Polymerizable Silicone Copolymer Macromers and Polymers Made Therefrom

Abstract

A polymerizable dimethicone copolyol macromer composition is synthesized by reacting itaconic anhydride with a dimethicone copolyol. During the reaction itaconic anhydride spontaneously isomerizes to citraconic anhydride which in turn is esterified by the dimethicone copolyol. The obtained macromers are copolymerizable with olefinically unsaturated monomers. Polymers containing the macromer repeating units are useful in a variety of applications including personal care, textile and industrial formulations to deliver softness, lubricity, fixative, water repellency, gloss, surface modification, and surfactant properties.

1 . A free radically polymerizable macromer represented by the formula: 
       
         
           
           
               
               
           
         
         wherein in formula III R and R′ independently represent hydrogen and a cyclic anhydride residue, subject to the proviso that R and R′ do not both represent hydrogen at the same time, R 1  and R 2  independently represent a radical selected from C 1  to C 30  alkyl, C 1  to C 20  halo substituted alkyl, C 3  to C 8  cycloalkyl, C 6  to C 14  aryl, and C 2  to C 20  alkenyl, E represents a divalent ethylene radical, P independently represents a divalent propylene radical, a, b, and c are independently 0 to 100; and n is 0 to 200, E taken together with the oxygen atom to which is attached represents an ethylene oxide residue (EO or OE) and P taken together with the oxygen atom to which it is attached represents a propylene oxide residue (PO or OP) wherein the EO/PO and OE/OP residues can be arranged in random, non-random, or blocky sequences; 
         wherein in formula IV R 1  and R 2 , E, P, a, b, and c are as defined above, R 3  represents a radical selected from C 1  to C 30  alkyl, C 1  to C 20  halo substituted alkyl, C 3  to C 8  cycloalkyl, C 6  to C 14  aryl, and C 2  to C 20  alkenyl, R 4  represents a radical selected from C 1  to C 30  alkyl, C 6  to C 14  aryl, and C 2  to C 20  alkenyl, x is 0 to 200, y is 1 to 200, z≦y; and 
         wherein said cyclic anhydride residue in formulae III and IV is represented by the formula: 
       
       
         
           
           
               
               
           
         
         wherein R 5  and R 6  are independently selected from hydrogen and methyl, subject to the proviso that R 5  and R 6  do not both represent methyl at the same time. 
       
     
     
         2 . A macromer of  claim 1  wherein said cyclic anhydride residue is represented by the formulae: 
       
         
           
           
               
               
           
         
       
     
     
         3 . A free radically polymerizable macromer composition comprising the reaction product of maleic anhydride and a dimethicone copolyol containing at least one terminal and/or pendant hydroxyl group. 
     
     
         4 . A composition of  claim 3  wherein said dimethicone copolyol is represented by the formula: 
       
         
           
           
               
               
           
         
         wherein R 1  and R 2  independently represent a radical selected from C 1  to C 30  alkyl, C 1  to C 20  halo substituted alkyl, C 3  to C 8  cycloalkyl, C 6  to C 14  aryl, and C 2  to C 20  alkenyl, E represents a divalent ethylene radical, P independently represents a divalent propylene radical, a, b, and c are independently 0 to 100; and n is 0 to 200, E taken together with the oxygen atom to which is attached represents an ethylene oxide residue (EO or OE) and P taken together with the oxygen atom to which it is attached represents a propylene oxide residue (PO or OP) wherein the EO/PO and OE/OP residues can be arranged in random, non-random, or blocky sequences. 
       
     
     
         5 . A composition of  claim 3  wherein said dimethicone copolyol is represented by the formula: 
       
         
           
           
               
               
           
         
         wherein R 1 , R 2 , and R 3  independently represent a radical selected from C 1  to C 30  alkyl, C 1  to C 20  halo substituted alkyl, C 3  to C 8  cycloalkyl, C 6  to C 14  aryl, and C 2  to C 20  alkenyl, R 4  independently represents a radical selected from C 1  to C 30  alkyl, C 6  to C 14  aryl, and C 2  to C 20  alkenyl, x is 0 to 200, y is 1 to 200, E represents a divalent ethylene radical, P independently represents a divalent propylene radical, a, b, and c are independently 0 to 100, E taken together with the oxygen atom to which is attached represents an ethylene oxide residue (EO or OE) and P taken together with the oxygen atom to which it is attached represents a propylene oxide residue (PO or OP) wherein the EO/PO and OE/OP residues can be arranged in random, non-random, or blocky sequences. 
       
