Water-absorbent adhesive compositions and associated methods of manufacture and use

Abstract

An adhesive composition is provided that is water-insoluble yet water-absorbent, i.e., capable of absorbing up to 15 wt. % water or more. The composition is composed of a film-forming hydrophilic polymer with at least one linear segment having a plurality of recurring polar groups along the polymer backbone, a complementary multifunctional polymer with a plurality of recurring functional groups that noncovalently bind to the polar groups on the film-forming polymer, and a plasticizer. A method for manufacturing the adhesive composition is provided as well.

1 . A method for preparing a water-insoluble, water-absorbent adhesive composition, comprising combining, under conditions effective to form a substantially homogeneous admixture: 
 (a) a film-forming, hydrophilic polymer comprising at least one linear segment containing a plurality of recurring polar groups;    (b) a complementary multifunctional polymer containing a plurality of recurring functional groups along the polymer backbone, said recurring functional groups capable of noncovalently binding to the recurring polar groups so that a ladder-like interpolymer complex is formed between the at least one linear segment and the complementary multifunctional polymer; and    (c) a plasticizer capable of plasticizing the film-forming polymer,    wherein the weight fraction of the film-forming polymer in the admixture is greater than the weight fraction of either the complementary multifunctional polymer or the plasticizer.    
   
   
       2 . The method of  claim 1 , wherein the plasticizer is selected from the group consisting of dialkyl phthalates, dicycloalkyl phthalates, diaryl phthalates, mixed alkyl-aryl phthalates, alkyl phosphates, aryl phosphates, alkyl citrates, citrate esters, alkyl adipates, dialkyl tartrates, dialkyl sebacates, dialkyl succinates, alkyl glycolates, alkyl glycerolates, glycol esters, glycerol esters, and mixtures thereof.  
   
   
       3 . The method of  claim 2 , wherein the plasticizer is selected from dimethyl phthalate, diethyl phthalate, dipropyl phthalate, di(2-ethylhexyl)phthalate, di-isopropyl phthalate, diamyl phthalate, dicapryl phthalate, tributyl phosphate, trioctyl phosphate, tricresyl phosphate, triphenyl phosphate, trimethyl citrate, triethyl citrate, tributyl citrate, acetyl triethyl citrate, trihexyl citrate, dioctyl adipate, diethyl adipate, di(2-methylethyl)adipate, dihexyl adipate, diethyl tartrate, dibutyl tartrate, diethyl sebacate, dipropyl sebacate, dinonyl sebacate, diethyl succinate, dibutyl succinate, glycerol diacetate, glycerol triacetate, glycerol monolactate diacetate, methyl phthalyl ethyl glycolate, butyl phthalyl butyl glycolate, ethylene glycol diacetate, ethylene glycol dibutyrate, triethylene glycol diacetate, triethylene glycol dibutyrate, triethylene glycol dipropionate, and mixtures thereof.  
   
   
       4 . The method of  claim 3 , wherein the plasticizer is selected from tributyl phosphate, trioctyl phosphate, triphenyl phosphate, trimethyl citrate, triethyl citrate, and tributyl citrate.  
   
   
       5 . The method of  claim 1 , wherein the plasticizer is a bifunctional, linear oligomer having a functional group at each terminus, each of said terminal functional groups capable of noncovalently binding to one of the polar groups so that a bridged interpolymer complex is formed in which the bifunctional linear oligomer links two of said linear segments to each other.  
   
   
       6 . The method of  claim 1 , further comprising extruding the admixture onto a substrate.  
   
   
       7 . The method of  claim 1 , further comprising combining a solvent with components (a), (b), and (c) in an amount effective to provide a solution, casting the solution onto a substrate, and heating the solution-coated substrate to volatilize the solvent and provide the substantially homogeneous adhesive admixture on the substrate.  
   
   
       8 . The method of  claim 1 , wherein: 
 the film-forming, hydrophilic polymer represents approximately 20 wt. % to approximately 95 wt. % of the admixture;    the complementary multifunctional polymer represents approximately 0.5 wt. % to approximately 40 wt. % of the admixture; and    the bifunctional, linear oligomer represents approximately 1 wt. % to approximately 50 wt. % of the admixture.    
   
