MXPA01002536A - A film-forming polymeric sol composition - Google Patents

Abstract

The present invention relates to a quick set composition and a method for preparing the composition. The composition comprises an aqueous sol of a polymer having a backbone that contains pendant cationic groups and pendant acid groups. The sol is prepared by forming a solution of a polymer that contains pendant cationic groups and pendant acid groups in an aqueous-based solvent that contains water and a suitable organic solvent and removing a sufficient amount of the organic solvent from the solution to form a composition characterized by beingreversibly dissolvable and reconstitutable by addition and removal of a suitable organic solvent. The composition of the present invention provides quick-set films that can be prepared in the absence additional surface active agents and with a substantial absence of organic solvents.

Description

wr A COMPOSITION OF POLYMERIC SUN FILM FORMER Field of the Invention The present invention relates to a polymer composition 5 dispersible in water that can be used to prepare fast hardening films or coatings.

Background of the Invention Coatings provide protective barriers for a variety of things including floors, cars, interiors and exteriors of houses, and human skin. Protective floor coverings, for example, have been known since the mid-1950s. Many of the previous coating materials were applied using petroleum or naphthalene based solvents and therefore were undesirable due to the toxicity and flammability of these solvents. Synthetic water-based emulsion compositions such as styrene resin emulsions, styrene-acrylate copolymer resin emulsions, and acrylate emulsions were developed in the early 1960's, and gradually replaced compositions based on organic solvents. Although these water-based compositions are less toxic and more environmentally friendly than organic solvent-based compositions, water-based compositions tend to be slow to harden and difficult to remove in an application where it is desired that they can be removed. . The removal of coating may be desirable because even the most coatings . Durable tend to deteriorate due to dirt or use and breakage. In other applications, such as skin care protective products, the advantages of removable water-based coatings are obvious. Water-based removable coatings are known. For example, polymers containing ammonium carboxylate functionality are compatible with water, but become incompatible through the loss of solvent and ammonia.

Polymer -COO ". NHL» * * »Polymer -COOH + 10 NH3 Compatible in Incompatible Water in Water Coatings made by the process illustrated above may be subsequently removed by contact with a alkaline aqueous liquid, which converts the acid back into a compatible salt. For example, in U.S. Patent No. 4,622,360, Gomi et al. describes a removable polyurethane resin that is transported in water containing carboxyl groups. The coating compositions can be prepared by adding a polyvalent metal forming a complex to the resin carried by the water. The polyvalent metal forms a stable complex dispersible in water with a mine or ammonia in the aqueous solution. When the dispersion is applied to the floor surface, the volatile noxious materials evaporate to allow the metal ions polyvalent initiate a cross link of two or more carboxyl groups, "-.-handle. A ^ tr,. In this way a hardened coating, not compatible with water, is formed, this hardened coating can be removed, but only with a hard alkaline solution containing binders such as ethylene diamine tetraacetic acid. 5 The ammonium carboxylate coating suffers from several disadvantages: 1) the formulations are malodorous and irritating to the eyes and the skin, 2) long periods of time are required for hardening to achieve the acceptable physical properties of the coating, and 3) the removal or detachment process requires the use of hazardous alkaline liquids.10 In view of the deficiencies of the known art, it would be desirable to have a composition that provides a fast hardening film or coating that can be removed without the use of harsh chemicals. applications where said removal is desirable, and it would be desirable to make said coating resistant to organic solvents. smithereens common in applications where general resistance to solvents is desired. It would also be useful to have a non-toxic, water-based, hypoallergenic composition that provides a coating that gives long-lasting protection to the skin from sun, dryness, and harsh chemicals. The present invention is a composition comprising a water-based sol of a polymer having a structure containing pendant cationic groups and pendant acid groups, whose sol is prepared by the steps of: ? .Í! Z- * 4? sL- - »> < »... -'-" • _-_ «irt__M _». * .4, -. »_,. , < »_. - - ^ ^ ^^^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^^^^^^^^^^^^^^^^^^^^^^^^ a polymer containing pendant cationic groups and pendant acid groups in a water-based solvent for the polymer, which solvent contains a first organic solvent, and 5 b) removing a sufficient amount of the first organic solvent from the solution to form a composition characterized by can be dissolved in a reversible way and reconstituted by the addition and removal of a second organic solvent.

