JPS5996163A - Manufacture of room temperature curable silicone rubber by using devolatile extruder - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a one-component alkoxy-functional room temperature curable (hereinafter referred to as RTV) silicone rubber composition, and more particularly, the present invention relates to a method for producing a one-component alkoxy-functional room temperature curable (hereinafter referred to as RTV) silicone rubber composition. (
dovolatilizing extruder)
The present invention relates to a method of making a one-component alkoxy-functional RTV silicone rubber composition using.

One-component alkoxy-functional RTV silicone rubber compositions are disclosed in U.S. Pat. No. 410,012 to Beers.
It is well known as exemplified by No. 9.

An important innovation in the processing of such compositions is the anhydrous mixing of the ingredients prior to packaging in a twin screw devolatilizing extruder, as disclosed in U.S. Pat. No. 3,960,802 to Bears et al. It was a method. As pointed out in the above patent, mixing was done more effectively in the devolatilizing extruder. Furthermore, it has been found that lower viscosity mixed compositions can be obtained by use of a devolatilizing extruder. Alkoxy functional one-component type R
The process was an important innovation in the manufacture of TV compositions because it allowed such compositions to be produced continuously at a somewhat lower cost than previous mixing methods.

Recently, for example, White (Whiteθ) et al.
One-component storage-stable alkoxy-functional RTs as disclosed in U.S. Patent Application No. 277,524, filed May 6,
V silicone rubber compositions have been developed. This US patent application discloses the initial preparation of polyalkoxy-terminated diorganopolysiloxane polymers. When making this polymer, scavengers are added to link free alcohol and hydroxy groups, and the uncured polymer mixture is combined with other additive components such as fillers, adhesion promoters, condensation catalysts, etc. Together they are used in the production of the first R old series. The innovation disclosed in this invention is to add a scavenger to this polymer following polyalkoxy end-capped diorganoborisiloxane borimano formation to link all free hydroxy groups degenerating the polymer. .

The production of an uncured composition in which the free hydroxyl groups and alcohol in the blended bone are linked provides a storage-stable composition. Namely, Bears' U.S. Patent No. 4
Although the compositions of No. 100,129 and US Pat. No. 3,960,802 were storage stable, the cure rate after storage for 6 months or more was still not fast enough.

Indeed, as pointed out in the above-mentioned US patent application to White et al., such compositions appear to suffer from decreased storage stability after storage for a short period of two weeks.

Therefore, as pointed out in U.S. patent application Ser. Alkoxy-functional RTs that can maintain long storage stability of products and traditionally have slow curing speeds
It is believed that the V composition had an even faster cure rate.

There have been other developments in this area. For example, Changgu (C
No. 338,518 discloses the use of certain cyclic amides as scavengers. Additionally, Bears, U.S. patent application filed November 11, 1981; U.S. Patent Application No. 349,537, filed on the date Dziark, February 17, 1982, discloses the preparation of storage-stable alkoxy-functional compositions that cure to
US Pat. No. 1!1iii. No. 349,695, filed on D. This application discloses the use of certain silazane scavengers for the above compositions. Then there is the disclosure of Lucas et al., US Patent Application No. 349,538, filed February 17, 1982. This application describes the use of certain adhesion promoters in the alkoxy-functional one-component RTV system of White et al., U.S. Patent Application No. 277,524, as well as in U.S. Patent Application No. 277,524 of Zujak and U.S. Pat. Disclosed. Further advances are being made in this area. For example, U.S. Patent Application ff!, filed September 29, 1982, by Chang et al. There is No. 428038. this?
['A discloses the use of strains of alkoxy-functional silazane as either scavengers or composite scavengers and crosslinkers. Furthermore, Chang's 1982
US patent filed on September 29th! j, I No. 42793
There is a disclosure of No. 0. This application discloses the use of certain acidic catalysts and combinations of acidic and amine catalysts as coupling catalysts for end-capped IOs of polyalkoxy-terminated diorganopolysiloxane polymers. All of these compositions were highly desirable and innovative in the production of Kf ii stable fast curing Modulus 1 molded RTV silicone rubber compositions.

I must make one point clear. Bears, U.S. Pat. No. 4,100,129 and Bears et al., U.S. Pat.
Most of the compositions of No. 060802 appear to cure even after periods as long as one or two years. However, the handling of this composition has not always been simple, efficient or economical, since its curing rate is substantially affected and undesirably decreases after long-term storage.

As with other U.S. patent applications, improvements in White et al.
That is, after the composition has been stored, the composition has a cure rate that is not reduced to the extent that it reduces the cure rate of the compositions of Bears et al. It was about manufacturing things. Accordingly, White et al., US Pat. No. 277,524, H'! The compositions of No. 5,349,695 and other U.S. patent applications provide more storage stable, rapid curing compositions than the earlier compositions of both Bears patents.

The method for making such compositions involves mixing the silanol-terminated backbone polymer with a crosslinking agent and an end-coupling catalyst without a scavenger in a first mixing step, and then combining the condensed catalyst mixture with a scavenger in a second mixing step. It was highly desirable to mix them together.

More thorough mixing methods, particularly continuous mixing methods, would be desirable for such compositions.

If a continuous mixing method were developed for such compositions, it would result not only in the production of a larger number of sets of materials in a given time, but also in labor savings.

One object of the present invention is to provide a continuous mixing process for producing scavenger-containing alkoxy-functional one-component RTV compositions.

Another object of the present invention is to provide an efficient method for producing storage stable, fast curing, alkoxy functional RTV silicone rubber compositions in which mixing is carried out by a devolatilizing extruder.

Yet another object of the present invention is to provide an efficient continuous mixing method. This method involves first mixing in a static mixer to form an end-capped polyalkoxydiorganopolysiloxane, then placing the polymer in a devolatilizing extruder and mixing in other ingredients such as fillers. - To provide a low viscosity, rapid curing, storage stable alkoxy-functional one-component RTV silicone rubber composition.

These and other objects of the invention are achieved by the disclosure set forth below.

In accordance with the above objectives, a stable, substantially anhydrous and substantially acid-free organopolysiloxane composition capable of being transformed into a stable, tack-free elastomer under substantially moisture-free ambient conditions for extended periods of time. A continuous process is provided by the present invention for producing (a) an organopolysiloxane in which the silicon atom at the end of each polymer chain is terminated with at least one hydroxy group; is a composite cross-linking agent scavenger, an end-capping flux which is an acid selected from a Lewis acid, an a-Liebrensted acid and a stearic acid treated calcium carbonate; the resulting cocatalyst through a static mixer and then passing the resulting mixture through a devolatilizing extruder while adding other ingredients to the devolatilizing extruder to form the HTv composition. Become.

In the above method, the polymer is first end-capped with a polyalkoxysilane or composite crosslinker in a static mixer. Once such a polyalkoxy-terminated diorganopolysiloxane polymer is formed, the polymer is then mixed continuously with the other components at the desired stage in the extruder to form R'
ff A silicone rubber composition is manufactured. When all the individual components, i.e., the end-capping polymer-forming components and other components such as fillers, adhesion promoters and condensation catalysts, plasticizers, etc., are added into the extruder, the viscosity of the resulting composition is very high. is known to be high.

It is hypothesized that this high viscosity is due to the silanol groups in the filler reacting with the silanol groups in the silanol-terminated polymer prior to the alkoxy endcapping reaction that connects the hydroxy groups. As a result, substantial crosslinking occurs between the filler and the backbone polymer, resulting in excessively high viscosity.

The viscosity of this composition does not reduce the status of the composition. In the present invention, it is desirable to end-cap the backbone polymer along with the other components in a devolatilizing extruder. If a low viscosity uncured composition is not desired, the composition and all ingredients can be mixed in a devolatilizing extruder.

For purposes of this invention, a scavenger is defined as any compound that links any free hydroxy groups in the composition. That is, it reacts with unbound -OH in order to prevent unbound -DH from further reacting in any polymer decomposition reactions in the composition, and with respect to all other components in the composition. is inert. A decondensing crosslinking agent scavenger is a compound in which one portion of the compound exhibits the same scavenging activity as the scavenger compound and the other portion is capable of endcapping the silanol-terminated diorganopolysiloxane polymer with one or more alkoxy crosslinking sites. , ie, a compound capable of endcapping a silanol-terminated diorganopolysiloxane polymer with one or more alkoxy groups.

I have to point out just one point. Although it is desirable for the chain-terminated diorganopolysiloxane polymer to have two or more alkoxy groups to form the main component of the one-component RTV silicone rubber composition,
If the polymer of a given rod is endcapped with only one alkoxy end of the polymer, the composition still behaves like a one-component RTV composition.

Birch viscosity reducers and plasticizers can be used in the present invention to reduce the viscosity of the final composition so that the final composition has a suitable application rate. However, such viscosity-lowering agents are preferably used in accordance with the present invention to produce one-component RTV silicone rubber compositions. Whatever laxatives or plasticizers are used, these components reduce the final viscosity of the RTV silicone coat composition. producing a polyalkoxy-terminated diorganoborisiloxane polymer in a static mixer;
It is then desirable to mix this compound with the other ingredients in a continuous manner in a devolatilizing extruder. It is noted that the process of the present invention is completely continuous in nature, ie, the mixing of all components during the production and packaging of the uncured RTV silicone rubber composition occurs in a substantially continuous manner. Should.

To prepare the low viscosity 1u RTv silicone rubber composition of the present invention having a speed of more than about 50 to 1001 mW per minute, which is an applied mW corresponding to the specific gravity range of 1.010 to 1.050 of the RTV composition. The viscosity reducing agents and plasticizers can be added to low viscosity, i.e. triorganosiloxy-terminated diorganopolysiloxane polymers and possibly the same (i. The scavengers described above absorb the silanol groups in the low viscosity silyl polymer and reduce the viscosity of the polymer. , e , is believed to be able to perform.

In the broadest concept of the invention, all ingredients, ie, silanol polymer, filler, plasticized LFli cocatalyst, adhesion promoter, etc., can be mixed in one devolatilization extrusion. In such a substantially continuous process, the devolatilization extrusion is operated at a force <= 40 to 100°C, more preferably 40 to 60°C, and the extruder is A slight vacuum is operated to remove volatiles during the mixing process. while)
The method of mixing all the components described herein in a devolatilizing extruder is suitable for producing high viscosity, i.e.
It is known to give R'I'V products which tend to have a velocity smaller than the velocity of the uncured composition (i, aimed at the specific gravity of the uncured composition in the range of 1.050 to 1.050). . It should be noted that this application rate range will vary for different 4M compositions depending on the desired specific gravity of the particular RTV composition. Application speed is inversely proportional to specific gravity.

Therefore, in accordance with a preferred embodiment of the present invention, it is desirable to first prepare the polyalkoxy-terminated diorganopolysiloxane polymer in a static mixer. The total amount of silanol-terminated diorganopolysiloxane polymer and a methyltrimethoxysilane crosslinker or a broad range polyalkoxysilane crosslinker, along with an endcapping catalyst or catalysts, are initially mixed in a static mixer at 40 to 100°C. The mixture is operated at a temperature range of 40 to 60°C, preferably 40 to 60°C. This mixing is accomplished in a substantially continuous manner to produce a polyalkoxy-terminated diorganoborisiloxane polymer. This polymer mixture is continuously fed to a devolatilizing extruder in which it is further mixed with other ingredients. The endcapping catalyst added with the polyalkoxysilane crosslinker can be either an acid alone or preferably an acid with an amine cocatalyst as disclosed in Chang U.S. Patent Application No. 427,930. .

However, because of the method of continuous operation, the end-capping catalyst system is
No. 30 acid catalyst in combination with the basic amine catalyst described in that application. RTV
It is believed that endcapping will not be achieved at a sufficient rate if the endcapping is carried out solely with acid or amine catalysts, where it is extremely difficult to make the composition manufacturing process truly continuous.

Furthermore, before mixing the remaining components in the devolatilization extruder, alkoxy+? , % It is undesirable to add scavenger in a static mixer unless you plan to store the cured polymer, otherwise the cured silicone elastomer formed from the alkoxy-containing polymer will be soft (as it tends to be). It should be noted that before forming the RTV silicone rubber composition from the alkoxy-terminated polymer,
If the alkoxy-terminated polymer is to be stored for a period of up to 20 years, the scavenger compound can be added in a static mixer. If a composite strip 6-part scavenger is used, the above instructions apply since the crosslinker scavenger compound must always be added in the static mixer unless the silanol polymer is end-capped in the devolatilizing extruder. Not done.

In particular, one-component uRTV compositions cannot be cured with alkoxy termination until copper or other types of condensation catalysts are added, since the compositions below will not cure at a sufficient rate or with sufficient density without a condensation catalyst. It should be noted that it is formed from a diorganopolysiloxane end-capped polymer.

The method of the present invention is applicable to any one-component RT, such as those described above, that uses a scavenger or a composite crosslinker scavenger.
The V compositions can be applied to produce continuously or semi-continuously or batchwise. Therefore, in a static mixer, the silyl/-terminated diorganosiloxane backbone polymer is reacted with the polyalkoxysilane crosslinking agent of the following formula, and is continuously mixed. A polysiloxane polymer is formed at the beginning of the tatami mat. The scavenger may be any scavenger, but is preferably a silazane, preferably hexylmethyldisilazane. These scavengers can be added (HB) in a static mixer to remove free hydroxyl groups from the polymer mixture only if the composition is to be stored.

When using a composite crosslinker scavenger in the present invention, it should be noted that the scavenger should not be added separately in the static mixer.

The composite crosslinker scavenger will be added to the end-coupled catalyst system and the silanol-terminated diorganopolysiloxane polymer and -M in a static mixer.

Additionally, in a preferred embodiment of the present invention, the polyalkoxy-terminated diorganopolysiloxane formed after continuous end-sealing of the silanol-terminated diorganopolysiloxane polymer with a polyalkoxysilane in a static mixer. The mixture is continuously fed to the first stage of the devolatilizing extruder. In the first step of the devolatilizing extruder, the polyalkoxydiorganopolysiloxane formed in the static mixer as well as the polyether sag (S
ag) a plasticizer mixture consisting of a control agent and a trimethylsiloxy-terminated diorganoborisiloxane polymer, preferably having a stiffness in the range of 10 to 10,000 centipoise at 25°C; Add a filler, preferably treated fumed silica. The devolatilizing extruder section is preferably operated under a slight vacuum, such as 20 inches of mercury or less. Preferably, the devolatilization extruder has a temperature in the range of 40 to 100°C,
More preferably, the entire process of the devolatilization extruder is 40 to 60
℃ range and under vacuum below 20 inches of mercury. Near an intermediate step of the devolatilization run, an amount of silazane scavenger in a preferred embodiment is added to the mixture to further link free hydroxy groups in the mixture.

