Surfactant Responsive Emulsion Polymerization Micro-Gels

Abstract

A stable, aqueous composition containing a crosslinked, nonionic, amphiphilic polymer capable of forming a yield stress fluid in the presence of a surfactant is disclosed. The yield stress fluid is capable of suspending insoluble materials in the form of particulates and/or droplets requiring suspension or stabilization.

1 . A nonionic amphiphilic polymer composition polymerized from a monomer composition comprising:
 (i) at least one hydrophilic monomer,   (ii) at least one hydrophobic monomer, and   (iii) about 0.01 to about 5 wt. % of at least one amphiphilic crosslinking agent containing more than one unsaturated moieties.   
     
     
         2 . The polymer composition of  claim 1 , wherein the more than one reactive moieties of said at least one amphiphilic crosslinking agent comprise at least one allyl group. 
     
     
         3 . The polymer composition according to  claim 1  wherein the more than one reactive moieties of said at least one amphiphilic crosslinking agent comprise at least two allyl groups. 
     
     
         4 . The polymer composition according to  claim 1  wherein the amphiphilic crosslinking agent is a compound of formula (III): 
       
         
           
           
               
               
           
         
       
       where:
 R1 is a C 10-24  alkyl, alkaryl, alkenyl, or cycloalkyl; 
 R2 is CH 3 , CH 2 CH 3 , C 6 H 5 , or C 14 H 29 ; 
 R3 is H or Z − M +   
 Z −  is SO 3   − , or PO 3   2 ; 
 M +  is Na + , K + , NH 4   + , or an alkanolamine; 
 x is 2-10; 
 y is 0-200; and 
 z is 4-200. 
 
     
     
         5 . The polymer composition according to  claim 1  wherein the amphiphilic crosslinking agent is a compound of formula (IV): 
       
         
           
           
               
               
           
         
       
       where:
 n is 1 or 2; 
 z is 4 to 40; and 
 R 4  is H, SO 3   − M +  or PO 3   − M + , and M is selected from Na + , K + , NH 4   +  or an alkanolamine. 
 
     
     
         6 . (canceled) 
     
     
         7 . (canceled) 
     
     
         8 . The polymer composition according to  claim 1  wherein:
 said hydrophilic monomer is selected from hydroxy(C 1 -C 5 )alkyl (meth)acrylates, N-vinyl amides, amino group containing monomers, or mixtures thereof; and said hydrophobic monomer is selected from esters of (meth)acrylic acid with alcohols containing 1 to 30 carbon atoms, vinyl esters of aliphatic carboxylic acids containing 1 to 22 carbon atoms, vinyl ethers of alcohols containing 1 to 22 carbon atoms, vinyl aromatic monomers, vinyl halides, vinylidene halides, associative monomers, semi-hydrophobic monomers, or mixtures thereof. 
 
     
     
         9 . The polymer composition according to  claim 8  wherein said hydroxy(C 1 -C 5 )alkyl (meth)acrylate is selected from at least one compound represented by the formula: 
       
         
           
           
               
               
           
         
       
       wherein R is hydrogen or methyl and R 1  is an divalent alkylene moiety containing 1 to 5 carbon atoms, wherein the alkylene moiety optionally can be substituted by one or more methyl groups. 
     
     
         10 . The polymer composition according to  claim 8  wherein said amino group containing monomer is selected from (meth)acrylamide, diacetone acrylamide and at least one monomer structurally represented by the following formulas: 
       
         
           
           
               
               
           
         
       
       wherein R 2  is hydrogen or methyl, R 3  independently is selected from hydrogen, C 1  to C 5  alkyl and C 1  to C 5  hydroxyalkyl, and R 4  independently is selected from is C 1  to C 5  alkyl or C 1  to C 5  hydroxyalkyl, R 5  is hydrogen or methyl, R 6  is C 1  to C 5  alkylene, R 7  independently is selected from hydrogen or C 1  to C 5  alkyl, and R 8  independently is selected from C 1  to C 5  alkyl; or mixtures thereof. 
     
     
         11 . The polymer composition according to  claim 8  wherein said N-vinyl amide is selected from a N-vinyllactam containing 4 to 9 atoms in the lactam ring moiety, wherein the ring carbon atoms, optionally, can be substituted by one or more C 1 -C 3  lower alkyl group. 
     
     
         12 . The polymer composition according to  claim 8  wherein said ester of (meth)acrylic acid with alcohols containing 1 to 30 carbon is selected from at least one compound represented by the formula: 
       
         
           
           
               
               
           
         
       
       wherein R 9  is hydrogen or methyl and R 10  is C 1  to C 22  alkyl. 
     
