Compounding filled silicone compositions

Abstract

High levels of silica, processing fluid and high molecular weight silicone polymer are compounded into a homogeneous silica filled composition without forming a preconcentrate of fumed silica and polymer. A fumed silica is fed into a unitary continuous compounding apparatus at a first location prior to addition of the silicone polymer. The fumed silica is then compounded with the silicone polymer, which is fed into the compounding apparatus at a location down-stream in the compounding apparatus from the first location. The compounding apparatus can be a co-rotating, intermeshing double screw extruder.

What is claimed is:  
     
         1 . A process of compounding a filled silicone composition, comprising: 
 mixing a filler with a processing fluid at a first location of a unitary continuous compounding apparatus prior to addition of a silicone polymer, and    mixing said filler with said silicone polymer at a location down-stream from said first location in said unitary continuous compounding apparatus.    
     
     
         2 . The process of  claim 1 , wherein said unitary compounding apparatus is a co-rotating, intermeshing double screw extruder.  
     
     
         3 . The process of  claim 1 , wherein said processing fluid is a silanol-reacting treating agent.  
     
     
         4 . The process of  claim 1 , wherein said filler contains silanol groups and is pretreated with a silanol-reacting treating agent prior to introduction into said compounding apparatus.  
     
     
         5 . The process of  claim 1 , wherein said filler contains silanol groups and said processing fluid is a treating agent comprising silanol-stopped polydimethylsiloxane, octamethylcyclotetrasiloxane (D4) or hexamethyldisilazane (HMDZ).  
     
     
         6 . The process of  claim 1  wherein said filler contains silanol groups, comprising reacting said silanol-reacting treating agent with silanol groups in said filler to reduce available groups to a concentration of between about 8 to about 2 hydroxyl groups/(nanometer)2 of filler.  
     
     
         7 . The process of  claim 1  wherein said filler contains silanol groups, comprising reacting said silanol reacting treating agent with silanol groups in the filler to reduce available groups to a concentration of between about 5 to about 3 hydroxyl groups/(nanometer)2 of filler.  
     
     
         8 . The process of  claim 1 , wherein said processing fluid is selected from the group consisting of silanol-stopped polydimethylsiloxane, vinyl-stopped dimethyl-methylvinylsiloxane and hydroxy-terminated polydimethyl-methylvinylsiloxane  
     
     
         9 . The process of  claim 1 , wherein said filler is a fumed silica.  
     
     
         10 . The process of  claim 1 , wherein said filler is a fumed silica and said fumed silica is force-fed under pressure into said first location.  
     
     
         11  The process of  claim 1 , wherein said silicone polymer is a poiydiorganosiloxane.  
     
     
         12 . The process of  claim 1 , wherein said compounding is completed in a compounding apparatus of at least some length that is about 42 diameters or less in length.  
     
     
         13 . The process of  claim 1 , wherein said compounding is completed in a compounding apparatus of at least some length that is about 30 diameters or less in length.  
     
     
         14 . The process of  claim 1 , wherein said compounding apparatus is an extruder operated at a screw speed between about 100 rpm and about 1000 rpm.  
     
     
         15 . The process of  claim 1 , wherein said compounding apparatus is an extruder operated at a screw speed between about 200 rpm and about 800 rpm.  
     
     
         16 . The process of  claim 1 , wherein said compounding apparatus is an extruder operated at a screw speed between about 280 rpm and about 450 rpm.  
     
     
         17 . The process of  claim 1 , wherein said compounding apparatus is an extruder operated at a ratio of throughput (lb/hr) to screw speed (rpm) of between about 0.01 and about 100.  
     
     
         18 . The process of  claim 1 , wherein said compounding apparatus is an extruder operated at a ratio of throughput (lb/hr) to screw speed (rpm) of between about 0.1 and about 70.  
     
     
         19 . The process of  claim 1 , wherein said compounding apparatus is an extruder operated at a ratio of throughput (lb/hr) to screw speed (rpm) of between about 0.5 and about 50.  
     
     
         20 . The process of  claim 1 , comprising controlling said process to provide a total throughput to screw speed ratio between about 0.5 and about 50 (lb/hour/rpm).  
     