The preferred methods above and below are described with certain ingredients. However, as far as the present invention is concerned,
It should be noted that these components are merely exemplary. Add the other ingredients in a different order than described below.
It can be added to alkoxy-terminated diorganopolysiloxane polymers. In a preferred embodiment, the alkoxy-terminated diorganopolysiloxane polymer is first formed in a static mixer and it is only necessary to mix the other ingredients in a devolatilizing extruder in any order desired.

Finally, in the last part of the devolatilizing extruder, a mixture of tin condensation catalyst and adhesion promoter and excess polyalkoxysilane crosslinking agent are mixed into the above mixture. The mixture is then mixed in a few more steps in a devolatilizing extruder,
Extrude continuously from a devolatilizing extruder. It is then packaged continuously. The adhesion promoter can be any adhesion promoter, but preferably Luoa
It must be pointed out that the adhesion promoters are those shown in US Pat. Fumed silica is a polyalkoxy terminated diorganopolysiloxane polymer 10
The triorganosiloxy-terminated diorganopolysiloxane plasticizer can be used at a concentration of 10 to 50 parts by weight, and the sag control agent can be used at a concentration of 1 to 50 parts by weight per 0 parts by weight. Any amount from 1 to 2 parts by weight can be used. The amounts used above are within their preferred usage ranges. Furthermore, the devolatilizing extruder is preferably a twin-screw Wernerpfrider (We
rner-Pf'1eider) devolatilization extruder.

Using such a method, i.e., a static mixer and a devolatilizing extruder, and performing the mixing described above, 1.03
It is now possible to produce uncured RT'/silicone rubber compositions with application rates greater than 50 f/min corresponding to specific gravity of the composition in the range of 0 to 1.050.

Another preferred product formed in a devolatilizing extruder is to prepare a polyalkoxy-terminated diorganopolysiloxane polymer in a static mixer as described above, which is then taken and passed through a devolatilizing extruder. In the first step it is obtained by mixing with calcium carbonate and octamethylcyclotetrasiloxane treated fumed silicate. Furthermore, in the first step of the devolatilization extruder, a sag control agent, 10~
A mixture of a triorganosiloxy-terminated diorganopolysiloxane polymer, preferably a trimethylsiloxy-terminated dimethylpolysiloxane polymer, having a density in the range of 20,000 centipoise, and a combination of a plasticizer and/or an adhesion promoter is added. This combination is
(i115 to 60 mole percent monoalkylsiloxy units or mixtures of such units, (ill
MTD q % agent having from 1 to 6 mole percent trialkylsiloxy units, and from 34 to 94 mole percent dialkylsiloxy units, the plasticizer having about 0.1 to 2 weight percent silicon bonding. It has a hydroxy group. This mixture is then passed through a devolatilization extruder.

An additional amount of scavenger is then added approximately halfway through the devolatilization extruder. Preferred implementation of the invention! f
The scavenger in the strain is a silazane scavenger. Near the end of the devolatilizing extruder, a condensation catalyst mixture consisting of an adhesion promoter and an excess of polyalkoxysilane crosswetting agent are then added. Mixing is then carried out in a continuous manner in a devolatilizing extruder in a further step 2.3, from which the RTV mixture exits the devolatilizing extruder to be continuously packaged and stored or shipped as is. . Also, by using this method, uncured RTV silicone rubber compositions with application rates of 50 to 100 V per minute or more and high amounts of calcium carbonate can be produced. Regarding this product, the temperature of the devolatilization extruder is in the range of 40 to 60°C, more preferably in the range of 40 to 60°C, and the entire extruder is heated to 2 mercury columns.
Preferably, a vacuum of less than 0 inches is maintained. A vacuum is desirable to remove volatiles, especially moisture, that leave the mixture as it is being mixed. Preferably, in addition to the ranges indicated below, 50 to 200 parts by weight of calcium carbonate, 0.1 to 2.
A second preferred composition of up to 0 parts by weight polyether, 10 to 50 parts by weight triorganosiloxy-terminated diorganopolysiloxane polymer, and 2 to 20 parts by weight MTD plasticizer is used.

The concentration of components in the catalyst mixture per 100 parts of polyalkoxy-terminated diorganopolysiloxane polymer is preferably parts of excess polyalkoxysilane crosslinker. This excess polyalkoxysilane crosslinker is used in both preferred methods of the invention to completely terminate the diorganopolysiloxane polymer with alkoxy groups if there are any alkoxy groups that are hydrolyzed during the mixing step. .

Even though the particular type of preferred composition used in the mixing method described above, the mixing process of the present invention is similar to that disclosed with respect to the alkoxy-functional one-component RTV systems of White et al., US Patent Application No. 277,524 and related applications. It should be noted that it can be used to mix any and all of the ingredients.

Additionally, the continuous process of the present invention using a static mixer and devolatilization extruder has not been tested with all such compositions, but is described in the earlier U.S. patent applications disclosed above and below. It is believed that all compositions described herein and compositions of the components disclosed in this invention can be made. Preferred ingredients and alkoxy-functional one-component RTV compositions that can be used and produced continuously according to the present invention using a devolatilizing extruder with or without a static mixer are disclosed below.

The present invention of continuous mixing in a devolatilizing extruder with or without a static mixer is similar to that disclosed in U.S. Patent Application No. 277,524 to White et al. It is believed that several compositions can be made.

The devolatilization extruder is a twin-screw Wernapfryder devolatilization extruder or a Buss or a Koknaa devolatilizer (P, B, Koknaa).
der) can be any devolatilizing extruder, such as a devolatilizing extruder.

Having been described above, the various components and compositions that can be used in the methods of the invention are now more specifically described.

All such compositions and ingredients will not be disclosed below, but are mentioned in the US patents and patent issues cited as prior art to the present invention.

As mentioned above, all different acidic agents can be used as endcapping catalysts. By end-capping catalyst is meant a catalyst used in the reaction of a silanol-containing organopolysiloxane backbone polymer with a polyalkoxy-functional silane crosslinker or a composite crosslinker scavenger.

A third type of acidifying agent that has been found to work in the present invention is stearate treated calcium carbonate. Stearic acid treated calcium carbonate has been found to catalyze the endcapping reaction of alkoxy-functional silazane composite crosslinking scavengers according to the present invention. This catalytic action is assumed to be due to the presence of stearic acid in the stearic acid-treated calcium carbonate. However, this is just a hypothesis. As such, such calcium stearate carbonate may also catalyze the endcapping reaction of any other complex crosslinker scavenger compound or polyalkoxy functional crosslinker such as methyltrialkoxysilane, preferably methyltrimethoxysilane. is assumed. However, this is also just a hypothesis.

In addition to stearate-treated calcium carbonate, the types of acidifiers that fall within the broad definition above include, of course, traditional acid anhydrides, traditional inorganic acids, traditional silane acidifiers, and traditional organic acids. There is. Additionally, within the broad definition above:
Also included are traditional acids classified as Lewis acids, such as aluminum chloride and the like. However, before discussing the definition of such acids, it is necessary to consider some limitations regarding the use of such acidifying agents in endcapping reactions.

First, the concentration of acid used must be at least as effective as necessary to promote the endcapping reaction.

The concentration of acidifying agent should not be so high as to cause or catalyze the breaking of any of the siloxane bonds in the silanol-containing organopolysiloxane compound that is being endcapped.

In other words, preferably the rancidity of the acidifying agent in the reaction medium is carried out by General
Electric Company's silicon product department's C2O
Rancidity as determined by the 4 test method to be at least 0.1 and not greater than 15.

Briefly, the C2O4 test method uses a 250 g flask containing 100 rrLl of isoprophenol and 25 tnl. of phenolphthalein indicator to the flask.

The sample whose rancidity is to be determined is then weighed and added to the flask. The resulting solution was reduced to 0. Titrate with IN KOH (methanol solution) to a pink endpoint. The amount of KOH in methanol used in the titration is recorded as vt. Then, calculate the total acid number using the following formula.

Rephrasing the above in another way, the total number of acids is the sample lf
is the m7 number of KOH that neutralizes the free acid in.

Generally, for most acidifying agents of the type disclosed above, this means that the acid concentration of the acidifying agent is between 0.01 and 100 parts by weight of the silanol-containing organopolysiloxane.
This means that it must be within the range of 0.5 parts by weight. It is noteworthy that most of the acidifying agents as disclosed in this invention result in faster endcapping reactions than are experienced with relatively slow basic endcapping catalysts such as amine catalysts. Nevertheless, in one embodiment of the present invention, the rate of the acidifying agent when used as an endcapping catalyst is such that the acidifying agent is
Further enhancement can be achieved by combining traditional basic amine catalysts such as those disclosed in No.

All amines, whether sylated or complete, in one form or the other, may be used in cocatalysts within the scope of this invention, including primary, secondary and tertiary amines. be able to.

The more basic the amine, the more effective it is as a catalyst. Examples of preferred amines that can be used within the scope of the invention are for example (Mo2N)2-C=NCNC3H75i(OCH
3) 3(□N)2-C=NC4H8 H2,NC3H75i(OEC)3 H2NC3H7Si(OCH3)3 H2NC3H7NC3H,5i(OCH3)3 Siefamine T -403 Tetramethylpiperidinepiperidine1.4-diazobicyclo(2,2, 2]]Octane N-
Methylmorpholine, N-dimethylethylenediamine N-methylpiperidine N-hexylamine tributylamine dibutylamine cyclohexylamine di-N-hexylamine triethylamine benzylamine dipropylamine N-ethylphenylamine.

Thus, primary, secondary and sylated secondary amine silanes can be combined with the acidifying agents of the present invention to further increase the rate of endcapping beyond that achieved by the acidifying endcapping catalyst itself. can be used. The primary, secondary, and tertiary amines described above and the sylated amines disclosed above are merely exemplary, and any type of such amine may be used in combination with the acidifying agent of the present invention to form an endcapping cocatalyst. It should be noted that it can be used as

Generally, such amines, when used as endcapping catalysts, are used at concentrations anywhere from 0.1 to 1.0 parts by weight per 100 parts by weight of the silanol-terminated diorganopolysiloxane polymer to be endcapped. . However, such use of a basic cocatalyst in combination with the acidification catalyst of the present invention is optional. However, such basic catalysts are necessary if the process is to be continuous. In other cases, such basic amine promoters are not necessary. Thus, in many cases, the acidifying agents of the present invention perform and catalyze endcapping reactions for which sufficient efficiency is desired. U.S. Patent Application No. 4 of Chang et al.
Regarding the alkoxy-functional silazane composite crosslinker scavengers of No. 28038, it is noteworthy that these acidifying agents promote endcapping reactions at a sufficient rate compared to the amine catalysts used in the past by Chang et al. Should.

Preferably, such acidifying agents are used as endcapping catalysts in the present invention at the concentrations indicated above. Preferably, the acidification catalyst, which in particular applies to inorganic acids, must have the aforementioned rancidity in the reaction medium. This is especially true regarding maximum rancidity. If the rancidity exceeds the maximum values indicated above, the acidifying agent may be used during the immediate reaction period or subsequent period during which the composition is formed and stored before use, or indeed, as is the case when siloxane elastomers are formed. Even then, it may have a tendency to catalyze the destruction of siloxane bonds.

Therefore, the maximum rancidity indicated above is not exceeded and generally 1
It is particularly desired that the number not exceed 5, preferably not exceed the number 5 determined by the method C2O4.

Any of the acidic catalysts can be used alone as described above or in combination with one of the amine cocatalysts defined above. This amine cocatalyst is a prior art amine end-capped catalyst to the extent indicated above and for the reasons indicated above. However, as pointed out, in most cases this is not necessary. Additionally, as noted, for most endcapping reactions, the acid/amine endcapping catalysts of the present invention are significantly more efficient than the basic amine catalysts of the prior art.

In the reaction in which such an acidifying catalyst is used, a silanol-containing organopolysiloxane polymer, more preferably a silanol-terminated polymer, is combined with a polyalkoxy-functional silane or the aforementioned U.S. Patent Applications, particularly White et al. U.S. Patent Application No. 27
No. 7524 and U.S. Patent Application No. 1534 to Zujak et al.
Regarding an alkoxy-functional one-component R'rV type composition intended for end-capping with one of the alkoxy-containing and composite cross-linking agent scavengers disclosed in No. 9695, the present invention is regarded as prior art to the present invention. Used in any composition and reaction.

The endcapping reaction is one of the reactions in which polyalkoxy-terminated diorganopolysiloxane polymers are initially formed according to the disclosure of the White et al. patent application in which a scavenger is added during or subsequent to the reaction. I have to point this out. This scavenger acts to link all free hydroxy groups in the RTV polymer composition to maintain storage stability of the composition. In the most preferred form, the end-capping catalyst of the present invention is used in the reaction of a polyalkoxy-functional silane of formula (4) below, which is the more preferably used crosslinking agent to produce the end-capping polymer. This crosslinking agent reacts with the backbone silanol-containing diorganopolysiloxane polymer and is used in White et al., US Patent Application No. 277,524.
To form a polyalkoxy-terminated diorganopolysiloxane backbone polymer to which a scavenger is added according to the present invention.

The polyalkoxy-terminated diorganopolysiloxane polymer is preferably first formed using a polyalkoxy-functional silane of formula (4) below or by using a composite crosslinker scavenger. This is the R of the present invention.
This is the most preferred method of forming TV polymer compositions. To promote and increase the efficiency of end-capping reactions,
It is desirable to use the end-capped acid/amine catalyst of the present invention. Without such an end-capping catalyst, either a basic catalyst or an acidic catalyst, the polyalkoxy-functional silane of formula (4) below would react only slowly, if at all, with the silanol-containing organopolysiloxane. . Therefore, in order to commercialize this reaction, accelerate the manufacturing process, and in terms of economic benefits, it is highly desirable to use end-capping catalysts consisting of acidifying agents and basic amines.

