Method of making a polydiorganosiloxane-silica mixture, the resulting mixture and a room temperature curing sealant

Abstract: A process is disclosed of making a polydiorganosiloxane-silica universal mixture from a free-flowing, powdered, surface-modified, reinforcing silica-polydiorganosiloxane composition used to make, for example, RTV silicone sealant compositions which are non-sag. These mixtures are made by combining, mixing and heating a reinforcing silica filler and a diol surface modifying agent at 20°C. to 180°C. using 0.05 to 0.5 part by weight of the diol per one part by weight of the silica. Polydiorganosiloxane is added gradually to the resulting fluidized filler over a time period of less than 10 minutes to obtain the free flowing powdered reinforcing silica-polydiorganosiloxane. The foundation mixture is obtained by massing the above composition and adding more polydiorganosiloxane to obtain a mixture which has from 5 to 20 weight percent of silica filler. The product mixtures have a plateau stress of greater than 700 dynes/cm 2 and a shear-thinned viscosity of no more than 1,000 Pa·s at a shear stress of 50,000 dynes/cm 2 . RTV silicone sealant compositions are obtained in 10 to 15 minutes from the start of making the surface modified silica filler to the final sealant composition.

Description: This invention provides a process of preparing a universal polydiorganosiloxane-silica mixture and a non-slump room temperature vulcanizable (RTV) silicone sealant therefrom. RTV silicone sealants are used in the art for a variety of adhesive and weatherproofing applications. Many of these applications require a material consistency that allows it to be installed in the uncured state in a vertical configuration and to maintain that shape until cure has occurred. Such sealant is said to have non-slump or non-sag properties. If a sealant sags or flows from its initial configuration, the desired weatherproofing or adhesive property is not obtained. A typical silicone sealant formulation comprises a silicone polymer, a curing agent, such as a crosslinker or a combination of a crosslinker and a curing catalyst, and a filler, such as a reinforcing silica filler or an extending filler. The reinforcing silica, such as fumed silica, is used to provide reinforcement to the polymeric network; to give a thixotropic property to the uncured composition; and to induce a higher tensile strength and tear strength in the cured product. It is generally known that the silica must be treated to yield a non-sag sealant composition. Without treatment, a slumpy or saggy sealant composition can result. One way to prepare non-sag silicone sealants is to first react a crosslinker with a silicon-bonded hydroxyl endblocking group of a polydiorganosiloxane and to then follow with the addition of silica filler. Using this approach, crosslinker is used in an amount sufficient to react with the hydroxyl groups of the polydiorganosiloxane and the hydroxyl groups on the silica. This approach provides the desired non-sag sealant composition, but the process is limited to one type of cure chemistry, such as a sealant composition with organotriacetoxysilane crosslinker or organotrioximosilane crosslinker. However, if a universal mixture could be prepared without the curing agent, i.e. crosslinker and curing catalyst, and if this mixture could be used as the basis for the preparation of a variety of sealant compositions having different curing agent chemistries, the advantages are many. For example, one universal starting mixture means that only minor changes on continuous mixing equipment are required, and that change over from one sealant composition to another type, can be readily accomplished. The number of required ingredients in inventory can thus be reduced and items of equipment formerly utilized can become available for other manufacturing processes. Also, the flexibility of the kinds of products made from only one starting material is advantageous for meeting new customer needs in a hurry. To make a universal mixture viable for the manufacture of sealant compositions, it should be stable over the time period from immediately after its preparation to the time when the mixture is formulated into an RTV silicone sealant composition. "Stable", for the purposes of this invention, means that our mixture can be expediently used to formulate a sealant composition and the resulting composition will have a maximum slump of 0.51 cm (0.20 inch) as defined by ASTM D 2202, and preferably less. It is desirable to prepare a non-sag, one-package, RTV, silicone sealant composition from a universal mixture which avoids during storage the well-known silica-polymer interaction problems, such as crepe hardening or structure formation. Generally, it is believed that the use of pretreated reinforcing silica fillers eliminates these silica-polymer interactions and provides a stable composition comprising polydiorganosiloxane and reinforcing silica filler. However, we have found that a stable universal mixture of silica filler and polydiorganosiloxane, wherein the siloxane polymer has a viscosity at 25°C. of 400 Pa·s or less, is not obtained with ordinary pretreated reinforcing silica fillers. In fact, commercially available pretreated silica fillers, such as Cabot TS-610(R) and Cabot TS-530(R) available from Cabot Corporation, Tuscola, Illinois, require additional treatment to produce a mixture with long term stability such that an acceptable sealant composition is produced for times as long as one year. TS-610 is a dimethyldichlorosilane treated fumed silica with a surface area of 120 (+/-20) m 2 /g and TS-530 is a hexamethyldisilazane treated fumed silica with a surface area of 200 (+/-40) m 2 /g. US-A-4,724,167 discloses a method for treating finely divided silica reinforcing fillers which utilizes low temperature and hydroxy or alkoxy containing diorganopolysiloxanes as the treating agent. The treatment of fillers in this manner facilitates the manufacture and incorporation into silicone rubbers. EP-A-676 445 teaches a process comprising the steps of (A) mixing a base material which is obtained by mixing an organopolysiloxane and a reinforcing silica and then heating the resulting mixture with a specific aminosilane compound, and (B) heating the reaction mixture obtained in step (A) under normal pressure or reduced pressure to remove unreacted aminosilane and by-product amine contained in the reaction mixture. The silicone rubber composition prepared by this process can produce a silicone rubber cured product improved in compression set properties without compromising other good properties inherent in silicone rubbers. From EP-A-497 318 a room temperature-curable organopolysiloxane composition is known which does not suffer from surface fissuring even when subjected to external stress during the course of its cure comprising a hydroxyl-terminated polydiorganosiloxane, a hydrophobic silica with a silanol titer not exceeding 2.0 ml, a dry-method silica with a silanol titer of at least 5.0 ml, and an oxime group-containing silane or siloxane. One embodiment of this invention introduces a process for making a polydiorganosiloxane-silica universal mixture comprising (i) combining, while agitating and heating, reinforcing silica filler having a surface area of 90 to 500 m 2 /g and having a median aggregate-agglomerate particle size less than 600 micrometers and a diol surface modifying agent of the formula R'O(R 2 SiO) x R' wherein R is methyl, ethyl, vinyl, 3,3,3-trifluoropropyl or phenyl, each R' is selected from the group consisting of hydrogen atom, methyl radical and ethyl radical, up to 30 percent of the R' can be methyl radical or ethyl radical and x is a value of from 2 to 18 inclusive and the diol surface modifying agent has at least 