     
     
         6 . A process for making a free radically polymerizable dimethicone copolyol macromer comprising:
 a) mixing itaconic anhydride with a dimethicone copolyol to form a reaction mixture;   b) allowing said itaconic anhydride in said reaction mixture to isomerize to form isomerization products thereof; and   c) reacting said reaction mixture containing said isomerization products at a suitable temperature and permitting the esterification of said isomerization products with said dimethicone copolyol.   
     
     
         7 . A process of  claim 6  wherein said dimethicone copolyol contains a terminal and/or a pendant hydroxyl group. 
     
     
         8 . A process of  claim 7  wherein said dimethicone copolyol is represented by the formula: 
       
         
           
           
               
               
           
         
         wherein R 1  and R 2  independently represent a radical selected from C 1  to C 30  alkyl, C 1  to C 20  halo substituted alkyl, C 3  to C 8  cycloalkyl, C 6  to C 14  aryl, and C 2  to C 20  alkenyl, E represents a divalent ethylene radical, P independently represents a divalent propylene radical, a, b, and c are independently 0 to 100; and n is 0 to 200, E taken together with the oxygen atom to which is attached represents an ethylene oxide residue (EO or OE) and P taken together with the oxygen atom to which it is attached represents a propylene oxide residue (PO or OP) wherein the EO/PO and OE/OP residues can be arranged in random, non-random, or blocky sequences 
       
     
     
         9 . A process of  claim 6  wherein said dimethicone copolyol is represented by the formula: 
       
         
           
           
               
               
           
         
         wherein R 1 , R 2 , and R 3  independently represent a radical selected from C 1  to C 30  alkyl, C 1  to C 20  halo substituted alkyl, C 3  to C 8  cycloalkyl, C 6  to C 14  aryl, and C 2  to C 20  alkenyl, R 4  independently represents a radical selected from C 1  to C 30  alkyl, C 6  to C 14  aryl, and C 2  to C 20  alkenyl, x is 0 to 200, y is 1 to 200, E represents a divalent ethylene radical, P independently represents a divalent propylene radical, a, b, and c are independently 0 to 100, E taken together with the oxygen atom to which is attached represents an ethylene oxide residue (EO or OE) and P taken together with the oxygen atom to which it is attached represents a propylene oxide residue (PO or OP) wherein the EO/PO and OE/OP residues can be arranged in random, non-random, or blocky sequences. 
       
     
     
         10 . A process of  claim 6  wherein said isomerization products of itaconic anhydride includes citraconic anhydride. 
     
     
         11 . A process of  claim 6  wherein said reaction mixture is reacted at a temperature ranging from about 75° C. to about 90° C. 
     
     
         12 . A process of  claim 6  wherein said reaction mixture is reacted in the presence of an esterification catalyst at a temperature ranging between ambient room temperature and 90° C. 
     
     
         13 . A process of  claim 12  wherein said esterification catalyst is selected from sulfuric acid, elemental tin, elemental zinc, elemental titanium, organo titanate compounds, organo tin compounds, organo zinc compounds, zinc oxide, magnesium oxide, calcium oxide, stannous oxide, and alkali metal acetates. 
     