The foregoing is incorporated herein by reference in U.S. patent application no.
It is particularly desirable if the end-capping polymer is formed before adding the scavenger to the RTV system as disclosed in No. 5.

Additionally, as described when endcapping silanol-terminated diorganopolysiloxane polymers of formula (1) using a combination of decoupling crosslinker scavengers, the endcapping catalyst of the present invention can be promoted to be as efficient as possible. In order to promote endcapping of the silanol-terminated diorganopolysiloxane polymer of formula (1), it is necessary to use one of the acidified endcapping catalysts of the present invention in reverse order.

Therefore, preferred RTV systems in which the acidification catalysts of the present invention may be used to form end-capped polymers are described. It should be understood that these catalysts may generally be used in any endcapping reaction between an alkoxy-functional silane and a silanol-containing organopolysiloxane polymer.

The silanol-terminated polyorganosiloxane has the formula where R is a C1-13 monovalent substituted or unsubstituted hydrocarbon group, preferably methyl, or a mixture of a large amount of methyl and a small amount of phenyl, cyanoethyl, trifluoro propyl, vinyl and mixtures thereof, where n is approximately 50
is an integer having a value from about 2,500 to about 2,500. This is a crosslinker silane that has a hydrolyzable group attached to the silicone.

The term vapor stable I applied to the one-package polyalkoxy-terminated organopolysiloxane RTV of the present invention, as used below, means substantially unchanged during exclusion of atmospheric moisture and unchanged after long-term storage. Refers to a moisture-curable mixture that cures into a tacky elastomer. Furthermore, stable R'
FV also indicates that the tack-free time exhibited by freshly mixed RTV components under ambient conditions is longer than that when stored in a moisture-resistant and moisture-free container for an equivalent period of time under ambient conditions or due to accelerated degradation at elevated temperatures. after the same time as that exhibited by the same mixture components exposed to atmospheric moisture.

Stable, substantially acid-free, one-pack, moisture-curable polyalkoxy-terminated organopolysiloxane RTV
The composition comprises a silanol-terminated polydiorganosiloxane consisting essentially of chemically bonded diorganosiloxy units of formula (2), such as a silanol-terminated polydiorganosiloxane of formula (1), with chemically bonded hydroxy groups. A silane scavenger can be used in combination with an effective amount of a silane scavenger.

In the above formula, R is as defined above. In the silanol-bonded polydiorganosiloxane which becomes woody from chemically bonded units of formula (2), the presence of silicon bonded to a C1-a alkoxy group such as a methoxy group is not excluded. The hydroxy groups that are eliminated by the silane scavenger include the silanol groups of materials normally present in the RTV compositions of the present invention, such as trace amounts of water, methanol, silica fillers (if used), and the silanol groups of formula (1). silanol polymers or silanol-terminated polymers having units of formula (2). In accordance with the practice of this invention, silane scavengers useful for scavenging chemically bonded hydroxy groups preferably have the formula, where R1 is an alkyl group, an alkyl ether group, an alkyl ester group, an alkyl ketone group, and an alkyl C1 selected from cyano. . is amide, amino,
Hydrolyzable leaving groups selected from carbamate, enoxy, imidate, incyanato, oximate, thioisocyanate and ureido and other groups.

Preferred groups are amino, amido, enoxy, more preferred groups are amido, such as N-C a-8 sylamide, a is an integer of 1 or 2, preferably 1, and b is an integer of 0 or 1. and the sum of a tens is equal to 1 or 2. In formula (3) where a is 2, X can be the same or different. The leaving group, The silane scavenger of 3) is a silane scavenger for hydroxy functional groups and a polyalkoxysilane crosslinking agent for terminating the silicon atom at the end of each organopolysiloxane chain with at least two alkoxy groups.

Among the components of the RTV compositions formed as a result of using the hydroxy scavenger of formula (6) are silanol-free polydiorganosiloxanes terminated with two or three -OR' groups. The silanol-free polydiorganosiloxane can optionally be combined with an effective amount of a crosslinked silane as defined below under substantially submerged conditions. formula(
The crosslinked polyalkoxysilane that can be used in combination with the scavenger silane of 3) has the formula, where p, 1, R2 and b are as defined above. Preferred condensation catalysts that can be used in the practice of this invention include metal compounds selected from tin compounds, zirconium compounds, and titanium compounds or mixtures thereof.

The polyalkoxy-terminated organopolysiloxane compound of the present invention can be used for a long period of time in a substantially moisture-free condition.
The reason for its stability in the presence of certain condensation catalysts is not completely understood.

The theory is that use of a scavenger silane of formula (3) or formula (5) below in combination with a crosslinked silane of formula (4) in accordance with the present invention will minimize harmful R''OHO formation during storage. is supported by the mechanistic studies of the RTV of the present invention. R"OH terminates the silanol polymer of formula (1) or the polymer having units of formula (2) to form a polymer having terminal units of (5) Therefore, the generation of ROH can be observed. These polymers in which the silicon atom at each polymer end is terminated with only one alkoxy group can have slow cure times. Furthermore, R”
OH can decompose organopolysiloxane polymers in the presence of condensation catalysts.

The use of silane scavengers for hydroxys of formulas (3) and (5) where the leaving group substantially removed. Formula (3) or (
By determining the age of the silane scavenger in 5), the total hydroxyl functionality in the RTv composition can be calculated. The total hydroxy functionality of the polymer can be determined by infrared analysis. An effective or stabilizing amount of scavenger is used to end-stop the polymer to ensure maintenance of stability of the composition over long-term storage periods of 6 months or more in a closed container at ambient temperature. Additional scavengers beyond the required mother can be used. The scavenger can be up to about 3% by weight based on the weight of the polymer. The aforementioned 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 between the OH functionality and the X group. In compositions that also include fillers and other additives, the formula (
The additional amount of scavenger required for 5) and (6) is:
Stability for 48 hours at 100° C. was determined to determine whether the tack-free time was substantially unchanged compared to the tack-free time of the composition before degradation measured under substantially the same conditions. By checking, 9i is calculated.

In formulas (1 to 5), R is preferably selected from a monovalent hydrocarbon group of Cl-13, a halogenated hydrocarbon group, and a cyanoalkyl group, and R1 is preferably an alkyl group of C□-8 or a C7- 13 aralkyl group, and R2 is preferably a methyl, phenyl or vinyl group.

Definition of elastomers produced from the RTV compositions of the invention by exposure to atmospheric moisture The expression "substantially acid free" means 5.5 or more, preferably 6 or more, particularly preferably 10 This means that a by-product with a pKa greater than that is produced.

Additionally, it has been found that when small amounts of amines, substituted guanidines, or mixtures thereof are used as cure accelerators in the polyalkoxy compositions of the present invention, rapid cure can be improved. RT' of the present invention/stick-free time of the composition ('1!
. From 1 to 5 parts, preferably from about 0.3 to 1 part, of curing accelerator can be used. This enhanced curing rate is due to long storage periods, e.g. 6 months or more at ambient temperature.
or persist after aging for a corresponding period under aging-promoting conditions. The curing properties after a long storage period are determined by its initial curing properties,
For example, freshly mixed R
It appears to be substantially similar to the tack free time (TPT) exhibited by TV compositions.

In addition to reducing the tack-free time of the RTV compositions of the present invention, the curing accelerators described herein are suitable for certain condensation catalyst catalyzed polymers that exhibit significant lengthening of the tack-free time after accelerated aging. It also has a surprising stabilizing effect on RTV compositions.

For this class of condensation catalysts, the addition of the amines, substituted guanidines, and mixtures thereof described herein:
Stable RTV compositions are obtained that exhibit rapid curing initially, i.e., within 30 minutes, and remain substantially unchanged after accelerated aging.

The present invention also includes a method of making a room temperature curable organopolysiloxane composition using an effective amount of a condensation catalyst with a silanol-terminated organopolysiloxane and a polyalkoxysilane crosslinker under substantially canned water conditions. An improvement to this process is to add a silanol-terminated organopolysiloxane in a static mixer to a silanol-terminated organopolysiloxane in the presence of the endcapping catalyst of the present invention, which is a scavenger for hydroxyl functional groups and has the formula (R1, R2, , a and b are as defined above), followed by addition of an effective amount of catalyst; The improvement in stability is coupled with the improved room temperature curable compositions.

In a particular embodiment, (11fa1) of a silanol-terminated polydiorganopolysiloxane consisting essentially of chemical bonding units of formula (2)
0 parts, (bl RTV composition composition - an amount of silane of formula (3) sufficient to scavenge H and provide up to 3% excess based on the weight of the polydiorganosiloxane composition; fC1 a mixture consisting of 0 to 10 parts by weight of a crosslinked silane of formula (4), 100 parts of (ilHa] polyalkoxy-terminated organopolysiloxane, tb1 0 to 10 parts of a crosslinked silane of formula (4), (C ) effective amount of condensation catalyst, (stabilizing amount of dl silane scavenger and required (=1
A stable, one-pack room temperature curable product comprising stirring a room temperature curable material selected from a mixture consisting of 0 to 5 parts of a curing accelerator in a devolatilizing extruder under substantially anhydrous conditions. A method of making a polyalkoxy g-linked organopolysiloxane composition is provided.

The radicals R in formulas (1) and (21) include, for example, aryl groups and halogenated aryl groups such as phenyl, tolyl, chlorophenyl, naphthyl; aliphatic and cycloaliphatic groups such as cyclohexyl, cyclobutyl; methyl, ethyl , propyl, chloropropyl, vinyl, allyl, trifluoropropyl; cyanoalkyl groups such as cyanoethyl, cyanopropyl, cyanobutyl. The groups contained in R1 are preferably for example C1- a alkyl group (
For example, methyl, ethyl, propyl, butyl, pentyl), C7-□3 aralkyl group (e.g. benzyl, phenethyl), alkyl ether group (e.g. 2-methoxyethyl), alkyl ester group (e.g. 2-acetoxyethyl) ), alkylketone groups (e.g. 1-butan-3-oneyl group), alkylcyano groups (e.g.
2-cyanoethyl). The group contained in R2 is the same as or different from the group contained in R group.

Examples of the crosslinked polyalkoxysilane included in formula (4) include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, tetraethoxysilane, and vinyltrimethoxysilane.

Among the curing accelerators that may be used in the practice of this invention are compounds of the formula % (61 [wherein is as defined above and Z is the formula (wherein R3 is a divalent 02-8 is a guanidine group having an alkylene group, R'o and R5 are selected from hydrogen and a C0-8 alkyl group, and g is an integer from 1 to 3.Furthermore, there are silyl-substituted guanidines having the following:
Formula (wherein R4 and R5 are as defined above)
Alkyl Km guanidines having R6 is a C1-8 alkyl group can also be used.

Some of the silyl-substituted guanidines included in formula (6) are
Takago U.S. Patent No. 4180642
No. 4248993.

In addition to the above-mentioned substituted guanidines, for example di-n-hexylamine, dicyclohexylamine, di-n-butylamine, di-n-butylamine, hexamethoxymethylmelamine and silylated amines such as y-aminopropyltrimethoxysilane and methyldimethoxy A variety of amines may be used, such as di-n-hexylaminosilane. Methyldimethoxy-di-n-hexylaminosilane acts as both a scavenger and a cure accelerator. Primary amines, secondary amines, and silylated secondary amines are preferred, and secondary amines and silylated secondary amines are particularly preferred. Silylated secondary amines such as alkyldialkoxy-n-dialkylaminosilanes and guanidines such as alkyldialkoxyalkylguanidylsilanes used as curing accelerators also act as scavengers and, in some cases, It also acts as a stabilizer in the compositions of the invention.

An effective amount of condensation catalyst that may be used in the practice of the present invention to promote curing of RTV compositions is, for example, from 0.001 to 1 part per 100 parts by weight of silanol 1 flj k polydiorganosiloxane of formula (1). The tin compounds include, for example, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin dimethoxide, carbomethoxyphenyltin trisuseroate, dimethyltin dibutyrate, dimethyltin dineodeconoate, triethyltin tartrate, dibutyl flammable dibensoate, 4 me: Cb
s bs naphthinate, butyltin tri-2-ethyl
Contains thorate, tin butyrate.

Preferred fflJ cocatalysts are tin compounds, with dibutyltin diacetate being most preferred.

The titanium compound used is, for example, 1,3-propanedioxytitanium bis(ethylacetoacetate).
), 1. '3-propanedioxytitanium bis(acetylacetonate), diisopropoxytitanium bis(acetylacetonate), titanium naphthinate,
Examples include tetrabutyl titanate, tetra-2-ethylhexyl titanate, tetraphenyl titanate, tetraoctadecyl titanate, and ethyltriethanolamine titanate. Additionally, Weyenberg
The beta-dicarbonyl titanium compounds shown in US Pat.

Zirconium compounds, for example zirconium octoate, can also be used.

Other examples of metal condensation catalysts are, for example, lead 2-ethyl octoate, iron 2-ethylhexoate, cobalt 2-ethylhexoate, manganese 2-ethylhexoate, zinc 2-ethylhexoate, antimony These are octoate, bismuth naphthinate, zinc naphthinate, and zinc stearate.

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

Various fillers and colorants can be added to the silanol or alkoxy terminated organopolysiloxane. They include, for example, titanium dioxide, zirconium silicate, silica aerogel, iron oxide, diatomaceous earth,
These include fumed silica, carbon black, precipitated silica, glass fiber, polyvinyl chloride, powdered quartz, calcium carbonate, etc. The amount of filler used can obviously vary within limits depending on the intended use. For example, when used as a waterproofing agent, the curable compositions of the present invention can be used without fillers.

7 parts by weight of organopolysiloxane when the curable composition is used for other applications, such as in the production of binders.
Larger amounts of filler, such as 0.00 parts or more, can also be used. In such applications, the filler may consist of powdered quartz, polyvinyl chloride, or mixtures thereof, preferably a bulk filler having an average particle size ranging from about 1 to 10 microns.

