Highly elastomeric and paintable silicone compositions

Abstract

Highly elastomeric, curable, paintable silicone compositions are provided. The paintable silicone compositions comprise an organopolysiloxane, a silicone functional crosslinker, and an organic polymer. The highly elastomeric, curable, paintable silicone compositions have an elongation of at least 150% and are useful as paintable sealants and caulks.

1 . A curable silicone composition comprising: organopolysiloxane, silicone functional crosslinker; and organic polymer; 
 wherein the curable silicone composition, once cured, can be painted without fish eyes; and    wherein the curable silicone composition, once cured, has an elongation of at least 150%.    
   
   
       2 . The curable silicone composition of  claim 1  wherein the curable silicone composition, once cured has an elongation of at least 200%.  
   
   
       3 . The curable silicone composition of  claim 2  wherein the curable silicone composition, once cured, has an elongation of at least 800%.  
   
   
       4 . A curable silicone composition comprising: 
 a) from 50% to 95% (by weight, based on total polymer) organopolysiloxane polymer;    b) from 1% to 10% (by weight, based on organopolysiloxane) silicone functional crosslinker; and    c) from 5% to 50% (by weight, based on total polymer) dispersed organic polymer.    
   
   
       5 . The curable silicone composition of  claim 4  wherein the curable silicone composition comprises from 55% to 93% by weight organopilysiloxane polymer.  
   
   
       6 . The curable silicone composition of  claim 5  wherein the curable silicone composition comprises from 57% to 91% by weight organopilysiloxane polymer.  
   
   
       7 . The curable silicone composition of  claim 4  wherein the curable silicone composition comprises from 7% to 45% by weight organic polymer.  
   
   
       8 . The curable silicone composition of  claim 7  wherein the curable silicone composition comprises from 9% to 43% by weight organic polymer.  
   
   
       9 . The curable silicone composition of  claim 4  wherein the organopolysiloxane polymer has at least two reactive functional groups on the polymer chain.  
   
   
       10 . The curable silicone of  claim 9  wherein the reactive functional groups are selected from the group consisting of hydroxyl, alkoxy, silicone alkoxy, acyloxy, ketoximo, amino, amido, aminoxy, alkenoxy, alkenyl, enoxy and mixtures thereof.  
   
   
       11 . The curable silicone composition of  claim 10  wherein the reactive functional groups are end groups.  
   
   
       12 . The curable silicone composition of  claim 4  wherein the organic polymer is selected from the group consisting of silylated polyurethane, non-silylated polyurethane, silylated allylic terminated polyether, a polyether that contains a silicone functional group, a silylated and non-silated acrylic functional polymer, a silylated and non-silated butyl functional polymer, and copolymers and mixtures thereof.  
   
   
       13 . The curable silicone composition of  claim 12  wherein the elongation of the silicone composition, once cured, is at least 150%.  
   
   
       14 . The curable silicone composition of  claim 13  wherein the curable silicone composition, once cured, can be painted without the formation of fish eyes.  
   
   
       15 . The curable silicone composition of  claim 4  wherein the curable silicone composition, once cured, passes a paint adhesion tape test.  
   
   
       16 . A curable silicone composition comprising: 
 a) from 50% to 95% (by weight based on total polymer weight) organopolysiloxane polymer;    b) from 1% to 10% by weight silicone functional crosslinker; and    c) an organic polymer or oligomer, wherein the organic polymer or oligomer is selected from the group consisting of silylated polyurethane, silylated allylic terminated polyether, polyether having a silicone functional group, silylated acrylic multipolymer, butyl functional polymer, and combinations thereof;    wherein the ranges of organic polymer (by weight based on total polymer) are from 15% to 50% for silylated polyurethane; from 15% to 50% for non-silylated polyurethane; from 15% to 50% for silylated allylic terminated polyether; from 15% to 50% silylated allylic terminated acrylic polyether; from 15% to 50% for polyether having a silicone functional group; from 10% to 50% for silylated and non-silylated acrylic multipolymer; and from 5% to 50% for silylated and non-silylated butyl functional polymer.    
   
   
       17 . The curable silicone composition of  claim 16  wherein the organopolysiloxane has a molecular weight in the range from 20,000 to 100,000 grams/mole.  
   
   
       18 . The curable silicone composition of  claim 16  wherein the organopolysiloxane has at least two reactive groups and an organic polymer selected from the group consisting of silylated polyurethane, non-silylated polyurethane, silylated allylic terminated polyether, a polyether that contains a silicone functional group, a silylated acrylic functional polymer, a non-silylated acrylic functional polymer, a silylated acrylic functional polymer, a non-silylated acrylic functional polymer, and mixtures thereof.  
   
   
       19 . The curable silicone composition of  claim 18  wherein the reactive groups are selected from end groups, pendant groups, and combinations thereof.  
   
   
       20 . The curable silicone composition of  claim 16  wherein the silicone crosslinker is selected from the group consisting of oximes, alkoxysilanes, epoxyalkylalkoxysilanes, amido silanes, aminosilanes, enoxysilanes, tetraethoxysilanes, methyltrimethoxysilane, vinyltrimethoxysilane, glycidoxypropyltrimethoxsilane, vinyltris-isopropenoxysilane, methyltris-isopropenoxysilane, methyltris-cyclohexylaminosilane, methyltris-secondarybutylaminosilane, condensation cure catalysts, and combinations thereof.  
   
   
       21 . The curable silicone composition of  claim 20  wherein the crosslinker is an oxime crosslinker.  
   