     
         14 . A polymer polymerized from a monomer composition comprising at least one dimethicone copolyol macromer selected from formulae III and IV: 
       
         
           
           
               
               
           
         
         wherein in formula III R and R′ independently represent hydrogen and a cyclic anhydride residue, subject to the proviso that R and R′ do not both represent hydrogen at the same time, R 1  and R 2  independently represent a radical selected from C 1  to C 30  alkyl, C 1  to C 20  halo substituted alkyl, C 3  to C 8  cycloalkyl, C 6  to C 14  aryl, and C 2  to C 20  alkenyl, E represents a divalent ethylene radical, P independently represents a divalent propylene radical, a, b, and c are independently 0 to 100; and n is 0 to 200, E taken together with the oxygen atom to which is attached represents an ethylene oxide residue (EO or OE) and P taken together with the oxygen atom to which it is attached represents a propylene oxide residue (PO or OP) wherein the EO/PO and OE/OP residues can be arranged in random, non-random, or blocky sequences; 
         wherein in formula IV R 1  and R 2 , E, P, a, b, and c are as defined above, R 3  represents a radical selected from C 1  to C 30  alkyl, C 1  to C 20  halo substituted alkyl, C 3  to C 8  cycloalkyl, C 6  to C 14  aryl, and C 2  to C 20  alkenyl, R 4  represents a radical selected from C 1  to C 30  alkyl, C 6  to C 14  aryl, and C 2  to C 20  alkenyl, x is 0 to 200, y is 1 to 200, z≦y; and 
         wherein said cyclic anhydride residue in formulae III and IV is represented by the formula: 
       
       
         
           
           
               
               
           
         
         wherein R 5  and R 6  are independently selected from hydrogen and methyl, subject to the proviso that R 5  and R 6  do not both represent methyl at the same time. 
       
     
     
         15 . A polymer of  claim 14  wherein said monomer composition further comprises one or more monomers selected from:
 a) at least one non-ionic vinyl monomer;   b) at least one acidic vinyl monomer;   c) at least one cationic vinyl monomer;   d) at least one associative vinyl monomer;   e) at least one semihydrophobic vinyl monomer;   f) at least one crosslinking monomer; and mixtures thereof.   
     
     
         16 . A polymer of  claim 15  wherein said non-ionic vinyl monomer is selected from at least one monomer represented by the formulae:
   CH 2 ═C(X)Z;     CH 2 ═CH—OC(O)R 7      wherein, X is H or methyl; and Z is —C(O)OR 8 , —C(O)NH 2 , —C(O)NHR 8 , —C(O)N(R 8 ) 2 , —C 6 H 4 R 8 , —C 6 H 4 OR 8 , —C 6 H 4 Cl, —C 6 H 11 , —C 6 H 7 (R 8 )(R 8 )(R 8 ), —CN, —NHC(O)CH 3 , —NHC(O)H, N-(2-pyrrolidonyl), N-caprolactamyl, —C(O)NHC(CH 3 ) 3 , —C(O)NHCH 2 CH 2 —N-ethyleneurea, —Si(R 7 ) 3 , —C(O)O(CH 2 ) x Si(R 7 ) 3 , —C(O)NH(CH 2 ) x Si(R 7 ) 3 , or —(CH 2 ) x Si(R 7 ) 3 ; x is an integer ranging from about 1 to about 6; R 7  independently represents linear and branched C 1  to C 18  alkyl; R 8  independently represents linear and branched C 1  to C 30  alkyl, hydroxy substituted C 2  to C 30  alkyl, and halogen substituted C 1  to C 30  alkyl.   
     
     
         17 . A polymer of  claim 15  wherein said acidic vinyl monomer contains at least one acidic group selected from a carboxylic acid group and salts thereof, a sulfonic acid group and salts thereof, and a phosphonic acid group and salts thereof. 
     
     
         18 . A polymer of  claim 17  wherein said acidic vinyl monomer is selected from acrylic acid, methacrylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid, crotonic acid, aconitic acid, C 1  to C 18  alkyl monoesters of maleic, fumaric, itaconic, or aconitic acid, anhydrides of dicarboxylic acids, vinyl sulfonic acid, 2-sulfoethyl methacrylate, styrene sulfonic acid, 2-acrylamido-2-methylpropane sulfonic acid, allyloxybenzene sulfonic acid, vinyl phosphonic acid, allyl phosphonic acid, 3-acrylamidopropyl phosphonic acid; and salts thereof; and mixtures thereof. 
     