In connection with the present invention, the expressions "moisture-free conditions" and "substantially anhydrous conditions" used below refer to dry chambers or vacuum strainers to remove air, which is then replaced with a dry inert gas such as nitrogen. This means mixing in a sealed container. Experience has shown that the scavenger silane of formula (3) should be used in sufficient amounts as revealed above.

The hot liquid can vary from about 0°C to 180°C depending on the degree of mixing, type and amount of filler.

Pursuant to Zujak U.S. Patent Application No. 349,695,
The scavenger can be silazane. Room-temperature curable organopolysiloxane compositions are prepared by preparing an organopolysiloxane in which the silicon atom at the end of each polymer chain is terminated with at least two alkoxy groups in a static mixer, and then subjecting the end-capped polymer to devolatilization extrusion. It is prepared by mixing in-machine an effective amount of a condensation catalyst and a stabilizing amount of a silane scavenger for hydroxy functionality selected from the following classes of silicon nitrogen compounds: The class is (Y)(R')2Si-N-5i(R”)2Y
(7) (wherein Y is selected from bi and R'2N-) and (bl (11)
mole percent of chemically bonded structural units and (2
) a silicon-nitrogen polymer consisting of 0 to 97 mole percent of chemically bonded structural units of the formula % (81 The free valences of the silicon atoms, which are bonded to each other by selected members of the ``Si bond'' and other than those bonded to the oxygen forming the siloxy unit and the nitrogen forming the silazane unit, are is bonded to a member selected from N groups, and wherein the R″ group and the (R/#) to the silicon atom of the silicon-nitrogen polymer
, the ratio of the total number of N groups has a value from 1.5 to 3, and R' is a member selected from the class consisting of hydrogen and monovalent C□-12 hydrocarbon groups and fluoroalkyl groups. , R′″ is a member selected from hydrogen, a monovalent hydrocarbon group, and a fluoroalkyl group, and C
is an integer from O to 3) and, if necessary, (3
) an effective amount of a cure accelerator selected from the group consisting of substituted guanidines, amines, and mixtures thereof.

The most preferred compound within the silicon-nitrogen compound formula is silazane, more preferably hexamethyldisilazane. Other compounds within the formula can be used as scavengers herein, such as hydrogen-containing amines, as explained below.

Within the present invention, such scavengers are not considered mixed crosslinker scavenger compounds, but rather independent crosslinkers are used and the silyl nitrogen material is a separate compound added to the composition.

Thus, in a preferred embodiment of the invention, the crosslinking agent is first added to the silanol-terminated diorganopolysiloxane polymer in the presence of an endcapping catalyst. A preferred endcapping catalyst for this purpose is one of the acidifying and basic amine catalysts of this invention.

Once the polyalkoxy-terminated polymer is formed, it is then used in a devolatilizing extruder to adsorb the scavenger, i.e., the silicon-
Add one of the nitrogen compounds. All other ingredients can then be added to the composition, and the scavenger will also absorb the free hydroxyl groups of such materials. Preparation of the composition by this method results in the preparation of a composition that is substantially free of hydroxy groups and therefore storage stable and rapidly curing. 6 after manufacture by the expression storage stable.
This means that the speed and degree of curing after a month or one year is substantially the same as immediately after manufacture.

In the above formulas of silicon-nitrogen compounds and silicon-nitrogen polymers, the R' and RI' groups can be selected from hydrogen and monovalent hydrocarbon groups (including fluoroalkyl groups).

Examples of groups from which R'' and Bi can be selected are, for example, methyl,
Alkyl groups such as ethyl, propyl etc., cycloalkyl groups such as cyclohexyl, cycloheptyl etc., mononuclear aryl groups such as phenyl, methylphenyl, ethylphenyl etc., alkenyl groups such as hinyl, allyl etc.
It is a fluoroalkyl group such as 3,3°3-trifluoropropyl. Generally R'' and R2 groups are from 1 to 12
more preferably the group can have from 1 to 8 carbon atoms.

In addition to the silicon-nitrogen materials described above, the present invention also includes silicon-nitrogen materials having divalent hydrocarbon groups bonded to silicon atoms via silicon-carbon bonds. For example, silicon-nitrogen materials that may be used in the practice of the present invention also include arylene silazane, such as phenylene silazane, and alkylene silazane, such as methylene silazane. Furthermore, various other silicon-containing divalent hydrocarbon groups
Nitrogen materials are also contemplated to include copolymers and tapolymers, such as silicon-nitrogen materials containing co-condensed siloxane units and dylarylene silazane units, co-, monovalent silazane units, dyarylene siloxane units, siloxane units, and the like. The silicon-nitrogen polymer in the form of a silazane/siloxane copolymer has at least 3 mole percent chemically bonded siloxy units and up to 97 mole percent bonded siloxy units.

Therefore, the silazane polymer contains chemically bonded R1 units (wherein R" and Rnt represent the ratio of the total number of RM and R"N groups to silicon atoms in the silazane polymer from 1.5 to 3.0. (as defined above to be) is included.

The definition of a silazane polymer includes ■ (R'2N)(R") -8i -N - units and 1, where R" and RM are the total number of RN and R"2N groups per silicon atom in the silazane polymer. The ratio of 1.
Included are linear polymers having at least one unit of the class consisting of (as defined above to be from 5 to 3).

Other silazane polymers included within the above definition of polymers include R/IF units (where RM and R'' are the ratios of R/F and R''N groups per silicon atom in the silazane polymer, ranging from 0 to
3.0) consists of more essentially linear polymers.

Furthermore, in the silazane polymer, RM (R/')SiN - (wherein R'' and R'' are such that the ratio of the total number of R''' and R//N groups per silicon atom in the silazane polymer is 1).
．． Polymers having at least one unit selected from the class consisting of (as defined above to be from 5 to 3) are included.

Furthermore, the silazane polymer is composed of h'' (where R'' and R1 are pre-defined such that the ratio of the total number of R''/ and R//2N groups per silicon atom in the silazane polymer is from 1.5 to 3. (as defined in )
It can consist of a polymer having a sufficient amount of units selected from:

The silazane/siloxane copolymer can also be cyclic and consist of chemically bonded R''2SiO and ■ R/1 units, where R'' and R1 are as defined above. can.

Linear silazane/siloxane copolymers include (R#/
). The mole percent of 81-2 units is (R11) 5iN C mauni (where R" and Hnt are R1/+R'N groups per silicon of the silazane/siloxane copolymer, the ratio of the total number of N groups is from 1.5 to 3. (as defined above to be up to 0) are also included as high as 97 mole percent.

Other linear silazane within the scope of the above formula may be of the formula and d is an integer between O and 1, and when d is 0, n is preferably from 3 to 7).

Examples of silazane that can be used in the practice of the invention within the above formula are hexamethylcyclotrisilazane, octamethylcyclotetrasilazane, trimethyltriphenylcyclotrisilazane, trivinyltrinotylcyclotrisilazane, and the like.

In addition to the silazane of the above formula, a terminal silylamine unit or a compound of the formula [where fill and R" are as defined above and Z is R" and 5IRb (wherein R" and RM
is as defined above) and n is as defined above]. Polysiloxanes of the above formula are prepared by taking ammonia or an amine and at a temperature within the range of about 0°C to 60°C, a polysiloxane of the formula (wherein R" and n are as defined above and It can be prepared by reacting with a halogenated polysiloxane having 10 gen groups).

If terminal silazane groups are desired, for example molar amounts of (
R'')3SiX can be reacted with at least equimolar halogenated polysiloxane of the halogen atoms contained in the 10genated polysiloxane. Of course, the formula (wherein R' is as defined above) Although it is appreciated that amines of the above formula can be used to form the Silexy chain-terminated polysiloxanes of the present invention, if a material with terminal silylamine groups is desired, amines containing amines of the above formula can be used to form the desired polysiloxanes. can be used to have at least one hydrogen available for the reaction to produce.

Accordingly, methods for making such polymers and compounds are well known.

Fluoro-substituted silazane compounds are manufactured by Matso
moto), U.S. Patent Application No. 195,579, filed Oct. 8, 1980.

The existence of such silyl-nitrogen compounds and silyl-nitrogen polymers, as well as methods of their preparation, are described in U.S. Pat.
No. 34Q4, to which one skilled in the art may be referred for further information.

In addition to the above-mentioned silyl-nitrogen compounds and silyl-nitrogen polymers, in the present invention, compounds of the formula (wherein R20 is a C1-8 monovalent hydrocarbon group and 0
is a group selected from the class consisting of 1-8 alkoxy groups and fluoroalkyl groups, and RI is hydrogen and C
selected from 1-8 monovalent hydrocarbon groups, g is an integer varying from 1 to 3, h is an integer varying from 0 to 2, and the total number of h0g does not exceed 3) Scavengers that are silylamines can also be used.

Compounds within the above formulas include, for example, methyldi(methylamino)silane, tris(methylamino)silane, methylbis(diethyl)silane and the following tris(diethylamino)silanemethylbis(dimethylamino)silanetri(ethylamino)silaneethyldi( methyldi(ethylamino)silane ethylbis(dimethylamino)silane.

Such amines are disclosed in US Pat. No. 3,243,404 and can be prepared by the methods disclosed therein. Silyl-nitrogen compounds and polymers are most preferred as scavengers in the compositions of this invention. The above amines can also be used as scavengers in the RTV compositions of the invention. The only drawback with hydrogenated amines is that they tend to continually liberate hydrogen and also tend to add undesirable amine odor to RTV compositions. However, if this is not a problem, the amines are acceptable for use in the compositions of the invention. Preferably, the silyl-nitrogen compound, such as hexamethyldisilazane, is used at a concentration of 0.5 to 10 parts per 100 parts by weight of the backbone organopolysiloxane polymer.

Accordingly, preferred silyl-nitrogen compounds and polymers within the above formulas can be used in the present invention. As mentioned above, generally from 0.5 to 10 parts of scavenger are preferably used per 100 parts by weight of either silanol-based polymer or polyalkoxy-based polymer. As explained below, there is almost no difference in the concentration of the scavenger depending on whether the trunk polymer is dasilanol or polyalkoxy terminated, since the molecular weights of both compounds are almost the same.More generally, Scavengers can also be used in concentrations from 1 part to any concentration desired.

It is undesirable to add too much scavenger, as about 10 parts can reduce the curing physical properties of the composition. Generally at least 3d1 in one composition
It is desirable to have 3 scavengers. That is, an amount of 3% or more is required to absorb or end-cap all free hydroxy groups in the composition.

Furthermore, in accordance with Chang et al., U.S. Pat. Acyclic silyl-nitrogen scavengers of the fB1 formula, as well as cyclic silyl-nitrogen scavengers having at least one or all of the formula units and the remaining units (if any) having the formula [in the above three formulas, R10 is alkyl, an aliphatic organic group selected from the group consisting of alkyl ether, alkyl ester, alkyl ketone, alkylcyano, and aryl, Hu is a monovalent substituted or unsubstituted hydrocarbon group of C□, Q is hydrogen, C1-8 monovalent substituted or unsubstituted hydrocarbon group and the formula (wherein RIO and R11 are as defined above, a varies from 0 to 2, and f varies from 0 to 3) , h is 0 or l, 1S is an integer varying from 1 to 25, d is an integer varying from 1 to 25, and R22 is hydrogen and C1-8 monovalent hydrocarbon. selected from the groups i-L, and B21 is selected from monovalent hydrocarbons and hydrocarboxy groups), il,, A is hydrogen and C1-8 monovalent substituted or unsubstituted Substituted hydrocarbon group and the formula (wherein RIO and R11 are as defined above, g
varies from 0 to 3 and in said scavenger at least one hydrocarboxy group is present in the molecule), R12 is R
IO, R13 is defined as R11, R14 is defined as R11] and devolatilization extrusion. consisting of mixing in the machine the formed polymer with a condensation catalyst and 4 m components,
A stable, one-package, substantially anhydrous and substantially acid-free, room-temperature-curing organopolysiloxane that is stable for long periods under substantially moisture-free ambient conditions and can be converted into a tack-free elastomer. A continuous method of forming a composition is provided.

If in the RTV system it is desired to have a composite crosslinker scavenger compound with s = l and a = 1, at least 3, preferably 4 alkoxy or hydrocarboxylic groups are present in the linear or cyclic silazane compound. The compounds disclosed above can be used, with the exception of those compounds in which there is one alkoxy group on each silicon atom of the group or cyclic compound. When 6 and d are greater than 1, some components or polymers generally also act as composite crosslinkers with silicon atoms free of hydrocarboxylic groups, but preferably silicon-terminated There are at least two hydrocarboxy groups attached to the atoms and 11 hydrocarboxy groups attached to each internal silicon atom.

Although two or one alkoxy groups in a compound allow the compound to act effectively as a scavenger, unfortunately the compound does not have sufficient alkoxy functionality to provide the necessary crosslinking ability to the composition. I haven't. Furthermore, all of these alkoxy compounds are described in the above cited February 1982 1
It can also be made by traditional methods, such as those disclosed in U.S. Patent Application Ser.

In the formula for linear or branched acyclic silyl-nitrogen scavengers, the group RIO is; an alkyl group such as methyl, ethyl, propyl, etc.; methyl methyl ether, methyl ethyl ether, methyl propyl ether, ethyl ethyl ether, Alkyl ether groups such as ethylpropyl ether, 2-methoxyethyl, 2-ethoxyethyl, 2-propoxymethyl, etc.; such as methyl ester, ethyl ester, propyl ester, methyl ester, 2-acetoxyethyl, 2-acetoxypropyl, etc. alkyl ester groups; alkyl ketone groups such as 1-butan-3-oneyl, methyl methyl ketone, methyl ethyl ketone, ethyl methyl ketone, ethyl ethyl ketone, etc.;
Alkylcyano groups such as methylnitrile; phenyl,
It can be selected from aryl groups such as methylphenyl and the like. Basically, the RIO group is any alkyl and phenyl group having 1 to 8 carbon atoms, more preferably - of the groups disclosed above. Most preferably RIO is selected from methyl. In the compound of formula (13), R11 is methyl, ethyl,
Alkyl groups such as furovyl, etc.; cycloalkyl groups such as cyclohexyl, cycloheptyl, etc.; olefinic groups such as vinyl, allyl, etc.; monocyclic aryl groups such as phenyl, methylphenyl, ethylphenyl, etc.
Substituted hydrocarbon groups such as □-8 monovalent substituted or unsubstituted hydrocarbon groups or fluoroalkyl groups such as 3,3°3-trifluoropropyl are selected.

