High consistency elastomer for fluid handling applications

Abstract: The present invention is a heat curable polyorganosiloxane composition comprising (A) a first polydiorganosiloxane having two diorganoalkenylsiloxy terminal groups per molecule and a total concentration of unsaturated hydrocarbon radicals of 0.118 to 0.156 mole percent; (B) a second polydiorganosiloxane having two diorganoalkenylsiloxy terminal groups per molecule and no detectable concentration of pendant unsaturated hydrocarbon radicals; (C) a third polydiorganosiloxane having two diorganoalkenylsiloxy terminal groups per molecule and a total concentration of unsaturated hydrocarbon radicals of 1.37 to 2.24 mole percent; wherein the weight ratio of polydiorganosiloxanes (A), (B) and (C) satisfy the relationship (C)/(A+B) = 0.0379 to 0.1071 and A/B = 1.460 to 2.115; (D) a crosslinker containing silicon-hydrogen bonds, wherein the ratio of silicon-hydrogen bonds to the total ethylenically unsaturated hydrocarbon radicals present on the polydiorganosilanes (A), (B) and (C) is from 1.00 to 2.25; (E) from 5 to 50 weight percent of a silica filler; and (F) a catalytically effective amount of a platinum group metal catalyst. Optionally, our composition may also include an inhibitor.

Description: This invention relates to extrudable and moldable organosiloxane compositions that cure by a hydrosilation reaction to form elastomers exhibiting superior physical properties, particularly superior dimensional stability and resiliency. Curable organosiloxane compositions containing at least one polydiorganosiloxane with at least two silicon-bonded vinyl radicals, an organohydrogensiloxane or organic peroxide curing agent and a silica filler are well known in the art of silicone elastomers. It is also known to improve the cured physical properties, particularly tensile and tear strengths, of these curable compositions by using two vinyl-containing polydiorganosiloxanes of different molecular weights or a single vinyl-containing polydiorganosiloxane having a bimodal molecular weight distribution. The background art of such curable compositions are generally represented by the following U.S. Patents 2,803,619; 2,819,236; 3,652,475; 3,671,480; 3,884,866; 4,057,596; 4,162,243 and 4,539,357. EP-A-0 798 342 describes a curable organosiloxane composition with improved hysteresis characteristics comprising a diorganovinylsiloxy terminated polydiorganosiloxane having a viscosity of 20 to 200 Pa.s at 25°C and containing no ethylenically unsaturated hydrocarbon radicals bonded to non-terminal silicon atoms and a diorganovinylsiloxy terminated polydiorganosiloxane having a viscosity of 0.1 to 200 Pa.s at 25°C where from 1 to 5 percent of the non-terminal repeating units of the siloxane comprise a vinyl radical, a pre-treated reinforcing silica filler and an organohydrogen siloxane crosslinker. An objective of this invention is to provide trimodal, platinum-cured polyorganosiloxane elastomer compositions that have superior dimensional stability and resiliency. These properties are particularly desirable for elastomeric articles that are subjected to stresses such as repeated flexing, tension and compression during use. Examples include medical applications such as pump tubing used for cardiopulmonary bypass, infusion and drugfill or for central venous catheters and pacing leads. It has now been unexpectedly found that the aforementioned objective is achieved by employing the curable elastomer compositions of this invention. Our invention is a heat curable polyorganosiloxane composition comprising (A) a first polydiorganosiloxane having pendant alkenyl groups and two diorganoalkenylsiloxy terminal groups per molecule and a total concentration of unsaturated hydrocarbon radicals of 0.118 to 0.156 mole percent; (B) a second polydiorganosiloxane having two diorganoalkenylsiloxy terminal groups per molecule and no detectable concentration of pendant unsaturated hydrocarbon radicals; (C) a third 1polydiorganosiloxane having pendant alkenyl groups and two diorganoalkenylsiloxy terminal groups per molecule and a total concentration of unsaturated hydrocarbon radicals of 1.37 to 2.24 mole percent; wherein the weight ratio of polydiorganosiloxanes (A), (B) and (C) satisfy the relationship (C)/(A+B) = 0.0379 to 0.1071 and A/B = 1.460 to 2.115; (D) a crosslinker containing silicon-hydrogen bonds, wherein the ratio of silicon-hydrogen bonds to the total ethylenically unsaturated hydrocarbon radicals present on the polydiorganosiloxanes (A), (B) and (C) is from 1.00 to 2.25; (E) from 5 to 50 weight percent of a silica filler; and (F) a platinum group metal catalyst. Optionally, our composition may also include an inhibitor. The inventive feature herein responsible for our unique combination of physical properties, particularly the high dimensional stability and resiliency exhibited by elastomers