3 weight percent silicon-bonded hydroxyl group, making a filler mixture where there is 0.05 to 0.5 part by weight of diol per one part by weight of silica filler; (ii) mixing the filler mixture at a temperature in the range of from 20°C. to 180°C. and maintaining the filler mixture in a fluidized powder state until the diol is dispersed throughout the silica filler and the median aggregate-agglomerate particle size of the filler mixture is less than the median aggregate-agglomerate particle size of the silica filler, this mixing process not exceeding 5 minutes in duration and removing volatiles from the filler mixture during the mixing process; (iii) adding gradually, with mixing, a polydiorganosiloxane having a viscosity measured at 25°C. of from 0.1 to 400 Pa·s to the modified silica filler obtained from step (ii) and completing the addition in less than 10 minutes after the modified silica filler is obtained at the conclusion of step (ii), where the amount of polydiorganosiloxane is added to provide from 25 to 40 weight percent of silica filler, based on the total weight of the polydiorganosiloxane and the modified silica filler; thereafter (iv) mixing until a uniform free flowing powder of a reinforcing silica-polydiorganosiloxane composition is obtained where the total mixing time of steps of (iii) and (iv) does not exceed 10 minutes; thereafter (v) massing the uniform free-flowing silica-polydiorganosiloxane composition obtained from step (iv) until a paste consistency mixture is obtained; and (vi) admixing gradually more polydiorganosiloxane making a uniform mixture having a higher concentration of polydiorganosiloxane, than the free-flowing silica-polydiorganosiloxane (iv), with a silica filler content from 5 to 20 weight percent, based on the total weight of the mixture. Another embodiment of this invention is a process for making a polydiorganosiloxane-silica mixture comprising (a) heating reinforcing silica filler having a surface area of 90 to 500 m 2 /g and having a median aggregate-agglomerate particle size less than 600 micrometers to a temperature in a range of 100°C. to 180°C., removing volatiles from the silica filler; thereafter (b) adding to the heated reinforcing silica filler while mixing, a diol surface modifying agent of the formula R'O(R 2 SiO) x R' wherein R is methyl, ethyl, vinyl, 3,3,3-trifluoropropyl or phenyl, each R' is selected from the group consisting of hydrogen atom, methyl radical and ethyl radical, up to 30 percent of R' can be methyl radical or ethyl radical and x is a value of from 2 to 18 inclusive and has at least 3 weight percent silicon-bonded hydroxyl group, making a filler mixture where there is 0.05 to 0.5 part by weight of diol per one part by weight of silica filler; and (c) heating and mixing the filler mixture at a temperature in the range of 100°C. to 180°C. and maintaining the filler mixture in a fluidized state until the diol is dispersed throughout the silica filler and the median aggregate-agglomerate particle size of the filler mixture is less than the median aggregate-agglomerate particle size of the silica filler, the mixing process not exceeding 5 minutes in duration and removing volatiles from the filler mixture during the mixing process where a modified silica filler is obtained; (d) adding gradually, with mixing, a polydiorganosiloxane having a viscosity measured at 25°C. of from 0.1 to 400 Pa·s to the modified silica filler of step (c) and completing the addition in less than 10 minutes after the modified silica filler is obtained at the conclusion of step (c), where the amount of polydiorganosiloxane is added to provide from 25 to 40 weight percent of silica filler, based on the total weight of the polydiorganosiloxane and the modified silica filler; thereafter (e) mixing until a uniform, free-flowing, powdered, surface-modified, reinforcing silica-polydiorganosiloxane composition is obtained where the total mixing time of steps (d) and (e) does not exceed 10 minutes, (f) massing the uniform free-flowing silica-polydiorganosiloxane composition (e) until a paste consistency mixture is obtained; and thereafter (g) admixing gradually more polydiorganosiloxane making a uniform mixture having a higher concentration of polydiorganosiloxane than the uniform free-flowing silica-polydiorganosiloxane composition obtained in step (e) and the silica filler content of the mixture is from 5 to 20 weight percent based on the total weight of the mixture. A further embodiment provides a universal mixture comprising 5 to 20 parts by weight of reinforcing silica filler having a surface area of 90 to 500 m 2 /g and 80 to 95 parts by weight of a polydiorganosiloxane having a viscosity of from 0.1 to 400 Pa·s, where such mixture has a plateau stress of greater than 70 Pa [700 dynes/cm 2 ] and a shear-thinned viscosity of no more than 1,000 Pa·s at a shear stress of 5,000 Pa [50,000 dynes/cm 2 ] and the plateau stress and the shear-thinned viscosity are measured at 25°C. The process of this invention prepares a universal mixture of polydiorganosiloxane and reinforcing silica which is used to make one-package, RTV, silicone sealant compositions which are non-sag. In the process of combining reinforcing silica filler with silanol terminated polydiorganosiloxane, non-sag silicone sealants are made from our universal mixture, if the reinforcing silica filler is expediently combined with a short chain polydiorganosiloxane having silicon-bonded hydroxyl groups using certain process steps to modify the silica filler surface. The short chain polydiorganosiloxane having silicon-bonded hydroxyl groups for the purposes of this invention is defined as a diol surface modifying agent (referred to herein as diol) of the formula R'O(R 2 SiO) x R' wherein R is methyl, ethyl, vinyl, 3,3,3-trifluoropropyl or phenyl, each R' is hydrogen atom, methyl radical or ethyl radical and x is a value of from 2 to 18 inclusive and has at least 3 weight percent silicon-bonded hydroxyl group. The preferred diols are those which are mixtures of molecules where at least 50 percent of the molecules have values for x of no more than 6 and the hydroxyl content of the mixture is at least 6 weight percent. Diols which have values of x of less than 6 provide foundation mixtures with longer stable storage times than those diols having a value of x greater than 6. Particularly useful diols are those which are mixtures of molecules where x has a value of 4 and the R and R' groups are methyl and R' is from 10 to 20 percent methyl. The reinforcing silica fillers are those which have a surface area of 90 to 500 m 2 /g and have a median aggregate-agglomerate particle size of less than 600 micrometers. The aggregate-agglomerate particle sizes are determined by a Coulter Particle Size Analyzer Model No. LS130, Hialeah, Florida. Many of these silica fillers are available commercially and are well known, such as fumed silica and precipitated silica. The silica fillers can be either untreated or treated. Treated silica fillers are also well known in the art and are available commercially, such as TS-610 and TS-530. The silica filler treatments include triorganosiloxy surface treatment from reaction with triorganochlorosilane, hexaorganodisiloxane or hexaorganodisilazane; other silanes such as dimethyldichlorosilane; and various polydiorganosiloxanes that are endblocked with silicon-bonded hydroxyl groups or silicon-bonded alkoxy groups. The diol and the silica filler are combined while mixing and heating in step (i). They are combined such that there is is from 0.05 to 0.5 part by weight of diol per part by weight of silica filler. The amount of diol used in making the modified silica filler which provides the most stable mixtures, i.e., those having the longest storage times and still producing a