amounts of water, methanol, silanol groups associated with silica fillers (if used), silanol polymers of formula (2) or silanol terminated polymers with units of formula (3). Silane scavengers useful in removing chemically bound hydroxyl groups in the practice of the present invention include:
Preferably the following formula:

[0027]

[Chemical formula 26] Have. R ¹ in the above formula represents a C _(1-8) aliphatic organic group or a C _(7-13) aralkyl group selected from an alkyl group, an alkyl ether group, an alkyl ester group, an alkyl ketone group and an alkyl cyano group. , R ² represents a monovalent C _(1-13) organic group selected from the R groups as defined above and as defined in more detail below, and X is an amide, amino, carbamato, enoxy, Shown is a hydrolyzable leaving group selected from imidato, isocyanato, oximato, thioisocyanato and ureido groups. Suitable X groups are amino, amido, enoxy, eg N—C _(1-8) alkyl, C _(1-8) acylamide. a is an integer equal to 1 or 2, preferably 1, b is 0 or an integer equal to 1, and the sum of a + b is equal to 1 or 2. In the formula (4), when a is 2, X may be the same group or different groups. The leaving group X is preferentially RT before -OR ^1.
Reacts with the -OH obtained in the V composition to produce an RTV composition that is substantially free of halogen acids and carboxylic acids.
The silane scavenger of formula (4) is a silane scavenger for hydroxy functional groups and is a polyalkoxysilane cross-linking agent for terminating each organopolysiloxane chain terminal silicon atom with at least two alkoxy groups. But also.

The present invention can be otherwise expressed by defining its base polyalkoxy polymer. Therefore, among the components of the present RTV composition formed as a result of the use of the hydroxy scavenger of formula (4) are 2
Included are silanol-free polydiorganosiloxanes chain-terminated with ¹ or 3 —OR ¹ groups. The silanol-free polydiorganosiloxane can optionally be combined with an effective amount of a crosslinking silane as defined below under substantially anhydrous conditions. Crosslinking polyalkoxysilanes that can be used in combination with the scavenging silane of formula (4) have the formula:

[0029]

[Chemical 27] (Wherein R ¹ , R ² and b are as defined above). Suitable condensation catalysts that can be used in the practice of the present invention are metal compounds selected from tin compounds, zirconium compounds and titanium compounds or mixtures thereof. Other condensation catalysts that can be used are defined in more detail below.

The reason why the polyalkoxy-terminated organopolysiloxane compositions of the present invention are stable for long periods of time in the presence of certain condensation catalysts in the substantial absence of moisture is not completely understood.

US Patent Application No. 277,5 to White et al.
The reason why the composition of No. 24 is so stable is that the scavenger binds all the hydroxyl groups in the RTV system, which during storage of the system further crosslinks with the uncured polymer to increase its viscosity and its shelf life. It is believed to be due to the fact that the free hydroxyl groups responsible for shortening the Moreover, such free hydroxyl groups tend to degrade and degrade the alkoxy polymer within the package during storage in various ways.

By using a hydroxy silane scavenger of formula (1) or (4) where the leaving group X is not a halogen group, unwanted water in the filler and silicone polymer as well as residual moisture in the RTV composition are removed. It can be virtually eliminated during the storage period. When determining what level of silane scavenger of formula (1) or (4) to use in the practice of the present invention, the total hydroxy functionality of the RTV composition can be evaluated. The total hydroxy functionality of the polymer can be measured by infrared analysis. In order to ensure that the composition is stabilized in a sealed container at ambient temperature for extended storage periods of 6 months or more, using an effective or stabilizing amount of the scavenger.
The scavenger can be used in excess of that required to terminate the polymer. The excess of scavenger can be up to about 3% by weight, based on the weight of polymer. The above mentioned 3% by weight of scavenger exceeds the amount required to substantially remove the hydroxy functionality obtained in the polymer as a result of the reaction of the OH functionality with the X groups. In compositions that also contain certain fillers and other additives,
The required additional amount of scavenger of formula (1) or (4) is 10
A stability test is performed at 0 ° C. for 48 hours to determine if the tack free time is substantially unchanged as compared to the tack free time of the composition prior to aging measured under substantially the same conditions. It can be estimated by

When the polyalkoxy-terminated polymer of the following formula (6) is prepared without using the silane scavenger of the formula (4), in the practice of the present invention, the following formula:

[0034]

[Chemical 28] (Wherein R ¹ , R ² and X are as defined above, c is 0
~ An integer equal to 3, d is an integer equal to 1 to 4, c + d
A silane scavenger having less than 2 silicon-bonded —OR ¹ groups can be used. Under these circumstances, equation (6)
The scavenging silane of (4) can be used in an amount sufficient to stabilize the RTV composition, as defined above for the scavenging silane of formula (4). Further, 0.01 to 10 parts of the crosslinking silane of formula (5) can be used with the scavenger of formula (4) or (6).

The polyalkoxy-terminated organopolysiloxane of the present invention has the formula:

[0036]

[Chemical 29] Have. In the formula, R, R ¹ , R ² , X, n and b are as defined above, e is equal to 0 to ¹ , and the sum of b + e is 0 to
Is equal to 1. The polyalkoxy-terminated organopolysiloxane of formula (7) can be made in a variety of ways. One method is taught in Cooper et al., US Pat. No. 3,542,901, which, as noted above,
Polyalkoxysilanes are used with silanol terminated polydiorganosiloxanes in the presence of amine catalysts. Co
A method not taught by oper et al. is to use a silane scavenger of formula (4) as an endcapper with the silanol terminated polydiorganosiloxane used in the practice of the present invention. When using the additives of the present invention, it is preferred to first form the polyalkoxydiorganopolysiloxane of formula (7) and then add the additives.

In the formulas (1) to (7), R is a monovalent C.
_(1-13) preferably selected from a hydrocarbon group, a halogenated hydrocarbon group and a cyanoalkyl group, and R ¹ is C
_It is preferably a _(1-8) alkyl group or a C _(7-13) aralkyl group, and R ² is preferably methyl, phenyl or vinyl.

The X groups in the formulas (3), (5) and (6) are preferably amide, amino and enoxy, particularly preferred groups being amide.

Further, it was confirmed that the curing rate can be improved by using a small amount of amine, substituted guanidine or a mixture thereof as a curing accelerator in the polyalkoxydiorganopolysiloxane composition of the present invention. The cure accelerator also catalyzes the ability of the enoxy leaving group to act as a scavenger. 0.1 to 5 parts, preferably about 0.3, per 100 parts of silanol-terminated polymer of formula (2) or silanol-terminated polymer of formula (3) or 100 parts of polyalkoxy-terminated polymer of formula (7). ~ 1 part of the curing accelerator can be used, which allows the RTV composition of the present invention to have a tack free time (TFT = tack).
-Free time) can be significantly shortened. This enhanced cure rate is maintained even after aging the composition at ambient temperature for extended storage periods, such as 6 months or more, or for a substantial period under accelerated aging conditions. The curing characteristics after a long storage period are the initial curing characteristics exhibited by the RTV composition that is first mixed and immediately exposed to atmospheric moisture,
For example, it is substantially the same as the tack free time (TFT).

The cure accelerators described above contain certain condensation catalysts as catalysts which not only shorten the tack free time of the RTV compositions of the present invention, but which also exhibit a significant extension of the tack free time after accelerated aging. It has been found that it also has a surprising stabilizing effect on RTV compositions. In the case of this class of condensation catalysts, the addition of the amines, substituted guanidines, and mixtures thereof described herein gives an initially fast cure rate, i.e., about 30 minutes or less, and this fast cure rate remains substantially after accelerated aging. A stable RTV composition is obtained which remains stable in time.

The RTV composition of the present invention can cure to a depth of about 1/8 inch (thickness) within 24 hours. Therefore, as shown in the examples, the durometer hardness (Shore A) can be measured and used to evaluate the cure of the composition.

The polymer system of White et al. Is generally expressed as follows: (1) an organopolysiloxane in which each polymer chain terminal silicon atom is terminated by at least two alkoxy groups; (2) an effective amount of a condensation catalyst. And (3) the following formula for the amount of stabilizing action:

[0043]

[Chemical 30] (Wherein R ¹ , R ² , X and c are as defined above, f
Is an integer equal to 1 to 4, and the sum of c + f is equal to 1 to 4)
Scavenging silane. What is claimed is: 1. A one-component, substantially anhydrous, room temperature curable organopolysiloxane composition capable of being converted to a substantially acid-free, tack-free elastomer that is stable for extended periods of time under ambient conditions substantially free of moisture. Will be provided. In addition to the above components, an effective amount of a cure accelerator selected from substituted guanidines, amines and mixtures thereof is used.

According to another aspect of the invention, (A) 100 parts of a polyalkoxy-terminated organopolysiloxane of the formula (7); (B) 0 to 10 parts of a crosslinking silane of the formula (5); ) Converting to a substantially acid-free elastomer that is tack-free under ambient conditions, containing an effective amount of a condensation catalyst; and (D) a stabilizing amount of a scavenging silane of formula (1). A stable, room temperature curable polyalkoxy-terminated organopolysiloxane composition is provided.