     
         21 . The process of  claim 1 , comprising conducting said process in a compounding apparatus comprising at least one filler addition port and at least one vacuum port associated with said filler addition port.  
     
     
         22 . The process of  claim 1 , wherein said silicone composition is a heat-vulcanizable silicone polymer rubber composition.  
     
     
         23 . The process of  claim 1 , comprising venting volatiles from said filled silicone composition to a level less than about 2% by weight of the silicone composition.  
     
     
         24 . The process of  claim 1 , comprising venting volatiles from said filled silicone composition to a level less than about 1% by weight of the silicone composition.  
     
     
         25 . The process of  claim 1 , comprising conducting said process in a compounding apparatus comprising at least one venting zone having a vacuum venting port.  
     
     
         26 . The process of  claim 25 , comprising controlling pressure at said venting zone in mm of Hg between about 10 and about 300.  
     
     
         27 . The process of  claim 25 , comprising controlling pressure at said venting zone in mm of Hg between about 20 and about 100.  
     
     
         28 . The process of  claim 25 , comprising controlling pressure at said venting zone in mm of Hg between about 30 and about 80.  
     
     
         29 . The process of  claim 1 , comprising conducting said process in a compounding apparatus comprising a barrel wherein barrel temperature is controlled between about 100° C. and about 200° C.  
     
     
         30 . The process of  claim 1 , comprising conducting said process in a compounding apparatus comprising a barrel wherein barrel temperature is controlled at between about 130° C. and about 190° C.  
     
     
         31 . The process of  claim 1 , comprising conducting said process in a compounding apparatus comprising a barrel wherein barrel temperature is controlled at between about 160° C. and about 180° C.  
     
     
         32 . The process of  claim 1 , wherein said mixing of filler and processing fluid is conducted in a conveying stage of said compounding apparatus prior to said mixing of said filler with said silicone polymer.  
     
     
         33 . The process of  claim 1 , wherein said filler is fed into said unitary continuous compounding apparatus prior to mixing with said processing fluid.  
     
     
         34 . The process of  claim 1 , wherein said filler is fed into said unitary continuous compounding apparatus at a plurality of feed ports for mixing with said processing fluid.  
     
     
         35 . The process of  claim 1 , wherein said filler is combined with said silicone polymer in a range of from about 5 to about 200 parts filler per 100 parts by weight of polymer.  
     
     
         36 . The process of  claim 1 , wherein said filler is combined with said silicone polymer in a range of from about 10 to about 100 parts filler per 100 parts by weight of polymer.  
     
     
         37 . The process of  claim 1 , wherein said filler is combined with said silicone polymer in a range of from about 20 to about 60 parts filler per 100 parts by weight of polymer.  
     
     
         38 . The process of  claim 1 , wherein said filler is a surface-treated silica combined with said silicone polymer in a range of from about 20 to about 60 parts filler per 100 parts by weight of polymer.  
     
     
         39 . The process of  claim 1 , wherein said processing fluid is combined with said filler in a range of from about 0.1 to about 100 parts fluid per 100 parts by weight of filler.  
     
     
         40 . The process of  claim 1 , wherein said processing fluid is combined with said filler in a range of from about 0.5 to about 75 parts fluid per 100 parts by weight of filler.  
     
     
         41 . The process of  claim 1 , wherein said processing fluid is combined with said filler in a range of from about 1.0 to about 50 parts fluid per 100 parts by weight of filler.  
     
     
         42 . The process of  claim 1 , wherein said processing fluid is added at a plurality of locations for mixing with said filler.  
     
     
         43 . The process of  claim 1 , wherein said processing fluid comprises a treating agent and water.  
     
     
         44 . The process of  claim 1 , wherein said filler is silica and said processing fluid comprises a treating agent and water in a weight ratio of treating agent to 100 parts silica of between about 0.1 and about 100 and a weight ratio of water to 100 parts silica of between about 0.1 and about 100.  
     
     
         46 . The process of  claim 1 , wherein said filler is silica and said processing fluid comprises a treating agent and water in a weight ratio of treating agent to 100 parts silica of between about 0.5 and about 50 and a weight ratio of water to 100 parts silica of between about 0.5 and about 20.  
     