The groups R are independently selected from the same groups as R and C□-8 hydrocarboxy groups. Furthermore, the worms are hydrogen and R
selected from the same groups as 11.

Therefore, preferably R11 is selected from alkyl groups having 1 to 8 carbon atoms, most preferably selected from hydrogen. On the other hand, the group Q can be any group defined for R11 with the caveat that the number of carbon atoms in the group is preferably 8 or less, and any C□-8 monovalent substitution or It can be selected from unsubstituted hydrocarbon groups.

Another part of the definition of the compound of formula (10) is that a varies from 0 to 2 and f varies from O to 3, where Q is a monovalent hydrocarbon group of hydrogen and C. , the total number of a to f does not exceed 5, and at least one alkoxy group is present in the compound of formula (10). The reason for this restriction regarding a and f is that a and f
is in accordance with the description of the silazane compound of the present invention, and at least one alkoxy group is present in the molecule. The method of the present invention (part 1, the compound of the present invention)
It should be noted that the difference from the compound of No. 695) is the presence of a hydrocarbo/oxy group in the compounds of the present invention. There are no hydrocarboxy groups present in the compounds of the Zujak US patent application. The advantages of the hydrocarboxy group of the present invention are as explained above.

Furthermore, in the definition of the compound of formula (10), preferably B is an integer varying from 1 to 25, most preferably 1, and d is preferably an integer varying from 1 to 25, most preferably Preferably it is 1-10. It should be noted that relatively simple alkoxysilazane compounds are desirable because they are the most easily obtained and most commonly obtained. However, relatively high molecular weight hydrocarboxydisilazane compounds can also be used in the present invention within the scope of the above formula.

Furthermore, in the above formula (1o), A is preferably hydrogen and C□-8 as defined above with respect to R11.
selected from the class consisting of monovalent substituted or unsubstituted hydrocarbons. Most preferably A can be selected from hydrogen, methyl or ethyl groups.

-si(CH3)3. -5i(OCH3) (CH3
)2゜-3i(OCH3)2(CH3), -3
i(OCH3)3 For compounds of formulas (13) and (14) above, in embodiments when the silazane compound is a scavenger, it is preferred that RIO and R11 are methyl and the Q group is hydrogen.

In addition to the linear and branched acyclic silazane compounds described above, alkoxy-functional cyclic silazane compounds can be used in the present invention. Thus, a cyclic silyl-nitrogen scavenger may be present having at least one or all of the units of formula (14) and the remaining units (if any) of formula (15). Preferably, the compound has the formula (14
), but the cyclic compound has the formula (15)
It is also possible to have units of formula (14) interposed. However, it should be noted that the cyclic compound must have at least one hydrocarboxy or alkoxy group in the compound as well as it must be a cyclic silazane compound that can be used in the present invention. It takes.

In the present invention, a hydrocarboxylic disilazane compound having at least one hydrocarboxy group in the compound, either linear or cyclic, and at least 3 or 4 hydrocarboxylic groups in the compound when s = l and d = 1, are used. It should be noted that there is a difference between hydrocarboxylic disilazane compounds having more than one hydrocarboxy group. Those having at least one but less than three alkoxy groups can be used only as scavengers in the present invention. at least 3 or 4 hydrocarboxy groups when 8=1, d=l or more hydrocarboxy groups when S and d are greater than 1 according to the above disclosure The hydrocarboxy compounds of the invention can be used both as scavengers and as complex crosslinking agents. That is, when the compound is used in an appropriate amount, it can react with the backbone silanol material to form an alkoxy-endcapped diorganopolysiloxane polymer that hydrolyzes upon exposure to ambient moisture to form a silicone elastomer. The same acts as a crosslinking agent (to link unbound hydroxy groups in the polymer mixture).

Furthermore, it should be noted that compounds with at least three or more hydrocarboxy groups can also be used as scavengers, regardless of whether they act as composite crosslinkers. In any case, if a crosslinking agent is used and the silazane compound has at least three hydrocarboxylic groups, some of the hydrocarboxydisilazane compounds will act as scavengers by statistical reaction products of the composition. It is also believed to act as a crosslinking agent.

βJ to this point, hydrocarboxylic disilazane compounds with less than 3 hydrocarboxy groups can be used as scavengers, with the possible exception of the case 9=1, Q=4 according to U.S. Patent Application No. 428,038. Since it only works, we should keep this in mind and be aware that we have to use it extensively. As for the amount of compound used, as discussed elsewhere in this invention, a guideline is 1 to 12 parts, more preferably 3 to 7 parts of hydrocarboxydisilazane compound per 100 parts by weight of silanol polymer. can be used. When the hydrocarbodisilazane compound acts both as a crosslinker and as a scavenger, there will generally be from 2.0 to 12 parts of the hydrocarbodisilazane compound, preferably the trunk silanol, per 100 parts by weight of the trunk silanol polymer. Polymer 1
3 to 8 parts per 00 parts of the compound are used. These concentration ranges are m-like, and the second case is particularly common. Because the amount of hydrocarboxy compound used both as crosslinker and scavenger, ζ,
This is because it depends on the amount of hydrocarboxy groups in the hydrocarboxy compound molecule. Furthermore, the cyclic silazane compound can be any cyclic silazane, but
Most preferred are trisilazane or tetrasilazane. This is because these are the most easily available cyclic silazane. However, pentasilazane or higher cyclosilazane can also be used.

It must be recognized that in the normal process of producing such cyclic silazane, the majority of the compounds produced are cyclic tetrasilazane and cyclic trisilazane. However, some higher cyclic silazane have also been prepared, and these higher cyclic silazane in mixtures with cyclic trisilazane and cyclic tetrasilazane, according to their hydrocarboxy functionality, as described below.
It can be used as a scavenger or as both a scavenger and a crosslinker in the present invention.

The reason that at least three hydrocarboxyl groups must be present in the silazane molecule for the silazane to act as a crosslinker as well as a scavenger is because the end capping group connects the silanol groups at the end of the polymer. This is because when doing so, it is desirable to add at least two alkoxy groups to the silyl group. In such cases, i.e., when the majority of the polymer is terminated with at least two hydrocarboxy or alkoxy groups, the backbone polymer thus terminated is storage stable and can be effectively crosslinked to become storage stable. to produce a composition. The remaining hydrocarboxydisilazane can readily serve to link other unbound hydroxy groups in the polymer mixture present other than the terminal hydroxy groups of the silanol-terminated diorganopolysiloxane backbone polymer. Furthermore, as mentioned above,
Although the above concentration ranges are given for silazane compounds, whether used only as scavengers or as scavengers and crosslinkers, these concentrations are purely general guidelines and are not limiting. isn't it.

What is important is that a minimum amount of silazane compound is present, whether only as a scavenger or as both a scavenger and a cohesive crosslinker. Therefore, the minimum amount of this silazane compound is at least 3% excess of the stoichiometric amount needed to react with any excess water and any excess unbound hydroxy groups in the polymer mixture, and generally can be determined in most compositions at a level of at least 1 part by weight of the scavenging silazane compound per 100 parts of the trunk silanol-terminated diorganopolysiloxane polymer.

When using a composite crosslinker scavenger, it is preferred to catalyze the endcapping reaction with the catalyst of the invention and the scavenger added in a static mixer. For further information regarding these alkoxy-functional silazane as composite crosslinker scavenger silazane, see Teyoung et al., US Pat. No. 4,280,038.

Before describing embodiments, it is necessary to clarify the main points of the present invention. First of all, for the silanol-terminated organopolysiloxane polymers of formula (1), it is preferred that the silanol groups are present on the terminal silicon atoms. In such polymers, ie of formula (1), several silanol groups may be present in the polymer chain.

Such silanol groups in the polymer chain cause less crosslinking to occur during curing of the polymer. If there are too many silanol groups in the polymer chain, it may be difficult to fully cure the polymer. However, preferably the majority of the silanol groups are present at the terminal silicon atoms in the polymer chain of the polymer of formula (1).

The second point to point out is that in the formation of end-stopped polymers prepared by the reaction of either a polyalkoxy-functional silane crosslinker or a composite crosslinker scavenger reacting with a silanol-end-stopped diorganopolysiloxane polymer, After forming such an end-stopped polymer, there may be some polymers with only monomethoxy groups at one or both ends of the polymer chain. Not all polymers must be of this particular type.

That is, if this is the case, considerable difficulties may be encountered in curing the composition.

Thus, in order to have an adequate cure rate or to have a fast curing RTv composition, it is desirable to have polyalkoxy groups on the terminal silicon atoms of the majority of the polymer in the R'rvg composition.

Finally, as mentioned above, previous amine endcapping catalysts are endcapping catalysts for composite crosslinker scavengers used to endcapping silanol-terminated diorganopolysiloxane polymers such as those of formula (1). It acts very effectively or not at all. In the case of the alkoxy-functional silazane composite crosslinker scavenger of Chang et al., U.S. Patent Application No. 428,038,
Traditional basic amine end-capping catalysts act only poorly as end-capping catalysts.

do not have. The end-capping acidifiers of the present invention are by far the best end-capping catalysts for such materials and continuous processes and must be used in combination with amines.

A preferred method of making RTV compositions of the present invention, i.e. storage stable, low modulus non-corrosive, fast curing compositions, is to use polyalkoxy-terminated diorganopolysiloxane polymers, i.e. polyalkoxydiorganopolysiloxane polymers. The siloxane is first formed, the hydroxy groups in the composition are removed or scavenged, and the desired other ingredients are then added. In this method, the crosslinking agent of formula (4) is added to the crosslinker of formula (1).
of the silanol polymer, i.e. the silanol polymer is pre-reacted with the cross-linking agent, preferably in the presence of a catalyst and preferably an end-capping catalyst, to produce the desired dialkoxy end-capping polymer, and then this di- or tri-silanol polymer is This is done by taking an alkoxy end-capped polymer and adding a scavenger to absorb the silanol groups. Other components can then be added to the composition under substantially anhydrous conditions to produce a one-component R'rV package. This RTV composition is storage stable and cures at a sufficiently fast rate, ie, even with the tin soap catalyst in the composition. The above method [i.e., the polyalkoxy material is a diorganopolysiloxane backbone polymer with 100 polymerized parts (i.e., either in terms of 100 parts by weight of the silanol polymer of formula (1) or in terms of 100 parts by weight of the polyalkoxy-terminated organopolysiloxane polymer)]
2 to 20 parts by weight per portion] according to the above R'l'V
The first basic component according to the invention that can be added to this RTV system after the system has been manufactured is first the plasticizer fluid polysiloxane. It contains a high degree of tri-functionality or a mixture of tri- and tetra-functionality, (l l 5 to 60 mole percent monoalkylsiloxy, siloxy units or mixtures of such units, (il 1 color 6 mole percent trialkoxysiloxy units and (inl 34 to 94 mole percent dialkylsiloxy units), wherein the first plasticizer polysiloxane has 0 to 94 mole percent dialkylsiloxy units.
．． Contains from 1 to about 2% by weight silicon-bonded hydroxy groups.

This polysiloxane first plasticizer polysiloxane fluid is
Generally at a concentration of 2 to 20 parts by weight of backbone polymer, or more preferably 5 to 15 parts by weight of backbone polymer.
It must be pointed out that it can be added in concentrations of parts by weight. Such polysiloxanes act as plasticizers and adhesion promoters and especially as plasticizers in the compositions of the invention. It is undesirable to exceed 20 parts per 100 parts by weight of backbone polymer. Therefore, it is generally not used in an amount exceeding 20 parts by weight, and does not have much effect if it is less than 2 parts by weight.

Preferably, the fluid has a viscosity in the range of 15 to 300 centipoise at 25°C. Preferably, also in the fluid polysiloxane plasticizer, at least 50% of the alkyl Mk groups are methyl, and the fluid has a polysiloxane plasticizer of between 0.2 and 0.
It consists of 6% by weight of silanol. Particularly preferably, monoalkylsiloxy units, siloxy units or mixtures thereof comprise about 10 to 30 mole percent, trialkylsiloxy units comprise from 3 to 5 mole percent, and dialkylsiloxy units constitute about 65 mole percent.
to 85 mole percent and the silanol content is about 0.2 to 0.6 weight percent.

Thus, although such trifunctional fluids plasticize the base composition to make it low modulus, in all cases they do not make it sufficiently low modulus, nor do they alone make it sufficiently low viscosity. Accordingly, in the above-described trunk polymer 1, 10 to 50 parts by weight of a second plasticizer per 100 parts of nopolysiloxane polymer were used in addition to the trifunctional fluid.
It is highly desirable that 00 parts be present.

As mentioned above, by backbone organopolysiloxane polymer is meant either a silanol-terminated diorganopolysiloxane polymer of formula (1) or a polyalkoxy-terminated diorganopolysiloxane polymer, or various mixtures of both.

Because the alkoxy groups add very little to the molecular weight of the polymer, the concentrations of the various additives in addition to the trifunctional fluid discussed below are substantially the same as those described in the section for either polymer system. seems to be the same.

Accordingly, from 5 to 60 parts by weight of the second plasticizer can be used per 100 parts by weight of the backbone organopolysiloxane polymer. The plasticizer is a linear triorganosiloxy-terminated diorganopolysiloxane polymer whose viscosity varies from 10 to 20,000 centipoise at 25°C and whose organic groups are selected from monovalent hydrocarbon groups of Cl-8. . More preferably, these monovalent hydrocarbon groups are alkyl groups of 1 to 8 carbon atoms. (Then, preferably, the second plasticizer has the formula -8 alkyl or aryl group, and t is the viscosity of the polymer from 10 to 2000 at 25°C.
(changes in the same way as it changes to 0 centipoise)
has. Most preferably the R20 group is methyl;
The polymer has a viscosity varying from 10 to 10,000 centipoise at 20°C, preferably from 10 to 1 centipoise at 25°C.
It has a viscosity varying up to 0,000 centipoise. Generally, depending on the method of manufacture, such polymers have from 500 to 1500 parts of OH per million parts of silanol. A common method for preparing such plasticizers of formula (15) above is to hydrolyze appropriate rolosilanes. Thus, triorganochlorosilane is hydrolyzed with diorganodichlorosilane in water, and the hydrolyzate is then removed.
Purification by decanting and other methods used to yield the desired linear diorganopolysiloxy polymer of formula (15).