Within the scope of the present invention is the use of an effective amount of a condensation catalyst with a silanol terminated organopolysiloxane and a polyalkoxysilane crosslinker to provide a room temperature curable organopolysiloxane composition under substantially anhydrous conditions. The present invention also includes a method for producing a silanol-terminated organopolysiloxane, wherein the method also serves as a scavenger and a cross-linking agent for a hydroxy functional group in a stabilizing amount.
The following formula:

[0046]

[Chemical 31] The polyalkoxysilane (wherein R ¹ , R ² , X, a and b are as defined above) is added, followed by the addition of an effective amount of condensation catalyst, resulting in a room temperature curable organopolysiloxane composition. It is characterized by imparting excellent stability to objects.

According to another aspect of the present invention, the present invention uses an effective amount of a condensation catalyst with an organopolysiloxane in which each polymer chain end is terminated by at least two alkoxy groups. Provides a room temperature curable organopolysiloxane composition under substantially anhydrous conditions, wherein the method comprises the step of: (1) stabilizing the polyalkoxy-terminated organopolysiloxane :

[0048]

[Chemical 32] A silane scavenger for a hydroxy functional group (wherein R ¹ , R ² , X, c and f are as defined above) and (2) an effective amount of a condensation catalyst are added to obtain a room temperature curability. It is characterized by imparting excellent stability to the organopolysiloxane composition.

According to yet another aspect of the present invention, the present invention relates to (i) a silanol-terminated polydiorganosiloxane consisting essentially of (a) 100 parts by weight of chemical bond units of formula (3); (B) an amount of silane of formula (4) sufficient to scavenge the -OH groups obtained in the RTV composition, giving up to a 3% by weight excess based on the weight of the RTV composition; (c) 0 10 parts to 10 parts of a crosslinking silane of formula (5); (d) an effective amount of a condensation catalyst; and (e) 0 to 5 parts of a curing accelerator selected from substituted guanidines, amines and mixtures thereof, silanols. A mixture in which the condensation catalyst is added after mixing the terminated polydiorganosiloxane and the scavenging silane, and (ii) 100 parts by weight of the polyalkoxy-terminated organopolysiloxane of formula (7); Cross-linking silane of 0 parts of formula (5); (c) an effective amount of a condensation catalyst; (d) a silane scavenger amount of a compound of formula (1) forming a stabilizing effect,
And (e) stirring at room temperature curable material selected from a mixture consisting of 0-5 parts of a substituted guanidine, an amine and a curing catalyst selected from mixtures thereof under substantially anhydrous conditions, A method for producing a one-component room temperature curable polyalkoxy-terminated organopolysiloxane composition is provided.

The groups contained in R in the formulas (2), (3) and (7) are, for example, aryl groups and halogenated aryl groups such as phenyl, tolyl, chlorophenyl, naphthyl; aliphatic and alicyclic groups, For example cyclohexyl,
Cyclobutyl; alkyl and alkenyl groups such as methyl, ethyl, propyl, chloropropyl, vinyl, allyl, trifluoropropyl; and cyanoalkyl groups such as cyanoethyl, cyanopropyl, cyanobutyl. The group contained in R ¹ is, for example, a C _(1-8) alkyl group such as methyl, ethyl, propyl, butyl, pentyl; a C _(7-13) aralkyl group such as benzyl or phenethyl; an alkyl ether group such as 2- Methoxyethyl; alkyl ester groups such as 2-acetoxyethyl; alkylketone groups such as 1-butane-3-onyl; alkylcyano groups such as 2-cyanoethyl. The groups contained in R ² are the same or different groups contained in the R group. In formulas (1) to (7), when R, R ¹ and R ² are two or more groups, these groups may be the same or different.

Examples of scavengers for chemically bonded hydroxyl groups contained in one or more of formulas (4), (6) and (1) include:

Oximatosilanes such as methyldimethoxy (ethylmethylketoximo) silane, methylmethoxybis- (ethylmethylketoximo) silane, methyldimethoxy (acetoaldoximo) silane.

Carbamatosilanes such as methyldimethoxy (N-methylcarbamato) silane, ethyldimethoxy (N-methylcarbamato) silane.

Enoxysilanes such as methyldimethoxyisopropeneoxysilane, trimethoxyisopropeneoxysilane, methyltriisopropeneoxysilane,
Methyldimethoxy (2-butene-2-oxy) silane,
Methyldimethoxy (1-phenylethenoxy) silane,
Methyldimethoxy-2 (1-carbethoxypropenoxy) silane.

Aminosilanes such as methylmethoxydi-
N-methylaminosilane, vinyldimethoxymethylaminosilane, tetra-N, N-diethylaminosilane, methyldimethoxymethylaminosilane, methyltricyclohexylaminosilane, methyldimethoxyethylaminosilane, dimethyldi-N, N-dimethylaminosilane,
Methyldimethoxyisopropylaminosilane, dimethyldi-N, N-diethylaminosilane.

Amidosilanes such as ethyldimethoxy (N-ethylpropionamide) silane, methyldimethoxy (N-methylacetamido) silane, methyltri (N-methylacetamido) silane, methyltri (N-).
Methylbenzamido) silane, ethyldimethoxy (N-
Methylacetamido) silane, methyltri (N-methylbenzamido) silane, methylmethoxybis (N-methylacetamido) silane, methyldimethoxy (caprolactamo) silane, trimethoxy (N-methylacetamido) silane.

Imidatosilanes such as methyldimethoxyethylacetoimidatesilane, methyldimethoxypropylacetimidatosilane.

Ureidosilanes such as methyldimethoxy (N, N ', N'-trimethylureido) silane, methyldimethoxy (N-allyl-N', N'-dimethylureido) silane, methyldimethoxy (N-phenyl-).
N ', N'-dimethylureido) silane, isocyanatosilane, such as methyldimethoxyisocyanatosilane,
Dimethoxydiisocyanatosilane.

Thioisocyanatosilanes such as methyldimethoxythioisocyanatosilane, methylmethoxydithioisocyanatosilane.

In addition to these, the scavenging silane of formula (6) is methyltris (N-methylacetamido) silane,
Includes silanes such as tetra (isopropenoxy) silane. Further, silanes having different leaving groups, such as diethylamino (N-methylcarbamato) isopropeneoxy (N-allyl-N ', N'-dimethylureido).
Silanes are also included.

Examples of the cross-linking polyalkoxysilane included in the formula (5) include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, tetraethoxysilane and vinyltrimethoxysilane.

Among the cure accelerators that can be used to practice the invention are the following formulas:

[0063]

[Chemical 33] There is a silyl-substituted guanidine having R ¹ in the above formula is as defined above, and Z is the following formula:

[0064]

[Chemical 34] (In the formula, R ³ is a divalent C _(2-8) alkylene group, R ⁴ and R ⁵ are selected from hydrogen and a C _(1-8) alkyl group), and g is 1 to 1 It is an integer of 3.
In addition, the following formula:

[0065]

[Chemical 35] (Wherein R ⁴ and R ⁵ are as defined above, R ⁶ is C
Alkyl-substituted guanidines having _{(1-8) representing} an alkyl group) can also be used. Examples of silyl-substituted guanidines encompassed by formula (8) are described in Takago, US Pat. No. 4,180,64
2 and 4,248,993.

In addition to the above substituted guanidines, various amines such as di-n-hexylamine, dicyclohexylamine, di-n-octylamine, hexamethoxymethylmelamine and silylated amines such as σ-aminopropyltrimethoxysilane and Methyldimethoxydi-
n-Hexylaminosilane can also be used. Methyldimethoxy-di-n-hexylaminosilane acts as both a scavenger and a cure accelerator. Primary amines, secondary amines, silylated secondary amines are preferred, secondary amines and silylated secondary amines are particularly preferred. Silylated secondary amines useful as cure accelerators, such as alkyldialkoxy-N-dialkylaminosilanes, and guanidines, such as alkyldialkoxyalkylguanidylsilanes, also act as scavengers in the compositions of this invention. It also works as a stabilizer and in some cases as a stabilizer.

An effective amount of a condensation catalyst that can be used in the practice of the present invention to accelerate the cure of the RTV composition is, for example, 0.001 to 1 part by weight per 100 parts by weight of the silanol terminated polydiorganosiloxane of formula (1). is there. The condensation catalyst may be a tin compound such as dibutyltin dilaurate, dibutyltin diacetate, dibutyltin dimethoxide, carbomethoxyphenyltin trisuberate, tin octanoate, isobutyltin tricelloate, dimethyltin dibutyrate, dimethyltin dineodeconoate, triethyl. Examples thereof include tin tartrate, dibutyltin dibenzoate, tin oleate, tin naphthenate, butyltin tri-2-ethylhexoate, and tin butyrate. Suitable condensation catalysts are tin compounds, especially dibutyltin diacetate.

Titanium compounds that can be used include, for example, 1,
3-propanedioxytitanium bis (ethylacetoacetate), 1,3-propanedioxytitanium bis (acetylacetonate), diisopropoxytitanium bis (acetylacetonate), titanium naphthenate, tetrabutyl titanate, tetra-2-ethylhexyl titanate ,
There are tetraphenyl titanate, tetraoctadecyl titanate and ethyl triethanolamine titanate.
In addition, Weyenberg U.S. Pat. No. 3,334,067
.Beta.-dicarbonyltitanium compounds such as those shown in US Pat.

Zirconium compounds such as zirconium octoate can also be used.