     
         47 . The process of  claim 1 , wherein said filler is silica and said processing fluid comprises a treating agent and water in a weight ratio of treating agent to 100 parts silica of between about 1.0 and about 20 and a weight ratio of water to 100 parts silica of between about 1.0 and about 10.  
     
     
         48 . The process of  claim 1 , wherein said filler is silica and said processing fluid comprises a treating agent and water in a weight ratio of treating agent/water of between about 0.05 to about 50.  
     
     
         49 . The process of  claim 1 , wherein said filler is silica and said processing fluid comprises a treating agent and water in a weight ratio of treating agent/water of between about 0.1 and about 20.  
     
     
         50 . The process of  claim 1 , wherein said filler is silica and said processing fluid comprises a treating agent and water in a weight ratio of treating agent/water of between about 1 and about 6  
     
     
         51 . The process of  claim 1 , wherein said filler is silica and said processing fluid comprises HMDZ and water.  
     
     
         52 . The process of  claim 1 , wherein said filler is silica and said processing fluid comprises an amount of HMDZ of about 0.1 parts to about 100 parts by weight to about 100 parts silica and an amount of water of about 0.1 to about 100 parts by weight to 100 parts silica.  
     
     
         53 . The process of  claim 1 , wherein said filler is silica and said processing fluid comprises an amount of HMDZ of about 0.5 parts to about 50 parts by weight to about 100 parts silica and an amount of water of about 0.5 to about 20 parts by weight to 100 parts silica.  
     
     
         54 . The process of  claim 1 , wherein said filler is silica and said processing fluid comprises an amount of HMDZ of about 1.0 parts to about 20 parts by weight to about 100 parts silica and an amount of water of about 1.0 to about 10 parts by weight silica.  
     
     
         55 . The process of  claim 1 , additionally comprising injecting an inert gas into said compounding extruder to suppress oxidative reaction between a flammable processing fluid and air.  
     
     
         56 . The process of  claim 1 , additionally comprising injecting an amount of inert gas in the range of from about 20 to about 800 parts by weight per 100 parts of filler, into said compounding extruder to suppress oxidative reaction between a flammable processing fluid and air.  
     
     
         57 . The process of  claim 1 , additionally comprising injecting an amount of inert gas in the range of from about 50 to about 600 parts by weight per 100 parts of filler, into said compounding extruder to suppress oxidative reaction between a flammable processing fluid and air.  
     
     
         58 . The process of  claim 1 , additionally comprising injecting an amount of inert gas in the range of from about 100 to about 400 parts by weight per 100 parts of filler, into said compounding extruder to suppress oxidative reaction between a flammable processing fluid and air.  
     
     
         59 . The process of  claim 1 , wherein said filler is raw, untreated silica.  
     
     
         60 . The process of  claim 1 , wherein said silicone polymer is represented by recurring units of Formula I:  
       
         
           
           
               
               
           
         
       
       wherein, R 1  independently at each occurrence represents C 1-4  alkyl, or C 2-4  alkylene; R 2  independently at each occurrence represents C 1-4  alkyl, C 1 -C 4  haloalkyl or C 2-4  alkylene; R 3  independently at each occurrence represents H, C 1-10  alkyl, C 2-4  alkylene, C 4-6  cycloalkyl, OH or C 1 -C 4  haloalkyl; and n represents an integer from 100 to 20,000.  
     
     
         61  The process of  claim 60 , wherein R 1  independently at each occurrence represents, CH 3  or CH═CH 2 ; R 2  independently at each occurrence represents, CH 3 , CH═CH 2  or CH 2 CH 2 CF 3 ; R 3  independently at each occurrence represents CH 3 , CH═CH 2 , OH or CH 2 CH 2 CF 3 ; and n represents an integer from about 4,000 to about 10,000.  
     
     
         62 . The process of  claim 1 , wherein said processing fluid excludes silicone polymers of a molecular weight greater than about 7000.  
     
     
         63 . The process of  claim 1 , wherein said unitary continuous compounding apparatus comprises a co-rotating, intermeshing double screw extruder.  
     
