JPH0521939B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a one-component RTV silicone rubber composition. In particular, the present invention is a one-liquid type RTV.
The present invention relates to adhesion promoters or adhesion additives for compositions. Early types of one-part RTV compositions are found in US Pat. No. 3,133,891 to Ceyzeriat and US Pat. No. 3,035,016 to Bruner.
These publications relate to acyloxy-functional one-part compositions. Over time, various other types of RTV compositions with other functional groups were invented. For example, one-part ketoxime functional RTV
compositions, amine-functional RTV compositions, amide-functional RTV compositions, aminooxy-functional RTV compositions, and the like. During the course of the development of such compositions, the inclusion of tackifier additives, i.e., the incorporation of tackifier additives, has made it possible for the compositions to be compatible with various types of adherends. It has become clear that adhesion with good adhesion without the need for a primer is desirable. Such acyloxy functionality
Examples of adhesive additives for RTV compositions include, for example, U.S. Pat. No. 3,296,161 to Kulpa;
Found in publications U.S. Pat. No. 3,296,195 to Goossens and U.S. Pat. No. 3,438,930 to Beers. A disadvantage of such acyloxy-functional compositions is that they are somewhat corrosive. That is, although the compositions are fast curing and have other advantages, they are somewhat corrosive and provide a pungent odor. Accordingly, it has become desirable to develop a composition that is substantially non-corrosive and can be used indoors with a large number of people without imparting an unpleasant odor.
As mentioned above, the above composition is a one-component type. An example of a two-part RTV composition is, for example, Nitzsche
No. 3,127,363, issued to et al. This patent discloses a two-part composition consisting of a silanol polymer, a polysilicate crosslinker, and preferably a tin salt of a carboxylic acid as a catalyst. Since such compositions are packaged as two-parts, the two parts are mixed when it is desired to cure the composition. The composition cures into a silicone elastomer. Although this composition has a sufficiently fast curing time and is non-corrosive, the composition must be mixed before use, which requires additional labor costs. On top of that,
The shelf life of the composition once mixed is not long. One of the early one-component systems was a silanol polymer,
See US Pat. No. 3,065,194 to Nitzsche et al., which discloses the use of alkoxysilane crosslinkers and tin soaps. Although such compositions are one-part, the compositions do not have sufficient shelf life. In addition, special mixing operations to produce the composition,
That is, long drying periods must be used. It was early recognized that such alkoxy-functional one-component RTV systems have many advantages;
Attempts have been made to prepare such compositions as disclosed in US Pat. No. 3,161,614 to Brown et al. However, these compositions did not have sufficiently fast curing speeds and had very poor storage properties. Other alkoxy-functional RTV compositions are disclosed, for example in U.S. Pat. No. 3,334,067 to Weyenberg.
No. 1, U.S. Patent No. 1, issued to Cooper et al.
No. 3,542,901, and US Pat. Nos. 3,689,454 and 3,779,986 to Smith et al. The latter of these, particularly the Weyenberg and Smith patents, use special titanium chelate catalysts as condensation catalysts for alkoxy-functional one-part RTV compositions. The titanium chelate catalyst is desirable in that it provides the alkoxy-functional RTV with a commercially acceptable cure rate, ie, a cure rate that allows the composition to be commercially available. but,
This composition is still not a fast-curing one-component RTV system. Other attempts to make such compositions fast-curing and have desirable storage stability and tack include
Found in publication US Pat. No. 4,100,129 to Beers. However, still such compositions do not cure as quickly as desired or have a good shelf life. Recently, it has been reported that such early compositions suffer from the fact that, even though they are prepared in a substantially moisture-free environment, there is an excess of methanol, silanol, or hydroxyl groups present in the prepared polymer system. A theory was established. The presence of such hydroxyl groups in the polymer system results in poorly curable compositions, ie, compositions that do not have sufficient cure rates and good storage properties. Therefore, a scavenger is used in the composition to react with the excess hydroxyl groups, whether derived from methanol, silanol or water;
Moreover, a system has been invented that does not react with alkoxy groups and cause premature crosslinking of the RTV system. How this is accomplished and what are the scavenger systems for such compositions are discussed, for example, in U.S. Patent Application No. 277,524, filed June 26, 1981 by White et al., docket RD- 13275 and John B.
Halgren, U.S. Patent Application No. 277,525, filed June 26, 1981, and published in docket RD-13421. Although White et al.'s compositions are sufficiently fast curing and storage stable, they require modification to meet certain requirements. That is, the composition does not adhere closely to many adherends. Without a primer, such compositions have little or no tack. Therefore, there has been a strong desire to develop adhesive additives for use in such compositions.
In addition to the tack additives described above, there are other patents relating to tack additives useful for both two-part and one-part RTV systems (as used herein, "RTV" refers to shall indicate the vulcanized type). For example, U.S. patent no. Bessemer et al.
See No. 3888815. This patent states that the functional groups of the adhesive additive include, in addition to alkoxy groups, amino, carbonyl, carboxy, isocyano, azo, diazo,
Thio, thia, dithia, isothiocyano, oxo,
The present invention relates to an adhesive additive for two-component RTV selected from oxa, halo, ester, nitroso, sulfohydryl, hydrocarbonylamide, sulfonamide groups, and plurals and combinations thereof. Also, U.S. Patent No. 4,147,685 to Smith, which relates to primer compositions.
No. 1, in particular that patent's acrylate-functional silanes that can be used as tack additives for RTV compositions, and the publication of U.S. Pat. No. 109,727, filed by Keating on January 4, 1980. Other publications of adhesive additives for RTV systems include, for example, US Pat.
No. 4,100,129 and U.S. Pat. No. 4,273,698 docket 60Si-225 to Mitchell et al. Mitchell et al. discloses various silyl fumarates, silyl succinates, and silyl maleates that can be used as tack additives in one-component RTV systems. However, all of these patents, which are incorporated herein by reference, are incorporated by reference into White et al., U.S. Pat.
The adhesive additive used in the composition of 13275 is not disclosed. A tackifying additive is desirable, otherwise a primer must be used. Use of primer adds labor costs. The labor costs are significantly greater than the additional costs of incorporating adhesive additives into the composition during composition manufacture. Accordingly, it is highly desirable to include a tackifying additive in the compositions of White et al., US Pat. No. 2,775,24. One object of the present invention is to provide a one-component alkoxy functional
It is an object of the present invention to provide adhesion promoters or tack additives for RTV compositions. An additional object of the present invention is to provide a tackifier additive for use in alkoxy-functional one-part RTV compositions that imparts tack to most adherends. Yet another additional object of the present invention is an alkoxy-functional one-component formulation that is fast curing and storage stable.
It is an object of the present invention to provide a tack additive or tack promoter that can be added to an RTV composition without adversely affecting the physical properties and curability of the RTV composition. Yet another object of the present invention is to create a tacky one-component alkoxy-functional RTV composition that has a fast cure rate and is storage stable by incorporating a tacky additive into the one-component alkoxy-functional RTV composition. To provide a method for manufacturing. These and other objects of the invention are accomplished by the disclosed techniques hereinafter described. According to the above object, according to the present invention, R ¹⁰ , R ¹¹
is a C _1-8 monovalent hydrocarbon group, and t is 0 to 3
and Z is a saturated, unsaturated or aromatic hydrocarbon residue, and the residue further includes amino, ether, epoxy, isocyanato, cyano, acryloxy, acyloxy groups and a plurality of such groups, and When the functional group can be given by a member selected from the group consisting of the combination,
Structural formula Provided are stable, substantially anhydrous, substantially acid-free cold vulcanizable organopolysilazane compositions having an effective amount of an adhesion promoter having a tackification promoter. The most preferred adhesive additives within structure (1) are amino-functional silanes, followed by epoxy-functional compounds, and lastly other compounds within structure (1). . The present invention is also directed to methods of forming RTV compositions within the scope of the present invention. Tackifying additives are most preferably used in end-capped polymers. In other words, White
No. 277,524 docket filed by et al.
It is preferably used in one-part RTV compositions in which the crosslinking agent is first added to the silanol polymer in the presence of a catalyst, as disclosed in RD-13275. It is also used where after the end-capped polymer is formed, a scavenger is added to absorb the hydroxyl groups in the polymer system. After the scavenger has absorbed the excess hydroxyl groups in the system, the tin soap condensation catalyst is added and other ingredients are added to form the finished composition. In this way,
Best composition: fast curing, non-corrosive adhesive
An RTV composition is obtained. It has good storage stability. This invention relates to tack promoters or adhesion additives for use in special types of one-part RTV silicone rubber compositions. Here, such a one-component RTV
It is necessary to give some description of the composition. For a more complete description of such compositions, see US patent application Ser.
Reference should be made to the description in docket No. 277524, RD-13275. Certain number special expressions are used herein. One is to refer to the composition as a "stable" composition. As far as the present specification is concerned, the one-package polyalkoxy-terminated organopolysiloxane of the present invention
The term "stable" as used in RTV refers to a moisture-curable mixture that remains substantially unchanged while isolated from atmospheric moisture and is capable of curing to a dry-to-touch elastomer even after extended periods of storage. means. In addition, stable RTV also means that the tack-free time that freshly mixed RTV components exhibit under atmospheric conditions is longer than that of the same mixture of components under ambient conditions for extended periods of storage or is the same as the tack-free time it exhibits when exposed to atmospheric moisture after being kept in a moisture-proof, moisture-free container for a period of accelerated aging at elevated temperatures corresponding to . The expression "substantially acid-free" is used in defining RTV silicone compositions. of the present invention
The term "substantially acid-free" when used to define an elastomer made by exposing an RTV composition to atmospheric moisture means a pKa of 5.5 or higher, preferably 6 or higher, and particularly preferably 10 or higher. It means producing by-products with . Turning now to RTV compositions, the present invention provides stable, substantially acid-free, one-package moisture-curable polyalkoxy-terminated organopolysiloxanes.
Based on adhesion promoters for RTV compositions.