Other examples of the metal condensation catalyst include lead 2-ethyloctanoate, iron 2-ethylhexanoate, cobalt 2-ethylhexanoate, manganese 2-ethylhexanoate, and the like.
Examples include zinc 2-ethylhexanoate, antimony octoate, bismuth naphthenate, zinc naphthenate, and zinc stearate.

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

The preferred catalyst for the composition of the present invention is dibutyltin diacetate. However, almost the same efficacy is obtained with other tin soaps.

As used herein, the expressions "moisture free conditions" and "substantially anhydrous conditions" as used in connection with the manufacture of the RTV compositions of the present invention refer to pre-vacuum evacuated and then nitrogen. It means mixing in a dry box or a closed container replaced with a dry inert gas such as. Experience has shown that a sufficient amount of silane of formula (1) must be used as defined above. The temperature can vary from about 0 ° C. to about 180 ° C., but the type and amount of filler, and also the silanol-terminated polydiorganosiloxane, the filler, and the end-capping of the polymer with substantial elimination of hydroxy functional groups. Depending on the compounding degree of the mixture of the scavenging silane of the formula (4) and the like. This "end-capped" and scavenging process, the nature of the X leaving group of scavenging silane, depending on factors such as the number of ¹ group -OR, from several minutes to several hours, take several days in some cases. After this, a mixture containing substantially no silanol,
Condensation catalysts, cross-linking silanes or mixtures thereof can be added together with other ingredients such as cure accelerators and pigments.

The preferred procedure for making the RTV compositions of this invention is to provide an effective amount of a silanol-terminated polydiorganosiloxane, a filler, and a hydroxy functional group sufficient to effect substantial endcapping of the polymer. The mixture of scavenging silanes of formula (4) is stirred under substantially anhydrous conditions. This "end-capped" and scavenging process, the nature of the X leaving group of scavenging silane, depending on factors such as the number of ¹ group -OR, from several minutes to several hours, take several days in some cases. After this, a mixture containing substantially no silanol,
Condensation catalysts, cross-linking silanes or mixtures thereof can be added together with other ingredients such as cure accelerators and pigments. If desired, a stabilizing excess of the scavenging silane can be used in the first or last stage of the mixing process, in the amount as defined above.

When the polyalkoxy-terminated organopolysiloxane of formula (7) is prepared by a procedure which does not require the use of a scavenging silane of formula (4), it should be stable before or after or with the addition of a condensation catalyst. A scavenging silane can be added in an amount that has a chemical action. Another procedure for making polyalkoxy-terminated organopolysiloxanes is, as mentioned above,
No. 3,542,901 to Cooper et al.

A preferred method of making the RTV compositions of the present invention, ie, storage stable, low modulus, non-corrosive, fast setting compositions, employs polyalkoxy terminated diorganopolysiloxane polymers, ie polyalkoxy. The diorganopolysiloxane is first formed and the hydroxyl groups in the composition are removed or scavenged, after which other components as desired are added. To carry out this procedure, preferably the silanol polymer of formula (1) is added to the crosslinker of formula (5) in the presence of a catalyst, in particular an amine catalyst such as hexylamine, ie the silanol polymer is pre-reacted with the crosslinker. To produce the desired dialkoxy endblocked polymer, then take the di- or tri-alkoxy endblocked polymer and add a scavenger to it to absorb silanol groups. The other components can then be added to the composition under substantially anhydrous conditions to produce a one-component RTV package, the resulting RTV package having a tin soap catalyst present in the composition. It is storage stable and cures at a sufficiently fast rate, i.e. fast hardening. The RTV system,
That is, after preparing an RTV system consisting of a polyalkoxy material, a scavenger and a condensation catalyst, the first basic component according to the invention to be added to this RTV system is 100 parts by weight of diorganopolysiloxane base polymer (ie 2 to 20 parts by weight per 100 parts by weight of silanol polymer of (2) or 100 parts by weight of polyalkoxy-terminated organopolysiloxane polymer of formula (7)) or having a high degree of trifunctionality or trifunctionality and tetrafunctionality. (I) 5
To 60 mol% monoalkylsiloxy units, siloxy units or mixtures of these units, (ii) 1 to 6 mol% trialkylsiloxy units, and (iii) 34 to 94 mol% dialkylsiloxy units, 0.1 to about 2
A polysiloxane first plasticizer fluid containing weight percent silicon-bonded hydroxyl groups.

The polysiloxane first plasticizer fluid may be added at a concentration of usually 2 to 20 parts by weight, preferably 5 to 15 parts by weight, based on 100 parts by weight of the base polymer.
Such polysiloxanes function as plasticizers and adhesion promoters in the composition, especially as plasticizers. It is not possible to add too much polysiloxane to plasticize the composition. This is because the polysiloxane crosslinks alone as a result of its tri-functionality, unduly increasing the viscosity of the system. 2 per 100 parts by weight of base polymer
Amounts above 0 parts by weight are undesirable. Therefore, in general,
An amount exceeding about 20 parts by weight should not be used, and if less than 2 parts by weight, a sufficient effect cannot be obtained.

The highly trifunctional polysiloxane component can be made by means known to those skilled in the art. For example, (i)
Injecting a mixture of monoalkyltrichlorosilane, (ii) dialkyldichlorosilane, and (iii) alkyltrichlorosilane, silicone tetrachloride or a mixture thereof in appropriate molar ratios into toluene and water to co-hydrolyze them. You can

The mixture can then be heated to, for example, about 60 ° C. for a time sufficient to ensure complete reaction, for example 3 hours. The oily phase is separated and neutralized, for example by washing with an aqueous solution of sodium carbonate or sodium bicarbonate. After removal of insolubles by filtration and devolatilization by heating under vacuum, eg at about 2 mm Hg to about 140 ° C., the polysiloxane fluid component remains as a residue. For economic reasons, silicon-bonded hydroxyl content of 0.6% by weight
It is preferred to keep the viscosity of the final composition as low as possible and to minimize the level of crosslinker by: This is done by heating the product to 110 ° C. in the presence of about 1% sodium carbonate. The water leaving the silanol condensation is conveniently removed, for example by azeotropic distillation with toluene. After removing the toluene by distillation, the product is filtered before use. Specific teachings regarding this technique are provided by Beers in US Pat. No. 3,382,205.
Found in the issue.

Preferably, the polysiloxane fluid is 25 ° C.
It has a viscosity in the range of 15 to 300 centipoise. Also preferably, in this polysiloxane plasticizer fluid, at least 50% of the alkyl substituents are methyl,
The fluid contains 0.2-0.6% by weight silanol.
Particularly preferably, monoalkylsiloxy units, siloxy units or mixed units thereof account for about 10 to 30 mol% and trialkylsiloxy units account for 3 to 5 mol%,
The dialkylsiloxy units account for 65 to 87 mol% and the silanol content is about 0.2 to 0.6% by weight.

Accordingly, such trifunctional fluids plasticize the base composition to make it low modulus, but in all cases the base composition alone is sufficiently low modulus and sufficiently low viscosity. It cannot be done. Therefore, it is highly desirable to use 10 to 50 parts by weight of the second plasticizer per 100 parts by weight of the organopolysiloxane base polymer in addition to the trifunctional fluid.

As mentioned above, the term organopolysiloxane base polymer herein means a silanol-terminated diorganopolysiloxane polymer of formula (2), or a polyalkoxy-terminated diorganopolysiloxane polymer of formula (7), or both. Means various mixtures. Since the alkoxy groups increase the molecular weight of the polymer only slightly, the concentrations of the various additives detailed below used in addition to the trifunctional fluid are approximately the same expressed based on any polymer system. is there.

Therefore, it is possible to use 5 to 60 parts by weight of the second plasticizer per 100 parts by weight of the organopolysiloxane base polymer. The second plasticizer is 10 at 25 ° C.
A linear triorganosiloxy-terminated diorganopolysiloxane polymer having a viscosity in the range of 20,000 centipoise and the organo groups selected from monovalent C _(1-8) hydrocarbon groups. It is particularly preferable that the monovalent hydrocarbon group is an alkyl group having 1 to 8 carbon atoms. Therefore, preferably the second plasticizer has the formula:

[0084]

[Chemical 36] R ²⁰ in the above formula is a monovalent hydrocarbon group, usually C
_{(1-8) represents} an alkyl or aryl group, preferably an alkyl or phenyl group having 1 to 8 carbon atoms,
t varies so that the viscosity of the polymer is in the range of 10 to 20,000 centipoise at 25 ° C. Most preferably the R ²⁰ group is methyl and the polymer is 10 at 25 ° C.
It has a viscosity in the range of 10,000 centipoise, especially in the range of 10 to 1000 centipoise at 25 ° C. Generally, such polymers are
It has 500 to 1500 ppm of silanol as OH. The general method for producing the second plasticizer of formula (11) is:
This is a method of hydrolyzing a suitable chlorosilane. That is, the triorganochlorosilane is hydrolyzed in water with the diorganodichlorosilane, and then the hydrolysis product is decanted or otherwise separated and purified, thus providing the desired linear diorganopolysilane of formula (11). A siloxane polymer is obtained. The polymer obtained by this natural hydrolysis method usually contains 500 to 1500 ppm of silanol as OH.
And can be further purified by other methods.
However, refining is not usually done because it is expensive. Furthermore, if there is a scavenger that absorbs almost all of the hydroxyl groups present in such polymers, the silanol or hydroxyl groups as above do not cause any particular difficulties in the context of the present invention. As mentioned above, the system of the present invention must use a scavenger that absorbs all the free hydroxyl groups in such plasticizers.