     
         13 . The polymer composition according to  claim 8  wherein said vinyl ester of aliphatic carboxylic acids containing 1 to 22 carbon atoms is selected from at least one compound represented by the formula: 
       
         
           
           
               
               
           
         
       
       wherein R 11  is a C 1  to C 22  aliphatic group which can be an alkyl or alkenyl. 
     
     
         14 . The polymer composition according to  claim 8  wherein said vinyl ether of alcohols containing 1 to 22 carbon atoms is selected from at least one compound represented by the formula: 
       
         
           
           
               
               
           
         
       
       wherein R 13  is a C 1  to C 22  alkyl. 
     
     
         15 . The polymer composition according to  claim 8  wherein said associative monomer comprises (i) an ethylenically unsaturated end group portion; (ii) a polyoxyalkylene mid-section portion, and (iii) a hydrophobic end group portion containing 8 to 30 carbon atoms. 
     
     
         16 . The polymer composition according to  claim 15  wherein said associative monomer is represented by formulas VII and/or VIIA: 
       
         
           
           
               
               
           
         
       
       wherein R 14  is hydrogen or methyl; 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 arylene (e.g., phenylene); E is H or methyl; z is 0 or 1; k is an integer ranging from about 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; D represents a vinyl or an allyl moiety; (R 1-5 —O) n  is a polyoxyalkylene moiety, which can be a homopolymer, a random copolymer, or a block copolymer of C 2 -C 4  oxyalkylene units, R 15  is a divalent alkylene moiety selected from C 2 H 4 , C 3 H 6 , or C 4 H 8 , and combinations thereof; and n is an integer in the range of about 2 to about 150; Y is —R 15 O—, —R 15 NH—, —C(O)—, —C(O)NH—, —R 15 NHC(O)NH—, or —C(O)NHC(O)—; R 16  is a substituted or unsubstituted alkyl selected from a C 8 -C 30  linear alkyl, a C 8 -C 30  branched alkyl, a C 8 -C 30  carbocyclic alkyl, a C 2 -C 30  alkyl-substituted phenyl, an araalkyl substituted phenyl, and an aryl-substituted C 2 -C 30  alkyl; wherein the R 16  alkyl group, aryl group, phenyl group optionally comprises one or more substituents selected from the group consisting of a hydroxyl group, an alkoxyl group, benzyl group styryl group, and a halogen group. 
     
     
         17 . The polymer composition according to  claim 16  wherein said associative monomer is represented by formula VIIB: 
       
         
           
           
               
               
           
         
       
       wherein R 4  is hydrogen or methyl; R 5  is a divalent alkylene moiety independently selected from C 2 H 4 , C 3 H 6 , and C 4 H 8 , and n represents an integer ranging from about 10 to about 60, (R 15 —O) can be arranged in a random or a block configuration; R 16  is a substituted or unsubstituted alkyl selected from a C 8 -C 30  linear alkyl, a C 8 -C 30  branched alkyl, a C 8 -C 30  carbocyclic alkyl, a C 2 -C 30  alkyl-substituted phenyl, an araalkyl substituted phenyl, and an aryl-substituted C 2 -C 30  alkyl, wherein the R 16  alkyl group, aryl group, phenyl group optionally comprises one or more substituents selected from the group consisting of a hydroxyl group, an alkoxyl group, benzyl group styryl group, and a halogen group. 
     
     
         18 . The polymer composition according to  claim 8  wherein said semi-hydrophobic monomer comprises (i) an ethylenically unsaturated end group portion; (ii) a polyoxyalkylene mid-section portion, and (iii) an end group portion selected from hydrogen or an alkyl group containing 1 to 4 carbon atoms. 
     
     
         19 . The polymer composition according to  claim 18  wherein said semi-hydrophobic monomer is selected from at least one monomer represented by formulas VIII and IX: 
       
         
           
           
               
               
           
         
       
       wherein R 14  is hydrogen or methyl; 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 arylene (e.g., phenylene); E is H or methyl; z is 0 or 1; k is an integer ranging from about 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 15 —O) n  is a polyoxyalkylene moiety, which can be a homopolymer, a random copolymer, or a block copolymer of C 2 -C 4  oxyalkylene units, R 15  is a divalent alkylene moiety selected from C 2 H 4 , C 3 H 6 , or C 4 H 8 , and combinations thereof; and n is an integer in the range of about 2 to about 150; R 17  is selected from hydrogen and a linear or branched C 1 -C 4  alkyl group; and D represents a vinyl or an allyl moiety. 
     