The composition has the structure: silanol-terminated polydiorganosiloxanes consisting essentially of chemically bonded diorganosiloxane units, together with effective amounts of certain scavengers for chemically bonded hydroxyl groups. . In silanol-terminated polydiorganosiloxanes consisting essentially of chemically bonded units of structural formula (2), the presence of C _1-8 alkoxy groups bonded to silicon atoms, such as methoxy groups, is not excluded. Hydroxyl groups that can be removed with silane scavengers are, for example, trace amounts of water, methanol,
(as used) silanol groups on a silica filler, a silanol polymer of structure (8), or a silanol-terminated polymer having units of structure (2), typically present in the RTV compositions of the present invention. can be found in substances. The silane scavenger that removes chemically bonded hydroxyl groups in accordance with the practice of the present invention preferably has the structural formula have. In this structural formula, R ¹ is an alkyl group,
selected from alkyl ether group, alkyl ester group, alkyl ketone group, alkyl cyano group
a C _1-8 aliphatic organic group or a C _7-13 aralkyl group, and R ² is a C _1-13 monovalent organic group selected from the R groups defined above and further defined hereinafter; and X is amide, amino, carbamate,
A hydrolyzable leaving group selected from enoxy, imidato, isocyanato, oximato, thioisocyanato, and ureido groups. Desirable ones of these are amino groups and amide groups, and more preferred are amino groups such as N-C _1-8 alkyl-C _1-8 acylamino groups, where a is 1 or an integer thereof, and preferably is 1. b is equal to an integer of 0 or 1, and the sum of a+b is equal to 1 or 2. In structural formula (3) when a is 2, X can be the same group or different groups. The leaving group X is a possible - in the RTV composition.
It reacts preferentially with OH and -OR' to provide RTV compositions that are substantially free of halogen acids or carboxylic acids. The silane scavenger of structure (3) is also a silane scavenger for hydroxyl functionality, and is a polyalkoxysilane for terminating the silicon atom with at least two alkoxy groups at each end of the organopolysiloxane. It is also a crosslinking agent. As one of the components of the RTV composition formed as a result of using the hydroxyl scavenger of structural formula (3), 2
There are silanol-free polydiorganosiloxanes chain-terminated with one or three -OR' groups. The silanol-free polydiorganosiloxane is sometimes combined under substantially anhydrous conditions with an effective amount of a crosslinking silane as defined below. Polyalkoxysilane crosslinkers that can be used in combination with scavenger silanes of structure (3) have the structure formula (3) when R ¹ , R ² and b are as defined above. have. Suitable condensation catalysts that can be used in the practice of this invention include metal compounds selected from tin compounds, zirconium compounds, titanium compounds, or mixtures thereof. Condensation catalysts to be used are additionally defined later. It is not completely understood why the polyalkoxy-terminated organopolysiloxane compositions of the present invention are stable for extended periods of time in the presence of certain condensation catalysts in the substantial absence of water. It is self-evident that excess hydroxyl groups in the form of alcohol or silanol groups or water will crosslink and prematurely harden the polyalkoxy polymer in the package, or that the alcohol groups will cap the ends of the silanol polymer with monoalkoxy groups. It is assumed. If this happens, this is one reason why it is believed that the cure rate of the polymer will decrease over time. The use of silane scavengers for hydroxyl groups having structure (3) or structure (5) below in which the leaving group substantially removes residual moisture. Structural formula used in carrying out the invention
To determine the proportion of silane scavenger in (3) or (5),
The total number of hydroxyl functional groups in the RTV composition may be evaluated. The total number of hydroxyl functional groups on a polymer can be determined by infrared analysis. Ensuring that an effective or stabilizing amount of scavenger is used to maintain the stability of the composition over extended storage periods of six months or more in a sealed container at ambient temperature includes: Additional amounts of scavenger can be used beyond the amount needed to endstop the polymer. This excess amount of scavenger can be up to about 3% by weight based on the weight of the polymer. This 3% by weight of scavenger is in excess of the amount necessary to substantially eliminate reactive OH functional groups in the polymer as a result of reaction of the X groups with the functional groups. In compositions that also include fillers and other additives, structural formula (3) or
(5) Said additional amount of scavenger is 48% stable at 100℃.
It is estimated by performing a time test to determine whether the tack-free time is unchanged compared to the tack-free time measured under substantially the same conditions for the pre-aged composition. When the polyalkoxy-terminated polymer of Structural Formula (6) below is prepared without the use of a silane scavenger of Structural Formula (3), the silicon-bonded Silane scavengers having less than two -OR' groups can be used in the practice of this invention. In this formula, R ¹ , R ² and X are as previously defined, c is an integer from 0 to 3, d is from 1 to 4, and the sum of c+d is equal to 3 to 4. In this case, the scavenger silane of structure (5) is as defined above for the scavenger silane of structure (3).
A sufficient amount can be used to stabilize the RTV composition. Additionally, at least 0.01 part up to 10 parts of a crosslinker silane of structure (4) can be used with the scavenger of structure (3) or (5). The polyalkoxy-terminated organopolysiloxane of the present invention has the following structural formula (6). In this formula, R, R ¹ , R ² , X, n, b are the same as defined before, e is equal to 0 to 1, and the sum of b+e is equal to 0 to 1. Structural formula (6)
The polyalkoxy-terminated organopolysiloxanes can be prepared in a variety of ways. One is the method taught by Cooper et al., US Pat. No. 3,542,901, which involves using a polyalkoxysilane and a silanol terminated polydiorganosiloxane in the presence of an amino catalyst. A method not taught by Cooper et al. is to use a silane scavenger of structure (3) as an end-capper with the silanol-terminated polydiorganosiloxane used in the practice of this invention. In structural formulas (1 to 6), R is preferably
C _1-13 monovalent hydrocarbon group, halogenated hydrocarbon group,
and a cyanoalkyl group, R ¹ is preferably a C _1-8 alkyl group or a C _7-13 aralkyl group, and R ² is preferably a methyl group, a phenyl group,
Or a vinyl group. In structural formulas (3), (5), and (6), preferred X groups are amide, amino, and enoxy groups, and the most preferred is amide. It has been found advantageous to first cap the silanol polymer with a crosslinker of structure (4) and then add a scavenger to absorb all free silanol groups in the mixture. Therefore,
In the production of RTV compositions, a polyalkoxy end-capped polymer is prepared as described above, and a scavenger is then added to the composition to remove water in fillers or other ingredients if added. It is desirable that the scavenger absorb all of the moisture, including the moisture, to prevent deterioration of the composition. Of course, except for the silanol groups in the polymer, the crosslinker and silanol polymer must be as dry as possible. A preferred method of doing this is to take a silanol polymer and introduce the presence of one of the condensation catalysts disclosed in Docket No. RD-13275, filed by White et al. Below, the silanol polymer is reacted with a crosslinking agent such as methyltrimethoxysilane. Other amines can also be used in the condensation catalyst, as disclosed in the co-pending patent application. Once a suitable end-capped polymer is prepared, a scavenger is then added along with other ingredients to remove any excess hydroxyl groups that may be present in the end-capped polymer to create a one-component RTV system. The scavenger also removes moisture in fillers and other ingredients added to the container. Additionally, it has been found that if small amounts of amines, substituted guanidines, or mixtures thereof are used as cure accelerators in the polyalkoxy compositions of the present invention, the cure rate is improved. Curing accelerators also serve to catalyze the ability of the enoxy leaving group to act as a scavenger. 0.1 to 5 per 100 parts of a silanol-terminated polymer of structural formula (1), that is, a polymer consisting of chemically bonded units of structural formula (2), or per 100 parts of a polyalkoxy-terminated polymer of structural formula (6). 1 part, preferably about 0.3 to 1 part of curing accelerator, can be used to substantially reduce the tack free time (TFT) of the RTV compositions of the present invention. This increased cure rate is possible even after the composition has been aged for a long shelf life, such as 6 months, and even after aging under aging-promoting conditions for a corresponding period of time.
maintained. The cure properties after a long storage period are substantially similar to the initial cure properties, such as tack free time (TFT), that a freshly mixed RTV composition exhibits when immediately exposed to atmospheric moisture. It is something that The curing accelerator described herein is the RTV of the present invention.