prepared from our curable compositions, is the presence of three specific types of miscible diorganoalkenylsiloxy-terminated polydiorganosiloxanes within a certain range of relative concentrations. The first diorganoalkenylsiloxy-terminated polydiorganosiloxane, ingredient A, contains both terminal and non-terminal (i.e., pendant groups) alkenyl radicals. This configuration provides a total alkenyl content of from 0.118 to 0.156 mole percent of the total siloxane units on the polymer. The second polydiorganosiloxane, ingredient B, exhibits a plasticity of 1.40 to 1.65 mm and contains vinyl or other unsaturated hydrocarbon radicals only at the terminal positions of the molecule. The third diorganoalkenylsiloxy-terminated polydiorganosiloxane, ingredient C, also contains both terminal and non-terminal alkenyl radicals (i.e., pendant groups) and has an alkenyl content of from 1.370 to 2.240 mole percent of the total siloxane units on the polymer. The polydiorganosiloxanes (A), (B) and (C), are individually fluids having a viscosity of as low as 0.5 Pa·s, but will preferably be gums having viscosities of at least 500 Pa·s. At least one of the polydiorganosiloxanes herein (A), (B) or (C) will be such a gum in our preferred embodiments. The weight ratio of polydiorganosiloxanes (A), (B) and (C) satisfy the relationship (C)/(A+B) = 0.0379 to 0.1071 and A/B = 1.460 to 2.115. The relative amounts of polydiorganosiloxanes (A), (B) and (C) must satisfy the above relationship and are critical to achieve the desired properties of the invention. The total amounts of ingredients A, B, C and D will comprise between 50 to 95 weight percent of the total composition. Experimental data for our preferred elastomers demonstrates that the resiliency, as measured by hysteresis loss, is less than 45%. The unsaturated hydrocarbon radicals present in ingredients A , B and C are preferably alkenyl radicals which contain from 2 to 10 carbon atoms. Preferred alkenyl radicals are terminally unsaturated and include vinyl, allyl and 5-hexenyl groups. The silicon-bonded organic groups present in ingredients A, B and C, in addition to alkenyl radicals, are the monovalent hydrocarbon or substituted hydrocarbon radicals described in detail in the following portions of this specification. The term "no detectable concentration of pendant unsaturated hydrocarbon radicals," as used herein, means that the only unsaturated hydrocarbon radicals present on the non-terminal silicon atoms of this ingredient result from impurities present in the reactants used for this ingredient or from undesired rearrangements occurring during its preparation. Ingredients A and C are diorganoalkenylsiloxy-terminated polydiorganosiloxanes that are represented by the average formula YR 2 SiO(R 2 SiO) a (YRSiO) b SiR 2 Y where Y represents an alkenyl radical containing from 2 to 10 carbon atoms, R is independently a monovalent hydrocarbon radical or substituted monovalent hydrocarbon radical containing from 1 to 20 carbon atoms and R is substantially free of ethylenic unsaturation. The degree of polymerization for ingredients A and C is represented by the sum of a and b and is greater than or equal to 1600. The R radicals can be identical or different. It is also preferred that ingredient A is an extrudable liquid at 25°C. with at least one of the R radicals on each of the non-terminal silicon atoms being lower alkyl (C 1 -C 10 ), most preferably methyl. The remaining R radical is alkyl such as methyl or ethyl; substituted alkyl such as chloromethyl, 3-chloropropyl or 3,3,3-trifluoropropyl; cycloalkyl such as cyclohexyl; or aryl such as phenyl. Any R radicals other than methyl are preferably phenyl or 3,3,3-trifluoropropyl. This preference is based on the availability of intermediates used to prepare these polydiorganosiloxanes and the properties of cured elastomers prepared by curing the compositions containing these polymers. The radicals defined by Y are alkenyl radicals and have from 2 to 10 carbon atoms and include vinyl, allyl and 5-hexenyl. Ingredient B is a diorganoalkenylsiloxy-terminated polydiorganosiloxane and is represented by the average formula YR 2 SiO(R 2 SiO) c SiR 2 Y. In this formula Y represents an alkenyl radical as defined above and R is as defined above. c represents the degree of polymerization and is equal to or greater than 1600. Because ingredients A, B and C are miscible with one another, the silicon-bonded hydrocarbon radicals present in these ingredients are preferably selected from the same class. Thus, the R groups are preferably the same group, i.e., lower alkyl (C 1 -C 10 ), such as methyl. Ingredient B has no detectable concentration of pendant ethylenically unsaturated hydrocarbon radicals. In preferred embodiments, the plasticity of ingredient B is from 1.40 to 1.65 mm. Preferred polymers for ingredient B are dimethylvinylsiloxy-terminated