non-sag, one-package, RTV, silicone sealant composition, are those which have more than 0.25 part by weight of diol per part of silica filler. The storage stability of the mixture and its ability to be formulated into non-sag sealant compositions is related to the chain length of the diol and its hydroxyl content. In both our universal mixture and the sealant composition, where everything is substantially equal except for the diol, the higher the diol chain length, such as x being 18 and the lower the hydroxyl content of the diol, such as about 3 weight percent, the more diol is required to obtain equivalent storage stability for our mixture and the ultimate sealant composition slump, compared to that which is obtainable from using diols with shorter chain lengths and higher hydroxyl content. Conversely, the shorter the diol chain length, such as x being 2 to 4 and the higher the hydroxyl content of the diol, the lower the concentration of diol required to obtain equivalent storage stability for our mixture and the ultimate sealant composition slump. Preferably, the diol is present in an amount of from 0.015 to 0.025 part by weight of silicon-bonded hydroxyl group per one part by weight of silica filler. The mixture of diol and silica filler are fluidized (agitated) at a temperature of from 20°C. to 180°C., preferably from 100°C. to 180°C., and more preferred 150°C. to 180°C. The resulting filler mixture is maintained in a fluidized powder state until the diol is thoroughly dispersed throughout the silica filler and the median aggregate-agglomerate particle size of the filler mixture is less than the median aggregate-agglomerate particle size of the starting silica filler of step (ii). The filler mixture becomes more flowable and may be called "more fluffy" than the starting silica filler at this point of our process. At the more fluffy point, a modified silica filler is obtained. The density of the filler mixture may be reduced to 32-48 kg/m 3 [2 or 3 pounds per cubic foot] at this point of the process. This fluffy state is an indication that the diol is dispersed throughout the silica filler. The mixing and heating step to obtain the modified silica filler should not exceed 5 minutes. Preferably, it is one minute or less. During this mixing and heating step the volatiles are removed. This is accomplished by means of a partial vacuum, by a nitrogen gas sweep or purge or using a combination of both partial vacuum and nitrogen gas sweep. When this mixing and heating step goes beyond 5 minutes of duration, no advantages are observed. The rate of dispersion of the diol with the silica filler is increased by the addition of small amounts of hexamethyldisilazane, such as less than 0.1 weight percent based on the weight of the diol. The heating and mixing is accomplished in any mixing equipment which provides the necessary fluidization and agitation to maintain the diol and the silica filler in a constant fluid state, heat as required and removal of the volatiles. One such mixer is a Littleford™ Plowshear mixer/granulator, from Littleford Bros., Inc, Florence, Kentucky. This mixer provides a hurling and whirling action which are imparted by plow shaped mixing tools. The plow blades are coupled with high speed blending chopper blades which rotate at 3600 rpm and introduce high impact and shear. This particular mixer provides the required mixing for the preparation of our modified silica filler along with the ability to heat and remove volatiles. There is a window of mixing and heating time for which the resulting modified silica filler has excellent properties to provide storage stable products in which it is used. For instance, our universal mixture or the one-package RTV silicone sealant compositions therefrom which have non-sag properties. In this window of time, there is a relationship between the amount of diol and the temperature present to provide excellent properties. At temperatures in the high part of the described range, smaller amounts of diol are used to obtain the desired properties. Contrastingly, at temperatures in the lower part of the range, larger amounts of diol are needed to achieve the same excellent results. "Storage stable" means that the products maintain their properties throughout the time period beginning at the time when they are made, to the time when they are finally used to produce an RTV silicone sealant composition and through to the time while the RTV composition is cured. It is desirable to retain both the uncured properties, such as rheology and non-sag features of our RTV silicone sealant composition, as well as, the properties of the cured sealant, such as tensile strength, elongation, modulus and tear strength. A preferred process for making the modified silica filler is to heat the reinforcing silica filler to a temperature in the range of 100°C. to 180°C. and remove volatiles from the silica filler, such as water which is often associated with silica fillers in step (a). The volatiles are removed by a partial vacuum, by a nitrogen gas sweep or by a combination of these two. The time is usually rather short for this step in view of the temperature used and with a gas sweep, the volatiles are readily removed in times of one minute or less. Preferably, the temperature is between 150°C. and 180°C. and the time is about one minute. After the volatiles are removed, the heating and mixing is continued and the diol is added in step (b), as defined above and in the amounts as stated. The duration of the heating and additional mixing is as described above. The filler mixture is heated at a temperature in the range of 100°C. to 180°C., preferably 150°C. to 180°C., while maintaining it in a fluidized state until the diol is thoroughly dispersed throughout the silica filler and the particle sizes are observed to change as described above in step (c). This mixing process does not exceed more than 5 minutes in duration and the volatiles are removed as discussed previously to obtain a modified silica filler. Preferably, this mixing process is from 30 seconds to 60 seconds in duration. Steps (d), (e), (f) and (g) of the preferred process are the same as the steps (iii), (iv), (v) and (vi) as found in the above description. After the modified silica filler is prepared, a polydiorganosiloxane having a viscosity measured at 25°C. of from 0.1 to 400 Pa·s is gradually added to the modified silica filler, such that, the addition is completed in less than 10 minutes, preferably less than 5 minutes (step iii). A sufficient amount of polydiorganosiloxane is added to provide a uniform free flowing powder having from 25 to 40 weight percent of silica filler, based on the total weight of the powder. The modified silica filler and polydiorganosiloxane are then mixed until a uniform free flowing powder of polydiorganosiloxane and silica filler is obtained (step iv). The total mixing time in steps (iii) and (iv) should not exceed 10 minutes to obtain the uniform, free-flowing, powdered, polydiorganosiloxane-silica filler composition. By exceeding the 10 minute mixing time for steps (iii) and (iv), the powder will agglomerate creating lumps and other inconsistencies such that the powdered concentrate is not free flowing as needed and results in more difficult processing conditions when making sealant compositions. In step (iii), the polydiorganosiloxane can be added incrementally to the modified silica filler obtained from step (ii). There does not seem to be any significant property variation to adding the polydiorganosiloxane continuously at a gradual pace or incrementally, except that by adding it continuously at a gradual pace an easier processing results to obtain a product. The polydiorganosiloxane is selected from those having silicon-bonded hydroxyl groups at both ends or a mixture of