It reduces the tack-free time of the composition and in addition has a surprising stabilizing effect on special RTV compositions which have been exposed to certain condensation catalysts and have a longer tack-free time after accelerated aging. For this type of condensation catalyst, the addition of the amines, substituted guanidines, and mixtures of both described herein provides an initially fast cure rate, i.e., faster than about 30 minutes; remains virtually unchanged after accelerated aging. The RTV compositions of the present invention can be cured to a depth of 1/8'' within 24 hours, at which point the durometer hardness (Shoer A) is measured and the compositions are cured as shown in the Examples below. In a broader aspect of the invention disclosed herein, the invention provides a method for evaluating the curing of polymers in which: (1) each polymer chain has one silicon atom and terminates in at least two alkoxy groups; (2) an effective amount of a condensation catalyst; (3) R ¹ , R ² , X and c are as defined above and f is from 1 to 4;
When the sum of c+f is 1 to 4, the structural formula a stabilizing amount of a scavenger, and is stable under substantially moisture-free ambient conditions for extended periods of time and is convertible to a substantially acid-free tack-dry elastomer; It contains an anhydrous room temperature vulcanizable organopolysiloxane composition. Additionally, an effective amount of a cure accelerator selected from substituted guanidines, amines and mixtures thereof is used. In another aspect of the invention, (A) 100 parts of a polyalkoxy-terminated organopolysiloxane of structural formula (6), (B) 0 to 10 parts of a crosslinking silane of structural formula (4), and (C) a condensation catalyst. (D) a stabilizing amount of a scavenger of structural formula (7); A sulfur type polyalkoxy terminated organopolysiloxane composition is provided. A method for producing a cold-vulcanizable organopolysiloxane composition under substantially anhydrous conditions using a silanol-terminated organopolysiloxane and a polyalkoxysilane crosslinker together with an effective amount of a condensation catalyst, comprising: (1)R ¹ , R ² , X, a and b are defined as above, the structural formula silanol-terminated organopolysiloxane, (2) then add an effective amount of condensation catalyst; A method for producing an improved room temperature vulcanizable organopolysiloxane composition, characterized in that the stability of the room temperature vulcanizable organopolysiloxane composition obtained is improved, is included within the scope of the present invention. Ru. Another method of the invention employs an effective amount of a condensation catalyst in conjunction with an organopolysiloxane in which each terminal silicon atom of the polymer chain is terminated with at least two alkoxy groups. In the method for producing a room temperature vulcanizable organopolysiloxane composition described below, the polyalkoxy-terminated organopolysiloxane contains (1) R ¹ , R ² , X,
When c and f are defined as above, the structural formula and (2) an effective amount of a condensation catalyst, thereby improving the stability of the resulting room-temperature vulcanizable organopolysiloxane composition. The present invention is characterized by an improved method for producing the room-temperature vulcanizable organopolysiloxane composition. In yet another aspect of the present invention, a cold vulcanizable material is stirred under substantially anhydrous conditions, and the cold vulcanizable material has (i)(a) a unit of structural formula (2); (b) 100 parts by weight of a silanol-terminated polydiorganosiloxane, consisting essentially of a chemically bonded polydiorganosiloxane, sufficient to scavenge the reactive -OH in the RTV composition, based on the weight of the RTV composition; (c) 0 to 10 parts by weight of a crosslinker silane of structure (4) in excess of up to 3% by weight; (d) an effective amount of a condensation catalyst; (e) substitution. 0 to 5 parts by weight of a curing accelerator selected from guanidine, amines, and mixtures thereof; (ii)(a) a mixture in which a silanol-terminated polydiorganosiloxane and a scavenger silane are mixed and then a condensation catalyst is added; 100 parts by weight of polyalkoxy-terminated organopolysiloxane of structural formula (6), (b) 0 to 10 parts by weight of a crosslinking silane of structural formula (4), (c) an effective amount of a condensation catalyst, (d) structural formula ( 7) a stabilizing amount of the silane scavenger; (e) 0 to 5 parts by weight of a curing accelerator selected from substituted guanidines, amines and mixtures thereof; A method for producing a stable one-package cold-curable polyalkoxy-terminated organopolysiloxane composition is provided. Examples of R in structural formulas (2) and (6) include aryl groups and halogenated aryl groups such as phenyl, tolyl, chlorophenyl, and naphthyl; aliphatic groups and alicyclic groups such as cyclohexyl and cyclobutyl; methyl , ethyl, propyl, chloropropyl, vinyl, allyl, trifluoropropyl; and cyanoalkyl groups such as cyanoethyl, cyanopropyl, cyanobutyl. Suitable groups within the scope of R ¹ include, for example, C _1-8 alkyl groups such as methyl, ethyl, propyl, butyl, pentyl; C _7-13 aralkyl groups such as benzyl; phenethyl; Alkyl ether groups such as; for example, alkyl ester groups such as 2-acetoxyethyl; for example, 1-butan-3-onyl alkyl ketone groups; and alkyl cyano groups such as 2-cyanoethyl. The groups represented by R ² are the same or different groups included in the R group. R, R ¹ and R ² are 1
In structural formulas (1 to 7) when there are more than
R, R ¹ and R ² may be the same or different. Examples of scavengers for chemically bonding hydroxyl groups contained in one or more of structural formulas (3), (5), and (7) include: Methyl dimethoxy (ethyl methyl Oxymatosilanes such as methylmethoxybis-(ethylmethylketoximo)silane, methyldimethoxy(acetaldooximo)silane; methyldimethoxy(N-methylcarbamato)silane, ethyldimethoxy(N-methylcarbamato)silane; -methylcarbamato)silane; Carbamatosilanes such as methyldimethoxyisopropeneoxysilane, trimethoxyisopropeneoxysilane, methyltri-iso-propeneoxysilane, methyldimethoxy(but-2-en-2-oxy)silane, methyldimethoxy (1-phenyletheneoxy)silane, methyldimethoxy-2-(1-carboethoxy-propenoxy)silane, enoxysilanes such as methylmethoxydi-N-methylaminosilane, vinyldimethoxymethylaminosilane, tetra-N, N-diethylaminosilane, methyldimethoxymethylaminosilane, methyltricyclohexylaminosilane, methyldimethoxyethylaminosilane, dimethyldi-N,N-dimethylaminosilane,
Aminosilanes such as methyldimethoxyisopropylaminosilane, dimethyldi-N,N-dimethylaminosilane; ethyldimethoxy(N-ethylpropionamide)silane, methylmethoxydi(N-methylacetamide)
Silane, methyldimethoxy (N-methylacetamide)
Silane, Methyltri(N-methylacetamide)silane, Ethyldimethoxy(N-methylacetamide)
silane, methyltri(N-methylbenzamide)silane, methylmethoxybis(N-methylacetamido)silane, methyldimethoxy(caprolactamo)silane, trimethoxy(N-methylacetamido)silane, amidosilanes such as methyldimethoxyethylacetimidatosilane, Imidatosilanes such as methyldimethoxypropylacetimidatosilane, methyldimethoxy(N,N′,N′-trimethylureido)silane, methyldimethoxy(N-allyl-N′,N′-dimethylureido)silane, methyldimethoxy(N -Phenyl-N', N'-
ureidosilanes such as dimethylureido)silane; isocyanatosilanes such as methyldimethoxyisocyanatosilane, dimethoxydiisocyanatosilane; thioisocyanatosilanes such as methyldimethoxythioisocyanatosilane, methylmethoxydithioisocyanatosilane. In addition, U.S. Pat.
569 disclosure. The patent application discloses the use of certain pyrrolidone silanes as scavengers in the compositions of the present invention. This pyrrolidonal silane belongs to the amidosilanes of the definition of scavenger mentioned herein above. Cyclic amidosilanes of this type are described in detail in the referenced US patent application by Chung, supra. In addition, scavenger silanes of structure (5) include silanes such as methyltris(N-methylacetamido)silane, tetra(isopropenoxy)silane. Also, diethylamino(N-methylcarbamato)isopropeneoxy(N-allyl-
Also included are silanes with different leaving groups, such as N',N'-dimethylureido)-silane. Some of the crosslinking polyalkoxysilanes included in structural formula (4) include, for example, methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, tetraethoxysilane, and vinyltrimethoxysilane. Curing accelerators that can be used in the practice of the present invention include:
There is a silyl-substituted guanidine with the following structural formula. (Z) _g Si(OR ¹ ) _4-gIn this formula, R ¹ is defined above and
g is an integer equal to one from 1 to 3, and Z is
When R ³ is a divalent C _2-8 alkylene group, and R ⁴ and R ⁵ are selected from hydrogen and C _1-8 alkyl group, the structural formula In addition, an alkyl-substituted guanidine is a guanidine group with a guanidine group, when R ⁴ and R ⁵ are as defined above and R ⁶ is a C _1-8 alkyl group,
Structural formula Alkyl-substituted guanidines may also be used. Some of the silyl-substituted guanidines included within the above structural formulas are described in U.S. Pat.
No. 4180642 and No. 4248993. In addition to the substituted guanidines, e.g.
- Various amines such as hexylamine, dicyclohexylamine, di-n-octylamine, hexamethoxymethylmelamine, and silylated amines such as γ-aminopropyltrimethoxysilane, methyldimethoxy-di-n-hexylaminosilane. can be used. Methyldimethoxy-di-n-hexylaminosilane acts as both a scavenger and a cure accelerator. Primary amines, secondary amines and silylated secondary amines are preferred, among which secondary amines and silylated secondary amines are particularly preferred. Silylated secondary amines, such as alkyldialkoxy-n-dialkylaminosilanes, and guanidines, such as alkyldialkoxyalkylguanidylsilanes, which are useful as curing accelerators, also serve as scavengers in the present invention, and in some cases In addition, it acts as a stabilizer for the composition of the invention. In describing the composition, the composition first caps the ends of a silanol-terminated diorganosiloxane polymer with an alkoxy-functional crosslinker;
An alternative method is to simultaneously mix the scavenger, crosslinker, and silanol-terminated diorganopolysiloxane polymer, then add the scavenger to the desired mixture with the other ingredients. It should be noted that it has been published that one-component RTV mixtures can be made or that the above two methods can be combined and applied. Regardless of which of the above two methods is used, R is a monovalent substituted or unsubstituted C _1-13 hydrocarbon group as defined above, preferably methyl or mostly methyl. consisting of a small portion of phenyl, cyanoethyl, trifluoropropyl, vinyl, or mixtures thereof, where n is about 50
When the structural formula is an integer with a valency of from 2500 to A preferred silanol-terminated diorganopolysiloxane polymer with a crosslinker silane having a hydrolyzable group bonded to the silicon atom is used. Methods for making such polymers are well known in the art and are not discussed herein. An example of a description of the use and manufacture of such polymers is, for example, U.S. Pat.