   
       9 . The method of  claim 1 , wherein the recurring functional groups, the terminal functional groups, or both the recurring functional groups and the terminal functional groups bind to the recurring polar groups through a mechanism selected from hydrogen bonding, electrostatic bonding, and ionic bonding.  
   
   
       10 . The method of  claim 9 , wherein the recurring functional groups and the recurring polar groups are ionogenic.  
   
   
       11 . The method of  claim 10 , wherein prior to forming the admixture, zero to approximately 30% of the ionogenic groups are ionized.  
   
   
       12 . The method of  claim 11 , wherein prior to forming the admixture, approximately 5% to approximately 10% of the ionogenic groups are ionized.  
   
   
       13 . The method of  claim 10 , wherein the recurring functional groups bind to the recurring polar groups via electrostatic bonding.  
   
   
       14 . The method of  claim 10 , wherein the recurring functional groups bind to the recurring polar groups via ionic bonding.  
   
   
       15 . The method of  claim 1 , wherein the recurring polar groups are pendant groups.  
   
   
       16 . The method of  claim 1 , wherein the recurring polar groups comprise backbone heteroatoms.  
   
   
       17 . The method of  claim 1 , wherein the recurring functional groups are pendant groups.  
   
   
       18 . The method of  claim 1 , wherein the recurring functional groups comprise backbone heteroatoms.  
   
   
       19 . The method of  claim 1 , wherein the molecular weight of the film-forming hydrophilic polymer is in the range of approximately 20,000 to 3,000,000.  
   
   
       20 . The method of  claim 19 , wherein the molecular weight of the film-forming hydrophilic polymer is in the range of approximately 100,000 to 2,000,000.  
   
   
       21 . The method of  claim 20 , wherein the molecular weight of the film-forming hydrophilic polymer is in the range of approximately 100,000 to 1,500,000.  
   
   
       22 . The method of  claim 1 , wherein the molecular weight of the complementary multifunctional polymer is in the range of approximately 10,000 to 1,000,000.  
   
   
       23 . The method of  claim 22 , wherein the molecular weight of the complementary multifunctional polymer is in the range of approximately 100,000 to 1,000,000.  
   
   
       24 . The method of  claim 1 , wherein: 
 the recurring polar groups and the recurring functional groups are selected from hydroxyl, sulfhydryl, hydrocarbyloxy, acyl, acyloxy, hydrocarbyloxycarbonyl, carboxy, carboxylato, carbamoyl, cyano, isocyano, cyanato, isocyanato, formyl, amino, secondary amino, tertiary amino, pendant cyclic amino, quaternary ammonium groups, amido, alkylamido, arylamido, nitro, sulfo, sulfonato, hydrocarbylsulfanyl, phosphono, phosphonato, phosphinato, phospho, backbone nitrogen atoms, backbone oxygen atoms, and backbone sulfur atoms.    
   
   
       25 . The method of  claim 24 , wherein the recurring polar groups and the recurring functional groups are selected from hydroxyl, acyloxy, alkoxy, alkoxycarbonyl, carboxy, carboxylato, amino, alkylamino, dialkylamino, pendant cyclic amino, quaternary ammonium, sulfo, sulfonato, phosphono, and phosphonato.  
   
   
       26 . The method of  claim 1 , wherein: 
 the film-forming hydrophilic polymer is selected from poly(dialkyl aminoalkyl acrylates), poly(dialkyl aminoalkyl methacrylates), poly(N,N-dialkyl acrylamides), poly(vinyl amine), poly(alkylene imine), poly(N-vinyl acrylamide), poly(N-vinyl alkylacrylamides), poly(trimethylammonioethyl methacrylate), poly(N-vinyl lactams), chitosan, copolymers thereof, and combinations of any of the foregoing; and    the complementary multifunctional polymer is selected from poly(acrylic acid), poly(methacrylic acid), poly(maleic acid), poly(sulfonic acid), poly(vinyl alcohol), poly(vinyl phenol), poly(ethylene oxide), poly(hydroxyalkyl methacrylates), cellulose derivatives, alginic acid, copolymers thereof, and combinations of any of the foregoing.    
   