polydiorganosiloxanes wherein more than 50 percent of the polymer molecules have silicon-bonded hydroxyl groups at both ends and the remaining polymer molecules contain silicon-bonded hydroxyl groups on one end and triorganosiloxy units on the other end. Those polydiorganosiloxanes which are mixtures of polydiorganosiloxanes with silicon-bonded hydroxyl groups on both ends and polydiorganosiloxanes with silicon-bonded hydroxyl groups on one end and triorganosiloxy units at the other are known in the art from U.S. Patent 3,274,145, which teaches polydiorganosiloxane mixtures having both silicon-bonded hydroxyl groups and triorganosiloxy groups. For this invention, when polymers having both silicon-bonded hydroxyl groups and triorganosiloxy groups are used in step (iii), those which are preferred have at least 80 percent of the ends terminated with silicon-bonded hydroxyl groups. The polydiorganosiloxanes preferably have a viscosity at 25°C. of from 5 to 100 Pa·s. The polydiorganosiloxanes comprise diorganosiloxane units of the formula R'' 2 SiO where R'' is a monovalent hydrocarbon radical or a halogenated monovalent hydrocarbon radical which are illustrated by alkyl radicals including methyl, ethyl, propyl, isopropyl, butyl, pentyl and hexyl; alkenyl radicals, such as vinyl, allyl and hexenyl; cycloalkyl, such as cyclopentyl and cyclohexyl; aryl such as phenyl or tolyl; and haloalkyl such as chloropropyl, trifluoropropyl and (2-perfluoropropyl)ethyl. The preferred polydiorganosiloxanes are those which have mostly methyl with minor amounts of vinyl and phenyl radicals. Although these polymers are defined as polydiorganosiloxanes, small amounts of other units such as monoorganosilsesquioxane units or SiO 2 units may be present as frequently found in polydiorganosiloxanes as a result of the manufacturing methods used. By small amounts, it is meant that there are less than 5 mole percent of such units, preferably less than 2 mole percent. Other kinds of polydiorganosiloxanes can be used such as those which are endblocked with hydrolyzable containing silicon units, such as trimethoxysiloxy units, triethoxysiloxy units, methyldimethoxysiloxy units and methyldiethoxysiloxy units, as described in U.S. Reissue Patent 29,760, which more completely describes such polyalkoxy terminated polydiorganosiloxanes and their method of preparation. These polyalkoxy terminated polydiorganosiloxanes are illustrated by the formula in which R 2 is an aliphatic hydrocarbon radical or halogenated aliphatic hydrocarbon radical of from 1 to 8 inclusive carbon atoms, R 3 and R 4 are each selected from monovalent hydrocarbon radicals or monovalent halohydrocarbon radicals from 1 to 18 inclusive carbon atoms, n has an average value of from 2 to 3 inclusive, y has an average value of from 1.99 to 2 inclusive, z has an average value of from 1 to 1.01, the sum of y and z is 3 and w has a value such that the viscosity at 25°C. is from 0.1 to 400 Pa·s. Some other polyalkoxy terminated polydiorganosiloxanes are those which contain divalent hydrocarbon linkages at the terminal portion of the polydiorganosiloxane, such as those described in U.S. Patents 3,175,993; 4,898,910 and 4,871,827, which show such polydiorganosiloxanes and methods of their preparation. These polydiorganosiloxanes have a formula in which each R 5 is methyl, ethyl, propyl or butyl, each R 6 is free of aliphatic unsaturation and is a monovalent hydrocarbon or monovalent halogenated hydrocarbon all of 1 to 18 inclusive carbon atoms, R 3 and w are as defined above, Z is a divalent hydrocarbon radical or combination of divalent hydrocarbon radicals and siloxane radicals and a is 0 or 1. Polydiorganosiloxanes which have other silicon-bonded hydrolyzable groups at their terminals may also be useful, for example acetoxy groups and ketoximo groups. After the product of step (iv) is obtained, it is then massed until a paste consistency mixture is obtained (step v). This massing process is easily accomplished when the amount of silica filler in the concentrate is in the 25-40 weight percent range and especially when the viscosity of the polydiorganosiloxane is less than 50 Pa·s when measured at 25°C. The massing process requires equipment with high shear when the amount of silica filler is at the higher concentration, for example, 35-40 weight percent range and especially when the viscosity of the polydiorganosiloxane is greater than 50 Pa·s when measured at 25°C. More polydiorganosiloxane is gradually admixed with the massed product of step (iv) to provide a universal mixture which contains from 5 to 20 weight percent of silica filler, based on the total weight of the universal mixture, and preferably the mixture contains from 5 to 15 weight percent of silica filler. As the concentration of silica filler increases above 15 weight percent, the processing becomes more difficult as the viscosity increases and it requires greater energy to produce sealant compositions as well as initially making our claimed mixture. The concentration of the polydiorganosiloxane in this mixture is higher than in the free-flowing silica-polydiorganosiloxane composition. The polydiorganosiloxane is preferably added and mixed under conditions which keep the formation of voids at a minimum. This results in a quicker preparation of our universal mixture. When a paste consistency material is mixed with a fluid material, such as the polydiorganosiloxane, the incorporation of voids from a gas atmosphere is very likely to occur and extra care is required to keep the formation of such voids at a minimum. Other kinds of polydiorganosiloxanes can be used, such as those which are endblocked with hydrolyzable containing silicon units, like the polyalkoxy terminated polydiorganosiloxanes described in U.S. Reissue Patent 29,760; U.S. Patent 3,175,993 and U.S. Patent 4,871,827. Our universal mixtures have a "plateau stress" value of greater than 70 Pa [700 dynes/cm 2 ], preferably more than 100 Pa [1,000 dynes/cm 2 ]. This plateau stress value is a measure of polymer/filler interaction. After initial preparation plus any storage aging, our universal mixture is considered stable when the plateau stress value is greater than 70 Pa (700 dynes/cm 2 ). Sealant compositions made from such mixtures that have a plateau stress more than 100 Pa (1,000 dynes/cm 2 ), produce a composition with 0.5 cm (0.2 inch) flow or less when measured by ASTM D 2202. Our mixtures also have a shear-thinned viscosity of no more than 1,000 Pa·s at a shear stress of 5,000 Pa (50,000 dynes/cm 2 ), and preferably no more than 600 Pa·s where the viscosity is measured at 25°C. Therefore, the typical mixture will have a plateau stress of greater than 70 Pa (700 dynes/cm 2 ) and a shear-thinned viscosity of no more than 1,000 Pa·s. Preferred mixtures are those having a plateau stress of more than 100 Pa (1,000 dynes/cm 2 ) and a shear-thinned viscosity of no more than 600 Pa·s at 25°C. Plateau stress values were determined on a Carri-Med™ Rheometer (Model CSL 500) using cone and plate. The flow method was used to determine these plateau stress values. The cone was a 0.5 degree, 2 cm diameter cone and the gap between the cone and the plate during testing was 13 micrometers (the test specimen thickness). Our claimed mixture was gently removed from the storage container. A few grams were placed on the temperature controlled bottom plate (at 25°C.) before the plate was raised into position with the top cone to provide a specimen thickness of 13 micrometers. The test specimen was allowed to equilibrate for 1 to 5 minutes to reach the 25°C. condition. An initial stress of 10 Pa (100 dynes/cm 2 ) was applied to the test specimen. After equilibration, the shear stress was increased until 5,000 Pa (50,000 dynes/cm 2 ) was attained over a 5 minute period in a