polydimethylsiloxanes, dimethylvinylsiloxy-terminated polymethyl-3,3,3-trifluoropropylsiloxanes, dimethylvinylsiloxy-terminated dimethylsiloxane/3,3,3-trifluoropropylmethylsiloxane copolymers and dimethylvinylsiloxy-terminated dimethylsiloxane/methylphenylsiloxane copolymers. Preferred polymers of ingredient A encompass all of the preferred polydiorganosiloxanes for ingredient B with the addition of 0.118 to 0.156 mole percent of non-terminal organoalkenylsiloxane units, where the preferred organic groups are alkyl containing from 1 to 4 carbon atoms, fluoroalkyl such as 3,3,3-trifluoropropyl and aryl such as phenyl. Preferred polymers of ingredient C encompass all of the preferred polydiorganosiloxanes for ingredient B with the addition of 1.370 to 2.240 mole percent of non-terminal organoalkenylsiloxane units, where the preferred organic groups are alkyl containing from 1 to 4 carbon atoms, fluoroalkyl such as 3,3,3-trifluoropropyl and aryl such as phenyl. Methods for preparing the liquid polydiorganosiloxanes used as ingredients A, B and C of the present compositions are by hydrolysis and condensation of the corresponding halosilanes or cyclic polydiorganosiloxanes. These methods are sufficiently disclosed in patents and other literature that a detailed description in this specification is not necessary. The organosiloxane compositions of this invention are cured by a hydrosilation reaction using an organohydrogensiloxane containing an average of more than two silicon-bonded hydrogen atoms per molecule. (Ingredient D). The organohydrogensiloxane contains from as few as four silicon atoms per molecule up to an average of 20 or more and has a viscosity of up to 10 Pa·s or higher at 25°C. The repeating units of this ingredient include HSiO 3/2 , RHSiO and/or R 2 HSiO 1/2 in addition to one or more of monoorganosiloxy, diorganosiloxane, triorganosiloxy and SiO 4/2 units. In these formulae R represents a monovalent hydrocarbon or halocarbon radical as described above. One preferred type of crosslinker is tris(hydridodimethylsiloxy)propyl silane. A second class of organohydrogensiloxanes contains repeating units represented by the repeating units of R 3 SiO 1/2 , RHSiO and SiO 4/2 . The concentration of RHSiO units is equivalent to a concentration of silicon-bonded hydrogen atoms in the copolymer of from 0.02 to 1.65 weight percent. A third preferred class of organohydrogensiloxanes are copolymers consisting essentially of the repeating units R 3 SiO 1/2 , R 2 SiO, RHSiO and RSiO 3/2 units. The concentration of RHSiO units is equivalent to a concentration of silicon-bonded hydrogen atoms in the copolymer of from 0.45 to 1.67 weight percent. Copolymers of this type are prepared by controlled hydrolysis of a mixture comprising the corresponding organosilicon halides, such as the chlorides or the corresponding alkoxides. These and other methods for preparing the preferred organohydrogensiloxanes of this invention are sufficiently well known that a detailed description is not required in this specification. Proper curing of the present compositions requires that ingredients A, B, C and D be miscible with one another. To ensure sufficient miscibility, the silicon-bonded hydrocarbon radicals that are present in the highest concentration of these ingredients are usually selected from the same class, e.g. alkyl radicals. These hydrocarbon radicals are preferably identical. In particularly preferred compositions, these hydrocarbon radicals are methyl or combinations of methyl with either 3,3,3-trifluoropropyl or phenyl. The molar ratio of silicon-bonded hydrogen atoms to vinyl or other ethylenically unsaturated hydrocarbon radicals in our claimed compositions, curable by a hydrosilation reaction, is critical with respect to the properties of the ultimate cured elastomer. The optimum ratio for said compositions will be determined at least in part by the molecular weights of ingredients A, B and C; the type of curing agent and the concentration of any resinous organosiloxane copolymer described hereinafter. For preferred compositions of this invention, this ratio is preferably from 1.0 to 2.25. The optimum range of this ratio for other curable compositions of this invention can readily be determined by those skilled in the art with a minimum amount of routine experimentation. For particularly preferred compositions of this invention, the molar ratio of silicon-bonded hydrogen atoms to vinyl or other ethylenically unsaturated hydrocarbon radicals is between 1.4 to 2.25. To achieve the properties that characterize the cured elastomers prepared by using the claimed compositions of our invention, the compositions must contain from 5 to 80 weight percent of a silica filler. This silica filler may, but need not be, treated with one or more of the known silica treating agents to prevent a phenomenon referred to as "creping" or "crepe hardening" during