Found in No. 3888815. That US patent is incorporated herein by reference. Preferably, the viscosity of the silanol polymer base is in the range of 30,000 to 500,000 centipoise at 25°C. The condensation catalyst may be a metal salt of a carboxylic acid, or a titanium salt or chelate. Preferably, inexpensive tin soap is used. Compared to the titanium chelate catalyst, Zusu soap has
It allows curing of the composition to proceed at a sufficiently fast rate and is not as expensive as the latter. An effective amount of condensation catalyst that can be used in the practice of this invention to facilitate curing of RTV compositions is, for example, 0.001
or 1 part by weight. Examples of condensation catalysts include dibutyltin dilaurate, dibutyltin diacetate, dibutyltin dimethoxide, carbomethoxyphenyltin trisuberate, tin octoate, isobutyltin triceroate, dimethyltin dibutyrate, dimethyltin dineodeconoate, and triethyl. These include tin compounds such as tin tartrate, dibutyltin dibenzoate, tin oleate, tin naphthenate, butyltin 2-ethylhexoate, and tin butyrate. A preferred condensation catalyst is dibutyltin diacetate, dibutyltin dilaurate being particularly preferred. 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, tetraphenyl titanate, tetraoctadecyl titanate, and ethyltriethanolamine titanate. In addition, U.S. Patent No. 2334067 issued to Weyenberg
A β-dicarbonyl titanium compound as shown in No. 1 can be used as a condensation catalyst in the present invention. Zirconium compounds such as zirconium octoate may also be used. Other examples of metal condensation catalysts are, for example, lead 2-ethyl octoate, iron 2-ethylhexanoate, cobalt 2-ethylhexanoate, manganese 2-ethylhexanoate, zinc 2-ethylhexanoate, antimony octoate, naphthenes. bismuth acid, zinc naphthenate, and zinc stearate. Examples of non-metallic condensation catalysts are hexylammonium acetate and benzyltrimethylammonium acetate. For example, titanium dioxide, zirconium silicate,
Various fillers or pigments such as silica aerogels, iron oxides, diatomaceous earth, fumed silica, carbon black, precipitated silica, glass fibers, polyvinyl chloride, quartz powder, calcium carbonate, etc., in silanol-terminated or alkoxy-terminated organopolysiloxanes. Can be combined. The amount of filler used can vary within wide limits depending on the intended use. For example, for use in certain sealants, the curable compositions of the present invention may be filler-free. In other applications, such as using curable compositions to make binders, higher amounts of filler, such as 700 parts or more per 100 parts organopolysiloxane, on a weight basis, may be used. For such applications, the bulk of the filler is preferably between about 1 and
It may consist of a filler such as quartz powder, polyvinyl chloride, or mixtures thereof, with an average particle size in the range of 10 microns. The compositions of the invention can also be used as architectural sealants or caulking compounds. The exact amount of filler will therefore depend on such factors as the intended use of the organopolysiloxane composition, the type of filler used (ie, filler density and particle size). Preferably, silanol-terminated organopolysiloxane 100
per part, a filler proportion of 10 to 300 parts is used, up to about 35 parts of which may be fumed silica. In the practice of this invention, silanol-terminated polydiorganosiloxanes, hereinafter referred to as structural formula (8) or including polymers consisting essentially of units of structural formula (2), and structural formula (3) are used. A cold vulcanizable composition can be prepared by agitating, for example by stirring, a material mixture of the scavenger silane of ) and the crosslinker silane of structural formula (4). In this case compounding is carried out in the substantial absence of atmospheric moisture.
Thereafter, the condensation catalyst is added, also in the substantial absence of atmospheric moisture. As used hereinafter in connection with the manufacture of the RTV compositions of the present invention, the expressions "moisture-free conditions" and "substantially anhydrous conditions" refer to dry box or vacuum extraction followed by nitrogen removal. This means mixing in a closed container in place of a dry inert gas such as a dry inert gas. Experience has taught that a sufficient amount of scavenger silane of structure (3) as defined above should be used. Depending on the degree of incorporation, type and amount of filler, the temperature can vary between about 0°C and about 180°C. One preferred method of making RTV compositions of the invention is to
A mixture of a silanol-terminated polydiorganosiloxane, a filler, and an effective amount of scavenger silane sufficient to substantially eliminate the hydroxyl functionality and cap the ends of the polymer under substantially anhydrous conditions. to stir. This “capturing the end”
The scavenging operation may require minutes, hours, or even days, depending on factors such as the type of X-leaving group, the number of -OR' groups on the scavenger silane, etc. . The condensation catalyst and crosslinker silane, or mixtures thereof, can then be added to the mixture substantially free of silanol groups, along with other ingredients such as curing accelerators and pigments. If desired, an excess of scavenger can be used for stabilization purposes in the amounts defined above in the first or last stage of the mixing operation. Whatever mixing operation is used, a suitable one-component RTV system that is storage stable and has a sufficiently fast cure rate in humid conditions will be obtained in accordance with the disclosure of White et al. For more information on the preparation of such compositions, see U.S. Pat. No. 277,524, filed by White et al.
You should see RD-13275. however,
The present invention does not reside in such one-component systems per se, but in specifically defined adhesion promoters of structural formula (1) for such systems. In the structural formula, R ¹⁰ and R ¹¹ are monovalent C _1-18 hydrocarbon groups,
t is 0 to 3, preferably 0. ^R10 ,
^R11 group is an alkyl group such as methyl, ethyl, propyl, etc., an alkenyl group such as vinyl, allyl, etc., a cycloalkyl group such as cyclohexyl, cyclopentyl, etc., a mononuclear aryl group such as methylphenyl, etc., 3,3,3-trifluoro selected from fluoroalkyl groups such as propyl. Most preferably,
R ¹⁰ and R ¹¹ are selected from methyl or ethyl groups. The definitions of these symbols are the same in the structural formulas that follow. The Z group in structural formula (1) is generally a saturated, unsaturated, or aromatic hydrocarbon residue, and this residue includes amino, ether, epoxy, isocyanato, cyano, acryloxy, acyloxy groups, and The functionality may be imparted by a member selected from the group consisting of a plurality of these or a combination thereof. Generally, any effective amount of such adhesion promoters may be used in the composition. Effective amounts vary somewhat from adhesion promoter to adhesion promoter. Excessive amounts of adhesion promoter do not promote any desirable results and in some cases may impair the physical properties of the cured RTV composition. Thus, in general, the adhesion promoter is present in amounts ranging from 0.1 to 100 parts by weight per 100 parts by weight of polyalkoxyorganopolysiloxane or per 100 parts by weight of silanol-terminated diorganopolysiloxane polymer of structure (8).
It is used in a proportion of 10 parts by weight, more preferably 0.1 to 5 parts by weight. Because the increase in molecular weight of the polymer due to end-capping groups is very small, the proportion of adhesion promoter is essentially the same whether the polymer is silanol-terminated or end-capped. One suitable adhesion promoter has the following structural formula. In this formula, R ¹⁰ , R ¹¹ and t are the same as defined above, R ¹² is a divalent C _2-12 hydrocarbon group,
R ¹³ and R ¹⁴ are selected from the group consisting of a hydrogen atom, an amino group, a C _1-8 hydrocarbon group-substituted amino group, a monovalent C _1-8 hydrocarbon group, and mixtures thereof. In particular, R ¹² is selected from alkylene or arylene divalent substituted or unsubstituted hydrocarbon groups having 2 to 12, preferably 2 to 8 carbon atoms. Groups R ¹³ and R ¹⁴ are hydrogen atoms or groups.
It may be any of the same monovalent C _1-8 hydrocarbon groups as defined for R ¹⁰ and R ¹¹ . However, preferably
R ¹³ and R ¹⁴ are selected from amine groups and substituted amine groups such as aminoethyl. US Patent No.
It is anticipated that many of the narrow amine adhesion promoters or nitrogen functional adhesion promoters disclosed in US Pat. For a more complete description of such compounds, see
U.S. Patent No. 3,888,815 to Bessemer et al.
You should see the disclosure in the issue. Such compounds are described, for example, in U.S. Pat. No. 2,930,809;
Manufactured as described in No. 2971864. Both patents are incorporated herein by reference. Suitable compounds within the scope of the above structural formula (9) include, for example, 3-
(2-aminoethylamino)-propyltrimethoxysilane. Others include γ-aminopropyltriethoxysilane and γ-aminopropyltrimethoxysilane. Other suitable amine adhesion promoters within the scope of structural formula (9) that may be used in the present invention include: γ-aminopropylmethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane, bis[3-(triethoxysilyl)propyl]
Amine, bis[3-(triethoxysilyl)propyl]
Ethylenediamine, 3-(2-aminoethylamino)-propyldimethoxy-t-butoxysilane, methacryloxyethylaminoethylaminopropyltrimethoxysilane, methylaminopropyltrimethoxysilane, methylaminopropyltriethoxysilane, (N,N- Dimethyl-3-amino)propyltrimethoxysilane, N,N-dimethylaminophenyltriethoxysilane, N,N-dimethylaminomethyldimethoxysilane, thus many of the amine-functionalized silanes have not been tested. Although not included, it is believed that many amine-functionalized silanes could be used as adhesion promoters in the present invention. These compounds are readily available in the silicone industry, specialty chemical stores, and can be prepared by combining trimethoxysilane or hydrogenated silanes with suitable substituents and suitable unsaturated silanes in the presence of platinum catalysts. It can be easily prepared by reacting an amine intermediate. Additionally, there are other methods of making these compounds. Since the manufacturing method is well known to those skilled in the art, as illustrated by the aforementioned U.S. Pat. No. 3,888,815,
The details of the manufacturing method will not be described here. Another adhesion promoter that can be used in the present invention has the following structural formula. In this formula, G is R ²⁰ or (R ²¹ O) _3-b R ²⁰ _b −Si
^-R22 is selected from styryl, vinyl, allyl, chloroallyl, and cyclohexanyl, and ^R22 is a divalent _C2-12 selected from alkylenearylene, alkylene, and cycloalkylene.
is a hydrocarbon group or a halogen-substituted product thereof, R ²⁰ and R ²¹ are selected from the same groups as R ¹⁰ and R ¹¹ and a cyanoalkyl group, and b is 0.
It is 3 to 3. For further knowledge of such compounds, see U.S. Pat.