     
         20 . The polymer composition according to  claim 19  wherein said semi-hydrophobic monomer is selected from at least one monomer represented by formulas VIIIA and VIIIB:
   CH 2 ═C(R 14 )C(O)O—(C 2 H 4 O) a (C 3 H 6 O) b —H  VIIIA
 
   CH 2 ═C(R 14 )C(O)O—(C 2 H 4 O) a (C 3 H 6 O) b —CH 3   VIIIB
 
 
       wherein R 14  is hydrogen or methyl, and “a” is an integer ranging from 0 or 2 to about 120, and “b” is an integer ranging from about 0 or 2 to about 120, subject to the proviso that “a” and “b” cannot be 0 at the same time. 
     
     
         21 . (canceled) 
     
     
         22 . (canceled) 
     
     
         23 . A polymer composition according to  claim 1  wherein said amphiphilic polymer comprises a conventional crosslinking agent which is present in an amount sufficient to be incorporated into said polymer from about 0.01 to about 1 wt. %, based on the dry weight of the polymer. 
     
     
         24 . A polymer composition according to  claim 23  wherein said conventional crosslinking agent contains an average of about 3 crosslinkable unsaturated moieties. 
     
     
         25 . A polymer composition according to  claim 23  wherein said monomer mixture comprises a conventional crosslinking agent which is present in an amount sufficient to be incorporated into said polymer from about 0.01 to about 0.3 wt. %, based on the dry weight of the polymer. 
     
     
         26 . A polymer composition according to  claim 23  wherein the at least one conventional crosslinking agent is selected from polyallyl ethers of trimethylolpropane, polyallyl ethers of pentaerythritol, polyallyl ethers of sucrose, or mixtures thereof. 
     
     
         27 . A polymer composition according to  claim 26  wherein the at least one conventional crosslinking agent is selected from pentaerythritol diallyl ether, pentaerythritol triallyl ether, pentaerythritol tetraallyl ether; or mixtures thereof. 
     
     
         28 . A polymer composition according to  claim 1  wherein said polymer is an emulsion polymer. 
     
     
         29 . (canceled) 
     
     
         30 . (canceled) 
     
     
         31 . A polymer composition according to  claim 1  wherein said polymer is polymerized from a monomer composition comprising:
 a) from about 20 to about 60 wt. % of at least one C 1 -C 4  hydroxyalkyl (meth)acrylate; 
 b) from about 10 to about 70 wt. % of at least one C 1 -C 12  alkyl (meth)acrylate or from about 10 to about 70 wt. % of at least one C 1 -C 5  alkyl (meth)acrylate; 
 c) from about 0, 1, 5 or 15 to about 40 wt. % of at least one vinyl ester of a C 1 -C 10  carboxylic acid; 
 d) from about 0, 1, 5 or 15 to about 30 wt. % of a vinyl lactam (e.g., vinyl pyrrolidone); 
 e) from about 0, 0.1, 1, 5, or 7 to about 15 wt. % of at least one associative and/or a semi-hydrophobic monomer (wherein all monomer weight percentages are based on the weight of the total monomers); and 
 f) from about 0.01 to about 5 wt. % of at least one crosslinker (based on the dry weight of the polymer) selected from an amphiphilic crosslinking agent or a combination of an amphiphilic crosslinking agent and said conventional crosslinking agent. 
 
     
     
         32 . A polymer composition according to  claim 31  wherein said polymer is polymerized from a monomer composition comprising:
 a) from about 20 to about 60 wt. % of at least one C 1 -C 4  hydroxyalkyl (meth)acrylate; 
 b) from about 10 to about 30 wt. % ethyl acrylate; 
 c) from about 10 to about 35 wt. % butyl acrylate; 
 d) from about 0, 1, 5 or 15 to about 25 wt. % of a vinyl ester of a carboxylic acid selected from vinyl formate, vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, and vinyl valerate; 
 e) from about 0, 1 or 15 to about 30 wt. % of vinyl pyrrolidone; 
 f) from about 0, 0.1, 1, 5 or 7 to about 15 wt. % of at least one associative monomer and/or semi-hydrophobic monomer (wherein all monomer weight percentages are based on the weight of the total monomers); and 
 g) from about 0.01 to about 5 wt. % of at least one crosslinker (based on the dry weight of the polymer) selected from an amphiphilic crosslinking agent or a combination of an amphiphilic crosslinking agent and said conventional crosslinking agent. 
 