Such polymers from this conventional hydrolysis process usually have from 500 to 1500 parts of OH per million parts of silanol and can be further purified by other methods.

However, such hydrolysis is usually not carried out because it is expensive.

Furthermore, such silanol groups or hydroxy groups,
If there is a scavenger that absorbs substantially all the hydroxy groups present in such polymers, it would not present difficulties in the context of the present invention. As mentioned above, a scavenger that absorbs all free hydroxy groups in such plasticizers should be used in the present system.

As mentioned above, to obtain the desired low values of composition modulus, two plasticizers should be used since trifunctional fluids alone do not produce the maximum reduction in both viscosity and modulus.

Thus, it is necessary to use both plasticizers when it is desired to obtain the lowest modulus, maximum adhesion, and minimum viscosity to enhance the ease of waterproofing agent application. Accordingly, the most preferred low modulus, one-component W RTV system of the present invention is prepared by using the two plasticizers of the present invention in the proportions described above. Within the above broad range of from 5 to 60 parts of second plasticizer, preferably 2
It should be noted that concentrations of 0 to 45 parts by weight are used.

Another aspect is to reduce the cost of the composition.

This composition contains, per 100 parts of trunk organopolysiloxane,
Costs can be reduced by adding either 50 to 300 parts by weight or more of a bulking photonic agent as described above. Bulking photonic agents are desirable in the composition and increase the strength of the composition without reducing its low modulus properties. Most preferably the filler is calcium carbonate. The most desirable calcium carbonate is one that has been treated with stearic acid. This gives the uncured compositions of the invention the best flow properties and the best low modulus properties as defined above. Other bulking photostimulants can be incorporated into the compositions of the present invention at the above concentrations of calcium carbonate disclosed above.

Thus, other bulking and reinforcing photonic agents that can be used in various concentrations include, for example, titanium dioxide,
Zirconium silicate, silica aerogel, iron oxide,
These include diatomaceous earth, fumed silica, carbon black, precipitated silica, glass fiber, polyvinyl chloride, and powdered quartz. The amount of filler used can obviously vary within wide limits according to the intended use.

For example, in some waterproofing applications, as much as 700 parts or more of filler per 100 parts of organopolysiloxane, by weight, of the bond cracking curable composition is used. In such applications, the filler may consist of bulk bulking materials such as powdered quartz, polyvinyl chloride or mixtures thereof, which preferably have an average particle size in the range of about 1 to 10 microns. .

However, the filler used at a concentration of 50 to 300 parts by weight should be a bulking photonic agent such as calcium carbonate for the low modulus compositions of the present invention. In addition to the bulking photonic agent, from 1 to 50 parts by weight, preferably from 1 to 10 parts by weight, of reinforcing photonic agent is used per 100 parts of the trunk organopolysiloxane. The reinforcing photonic agent can be selected from precipitated silicas and fumed silicas, most preferably fumed silicas. More preferably, cyclopolysiloxanes such as those disclosed in Lucas U.S. Pat. No. 2,938,009 or Sm
A fumed silane treated with either a silazane such as that disclosed in U.S. Pat. More preferably, 1 to 1 of the above treated fumed silicone strength treated with cyclopolysiloxane
0 parts by weight are used.

Such fumed strength acts as a sag control agent making the composition chicken-tropic.

Chicken Tropic suffers from the fact that the composition placed on a vertical surface does not flow or has minimal flow in the uncured state. Another method of making a composition chickentropic is as disclosed in Lamps, US Pat. No. ff14261758, referenced herein.

Thus, for every 100 parts of the backbone organopolysiloxane polymer with reinforcing fumed silicone properties in addition to the bulking photonic agent, 0.1 parts per 100 parts of the organopolysiloxane polymer is added.
up to 2.0 parts by weight of a second sag control agent can be added to the RTV composition. This control agent is A-0-(CxH2xO)'-B and A-0-(CxH2xO)nfO.

[In the formula, A and B are hydrogen, an alkyl group containing 1 to 12 carbon atoms, a cycloalkyl group containing 5 to 7 hydrogen atoms in the ring, a monocyclic and bicyclic aryl group, and a monocyclic aryl lower alkyl group. 1 R-C-0- (wherein R represents 1 to 5 carbon atoms); alkyl containing up to 11 carbon atoms), Q is at least two hydroxy groups selected from the class consisting of ethylene glycol, glycerin, trimethylolpropane and other polyhydric alcohols having from 2 to 6 hydroxy groups. is the residue of a polyhydric initiator group containing n is a number having a value from 2 to 4, y has a value from 2 to 10, and 2 is 1
or having a value up to 65]. The polyether has a molecular weight of about 300 to about 200,000.

Polyethers, which are sag control agents, can be used in addition to or in place of fumed silicate agents to impart chicken-tropic properties to the desired uncured RTV composition in waterproofing agents.

Preferred RTV compositions of the present invention, i.e., non-corrosive, low modulus, fast curing, storage stable, low modulus compositions, are suitable for waterproofing applications in structural building, glazing, and other manufacturing industries. It must be noted that it is highly desirable as a waterproofing agent. It is therefore highly desirable that such waterproofing agents be chicken-tropic, ie, do not run off when inserted into a crevice in an uncured state. Such chickentropy can be incorporated into the compositions of the present invention by using small amounts of fumed silica in combination with the polyethers described above. Furthermore, this polyether in combination with fumed silica preferably has a
Present in parts by weight. Although fumed silicate properties impart sag control properties to the composition, these properties are significantly enhanced with the introduction of polyether.

For further information regarding the use of polyethers as sag control agents, reference is made to the disclosure of Lampe, US Pat. No. 4,261,758, incorporated herein by reference.

Examples of commercially available polyethers that can be used in the present invention are manufactured by Wyandotte Chemi-ca
Pluraol V-7 sold by IICorporatic+n and Union Carbide Corporation of Connecticut.
), such as UCON LB-1145.

In place of or in addition to both of these sag control agents, 0.0.
2 to 2.0 fold, more preferably 0.2 to 1
, up to 5 parts by weight of hydrogenated castor oil can be used.

An example of hydrogenated castor oil that can be used as a sag control agent is that known as Thixcin (trade name of NL Chemicals, Hightstown, New Chassis).

Therefore, neither fumed silicone nor polyethers should be used when hydrogenated castor oil is used as a sag control agent. However, when hydrogenated castor oil is not used as a sag control agent, fumed silicone should be used with polyether. Instead, fumed silica or polyether alone can be used. It must be emphasized that reinforcing brighteners are not necessary in the compositions as it is desired to have a low modulus in the compositions of the present invention. Large amounts of reinforcing photonic agents appear to undesirably increase the modulus of the compositions of this invention. Most preferably, the fumed silica (if used) is treated with calcium carbonate, especially stearic acid, which reduces the cost of the composition and maintains the viscosity of the uncured composition and the modulus of the uncured composition at low values. Used in addition to bulking fillers such as calcium carbonate. Many other types of additives that become available or are invented can be added to the present invention.

Thus, 0.1 per 100 parts of organopolysiloxane
~10 parts by weight of an adhesion promoter can be added to the composition of the invention. The compositions of the present invention, ie, White et al., do not bond as well to substrates. It is therefore desirable to use primers or adhesion promoters with such compositions. Primers are undesirable because they add additional labor costs to the waterproofing agent application. Therefore, it is highly desirable to use or incorporate self-bonding additives into the composition. For example, Lucas et al. 19822, referenced here.
Note the self-binding additives disclosed and listed in U.S. Patent Application No. 349,538, dated May 17, 2013.

Adhesion promoters that can be used in the present invention are described in U.S. Pat.
No. 9600.

Other adhesion promoters developed can be used in the compositions of the present invention in addition to those disclosed in the earlier Lucas et al. US Patent Application No. 349,538. It is noteworthy that the compositions of the present invention, in addition to other properties, are low modulus, rapidly curing and storage stable, and that this low modulus property of the compositions is imparted by the plasticizer. When using the preferred bulking photostimulants of the present invention, the composition is also chickentropic by the addition of the chickentropic agents disclosed above and is low cost.

Any other adhesion promoter disclosed in Lucas et al. US Pat. No. 3,495,38 or the present invention may be used. Additionally, other additives that are developed can also be used in the compositions of the present invention.

MTD oils and triorganosiloxy-terminated diorganopolysiloxane plasticizers are necessary components of the present compositions if the uncured silicone compositions are to have application rates within the preferred ranges noted above. I have to admit something. In accordance with the present invention, the RTv silicone rubber compositions produced in a static mixer and devolatilization extruder, without plasticizer, are produced at a rate corresponding to a specific gravity of the uncured composition ranging from 1.010 to 1.050. It also does not have application speeds of 50-150 f/min or higher. In order to obtain an uncured RTV silicone rubber composition having the above application rate in the uncured state, it is not only necessary to manufacture it by a combination of a static mixer and a devolatilizing extruder as outlined above. In addition, it is necessary to use one or more plasticizers in the preparation of the composition. Thus, in order to obtain favorable application rates, it is desirable to use at least an MTD oil as defined above in the preparation of the composition. In a most preferred embodiment, an MTD oil as defined above and a triorganosiloxy-terminated diorganopolysiloxane also as defined above are used to obtain an uncured R'FV silicone rubber composition having an application rate within the preferred ranges indicated above. Preference is given to using both polymers in the amounts mentioned above.

U.S. Patent Application No. 277,524 to White et al., U.S. Pat.
The disclosures of No. 038 and other US patents and US patent applications cited herein are specifically incorporated by reference into the application of the invention.

Additionally, the continuous method of the present invention may be used in any one of the
It should be noted that it can be used to prepare component-type alkoxy-functional RTV compositions.

In addition, the method of the present invention does not contain any scavengers, keeping in mind that the polymer is first end-capped in a static mixing mode and then the end-capped polymer is mixed with the other ingredients in a devolatilizing extruder. Alternatively, it can be used with a composite crosslinker scavenger. Other ingredients are one-component type RT
It can be any ingredient normally associated with V compositions. Alternatively, if increased viscosity is not a factor, all components can be mixed in a devolatilizing extruder. Regarding the application rate, whether mentioned in the detailed description of the invention or in the claims, the application rate values given in this invention apply to compositions having a specific gravity in the range 1.030 to 1.050. It should be noted that it corresponds to a thing.

Furthermore, the process can be carried out semi-continuously or batchwise by first mixing in a static mixer and then after a while in an extruder, but this is generally undesirable.

The following examples are provided for the purpose of illustrating the invention and are not intended to limit or delimit the invention. All parts in the examples are by weight.

Example 1 Examples 1-5 were conducted solely in a devolatilization extruder. This example, similar to Examples 2-5, describes the preparation of a continuous composition solely in a devolatilizing extruder. The devolatilizing extruder used was a Wernerpfrieder twin screw devolatilizing extruder. In the hopper of the extruder, 17
Miyako's octamethyltetrasiloxane treated fumed silica was applied continuously. In the first barrel in the extruder, 1
00 parts by weight of silanol-terminated dimethylpolysiloxane (having a viscosity in the range of 100,000 to 200,000 centipoise at 25°C), 10 parts by weight of plasticizer fluid (3
mole percent trimethylsiloxy monofunctional units, 20
It has mole percent methylsiloxy trifunctional units, 77 mole percent dimethylsiloxy difunctional units, and 25
(having a viscosity of 50 centipoise at °C) and 0.5% by weight of silanol were added.

In the examples, this fluid will be referred to as "MTD J fluid".
＋! -! J methylsiloxy-terminated dimethylfolysiloxane (having about 500 parts per million parts of silanol,
100 centipoise at 25 DEG C.) and 0.2 parts by weight of a polyether sag control agent sold under the name Pluracol V-7 were added to the first barrel of the extruder.

In the barrel @2 of the devolatilizing extruder were added 5 parts by weight of methyltrimethoxysilane, 0.33 parts by weight of acetic acid and 0.3 parts by weight of acetic acid.
67 parts by weight of n-dihexylamine were added continuously.

In barrel 11 or near the holly of the devolatilizing extruder, 5 parts by weight of hexamethyldisilazane, 1.7 parts by weight of 3-(2-ami/ethylamino)-propyl-tri as an adhesion promoter. Methoxysilane and 0.33 parts dibutyltin diacetate were added. The devolatilization extruder is approximately 50°±
Maintained at a temperature of 5°C, the production rate of the RTV uncured silicone rubber composition was about 151 bonds per hour. This composition had an application rate of 38 grams per minute. The devolatilizing extruder had 13 separate mixing steps or compartments where mixing could occur and components could be added if desired.

Example 2 The extruder of Example J was operated similarly and the same ingredients were added in barrel 1 or step 1 and barrel 11 or step 11. However, in Norrel 2 or Step 2, instead of the catalyst mixture of Example 1, 6.25 parts by weight of methyltrimethoxysilane, 0.41 parts by weight of acetic acid, and 0.41 parts by weight of acetic acid and 0.25 parts by weight of methyltrimethoxysilane,
84 parts of n-dihexylamine were added in this example.

The extruder processing temperature was approximately 50°C ± 5°C, and the composition produced had an application rate of 48 grams per minute. The application speed values obtained in Examples 1 and 2 ranged from 1.010 to 1.01.
This corresponded to a composition having a specific gravity in the range of 0.050.

Example 3 This method was operated similarly to Example 1 using the same ingredients and the same extruder. The process was operated continuously as in Examples 1 and 2.

However, if the catalyst composition of Example 1 was replaced with the catalyst*1m acid listed below, barrel 2 of the extruder or step 2 of the extruder was used.
I added it. The types of ingredients and amounts of ingredients added to Barrel 1 and Barrel 11 were the same as in Example 1. The catalyst composition added sequentially to barrel 2 in the Example was 7.5 parts by weight methyltrimethoxysilane, 0.5 parts by weight acetic acid, and 1.0 parts by weight n-dihexylamine.

The extruder processing temperature was maintained at approximately 50°C ± 5°C and the application rate of the uncured composition was 572 per minute for compositions having specific gravity within the range of 1.010 to 1.050.