   
       27 . The method of  claim 26 , wherein: 
 the film-forming hydrophilic polymer is selected from poly(dialkyl aminoalkyl acrylates), poly(dialkyl aminoalkyl methacrylates), poly(N,N-dialkyl acrylamides), poly(trimethylammonioethyl methacrylate), poly(N-vinyl lactams), copolymers thereof, and combinations of an of the foregoing; and    the complementary multifunctional polymer is selected from poly(acrylic acid), poly(methacrylic acid), poly(maleic acid), poly(hydroxyalkyl methacrylates), cellulose derivatives, copolymers thereof, and combinations of any of the foregoing.    
   
   
       28 . The method of  claim 1 , wherein: 
 the film-forming hydrophilic polymer is selected from poly(acrylic acid), poly(methacrylic acid), poly(maleic acid), poly(sulfonic acid), poly(vinyl alcohol), poly(vinyl phenol), poly(ethylene oxide), poly(hydroxyalkyl methacrylates), cellulose derivatives, alginic acid, copolymers thereof, and combinations of any of the foregoing; and    the complementary multifunctional polymer is selected from poly(dialkyl aminoalkyl acrylates), poly(dialkyl aminoalkyl methacrylates), poly(N,N-dialkyl acrylamides), poly(vinyl amine), poly(alkylene imine), poly(N-vinyl acrylamide), poly(N-vinyl alkylacrylamides), poly(trimethylammonioethyl methacrylate), poly(N-vinyl lactams), chitosan, copolymers thereof, and combinations of any of the foregoing.    
   
   
       29 . The method of  claim 28 , wherein: 
 the film-forming hydrophilic polymer is selected from poly(acrylic acid), poly(methacrylic acid), poly(maleic acid), poly(hydroxyalkyl methacrylates), cellulose derivatives, copolymers thereof, and combinations of any of the foregoing; and    the complementary multifunctional polymer is selected from poly(dialkyl aminoalkyl acrylates), poly(dialkyl aminoalkyl methacrylates), poly(N,N-dialkyl acrylamides), poly(trimethylammonioethyl methacrylate), poly(N-vinyl lactams), copolymers thereof, and combinations of any of the foregoing.    
   
   
       30 . The method of  claim 1 , wherein the film-forming hydrophilic polymer is an acrylic acid or methacrylic acid polymer or copolymer, the complementary multifunctional polymer is selected from poly(dialkyl aminoalkyl acrylate), poly(dialkyl aminoalkyl methacrylate), and poly(trimethylammonioethyl methacrylate) copolymers, and the plasticizer is a C 2 -C 8  dicarboxylic acid.  
   
   
       31 . The method of  claim 30 , wherein the film-forming hydrophilic polymer is a methacrylic acid—methacrylate copolymer, the complementary multifunctional polymer is a copolymer of dimethylaminoethyl methacrylate and a neutral methacrylate, and the plasticizer is adipic acid.  
   
   
       32 . The method of  claim 5 , wherein the bifunctional, linear oligomer has a molecular weight in the range of approximately 45 to approximately 800 g/mol.  
   
   
       33 . The method of  claim 32 , wherein the bifunctional, linear oligomer has a molecular weight in the range of approximately 45 to approximately 600 g/mol.  
   
   
       34 . The method of  claim 5 , wherein the terminal functional groups are selected from hydroxyl, carboxy, and amino groups.  
   
   
       35 . The method of  claim 34 , wherein the terminal functional groups are selected from hydroxyl and carboxy groups.  
   
   
       36 . The method of  claim 35 , wherein the terminal functional groups are hydroxyl groups.  
   
   
       37 . The method of  claim 1 , further comprising combining at least one optional additive with the film-forming hydrophilic polymer, the complementary multifunctional polymer, and the bifunctional, linear oligomer in the formation of the admixture.  
   
   
       38 . The method of  claim 37 , wherein the at least one additive includes an active agent.  
   
   
       39 . The method of  claim 38 , wherein the additive is a pharmacologically active agent.  
   
   
       40 . The method of  claim 39 , wherein the pharmacologically active agent is a drug.  
   