     
         64 . The process of  claim 1 , wherein said unitary continuous compounding apparatus comprises a counter-rotating, non-intermeshing double screw extruder.  
     
     
         65 . The process of  claim 1 , wherein said unitary continuous compounding apparatus comprises a single screw reciprocating extruder.  
     
     
         66 . The process of  claim 1 , wherein said unitary continuous compounding apparatus comprises a single screw non-reciprocating extruder  
     
     
         67 . A process for the continuous preparation of a heat-vulcanizing silicone polymer, comprising: 
 feeding a fumed silica continuously to a co-rotating, intermeshing double screw extruder at a first location, prior to addition of a silicone polymer;    compounding said fumed silica with a processing fluid, or combination of processing fluid and treating agent as said fumed silica advances through said extruder to a second location;    feeding a silicone polymer into said compounding apparatus at said second location; and    compounding said fumed silica with said silicone polymer by means of said extruder as said fumed silica and silicone polymer advance through said extruder from said second location.    
     
     
         68 . A processable silicone polymer filler composition comprising a processing fluid and a filler, wherein said processing fluid is combined with said filler in a range of from about 0.1 to about 100 parts fluid per 100 parts by weight of filler.  
     
     
         69 . The processable silicone polymer filler composition of  claim 68 , comprising a processing fluid and a filler, wherein said processing fluid is combined with said filler in a range of from about 0.5 to about 75 parts fluid per 100 parts by weight of filler.  
     
     
         70 . The processable silicone polymer filler composition of  claim 68 , wherein said processing fluid is combined with said filler in a range of from about 1.0 to about 50 parts fluid per 100 parts by weight of filler.  
     
     
         71 . The processable silicone polymer filler composition of  claim 68 , wherein said processing fluid comprises a treating agent and water.  
     
     
         72 . The processable silicone polymer filler composition of  claim 68 , wherein said filler is silica and said processing fluid comprises a treating agent and water in a weight ratio of treating agent to 100 parts silica of between about 0.1 and about 100 and a weight ratio of water to 100 parts silica of between about 0.1 and about 100.  
     
     
         73 . The processable silicone polymer filler composition of  claim 68 , wherein said filler is silica and said processing fluid comprises a treating agent and water in a weight ratio of treating agent to 100 parts silica of between about 0.5 and about 50 and a weight ratio of water to 100 parts silica of between about 0.5 and about 20.  
     
     
         74 . The processable silicone polymer filler composition of  claim 68 , wherein said filler is silica and said processing fluid comprises a treating agent and water in a weight ratio of treating agent to 100 parts silica of between about 1 and about 20 and a weight ratio of water to 100 parts silica of between about 1 and about 10.  
     
     
         75 . The processable silicone polymer filler composition of  claim 68 , wherein said filler is silica and said processing fluid comprises a treating agent and water in a weight ratio of treating agent/water of between about 0.05 to about 50.  
     
     
         76 . The processable silicone polymer filler composition of  claim 68 , wherein said filler is silica and said processing fluid comprises a treating agent and water in a weight ratio of treating agent/water of between about 0.1 and about 20.  
     
     
         77 . The processable silicone polymer filler composition of  claim 68 , wherein said filler is silica and said processing fluid comprises a treating agent and water in a weight ratio of treating agent/water of between about 1 and about 6.  
     
     
         78 . The processable silicone polymer filler composition of  claim 68 , wherein said filler is silica and said processing fluid comprises HMDZ and water.  
     
     
         79 . A processable silicone polymer composition, comprising a processing fluid, a filler and a silicone polymer, wherein said processing fluid is combined with said filler in a range of from about 0.1 to about 100 parts fluid per 100 parts by weight of filler and said filler is combined with said silicone polymer in a range of about 5 to about 200 parts filler per 100 parts by weight of polymer.  
     
     
         80 . The processable silicone polymer composition of  claim 79 , wherein said processing fluid is combined with said filler in a range-of from about 0.5 to about 75 parts fluid per 100 parts by weight of filler and said filler is combined with said silicone polymer in a range of about 10 to about 100 parts filler per 100 parts by weight of polymer.  
     