No. 4,100,129, US Pat. No. 3,821,218, filed by Berger on October 17, 1972 and later abandoned, US Pat. No. 3,821,218. These US patents are incorporated herein by reference. The most preferred adhesion promoters within structure (10) are 1,3,5-tristrimethoxysilylpropylisocyanurate and bis-1,3-trimethoxysilylpropylisocyanurate. We will not go into details about the preparation of these compounds. These compounds add to the unsaturated group, such as the allyl group, of the isocyanurate by taking the corresponding hydrogenated methoxysilane and reacting it with an unsaturated isocyanurate or cyanurate in the presence of a platinum catalyst. . The R ²² group may be selected from any divalent substituted or unsubstituted hydrocarbon group so long as it does not interfere with the adhesion promoting ability of the compound. It should be noted that highly complex compounds are less desirable because they are more difficult and therefore more expensive to prepare. Other specific compounds within the scope of the above structural formula (10) are as follows. 1,3,5-tristrimethoxysilylpropylisocyanurate, 1,3,5-tristrimethoxysilylethylisocyanurate, 1,3,5-trismethyldimethoxysilylpropylisocyanurate, 1,3,5 -trismethyldiethoxysilylpropylisocyanurate Other adhesion promoters that can be used in the present invention are, for example, those having the following general structural formula: This structural formula is within the range of structural formula (1), and R ¹⁰ ,
R ¹¹ , t are the same as defined above,
^R12 is a divalent _C2-12 hydrocarbon group, ^R16 is a divalent _C2-12 hydrocarbon group, and ^R17 consists of a hydrogen atom and a monovalent _C1-8 hydrocarbon group. It is selected from the group. The R ¹² and R ¹⁶ groups are either divalent hydrocarbon groups, such as saturated or unsaturated alkylene, arylene, alkylenearylene groups, as described above for other compounds; They may be substituted or unsubstituted with various groups such as ether groups, ether groups, ester groups, and other hydrocarbon groups. The R ¹⁷ group is a hydrogen atom or the same monovalent hydrocarbon group as R ¹⁰ and R ¹¹ defined above, most preferably a hydrogen atom.
The most preferred compound within the range of structural formula (11) is γ-
Glycidoxypropyltrimethoxysilane. Other specific compounds of the structural formula (11) that are suitable as the adhesion promoter of the present invention are, for example, the following. γ-glycidoxypropylmethyldimethoxysilane, γ-glycidoxypropyltriethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, γ-glycidoxyethyltrimethoxysilane, these compounds are described in the literature It can be made by a silicone manufacturer as described above and can be obtained from specialty chemical stores. One of the manufacturing methods for making a compound such as structural formula (11) is
For example, allyl glycidyl ether is taken and reacted with hydrogenated trimethoxysilane in the presence of a platinum catalyst. This reaction, well known to those skilled in the art, adds trimethoxysilane to the allyl group of the glycidyl ether to yield the desired specific adhesion promoters disclosed above. Following this general reaction, other compounds within the scope of structural formula (11) above can be made. Another group of compounds within the scope of structural formula (1) are adhesion promoters having the following structural formula: In this formula, R ¹⁰ , R ¹¹ , t are the same as defined above, R ¹² is a divalent C _2-12 hydrocarbon group, and Q is an epoxy functional group with a saturated hydrocarbon ring. It is the basis. The ^R12 group is a substituted or unsubstituted saturated or unsaturated divalent carbon hydrogen group, and the substituent is selected from monovalent hydrocarbon groups, halogen groups, ether groups, ester groups, etc. be. In all the above structural formulas of adhesion promoters presented herein, the R ¹² group has monovalent hydrocarbon groups, halogen groups, ester groups, ether groups and other substituents, and has a number of carbon atoms. It is to be understood that it can be any from 2 to 12 divalent hydrocarbon groups, and that the ^R12 group can be saturated or unsaturated, substituted or unsubstituted. Particular examples of such groups are alkyl groups, arylene groups, and alkylarylene combination groups. A specific adhesion promoter falling within the scope of structural formula (12) above is β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane. Other compounds falling within the scope of structural formula (12) are shown below. β-(3,4-epoxycyclohexyl)propyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethylmethyldimethoxysilane, β-(3, 4-Epoxycyclohexyl)ethylmethyldiethoxysilane, β-(3,4-epoxycyclohexyl)propylmethyldimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltris(methoxyethoxysilane), Z of structural formula (1) The group also includes vinyl, allyl, etc.
It should be noted that it can be a _C2-12 unsaturated group and can be substituted or unsubstituted with groups such as monovalent hydrocarbon groups, halogen groups, ester groups, and ether groups. be. Preferably, Z is a _C2-12 olefin hydrocarbon group such as vinyl, allyl. A preferred compound falling within the scope of structural formula (1) as defined above is vinyltrimethoxysilane. Other compounds falling within the scope of the above structural formula (1) are as follows. Compounds in which Z is an olefin group, such as vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, vinylmethyldiethoxysilane, vinyltrimethoxysilane, vinyltris(2-methoxyethoxy)silane, and vinyl compounds, can be used at high temperatures, for example. The vinylchlorosilane can be prepared by reacting silicon metal with vinyl chloride or allyl chloride in the presence of a copper catalyst to form the vinylchlorosilane, and then alkoxylating this intermediate. This is a well-known operation in silicone manufacturing technology, and the raw chemicals are readily available. Regarding the compound of structural formula (12) above, such a compound can be obtained by reacting hydrogenated trimethoxysilane with vinylcyclohexane oxide in the presence of a platinum catalyst at room temperature or a temperature in the range of room temperature to 150°C. It will be done. The resulting product is then purified by distillation or other means to yield the desired (3,4-epoxycyclohexyl)ethyltrimethoxysilane. As is well known in the art, other compounds within the scope of structural formula (12) above may be similarly prepared using the same procedures. Other compounds within the scope of this invention and within the scope of compounds of structural formula (1) have the following structural formula: In this formula R ¹⁰ , R ¹¹ , t are the same as defined above and R ¹² is a divalent C ₂ , consistent with the definition given above for R ¹² in other structures. _~12 hydrocarbon group, and ^R25 and ^R26 are selected from the group consisting of a hydrogen atom and a monovalent _C1-8 hydrocarbon group. R ²⁵ and R ²⁶ can be any of the groups given above for R ¹⁰ and R ¹¹ . Such substituents are well defined for R ¹⁰ and R ¹¹ and will not be discussed in further detail here. Additionally, compounds of structural formula (13) can be obtained by reacting an olefinic isocyanate, such as allyl isocyanate, with hydrotrimethoxysilane in the presence of a platinum catalyst. It was shown that in all cases alkoxylated products such as hydrogenated trialkoxysilanes were used. This is true if t is equal to 0. If the value of t has a value of 1, 2 or 3, intermediates with R ¹¹ corresponding to the desired product can be used. Therefore, in this case if an alkoxylated but not a semi-alkoxylated product is desired, hydrogenated monoalkyl or hydrogenated dialkylsilanes are of course used instead of hydrogenated trialkoxysilanes. Such intermediates are well known in the art. In any case, the compound of structure (13) can be added with the desired hydrogenated intermediate to the olefin isocyanate compound to obtain the desired reaction product. Therefore, in this case in particular, allyl isocyanate can be reacted with hydrogenated trimethoxysilane to produce the desired product in the presence of a platinum catalyst under much the same conditions as used to make other products. The product γ-isocyanatopropyltrimethoxysilane is obtained. A compound does not necessarily have to have three methoxy groups. 0, 1, 2, as desired
A suitable intermediate having three methoxy groups can be used. Such intermediates are well known in the art. Other compounds within the scope of structural formula (13) along with γ-isocyanatopropyltrimethoxysilane include: Other groups of adhesion promoters falling within the scope of the above structural formula (1) are It is a compound with the structural formula. In this formula, R ¹⁰ , R ¹¹ , t are as defined above, R ¹² is a divalent C _2-12 hydrocarbon group,
Any of the R ¹² groups defined herein above and may be saturated or unsaturated, substituted or unsubstituted. A specific preferred compound within structure (14) is γ-cyanopropyltrimethoxysilane. Other specific compounds are as follows. 3-(cyanoethoxy)-3-methylbutenyltrimethoxysilane, β-cyanoethylmethyldimethoxysilane, β-cyanoethyltriethoxysilane, β-cyanoethyltrimethoxysilane, 2-cyanoethylmethyldiethoxysilane, 3-cyanopropyltri Ethoxysilane, cyanopropylmethyldimethoxysilane, 1-cyanoethyltris(methoxyethoxy)
Silanes, such compounds are prepared by reacting a cyanated olefin with a hydrogenated trichlorosilane and then reacting this intermediate under conditions nearly identical to those used to react other compounds in the presence of a platinum catalyst to form the desired intermediate. is prepared by alkoxylation of γ-cyanopropyltrimethoxysilane to give the suitable γ-cyanopropyltrimethoxysilane. Thus, one example of a reaction would be, for example, to react allyl cyanide with trichlorosilane. This reaction involves reacting cyanide with chlorosilane. Instead, when a methoxylated intermediate is used in an addition reaction with a platinum catalyst, the methoxy group reacts with the cyano group, reducing the yield of the desired product. The use of such reactions to prepare such compounds is well known in the art. Such compounds are made by silicone manufacturers and are well known. Another group of compounds that fall within the scope of structural formula (1) and can be used as adhesion promoters are compounds having the following structural formula: In this formula, R ¹⁰ , R ¹¹ and t are as defined above. In structural formulas (9-15), t can vary from 0 to 3 and ^R22 is a divalent _C2-12 hydrocarbon group as defined above. moreover,
R ³⁰ and R ³¹ are selected from the group consisting of a hydrogen atom, a monovalent C _1-8 hydrocarbon group, and a mixture thereof. ^R30 and
It should be noted that R ³¹ can be unsubstituted or substituted. Specific compounds falling within the scope of the above structural formula (15) that can be used in the present invention include the following. γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, γ-methacrylpropyltriethoxysilane, γ-methacryloxypropyltris(methoxyethoxy)silane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacrylic Oxyethyltrimethoxysilane, such a compound is prepared by taking the corresponding acrylic acid olefin and reacting it with a hydrogenated alkoxysilane in the presence of a platinum catalyst under much the same conditions as in the production of other adhesion promoters. Manufactured by Such compounds were recognized on January 4, 1980.