processing of our curable composition. Any finely divided form of silica can be used as a reinforcing filler. Amorphous silicas are preferred because of their relatively high surface area, which is typically at least 50 m 2 /g. Fillers having surface areas of at least 150 m 2 /g are preferred for use in our claimed method. Amorphous silicas can be prepared by precipitation or a fume process. Both of these silicas are commercially available. The amount of finely divided silica used in the present compositions is at least in part determined by the physical properties desired in the cured elastomer. Liquid or pumpable polyorganosiloxane compositions typically contain from 10 to 60 percent by weight of silica, based on the weight of polydiorganosiloxane. This value is preferably from 30 to 50 percent. Silica treating agents are typically low molecular weight organosilicon compounds containing silicon-bonded hydroxyl groups or groups that are hydrolyzed to hydroxyl groups in the presence of water. Typical hydrolyzable groups include halogen atoms such as chlorine, amino groups or other groups such as alkoxy groups containing a silicon-bonded nitrogen atom. For example, a preferred silica is obtained from a hydrophobic reinforcing silica made by the alkaline hydrolysis of Si(OCH 3 ) 4 , in the presence of at least 70% of one-half of the stoichiometric amount of water required to completely hydrolyze the theoretical amount of -OCH 3 radicals present in the Si(OCH 3 ) 4 , at least one alcohol selected from the group consisting of methanol, ethanol, n-propanol and isopropanol, at least one basic catalyst and at least one organosilicon hydrophobing compound selected from the group consisting of [(CH 3 ) 3 Si] 2 NH, [(CH 3 ) 2 (CF 3 CH 2 CH 2 )Si] 2 NH, [(CH 3 OR 1 )SiO] d , CH 3 O[(CH 3 )R 1 SiO] e R 2 and (CH 3 )R 1 Si(OR 3 ) 2 where R 1 is a methyl radical, a 3,3,3-trifluoropropyl radical or a vinyl radical, each R 2 is hydrogen atom or a methyl radical, the average value of e is from 1 to 12 inclusive, and the average value of d is from 3 to 6 inclusive, said hydrophobing material being added prior to gellation of the compound formed upon hydrolysis of the Si(OCH 3 ) 4 . Preferably at least a portion of the silicon-bonded hydrocarbon radicals present on the treating agent are alkenyl radicals and the remainder are identical to a majority of the hydrocarbon radicals present in polydiorganosiloxanes A, B and C. Hydrosilation reactions are typically conducted in the presence of a catalyst (F) that is a metal from the platinum group of the periodic table or a compound of such a metal. Platinum, rhodium and compounds of these metals have been shown to effectively catalyze hydrosilation reactions. Platinum compounds such as hexachloroplatinic acid, and particularly complexes of these compounds with relatively low molecular weight vinyl-containing organosiloxane compounds, are preferred catalysts because of their high activity and compatibility with organosiloxane reactants. These complexes are more fully described in U.S. Patent 3,419,593. Complexes with low molecular weight organosiloxanes, wherein the silicon-bonded hydrocarbon radicals are vinyl and either methyl or 3,3,3-trifluoropropyl are particularly preferred because of their ability to catalyze a rapid curing of an elastomer at temperatures of at least 70°C. The hydrosilation catalyst is present in an amount equivalent to as little as one part by weight of platinum group metal per one million parts of curable composition. Catalyst concentrations equivalent to from 5 to 50 parts of platinum group metal per million of curable composition are preferred to achieve a practical curing rate. Higher concentrations of platinum provide only marginal improvements in curing rate and are therefore economically unattractive, particularly when the preferred catalysts are used. Mixtures of the aforementioned vinyl-containing reactants, curing agents and hydrosilation catalysts may begin to cure at ambient temperature. To obtain a longer working time or "pot life", the activity of the catalyst under ambient conditions is retarded or suppressed by addition of a suitable inhibitor. Varying the amount of inhibitor will alter the curing time of the elastomer from periods of several minutes or hours up to periods of weeks or months. Known platinum catalyst inhibitors include the acetylenic compounds disclosed in U.S. Patent 3,445,420. Acetylenic alcohols such as 2-methyl-3-butyn-2-ol constitute a preferred class of inhibitors that will suppress the activity of a hydrosilation catalyst at 25°C. Compositions containing these catalysts typically require heating at temperatures of 70°C. or above to cure at a practical rate. If it is desired to increase the pot life of a curable composition under ambient conditions, this is easily accomplished using an olefinically substituted siloxane as described in