   
       41 . The method of  claim 38 , wherein the additive is a cosmeceutically active agent.  
   
   
       42 . The method of  claim 41 , wherein the cosmeceutically active agent is a tooth whitening agent.  
   
   
       43 . The method of  claim 37 , wherein the at least one additive is selected from fillers, pH regulating agents, ionizing agents, tackifiers, electrolytes, antimicrobial agents, antioxidants, preservatives, colorants, and combinations thereof.  
   
   
       44 . A water-insoluble, water-absorbent adhesive composition, comprising a blend of: 
 (a) a film-forming, hydrophilic polymer comprising at least one linear segment containing a plurality of recurring polar groups;    (b) a complementary multifunctional polymer containing a plurality of recurring functional groups along the polymer backbone, said recurring functional groups capable of noncovalently binding to the recurring polar groups so that a ladder-like interpolymer complex is formed between the at least one linear segment and the complementary multifunctional polymer; and    (c) a plasticizer capable of plasticizing the film-forming polymer,    wherein the weight fraction of the film-forming polymer in the blend is greater than the weight fraction of either the complementary multifunctional polymer or the plasticizer.    
   
   
       45 . The composition of  claim 44 , wherein the plasticizer is selected from the group consisting of dialkyl phthalates, dicycloalkyl phthalates, diaryl phthalates, mixed alkyl-aryl phthalates, alkyl phosphates, aryl phosphates, alkyl citrates, citrate esters, alkyl adipates, dialkyl tartrates, dialkyl sebacates, dialkyl succinates, alkyl glycolates, alkyl glycerolates, glycol esters, glycerol esters, and mixtures thereof.  
   
   
       46 . The composition of  claim 45 , wherein the plasticizer is selected from dimethyl phthalate, diethyl phthalate, dipropyl phthalate, di(2-ethylhexyl)phthalate, di-isopropyl phthalate, diamyl phthalate, dicapryl phthalate, tributyl phosphate, trioctyl phosphate, tricresyl phosphate, triphenyl phosphate, trimethyl citrate, triethyl citrate, tributyl citrate, acetyl triethyl citrate, trihexyl citrate, dioctyl adipate, diethyl adipate, di(2-methylethyl)adipate, dihexyl adipate, diethyl tartrate, dibutyl tartrate, diethyl sebacate, dipropyl sebacate, dinonyl sebacate, diethyl succinate, dibutyl succinate, glycerol diacetate, glycerol triacetate, glycerol monolactate diacetate, methyl phthalyl ethyl glycolate, butyl phthalyl butyl glycolate, ethylene glycol diacetate, ethylene glycol dibutyrate, triethylene glycol diacetate, triethylene glycol dibutyrate, triethylene glycol dipropionate, and mixtures thereof.  
   
   
       47 . The composition of  claim 46 , wherein the plasticizer is selected from tributyl phosphate, trioctyl phosphate, triphenyl phosphate, trimethyl citrate, triethyl citrate, and tributyl citrate.  
   
   
       48 . The composition of  claim 44 , wherein the plasticizer is a bifunctional, linear oligomer having a functional group at each terminus, each of said terminal functional groups capable of noncovalently binding to one of the polar groups so that a bridged interpolymer complex is formed in which the bifunctional linear oligomer links two of said linear segments to each other.  
   
   
       49 . The composition of  claim 44 , wherein: 
 the film-forming, hydrophilic polymer represents approximately 20 wt. % to approximately 95 wt. % of the blend;    the complementary multifunctional polymer represents approximately 0.5 wt. % to approximately 40 wt. % of the blend; and    the bifunctional, linear oligomer represents approximately 1 wt. % to approximately 50 wt. % of the blend.    
   
   
       50 . The composition of  claim 44 , wherein the recurring functional groups, the terminal functional groups, or both the recurring functional groups and the terminal functional groups bind to the recurring polar groups through a mechanism selected from hydrogen bonding, electrostatic bonding, and ionic bonding.  
   
   
       51 . The composition of  claim 50 , wherein the recurring functional groups and the recurring polar groups are ionogenic.  
   