In a second aspect, the present invention is a method of coating a substrate containing the application step to a surface of the substrate of a composition containing a conglutinating agent compatible with water and a water-based sol of a polymer which has a structure containing pendant cationic groups and hanging acid groups where the sun is prepared following the steps that comprise: a) the formation of a water-based solution of the polymer, the solution of which contains an organic solvent; b) the removal of a sufficient amount of organic solvent from the solution to form a composition having a minimum solids content so that the viscosity of the sol is less than half that the viscosity of the solution having the same solids content; > 5- * < * - - "• • '> ~ - ~~~ ~ - - - -.« A - ^^ i- - «^ *» ~ - - -, --_: ... ".,., , wherein the conglutinating agent is an organic liquid having a boiling point greater than 1 00 ° C. In a third aspect the present invention is a composition comprising a water-based sol of a polymer having a structure containing pendant cationic groups and pendant acid groups wherein the sol is further characterized by being able to be reversibly dissolved and reconstituted by the addition and removal of an organic solvent for the sol.The composition of the present invention provides films of fast hardening which can be prepared in the absence of additional surfactants and with a substantial absence of organic solvents The sol provides a higher concentration of solids at viscosities considerably lower than a corresponding solution. invention comprises a water-based sol of a polymer having a structure containing pendant cationic groups and pendant acid groups. As used in the present invention, the terms "water-based sol" or "sol" refers to a suspension of a polymer in a medium containing water. The medium should include water and may include a suitable organic solvent. The sun is characterized by being able to be reversibly dissolved and reconstituted (that is, returned to the sun condition) by the addition and subsequent removal of a suitable organic solvent, which may be the same as, or different from, the solvent organic that may be present in the sun. It is also possible to remove all the solvent based ^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^ ^^^^^^^^? ^^^ - ^? á? ^ in water from the sun to form a solid, and later reconstitute the sol by dissolving the solid in a suitable solvent based on water, then stirring an amount enough of the organic solvent (and optionally adding enough water) to reconstitute the sol. The suspended particles preferably have an average particle size (measured by a particle submicron analyzer Coulter Model N4M D) of not less than 10 nm, and more preferably not less than about 20 nm, and preferably not more than 500 nm, more preferably not more than about 300 nm, and still more preferably not more than 200 nm. The dissolved polymer is differentiated from the sol by the differences in the viscosities of the two compositions in a certain minimum concentration of the polymer and the amount of organic solvent needed to form a solution. Specifically, the viscosity of the sol is preferably less than half, more preferably less than one third and still more preferably less than one tenth of the viscosity of the polymer dissolved in a polymer concentration of not less than about 5% by weight, more preferably not less than about 10%, based on the weight of the solution or sol. In addition, the minimum amount of organic solvent required to form a solution is greater than the maximum amount of organic solvent required by a sol. Specifically, the minimum amount of organic solvent required to form a solution is generally greater than 20% by weight based on the weight of the polymer and the water-based solvent. On the other hand, the maximum amount of organic solvent required by a sol is generally less than 20%, preferably less than 10% and still more preferably less than 6% by weight, based on the weight of the polymer and the sol. The polymer is characterized by containing pendant cationic groups and pendant acid groups. Generally, these pendant groups can be formed from the polymerization of a polymerizable cationic monomer, preferably a strong cationic monomer, which can be a strong acid monomer, or a weak acid monomer. As used in the present invention, the term "strong cationic monomer" refers to a monomer containing ethylenic unsaturation and a cationic group having a charge that is independent of pH. The term "polymerizable acid monomer" refers to a monomer containing ethylenic unsaturation and an acidic group. In addition to containing cationic groups and pendant acids, the polymer preferably includes structural units that can be formed from the polymerization of a polymerizable monomer that does not interfere. The term "non-interfering polymerizable monomer" is used in the present invention to refer to a non-charged monomer that does not adversely affect the formation and properties of a film or coating prepared from the sun. The term "structural units formed from the polymerization of a polymerizable monomer" is illustrated by the following example: Methyl Methacrylate Formed Structural Polymerization Units of Methyl Methacrylate The polymerizable acidic monomers which are suitable for the preparation of the dispersion used to prepare the fast hardening coating include ethylenically unsaturated compounds which are suitable for the preparation of the dispersion used to prepare the fast hardening coating. they have carboxylic, phenolic, thiophenolic, phosphinyl, sulfonic acid, sulfinic acid, phosphonic or sulfonamide