As pointed out above, in order to achieve the desired low levels of modulus in the composition, two plasticizers were used because the trifunctional fluid alone cannot achieve maximum reductions in both viscosity and modulus. There must be. Therefore, both plasticizers should be used where it is desirable to have the lowest modulus, highest adhesion, and lowest viscosity to increase the ease of application of the sealant. Therefore, the most preferable low-modulus one-component RT of the present invention
The V system is produced by using the above two plasticizers defined in the present invention in the ratios mentioned above. The second
The plasticizer is preferably used in a concentration of 20 to 45 parts by weight, within the wide range of 5 to 60 parts described above.

Another feature of the compositions of the present invention is their low cost. The composition can be made low cost by incorporating 50 to 300 parts by weight or more of any amount of extender filler per 100 parts by weight of the organopolysiloxane base polymer. Extended fillers are desirable in the composition because they reduce the cost of the composition and increase its strength without diminishing its low modulus properties. Optimally, the filler is calcium carbonate. The most desirable calcium carbonate is that treated with stearic acid. The treated calcium carbonate filler gives the uncured composition of the present invention the best flow properties and the best low modulus properties mentioned above. Other extender fillers can also be included in the composition at the same concentrations as for calcium carbonate described above. Other extending fillers and reinforcing fillers that can be used in such various concentrations include, for example, titanium dioxide, zirconium silicate, silica aerogel, iron oxide, diatomaceous earth, fumed silica, carbon black, precipitated silica, glass fiber. , Polyvinyl chloride, quartz powder, etc. It is clear that the amount of filler used can vary over a wide range, depending on the intended use. For example, in certain sealant applications, high amounts of filler, such as 700 parts or more per 100 parts by weight of organopolysiloxane can be used in the curable composition to make the bonding material. In such applications, the filler is predominantly bulking filler, such as quartz powder, polyvinyl chloride or mixtures thereof, preferably having an average particle size of about 1.
It consists of such bulking fillers in the range of -10 microns.

The compositions according to the invention can also be used as building sealants and caulking compounds.
Therefore, the exact amount of filler will depend on such factors as the application for which the organopolysiloxane composition is intended to be used and the type of filler used (ie, filler density and particle size). Silanol-terminated organopolysiloxane 1
It is preferred to use from 1 to 300 parts by weight of filler per 00 parts by weight, wherein the filler may contain up to about 20 parts of reinforcing filler such as fumed silica filler.

However, the filler used at a concentration of 50 to 300 parts by weight should be a bulking filler for the low modulus compositions of the present invention, such as calcium carbonate. Organopolysiloxane base polymer 1 in addition to bulking filler
1 to 50 parts by weight, preferably 1 to 10 parts by weight, of reinforcing filler are used per 00 parts by weight. The reinforcing filler is preferably selected from precipitated silica and fumed silica, preferably fumed silica. More preferably, Lu
treated with cyclopolysiloxane as disclosed in cas US Pat. No. 2,938,009, or
Fumed silica treated with silazane as disclosed in Smith, US Pat. No. 3,635,743 is used. More preferably, fumed silica treated with 1 to 10 parts by weight of cyclopolysiloxane is used. Such fumed silica also acts as a droop inhibitor to render the composition thixotropic. By thixotrope is meant that the composition, when applied to a vertical plane, does not flow in the uncured state or exhibits minimal flow. Another way to make the composition thixotropic is Lamp
e., U.S. Pat. No. 4,261,758.

Accordingly, the RTV composition of the present invention comprises, in combination with the reinforcing fumed silica and in addition to the extender filler, from 0.1 to 2.0 parts by weight of the second organopolysiloxane polymer per 100 parts by weight of the second organopolysiloxane polymer. A drooping inhibitor can be included, and this second drooping inhibitor has the formula:

[0090]

[Chemical 37] A polyether selected from the group consisting of A and B in the above formula
Is hydrogen, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 7 carbon atoms in the ring, a mononuclear annealed lower alkyl group (total of 5 alkyl groups bonded to the aromatic nucleus) A group selected from the group consisting of (including the following carbon atoms), or

[0091]

[Chemical 38] Wherein R is an alkyl group having 1 to 11 carbon atoms and Q is a group consisting of ethylene glycol, glycerol, trimethylolpropane and other polyhydric alcohols having 2 to 6 hydroxyl groups. Is a residue of a polyvalent initiator having at least two hydroxyl groups selected from, n is a number having a value of 2-4, y is 2
Has a value of -10, z has a value of 1-5, and the polyether has a molecular weight of about 300-200,000.

The above polyethers which are sagging inhibitors are used in addition to or instead of fumed silica,
The uncured RTV composition can be imparted with thixotropic properties desirable as a sealant. The preferred RTV composition of the present invention is non-corrosive, low modulus, fast setting,
It should be noted that the storage stable RTV composition is highly desirable as a sealant in building construction, glazing applications and other manufacturing sealant applications. Therefore, it is particularly desirable that such a sealant be thixotropic, that is, that the sealant does not flow when packed in the gap in the uncured state. Such thixotropic properties can be achieved in the present composition by using a small amount of fumed silica in combination with the above polyethers. Further, it is preferred that the polyether is combined with fumed silica and is present in an amount of 0.1 to 1.0 parts by weight.
Fumed silica imparts sag control properties to the composition, but these properties are significantly improved by the incorporation of the above polyethers. See Lampe et al., U.S. Pat. No. 4,261,758 for more information on the use of polyethers as sag inhibitors.

Commercial examples of polyethers that can be used in the present invention include Pluracol V-7 and Union Carbide Corpor sold by Wyandotte Chemicals Corporation.
UCONLB sold by ation of Connecticut
There are polyethers such as -1145.

Instead of or in addition to both of these sag inhibitors, 0.2 to 2.0 parts by weight, preferably 0.2 to 1.5 parts by weight, per 100 parts by weight of the base organopolysiloxane polymer are used. Hydrogenated castor oil can be used.

An example of a hydrogenated castor oil that can be used as a drooling inhibitor is that known as Thixcin (trademark, manufactured by NL Chemicals, Heightstown, NJ, USA).

Therefore, when hydrogenated castor oil is used as a droop inhibitor, it is not necessary to use fumed silica or polyether. However, when hydrogenated castor oil is not used as a drooling inhibitor, fumed silica must be used with the polyether. Alternatively, fumed silica or polyether may be used alone. It should be emphasized that reinforcing fillers are not necessary or desirable for the compositions of the present invention as it is desirable to have low modulus compositions. High amounts of reinforcing fillers are undesirable as they increase the modulus of the composition. Preferably, if fumed silica is used, it is used in addition to a bulking filler, such as calcium carbonate, especially stearic acid treated calcium carbonate, which reduces the cost of the composition and reduces the cost of the uncured composition. The viscosity and modulus of the uncured composition can be maintained at low levels. Other types of additives can also be added to the composition as they become available or when invented.

Therefore, 0.1 to 10 parts by weight of an adhesion promoter can be added to the present composition per 100 parts by weight of organopolysiloxane. This composition, the composition of White et al., US Pat. No. 277,524, does not adhere well to the substrate. Therefore, it is desirable to use a primer or adhesion promoter with this type of composition. However, primers are undesirable in that they add extra labor costs to the application of sealant. Therefore, it is highly desirable to use or incorporate tackifying additives into the composition. For example,
Adhesive additives such as those disclosed in the Lucas et al. U.S. patent application (previously) are included.

Another tackifying additive that can be used in the composition of the present invention is the following formula:

[0099]

[Chemical Formula 39] Of 0.1 to 10 parts by weight of the adhesion promoter. R ³⁰ and R ³¹ in the above formula are monovalent C
_(1-8) hydrocarbon group, R ³² and R ³⁶ are selected from divalent C _(1-12) hydrocarbon group, R ³⁸ and R ⁴⁰ are hydrogen and monovalent C _(1-8) hydrocarbon group. Selected from the group consisting of hydrogen groups, R ³⁴ is selected from hydrogen and C _(1-3) alkyl groups, R ³³ is selected from hydrogen and methyl, and p is 0-3.
Is an integer. In a preferred embodiment, R ³⁰ and R ³¹ are C
It is selected from the _(1-8) alkyl groups, especially preferably methyl, but can be any of the various groups mentioned above for the R group. In addition, R ³⁸ and R ⁴⁰ can be selected from hydrogen and the monovalent C _(1-8) hydrocarbon groups described above for R ³⁰ and R ³¹ . R ³⁸ and R ⁴⁰ are C
_{(1-8) It} is particularly preferable to select from an alkyl group, a phenyl group and a vinyl group. It is particularly preferred that R ³³ , R ³⁴ , R ³⁸ and R ⁴⁰ are hydrogen or an alkyl group, for example methyl. Specific compounds which are included in the above formula (14) and are preferable for the present invention include the following compounds.