Example 4 This example was operated in the same manner as Examples 1, 2 and 3 only in the devolatilization extrusion system. The types and amounts of ingredients added to extruder barrels 1 and 11 were the same as in Example 1. The catalyst components added in barrel 2 were different from Example 1: 10 parts by weight of methyltrimethoxysilane, 0.66 parts of Tanbe's acetic acid, and 1,34 parts of n-
It was dihexylamine. The processing temperature of the extruder is 50℃
±5°C, and the application rate of the uncured composition produced was
Uncured R with specific gravity in the range of 1.010 to 1.050
762, which corresponds to a TV silicone rubber composition.

Example 5 In this example, the composition was prepared by mixing only in the devolatilizing extruder 4, as in the previous four examples. 17 parts by weight of octamethylcyclotetrasiloxane treated fumed silicate was added to the extruder hopper. To barrel 1 of the extruder was added 100 mfa parts of a silanol-terminated dimethylpolysiloxane polymer having a viscosity in the range of 100,000 to 2 ooooo centipoise at 25°C. 1 part MTDJ fluid identical to Example 1, 40 parts by weight of trimethylsiloxy-terminated dimethylpolysiloxane polymer identical to Example 1, and 0.2 parts by weight of the polyether of Example 1 were also added to barrel 1. Barrel 2I
C-6,7 parts dimethyltetramethoxysilazane,
0.33 parts of acetic acid and 0.67 parts of n-dihexylamine were added. To barrel 11 was added sequentially 1.7 parts of 3-(2-aminoethylamino)-propyltrimethoxysilane and 0.6 parts of dibutyltin diacetate. The method was operated continuously. The processing temperature of the composition was maintained at about 80°C.

The production rate of the composition was 149 pounds per hour.

The uncured composition produced by the above method had the following physical properties.

EXAMPLES The examples in this section utilize both a static mixer and a devolatilizing extruder in processing the composition.

The composition was processed continuously. 1 at 25°C as per above.
100 parts by weight of a silanol-terminated dimethylpolysiloxane polymer having a viscosity in the range of ooooo to 200,000 centipoise, 1.05 parts by weight of methyltrimethoxysilane, 0.21 parts by weight of n-dihexylamine and 0.05 parts by weight of acetic acid. were mixed continuously in a static mixer. The temperature of the static mixer was controlled at 60°C±5°C. The endcapping reaction was allowed to proceed for 1 hour, at which time the presence of remaining silanol groups was determined by infrared spectroscopy. Then,
0.5 fold i1t@u) hexamethylsilazane was added to scavenge free methanol in the polymer.

The methyl dimethoxy end-capped polymer was stored in a closed container at room temperature for approximately one week before being mixed in an extruder. The pre-endcapped polyalkoxy-terminated dimethylpolysiloxane polymer was pumped into barrel 1 of the Wernerp-Frieder devolatilizing extruder at the end of storage. Add 17 parts by weight of octamethylcyclotetrasiloxane-treated fumed silicon to the hopper and then add 100 parts by weight to the barrel l.
parts by weight of pre-endcapped dimethylpolysiloxane polymer, 10 parts by weight of [MTD J Fluid, 20
Parts by weight of treated fumed silica and 0.2 parts by weight of polyether (sold by Union Fist Carbide Corporation under the trade name UCON LB-l 45) were added sequentially as described above. . To barrel 7 of the extruder, 37 parts by weight of hexamethyldisilazane were added continuously, to barrel 11 of the extruder, 0.7 parts by weight of methyltrimethoxysilane, 1.47 parts by weight
Parts by weight of aminoethylaminopropyltrimethoxysilane and 0.9 parts by weight dibutyltin diacetate were added sequentially. The extruder processing temperature was maintained at 50°C ± 5°C and the production rate of uncured material was 150 bonds per hour. The physical data of the uncured mixed composition is as shown in Table H below.

Table ■ TPT 20 (minutes) 2
0 (min) Shore hardness A 15
11 Tension 169 140 Extension 456 455 Modulus, 50 modulus 41 34
Modulus, 100% 53
45 Flow (hand/press) 0.110.45 inch 0.110.1 inch Application speed 17
6r/min 200r/min Specific gravity 1.02
6 Example 7 An uncured RTV composition was produced continuously as in Example 6. Mixing was carried out continuously in a static mixer and in a devolatilization extruder. 100000~2000 at 25℃
00 centipoise methyldimethoxy end-capped dimethylpolysiloxane polymer as described in Example 6.
Prepared in a static mixer. The polymer was continuously pumped into a devolatilizing extruder and mixed with other ingredients as follows. A 17 ffi volume of octamethylcyclotetrasiloxane treated fumed silicon was continuously applied to the devolatilization extruder hopper. In the barrel l of the extruder, 10
0 parts by weight of end-capped dimethylpolysiloxane polymer;
10 parts by weight of the "MTD" fluid of Example 1, 40 parts by weight of the trimethylsiloxy end-capped dimethylpolysiloxane polymer of Example 1, and 0.2 parts by weight of the polyether sag control agent of Example 6 were added. In barrel 11, 3.68 [
Part L of hexamethyldisilazane, 0.74 parts by weight of methyltrimethoxysilane, 1.47 parts by weight of 3-(2-aminoethylamino)-propyltrimethoxysilane and 0.19 parts of dibutyltin diacetate. was added continuously. The extruder processing temperature was maintained at approximately 50°C ± 5°C, and the extruder production rate was 150 pounds per hour. The physical data of the uncured compositions produced continuously by the above method are shown in Table 1 below.

Table ■ Aging 24 hours/room temperature 48 hours/10
0℃TPT 20 minutes 50 minutes Shore hardness A 14
11 Tensile 178 138 Extension 532 520 Modulus, 50 coefficient 34 26 Modulus, 100% 45 37 Flow 0.1 inch 10.1 inch/
(Hand/Press) 0.2 inch 0
．． 25 inch application speed 1901/min
171/min Specific Gravity 1.029 Example 8 The following example illustrates a preferred endcapping reaction for use in the present invention. However, a devolatilizing extruder and continuous mixing were not used in these two examples. These examples merely disclose and explain below the preferred endcapping reactions used and required for a continuous process within the scope of the invention. Polyalkoxy-terminated dimethylpolysiloxa having a viscosity of about 3000 centipoise at 25°C/4.5 parts methyltrimethoxysilane in 100 parts fjt, 0 to
0.2 parts of acetic acid and 0-0.5 parts of n-dihexylamine were mixed. Mixing was carried out at 80°C for 15 minutes. The degree of end-blocking was determined by infrared. The results are shown in Table ■ below.

Table ■ 1 0 0.5 34 2 0.2 0 193 0.2
0.5 1004 0.2 0.5
97 Example 9 A suitable mixer equipped with a vacuum system and nitrogen purification equipment was heated to 25°C.
100 parts of a silanol-terminated dimethylpolysiloxane polymer having a viscosity of about 120,000 centipoise, 17 parts of an octamethyltetrasiloxane-treated fumed silicone fluid, 35 parts of a silanol-containing trimethylsiloxy-terminated dimethylpolysiloxane fluid, 15 parts of Example 1. A silanol-containing MTD J fluid and 0.2 parts of polyether (sold by Union Carbide Corporation under the trade name UCON IJ-L 1145) were charged. The mixture was incubated under a full vacuum of approximately 20 WII Hf at room temperature for 2 hours. Stirred to obtain an RTV base. To 100 parts of this base preheated to 80°C were added 4.0 parts of methyltrimethoxysiloxane, 0.2 parts of acetic acid and 0.4 parts of n
- dihexylamine was added, then Semkit ■ (Se
The mixture was mixed for 15 minutes using a mixer (mkit ■). 0.1
A solution consisting of 1 part 3-(2-aminoethylamino)-propyltrimethoxysilane, 2.0 parts by weight hexamethyldisilazane and 0.2 parts dibutyltin diacetate was added to the above mixture, and then 2 was mixed for 15 minutes. Following mixing, the RTV composition was placed in sealed aluminum tubes and stored at room temperature for 24 hours and at 100° C. for 24 hours.

After aging, the material was pressed into an ASTM sheet and heated at room temperature for 50 minutes.
% relative humidity for 3 days. After curing, physical properties were measured and the results are shown in Table V.

Table ■ Flow, inch 0.1 0
．． 1 Applied speed, ? /min 216
19 parts 5 specific gravity 1.035 1.035
Thickness time (min) 30 30 Hardness, Shore A
15 12 tensile strength,
PBi 153 157 Extension, % 408 517 Modulus, 75% 42 35
Adhesion Peel ppi/%Coh.

Aluminum (low oxidation treatment) 42/90
No data Glass 51/95
Galvanized steel 44/80pvc
S8/100 Lexan
35/85 Example 10 A suitable mixer equipped with a vacuum system and nitrogen purification equipment was heated to 25°C.
100 parts of silanol-terminated dimethylpolysiloxane polymer having a viscosity of 120,000 centipoise, 17 parts of treated fumed silica of Example 9, 20 parts of silanol-containing trimethylsiloxy-terminated dimethylpolysiloxane polymer of Example 1, silanol-containing of Example 1 10 parts of 1'-MTD J fluid and 0.2 parts of the polyether of Example 10 were charged. Pour this mixture under full vacuum (
20rtbnHy) Stir at room temperature for 2 liters
Got TV Heath. The composition was mixed using a Semkit ■ mixer in two steps as follows.

First, by mixing for 15 minutes, 2.5 to 4.5 parts of methyltrimethoxysilane, 0.13 parts of acetic acid, and n-dihexylamine as shown in Table 1 below were added to 100 parts of the base prepared as described above. 0.33 parts were added.

This mixture was mixed for 15 minutes at 80°C, then a second
In a 5 minute mixing step, 2.7 parts of hexamethyldisilazane, 1.0 part of the adhesion promoter of Example 9 and 0.33 parts of dibutyltin diacetate were mixed. Following mixing, R'F
V compositions were placed in sealed aluminum lumen tubes and stored at room temperature for 24 hours and at 100° C. for 48 hours. After aging, the material is A
It was pressed into an STM sheet and cured for 3 days at room temperature and 50% relative humidity. Physical properties were then measured and the results are shown in Table 1 below.

Example 11 Using the base composition described in Example 8, Semkit ■
Various compositions were prepared by mixing in two steps in a mixer and mixing was performed as follows. During a 15 minute mixing period, in a mixer, 100 parts of the base of Example 1, 3.0 to 4.5 parts of methyltrimethoxysilane as shown in Table 1 below, and 0.0 parts of acetic acid as shown in Table 2 below. 1 to 0.25 parts and n
- 0.5 part of dihexylamine was mixed. In the second mixing step, 2 to 3.0 parts of dimethyltetramethoxydisilazane and 0.4 parts by weight of dibutyltin diacetate were mixed as shown in Table 1 below. To this was added 1.0 part of the adhesion promoter of Example 9. The tack-free time was measured after 24 hours at room temperature, 24 hours at 100°C and 48 hours at 100°C. The aging results are shown in Table 3 below.

=453

Claims (1)