functionality, or a combination thereof. Preferred polymerizable acidic monomers include acrylic acid, methacrylic acid, itaconic acid, β-carboxyethyl acrylate (generally as a mixture of acrylic acid oligomers), vinylbenzoic acid, vinylchlorophenol, vinyl bromophenol, vinyl thiophenol, 2-propenoic acid: 2-methyl -, estermethyl (hydroxyphosphonyl), vinylphosphonic acid, 2-acrylamido-2-methyl-1-propane sulphonic acid, and 2-sulfoethyl methacrylate acid. Acrylic acid, methacrylic acid, 2-acrylamido-2-methyl-1-propane sulfonic acid and vinylphosphonic acid are the most preferred acidic monomers, with acrylic acid and methacrylic acid being most preferred. The polymerizable cationic monomers are associated with a counter-ion, for example, halide such as chloride or bromide, nitrate, phosphate, carbonate, bicarbonate, acrylate, methacrylate, or sulfate. Suitable strong polymerizable cationic monomers include salts of ethylenically unsaturated compounds having functionality of quaternary ammonium, sulfonium, cyclic sulfonium and phosphonium. Examples of suitable monomers having quaternary ammonium functionality include ethylenically unsaturated trialkylammonium salts such as vinylbenzyl tri-alkylammonium chloride or bromide-C1-C4; acrylates or 25 trialkylammonioalkyl methacrylates such as 2-chloro - ** - - '- - - ^ - - ^ - - ^ ~ - ~ - - ** * ****? Mß ** ^ ^ a ^ _ ¿_ > . - ¿m * B ^ [(methacryloyloxy) ethyl] trimethylammonium, and methyl sulfate of N, N-diethyl-N-methyl-2- [(1-oxo-2-propenyl) oxy] ethanamine (Chemical Extracts Record No. 45076 - 54-8); and trialkylammonioacyl acrylamides such as N, N, N-trimethyl-3 - [(2-methyl-1-oxo-2-propenyl) amino] -1 -propanaminium chloride (Extracts Chemicals Registry No. 51441-64-6) and N, N-dimethyl-N- [3 - [(2-methyl-1-oxo-2-propenyl) amino] propyl] benzenemethamino chloride (Chemical Extracts Record No. 122988-32-3). A preferred polymerizable quaternary ammonium salt is 2 - [(methacryloyloxy) ethyl] trimethylammonium chloride. Other examples of suitable cationic monomers include salts of amine such as aminoalkyl methacrylate salts and substituted or unsubstituted aminoalkyl acrylates. Aminoethyl methacrylate hydrochloride is an example of a suitable amine salt. Examples of the polymerizable unsaturated sulfonium salts include dialkylsulfonium salts such as [4-ethoxy-3- (ethoxycarbonyl) -2-methylene-4-oxobutyl] dimethylsulfonium bromide (Chemical Abstracts Record No. 63810-34-4); and vinylbenzyl dialkylsulfonium salts such as vinylbenzyl dimethylsulfonium chloride. Examples of the polymerizable cyclic sulfonium salts include 1 - [4- [(ethenylphenyl) methoxy] phenyl] tetrahydro-2H-thiopyranium chloride (Chemical Extracts Register No. 93926-67-1); and vinylbenzyl tetrahydrothio-phenonium chloride, which can be prepared by the reaction of vinylbenzyl chloride with tetrahydrothiophene. Examples of the polymerizable phosphonium salts include salts of 2-methacryloxyethyltri-Ci-C ?alkyl, aralkyl, or aryl-phosphonium salts, such as 2-methacryloxyethyltri-n-octadecylphosphonium halide (Chemical Abstracts Record No. 166740-88-1); salts IjjfHri-C 1 -C 18 alkyl, aralkyl or aryl-vinylbenzylphosphonium such as trioctyl-3-vinylbenzylphosphonium chloride, trioctyl-4-vinylbenzylphosphonium chloride (Chemical Abstracts Record No. 1 51 38-12-4), tributyl chloride 3-vinylbenzylphosphonium, tributyl-4-vinylbenzylphosphonium chloride (Chemical Abstracts Record No., 1491 86-03-8), triphenyl-3-vinylbenzylphosphonium chloride and triphenyl-4-vinylbenzylphosphonium chloride (Chemical Abstracts Record No. 145425-78 -1 ); C3-C18 alkenyltrialkyl, aralkyl, or arylphosphonium salts such as 7-octenyltriphenyl-phosphonium bromide (Chemical Abstracts Record No. 82667-45-6); and salts of tris (hydroxymethyl) - (1-hydroxy-2-propenyl) phosphonium (Chemical Abstracts Record No. 73082-48-1). The polymer containing cationic groups and pendant acid groups can also be prepared from a monomer containing both an acidic group and a strong cationic group. The examples of said monomers include N- (4-carboxy) benzyl-N, N-dimethyl-2 - [(2-methyl-1-oxo-2-propenyl) -oxy] ethanaminium chloride and N- (3-sulfopropyl) betaine -N- metacroyloxyethyl-N, N-di methyl ammonium. It is also possible to prepare a polymer containing cationic groups and acid groups by the addition of the cationic functionality to a polymer already prepared. For example, a polymerizable monomer having a weak acid group can be copolymerized with a non-interfering polymerizable monomer containing an electrophilic group, such as vinylbenzyl halide, or glycidyl methacrylate, to form a polymer having a weak acid group and an elecrophilic group. This polymer then Can be reacted subsequently with a nucleophile such as a ^^ g _-. ^ -_ ^ -: • * > : _ • i &u asg? tertiary amine, pyridine, a dialkyl sulfide or a cyclic sulfide which can displace the halide group or open an oxirane ring to form an onium salt. An example of the formation of a benzyliumium salt is illustrated as follows: Polymer Column Wherein A is a pendant weak acid group; Ar is an aromatic group, preferably a phenyl group; L is a leaving group, preferably a halide group, more preferably a chloride group; and Nu is the nucleophile. In another example of the addition of the cationic functionality to an already prepared polymer, a polymer structure containing pendant acid groups and a tertiary amine or sulfide can be reactivated subsequently with an alkylating reagent such as an alkyl halide to form a polymer that contains acid groups and strong cationic groups: Polymer Column Where RL is an alkylation reagent. Examples of the non-interfering polymerizable monomers include