U.S. Patent 3,989,667. Cyclic methylvinylsiloxanes are preferred for this use. Inhibitor concentrations as low as one mole of inhibitor per mole of platinum group metal will in some instances impart satisfactory storage stability and cure rate. In other instances, inhibitor concentrations of up to 500 or more moles of inhibitor per mole of platinum group metal are required. The optimum concentration for a given inhibitor in a given composition is readily determined by routine experimentation and does not constitute part of this invention. In addition to the vinyl-containing polydiorganosiloxanes, curing agent, catalyst and silica filler, the organosiloxane compositions of this invention can contain one or more additives that are conventionally present in the art for curable compositions of this type. These materials are normally added to impart or enhance certain properties of the cured elastomer or to facilitate processing of the curable composition. A small amount of water can also be added together with the silica treating agent(s) as a processing aid. Typical additives are pigments, dyes, adhesion promoters, flame retardants, heat and/or ultraviolet light stabilizers and resinous organosiloxane copolymers employed to enhance the physical properties of the cured elastomer. Diatomaceous earth and calcium hydroxide are two preferred additives based on their ability to reduce the degradation in physical properties, particularly tensile strength and modulus and to reduce the compression set values that occur when our cured elastomer comes into contact with oil heated to 150°C. or higher. The presence of calcium hydroxide also further reduces the compression set values of the cured elastomer. The silica filler can be treated in the presence of at least a portion of the other ingredients of the present compositions by blending these ingredients together until the filler is completely treated and uniformly dispersed throughout the composition to form a homogeneous material. The components which are typically present during treatment of the silica include the silica treating agents and at least a portion of the polydiorganosiloxanes, ingredients A, B and C. The organohydrogensiloxane crosslinker and hydrosilation catalyst are usually added after treatment of the silica has been completed. If calcium hydroxide is one of the ingredients, it is also added at this time. Irrespective of the type of mixer used, blending of the silica, filler treating agent(s) and ingredients A, B and C is continued while the composition is heated at temperatures from 100 to 250°C. under reduced pressure to remove volatiles. The resultant product is then cooled before being blended with the organohydrogensiloxane (Ingredient D) and/or the platinum group metal catalyst (Ingredient E), depending upon whether it is desired to prepare a one-part or two-part curable composition of our invention. The optional additives referred to above can be added at this time or during blending of the silica with ingredients A, B and C. In-situ treatment of the silica requires anywhere from 15 minutes to 2 hours, depending upon the amount of material being processed, the viscosity of the material and the shear rate employed during processing. Alternatively, treatment of the silica can occur before the silica is blended with other ingredients of the present compositions. Methods for treating finely divided silica fillers prior to incorporating the silica into a polyorganosiloxane composition are well known in the art and not repeated here. To ensure adequate blending of all ingredients the mixing equipment in which the present compositions are prepared is capable of subjecting the composition to a high rate of shear. The advantage of using such "high intensity" mixers to prepare silica filled polyorganosiloxane compositions is taught in U.S. Patent 3,690,804. In accordance with the disclosure of that patent, the tip of the stirring device in the mixer is rotated at a speed of from 7.5 to 75 m/s, which generates considerable shearing forces. The compositions herein are blended in a Henschel™ high intensity mixer wherein the rotor was operated at a speed of 3800 revolutions per minute, equivalent to a rotor tip speed of 48 m/s. Curable compositions prepared using the present method will exhibit viscosities of 0.5 to 10,000 Pa·s at 25°C. Preferred compositions are readily extrudable. To facilitate blending and transfer of our compositions and to minimize entrapment of air during mixing, a viscosity of less than 10 Pa·s at 25°C. is preferred, particularly for extrudable compositions. Because mixtures of ingredients A, B and C with the crosslinker (ingredient D) and the hydrosilation catalyst may begin to cure under the conditions encountered during storage of these compositions, even in the presence of a catalyst inhibitor, it is desirable to ensure long term storage stability