U.S. patent application filed by Keating
No. 109,727, which more fully discloses the preparation and preparation of such compounds. According to Keating, the compounds can be made by those skilled in the art using published methods or other methods. The method presented above is the simplest method for preparing the compound. Finally, another group of compounds that fall within the scope of structural formula (1) that can be used as adhesion promoters of the present invention are compounds of the following structural formula. In this formula, R ¹⁰ , R ¹¹ , t are as defined above, R ¹² is a divalent C _2-12 hydrocarbon group as defined above, and R ³³ is a monovalent C _{1 ~8} hydrocarbon groups. The R ¹² group can be any of the R ¹² shown above in the preparation of other groups of compounds. R ¹² may be substituted or unsubstituted, saturated or unsaturated. Preferably R ³³ is a methyl group and the compound is acetoxypropyltrimethoxysilane. Other compounds falling within the scope of Structural Formula (16) above include: 2-acetoxyethyltrimethoxysilane, 2-acetoxyethyltriethoxysilane, 3-benzoxypropylmethyldimethoxysilane, 3-benzoxypropyltrimethoxysilane, 3-benzoxypropyltriethoxysilane, 3-benzoxypropyl Methyldiethoxysilane, 2-acetoxypropylmethyldimethoxysilane, 2-acetoxypropylmethyldiethoxysilane, 2-acetoxypropyltriethoxysilane In this case as well, the compound group of structural formula (16) can be any They may be made by reacting a suitable hydrogenated silane with a carboxylic olefin or acyloxy functional compound in the presence of a platinum catalyst under conditions substantially similar to those used to make other compounds. Conditions for such reactions range from room temperature to 120
The reaction temperature is from 150°C to 150°C, and the reaction is an addition reaction that is easily carried out in 30 minutes to 24 hours. The reaction can occur at atmospheric pressure or under reduced pressure. Using such procedures and using the above disclosure, one skilled in the art will be able to make the above compounds. In addition, the source chemicals may be purchased from Petrarch Systems, P.O. Box 141, Levittown, Pennsylvania 1905.
Inc., Connecticut Union Cdrbide, Michigan Dow-corning, New York 12302
Scotia Allaus 10 can be obtained from specialty chemical distributors such as Silar Laboratories. The adhesion promoters can be incorporated into one-part RTV compositions in any manner. For example, the adhesion promoter can be incorporated into the system by first making the end-capped polymer, then adding the scavenger, then adding the adhesion promoter, filler, or other ingredients. Alternatively, all components can be mixed at the same time. There are various variations of these mixing operations. The most preferred method of mixing consists in first capping the ends of the silanol polymer with the crosslinking agent and then adding the adhesion promoter along with the filler, condensation catalyst, and other ingredients. This method allows manufacturers to most easily obtain more suitable RTV compositions with the most desirable properties. The following examples are given for the purpose of illustrating the invention and are not given for the purpose of limiting or limiting the invention. All parts are by weight. Example 1 A mixer equipped with a pressure reduction line and a nitrogen purge facility,
Contains 0.6% di-n-hexylamine, 25
100 parts by weight of polydimethylsiloxane polymer capped with methyldimethoxy groups, having a viscosity of 120,000 centipoise at 25°C, 17 parts by weight of a fumed silica filler treated with cyclooctamethyltetrasiloxane, having a viscosity of 100 centipoise at 25°C. 20 parts by weight of a dimethylpolysiloxane liquid containing silanol and terminated with trimethylsiloxy groups, 20 mole percent monomethylsiloxy units, 76 mole percent dimethylsiloxy units, and 4
10 parts by weight of a silanol liquid with 0.5 mole % silanol groups along with mol % trimethylsiloxy units, CT as a thixotrope
Union Carbide Corporation to UCON LB−
Polymer L sold under the product name 1145
0.2 parts by weight was filled. This mixture was stirred at room temperature under strong vacuum (22 mmHg) for 2 hours to obtain the RTV base. Two parts of hexamethyldisilazane and one part of methyltrimethoxysilane were added to this base. At room temperature using a registered trademark Semkit mixer
After stirring for 15 minutes, a solution of 1 part 3-(2-aminoethylamino)propyltrimethoxysilane and 0.2 parts dibutyltin diacetate was added to the RTV composition and then heated to room temperature using a Semkit® mixer. I stirred it again for 15 minutes. After mixing, the compositions were placed in sealed aluminum tubes and stored for 24 hours, 24 hours at 100°C, and 48 hours at 100°C, respectively. After aging, the composition was made into ASTM sheets and kept at room temperature and 50% relative humidity.
It was cured for 3 days. The physical properties were delineated to indicate the nature of the composition. The flow rate of the uncured mixture was determined according to U.S. military standard MIL-A-46106A.
Tested using the flow test jig described in . A flow test was performed after 3 minutes. Application speed The equipment required for the application speed test was as follows. Equipment Semco #250, Sealant Gun Semco #250-C6, 6 oz. polyethylene cartridge and #250 polyethylene plunger Compressed air source with pressure reducing valve, 90 ± 0.5 psig stainless steel nozzle, 2.000 ± 0.005″ length , diameter 0.54
±0.005″, hole drilled in the center 0.1990±0.0005″, thread equivalent to 1/2″ pipe thread over 1/2″ length at one end Celsius Thermometer Stopwatch Aluminum pan, diameter 2 3/8″ depth 5 /8″ Balance, capable of measuring with an accuracy of 0.1g Standard conditions: 73±3〓, relative humidity 50±10% Thermostatic chamber, 23±1℃ Mixer, registered trademark Semkit Operation Measure the temperature of the sample, 23 If the temperature exceeded ±1°C, conditions were adjusted to obtain the test temperature. Attach the stainless steel nozzle to the cartridge,
Insert the cartridge into the Semco gun and check the gauge pressure.
Connected to an air source of 6.3±0.035 Kg/cm ³ (90±0.5 psig). Several grams of sealant were extruded to fill the nozzle and expel any air that might have been trapped in the nozzle. The sealant was extruded into a pre-weighed container for exactly 15 seconds. Open and close the air source accurately with respect to time
Care must be taken to maintain an interval of 15 seconds. The container containing the extruded sealant was weighed to determine the weight of sealant extruded in 15 seconds. The weight extruded in 60 seconds was obtained by multiplying the weight for 15 seconds by 4. Coating rates were reported in g/min. Adhesive free time Measured by a simple finger touch test. The following results were obtained from these tests.

Table: A profile of the physical properties of the compositions was also obtained for various accelerated and non-accelerated aged stored samples. The results are shown in the table below.

[Table] The RTV composition of this example was aged for 24 hours at room temperature and then tested for adhesion to aluminum, glass, polyacrylate, polycarbonate, polyvinyl chloride, and concrete without a primer. Peel test specimens were prepared and cured for 5 days at room temperature and 50% relative humidity before being stretched. The results are shown in the table below. Table Peel adhesion strength of adherend ppi/% Cohesive failure Glass 56/60 Aluminum (anodized) 37/80 Aluminum (Alclad) 42/60 Polyacrylate 10/0 Concrete 12/5 Polycarbonate 43/100 PVC 25/10 As shown by the values in the table above, the tack adhesion promoter provides the composition with additional good tack to many adherends, even in the absence of a primer. For certain adherends, such as polycarbonate, adhesion is excellent. Example 2 Same composition as Example 1, except that instead of 3-(2-aminoethylamino)propyltrimethoxysilane, a proportion of 1.50 parts of tri(trimethoxysilylpropyl)isocyanurate is present. was prepared. Using the same manufacturing technique and the same peel adhesive operation as outlined in Example 1, the following peel adhesive results were obtained. Peel adhesion strength to adherend ppi/% Cohesive failure Glass 22/100 Aluminum (anodized) 25/90 Aluminum (Alclad) 28/95 Concrete 33/10 Polyacrylate 0/0 Example 3 3-(2-amino- The same composition as in Example 1 was prepared, except that instead of ethyl-amino)-propyltrimethoxysilane, a proportion of 1.50 parts of glycidoxypropyltrimethoxysilane was present. Using the same manufacturing technique and the same peel adhesive operation as outlined in Example 1, the following peel adhesive results were obtained. Peel adhesion strength to adherend ppi/% Cohesive failure Glass 44/100 Aluminum (anodized) 46/60 Aluminum (Alclad) 55/100 Concrete 32/60 Polyacrylate 0/0 Example 4 3-(2-Aminoethyl) β-amino)-propyltrimethoxysilane in a proportion of 1.50 parts
Example 1, except that (3,4-epoxycyclohexyl)ethyltrimethoxysilane is present.