     
         19 . A polymer of  claim 15  wherein said cationic vinyl monomer is selected from mono-(C 1  to C 4 )alkylamino(C 1  to C 8 )alkyl(meth)acrylate, a di-(C 1  to C 4 )alkylamino(C 1  to C 8 )alkyl(meth)acrylate, a mono-(C 1  to C 4 )alkylamino(C 1  to C 8 )alkyl(meth)acrylamide, a di-(C 1  to C 4 )alkylamino(C 1  to C 8 )alkyl(meth)acrylamide, a nitrogen-containing heterocyclic(meth)acrylamide, a nitrogen-containing heterocyclic(meth)acrylate; and salts thereof; and mixtures thereof. 
     
     
         20 . A polymer of  claim 19  wherein said cationic vinyl monomer is selected from 2-(N,N-dimethylamino)ethyl(meth)acrylate, 3-(N,N-dimethylamino)propyl(meth)acrylate, 4-(N,N-dimethylamino)butyl(meth)acrylate, (N,N-dimethylamino)-t-butyl(meth)acrylate, 2-tert-butylamino)ethyl(meth)acrylate, 2-(N,N-diethylamino)ethyl(meth)acrylate, 3-(N,N-diethylamino)propyl(meth)acrylate, 2-(N,N-dimethylamino)neopentyl acrylate, 4-N,N-diethylamino)butyl(meth)acrylate, 2-(N,N-dipropylamino)ethyl(meth)acrylate, 3-N,N-(dipropylamino)propyl(meth)acrylate, 4-N,N-dipropylamino)butyl(meth)acrylate, 3-(N,N-dimethylamino)propyl(meth)acrylate, 2-(4-morpholinyl)ethyl(meth)acrylate, 2-(4-morpholinyl)ethyl acrylate, N′-(2-N,N-dimethylamino)ethyl(meth)acrylamide, 2-(N,N-dimethylamino)propyl(meth)acrylamide, N′-3-(N,N-dimethylamino)propyl(meth)acrylamide, N-(2-pyridyl)acrylamide, N-2-imidazoyl)(meth)acrylamide, N-(4-morpholinyl)(meth)acrylamide, N-(4-morpholinyl)acrylamide, 2-vinyl pyridine, 4-vinyl pyridine, N-vinyl-2-methylimidazole, N-vinylimidazole, N-vinyl-4-methylimidazole, and N-vinyloxazolidone; and salts thereof; and mixtures thereof. 
     
     
         21 . A polymer of  claim 19  wherein said cationic vinyl monomer is selected from 3-trimethylammonium propyl(meth)acrylamide chloride, 3-trimethylammonium propyl acrylamide chloride, quaternized N,N-dimethylaminoethyl(meth)acrylate with C 1  to C 30  alkyl sulphate, quaternized N,N-dimethylaminoethyl(meth)acrylate with methylchloride, quaternized vinyl imidazole, methacryloyl ethyl betaine, and methacryloyl N-oxide. 
     
     
         22 . A polymer of  claim 15  wherein said associative vinyl monomer is selected from at least one monomer represented by the formula: 
       
         
           
           
               
               
           
         
         wherein, each R 9  is independently H, C 1  to C 30  alkyl, —C(O)OH, or —C(O)OR 10 ; R 10  is C 1  to C 30  alkyl; A is —CH 2 C(O)O—, —C(O)O—, —O—, —CH 2 O—, —NHC(O)NH—, —C(O)NH—, —Ar—(CE 2 ) z -NHC(O)O—, —Ar—(CE 2 ) z -NHC(O)NH—, or —CH 2 CH 2 NHC(O)—; Ar is a divalent aryl; E is H or methyl; z is 0 or 1; k is an integer in the range of 0 to about 30, and m is 0 or 1, with the proviso that when k is 0, m is 0, and when k is in the range of 1 to about 30, m is 1; (R 11 -0) n  represents a polyoxyalkylene moiety of C 2  to C 4  oxyalkylene units, wherein R 11  is C 2 H 4 , C 3 H 6 , C 4 H 8 , or a mixture thereof, and n is an integer in the range of about 5 to about 250; Y is —R 11 O—, —R 11 NH—, —C(O)—, —C(O)NH—, —R 11 NHC(O)NH—, or —C(O)NHC(O)—; and R 12  is a substituted or unsubstituted alkyl selected from a C 8  to C 40  linear alkyl, a C 8  to C 40  branched alkyl, a C 8  to C 40  carbocyclic alkyl, a C 2  to C 40  alkyl-substituted phenyl, an aryl-substituted C 2  to C 40  alkyl, and a C 8  to C 80  complex ester; wherein R 11  and R 12  optionally includes one or more substituents selected from hydroxyl, alkoxyl, and halogen. 
       