     
         81 . The processable silicone polymer composition of  claim 79 , wherein said processing fluid is combined with said filler in a range of from about 1.0 to about 50 parts fluid per 100 parts by weight of filler and said filler is combined with said silicone polymer in a range of about 20 parts to about 60 parts filler per 100 parts by weight of polymer.  
     
     
         82 . The processable silicone polymer composition of  claim 79 , wherein said filler is a surface-treated silica combined with said silicone polymer in a range of from about 20 to about 60 parts filler per 100 parts by weight of polymer.  
     
     
         83 . The processable silicone polymer composition of  claim 79 , wherein said filler is a raw, untreated silica.  
     
     
         84 . The processable silicone polymer composition of  claim 79 , wherein said processing fluid comprises a treating agent and water.  
     
     
         85 . The processable silicone polymer composition of  claim 79 , wherein said filler is silica and said processing fluid comprises a treating agent and water in a weight ratio of treating agent to 100 parts silica of between about 0.1 and about 100 and a weight ratio of water to 100 parts silica of between about 0.1 and about 100.  
     
     
         86 . The processable silicone polymer composition of  claim 79 , wherein said filler is silica and said processing fluid comprises a treating agent and water in a weight ratio of treating agent to 100 parts silica of between about 0.5 and about 50 and a weight ratio of water to 100 parts silica of between about 0.5 and about 20.  
     
     
         87 . The processable silicone polymer composition of  claim 79 , wherein said filler is silica and said processing fluid comprises a treating agent and water in a weight ratio of treating agent to 100 parts silica of between about 1 and about 20 and a weight ratio of water to 100 parts silica of between about 1 and about 10.  
     
     
         88 . The processable silicone polymer composition of  claim 79 , wherein said filler is silica and said processing fluid comprises a treating agent and water in a weight ratio of treating agent/water of between about 0.05 to about 50.  
     
     
         89 . The processable silicone polymer composition of  claim 79 , wherein said filler is silica and said processing fluid comprises a treating agent and water in a weight ratio of treating agent/water of between about 0.1 and about 20.  
     
     
         90 . The processable silicone polymer composition of  claim 79 , wherein said filler is silica and said processing fluid comprises a treating agent and water in a weight ratio of treating agent/water of between about 1 and about 6  
     
     
         91 . The processable silicone polymer composition of  claim 79 , wherein said filler is silica and said processing fluid comprises HMDZ and water.  
     
     
         92 . A heat-vulcanizable silicone polymer composition compounded in an unitary extruder defined by a total throughput (lb/hr) to screw speed (rpm) ratio between about 0.01 to about 100, comprising a filled silicone polymer characterized by a Williams Plasticity of at least greater than 100, Shore A hardness of at least greater than 20, tensile strength of at least greater than 750 psi, Elongation at break of at least 100, Tear B (ppi) of at least 10 ppi, Specific Gravity of at least 1.05 and residual volatiles less than 1 weight percent.  
     
     
         93 . The heat-vulcanizable silicone polymer composition of  claim 92 , compounded in an extruder defined by a total throughput (lb/hr) to screw speed (rpm) ratio between about 0.1 to about 70.  
     
     
         94 . The heat-vulcanizable silicone polymer composition of  claim 92  compounded in an extruder defined by a total throughput (lb/hr) to screw speed (rpm) ratio between about 0.5 to about 50.  
     
     
         95 . The heat-vulcanizable silicone polymer composition of  claim 92 , comprising less than about 2% by weight volatiles based on the weight of the silicone polymer composition.  
     
     
         96 . The heat-vulcanizable silicone polymer composition of  claim 92 , comprising less than about 1% by weight volatiles based on the weight of the silicone polymer composition.  
     
     
         97 . A processing fluid comprising a silanol-stopped polydimethylsiloxane, a vinyl-stopped dimethyl-methylvinylsiloxane and a hydroxy-terminated polydimethyl-methylvinylsiloxane.  
     
     
         98 . The processing fluid of  claim 97 , comprising between about 0.49 and about 1.93 parts by weight of a silanol-stopped polydimethylsiloxane, between about 0.73 and about 2.91 parts by weight of a vinyl-stopped dimethyl-methylvinylsiloxane and between about 0.05 and about 0.19 parts by weight of a hydroxy-terminated polydimethyl-methylvinylsiloxane.  
     