The same composition was prepared. Using the same manufacturing technique and the same peel adhesive operation as outlined in Example 1, the following peel adhesive results were obtained. Peel adhesion strength to adherend ppi/% Cohesive failure Glass 35/100 Aluminum (anodized) 35/50 Aluminum (Alclad) 28/100 Concrete 13/0 Polyacrylate 0/0 Example 5 3-(2-aminoethyl) The same composition as in Example 1 was prepared, except that instead of amino)-propyltrimethoxysilane, a proportion of 1.50 parts of vinyltrimethoxysilane was present. Using the same manufacturing technique and the same peel adhesive operation as outlined in Example 1, the following peel adhesive results were obtained. Peel adhesion strength to adherend ppi/% Cohesive failure Glass 35/100 Aluminum (anodized) 35/95 Aluminum (Alclad) 35/100 Concrete 18/0 Polyacrylate 0/0 Example 6 3-(2-Aminoethyl) The same composition as in Example 1 was prepared, except that instead of amino)-propyltrimethoxysilane, a proportion of 1.50 parts of γ-isocyanatopropyltrimethoxysilane was present. Using the same manufacturing technique and the same peel adhesive operation as outlined in Example 1, the following peel adhesive results were obtained. Peel adhesion strength to adherend ppi/% Cohesive failure Glass 29/100 Aluminum (anodized) 9/0 Aluminum (Alclad) 31/100 Concrete 10/0 Polyacrylate 0/0 Example 7 3-(2-aminoethyl The same composition as in Example 1 was prepared, except that instead of amino)-propyltrimethoxysilane, a proportion of 1.50 parts of cyanopropyltrimethoxysilane was present. Using the same manufacturing technique and the same peel adhesive operation as outlined in Example 1, the following peel adhesive results were obtained. Peel adhesion strength to adherend ppi/% Cohesive failure Glass 29/95 Aluminum (anodized) 7/0 Aluminum (Alclad) 31/100 Concrete 17/50 Polyacrylate 0/0 Example 8 3-(2-Aminoethyl) The same composition as in Example 1 was prepared, except that instead of amino)-propyltrimethoxysilane, a proportion of 1.5 parts of methacryloxypropyltrimethoxysilane was present. Using the same manufacturing technique and the same peel adhesive operation as outlined in Example 1, the following peel adhesive results were obtained. Peel adhesion strength to adherend ppi/% Cohesive failure Glass 35/95 Aluminum (anodized) 8/0 Aluminum (Alclad) 12/5 Concrete 11/0 Polyacrylate 0/0 Example 9 3-(2-aminoethyl The same composition as in Example 1 was prepared, except that instead of amino)-propyltrimethoxysilane, a proportion of 1.5 parts of cyanoethyltrimethoxysilane was present. Example 1
The following peel adhesion results were obtained using the same fabrication technique and the same peel adhesion operation as outlined in . Peel adhesion strength to adherend ppi/% Cohesive failure Glass 24/100 Aluminum (anodized) 23/90 Aluminum (Alclad) 27/95 Concrete 14/10 Polyacrylate 0/0 Example 10 3-(2-aminoethyl The same composition as in Example 1 was prepared, except that instead of amino)-propyltrimethoxysilane, a proportion of 1.50 parts of aminopropylmethyldimethoxysilane was present. Using the same manufacturing technique and the same peel adhesive operation as outlined in Example 1, the following peel adhesive results were obtained. Peel adhesion strength to adherend ppi/% Cohesive failure Glass 8/0 Aluminum (anodized) 15/10 Aluminum (Alclad) 31/50 Concrete 17/10 Polyacrylate 0/0 Example 11 3-(2-aminoethyl The same composition as in Example 1 was prepared, except that instead of amino)-propyltrimethoxysilane, 3-acetoxypropyltrimethoxysilane was present in a proportion of 1.5 parts. Using the same manufacturing technique and the same peel adhesive operation as outlined in Example 1, the following peel adhesive results were obtained. Peel adhesion strength to adherend ppi/% Cohesive failure Glass 27/50 Aluminum (anodized) 0/0 Aluminum (Alclad) 23/100 Concrete 10/0 Polyacrylate 0/0 The adhesion promoter of the present invention is preferably For use with the RTV composition of Docket No. 60Si-579 filed by Dziark. In one example, Dziark et al., U.S. Pat.
discloses certain suitable silazane compounds for use as scavengers in RTV systems. Dziark's docket
A preferred system for 60Si-579 is to first form a polyalkoxyorganopolysiloxane polymer and then include a compound that is a silazane monomer or polymer, separate from the crosslinker, or some type of amine polymer compound as a scavenger. It is something. The adhesion promoters of the present invention may be used in combination with the compositions of White et al., U.S. Pat. can also be used to create advantageous one-component, low modulus, fast curing, storage stable adhesive RTV systems. It should be noted that the scavenger in Dziark Docket 60Si-579 is a separate compound from, and is used in conjunction with, the crosslinker. Such compositions, along with other alkoxy-functional RTV systems, are described in U.S. Patent No. 277,524 to White et al.
Published in 13275. Dziark Docket 60Si
A brief summary of the −579 system is provided below. To learn more about such scavengers and RTV systems,
See the disclosure in Dziark, docket 60Si-579. Substantially anhydrous and substantially acid-free stable material that is stable under ambient conditions for extended periods of time in the substantial absence of moisture and can be converted to a dry-to-touch elastomer in accordance with Dziark Docket 60Si-579. The adhesion promoter of the present invention can be used in a one-package room-temperature vulcanizable organopolysiloxane composition. The resulting composition comprises: (1) an organopolysiloxane in which the terminal silicon atom of each polymer chain is terminated with at least two alkoxy; (2) an effective amount of a condensation catalyst; (3) R'' is a hydrogen atom; A member selected from the group consisting of a monovalent hydrocarbon group and a fluoroalkyl group, R is a member selected from a hydrogen atom, a monovalent hydrocarbon group, and a fluoroalkyl group, and c is from 0 to 3. are equal integers and (A) Y is selected from R and R″ ₂ N-, then the structural formula A silicon-nitrogen compound with (B)(i) structural formula

【formula】

【formula】

【formula】

【formula】 【formula】

3 to 100 mol% of chemically bonded structural units selected from the group consisting of units having the following formula; (ii) 0 to 97 mol% of chemically bonded structural units represented by the following structural formula or a mixture thereof; , A silicon-nitrogen polymer containing the above (i) and (ii), wherein the silicon atom of the silicon-nitrogen polymer is
They are bonded to each other by members selected from SiOSi bonds and SiNR''Si bonds, and the valences that bond to the oxygen atom of the silicon atom to form a siloxy unit and the valences that bond to the nitrogen atom to form a silazi unit. The other free valences are selected from R″ groups and (R″) ₂ N groups and are bonded to the member, such that the sum of the numbers of the R groups and the (R″) ₂ N groups of the silicon-nitrogen polymer is a stabilizing amount of silane scavenger for hydroxyl functional groups, which is a silicon-nitrogen compound selected from the group consisting of (A) and (B), with a ratio of silicon atoms to number of 1.5 to 3; 4) One of the adhesion promoters of the present invention; 0.5 per 100 parts by weight of organopolysiloxane
From 10 parts by weight of silicone scavenger is present. The silazane polymer can include a cyclic silazane having chemically bonded units of the following structural formula. In this formula, R″, R are the same as defined above, and 1 silicon atom in the silazane polymer.
The total number of R groups and (R″) ₂ N groups per piece is 1.5
It is between 3.0 and 3.0. The silazane polymer can include a linear polymer having at least one unit selected from the group consisting of units of the following two types of structural formulas. In these formulas, R″ and R are the same as defined above, and the total number of R groups and (R″) ₂ N groups per silicon atom in the silazane polymer ranges from 1.5 to 3. It is. Silazane polymers can include linear polymers consisting essentially of units of the following structural formula: In this formula, R″ and R are the same as defined above, and the sum of the number of R groups and (R″) ₂ N groups per silicon atom in the silazane polymer is
1.5 to 3.0. The silazane polymer may have at least one unit selected from the group consisting of units of the following two structural formulas. In these formulas, R″ and R are the same as defined above, and the sum of the number of R groups and (R″) ₂ N groups per silicon atom in the silazane polymer is
It is 1.5 to 3. The silazane polymer can be a polymer having a sufficient amount of units selected from units having the following structural formula:

【formula】 【formula】

[Formula] In these formulas, R″ and R are the same as defined above, and the sum of the number of R groups and (R″) ₂ N groups per silicon atom in the silazane polymer is It is 1.5 to 3. Furthermore, silazane-siloxane compounds have an upper limit of 97
Structural formula to mol% unit and structure of

【formula】

It may be a copolymer consisting of a majority of units of the formula.
In these formulas, R″ and R are the same as defined above, and R groups per silicon atom of the silazane-siloxane copolymer and (R″) ₂ N
The total number of groups is 1.5 to 3. The cyclic silazane-siloxane compound is (R)
₂ It is a cyclic body consisting of a SiO unit and a unit of the following structural formula chemically bonded. In these formulas, R'' and R are as defined above. Additionally, the silazane nitrogen compound can be a linear or cyclic silazane having the following structural formula: In this formula, R″ and R are the same as defined above, and n is a positive integer, preferably between 0 and
20, α is an integer equal to 0 to 1, and α
When is equal to 0, n is preferably equal to 3 to 7. Additionally, the silazane nitrogen compound can be a polysiloxane having the following structural formula: In this formula, R'', R and n are the same as defined above, and Z is a member selected from R'' and -Si(R) ₃ . Preferably, the silicon nitrogen compound is hexamethyldisilazane, hexamethylcyclotrisilazane,
Octamethylcyclotetrasilazane, structural formula [CF ₃ −CH ₂ −CH ₂ −(CH ₃ ) ₂ −Si] Silicon nitrogen compound with ₂ NH, structural formula [CF ₃ −CH ₂ −CH ₂ −(CH ₃ ) -SiNH] ₃ is selected from silicon nitrogen compounds having the structural formula [CF ₃ -CH ₂ -CH ₂ -(CH ₃ ) ₂ -Si] ₂ N-CH ₃ .

Claims (1)

[Scope of Claims] 1. (1) An organopolysilosisane in which the silicon atom at the end of each polymer chain is terminated with at least two alkoxy groups; (2) An effective amount of a condensation catalyst; (3) A hydroxyl functional group (4) an effective amount of a curing accelerator selected from the group consisting of substituted guanidines, amines, and mixtures thereof; and (5) a stabilizing amount of a scavenger relative to the formula (In the formula, R ¹⁰ and R ¹¹ are C _1-8 monovalent hydrocarbon groups,
t varies from 0 to 3, and Z is a saturated, unsaturated or aromatic hydrocarbon group, which groups include amino groups, ether groups, epoxy groups, isocyanate groups, cyano groups, isocyanurate groups, acryloxy groups and further functionalized with a member selected from the group consisting of acyloxy groups and mixtures thereof under substantially moisture-free and ambient conditions. A stable, substantially anhydrous, substantially acid-free, one-pack room temperature vulcanizable organopolysiloxane composition that is stable over long periods of time and convertible into a tack-free elastomer. 2 formulas (In the formula, R ¹⁰ and R ¹¹ are C _1-8 monovalent hydrocarbon groups,
^R12 is a _C1-12 divalent hydrocarbon group, ^R13 and ^R14
is selected from the group consisting of hydrogen, amine groups and C _1-8 monovalent hydrocarbon groups and mixtures thereof, t varying from 0 to 3),
saturated, where Z is further functionalized by an amino group,
The composition according to claim 1, which is an unsaturated or aromatic hydrocarbon group. 3 formulas (In the formula, G is ^R20 group, formula group, styryl group, vinyl group, allyl group, chloroallyl group, and cyclohexenyl group, ^R20 is a _C1-8 monovalent hydrocarbon group or a cyanoalkyl group, and ^R21 is a _C1-8 monovalent hydrocarbon group or a cyanoalkyl group. a valent hydrocarbon group or a cyanoalkyl group, and R ²² is selected from alkylenearylene, alkylene and cycloalkylene groups and halogenated alkylenearylene, alkylene and cycloalkylene groups.