to separate the curing agent and the catalyst until it is desired to initiate cure of our composition. This is easily achieved by packaging the curing agent and curing catalyst in separate containers to form a multi-part system. The multi-part system will include all the ingredients of the invention, but individual ingredients may be separated into one or more separate containers. The contents of the containers are then mixed to achieve the elastomer of this invention. A typical two-part system includes portions of ingredients A, B, C, D and E in one part and portions of A, B, C, E and F in another. When parts one and two are subsequently mixed, the curing agent and the catalyst in combination cause the elastomer to cure. In another system, the curing catalyst is encapsulated in a thermoplastic organic or silicone resin that melts or softens at the temperature to which the composition is intended to be heated during the curing process. One part compositions curable by hydrosilation reaction and containing a platinum group metal as a catalyst, such as a liquid platinum compound that is microencapsulated within a thermoplastic organic polymer, together with methods for preparing the microencapsulated catalyst, are further described in U.S. Patent 4,766,176. The present curable compositions are conveniently formed into shaped articles by press molding, injection molding, extrusion or any of the other methods known to fabricate shaped articles. In the absence of one of the above catalyst inhibitors or an encapsulated catalyst, our compositions will cure at ambient temperature over a period of several hours or days or within several minutes when heated at temperatures of up to 250°C. Compositions containing one of these catalyst inhibitors are typically cured by heating them for several minutes at temperatures of from 50 to 250°C. A preferred range is from 100 to 200°C. It should be apparent that compositions containing a microencapsulated catalyst must be heated to at least the melting or softening point of the encapsulating polymer to liberate the catalyst and to promote cure. Cured elastomeric articles prepared using the curable compositions of this invention exhibit tear strengths above 125 lb/in (38 kN/m) and low values of compression set (typically below 25%) without adversely affecting other desirable properties of our cured elastomer or the extrudability of the composition from which it is formed. This unique combination of properties make our elastomers desirable for a number of end use applications, including pump tubing used for cardiopulmonary bypass, infusion and drugfill and other medical applications such as central venous catheters and pacing leads, as well as gaskets and fabricated articles wherein at least a portion of the article is relatively thin and subjected to large amounts of stress. The following examples describe preferred curable compositions of this invention and the desirable properties of elastomers, particularly low values of compression set and high tear strength, prepared by curing our claimed compositions. The example is provided to further illustrate and demonstrate the effectiveness of the present invention. Unless indicated to the contrary, all parts and percentages are by weight and all viscosities were measured at 25°C. Example 1 In the following examples, polydiorganosiloxane (A) was a diorganoalkenylsiloxy-terminated polydiorganosiloxane containing both terminal and non-terminal (pendant groups) vinyl radicals having a total vinyl content of from 0.124 to 0.225 mole percent of the polymer and a plasticity of 1.40 to 1.65 mm. Polydiorganosiloxane (B) was a polydimethylsiloxane having a plasticity of 1.40 to 1.65 mm and containing vinyl only at the terminal positions of the molecule. Polydiorganosiloxane (C) was a dimethylvinylsiloxy-terminated polydiorganosiloxane containing both terminal and non-terminal (pendant groups) vinyl radicals having a vinyl content of from 1.430 to 2.290 mole percent of the polymer and having a plasticity of 1.27 to 1.78 mm. The "mole percent of vinyl groups" on the polymers and "plasticity" of the polymers used are expressed in ranges, which is a typical method of characterizing specifications for similar commercially available materials. A base was made in a 3.8 liter (one gallon) sigma-blade mixer (Baker Perkins, Bay City, Mi) used to impart high shear into the formulation. The polydiorganosiloxanes A, B and C were added to the mixer in the appropriate proportions and slowly blended together 5 minutes along with 0.25 weight percent of a silanol-ended polydimethylmethylvinylsiloxane, having a hydroxyl content of 7 weight percent and a vinyl content of 10.3 weight percent and a silanol ended polydimethylsiloxane having a hydroxyl content of 3.8 weight percent. Then 24.5 weight percent of a fumed silica filler was added in increments at a slow rate to allow