acrylates such as methylacrylate, ethylacrylate, butylacrylate, 2-ethylexyl acrylate, 2-hydroxyethyl acrylate, 2-hydroxypropylacrylate, glycidyl acrylate and allyl acrylate; methacrylates such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, allyl methacrylate, glycidyl methacrylate, 2-hydroxyethyl methacrylate, glycol propylene mono methacrylate and 2-hydroxypropyl methacrylate; aromatic alkenyl hydrocarbons such as 4-methacryloxy-2-hydroxy-benzophenone, 2- (2'-hydroxy-5-methacryloyloxyethylphenyl) -2H-benzotriazole; and aromatic alkenyl hydrocarbons, or C 1 -C 4 alkyl or styrene substituted by alkenyl, preferably styrene chloride, α-methylstyrene, vinyltoluene and vinylbenzyl. Other examples of the species that do not interfere are the C3-C18 perfluoroalkyl methacrylates such as 2- (perfluorooctyl) ethyl methacrylate; C3-C18 perfluoroalkyl acrylates such as 2- [ethyl [(heptadecafluorooctyl) -sulfonyl] amino] ethyl-2-propenoate; and vinylbenzenes of perfluoroalkyl C3-C? 8. (See U.S. Patent No. 4,929,666, column 4, lines 54 through 68, and column 5, lines 1 through 30). Preferably, the mole ratio of the pendant acid groups to the pendant cationic groups is not less than about 0.1, more preferably not less than about 0.2, and more preferably not less than about 0.5; and preferably not greater than about 10, more preferably not greater than about 5 and still more preferably no greater than about 2. The proportion of preferred moles of the structural units formed from the polymerization of the polymerizable monomer does not interfere with the sum of the structural units formed from the polymerization of the polymerizable acid monomer, and the cationic monomer polymerizable (or alternatively, the sum of the acid groups and the pendant cationic groups) is preferably not less than 70:30, more preferably not less than 80:20, and more preferably not less than 85: 1; and preferably not greater than 99: 1, more preferably not greater than 98: 2, and still more preferably not greater than 95: 5. Generally the polymer has a number average molecular weight in the range of about 1000 to about 200,000 Daltons, preferably about 8000 to about 50,000 Daltons. The composition of the present invention can be prepared by the polymerization steps of the acid monomer, the cationic monomer and preferably the monomer that does not interfere in the presence of water and a sufficient amount of an organic solvent for the polymer to form a solution of the polymer formed subsequently. An organic solvent useful for the formation of a water-based solution of the polymer is one that a) forms a single phase with the water in the concentrations used; b) is substantially completely removable from the solution, preferably by rotary evaporation, without completely removing the water; and c) is, in some combination with water, a solvent for the polymer. More preferably, the organic solvent has a boiling point less than 100 ° C. It should be understood that the suitable solvent can be a combination of organic solvents. Examples of the organic solvents useful for the polymerization include ethers, alcohols, esters, nitriles, and ketones, and combinations thereof. An example of the most preferred organic solvents includes - * tA A¿ ft '-? Í? H *** Í »? ** ^^ £ > "- - - - - - - - - - methanol, ethanol, 1-propanol, 2-propanol, 2-methyl-2-propanol, 2-methyl-1-propanol, 1-butanol, and methyl glycol propylene ether, acetonitrile ethyl acetate or combinations thereof Preferably, the amount of organic solvent used in the polymerization step is not less than about 20%, more preferably not less than 30%, and more preferably not less than 40% by weight based on the weight of the water and the solvent, and preferably not more than 80%, more preferably not more than 70% and more preferably not more than 60% by weight based on the weight of the polymer and the water-based solvent. it is generally carried out at elevated temperatures, generally between about 50 ° C and about 100 ° C and in the presence of a polymerization initiator.At the end of the polymerization, a sufficient amount of the organic solvent is removed to form the sol. removal of the solvent This can be done by a number of different means. In one method, the water-based solution containing the polymer is preferably cooled, and the solids content is determined so that a sol with a desired solids content can be easily prepared. The solution can be optionally diluted with water and an organic solvent to maintain a solution and to achieve the desired final concentration of the sol in the subsequent removal of the organic solvent. The organic solvent is characterized by being completely removable, or almost completely removable, without completely removing the water; the simultaneous addition of water and the removal of the organic solvent are preferred. Then a sufficient amount of organic solvent can be removed preferably in vacuo, to form a = ¿J ^^^^^^^^^^^^^^ í | á2 | ^ j g | The solid having a solids content preferably not less than 5%, more preferably not less than 10% and even more preferably not less than 20% based on the weight of the water and the polymer. Both, the organic solvent that was used together with the water to form the polymer solution and the solvent that was added after the completion of the polymerization, (which may or may not be the same solvent), can be removed. Preferably the total amount of organic solvent removed in the ratio step of the solvent is at least 90%, more preferably at least 95%. In this way, the solution is preferably substantially free of organic solvent. In another method of preparation of the sol, the organic solvent