[Claims] 1. A crosslinking agent selected from (a) an organopolysiloxane whose silicon atom subpolymer chain ends are terminated with at least one hydroxy group, (b) a polyalkoxy crosslinking agent and a composite crosslinking agent scavenger. , and (Cl Lewis acid,
Acidifying agents selected from Lowry-Bronsted acid and stearic acid treated calcium carbonate and primary, secondary
An end-capping catalyst system, which is a mixture with an amine selected from primary and tertiary amines, is used to prepare polyalkoxy-terminated organopolysiloxanes, with additional components added to the polyalkoxy-terminated organopolysiloxanes. A stable, one-package product that can be converted into a long-term stable and tack-free elastomer under substantially moisture-free ambient conditions by passing through a static mixer (mixing to form the RTV 71Jl composition) A continuous process for producing a substantially anhydrous room temperature curable organopolysiloxane composition. 2. The method of claim 1, comprising admixing the additional ingredients to the polyalkoxy-terminated organopolysiloxane in a devolatilizing extruder. 3. Polyalkoxy-terminated organopolysiloxane, fumed silicate force, 25 in the initial mixing chamber of the devolatilization extruder
3. The method of claim 2, comprising mixing a triorganosiloxy-terminated diorganopolysiloxane plasticizer polymer with a viscosity of 10 to 20,000 centipoise at <0>C and a polyether as a sag control agent. 4. Polyalkoxy-terminated organopolysiloxane 10
1 to 50 parts by weight of fumed silica per 0 parts by weight, 1
A claim consisting of the presence of 0 to 50 parts by weight of a triorganosiloxy-terminated diorganopolysiloxane plasticizer polymer in which the organic groups are monovalent hydrocarbon groups and 0.1 to 2.0 parts by weight of a polyether. The method described in Clause 3 of the scope. 5. A method according to claim 4, comprising adding further silazane scavenger in a mixing chamber following the initial stage in the devolatilizing extruder. 6. The process according to claim UB$5, which comprises adding an additional amount of scavenger followed by adding in the mixing chamber an excess amount of condensation catalyst, adhesion promoter and optionally polyalkoxysilane crosslinker. 7. The method according to claim 6, which comprises operating the static mixer at a temperature of 40°C to 100°C. 8. The devolatilization extruder is operated at a temperature of 40°C to 100°C and 7. The method of claim 7, comprising operating at a vacuum less than 20 inches of mercury. 9. The method of claim 7, wherein the devolatilizing extruder is a single screw devolatilizing extruder. The method according to claim 8. 10. The method according to claim 9, wherein the devolatilization extruder is a twin screw devolatilization extruder. 11. 10. The method of claim 10 comprising producing a room temperature curable silicone rubber composition having an application rate greater than 502 and up to 100? or higher. 12. Initial mixing chamber of a devolatilizing extruder. Among them, polyalkoxy-terminated organopolysiloxane, fumed silicate, calcium carbonate, sagging control agent polyneedle,
The organic group is a monovalent hydrocarbon with a temperature of lO~200 at 25°C.
a triorganosiloxy-terminated diorganopolysiloxane having a viscosity of 0.00 centipoise;
60 mole percent monoalkylsiloxy, siloxy units and mixtures of said siloxy units, (fil 1-6
mole percent trialkylsiloxy units, (+i0
3. The method of claim 2 comprising incorporating an MTD plasticizer having from 34 to 94 mole percent dialkylsiloxy units and from about 0.1 to 2.0 weight percent silicon-bonded hydroxy groups. Claim 12: A method according to claim 12, comprising treating the 13,7-umed silica with a cyclic polysiloxante and treating the calcium carbonate with stearic acid. 14. Polyalkoxy-terminated organopolysiloxane 10
Fumed sealing force of 1 to 50 parts by weight per 0 parts by weight, 1
00-300 heavy-duty part of carbonic acid, 0.1-2.0
14. The method of claim 13, comprising the presence of 10 to 50 parts by weight of polyether, 10 to 50 parts by weight of triorganosiloxy-terminated diorganopolysiloxane, and 2 to 20 parts by weight of MTD plasticizer. 15. The method of claim 14 further comprising adding an additional amount of silazane scavenger in a mixing chamber following the initial stage in the devolatilization extruder. 16. Mixing the mixture of condensation catalyst, adhesion promoter and optionally an excess of polyalkoxysilane crosslinker in one subsequent mixing chamber after adding an additional amount of scavenger. Method described. 17. The method according to claim 16, which comprises operating a static mixer at a temperature of 40 to 100°C. 18. The method of claim 17, comprising operating the devolatilizing extruder at a temperature in the range of 40 to 100°C and less than 20 inches of mercury and 1 vacuum. 19. The method of claim 11, wherein the devolatilizing extruder is a twin screw devolatilizing extruder. 20. Process according to claim 19, comprising preparing a room-temperature curable silicone rubber composition having an application rate of more than 5 (liters per minute and up to 1002) in the uncured state. Cyclic silyl nitrogen scavenger, as well as a cyclic silyl nitrogen scavenger with remaining units (if any) having 21 (R) Si-N211 [in the above three formulas, RIO is alkyl, alkyl ether, alkyl ester, is an aliphatic organic group selected from the group consisting of alkylketone, alkylcyano, and aryl, and R1'' is 1 of Cl-11.
a substituted or unsubstituted hydrocarbon group, Q is hydrogen, C
1-3 monovalent substituted or unsubstituted hydrocarbon group and the formula (wherein RIO and R11 are as defined above, a
varies from O to 2, f varies from O to 3, h is 0 or 1, where B is an integer varying from 1 to 25, and d is an inverse integer from 1 to 25. can be,
R4 is selected from hydrogen and a C□-8 monovalent hydrocarbon group, and RIB is selected from a group independently selected from a C1-8 monovalent hydrocarbon and hydrocarboxylic paper. , A is hydrogen and a monovalent substituted or unsubstituted hydrocarbon group of 01-8 and the formula (wherein RIO and R11 are as defined above, g
varies from 0 to 3 and is selected from the class of groups consisting of fewer (at least one hydrocarboxy group is present in the molecule) in the scavenger, R12 is R
107, R13 is defined the same as R11, and R14 is defined the same as R11 (wherein R is a monovalent substituted or unsubstituted hydrocarbon group of C.
R1 is a C1-11 aliphatic group or a C7-13 aralkyl group selected from the group consisting of alkyl, alkyl ether, alkyl ester, alkyl ketone, and alkyl cyano group, and R2 is a C8-□3 monovalent group. @substituted or unsubstituted hydrocarbon group, X is a silazane hydrocarbon molecule t
, ' is a leaving group, b is an integer of O or 1, and θ
is an integer of 0 or 1, and the total number of b10 is O or l
and n is an integer having a value from about 50 to about 2500) to a devolatilizing extruder. The method according to claim 2. 22, formula (wherein R1 is a C1-8 aliphatic organic group selected from the group consisting of alkyl, alkyl ether, alkyl ester, alkyl ketone, and alkylsia 7 groups or C7
-18 aralkyl group, R2 is C monovalent substituted or unsubstituted hydrocarbon group -13, and b is an integer of 0 or 1]. Claim 1
The method described in section. 23. The method of claim 21, wherein the scavenger and crosslinker have the formula: 24. The method according to claim 21, wherein the crosslinking agent and the scavenger are cyclic silazane, and RI2 and RlB are methyl groups. 25. The method according to claim 21, wherein the scavenger and the crosslinking agent have the formula: 26. The method of claim 1, wherein the acid is an acid f(H%) selected from hydrates. 27. The acid has the formula % (formula %) R30 and R81 are monovalent hydrocarbons of cl-20
2. A method according to claim 1, wherein the Lowry-Bronsted acid is a group of 1, wherein j is an integer varying from 0 to 3. According to claim 1, the acid is a Lowry-Bronsted acid having the formula % (wherein R32 is a monovalent hydrocarbon group of cl-2°). the method of. 29. The method of claim 1, wherein the acid is a Lowry-Bronsted inorganic acid. 30, acid free is HCfl, H3PO4, HxSOa
30. The method of claim 29, comprising selected from the class consisting of oyohiho 9-phosphate. 31. The method according to claim 1, wherein the sour hydrate has the formula % (wherein Has, R34 is a monovalent hydrocarbon of Cl-20). 32, the acids are BF3, (CH,CH,)20 and Abc
13. The method of claim 1, wherein the Lewis acid is selected from the class consisting of 13. 33, CA1 formula % formula %) (wherein Y is selected from R" and R/#N-) and 3 to 100 selected from the class consisting of units having the formula R01I
mole percent of chemically bonded structural units, and (
A silicon nitrogen polymer consisting of 0 to 97 mole percent of chemically bonded structural units and mixtures thereof with the formula % 2J (wherein the silicon atoms of the silicon nitrogen polymer are 5iO8i @ and 5iNR#Si The free valences of silicon atoms other than those bonded to each other by selected members of the bond to the oxygen forming the siloxy unit and to the nitrogen forming the silacy unit are (R#):
It is bonded to a member selected from N groups, and the ratio of the total number of N groups to the silicon atoms of the silicon nitrogen polymer has a value from 1.5 to 3. , R# is a member selected from the class consisting of hydrogen and monovalent hydrocarbon groups and fluoroalkyl groups, Rtt is a member selected from the class consisting of hydrogen, monovalent hydrocarbon groups and fluoroalkyl groups, and C is O to 3
2. The method of claim 2 comprising adding in a devolatilizing extruder a stabilizing amount of a silane scavenger for hydroxy-functional groups, which is a silicon nitrogen compound selected from the class consisting of the method of. 34, the silazane polymer has chemically bonded R# units (in the formula R//, V/ is the ratio of the total number of R'# and (R")2"! per silicon atom in the silazane polymer or 1 34. The method of claim H 33, which may contain a cyclic silazane (as defined above to be between .5 and 3.0). 35, the silazane polymer has 1 R; and ('') as defined above such that the ratio of the total number of 2Nm is from 1.5 to 3. 3
The method described in Section 3. 36, the silazane polymer has... units (in the formula, R〃 and R'# are Bti and ('')2Nk per silicon atom in the above silazane polymer
34. The method according to claim 33, wherein the linear polymer has a woody appearance (as defined in such a way that the ratio of m numbers is 1.5 to 3.0). 37, the silazane polymer has R″′ SiN − units (in the formula, R′ and R″ are such that the ratio of the total number of R″ and (R′)2N groups per silicon atom in the silazane polymer is 1). 34. A composition according to claim 33, comprising at least one unit selected from the class consisting of (as defined above to be from 5 to 3). 38, the silazane polymer is 1 (wherein R″ and R″′ are R#″ and (R) per silicon atom in the silazane polymer so that the ratio of the total number of 39. The method of claim 32, wherein the silazane-siloxane compound comprises a polymer having sufficient parent units selected from 39.
, R'' and C are selected from Bi and (R#), as defined above, such that the ratio of the total number of N groups per silicon atom of the silazane-siloxane copolymer is from 1.5 to 3. 34. The composition of claim 33, wherein the composition is a copolymer having a majority of units with up to 97 mole percent (R") 5iO C" units. 40, the silazane-siloxane compound is cyclic, consisting of chemically bonded (R) 2810 units and R/lt units, where R" and R"' are as defined above. A composition according to Range 33. 41. The silazane nitrogen compound is of the formula and d is an integer from 0 to 1, and when d is 0, n is preferably an integer from 3 to 7). 42, the silazane nitrogen compound has the formula (wherein R", R" and n are as defined above and Z is a number selected from R" and 34. The composition according to claim 33, which is a polysiloxane having the formula % formula % (wherein R'' is hydrogen, a monovalent hydrocarbon group of cl-8, C
a group selected from the class consisting of 1-8 alkoxy groups and fluoroalkyl groups, 6 is an integer varying from 1 to 3, h is an integer varying from 0 to 2, and h 3. A method according to claim 2, comprising adding in a devolatilizing extruder a stabilizing amount of a silane scavenger for hydroxy functional groups, the total number not exceeding 3 silylamines. 44, (alorganopolysiloxane in which the silicon atom at the end of each polymer chain is terminated with at least one hydroxy group, (bl) a crosslinking agent selected from polyalkoxy crosslinkers and composite crosslinker scavengers, (Cl Lewis acid, Lori - an endcapping catalyst system consisting of an acid selected from Brønsted acids and stearic acid-treated calcium carbonate and an amine selected from primary, secondary and tertiary amines, (with an effective amount of condensation catalyst, and if By continuously mixing a stabilizing amount of a scavenger in a devolatilizing extruder, a stable, single-layer compound can be converted into a long-term stable, tack-free elastomer under substantially moisture-free ambient conditions. 45. A method for continuously preparing a substantially anhydrous and substantially acid-free, room temperature curable organopolysiloxane composition in a package. and the remaining units with the formula (
A cyclic silyl nitrogen scavenger with
In the above three formulas, R is an aliphatic organic circle of cl-8 selected from the group consisting of alkyl, alkyl ether, alkyl ester, alkyl ketone, alkylcyano, and aryl, and R11 is 1 of cl-8. Q is a monovalent substituted or unsubstituted hydrocarbon group with hydrogen% Cl-8 and the formula (wherein R1(+
and R11 are as defined above, where a varies from 0 to 2, f varies from 0 to 3, and h is O
or 1, where 8 is an integer varying from 1 to 25, d is an integer varying from 1 to 25, and R
22 is selected from hydrogen and C monovalent hydrocarbon groups, and R23 is selected from the group independently selected from monovalent hydrocarbons and hydrocarboxy groups, and A is hydrogen and A monovalent substituted or unsubstituted hydrocarbon of C1-8 and the formula (where F!10 and R41 are as defined above, g varies from O to 3, and in the scavenger is in which at least one hydrocarboxy group is present in the molecule;
12 is defined the same as R10, R13 is defined the same as R11, and R14 is defined the same as R11. . 46, formula (wherein R1 is a C□-8 aliphatic organic group selected from the group consisting of alkyl, alkyl ether, alkyl ester, alkyl ketone and alkyl cyano group or
7-□, R2 is 1 of Cl-13
is a valent substituted or unsubstituted hydrocarbon group, and b is 0
or an integer of 1) of the crosslinking agent silazane. 47. The method of claim 45, wherein the acid is a Lowry-Bronsted acid selected from acid anhydrides. 48, the acid has the formula (wherein R30 and R31 are monovalent hydrocarbon groups of Cl-20, and j is an integer varying from O to 3)
Claim 4 which is a Lowry-Bronsted acid of
The method described in Section 5. 49. The method according to claim 45J, wherein the acid is a Lowry-Bronsted acid of the formula % where R32 is a C1-20 monovalent hydrocarbon group. 50. The method of claim 45, wherein the acid is a Lowry-Bronsted inorganic acid. 51, Gu α machine acid is HCl, If3PO4, I(2So
46. The method of claim 45, comprising: selected from the class consisting of: 4 and polyphosphoric acids. 52. The method according to claim 45, wherein the acid anhydride has the formula % where R83 and R34 are monovalent hydrocarbon groups of C. 46. The method of claim 45, wherein the Lewis acid is a Lewis acid selected from the class consisting of 53, BP, (CH312), O, and AJICJts. 54, with a stabilizing amount of scavenger for the hydroxy functional group. (-1 formula % formula %) (wherein Y is selected from R'' and R''/2N) and (bl (3 to 100 selected from the class consisting of units having the formula
mole percent of chemically bonded structural units and (2
) a silicon-nitrogen polymer consisting of 0 to 97 mole percent of chemically bonded structural units of the formula % formula %) and mixtures thereof (wherein the silicon atoms of the silicon-nitrogen polymer have 5iO8i bonds and 5iNR The free valences of the above silicon atoms, other than those bonded to each other by selected members of the Si bond and to the oxygen forming the siloxy unit and the nitrogen forming the silacy unit, are (R) from the N group. and wherein the ratio of the total number of R″′ groups and (R#)N groups to silicon atoms of the silicon-nitrogen polymer has a value from 1.5 to 3. has, R
' is a member selected from the class consisting of hydrogen and monovalent hydrocarbon groups and fluoroalkyl groups, and C is an integer from 0 to 3). 46. The method of claim 45, comprising: 55, a stabilizing amount of the scavenger for the hydroxy functional group has the formula (where R/l is hydrogen, a C□-8 monovalent hydrocarbon group,
It is a group selected from the class consisting of C□-6 alkoxyha and fluoroalkyl, where 6 is an integer varying from 0 to 3, h is an integer varying from 0 to 2, and mo is h+g. 46. The method of claim 45, wherein the total number of silylamines does not exceed 3). (b) a crosslinker selected from polyalkoxy crosslinkers and composite crosslinker scavengers; ) a mixture of an acidifying agent and an amine, where the acid is selected from Lewis acids, Lowry-Bronsted acids and stearic acid treated calcium carbonate, while the amine is selected from primary, secondary If& and tertiary!A amines; )
A polyalkoxy-terminated diorganopolysiloxane is produced by passing an end-capped catalyst system through a static mixing sieve, and then (2) introducing the polyalkoxy-terminated organopolysiloxane into a devolatilizing extruder and condensing with it. Stable, one-package, substantially anhydrous room temperature curing convertible to long-term stable, tack-free elastomers under ambient conditions substantially free of moisture by mixing with additional components including catalysts. Continuous production method for polyorganopolysiloxane compositions.