the polysiloxanes to wet the surface of the filler. After filler addition, the mass was heated to 170°C. with mixing at 60 rpm for a period of 90 minutes under a reduced pressure of 33.8 kPa (345 g/cm 2 ) to remove any volatile components. After cooling to 100°C., the base prepared above was split and formulated into two parts: Part A which contained the chloroplatinic acid catalyst at a level of 5 ppm platinum metal and Part B containing either Crosslinker 1 or Crosslinker 2 and as an inhibitor 1-ethynlcyclohexanol at a level of 200 ppm. In these examples, Crosslinker 1 was tris(hydridodimethylsiloxy)propylsilane and Crosslinker 2 was an organohydrogensiloxane containing repeating units represented by the formula (CH 3 ) 3 SiO 1/2 , (CH 3 )HSiO and SiO 4/2 where the concentration of (CH 3 )HSiO units was equivalent to a concentration of silicon-bonded hydrogen atoms in the copolymer of from 0.02 to 1.65 weight percent. The crosslinkers were added in an amount required to keep the ratio of silicon/hydrogen bonds to silicon/vinyl bonds near 2.25. A 2-roll mill was used to incorporate the curing ingredients into the base by crossblending 12 times. Equal amounts by weight of Part A and Part B were then thoroughly mixed by crossblending 12 times on the 2-roll mill. A 1.9 mm (75 mil) thick slab of elastomer was then press-cured at a temperature of 115.6°C. (240°F.) for 10 minutes. The samples were then allowed to sit at room temperature for a minimum of 16 hours before testing. Durometer, tensile/elongation and tear Die B testing were performed by ASTM Test Methods 2240, 412 and 624, respectively. Hysteresis loss was measured using an Instron™, Model 1122 equipped with Series XII software. Physical properties determined on the samples containing Crosslinker 1 are shown in TABLE 1 compared to conventional platinum and peroxide cured elastomers. It is readily seen that % hysteresis loss is significantly reduced relative to the controls. Q7-4750 Biomedical Grade ETR Elastomer is a platinum catalyzed high consistency rubber available from the Dow Corning Corporation, Midland, Michigan, U.S.A. and Q7-4550 ETR Elastomer is also available from Dow Corning Corporation, Midland, Michigan, U.S.A. Neither of these comparative elastomers contained a trimodal polymer system. Effect of Polymer Blend on Physical Properties (SiH/SiVi=2.25) COMPONENT Base 1 Base 2 Base 3 Base 4 Q7-4750 Biomedical Grade ETR Elastomer (Pt) Q7-4550 ETR Elastomer (peroxide) POLYMER A (Pts) 87.4 94.5 85.1 100 POLYMER B (Pts) 58.3 47.3 56.7 50.0 POLYMER C (Pts) 10.3 14.2 14.2 6.00 Crosslinker Type 1 1 1 1 PROPERTY Durometer-Shore A 43 51 45 42 52 52 Tensile (MPa) 10.9 10.5 8.8 9.8 10.4 10.1 Elongation (%) 718 520 569 620 899 662 Tear Die B (MPa) 0.97 1.30 1.16 0.85 1.76 1.14 Hysteresis Loss (%) 37.44 43.98 41.15 38.17 52.90 44.96 With a more resinous crosslinker such as Crosslinker 2, good physical properties are maintained while durometer and tear values are increased. This is further illustrated in TABLE 2. Effect of Polymer Blend on Physical Properties (SiH/SiVi=2.25) COMPONENT Base 1 Base 2 Base 3 Base 4 Q7-4750 Biomedical Grade ETR Elastomer Control (Pt) Q7-4550 ETR Elastomer Control (peroxide) POLYMER A (Pts) 87.4 94.5 85.1 100 POLYMER B (Pts) 58.3 47.3 56.7 50.0 POLYMER C (Pts) 10.3 14.2 14.2 6.00 Crosslinker Type 2 2 2 2 PROPERTY Durometer-Shore A 50 58 53 49 52 52 Tensile (MPa) 8.3 9.6 7.6 8.4 10.4 10.1 Elongation (%) 613 537 503 616 899 662 Tear Die B (MPa) 1.50 1.72 1.67 1.48 1.76 1.14 Hysteresis Loss (%) 42.65 49.25 46.64 38.27 52.90 44.96 Example 2 Using the same procedures and conditions in Example 1 for the lab samples, the Base 1 formulation was manufactured in a 2000 litre Baker-Perkins™ mixer and compounded into Parts A and B on a 2-roll mill. Equal amounts by weight of Part A and Part B were then mixed by crossblending 12 times on a 2-roll mill. Then the product was extruded through a 8.9 cm (3.5 inch) Davis-Standard™ extruder into a heated oven maintained at a temperature of 204°C. The line speed for the extruder for size 16 tubing (3.17 mm ID, 6.48 mm OD) was 9.1 meters per second, for size 17 (6.3 mm ID, 9.65 mm OD) it was 7.6 meters per second and for size 73 (9.52 mm ID, 16.38 mm OD) it was 4.57 meters per second. Testing was then done on the tubing to see if the improvement in hysteresis, in fact, is reflected by improved pump life. Easy-Load™ Pump Heads, Model No. 7518-00 and 7529-00 and Standard Pump Heads, Model No. 7016-20, 7017-20 and 7019-20 were used to test the time to rupture on various sizes of tubing. Results of that testing compared to conventional platinum cured tubing is shown in TABLE 3. This data clearly demonstrates that the changes made in the formulation, which resulted in improved hysteresis loss, translate into significantly improved longevity in pump life performance compared to conventional platinum catalyzed tubing.