   
       52 . The composition of  claim 51 , wherein zero to approximately 30% of the ionogenic groups are ionized.  
   
   
       53 . The composition of  claim 52 , wherein approximately 5% to approximately 10% of the ionogenic groups are ionized.  
   
   
       54 . The composition of  claim 51 , wherein the recurring functional groups bind to the recurring polar groups via electrostatic bonding.  
   
   
       55 . The composition of  claim 51 , wherein the recurring functional groups bind to the recurring polar groups via ionic bonding.  
   
   
       56 . The composition of  claim 44 , wherein the recurring polar groups are pendant groups.  
   
   
       57 . The composition of  claim 44 , wherein the recurring polar groups comprise backbone heteroatoms.  
   
   
       58 . The composition of  claim 44 , wherein the recurring functional groups are pendant groups.  
   
   
       59 . The composition of  claim 44 , wherein the recurring functional groups comprise backbone heteroatoms.  
   
   
       60 . The composition of  claim 44 , wherein the molecular weight of the film-forming hydrophilic polymer is in the range of approximately 20,000 to 3,000,000.  
   
   
       61 . The composition of  claim 60 , wherein the molecular weight of the film-forming hydrophilic polymer is in the range of approximately 100,000 to 2,000,000.  
   
   
       62 . The composition of  claim 61 , wherein the molecular weight of the film-forming hydrophilic polymer is in the range of approximately 100,000 to 1,500,000.  
   
   
       63 . The composition of  claim 44 , wherein the molecular weight of the complementary multifunctional polymer is in the range of approximately 10,000 to 1,000,000.  
   
   
       64 . The composition of  claim 63 , wherein the molecular weight of the complementary multifunctional polymer is in the range of approximately 100,000 to 1,000,000.  
   
   
       65 . The composition of  claim 44 , wherein: 
 the recurring polar groups and the recurring functional groups are selected from hydroxyl, sulfhydryl, hydrocarbyloxy, acyl, acyloxy, hydrocarbyloxycarbonyl, carboxy, carboxylato, carbamoyl, cyano, isocyano, cyanato, isocyanato, formyl, amino, secondary amino, tertiary amino, pendant cyclic amino, quaternary ammonium groups, amido, alkylamido, arylamido, nitro, sulfo, sulfonato, hydrocarbylsulfanyl, phosphono, phosphonato, phosphinato, phospho, backbone nitrogen atoms, backbone oxygen atoms, and backbone sulfur atoms.    
   
   
       66 . The composition of  claim 65 , wherein the recurring polar groups and the recurring functional groups are selected from hydroxyl, acyloxy, alkoxy, alkoxycarbonyl, carboxy, carboxylato, amino, alkylamino, dialkylamino, pendant cyclic amino, quaternary ammonium, sulfo, sulfonato, phosphono, and phosphonato.  
   
   
       67 . The composition of  claim 44 , wherein: 
 the film-forming hydrophilic polymer is selected from poly(dialkyl aminoalkyl acrylates), poly(dialkyl aminoalkyl methacrylates), poly(N,N-dialkyl acrylamides), poly(vinyl amine), poly(alkylene imine), poly(N-vinyl acrylamide), poly(N-vinyl alkylacrylamides), poly(trimethylammonioethyl methacrylate), poly(N-vinyl lactams), chitosan, copolymers thereof, and combinations of any of the foregoing; and    the complementary multifunctional polymer is selected from poly(acrylic acid), poly(methacrylic acid), poly(maleic acid), poly(sulfonic acid), poly(vinyl alcohol), poly(vinyl phenol), poly(ethylene oxide), poly(hydroxyalkyl methacrylates), cellulose derivatives, alginic acid, copolymers thereof, and combinations of any of the foregoing.    
   
   
       68 . The composition of  claim 67 , wherein: 
 the film-forming hydrophilic polymer is selected from poly(dialkyl aminoalkyl acrylates), poly(dialkyl aminoalkyl methacrylates), poly(N,N-dialkyl acrylamides), poly(trimethylammonioethyl methacrylate), poly(N-vinyl lactams), copolymers thereof, and combinations of an of the foregoing; and    the complementary multifunctional polymer is selected from poly(acrylic acid), poly(methacrylic acid), poly(maleic acid), poly(hydroxyalkyl methacrylates), cellulose derivatives, copolymers thereof, and combinations of any of the foregoing.    
   