logarithmic stress sweep mode. This was called the up curve. Once 5,000 Pa (50, 000 dynes/cm 2 ) was reached, this stress was held for 30 seconds. The shear stress was reduced to 10 Pa (100 dynes/cm 2 ) over a 5 minute period. This was called the down curve. The plateau stress value in 1 / 10 Pa (dynes/cm 2 ) was the shear stress at the shear rate of 0.023 sec -1 on the down curve. The shear-thinned viscosity was that viscosity measured when the shear stress was at 5,000 Pa (50,000 dynes/cm 2 ). The product universal mixtures are non-sag and are used to make other silicone compositions which are non-sag, especially one-package, RTV, silicone sealant compositions. Such sealant compositions are prepared by adding a moisture hydrolyzable crosslinking silicone compound (as a curing agent) comprising a crosslinker or a crosslinker and a curing catalyst. The particular crosslinker can affect the non-sag property of the final RTV silicone sealant composition. Curing catalysts are used, as required, to provide the utility of cure for the one-package, RTV, silicone sealant compositions made using our universal mixture. The crosslinker is a silicon compound containing silicon-bonded hydrolyzable groups, preferably silanes. The silicon-bonded hydrolyzable group is exemplified by acyloxy groups such as acetoxy, octanoyloxy and benzoyloxy; ketoximo groups such as the dimethylketoximo, the methylethylketoximo, the diethylketoximo, the amylmethylketoximo and the isobutylmethylketoximo; alkoxy groups such as methoxy, ethoxy and propoxy; alkenyloxy groups such as isopropenyloxy or 1-ethyl-2-methylvinyloxy; amino groups such as dimethylamino, diethylamino, butylamino and cyclohexylamino; aminoxy groups such as dimethylaminoxy; and amido groups such as N-methylacetamido, N-ethylacetamido and N-methylbenzamido. The crosslinkers can have three or more silicon-bonded hydrolyzable groups per molecule. When the crosslinker is a silane and when the silane has three silicon-bonded hydrolyzable groups per molecule, the fourth group is a non-hydrolyzable silicon-bonded organic group. The silicon-bonded organic groups are exemplified by alkyl groups such as methyl, ethyl, propyl and butyl; cycloalkyl groups such as cyclopentyl and cyclohexyl; alkenyl groups such as vinyl and allyl; aryl groups such as phenyl and tolyl; aralkyl groups such as 2-phenylethyl; and groups obtained by replacing all or part of the hydrogen atom in the preceding organic groups with halogen. The preferred silicon-bonded organic groups are preferably methyl. The crosslinker can be a silane or siloxane, and for siloxanes the molecular structure can be straight chain, branched or cyclic. The silicon-bonded hydrolyzable groups are exemplified by acyloxy groups such as acetoxy, octanoyloxy and benzoyloxy; ketoximo groups such as dimethylketoximo, methylethylketoximo, methylamylketoximo, methylisobutylketoxime and diethylketoximo; alkoxy groups such as methoxy, ethoxy and propoxy; alkenyloxy groups such as isopropenyloxy and 1-ethyl-2-methylvinyloxy; amino groups such as dimethylamino, diethylamino, butylamino and cyclohexylamino; aminoxy groups such as dimethylaminoxy; and amido groups such as N-methylacetamido, N-ethylacetamido and N-methylbenzamido. The silanes and siloxanes are exemplified by methyl-trimethoxysilane, methyltriethoxysilane, vinyltrimethoxysilane, methylphenyldimethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, methyltriacetoxysilane, vinyltriacetoxysilane, phenyltripropionoxysilane, ethyltris(N,N-diethylamino)silane, vinyltris(N-methyl-N-cyclohexylamino)silane, dimethylbis(N,N-dibutylamino)silane, methyltris(N-methylacetamido)silane, methylvinyl-bis(N-ethylacetamido)silane, vinyltris(N-ethylacetamido)silane, methyltris(N,N-diethylaminoxy)silane, phenyltris(N,N-diethylaminoxy)silane, methyltris(methylethylketoximo)silane, vinyltris(methylethylketoximo)silane, 3,3,3-trifluoropropyltris(methylethylketoximo)silane, methyltris(isopropenoxy)silane, vinyltris(isopropenoxy)silane, ethylpolysilicate, n-propylortho-silicate, dimethyltetraacetoxydisiloxane, pentamethyltris(N,N-diethylaminoxy)cyclotetrasiloxane, hexamethylbis(N,N-diethylaminoxy)cyclotetrasiloxane and mixtures thereof. Some of the crosslinkers can be triketoximosilanes and tetraketoximosilane, triacetoxysilanes and other triacyloxysilanes, trialkoxysilanes and tetraalkoxysilanes, silanes which contain mixtures of ketoximo and alkoxy groups wherein various silanes having from 0 to 4 ketoximo groups per molecule and from 0 to 4 alkoxy groups per molecule wherein the total combined number of alkoxy and ketoximo groups per molecule are three or four. Silanes having both silicon-bonded ketoximo groups and alkoxy groups in the same molecule are known from U.S. Patents 4,657,967 and 4,973,623. A tribenzamidosilane crosslinker is an example of another crosslinker which can be used in making one-package, RTV, silicone sealant compositions of this invention. These are illustrations of crosslinker silanes which can be used to make RTV silicone sealant compositions which are non-sag. The curing catalysts for a particular RTV silicone sealant composition depends upon the speed of cure required. Most of the RTV silicone sealant compositions which contain oximosilanes or acetoxysilanes use a tin catalyst for curing, especially diorganotin dicarboxylate compounds such as dibutyltin dilaurate, dibutyltin diacetate and dimethyltin bis-neodecanoate. For the alkoxysilane crosslinker containing RTV silicone sealant compositions, the most preferred curing catalyst is a titanium catalyst such as tetrabutyltitantate, tetraisopropyltitanate, diisopropylbis(acetylacetonyl)titanate and diisopropyl bis(ethylacetoacetonyl)titanate. Such crosslinkers and curing catalysts are well known to silicone sealant artisans and are well known in the silicone sealant art. A typical one-package, RTV, silicone sealant is therefore made according to the present invention from the universal mixture, crosslinker, curing catalyst and may contain other kinds of ingredients which are known to be used in silicone sealants, such as extending fillers, pigments, fungicides, antioxidants, UV absorbers and other additives. The RTV silicone sealant compositions of this invention can be made from a universal mixture which has been stored for more than one year and a non-sag one-package RTV silicone sealant composition will still be obtained. Even longer storage times are obtainable if the universal mixture is kept cool, i.e. below 15°C. If, however, a conventional treated silica filler is used to make our universal mixture, a one-package, RTV, silicone sealant composition (at practical silica filler concentrations) could be prepared which would not result in a non-sag product. Commercially available pretreated silicas, such as TS-610 and TS-530, are used to make non-sag silicone sealant compositions, if diol is also used and the processes defined by this invention are used. In addition to obtaining non-sag one-package RTV silicone sealant compositions from our claimed mixture, the resulting sealant compositions have better clarity and better adhesion to plastics. An advantage of making non-sag silicone sealant composition from the mixture of this invention is the ability to change from one cure chemistry, such as condensation reaction of silicon-bonded acetoxy functionality, to another cure chemistry, such as condensation reaction of silicon-bonded ketoximo functionality. Heretofore, changing cure chemistries often created large amounts of waste and long non-productive time periods. However, with this invention, the change over from one cure chemistry to another is fast and the amount of waste is small. The flexibility of being able to change quickly and without loss of material or time is a great advantage. A significant feature of