can be removed by vapor release. In this technique, it may be desirable to add additional water during the release to adjust the solids content. The water-based sol of the present invention can generally be distinguished from a polymerized aqueous emulsion dispersion (latex) of a polymer having pendant cationic groups and pendant acid groups in different manners. First, unlike latex, the polymer particles dispersed in the sol can be dissolved in a suitable organic solvent (or a suitable water-based solvent such as the solvent used to form the sol), and reconstituted or concentrated to a gel and diluted to re-form the sol, or concentrated to a solid that is then redissolved to form a solution, which can then be reconstituted to form the sol. The suitable organic solvent can be the ^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^ ^^^^^^^^ & ^? ^ A 'same or different than the organic solvent that is used with water to dissolve the polymer. Second, the preferred sol of the present invention can still be further distinguished from the corresponding latex in that the sol is preferably prepared in a substantial absence of any additional surfactant (that is, not more than 0.5%, preferably not more than 0.1%). of an added surfactant) while the latex is preferably prepared in the presence of levels greater than 0.5% by weight of an additional surfactant. The term "additional surfactant" is refers to surfactants other than the cationic groups and pendent acids of the polymer, or to the cationic monomers and polymerizable acids used to prepare the polymer. Third, the average molecular weight of the solution is less than 50,000 Daltons while the latex tends to have a molecular weight that exceeds the 1 00,000 Daltons. One notable advantage of the sol compared to the solution is that the composition with a higher percentage of solids can be prepared without detrimental effects on the viscosity. A higher charge of solids is beneficial because these are more concentrated have properties most desirable physical. While solutions having a solids content greater than 20% are impractical due to their high viscosity, the preferred solids easily flow at a solids content of 20% and even higher. In addition, preferably the sun is substantially absent from organic solvents, except perhaps for a minimum amount that can be added as a conglutinating agent to the final formulation of the coating. A binding agent can advantageously be combined with the sol, particularly if it is necessary to reduce the minimum temperature of formation of the film. The conglutinating agent is an organic solvent, or a combination of organic solvents, which function to produce a clear adherent film. The conglutinating agent is generally an organic liquid of high boiling point preferably having a boiling point higher than 100 ° C. The agent of The conglutination is also compatible with water, that is, soluble in water at the concentrations used, or in combination with another water-soluble conglutination agent used in the concentrations. When the conglutinating agent is used, the aggregate amount is preferably not more than 20% by weight, more preferably not greater than 10% by weight. weight, and even more preferably no greater than 6% by weight based on the weight of the sol and the conglutinating agent. Preferred conglutinating agents include ghcol ethers, dibasic esters, nutrils, carbonates, sulfoxides, amides, pyrrolidones and combinations thereof. Examples of the most preferred conglutinating agents include benzonitrile, dimethisuccinate, dimethylglutarate, dimethyladipate, glycol dipropylene dimethyl ether, propylene glycol n-butyl ether, glycol dipropylene n-butyl ether, propylene glycol n-propyl ether, glycol propylene methyl ether acetate, dimethyl ether dipropylene glycol, dimethyl formamide, dimethyl sulfoxide, propylene carbonate, N-methyl-2-pyrrolidone, ethylene glycol phenyl ether, diethylene glycol methyl ether, n-butyl ether ? ^^^^^^^^^^^^^^^^ j ^^^^^^^^^^^^^^^ and ^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^^ ^^^^^^^^^^^^^^^^^ and ^ of diethylene glycol, ethylene glycol n-butyl ether, propylene glycol n-propyl ether, propylene glycol phenyl ether, methyl ether dipropylene glycol, tripropylene glycol methyl ether, dipropylene glycol methyl ether, and propylene carbonate and combinations thereof. I The conglutination agent can be added at any time during the sun preparation process, including during the polymerization step. If the agent is added during the polymerization step, a sufficient amount of the agent is advantageously recovered for both a) forming the sun; and b) maintain the conglutination capabilities. The coatings described are therefore quite resistant to water, but can be easily removed with a mixture of solvents or a combination of acid and solvent such as a combination of water and an organic solvent, more preferably, water and 1-propanol. These coatings can be made substantially permanent, ie, resistant to removal by organic solvents as well as water-based acids or bases, in at least three ways. First, an effective amount of a crosslinking reagent, such as melamine resin, or epoxy resin, or a diamine, can be added to react with the functional groups in the polymer to form covalent crosslinks; second, a polymerizable acid such as acrylic acid or methacrylic acid can be added to the composition, which can then be subsequently cured; and third, the polymer can be designed to include a pendant functional group that can cross-link such as an ethylenically or acetylenically unsaturated polymerizable group, a sulfonium group, an epoxy group, or 2-oxazoline. A * v - Aa $ «^ - a *.