Z is a saturated, unsaturated or aromatic hydrocarbon further functionalized with an isocyanurate group to provide an adhesion promoter (C _2-12 divalent hydrocarbon group, b varying from 0 to 3) Claim 1 which is the basis of
Compositions as described in Section. 4 formula (wherein R ¹⁰ and R ¹¹ are C _1-8 monovalent hydrocarbon groups, R ¹² and R ¹⁶ are C _2-12 divalent hydrocarbon groups,
R ¹⁷ is selected from the group consisting of hydrogen and C _1-8 monovalent hydrocarbon groups, and t varies from 0 to 3), so that Z is of the formula A composition according to claim 1, which is a saturated, unsaturated or aromatic hydrocarbon radical further functionalized with a group of the formula: R ¹² , R ¹⁶ and R ¹⁷ are as defined above. . 5 formula (where R ¹⁰ and R ¹¹ are C _1-8 monovalent hydrocarbon groups, R ¹² is a C _2-12 divalent hydrocarbon group, and Q is an epoxy functionality having a saturated hydrocarbon ring attached) and t varies from 0 to 3), wherein Z is a saturated, unsaturated or aromatic hydrocarbon group further functionalized with an epoxy group. Compositions as described in Section. 6 formula (where R ¹⁰ and R ¹¹ are C _1-8 monovalent hydrocarbon groups, R ¹² is C _2-12 divalent hydrocarbon groups, R ²⁵ and R ²⁶ are hydrogen and C _1-8 monovalent Z is a saturated, unsaturated or aromatic hydrocarbon group further functionalized with an isocyanate group to provide an adhesion promoter selected from the group consisting of hydrocarbon groups, where t varies from 0 to 3) A composition according to claim 1. 7 formula (In the formula, R ¹⁰ and R ¹¹ are C _1-8 monovalent hydrocarbon groups, R ¹² is C _2-12 divalent hydrocarbon groups, and t is 0-
3. The composition of claim 1, wherein Z is a saturated, unsaturated or aromatic hydrocarbon group further functionalized with a cyano group to provide an adhesion promoter of 3). 8 formula (where R ¹⁰ and R ¹¹ are C _1-8 monovalent hydrocarbon groups, R ¹² is C _2-12 divalent hydrocarbon groups, R ³⁰ and R ³¹ are hydrogen and C _1-8 monovalent Z is a saturated, unsaturated or aromatic hydrocarbon group further functionalized with an acryloxy group to provide an adhesion promoter selected from the group consisting of hydrocarbon groups, with t varying from 0 to 3). A composition according to claim 1. 9 formula (where R ¹⁰ and R ¹¹ are C _1-8 monovalent hydrocarbon groups, R ¹² is C _2-12 divalent hydrocarbon groups, and R ³³ is
Z is a saturated, unsaturated or aromatic hydrocarbon group further functionalized with an acyloxy group to provide an adhesion promoter (C _1-8 monovalent hydrocarbon group, t varying from 0 to 3) The composition according to claim 1. 10. The composition of claim 1, wherein the adhesion promoter is cyanoethyltrimethoxysilane. 11. The composition of claim 1, wherein the adhesion promoter is aminoethylaminopropyltrimethoxysilane. 12. The composition of claim 1, wherein the adhesion promoter is a mixture of cyanoethyltrimethoxysilane and aminoethylaminopropyltrimethoxysilane. 13. A method of producing a substantially acid-free, one-package room temperature vulcanizable composition which is curable to a solid elastomeric state, wherein the method comprises (i) (a) a silanol-terminated polydiorganosiloxane;
100 parts by weight, (b) a stabilizing amount of scavenger for hydroxyl functionality, (c) 0 to 10 parts by weight of polyalkoxy crosslinker, (d) an effective amount of condensation catalyst, (e) substituted guanidine, amine and Curing accelerator selected from the group consisting of mixtures thereof
5 parts by weight, formula (f) (wherein R ¹⁰ and R ¹¹ are C _1-8 monovalent hydrocarbon groups, t varies from 0 to 3, Z is a saturated, unsaturated or aromatic hydrocarbon group, and the hydrocarbon group is Amino group, ether group, epoxy group,
further functionalized with a member selected from the group consisting of isocyanate groups, cyano groups, isocyanurate groups, acryloxy groups and acyloxy groups and mixtures thereof. and (ii) (a) 100 parts by weight of a polyalkoxy-terminated polydiorganosiloxane, (b) 0 to 10 parts by weight of a polyalkoxy crosslinker, (c) an effective amount of a condensation catalyst, and (d) scavenging for hydroxyl functional groups. (e) a curing accelerator selected from the group consisting of substituted guanidines, amines and mixtures thereof;
5 parts by weight, and formula (f) (In the formula, R ¹⁰ and R ¹¹ are C _1-8 monovalent hydrocarbon groups, t varies from 0 to 3, Z is an amino group,
Saturated, unsaturated or aromatic hydrocarbon groups further functionalized with a member selected from the group consisting of ether groups, epoxy groups, isocyanate groups, cyano groups, isocyanurate groups, acryloxy groups and acyloxy groups and mixtures thereof. A method characterized in that a room temperature vulcanizable material selected from a mixture containing an effective amount of an adhesion promoter having the following properties is stirred under substantially anhydrous conditions at a temperature in the range of 0<0>C to 180[deg.]C. 14 formula (wherein R ¹⁰ and R ¹¹ are C _1-8 monovalent hydrocarbon groups, R ¹² is C _2-12 divalent hydrocarbon groups, R ¹³ and R ¹⁴ are hydrogen, amine groups and C _{1- 8} monovalent hydrocarbon groups and mixtures thereof, saturated, unsaturated, Z further functionalized by an amine group to provide an adhesion promoter (t varying from 0 to 3) or an aromatic hydrocarbon group, the method according to claim 13. 15 formula (In the formula, G is a monovalent hydrocarbon group, a halogenated monovalent hydrocarbon group, and the formula R ²⁰ is a C _1-8 monovalent hydrocarbon group or a halogenated monovalent hydrocarbon group, and R ²¹ is a C _1-8 monovalent hydrocarbon group, a halogenated monovalent hydrocarbon group. hydrogen group or cyanoalkyl group, R ²²
is a _C2-12 divalent hydrocarbon group selected from alkylenearylene, alkylene and cycloalkylene groups, and halogenated alkylenearylene, alkylene and cycloalkylene groups,
b varies from 0 to 3) wherein Z is a saturated, unsaturated or aromatic hydrocarbon group further functionalized with an isocyanurate group. the method of. 16 formula (wherein R ¹⁰ and R ¹¹ are C _1-8 monovalent hydrocarbon groups, R ¹² and R ¹⁶ are C _2-12 divalent hydrocarbon groups,
R ¹⁷ is selected from the group consisting of hydrogen and C _1-8 monovalent hydrocarbon groups, and t varies from 0 to 3), so that Z is of the formula The first claim is a saturated, unsaturated or aromatic hydrocarbon group further functionalized by a group in which R ¹² , R ¹⁶ and R ¹⁷ are as defined above.
The method described in Section 3. 17 formula (In the formula, R ¹⁰ and R ¹¹ are C _1-8 monovalent hydrocarbon groups, R ¹² is a C _2-12 divalent hydrocarbon group, and Q is an epoxy functional group with an attached saturated hydrocarbon ring. and t varies from 0 to 3), wherein Z is a saturated, unsaturated or aromatic hydrocarbon group further functionalized with an epoxy group. the method of. 18 formula (where R ¹⁰ and R ¹¹ are C _1-8 monovalent hydrocarbon groups, R ¹² is C _2-12 divalent hydrocarbon groups, R ²⁵ and R ²⁶ are hydrogen and C _1-8 monovalent patents in which Z is a saturated, unsaturated or aromatic hydrocarbon radical further functionalized with an isocyanate group to provide an adhesion promoter selected from the group consisting of hydrocarbon radicals (t varying from 0 to 3); The method according to claim 13. 19 formula (In the formula, R ¹⁰ and R ¹¹ are C _1-8 monovalent hydrocarbon groups, R ¹² is C _2-12 divalent hydrocarbon groups, and t is 0-
Claim 13, wherein Z is a saturated, unsaturated or aromatic hydrocarbon radical further functionalized with a cyano group to provide an adhesion promoter of
The method described in section. 20 formula (wherein R ¹⁰ and R ¹¹ are C _1-8 monovalent hydrocarbon groups, R ¹² is C _2-12 divalent hydrocarbon groups, R ³⁰ and R ³¹ are hydrogen and C _1-8 monovalent Z is a saturated, unsaturated or aromatic hydrocarbon group further functionalized with an acryloxy group to provide an adhesion promoter selected from the group consisting of hydrocarbon groups, with t varying from 0 to 3). 14. The method of claim 13. 21 formula (where R ¹⁰ and R ¹¹ are C _1-8 monovalent hydrocarbon groups, R ¹² is C _2-12 divalent hydrocarbon groups, and R ³³ is
Z is a saturated, unsaturated or aromatic hydrocarbon group further functionalized with an acyloxy group to provide an adhesion promoter (C _1-8 monovalent hydrocarbon group, t varying from 0 to 3) 14. The method according to claim 13.