our process is the remarkably short time from the start of making the modified silica filler to the finished, one-package RTV silicone sealant composition, which can take less than 15 minutes of total time. This is a substantial reduction in time over conventional manufacturing process for making silicone sealants wherein the silica modification is included in the process time calculations. The following examples are presented for illustrative purposes delineating the claims. In the following examples, "part" or "parts" are by weight, viscosities are as measured at 25°C. unless otherwise stated and Me is methyl radical. Example 1 Universal mixtures were prepared by first preparing a free flowing powdered silica-polydimethylsiloxane composition by heating 3,000 g of LM150D, a fumed silica filler having a BET surface area of 150 m 2 /g from Cabot Corporation, to a temperature specified in Table I while being agitated in a Littleford™ FM-130 plowshear mixer having a dry nitrogen gas sweep for removing volatiles. There was added an amount, as specified in Table II, of diol surface modifying agent of the formula R'O(Me 2 SiO) x R', where x has an average value of 4 and 20 percent of the R' groups are methyl radical. The length of time for the diol addition was as specified in Table I. The diol-silica mixture was agitated and heated at a temperature and for a time period which are specified in Table I. Thereafter, the diol-silica mixture was in a fluffy state. At this point, an amount of polydimethylsiloxane (Polymer A) having a viscosity of 12.5 Pa·s and having 85% of the endgroups being hydroxyl and 15 % of the endgroups being trimethylsiloxy units (prepared as described in U.S. Patent 3,274,145) where the amount was as specified in Table II. Polymer A was added incrementally in amounts beginning with a 5 weight percent increment of the total amount of polydimethylsiloxane, then another 5 weight percent increment, followed by a 10 weight percent increment, a 20 weight percent increment, another 20 weight percent increment, and finally the remaining 40 weight percent. The addition of polydimethylsiloxane was completed in a time period specified in Table I and a free flowing powdered silica-polydimethylsiloxane composition was obtained in each case. The heating was accomplished by an oil bath where the temperature was set at 180°C. The bulk densities were determined and the values observed are as shown in Table II and are reported in kilograms per cubic meter (kg/m 3 ). The various times and temperatures are shown in Table I. The total time to make the powdered composition in Table I is more than the sum of the minutes for diol addition, minutes heating diol-silica mixture and minutes to complete Polymer A addition because it includes the time for heating the silica filler and some time lapsed between the various steps. COMP Silica Temp. at start of diol addition Minutes for diol addition Minutes heating diol silica mixture Temp. at start of Polymer A Addition Minutes to complete Polymer A Addition Total Time to make COMP(1) minutes 1 100°C 1.0 1.0 105°C 6.0 9.0 2 132°C 2.5 0.5 128°C 3.0 7.5 3 127°C 2.5 1.0 126°C 2.5 7.5 4 140°C 2.5 1.0 140°C 2.5 10.0 5 142°C 0.5 1.0 135°C 2.0 7.5 6 134°C 2.5 0.5 128°C 2.5 7.5 7 142°C 2.0 0.5 140°C 3.0 8.0 8 130°C 2.5 1.0 141°C 1.5 6.5 COMP Amount diol, g Weight ratio diol to filler Polymer A grams Bulk Density of COMP(1) kg/m 3 1 880 0.293 6120 --- 1 770 0.257 6120 570 3 880 0.293 6120 560 4 441 0.147 6556 560 5 220 0.073 6789 560 6 880 0.293 6120 530 7 880 0.293 6103 560 8 880 0.293 6103 530 The powdered concentrate was stored in closed containers at room temperature for the time periods shown in Table III before making universal mixtures (referred to herein as UM). The powdered compositions were massed by placing an amount in a Haake™ mixer (Haake™ Fison Rheocord 90, from Haake, Paramus, New Jersey). The Haake™ mixer had a sigma blade and a wiper blade with heating capability and an ability to measure the energy required for mixing. The powdered composition was added to the mixer which had been heated to 120°C. prior to the addition. The heated powder was added to the mixer with the blades turning and completely filled the mixer. Massing began almost immediately upon the start of the addition. The mixer's ram was then lowered to force all the materials together to ensure good mixing and reduce void formation. Without the ram, partially massed material tended to rise from the mixer and a uniform paste was not obtained. The heated composition increased the rate of massing. Although the composition could be massed without heating, it massed slower and tended to be less uniform under such mixing conditions. Incremental amounts of a polydimethylsiloxane like Polymer A, except that the viscosity was 16.5 Pa·s (referred to as Polymer B) were then added to the Haake™ mixer. The total amounts of Polymer B added are as shown in Table III and were added in the following increments, which amounts were based on weight percentages of the total amount added, 5 wt%, 5 wt%, 10 wt%, 20 wt%, 20 wt% and 40 wt%. After the addition of each increment of Polymer B, the power required for mixing was decreased and the mixing time between each addition was one or two minutes. The time of mixing was determined by observation of the power requirement and after each addition, when the power stabilized, the next increment of Polymer B was added. The resulting mixtures (UM) were stored in sealed Semco(R) tubes. Semco(R) tubes protected the mixture from moisture. The Plateau Stress for each mixture after defined periods of storage was determined and are shown in Table IV in 1 / 10 Pa (dynes/cm 2 ). The Plateau Stress was measured on a Carri-Med™ Rheometer (Model CSL 500). Composition 5 was used to prepare a UM, but the resulting product was difficult to mix and was not uniform and contained lumps. Therefore, further evaluation of that composition was discontinued. Composition 5 would be expected to be useful in making UM with lower viscosity polydiorganosiloxanes than used in this example. Composition 5 also illustrated that the lower limit for the ratio of diol to filler was 0.05. UM COMP(1) Used Days COMP Aged Before Massing Weight COMP grams Total Weight Polymer B Added grams Silica Content in UM as pts/100 pts Polymers A & B A 3 250 17.47 21.46 22 B 3 250 19.49 30.51 13.5 C 4 250 19.65 30.35 14.6 D 5 272 19.65 --- --- E 6 252 19.49 30.51 13.5 F 8 250 19.49 30.51 13.5 UM Plateau Stress in dynes/cm 2 10 dynes/cm 2 = 1 Pa after 0 days 7 days 14 days 20 days 350 days A 5823 5823 --- --- 4867 B 1985 1985 --- --- 1326 C 1268 --- 1060 --- 593 E 1300 1108 --- --- 846 F 1268 --- --- 1260 1159 From Table IV, it can be observed that a drop in the Plateau Stress occurred during storage from 106 Pa (1060 dynes/cm 2 ) at 14 days to 59.3 Pa (593 dynes/cm 2 ) at 350 days for UM-C, whereas UM-A, UM-B, UM-E and UM-F maintained Plateau Stresses higher than 70 Pa (700) for at least 350 days (almost a year). Also observed in Table V, UM-C after 98 days of storage had a slump of 0.51 cm which indicates that this UM was reaching its storage stability limit. In contrast, UM-E after being stored for 350 days had a slump of 0.51 and UM-A, UM-B and UM-F each did not reach a slump of 0.51 cm after they had been stored for 350 days. This shorter stability time for UM-C directly relates to the lower weight ratio of diol to silica filler. The slump values of each UM were determined after various storage periods using the ASTM D 2202 test procedure and are shown in Table V. The extrusion rates of each UM were also determined by using the ASTM C 603 test procedure and are as shown in Table VI. The ASTM C 603 procedure was followed except the UM was extruded through a nozzle with a 0.3175 cm orifice at a pressure of 620.5 kPa. UM