Example of a preparation of a polymer containing ethylenic unsaturation is illustrated as follows: Polymer Column Wherein Nu- = is a nucleophile (such as a tertiary amine or a sulfide) containing ethylenic unsaturation; and A, Ar, and L are as described above. In the previous illustration, a polymerizable acid monomer, a polymerizable aryl halide, preferably benzyl chloride vinyl monomer and a polymerizable non-interfering are copolymerized to form a polymer having acid groups and benzyl halide groups. The polymer is then reacted with a nucleophile containing ethylenic unsaturation to impart cross-linking capabilities to the polymer. An example of a suitable nucleophile with ethylenic unsaturation is the following compound: In the case where the polymerizable polymeric acid is used as the crosslinking agent, it is preferred that it be added to the inner salt to form a When the composition including a crosslinking agent or a substrate, the coating is preferably allowed to harden before means such as free radical initiation or heating or UV radiation are used to promote cross-linking. It should be understood that the sol of the present invention can be used in 5 combinations with solutions or lates which contain similar polymers to form useful films and coatings. In addition, the composition may include enhancing additives such as fillers properties, pigments, leveling agents, viscosity modifiers, wax dispersions, antioxidants or combinations thereof. 10 The compositions of the present invention can be used, for example, to cover or protect floors, automobile parts, human skin, covers countertops, wood, furniture, and the interiors and exteriors of houses. The compositions may also include additives such as pigments, dyes, fungicides, or bactericides. The following examples are for illustrative purposes only and are not intended to limit the scope of the present invention. All percentages are by weight unless otherwise indicated. Example 1 - preparation of a solution of 20% by weight. To one liter reaction vessel, water (30 g), 1-20 propanol (30 g), methyl methacrylate (6.3 g), methacrylic acid (0.3 g), butylacrylate (2.6 g), and M-Quat ( 2.6 g chloride, 2 - [(methacryloyloxy) ethyl] trimethylammonium, as an active water to 74% obtained from Bimax, Inc.). The mixture was heated with stirring at a temperature of 80 ° C under nitrogen, then four liquid streams were added in a simultaneous to the container. The currents were added during ^^^^^^^^^^^^^^^^^^^^^^ _ ^^^^^^^^ _ ^^ ______________ ^^^^^^^^^^^ ^^^^^^^^^^ a period of 5 hours using 00-syringes 1 ml operated by a syringe pump Sage Instruments model 355 (Cole-Palmer Instrument Company). After the addition was completed, the reaction was maintained at a temperature of 80 ° C for an additional hour. The contents of the four streams are shown in Table 1. a2,2'-azobis (2,4-dimethylpentane nitrile) obtained from E. l. duPont de Nemours & Co., Inc. The polymer solution was cooled and the solids percentage was determined to be 24.8% using a Labwave 9000 Solids Moisture Analyzer (marketed by CEM Corp., Matthews, N.C.). the viscosity of the sample was 227 cps. A portion of the polymer solution (200 g) was diluted with 1-propanol (49.6 g) and water (49.6 g). The diluted solution was thoroughly mixed, and then placed in a Caframo mixer (marketed by Fisher Scientific) at 1200 rpms. The sample was further diluted with water (196.8g) to produce a solution with a solids content of 10%. This dispersion was placed in a rotary evaporator to remove substantially all 1-propanol for form a sol that contains 25% solids, which had a viscosity of 26.6 cps.