[0100]

[Chemical 40] Such compounds can be made by reacting ethylenediamine with the appropriate silyl acrylate. Such silyl acrylates are well known in the art and can be made by reacting a suitable olefinic methacrylate compound with a hydrotrialkoxysilane in the presence of a platinum catalyst. The hydrogen of the silane is added to the olefinic group of the acrylate, for example Keat.
US patent application No. 109,727 (ing 1980)
The application of the silyl acrylate compound as described in the application filed on March 4). Such a reaction is carried out in the presence of a platinum catalyst, at any temperature from room temperature to 150 ° C., in the presence or absence of a solvent, preferably at ambient pressure. Once the acrylate silane is obtained, it is then reacted with a suitable amine in a solvent without catalyst to produce the desired amine acrylate adduct of formula (14) above suitable for use as an adhesion promoter in the present invention. can do.
No catalyst is required for such reactions, and any ambient temperature from room temperature to 100 ° C. can be used. It is preferable to use ambient pressure. The desired amine acrylate adduct is obtained in high yield.

This adhesion promoter is one of the adhesion promoters that can be used in the compositions of White et al., US Patent Application No. 277,524.

For more information on the preparation of this adhesion promoter, see Mitchell's US patent application, the US patent application on which the present application claims priority.

In addition to the adhesion promoters described in the Lucas et al. US patent application (prior application), other adhesion promoters may be used in the compositions of the present invention as they were developed. it can. It should be noted that the composition of the present invention, in addition to its various properties, has low modulus, fast setting and storage stability, and that this low modulus property of the composition is imparted to the composition by the plasticizer. . The composition also becomes thixotropic according to the formulation of the thixotropic agent described above, and is low cost when the preferred bulking filler of the present invention is used.

Any of the other adhesion promoters described in the US patent application to Lucas et al. Or herein can be used. Moreover, other additives may be used in the compositions of the present invention at the time they are developed.

To prepare the low modulus, storage stable, fast setting compositions of the present invention, a polyalkoxydiorganopolysiloxane polymer is first formed. To accomplish this polymer formation, White et al., US Pat.
77,524, amine catalysts,
The silanol polymer is reacted with a crosslinker of formula (5), preferably in the presence of hexylamine, then the product is removed and a scavenger is added to absorb the hydroxyl groups. The scavenger is preferably an amine or silazane. To this, as will be specifically described in the following examples,
Add various additives. The low modulus single component RTV system obtained by this method can be made low cost, thixotropic and tacky. In addition, the composition is described in US Patent Application No. 277,524 to White et al.
It has storage stability and fast hardening properties as described in No.

For the purpose of specifically explaining the present invention, examples of the present invention will be shown below. These examples are not intended to set limits or boundaries on the present invention. All "parts" are by weight.

Example 1 100 parts by weight of a methyldimethoxy-terminated dimethylpolysiloxane polymer having a viscosity of 150,000 centipoise, 0.5 parts by weight of di-n-hexylamine, a viscosity of 100.
35 parts by weight of trimethylsiloxy-terminated dimethylpolysiloxane polymer with centipoise (25 ° C.), 3 mol% trimethylsiloxy monofunctional unit, 20 mol% methylsiloxy trifunctional unit and 77 mol% dimethylsiloxy difunctional unit. A base composition consisting of 10 parts by weight of a trifunctional fluid having a viscosity of 50 centipoise (25 ° C.) and containing 0.5% by weight of silanol was prepared. This base composition contains 130 stearic acid-treated calcium carbonate (sold under the trade name Hydrocard 95T by OMYA Inc. of Vermont, USA).
Part, octamethylcyclotetrasiloxane treated fumed silica 3 parts, polyether (Union Carbide Corp.
Oration, sold under the trade name UCON LB-1145) 0.2 parts, and methyldimethoxy-
4.2 parts of N-methylacetamidosilane were also mixed. This composition was prepared under substantially anhydrous conditions and further mixed under substantially anhydrous conditions with the catalyst at the concentrations shown in Table I below. Table I shows the flow properties of this RTV composition, the tack free time, the rate of application, and some of the physical properties the composition exhibits after curing. Flow characteristics are measured by the Boeing test, which test is performed as follows. The vertical jig used has a plunger housed in a cylindrical cavity at the top. Fill the cavity with sealant. Then push the plunger to the same level as the surface of the jig. Now when the tester is set in the vertical position, the sealant will protrude 0.5 inches above the surface. In this way, the droop is 1/10
Measure in inches. The cavity is 0.5 inches deep and 1.5 inches in diameter.

The tack-free time is about 1 inch with the sealant.
It is measured by applying an area of 5 inches x 1/8 inch, and then measuring the time for the surface to dry without touching with a finger.

To measure the rate of application, fill a 6 oz Semco tube with a 1/8 inch diameter orifice with a sealant. The application rate is then tested by applying an air pressure of 90 psi with an air tank. Measured amount of sealant sent out g /
Do about minutes.

The test results are shown in Table I.

[0111]

[Table 1] Example 2 Methyldimethoxy-terminated dimethylpolysiloxane polymer 1 having a viscosity of 150,000 centipoise (25 ° C.)
00 parts by weight, di-n-hexylamine 0.5 part, viscosity 1
35 parts of trimethylsiloxy-terminated dimethylpolysiloxane fluid having 00 centipoise (25 ° C.), 10 parts of the same trifunctional fluid used in Example 1, 130 parts of the same calcium carbonate as described in Example 1, polyether A base composition was prepared consisting of 0.2 parts (UCONLB-1145) and 3.0 parts octamethylcyclotetrasiloxane treated fumed silica having a surface area of about 200 m ² / g. This base composition was added to various amounts of methyldimethoxy-N- with a standard amount of dibutyltin diacetate and an adhesion promoter, as shown in Table II below.
Methylacetamidosilane was added. The adhesion promoter was of the formula:

[0112]

[Chemical 41] The samples were tested for tack free time using the same test method employed in Example 1. The results for various compositions are shown in Table II.

[0113]

[Table 2] Example 3 The same base composition as in Example 2 was used in this example. A scavenger, a catalyst and an adhesion promoter were added to this base composition to prepare a catalyst-containing state. These additives and the measured tack free times are shown in Table III below.

[0114]

[Table 3] As a result of the above test, the following conclusions were drawn. That is, the adhesion promoter (ethylenediamine-methacryloxypropyltrimethoxysilane adduct) helps stabilize the composition and bis- (dimethylamino) -diphenylsilane is insufficient as a scavenger. Other compounds appear to act effectively as scavengers.

Example 4 Methyldimethoxysiloxy-terminated dimethylpolysiloxane 1 having a viscosity of 150,000 centipoise (25 ° C.)
0.5 parts by weight of di-n-hexylamine was added to 100 parts by weight, and 35 parts by weight of the same trimethylsiloxy-terminated polydimethylsiloxane polymer as in Example 1 and 10 parts by weight of the same trifunctional fluid as in Example 1 were added thereto. 180 parts by weight of stearic acid-treated calcium carbonate the same as in Example 1, and polyether (UCON LB-1145) 0.2
A base composition was prepared by mixing parts by weight.
To this base composition, various amounts of ethylenediamine-methacryloxypropyltrimethoxysilane adduct and dibutyltin diacetate and various scavengers were added to achieve catalyst loading. The physical properties and tack free time of initial and aged samples of this composition were measured. The test results are shown in Table IV below. The difference in tack free time between the initial sample and the accelerated aged sample is a measure of the storage stability of the compound. If the tack free time does not show any measurable change after accelerated aging, the compound is excellent in storage stability.
The results are shown in Table IV below.

[0116]

[Table 4] The above data show that low modulus compositions with excellent storage stability were obtained.

As can be seen from the above data,
(Dimethylamino) dimethylsilane is unsuitable as a scavenger, while ethylenediamine-methacryloxypropyltrimethoxysilane adduct is not a storage stabilizer on its own, but a poor scavenger such as bis- (dimethylamino) dimethylsilane. When combined with an agent, it improves storage stability.

Bis- (monoethylamino) dimethylsilane is an excellent scavenger.

Example 5 A base compound was prepared in the same manner as in Example 1.
That is, the base polymer of methyldimethylpolysiloxane was the same as in Example 1 except that 0.5 part of di-n-hexylamine was present, and 15 parts of the same trifunctional fluid as in Example 1 was added thereto. 35 parts of the same trimethylsilyl-terminated polydimethylsiloxane as in Example 1, 185 parts of stearic acid-treated calcium carbonate as in Example 1, and Plurac
0.2 parts of ol V-7 (a polyether sag inhibitor sold by Wyandotte Chemicals Corporation) was added. As with all examples, 100 parts of base compound was added with varying amounts of scavenger, crosslinker, condensation catalyst and tackifying additive under substantially anhydrous conditions to achieve catalyst loading. Semc such a mixture in all cases
o Preferably performed under anhydrous conditions on a registered pressure mixer. The concentrations of the ingredients mixed in the base compound are shown in Table V below, along with the physical properties obtained from these particular compositions.

[0120]

[Table 5] As the results in Table V show, these compositions have good low modulus, good tack properties and good storage stability. Another conclusion that can be drawn from this data is that the concentration of trimethylmethoxysilane in the product is
It has a very significant effect on crosslink density, as indicated by the difference in durometer values, which changes from 12 to 25 and 30 durometer measurements as the amount varies from 0 to 1 part and 4 parts. It can also be seen that the highest peel adhesion values obtained from concrete are obtained with a concentration of 4 parts methyltrimethoxysilane.