used Slump (in cm) of UM stored for 0 days 7 days 14 days 20 days 98 days 350 days A 0 0 --- 0 --- 0 B 0 0.127 --- 0.076 --- 0.203 C 0.51 --- 0.51 --- 0.304 2.03 E 0.127 0.203 --- 0.254 --- 0.51 F 0.203 --- 0.127 --- 0.254 --- UM used Extrusion Rate (in gm/minute) of UM stored for 0 days 7 days 14 days 20 days 98 days 350 days A 172 100 --- 105 --- 125 B 400 284 --- 272 --- 318 C 307 --- 160 --- 155 176 E 333 275 --- 222 --- 251 F 400 --- 465 --- --- 438 Table VI shows that these UM's had acceptable and comparable extrusion rates both initially and after the UM was stored for substantial periods of time. This indicates that they had good storage stability. Each of the mixtures, A, B, C, E and F were compounded into silicone sealant compositions by mixing 95 parts of a specific UM with 5 parts of a crosslinker mixture of 99.5 weight percent, which was 50 weight percent of methyltriacetoxysilane and 50 weight percent of ethyltriacetoxysilane and 0.5 weight of percent dibutyltin dilaurate. The UM was deaired by centrifuging it in a Semco™ tube, admixing the crosslinker mixture to make a uniform composition. The slump values and extrusion rates were determined for these sealant compositions. The skin-over-time (SOT) in minutes was also determined by spreading out a sample of the sealant composition, 0.20 to 0.23 cm thick, the surface of the sample was touched lightly with a finger to determine if a skin had formed on the sample's surface. The SOT was the time period in minutes from the samples initial layout until the finger could be touched lightly to the surface of the sample without sealant composition adhering to the finger. The tack-free-time (TFT) in minutes was determined by the ASTM C 679 test procedure and results were recorded in minutes. The results for the slump values, the extrusion rates, the SOT and the TFT are reported in Tables VII, VIII, IX and X. UM used Slump (in cm) of Sealant Made with acetoxysilane crosslinker and from UM stored for 0 days 7 days 14 days 20 days 98 days 350 days A 0 0 --- 0 --- 0 B 0.102 0.025 --- 0.127 --- 0.051 C 0.127 --- --- --- 0.127 3.81 E 0.051 0.229 --- 0.025 --- 0.51 F 0.127 --- 0.254 --- --- 0.254 UM used Extrusion Rate (in gm/minute) of Sealant Made with acetoxysilane crosslinker and from UM stored for 0 days 7 days 14 days 20 days 98 days 350 days A 333 116 --- 202 --- 264 B 477 375 --- 441 375 548 C 400 --- --- --- 300 339 E 380 355 --- 376 --- 484 F 438 --- 453 --- --- 705 UM used SOT (in min) of Sealant Made with acetoxysilane crosslinker and from UM stored for 0 days 7 days 14 days 20 days 98 days 350 days A 5 2 --- 3 --- 4 B 8 7 --- 8 9 10 C 8 --- --- --- 8 10 E 9 8 --- 10 --- 12 F 8 --- 8 --- --- 9 UM used TFT (in min) of Sealant Made with acetoxysilane crosslinker and from UM stored for 0 days 7 days 14 days 20 days 98 days 350 days A 9 10 --- 9 --- 10 B 22 23 --- 24 24 24 C 22 --- --- --- 25 21 E 24 22 --- 20 --- 22 F 22 --- 26 --- --- 21 Table VI showed that the silicone sealant compositions prepared from these UM's had very usable extrusion rates whether made from a UM initially or after the UM was stored for substantial periods of time. Sealant compositions were also prepared by admixing 9 parts of a ketoximosilane mixture of 70 weight percent methyltri(methylethylketoximo)silane, 24 weight percent of methyldi(methylethylketoximo)silane, 0.5 weight percent of methyldimethoxy(methylethylketoximo)silane and 5.5 weight percent impurities, 1.8 parts N-beta-aminoethylgamma-aminopropyltrimethoxysilane and 0.18 part dibutyltin dilaurate with 100 parts of the specified UM in Table XI. After a storage period of one day, the slump value, the extrusion rate, the SOT, the TFT, the durometer on the Shore A scale according to ASTM C-661 and using the procedure of ASTM D-412, the tensile at break, the elongation at break and the 100% modulus were determined. The results were as reported in Table XI. UM Used Slump cm Extrusion rate g/min SOT min TFT min Durometer Shore A Tensile kPa Elongation % 100% Modulus kPa B 0.025 627 <12 43 38 2020 312 834 C 0.127 505 8 53 36 1296 219 752 E 0.025 --- 13 35 39 1407 234 793 F 0.025 597 9 40 38 1689 263 827 The results of Table XI show that UM's prepared in accordance with this invention can also be used to make RTV silicone sealant compositions which have very low slump, good extrusion rates and cure rates as shown by the SOT and TFT, as well as cured sealant properties. Comparison Example 1 Comparison foundation mixtures (CUMs) were prepared by conventional methods and using materials which were available in the prior art. These CUMs were prepared by admixing 100 parts of Polymer A, an amount of a commercially available treated silica filler as shown in Table XII and, in some CUM, a hydroxyl endblocked polydimethylsiloxane fluid (PDMS Fluid) having an average of 11 dimethylsiloxane units per molecule and 4 weight percent of hydroxyl group. These CUMs were mixed using a twin screw extruder which was cooled to maintain ambient temperature. Each of the CUMs after defined periods of aging were further mixed with an amount of crosslinker mixture of acetoxysilanes and tin catalyst as described in Example 1. The slump values of the catalyzed silicone composition were determined, as well as, the SOT and TFT. The results observed are shown in Table XIII, Table XIV, Table XV and Table XVI. CUM Used Silica Type Silica Amount, parts PDMS Fluid parts 1 M-7 11.5 0 2 TS-610 11.5 0 3 TS-610 13.5 0 4 TS-610 15.5 0 5 TS-610 15.5 4 6 TS-610 13.5 4 7 TS-530 13.5 4 CUM used Slump (in cm) of Sealant Made with acetoxysilane crosslinker and from Comparison UM stored for 0 days 7 days 21 days 56 days 98 days 1 0 --- --- --- --- 2 --- 0.51 10.2 >10.2 >10.2 3 0.51 2.03 7.6 >10.2 >10.2 4 0.76 2.03 --- 2.54 8.13 5 0.127 1.02 1.02 2.54 5.84 6 0.254 0.76 >7.6 >7.6 >10.2 7 0.76 0.76 2.03 2.03 1.78 CUM used SOT (in min) of Sealant Made With acetoxysilane crosslinker and from CUM stored for 0 days 7 days 21 days 56 days 98 days 1 6 --- --- --- --- 2 --- 7 8 --- --- 3 16 7 8 11 10 4 16 12 9 10 11 5 16 9 7 10 11 6 16 8 8 11 11 7 16 8 7 10 11 CUM used TFT (in min) of Sealant Made With acetoxysilane crosslinker and from CUM stored for 0 days 7 days 21 days 56 days 98 days 1 16 --- --- --- --- 2 --- 30 >22 --- --- 3 25 30 18 18 20 4 25 26 19 19 21 5 25 23 16 19 19 6 25 21 19 19 18 7 25 20 19 19 19 CUM used Extrusion Rate (in gm/minute) of Sealant Made With acetoxysilane crosslinker and from CUM stored for 0 days 7 days 21 days 56 days 98 days 1 335 --- --- --- --- 2 --- 329 328 --- --- 3 451 234 213 200 180 4 415 182 185 150 120 5 552 451 416 390 374 6 656 492 429 402 368 7 780 387 416 400 376 From Tables XIII, XIV, XV and XVI, it is shown that the conventional method of preparing RTV silicone compositions did not provide a low slump product although the SOT and TFT were acceptable. The CUMs 2, 3 and 4 were made using treated silica fillers and CUMs were also made from treated silica fillers plus an additional amount of a treating agent as suggested by the prior art. Even these treated silica fillers with additional treating agent did not provide an RTV silicone sealant composition with low slump properties beyond a one week storage. The extrusion rates dropped off rapidly for those comparison mixtures which did not contain the additional treating agent. Example 2 A free flowing powdered composition was prepared by mixing and processing in the manner described in Example 1, 35 parts of silica, 8.75 parts of a diol which had a formula HO(Me 2 SiO) x H in which x was such that 91.7 weight percent of the molecules had a value for x of 2 to 10 and 1.44 weight percent had a value for x of 11 to 18 and 56.25 parts of Polymer B. A universal mixture was prepared by massing and adding sufficient Polymer B to provide a mixture which had 22 weight percent