Claims: A heat curable polyorganosiloxane composition comprising: (A) a first polydiorganosiloxane having pendant alkenyl groups and two diorganoalkenylsiloxy terminal groups per molecule and a total concentration of unsaturated hydrocarbon radicals of 0.118 to 0.156 mole percent; (B) a second polydiorganosiloxane having two diorganoalkenylsiloxy terminal groups per molecule and no detectable concentration of pendant unsaturated hydrocarbon radicals; (C) a third polydiorganosiloxane having pendant alkenyl groups and two diorganoalkenylsiloxy terminal groups per molecule and a total concentration of unsaturated hydrocarbon radicals of 1.370 to 2.240 mole percent; wherein the weight ratio of polydiorganosiloxanes (A), (B) and (C) is (C)/(A+B) = 0.0379 to 0.1071 and A/B = 1.460 to 2.115; (D) a crosslinker containing silicon-hydrogen bonds, wherein the ratio of silicon-hydrogen bonds to unsaturated hydrocarbon radicals present on the total of polydiorganosiloxanes (A), (B) and (C) is from 1.00 to 2.25; (E) from 5 to 80 weight percent of a silica filler; and (F) a platinum group metal catalyst. A heat curable composition according to claim 1 where R is methyl, phenyl or 3,3,3-trifluoropropyl. A heat curable composition according to either of claims 1 or 2 where the terminal groups of polydiorganosiloxanes A, B and C are dimethylvinylsiloxy. A heat curable composition according to any of claims 1 to 3 wherein polydiorganosiloxanes A and C are dimethylvinylsiloxy-terminated dimethyl, methylvinyl siloxanes and polydiorganosiloxane B is a dimethylvinylsiloxy-terminated polydimethylsiloxane. A heat curable composition according to any of claims 1 to 4 where said silica filler comprises amorphous silica. A heat curable composition according to any of claims 1 to 5 wherein the crosslinker is an organohydrogensiloxane containing repeating units represented by the formula R 1 3 SiO 1/2 , R 1 HSiO and SiO 4/2 , where R 1 is an alkyl group containing 1 to 10 carbon atoms. A heat curable composition according to any of claims 1 to 6 wherein the silica filler is treated with silica treatment agents. A heat curable composition according to any of claims 1 to 7 wherein the composition additionally includes an inhibitor (G) . A heat curable composition according to any of claims 1 to 8 wherein at least one of the polydiorganosiloxanes A, B or C is a gum having a viscosity of greater than 500 Pa·s. A method for preparing a heat curable polyorganosiloxane elastomer comprising the steps of: (I) blending polydiorganosiloxanes (A), (B) and (C), wherein (A) has pendant alkenyl groups and two diorganoalkenylsiloxy terminal groups per molecule and a total concentration of unsaturated hydrocarbon radicals of 0.118 to 0.156 mole percent , polydiorganosiloxane (B) has two diorganoalkenylsiloxy terminal groups per molecule and no detectable concentration of pendant unsaturated hydrocarbon radicals and polydiorganosiloxane (C) has pendant alkenyl groups and two diorganoalkenylsiloxy terminal groups per molecule and a total concentration of unsaturated hydrocarbon radicals of 1.370 to 2.240 mole percent, wherein the weight ratio of polydiorganosiloxane (A), (B) and (C) is (C)/(A+B) = 0.0379 to 0.1071 and A/B = 1.460 to 2.115; (II) heating said blend; (III) adding to said heated blend from 0.46 to 10 parts by weight of a crosslinker (D) containing silicon-hydrogen bonds, wherein the ratio of silicon-hydrogen bonds to unsaturated hydrocarbon radicals present on the total of polydiorganosiloxanes (A), (B) and (C) is from 1.00 to 2.25; (IV) adding from 5 to 80 weight percent of a silica filler; (V) adding a platinum catalyst (E); (VI) optionally adding an inhibitor; and then (VII) heating the resultant curable polyorganosiloxane composition to cure it to an elastomer. A multi-part composition comprising: (A) a first polydiorganosiloxane having pendant alkenyl groups and two diorganoalkenylsiloxy terminal groups per molecule and a total concentration of unsaturated hydrocarbon radicals of 0.118 to 0.156 mole percent; (B) a second polydiorganosiloxane having two diorganoalkenylsiloxy terminal groups per molecule and no detectable concentration of pendant ethylenically unsaturated hydrocarbon radicals; (C) a third polydiorganosiloxane having pendant alkenyl groups and two diorganoalkenylsiloxy terminal groups per molecule and a total concentration of unsaturated hydrocarbon radicals of 1.370 to 2.240 mole percent; wherein the weight ratio of polydiorganosiloxanes (A), (B) and (C) is (C)/(A+B) = 0.0379 to 0.1071 and A/B = 1.460 to 2.115; (D) a crosslinker containing silicon-hydrogen bonds, wherein the ratio of silicon-hydrogen bonds to ethylenically unsaturated hydrocarbon radicals present on the total of polydiorganosiloxanes (A), (B) and (C) is from 1.00 to 2.25; (E) from 5 to 80 weight percent of a silica filler; and (F) a catalytically effective amount of a platinum group metal catalyst with the proviso that ingredient (D) and ingredient (F) are in separate parts.

Inventors: BAITRY JUDITH DIANE FAIRCLOUGH, EVANS CHANA WILSON, HIMSTEDT ALAN LAVERNE, BAITRY, JUDITH DIANE FAIRCLOUGH, EVANS, CHANA WILSON, HIMSTEDT, ALAN LAVERNE
Applicants: DOW CORNING, DOW CORNING CORPORATION
Application year: 1998
Main classification: C08L83
IPC codes: C08L83, C08G77, C08K3