   
       69 . The composition of  claim 44 , wherein: 
 the film-forming hydrophilic polymer is selected from poly(acrylic acid), poly(methacrylic acid), poly(maleic acid), poly(sulfonic acid), poly(vinyl alcohol), poly(vinyl phenol), poly(ethylene oxide), poly(hydroxyalkyl methacrylates), cellulose derivatives, alginic acid, copolymers thereof, and combinations of any of the foregoing; and    the complementary multifunctional polymer is selected from poly(dialkyl aminoalkyl acrylates), poly(dialkyl aminoalkyl methacrylates), poly(N,N-dialkyl acrylamides), poly(vinyl amine), poly(alkylene imine), poly(N-vinyl acrylamide), poly(N-vinyl alkylacrylamides), poly(trimethylammonioethyl methacrylate), poly(N-vinyl lactams), chitosan, copolymers thereof, and combinations of any of the foregoing.    
   
   
       70 . The composition of  claim 69 , wherein: 
 the film-forming hydrophilic polymer is selected from poly(acrylic acid), poly(methacrylic acid), poly(maleic acid), poly(hydroxyalkyl methacrylates), cellulose derivatives, copolymers thereof, and combinations of any of the foregoing; and    the complementary multifunctional polymer is selected from poly(dialkyl aminoalkyl acrylates), poly(dialkyl aminoalkyl methacrylates), poly(N,N-dialkyl acrylamides), poly(trimethylammonioethyl methacrylate), poly(N-vinyl lactams), copolymers thereof, and combinations of any of the foregoing.    
   
   
       71 . The composition of  claim 44 , wherein the film-forming hydrophilic polymer is an acrylic acid or methacrylic acid polymer or copolymer, the complementary multifunctional polymer is selected from poly(dialkyl aminoalkyl acrylate), poly(dialkyl aminoalkyl methacrylate), and poly(trimethylammonioethyl methacrylate) copolymers, and the plasticizer is a C 2 -C 8  dicarboxylic acid.  
   
   
       72 . The composition of  claim 71 , wherein the film-forming hydrophilic polymer is a methacrylic acid—methacrylate copolymer, the complementary multifunctional polymer is a copolymer of dimethylaminoethyl methacrylate and a neutral methacrylate, and the plasticizer is adipic acid.  
   
   
       73 . The composition of  claim 48 , wherein the bifunctional, linear oligomer has a molecular weight in the range of approximately 45 to approximately 800 g/mol.  
   
   
       74 . The composition of  claim 73 , wherein the bifunctional, linear oligomer has a molecular weight in the range of approximately 45 to approximately 600 g/mol.  
   
   
       75 . The composition of  claim 48 , wherein the terminal functional groups are selected from hydroxyl, carboxy, and amino groups.  
   
   
       76 . The composition of  claim 75 , wherein the terminal functional groups are selected from hydroxyl and carboxy groups.  
   
   
       77 . The composition of  claim 76 , wherein the terminal functional groups are hydroxyl groups.  
   
   
       78 . The composition of  claim 44 , further comprising at least one additive with the film-forming hydrophilic polymer, the complementary multifunctional polymer, and the bifunctional, linear oligomer in the formation of the admixture.  
   
   
       79 . The composition of  claim 37 , wherein the at least one additive includes an active agent.  
   
   
       80 . The composition of  claim 79 , wherein the additive is a pharmacologically active agent.  
   
   
       81 . The composition of  claim 80 , wherein the pharmacologically active agent is a drug.  
   
   
       82 . The composition of  claim 79 , wherein the additive is a cosmeceutically active agent.  
   
   
       83 . The composition of  claim 82 , wherein the cosmeceutically active agent is a tooth whitening agent.  
   
   
       84 . The composition of  claim 78 , wherein the at least one additive is selected from fillers, pH regulating agents, ionizing agents, tackifiers, electrolytes, antimicrobial agents, antioxidants, preservatives, colorants, and combinations thereof.