silica. The plateau stress was determined for the mixture which was 171.5 Pa (1715 dynes/cm 2 ) after 3 days aging at room temperature, 182.5 Pa (1825 dynes/cm 2 ) after 7 days aging at room temperature, 151.3 Pa (1513 dynes/cm 2 ) after 28 days aging at room temperature and 125.5 (1255 dynes/cm 2 ) after 56 days aging at room temperature. The slump for the UM was 0.025 cm after 3 days aging at room temperature. Example 3 A free flowing powdered composition was prepared by loading 200 g of M-7 silica filler, as defined in Comparison Example 1, into a Littleford Mixer™ (Model W-10 High Intensity Laboratory Mixer). It was mixed for 30 seconds at full speed without heating. The mixer was opened, the walls were scraped, the mixer was closed and then 50 g of the diol surface modifying agent defined in Example 1 was added with the mixer at half speed. The resulting mixture was mixed for 30 seconds after the diol addition was complete. The mixer was again stopped and the walls were scraped. Next 321 g of a polydimethylsiloxane (hereinafter identified as Polymer C and prepared as described in U.S. Patent 4,898,910) having 20% of the terminals being vinyldimethylsiloxy and 80% of the terminals being of the following formula and having a viscosity of 65 Pa·s, was added with the mixer at low speed, 50 rpm. After Polymer C addition was complete, the speed was increased to 100 rpm. Then, for every 15 seconds, the speed was increased by 100 rpm until the mixing speed reached 600 rpm and then held at 600 rpm for 50 seconds. The resulting product was a free flowing powdered composition which was removed from the mixer and stored at room temperature for 35 days. A universal mixture was then prepared by placing 50 g of powdered composition into a dental mixer and massing for 16 seconds at full speed. To the massed concentrate were added 10 parts of Polymer C and mixed for 16 seconds, next the walls of the mixer were scraped and then the composition was mixed for another 16 seconds. To the resulting mass, 19.54 g of Polymer C were added and the resulting paste was mixed for 26 seconds. The resulting massed material had 22 weight percent silica filler and was stored in a double friction can. 50 g of the massed material was massed and then in a Semco™ mixer, 49.81 g of Polymer C were added to the massed material and mixed to provide a universal mixture having 11 weight percent silica filler. A room temperature vulcanizable sealant was prepared by mixing 90.74 parts of this mixture with 5.79 parts of methyltrimethoxysilane, 2.47 parts of diisopropoxy bis(ethylacetoacetate) titanium and 1 part of beta-aminoethyl-gamma-aminopropyltrimethoxysilane. The resulting sealant had a slump of 0 (zero), an extrusion rate of 103, a SOT between 5 and 15 minutes and a TFT of 1.2 hours. A sample of the resulting sealant composition was exposed to atmospheric moisture and allowed to cure for seven days. Then, the cured properties were measured. The resulting sealant had a durometer on the Shore A scale of 34, a tensile strength at break of 1655 kPa and elongation at break of 292% and a 100% modulus of 683 kPa.

Claims: A process for making a polydiorganosiloxane-silica universal mixture comprising (i) combining, while agitating and heating, reinforcing silica filler having a surface area of 90 to 500 m 2 /g and having a median aggregate-agglomerate particle size less than 600 micrometers and a diol surface modifying agent of the formula R'O(R 2 SiO) x R' wherein R is methyl, ethyl, vinyl, 3,3,3-trifluoropropyl or phenyl, each R' is selected from the group consisting of hydrogen atom, methyl radical and ethyl radical, up to 30 percent of R' groups are methyl radical or ethyl radical and x is a value of from 2 to 18 inclusive and the diol surface modifying agent has at least 3 weight percent silicon-bonded hydroxyl group, making a filler mixture where there is 0.05 to 0.5 part by weight of diol per one part by weight of silica filler; (ii) mixing the filler mixture at a temperature in the range of from 20°C to 180°C and maintaining the filler mixture in a fluidized powder state until the diol is dispersed throughout the silica filler and the median aggregate-agglomerate particle size of the filler-mixture is less than the median aggregate-agglomerate particle size of the silica filler, this mixing process not exceeding 5 minutes in duration and removing volatiles from the filler mixture during the mixing process where a modified silica filler is obtained: (iii) adding gradually, with mixing, a polydiorganosiloxane having a viscosity measured at 25°C of from 0.1 to 400 Pa·s to the modified silica filler obtained from step (ii) and completing the addition in less than 10 minutes after the modified silica filler is obtained at the conclusion of step (ii), where the amount of polydiorganosiloxane is added to provide from 25 to 40 weight percent of silica filler, based on the total weight of the polydiorganosiloxane and the modified silica filler; thereafter (iv) mixing until a uniform free-flowing powder of a reinforcing silica-polydiorganosiloxane composition is obtained where the total mixing time of steps of (iii) and (iv) does not exceed 10 minutes; thereafter (v) massing the uniform free-flowing silica-polydiorganosiloxane composition obtained from step (iv) until a paste consistency mixture is obtained; and (vi) admixing gradually more polydiorganosiloxane making a uniform mixture having a higher concentration of polydiorganosiloxane, than the free-flowing silica-polydiorganosiloxane (iv), with a silica filler content from 5 to 20 weight percent, based on the total weight of the mixture The process according to claim 1 in which the polydiorganosiloxane in step (iii) is added incrementally to the modified silica filler of step (ii). The process according to any of the preceding claims further comprising the step of heating the reinforcing filler to a temperature in a range of 100°C to 180°C removing volatiles from the silica filler prior to step (i). A universal mixture obtainable from the process according to any of claims 1 - 3 which has a plateau stress of greater than 100 Pa (1,000 dynes/cm 2 ) and a shear-thinned viscosity of no more than 600 Pa·s at a shear stress of 5,000 Pa (50,000 dynes/cm 2 ) and the plateau stress and shear-thinned viscosity are measured at 25°C. A universal mixture comprising 5 to 20 parts by weight of reinforcing silica filler having a surface area of 90 to 500 m 2 /g and a diol surface modifying agent of the formula R'O(R 2 SiO) x R' wherein R is methyl, ethyl, vinyl, 3,3,3-trifluoropropyl or phenyl, each R' is selected from the group consisting of hydrogen atom, methyl radical and ethyl radical, up to 30 percent of R' groups are methyl radical or ethyl radical and x is a value of from 2 to 18 inclusive and the diol surface modifying agent has at least 3 weight percent silicon-bonded hydroxyl group in an amount of 0.05 to 0.5 part by weight of diol per one part by weight of silica filler; and 80 to 95 parts by weight of a polydiorganosiloxane having a viscosity of from 0.1 to 400 Pa·s at 25°C where such mixture has a plateau stress of greater than 70 Pa (700 dynes/cm 2 ) and a shear-thinned viscosity of no more than 1.000 Pa·s at a shear stress of 5,000 Pa (50,000 dynes/cm 2 ) and the plateau stress and the shear-thinned viscosity are measured at 25°C. A room temperature vulcanizable silicone sealant composition comprising the universal mixture according to claims 4 or 5 and further comprising a moisture hydrolyzable crosslinking silicon compound.

Inventors: GUTEK BETH IRENE, LOWER LOREN DALE, SPELLS SHERWOOD, GUTEK, BETH IRENE, LOWER, LOREN DALE, SPELLS, SHERWOOD
Applicants: DOW CORNING, DOW CORNING CORPORATION
Application year: 1996
Main classification: C08L83
IPC codes: C08K9, C08J3, C09K3, C08L83, C08K3