Example 6 100 parts by weight of the same dimethoxymethylsiloxy-terminated dimethylsiloxane polymer as in Example 1, 0.5 parts by weight of di-n-hexylamine, trimethylsiloxy having the same viscosity of 100 centipoise (25 ° C.) as in Example 1. 35 parts by weight of terminated polydimethylsiloxane, 10 parts by weight of the same trifunctional fluid as in Example 1, 145 parts by weight of the same stearic acid-treated calcium carbonate as in Example 1, and 3 parts by weight of the same treated fumed silica as in Example 1. A base compound consisting of To 100 parts of base compound, various amounts of scavenger, crosslinker, catalyst and tackifying additive were added as shown in Table VI below to achieve catalyst loading. The physical properties of these samples, the storage aging properties, i.e. the tack free time as well as the peel adhesion values of the samples, are shown in Table VI below.

[0122]

[Table 6] Example 7 100 parts of the same dimethoxymethylsiloxy-terminated dimethylsiloxane polymer as in Example 1, 0.5 parts of di-n-hexylamine, 35 parts of the same trimethylsiloxy-terminated dimethylpolysiloxane as in Example 1, the same trifunctional as Example 1. 10 parts of a fluid, 140 parts of the same stearic acid-treated calcium carbonate as in Example 1, 3 parts of the same treated fumed silica as in Example 1, and a polyether (Wyandotte Chemical).
A base compound consisting of 0.2 parts was manufactured by Corporation under the trade name Pluracol V-7). To 100 parts of this compound were added various amounts of scavenger, crosslinker, condensation catalyst and tackifying additive. The physical properties of the samples, the concentrations of the components and the results of the peel adhesion test are shown in Table VII below.

[0123]

[Table 7] It should be noted that Andersen Terrastone PVC is a thin PVC layer extruded over wood for the purpose of being used as a window frame.

The above data show that the composition has good adhesion properties on most substrates and a low modulus.

Example 8 100 parts of the same methyldimethoxy-terminated dimethylpolysiloxane as in Example 1, 0.5 parts of di-n-hexylamine, 35 parts of the same trimethylsiloxy-terminated dimethylpolysiloxane polymer as in Example 1 and Example 1 Same trifunctional fluid 1
0 parts, 160 parts of the same stearic acid-treated calcium carbonate as in Example 1, 3 parts of the same octamethylcyclotetrasiloxane-treated fumed silica as in Example 1, and 0.2 parts of the same Pluracol V-7 as in Example 6. The following base compound was produced. In much the same manner as the other examples, the base compound was added to the base compound in a Semco® pressure mixer under substantially anhydrous conditions with the addition of scavengers, crosslinkers, condensation catalysts and tackifying additives. I chose The physical properties obtained from these samples and the concentrations of the components used to catalyze the base compound are shown in Table VIII below, along with the results of the peel adhesion test.

[0126]

[Table 8] Example 9 100 parts of the same methyldimethoxypolysiloxane polymer as in Example 1, 0.5 parts of the same di-n-hexylamine as in Example 1, 10 parts of the same trifunctional fluid as in Example 1, trimethylsilyl as in Example 1. A base compound was prepared consisting of 35 parts of terminated polydimethylsiloxane, 220 parts of the same stearic acid treated calcium carbonate (Hydrocarb 95T) as in Example 1, and 3 parts of the same treated fumed silica as in Example 1. 2.5 parts of hexamethyldisilazane, 0.5 part of methyltrimethoxysilane, 1.0 part of aminoethylaminopropyltrimethoxysilane and 0.07 of dibutyltin diacetate were added to this base compound.
Added parts. Such a mixture of base compounds was prepared in a substantially anhydrous state in a continuous Werner Pfleiderer twin screw extruder and catalyzed. The results of measuring the physical properties of various samples of this composition are shown in Table IX below. Table IX also shows the results of the peel adhesion test of the samples.
These data show that most samples have good adhesion properties to many substrates, are stable, and have the low modulus desired in the present invention.

[0127]

[Table 9] Example 10 100 parts dimethoxymethylsiloxy-terminated polydimethylsiloxane polymer having a viscosity of 150,000 centipoise (25 ° C), 0.5 part di-n-hexylamine, 180 parts stearic acid-treated calcium carbonate, viscosity 10
A base composition consisting of 35 parts of a trimethylsiloxy terminated polydimethylsiloxane fluid having 0 centipoise (25 ° C.), 10 parts of the same highly trifunctional fluid as in the other examples, and 5.68 parts of Thixcin® (hydrogenated castor oil). Was manufactured. To 100 parts of this base composition, 2.5 parts of hexamethyldisilazane, 0.5 parts of methyltrimethoxysilane, 1.0 part of aminoethylaminopropyltrimethoxysilane, and 1.0 part of dibutyltindihydrate under substantially anhydrous conditions. 0.05 part of acetate was added. The physical properties of the resulting sample are shown in Table X below.

[0128]

[Table 10] The additive of the present invention is the RT of Dziark's US patent application (prior approval).
It is preferably used with the V composition. In one example, Dziark
White et al., U.S. Patent Application No. 277,524 (previously), discloses certain silazane compounds suitable as scavengers for RTV systems. The preferred system of Dziark's patent application first forms the polyalkoxydiorganopolysiloxane polymer and then blends the scavenging compound, which is a silazane monomer or polymer or some amine polymer compound, separately from the crosslinker. It consists of It should be noted that the scavenger of Dziark's patent application is a separate compound from the additive and is used in addition to the crosslinker. The White et al. Patent application discloses an RTV system as opposed to the scavenger of the Dziark patent application, along with other alkoxy-functional RTV systems. Below is a brief overview of Dziark's patent application. For more information on such scavengers and RTV systems, see the specification of the Dziark patent application. According to Dziark, the additive can be used with the following compositions. That is, (1) an organopolysiloxane in which each polymer chain terminal silicon atom is terminated by at least two alkoxy groups; (2) an effective amount of a condensation catalyst; (3) a stabilizing amount of a hydroxy function. A silane scavenger for a base is contained, and the silane scavenger has the following formula (A):

[0129]

[Chemical 42] (Y in the formula is selected from R '''andR'' ₂ N-)
A silicon-nitrogen compound having and (B) (i) 3-100 mol% of the following formula:

[0130]

[Chemical 43] A chemically bonded structural unit selected from the group consisting of units having (ii) 0-97 mol% of the following formula:

[0131]

[Chemical 44] A silicon-nitrogen compound selected from the group consisting of a silicon-nitrogen polymer consisting of a chemically bonded structural unit represented by and a mixture thereof, in which the silicon atoms of the silicon-nitrogen polymer are SiOSi bonds or SiNR ''. Si
Free valences of the silicon atoms other than the silicon atoms which are linked by a bond and are bonded to oxygen to form a siloxy unit among the silicon atoms and the nitrogen to be bonded to nitrogen to form a silazy unit are R ″. 'Group or (R'') ₂ N group, and the ratio of the sum of the R''' group and the (R '') ₂ N group to the silicon atom of the silicon-nitrogen polymer is 1.5 to 3
R ″ is selected from the group consisting of hydrogen, monovalent hydrocarbon groups and fluoroalkyl groups, R ′ ″ is hydrogen,
Selected from the group consisting of monovalent hydrocarbon groups and fluoroalkyl groups, c being an integer equal to 0-3; and further optionally (4) from the group consisting of effective amounts of substituted guanidines, amines and mixtures thereof. Can be converted to a tack-free elastomer containing a cure accelerator that is stable over extended periods of time under ambient conditions substantially free of moisture,
It can be used with stable, one-component, substantially anhydrous and substantially acid free, room temperature curable organopolysiloxane compositions.

0.5 to 10 parts by weight of silicone scavenger are present per 100 parts by weight of organopolysiloxane.

The silazane polymer was chemically bonded.

[0134]

[Chemical 45] Units of cyclic silazanes may be included. Where R '' and R
“″ Is as defined above, and the ratio of the sum of R ′ ″ and (R ″) ₂ N groups to the silicon atom in the silazane polymer is 1.
5 to 3.0.

The silazane polymer is

[0136]

[Chemical 46] It may be a linear polymer having at least one unit selected from the group consisting of units, wherein R ″ and R ′ ″ are as defined above and R ″ ′ and (R ″ ) ₂ N
The ratio of the total number of groups to the silicon atoms in the silazane polymer is 1.5 to 3.0. In addition, the silazane polymer is substantially

[0137]

[Chemical 47] It may be a linear polymer consisting of units only, where R ″ and R ′ ″ are as defined above and the sum of R ′ ″ and (R ″) ₂ N groups in the silazane polymer. The ratio of silicon atoms is 1.5 to 3.0.

The silazane polymer is

[0139]

[Chemical 48] It can be a polymer having at least one unit selected from the group consisting of units, where R ″ and R ″
'Is as defined above, and the ratio of the sum of R''' and (R '') ₂ N groups to the silicon atom in the silazane polymer is 1.5.
~ 3.0.

In addition, the silazane polymer is

[0141]

[Chemical 49] The polymer may be a polymer having a sufficient amount of units selected from the units, wherein R ″ and R ′ ″ are as defined above and the sum of R ′ ″ and (R ″) ₂ N groups. The ratio of silicon atoms in the silazane polymer is 1.5 to 3.0.

The silazane-siloxane compound is contained in an amount of 97 mol% or less.

[0143]

[Chemical 50] Units and most

[0144]

[Chemical 51] A unit selected from the group consisting of R ″, R ′ ″ and c as defined above, R ′ ″ +
The ratio of the total of (R ″) ₂ N groups to the silicon atom in the silazane-siloxane copolymer is 1.5 to 3.