     
     
         33 . A polymer composition according to  claim 31  wherein said polymer is polymerized from a monomer composition comprising:
 a) from about 20 to about 50 wt. % of hydroxyethyl methacrylate; 
 b) from about 10 to about 30 wt. % ethyl acrylate; 
 c) from about 10 to about 30 wt. % butyl acrylate; 
 d) from about 0, 1, or 15 to about 25 wt. % of vinyl pyrrolidone; 
 e) from about 0 or 15 to about 25 wt. % of vinyl acetate; 
 f) from about 0, 0.1, 1, 5 or 7 to about 10 wt. % of at least one associative and/or semi-hydrophobic monomer (wherein all monomer weight percentages are based on the weight of the total monomers); and 
 g) from about 0.01 to about 5 wt. % in one aspect, from about 0.1 to about 3 wt. % of at least one crosslinker (based on the dry weight of the polymer) selected from an amphiphilic crosslinking agent or a combination of an amphiphilic crosslinking agent and said conventional crosslinking agent. 
 
     
     
         34 . A polymer composition according to  claim 31  wherein said polymer is polymerized from a monomer composition comprising:
 a) from about 20 to about 50 wt. % of hydroxyethyl methacrylate; 
 b) from about 10 to about 40 wt. % ethyl acrylate; 
 c) from about 10 to about 20 wt. % butyl acrylate; 
 d) from about 0.1 to about 10 wt. % of at least one associative and/or semi-hydrophobic monomer (wherein all monomer weight percentages are based on the weight of the total monomers); and 
 e) from about 0.01 to about 5 wt. % in one aspect, from about 0.1 to about 3 wt. % of at least one crosslinker (based on the dry weight of the polymer) selected from an amphiphilic crosslinking agent or a combination of an amphiphilic crosslinking agent and said conventional crosslinking agent. 
 
     
     
         35 . A polymer composition according to  claim 31  wherein said polymer is polymerized from a monomer composition comprising:
 a) from about 20 to about 50 wt. % of hydroxyethyl methacrylate; 
 b) from about 10 to about 30 wt. % ethyl acrylate; 
 c) from about 10 to about 30 wt. % butyl acrylate; 
 d) from about 1 to about 10 wt. % of at least one associative and/or semi-hydrophobic monomer (wherein all monomer weight percentages are based on the weight of the total monomers); and 
 e) from about 0.01 to about 5 wt. % of at least one crosslinker (based on the dry weight of the polymer) selected from an amphiphilic crosslinking agent or a combination of an amphiphilic crosslinking agent and said conventional crosslinking agent. 
 
     
     
         36 . A polymer composition according to  claim 31  wherein said polymer is polymerized from a monomer composition comprising:
 a) from about 20 to about 35 wt. % of hydroxyethyl methacrylate; 
 b) from about 10 to about 30 wt. % ethyl acrylate; 
 c) from about 10 to about 30 wt. % butyl acrylate; 
 d) from about 15 to about 25 wt. % of vinyl pyrrolidone, 
 e) from about 15 to about 25 wt. % of vinyl acetate (wherein all monomer weight percentages are based on the weight of the total monomers); and 
 f) from about 0.01 to about 5 wt. % of at least one crosslinker (based on the dry weight of the polymer) selected from an amphiphilic crosslinking agent or a combination of an amphiphilic crosslinking agent and said conventional crosslinking agent. 
 
     
     
         37 . A polymer composition according to  claim 31  wherein said polymer is polymerized from a monomer composition comprising:
 a) from about 20 to about 40 wt. % of hydroxyethyl methacrylate; 
 b) from about 10 to about 30 wt. % ethyl acrylate; 
 c) from about 10 to about 30 wt. % butyl acrylate; 
 d) from about 15 to about 25 wt. % of vinyl pyrrolidone; 
 e) from about 1 to about 5 wt. % of at least one associative and/or semi-hydrophobic monomer (wherein all monomer weight percentages are based on the weight of the total monomers); and 
 f) from about 0.01 to about 5 wt. % of at least one crosslinker (based on the dry weight of the polymer) selected from an amphiphilic crosslinking agent or a combination of an amphiphilic crosslinking agent and said conventional crosslinking agent. 
 