     
     
         23 . A polymer of  claim 22  wherein said associative vinyl monomer is selected from cetyl polyethoxylated methacrylate, cetearyl polyethoxylated(meth)acrylate, stearyl polyethoxylated(meth)acrylate, arachidyl polyethoxylated(meth)acrylate, behenyl polyethoxylated(meth)acrylate, lauryl polyethoxylated(meth)acrylate, cerotyl polyethoxylated(meth)acrylate, montanyl polyethoxylated(meth)acrylate, melissyl polyethoxylated(meth)acrylate, lacceryl polyethoxylated(meth)acrylate, tristyryl phenolpolyethoxylated(meth)acrylate, hydrogenated castor oil polyethoxylated methacrylate, canola polyethoxylated(meth)acrylate, and cholesterol polyethoxylated(meth)acrylate, wherein the polyethoxylated portion of the monomer contains from about 5 to about 100 ethylene oxide repeating units. 
     
     
         24 . A polymer of  claim 15  wherein said semihydrophobic vinyl monomer is selected from at least one monomer represented by the formula: 
       
         
           
           
               
               
           
         
         wherein R 9  is independently H, C 1  to C 30  alkyl, —C(O)OH, or —C(O)OR 10 ; R 10  is C 1  to C 30  alkyl; A is —CH 2 C(O)O—, —C(O)O—, —O—, —CH 2 O—, —NHC(O)NH—, —C(O)NH—, —Ar—(CE 2 ) n -NHC(O)O—, —Ar—(CE 2 ) n -NHC(O)NH—, or —CH 2 CH 2 NHC(O)—; Ar is a divalent aryl; E is H or methyl; z is 0 or 1; k is an integer in the range of 0 to about 30, and m is 0 or 1, with the proviso that when k is 0, m is 0, and when k is in the range of 1 to about 30, m is 1; (R 11 —O) n  represents a polyoxyalkylene moiety of C 2  to C 4  oxyalkylene units, wherein R 11  is C 2 H 4 , C 3 H 6 , C 4 H 8 , or a mixture thereof, and n is an integer in the range of about 5 to about 250; Y is —R 11 O—, —R 11 NH—, —C(O)—, —C(O)NH—, —R 11 NHC(O)NH—, or —C(O)NHC(O)—; wherein R 11  optionally includes one or more substituents selected from hydroxyl, alkoxyl, and halogen; D is a C 8  to C 30  unsaturated alkyl, or a carboxy-substituted C 8  to C 30  unsaturated alkyl; and R 13  is H or C 1  to C 4  alkyl. 
       
     
     
         25 . A polymer of  claim 24  wherein said semihydrophobic vinyl monomer is represented by at least one monomer of the formulae:
   CH 2 ═CH—O(CH 2 ) a O(C 3 H 6 O) b (C 2 H 4 O) c H     CH 2 ═CH—CH 2 O(C 3 H 6 O) d (C 2 H 4 O) e H   wherein a is an integer of 2, 3, or 4; b is an integer in the range of 1 to about 10; c is an integer in the range of about 5 to about 50; d is an integer in the range of 1 to about 10; and e is an integer in the range of about 5 to about 50.   
     
     
         26 . A polymer of  claim 15  wherein said monomer composition comprises 0 to 5 weight percent (based on the weight of the total monomers of a crosslinking monomer. 
     
     
         27 . A polymer of  claim 15  wherein said monomer composition comprises at least 0.01 percent by weight based on the total monomer weight of a chain transfer agent.