Claims (10)

1 .- A composition comprising a water-based polymer solution having a structure containing pendent cationic groups and 5 pendant acid groups, whose solution is prepared by the steps of: a) the formation of a solution of a polymer containing pendant cationic groups and pendant acid groups in a water-based solvent for the polymer, whose water-based solvent contains a 10 first organic solvent; Y b) the removal of a sufficient amount of the first organic solvent from the solution to form a composition characterized by being able to be reversibly dissolved and reconstituted by the 15 addition and removal of a second organic solvent.

2. - The composition as described in the Claim 1, wherein the polymer additionally contains structural units formed from the polymerization of a non-interfering monomer, the Which is an acrylate, a methacrylate, a C 3 -C 8 perfluoroalkyl acrylate or methacrylate, an aromatic alkenyl hydrocarbon, an C 1 -C alkylstyrene and wherein the proportion of the structural units formed from the polymerization of the monomer that does not interfere with the sum of cationic groups and pendant acids is less than 25 70:30 and no greater than 99: 1. w1iiffiA & ---- > - ^ ^^^ & tea & ^ & ^^. .___ a___ _-_-. - .. ".., ^ -_._ to ____ A ____ M ___--.

3. - The composition as described in Claim 1 or 2, which includes in step (b) a simultaneous addition of water, and wherein the first organic solvent has a boiling point lower than 1 00 ° C. 5