The silazane-siloxane compound was chemically bonded to (R ′ ″) ₂ SiO units.

[0146]

[Chemical 52] It can be a ring such as a ring consisting only of units, where R ″ and R ′ ″ are as defined above.

Further, the silazane nitrogen compound has the following formula:

[0148]

[Chemical 53] Wherein R ″ and R ′ ″ are as defined above, n is a positive integer, preferably 0-20, and d is an integer equal to 0-1. , D
When is 0, n is preferably equal to 3-7.

The silazane nitrogen compound has the following formula:

[0150]

[Chemical 54] Can be a polysiloxane having R'wherein R '
', R''' and n are as defined above, Z is R '' or -Si (R ''') ₃ .

Suitable silicon-nitrogen compounds are hexamethyldisilazane, hexamethylcyclotrisilazane, octamethylcyclotetrasilazane or the following formulas:

[0152]

[Chemical 55] A silicon-nitrogen compound having the formula:

[0153]

[Chemical 56] And a silicon-nitrogen compound having the formula:

[0154]

[Chemical 57] Selected from silicon-nitrogen compounds having

Claims (55)

[Claims] 1. (a) 100 parts of substantially the following formula: A silanol-terminated polydiorganosiloxane consisting only of the chemical bond units of (b) a stabilizing amount of the following formula: A silane scavenger for hydroxy functional groups of (c) 0-10 parts of the following formula: A crosslinking silane of (d), (d) an effective amount of a condensation catalyst, and (e) a mixture of 0 to 5 parts of a curing accelerator selected from the group consisting of substituted guanidines, amines and mixtures thereof [in the above formula R is a monovalent substituted or unsubstituted C _(1-13) hydrocarbon group, R ¹ is a C _(1-8) fatty acid selected from the group consisting of alkyl, alkyl ether, alkyl ester, alkyl ketone and alkyl cyano groups. A group organic group or a C _(7-13) alkaryl group, R ² is a monovalent substituted or unsubstituted C _(1-13) hydrocarbon group, X is an amide, amino, carbamate, enoxy, imidate, Isocyanato, oximato, is a hydrolyzable leaving group selected from the group consisting of thioisocyanato and ureido groups,
a is an integer equal to 1 or 2, b is 0 or an integer equal to 1, and the sum of a + b is equal to 1 or 2, and the room temperature curable material is at a temperature in the range of 0 to 180 ° C. under substantially anhydrous conditions. 0.1% in the case where X represents enoxy before or with the scavenger.
~ 5 parts of a curing accelerator selected from the group consisting of substituted guanidines, amines and mixtures thereof, and 2 to 20 parts by weight of a polysiloxane first plasticizer fluid per 100 parts by weight of said organopolysiloxane. Having a high degree of trifunctionality or having both trifunctionality and tetrafunctionality, (i) 5 to 60 mol% of monoalkylsiloxy units, siloxy units or mixtures of these units, (ii) 1 to 6 mol % Trialkylsiloxy units, and (iii) 34-94 mol% dialkylsiloxy units, by adding about 0.1-2% by weight of a polysiloxane first plasticizer fluid containing silicon-bonded hydroxyl groups. Which can be cured into a solid elastomeric state 1
A method for producing a component-type room temperature curable composition containing substantially no acid. 2. The method of claim 1 wherein said organopolysiloxane has a viscosity at 25 ° C. in the range 60,000 to 500,000 centipoise. 3. Further, said organopolysiloxane 10
It contains 5 to 60 parts by weight of a second plasticizer per 0 parts by weight, the second plasticizer having a viscosity in the range of 10 to 20,000 centipoise at 25 ° C. and a monovalent hydrocarbon group as an organo group. A process according to claim 2 which is a linear triorganosiloxy terminated diorganopolysiloxane. 4. The second plasticizer polymer has the formula: 4. The method according to claim 3, wherein R ²⁰ is a monovalent hydrocarbon group, and t changes so that the viscosity of the polymer is in the range of 10 to 20,000 centipoise at 25 ° C. Method. 5. The above formula wherein R ²⁰ is methyl and t is varied so that the viscosity of the polymer is in the range of 10 to 10,000 centipoise at 25 ° C. and the second plasticizer polymer is 5
A method according to claim 4 having a hydroxy content of from 00 to 1500 ppm. 6. The method according to claim 4, which contains 100 to 300 parts by weight of an extender filler per 100 parts by weight of the organopolysiloxane. 7. A method according to claim 6 wherein the bulking filler is calcium carbonate. 8. The method of claim 7 wherein the calcium carbonate is treated with stearic acid. 9. A process according to claim 7, which contains 1 to 50 parts by weight of reinforcing filler per 100 parts by weight of said organopolysiloxane. 10. The method according to claim 8, wherein the reinforcing filler is a fumed silica which also functions as a sag inhibitor and is present in a concentration of 1 to 10 parts by weight per 100 parts by weight of the organopolysiloxane. Method. 11. Containing 0.1 to 2.0 parts by weight of a second sag inhibitor per 100 parts by weight of said organopolysiloxane, said second sag inhibitor having the following formula: A polyether selected from the group consisting of A and B in the above formula
Is hydrogen, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 7 carbon atoms in the ring, a mononuclear and binuclear aryl group, and a mononuclear aryl lower alkyl group (aromatic nucleus A group selected from the group consisting of alkyl groups attached to containing a total of 5 or less carbon atoms), or Wherein R is alkyl having 1 to 11 carbon atoms and Q is a group consisting of ethylene glycol, glycerol, trimethylolpropane and other polyhydric alcohols having 2 to 6 hydroxyl groups. Is a residue of a polyvalent initiator having at least two hydroxyl groups selected from, n is a number having a value of 2-4, y is 2
10. A process according to claim 9 having a value of -10, z having a value of 1-5 and the polyether having a molecular weight of about 300-200,000. 12. The method according to claim 9, which contains 0.2 to 2.0 parts by weight of a drooping inhibitor consisting of hydrogenated castor oil per 100 parts by weight of said organopolysiloxane. 13. The method of claim 2 wherein said reinforcing filler is treated with cyclopolysiloxane prior to incorporation into the composition. 14. 0.1 to 10 parts by weight of the following formula: Containing an adhesion promoter having R ³⁰ and R ³¹ selected from monovalent C _(1-8) hydrocarbon groups, R ³² and R ³⁶
Is selected from divalent C _(1-12) hydrocarbon groups, R ³⁸ and R
⁴⁰ is selected from the group consisting of hydrogen and monovalent C _(1-6) hydrocarbon groups, R ³⁴ is selected from hydrogen and C _(1-3) alkyl groups, R ³³ is selected from hydrogen and methyl, p Is 0
The method of claim 1, wherein the method is an integer from -3. 15. The adhesion promoter is of the formula: 15. A method according to claim 14, which comprises: 16. The method of claim 1 wherein R, R ¹ and R ² are methyl. 17. The method of claim 1 wherein the cure accelerator is selected from the group consisting of silylated guanidine and alkyl guanidine. 18. The method of claim 1 wherein said scavenging silane is polymethoxyacetamidosilane. 19. The method according to claim 1, wherein the cross-linking agent is methyltrimethoxysilane. 20. The method according to claim 1, wherein the condensation catalyst is a tin compound. 21. The method of claim 20, wherein the silane scavenger is methyldimethoxy-N-methylacetamidosilane. 22. (a) 100 parts of substantially the following formula: embedded image A silanol-terminated polydiorganosiloxane consisting only of the chemical bond units of (b) a stabilizing amount of the following formula: A silane scavenger for hydroxy functional groups of (c) 0-10 parts of the following formula: A cross-linking silane of (d), (d) an effective amount of a condensation catalyst, and (e) a curing accelerator selected from the group consisting of 0 to 5 parts of substituted guanidines, amines and mixtures thereof. R is a monovalent substituted or unsubstituted C
_(1-13) hydrocarbon group, R ¹ is a C _(1-8) aliphatic organic group or C _(7-13) selected from the group consisting of alkyl, alkyl ether, alkyl ester, alkyl ketone and alkyl cyano group An aralkyl group, R ² is a monovalent substituted or unsubstituted C _(1-13) hydrocarbon group, X is selected from the group consisting of amido, amino, carbamato, enoxy, imidate, isocyanato, oximato, thioisocyanato and ureido groups. Is a hydrolyzable leaving group, and a is 1 or 2
Is an integer equal to, b is an integer equal to 0 or 1, and a + b
Equal to 1 or 2], and 0.1-5 parts when X is enoxy, a curing accelerator selected from the group consisting of substituted guanidines, amines and mixtures thereof, and said organopolysiloxane. 2 to 20 parts by weight per 100 parts by weight of a polysiloxane first plasticizer fluid, having a high degree of trifunctionality or having both trifunctionality and tetrafunctionality, (i) 5 to 60 mol% Of monoalkylsiloxy units, siloxy units or mixtures of these units, (ii) 1 to 6 mol% of trialkylsiloxy units, and (iii) 34 to 94 mol% of dialkylsiloxy units. A mixture containing a polysiloxane first plasticizer fluid containing wt% silicon-bonded hydroxyl groups. 23. The organopolysiloxane is 25 ° C.
The mixture of claim 22 having a viscosity in the range of 60,000 to 500,000 centipoise at. 24. Further, the organopolysiloxane 1
Containing 5-60 parts by weight of the second plasticizer per 00 parts by weight,