     
     
         38 . A polymer composition according to  claim 31  wherein said associative monomer in said monomer composition is selected from lauryl polyethoxylated (meth)acrylate, cetyl polyethoxylated (meth)acrylate, cetearyl polyethoxylated (meth)acrylate, stearyl polyethoxylated (meth)acrylate, arachidyl polyethoxylated (meth)acrylate, behenyl polyethoxylated (meth)acrylate, cerotyl polyethoxylated (meth)acrylate, montanyl polyethoxylated (meth)acrylate, melissyl polyethoxylated (meth)acrylate, where the polyethoxylated portion of the monomer contains about 2 to about 50 ethylene oxide units. 
     
     
         39 . A yield stress fluid composition comprising
 (A) water;   (B) about 0.1 to about 5 wt. % of at least one nonionic amphiphilic polymer according to any of  claims 1  to  38 ; and   (C) from about 1 to about 70 wt % based on the total weight of the yield stress fluid of at least one surfactant.   
     
     
         40 . A composition according to  claim 39  wherein the concentration of said polymer ranges from about 0.5 to about 3 wt. %. 
     
     
         41 . The yield stress composition of  claim 39  wherein the at least one surfactant is selected from an anionic, cationic, amphoteric, nonionic, or mixtures thereof. 
     
     
         42 . A composition according to  claim 41  wherein the at least one surfactant is selected from an anionic surfactant. 
     
     
         43 . A composition according to  claim 41  wherein the at least one surfactant is selected from an anionic surfactant and an amphoteric surfactant. 
     
     
         44 . (canceled) 
     
     
         45 . (canceled) 
     
     
         46 . (canceled) 
     
     
         47 . A composition according to  claim 43  wherein the at least one anionic surfactant is selected from sodium dodecyl sulfate, sodium lauryl sulfate, sodium laureth sulfate, or mixtures thereof. 
     
     
         48 . A composition according to  claim 43  wherein the at least one amphoteric surfactant is cocamidopropyl betaine. 
     
     
         49 . (canceled) 
     
     
         50 . A composition according to  claim 39  wherein the concentration of surfactant is less than 25 wt. % (active), based on the weight of the yield stress fluid. 
     
     
         51 . A composition according to  claim 50  wherein the concentration of surfactant ranges from about 6 to about 20 wt. % (active material), based on the weight of the total composition. 
     
     
         52 . A composition according to  claim 43  wherein the ratio of anionic surfactant to amphoteric surfactant (active material) is 10:1 to about 2:1 in one aspect, and 9:1, 8:1, 7:1 6:1, 5:1, 4.5:1, 4:1, or 3:1 in another aspect. 
     
     
         52 - 59 . (canceled) 
     
     
         60 . A composition according to  claim 39  wherein said yield stress fluid is substantially independent of pH in the pH range 2 to 14. 
     
     
         61 . (canceled) 
     
     
         62 . A yield stress fluid of  claim 39  having a nephelometric turbidity unit (NTU) value of 50 or less. 
     
     
         63 - 70 . (canceled) 
     
     
         71 . A composition of  claim 39  further comprising an electrolyte. 
     
     
         72 . A composition according to  claim 71  wherein said electrolyte is selected from potassium pyrophosphate, potassium tripolyphosphate, sodium or potassium citrate, calcium chloride and calcium bromide, zinc halides, barium chloride calcium nitrate, potassium chloride, sodium chloride, potassium iodide, sodium bromide, and ammonium bromide, alkali metal or ammonium nitrates, and blends thereof. 
     
     
         73 . A composition according to  claim 72  wherein the amount of the electrolyte ranges from about 0.1 to about 4 wt. %, based on the weight of the total composition. 
     
     
         74 . A composition according of  claim 73  further comprising an insoluble material, a particulate material, or combinations thereof. 
     
     
         75 . A composition according to  claim 74  wherein said particulate material is selected from mica, coated mica, pigments, exfoliants, anti-dandruff agents, clay, swellable clay, laponite, microsponges, cosmetic beads, cosmetic microcapsules, flakes, or mixtures thereof. 
     
     
         76 . A composition according to  claim 74  wherein said particulate material is selected from sand, sintered bauxite, glass balls, ceramic materials, polystyrene beads, or mixtures thereof. 
     
     
         77 . A composition according to  claim 74  wherein said insoluble material is selected from gas bubbles, liposomes, silicones, or mixtures thereof. 
     
     
         78 . A drilling fluid for use in drilling subterranean formations comprising a yield stress fluid according  claim 39 . 
     
     
         79 . A hydraulic fracturing fluid for use in fracturing subterranean formations comprising a yield stress fluid according  claim 39 . 
     
     
         80 . A hydraulic fracturing fluid according to  claim 79  further comprising a proppant.