4.- The composition as described in any of Claims 1 to 3, wherein the aqueous-based solvent contains methanol, ethanol, 1-propanol, 2-propanol, 2-methyl-2-propanol or 2-methyl-1-propanol, ethyl acetate or acetonitrile or a combination thereof at a level of not less than 10% by weight and not more than 80% by weight based on the weight of the polymer and the aqueous-based solvent.

5. - The composition as described in any one of claims 1 to 4, wherein the pendant cationic groups include quaternary ammonium groups, and the pendant acid groups include carboxylic acid groups, and the proportion of the carboxylic acid groups to the quaternary ammonium groups is in the range of 0.1 to 10.

6. - The composition as described in any of the 20 claims from 1 to 5, wherein the pendant cationic groups include, structural units formed from the polymerization of 2 - [(methacryloyloxy) ethyl] trimethylammonium chloride, the pendant acid groups include structural units formed from the polymerization of methacrylic acid or acrylic acid or a combination thereof, and the 25 structural units formed from the polymerization of the groups which do not interfere include methylmethacrylate or 2-ethyl-ex-acrylate, or a combination thereof provided that the proportion of the structural units formed from the polymerization of the groups which do not interfere with the sum of the pendant acid groups and pendant cationic groups is less than about 85: 15 and not more than about 98: 2, and wherein the first organic solvent is the same as the second organic solvent.

7. - The composition as described in any of the Claims 1 through 6, which additionally includes a conglutinating agent which is an organic liquid that is miscible in water in the proportions used and which has a boiling point greater than about 100 ° C.

8. The composition as described in Claim 7, wherein the conglutinating agent comprises a glycol ether or a dibasic ether or a combination thereof in a concentration not greater than 10% by weight based on weight of the sun and the conglutination agent. 20 9.- The composition as described in any of the

Claims 1 through 8, wherein at least one of the following conditions is met: a) the sun does not contain any additional surfactant; or b) the sun contains a substantial absence of any organic solvents.

10. - A method for coating a substrate which comprises the step of applying to a surface of the substrate a composition containing a conglutination agent compatible with water and an aqueous sol of a polymer having a structure containing pendant cationic groups and groups Hanging acids, where the sun is prepared by the steps comprising: a) the formation of a water-based solution of the polymer, whose solution contains an organic solvent; b) removing a sufficient amount of the organic solvent from the solution to form a composition having a minimum solids content such that the viscosity of the sol is less than half the viscosity of the solution having the same content of solids; Where the conglutinating agent is an organic liquid that has a boiling point higher than 100 ° C.