The method according to claim 23, wherein the second plasticizer is a linear triorganosiloxy-terminated diorganopolysiloxane having a viscosity in the range of 10 to 20,000 centipoise at 25 ° C. and a monovalent hydrocarbon group as an organo group. The mixture according to the item. 25. The second plasticizer polymer has the formula: Claim 24, wherein R ²⁰ is a monovalent hydrocarbon group and t varies such that the viscosity of the polymer is in the range of 10 to 20,000 centipoise at 25 ° C.
The mixture according to the item. 26. R ^{20 in the} above formula is methyl, t is varied such that the viscosity of the polymer is in the range of 10 to 10,000 centipoise at 25 ° C., and the second plasticizer polymer is 500 to 1, A mixture according to claim 25 having a hydroxy content of 500 ppm. 27. The mixture according to claim 25, containing 100 to 300 parts by weight of an extender filler per 100 parts by weight of the organopolysiloxane. 28. The mixture according to claim 27, wherein the bulking filler is calcium carbonate. 29. The mixture according to claim 28, wherein the calcium carbonate is treated with stearic acid. 30. The mixture according to claim 28, containing 1 to 50 parts by weight of reinforcing filler per 100 parts by weight of said organopolysiloxane. 31. The method according to claim 29, wherein the reinforcing filler also functions as a sag inhibitor and is fumed silica, and is present at a concentration of 1 to 10 parts by weight per 100 parts by weight of the organopolysiloxane. blend. 32. Containing 0.1 to 2.0 parts by weight of a second sag inhibitor per 100 parts by weight of the organopolysiloxane, the second sag inhibitor having the following formula: A polyether selected from the group consisting of A and B in the above formula
Is hydrogen, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 7 carbon atoms in the ring, a mononuclear and binuclear aryl group, and a mononuclear aryl lower alkyl group (aromatic nucleus A group selected from the group consisting of alkyl groups bonded to containing a total of 5 or less carbon atoms, or Wherein R is an alkyl group having 1 to 11 carbon atoms and Q is composed of ethylene glycol, glycerol, trimethylolpropane and other polyhydric alcohols having 2 to 6 hydroxyl groups. Is a residue of a polyvalent initiator having at least two hydroxyl groups selected from the group, n is a number having a value of 2-4, y is 2
A mixture according to claim 29 having a value of 10, z having a value of 1 to 5 and having a molecular weight of about 300 to 200,000. 33. The mixture according to claim 28, containing 0.2 to 2.0 parts by weight of hydrogenated castor oil per 100 parts by weight of said organopolysiloxane, a sag inhibitor. 34. The mixture of claim 23, wherein the reinforcing filler is treated with cyclopolysiloxane prior to incorporation into the mixture. 35. 0.1 to 10 parts by weight of the following formula: Wherein R ³⁰ and R ³¹ are selected from monovalent C _(1-8) hydrocarbon groups and R ³² and R ³⁶ are divalent C _(1-12) hydrocarbon groups. Selected, R ³⁸ and R ⁴⁰
Is selected from the group consisting of hydrogen and monovalent C _(1-6) hydrocarbon groups, R ³⁴ is selected from hydrogen and C _(1-3) alkyl groups, R ³³ is selected from hydrogen and methyl, and p is 0 to
23. The mixture according to claim 22, which is an integer of 3. 36. The adhesion promoter has the formula: embedded image A mixture according to claim 35 having: 37. A substantially acid free room temperature curable organopolysiloxane composition is prepared under substantially anhydrous conditions using an effective amount of a condensation catalyst together with a silanol terminated organopolysiloxane and a polyalkoxysilane crosslinking agent. In doing so, the following formula, which is a scavenger for hydroxy functional groups and a cross-linking agent, is present in an amount that stabilizes the silanol-terminated organopolysiloxane: [In the above formula, R ¹ is a C _(1-8) aliphatic organic group or C _{(7 )} selected from the group consisting of alkyl, alkyl ether, alkyl ester, alkyl ketone and alkyl cyano groups. _{-13) an} aralkyl group, R ² is a monovalent substituted or unsubstituted C _(1-13) hydrocarbon group, and X is an amide, amino, carbamato, enoxy, imidato, isocyanato, oximato, thioisocyanato and ureido group. A hydrolyzable leaving group selected from the group consisting of: a is an integer equal to 1 or 2, b
Is an integer equal to 0 or 1 and the sum of a + b is 1 or 2
, Then an effective amount of condensation catalyst is added to impart excellent stability to the resulting room temperature curable organopolysiloxane composition, and prior to or with the addition of said scavenger. , A curing accelerator selected from the group consisting of substituted guanidines, amines and mixtures thereof, when X represents enoxy, and from 2 to 20 per 100 parts by weight of said organopolysiloxane.
1 part by weight of polysiloxane first plasticizer fluid, having a high degree of tri-functionality or a combination of tri- and tetra-functionality, (i) 5 to 60 mol% of monoalkylsiloxy units, siloxy Units or a mixture of these units, (ii) 1 to 6 mol% of a trialkylsiloxy unit, and (iii) 34 to 94 mol% of a dialkylsiloxy unit, and about 0.1 to 2% by weight of a silicon bond. A method for producing a room temperature curable organopolysiloxane composition, which comprises adding a polysiloxane first plasticizer fluid containing a hydroxyl group. 38. The organopolysiloxane is 25 ° C.
38. The method of claim 37 having a viscosity in the range of 60,000 to 500,000 centipoise at. 39. Further, said organopolysiloxane 1
5 to 60 parts by weight per 100 parts by weight of the second plasticizer is contained, and the second plasticizer has a viscosity in the range of 10 to 20,000 centipoise at 25 ° C. and a monovalent hydrocarbon group as an organo group. 39. The method of claim 38 which is a linear triorganosiloxy terminated diorganopolysiloxane. 40. The second plasticizer polymer has the formula: Claim 39. wherein R ²⁰ is a monovalent hydrocarbon group and t varies such that the viscosity of the polymer is in the range of 10 to 20,000 centipoise at 25 ° C.
Method described in section. 41. The above formula wherein R ²⁰ is methyl, t is varied such that the viscosity of the polymer is in the range of 10 to 10,000 centipoise at 25 ° C., and the second plasticizer polymer is present at 500 to 1500 ppm. The method of claim 40 having a hydroxy content. 42. A method according to claim 40 which contains 100 to 300 parts by weight of an extender filler per 100 parts by weight of said organopolysiloxane. 43. The method of claim 42, wherein the bulking filler is calcium carbonate. 44. The method of claim 43, wherein the calcium carbonate is treated with stearic acid. 45. A method according to claim 43, containing 1 to 50 parts by weight of reinforcing filler per 100 parts by weight of said organopolysiloxane. 46. The method according to claim 44, wherein the reinforcing filler is a fumed silica which also functions as a sag inhibitor and is present in a concentration of 1 to 10 parts by weight per 100 parts by weight of the organopolysiloxane. Method. 47. Containing 0.1 to 2.0 parts by weight of a second sag inhibitor per 100 parts by weight of the organopolysiloxane, the second sag inhibitor having the following formula: A polyether selected from the group consisting of A and B in the above formula
Is hydrogen, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 5 to 7 carbon atoms in the ring, a mononuclear and binuclear aryl group, and a mononuclear aryl lower alkyl group (aromatic nucleus A group selected from the group consisting of alkyl groups bonded to containing a total of 5 or less carbon atoms), or Wherein R is alkyl having 1 to 11 carbon atoms and Q is a group consisting of ethylene glycol, glycerol, trimethylolpropane and other polyhydric alcohols having 2 to 6 hydroxyl groups. Is a residue of a polyvalent initiator having at least two hydroxyl groups selected from, n is a number having a value of 2-4, y is 2
A process according to claim 43, having a value of -10, z having a value of 1-5, and having a molecular weight of about 300-200,000. 48. A method according to claim 43, containing 0.2 to 2.0 parts by weight of a drooling inhibitor consisting of hydrogenated castor oil per 100 parts by weight of said organopolysiloxane. 49. The method of claim 45, wherein the reinforcing filler is treated with cyclopolysiloxane prior to incorporation into the composition. 50. 0.1 to 10 parts by weight of the following formula: Containing an adhesion promoter having R ³⁰ and R ³¹ selected from monovalent C _(1-8) hydrocarbon groups, R ³² and R ³⁶
Is selected from divalent C _(1-12) hydrocarbon groups, R ³⁸ and R
⁴⁰ is selected from the group consisting of hydrogen and monovalent C _(1-6) hydrocarbon groups, R ³⁴ is selected from hydrogen and C _(1-3) alkyl groups, R ³³ is selected from hydrogen and methyl, p Is 0
38. The method of claim 37, which is an integer from -3. 51. The adhesion promoter is of the formula: 51. The method of claim 50, which comprises: 52. The method of claim 37, wherein the silane scavenger is methyldimethoxy-N-methylacetamidosilane. 53. The method of claim 37, wherein the silane scavenger is methyldimethoxyisopropeneoxysilane.
Method described in section. 54. The method of claim 37, wherein the silane scavenger is methyltriisopropeneoxysilane. 55. The method according to claim 37, wherein an effective amount of dibutyltin diacetate is used as the condensation catalyst.