     
         99 . The processing fluid of  claim 97 , comprising between about 0.85 and about 1.57 parts by weight of a silanol-stopped polydimethylsiloxane, between about 1.27 and about 2.37 parts by weight of a vinyl-stopped dimethyl-methylvinylsiloxane and between about 0.08 and about 0.16 parts by weight of a hydroxy-terminated polydimethyl-methylvinylsiloxane.  
     
     
         100 . The processing fluid of  claim 97 , comprising between about 1.09 and about 1.32 parts by weight of a silanol-stopped polydimethylsiloxane, between about 1.64 and about 2.0 parts by weight of a vinyl-stopped dimethyl-methylvinylsiloxane and between about 0.11 and about 0.13 parts by weight of a hydroxy-terminated polydimethyl-methylvinylsiloxane.  
     
     
         101 . A compounding apparatus, comprising: 
 a barrel encompassing at least one shaft with screw elements arranged in sections along said shaft according to type of materials processing;    said sections comprising (1) a first conveying section, (2) a second kneading section, and (3) a third devolatilization section.    
     
     
         102 . The compounding apparatus of  claim 101 , comprising a barrel encompassing two shafts.  
     
     
         103 . The compounding apparatus of  claim 101 , comprising a filler feed port and at least one atmospheric or vacuum vent associated with said filler feed port.  
     
     
         104 . The compounding apparatus of  claim 101 , comprising a co-rotating, intermeshing double screw extruder.  
     
     
         105 . The compounding apparatus of  claim 101 , comprising a counter-rotating, non-intermeshing double screw extruder.  
     
     
         106 . The compounding apparatus of  claim 101 , comprising a counter-rotating, intermeshing double screw extruder.  
     
     
         107 . The compounding apparatus of  claim 101 , comprising a single screw reciprocating extruder.  
     
     
         108 . The compounding apparatus or  claim 101 , comprising a single screw non-reciprocating extruder.  
     
     
         109 . The compounding apparatus of  claim 101 , comprising an extruder of at least some length that is less than 42 diameters.  
     
     
         110 . The compounding apparatus of  claim 101 , comprising an extruder of at least some length that is about 30 diameters or less in length.  
     
     
         111 . The compounding apparatus of  claim 101 , comprising at least one filler addition port and at least one vacuum vent associated with said filler addition port.  
     
     
         112 . The compounding apparatus of  claim 101 , comprising at least one venting zone having a vacuum vent.  
     
     
         113 . The compounding apparatus of  claim 101 , wherein said section comprises a densifying stage to mix a processing fluid with filler, said second section comprises a compounding stage for distributing filler into silicone polymer and said third section comprises a devolatilization stage to remove volatiles.  
     
     
         114 . The compounding apparatus of  claim 101 , wherein said densifying stage is between about 3 and about 12 extruder barrel diameters in length, said compounding stage is between about 6 and about 18 diameters in length, and said devolatilization stage is between about 6 and about 18 diameters in length.  
     
     
         115 . The compounding apparatus of  claim 101 , wherein said densifying stage is between about 5 and about 10 extruder barrel diameters in length, said compounding stage is between about 9 and about 1,5 diameters in length, and said devolatilization stage is between about 9 and about 15 diameters in length.  
     
     
         116 . The compounding apparatus of  claim 101 , wherein said densifying stage is between about 6 and about 8 extruder barrel diameters in length, said compounding stage is between about 10 and about 12 diameters in length, and said devolatilization stage is between about 10 and about 12 diameters in length.  
     
     
         117 . The compounding apparatus of  claim 101 , wherein said densifying stage comprises conveying elements for bringing processing fluid in contact with filler.  
     
     
         118 . The compounding apparatus of  claim 101 , wherein said second kneading section comprises kneading elements to disperse and distribute filler into silicone polymer.  
     
     
         119 . The compounding apparatus of  claim 101 , wherein said third devolatilization section comprises surface generating elements for deairation and devolatilization.  
     
     
         120 . The compounding apparatus of  claim 101 , comprising a co-rotating, intermeshing double screw extruder.