   
       22 . The curable silicone composition of  claim 21  wherein the oxime crosslinker is selected from vinyltris-methylethylketoximosilane, methyltris-methylethylketoximosilane, and combinations thereof.  
   
   
       23 . The curable silicone composition of  claim 16  wherein the silicone composition is selected from the group consisting of 1-part curable compositions, 2-part curable compositions, and combinations thereof.  
   
   
       24 . The curable silicone composition of  claim 16  wherein the polyorganosiloxane is selected from the group consisting of thermally curing systems and room temperature curing systems.  
   
   
       25 . The curable silicone composition of  claim 16  wherein the composition comprises an extrusion or an in situ cured system.  
   
   
       26 . The curable silicone composition of  claim 16  further comprising from 0.01% to 2% (by total weight) catalyst.  
   
   
       27 . The curable silicone composition of  claim 26  wherein the catalyst is selected from the group consisting of metal salts of carboxylic acids, organotitanates, platinum complexes, peroxides, and combinations thereof.  
   
   
       28 . The curable silicone composition of  claim 27  wherein the catalyst comprises metal salts of carboxylic acids selected from the group consisting of dibutyltindilaurate, dibutyltindiacetate, dimethyltindi-2-ethylhexanoate, and combinations thereof.  
   
   
       29 . The curable silicone composition of  claim 27  wherein the catalyst comprises organotitanates selected from the group consisting of tetrabutyltitanate, tetra-n-propyltitanate, diisopropoxydi(ethoxyacetoacetyl)titanate, bis(acetylacetonyl)diisopropyl titanate and combinations thereof.  
   
   
       30 . The curable silicone composition of  claim 27  wherein the catalyst comprises a platinum complex.  
   
   
       31 . The curable silicone composition of  claim 27  wherein the catalyst comprises a peroxide.  
   
   
       32 . The curable silicone composition of  claim 16  further comprising from 3% to 60% (by total weight) reinforcement agents, semi-reinforcing agents, or combinations thereof.  
   
   
       33 . The curable silicone composition of  claim 32  wherein the reinforcement agent is selected from the group consisting of hydrophobic treated fumed silicas, untreated fumed silicas, hydrophobic precipitated calcium carbonates, ground calcium carbonates, talc, zinc oxides, polyvinyl chloride powders, soft acrylic polymers and combinations thereof.  
   
   
       34 . The curable silicone composition of  claim 16  further comprising from 0.5% to 2% (by total weight) adhesion promoter.  
   
   
       35 . The curable silicone composition of  claim 16  wherein the tensile elongation, once cured, is at least 150%.  
   
   
       36 . The curable silicone composition of  claim 35  wherein the tensile elongation, once cured is at least 200%.  
   
   
       37 . The curable silicone composition of  claim 36  wherein the tensile elongation, once cured is at least 800%.  
   
   
       38 . The curable silicone composition of  claim 16  wherein the organic polymer is a silylated polyurethane polymer, wherein the silylated polyurethane polymer is derived by the steps of 
 a) reacting a diisocyanate compound with a polyol to form an intermediate, wherein the intermediate is selected from isocyantates and hydroxyl terminated polyurethane prepolymers; and    b) silylating the intermediate.    
   
   
       39 . The curable silicone composition of  claim 38  wherein intermediate is silylated with an organo functional silane having one or more hydrolyzable groups.  
   
   
       40 . The curable silicone composition of  claim 39  wherein the hydrolyzable group is selected from the group consisting of (OCH 3 ) 3 , (OCH 2 CH 3 ) 3 , oximo, enoxy, isopropenoxy,  
     
       
         
         
             
             
         
       
     
     and combinations thereof.  
   
   
       41 . The curable silicone composition of  claim 39  wherein the organo functional silane is of the formula:  
       R″—X—Si—R′ 
     wherein 
 R′ is selected from the group consisting of (OCH 3 ) 3 , (OCH 2 CH 3 ) 3 , CH 3 (OCH 3 ) 2 , or CH 3 (OCH 2 CH 3 ) 2 , other hydrolyzable groups such as oximo substituents, enoxy, and isopropenoxy;  
 R″ is selected from the group consisting of amino, ureido, mercapto, isocyanato, and epoxy; and  
 X is C 1  to C 8 .  
 
   
   
       42 . The curable silicone composition of  claim 38  wherein the molecular weight of the polyurethane prepolymer intermediate ranges from 5,000 to 50,000 g/mol.  
   
   
       43 . The curable silicone composition of  claim 38  wherein the polyurethane prepolymer intermediate has a NCO:OH ratio in the range from 1.4:1 to 3:1 or an OH:NCO ratio in the range from 1.4:1 to 3:1.  
   
   
       44 . The curable silicone composition of  claim 16  wherein organic polymer is a silylated allylic terminated polyether; wherein the silylated allylic terminated polyether is derived from the reaction of a vinyl alkyl terminated polyol with a hydride functional silane.  
   
   
       45 . The curable silicone composition of  claim 44  wherein the hydride functional silane is selected from the group consisting of triethoxysilane, trimethoxysilane, methyldiethoxysilane, methyldimethylsilane and combinations thereof.  
   
   
       46 . The curable silicone composition of  claim 16  wherein the organic polymer is a polyether having a silicone functional group.  
   
   
       47 . The curable silicone composition of  claim 46  wherein the silicone functional group is a hydrolyzable silane group.  
   
   
       48 . The curable silicone composition of  claim 46  wherein the polyether having a silicone functional group has a molecular weight that ranges from 2,000 to 50,000 g/mole.