MXPA99001504A - Water-based sulfonated polymer compositions - Google Patents

Abstract

A method for the preparation of sulfonated polymer compositions wherein water dispersible isocyanate-terminated polyurethane prepolymers are reacted in the presence of aqueous polyvinyl dispersions which may contain active hydrogen atoms. The invention is further directed to a water-based sulfonated polyurethane polyvinyl hybrid latex wherein a sulfonated polyurethane is used as a seed for the polymerization of ethylenically unsaturated monomers and a method for preparing the same. The inventive compositions develop interpenetrating polymer networks or may form core-shell type structures, and are characterized as having enhanced mechanical and adhesion properties.

Description

WATER-BASED SULPHONATED POLYMER COMPOSITIONS DESCRIPTION OF THE INVENTION This invention relates to water-based polymers, specifically to a method for the preparation of water-based sulfonated polymer compositions having improved mechanical and adhesion properties. There are several patents that describe the preparation of sulfonated water-based polymer compositions: U.S. Patent No. 5,334,690 (Hoechst Aktiengesellschaft) describes sulfonated water-based polyurethane-urea polymers, which can be combined with and in general are compatible with other aqueous polymer dispersions. U.S. Patent No. 4,888,383 (E.l.

DuPont De Nemours and Company) describes a process in which water-based polyurethane-urea-modified acrylic polymers are prepared by reacting amine and / or polyacryl functional polymers of hydrazide with polyurethane prepolymers terminated in isocyanate. US Patent No. 4,491,646 (Ashland) discloses adhesives wherein polyvinyl functional polymers with hydroxyl are mixed with polyfunctional isocyanates dispersible in water.

Other related patents include U.S. Patent No. 5,371,133 (National Starch), U.S. Patent No. 5,200,463 (Huels), U.S. Patent No. 5,204,404 (DuPont), U.S. Patent No. 5,173,526 (Air Products &Chemicals, Inc.) and U.S. Pat. North American No. 5,071,904 (PPG). The present invention describes water-based sulfonated polymer compositions comprising: A) at least one sulfonated water-based polyurethane-urea polymer comprising: 1) at least one polyisocyanate; and 2) at least one sulfonated polyol polyester, wherein the sulfonate groups are present in the form of alkali metal salts; B) at least one aqueous polyvinyl dispersion comprising: 1) at least one ethylenically unsaturated monomer; 2) and optionally, at least one radically reactive protective colloid comprising active hydrogen atoms; and optionally C) at least one sulfonated polyurethane-vinyl polymer composition, comprising the reaction of: 1) at least one isocyanate-terminated polyurethane prepolymer comprising: a) at least one polyisocyanate; and b) at least one polyester polyol. sulphonated, wherein the sulfonate groups are present in the form of alkali metal salts; with 2) a dispersion of aqueous polyvinyl comprising; a) at least one ethylenically unsaturated monomer; and optionally, b) at least one radically reactive protective colloid comprising active hydrogen atoms. Surprisingly, the sulfonated polymer compositions have improved mechanical and adhesion properties and exhibit stability at pH values greater than about 2.0. It is summarized that some of these unique properties can be attributed to the development of the interpenetration of polymer networks and the character of the sulfonate charged in the polyol segment of the polyurethane polymer. The compositions of the invention are useful as adhesives, binders, coatings and primers on any substrate including synthetic paper, wood, metals, concrete, glass, cloth and polymer and are useful in applications including fiberglass sizing, woodworking, automobiles, film lamination and in, the manufacture of shoes. In another aspect, the present invention describes a method for the preparation of sulfonated polymer compositions, wherein isocyanate terminated polyurethane prepolymer is dispersed in aqueous polyvinyl dispersions, which may contain primary amines, secondary amines, primary hydroxyl groups, secondary hydroxyl, and formamide groups. The method comprises: A) forming an isocyanate-terminated polyurethane prepolymer dispersible in water by reacting: 1) at least one polyisocyanate; and 2) at least one sulfonated polyol polyester, wherein the sulfo groups are present in the form of alkali metal salts; B) forming an aqueous polyvinyl dispersion through the free radical polymerization; 1) at least one ethylenically unsaturated monomer; and optionally, 2) at least one free radically reactive protective colloid comprising active hydrogen atoms; and then C) dispersing the product of A) in B). In another aspect, the present invention describes a sulfonated water-based polymer composition and a method for making the same through seed emulsion polymerization. The composition comprises the reaction product of: a) At least one sulfonated polyurethane dispersion; b) at least one pre-emulsion of an ethylenically unsaturated aqueous monomer comprising at least one ethylenically unsaturated monomer; and c) an initiator. The method for preparing the same comprises the steps of: a) forming an aqueous pre-emulsion comprising at least one pre-emulsion of ethylenically unsaturated monomer comprising at least one ethylenically unsaturated monomer and optionally at least one surfactant, and b) reacting the aqueous pre-emulsion with at least one sulfonated polyurethane dispersion optionally in the presence of an initiator solution and optionally in the presence of a reducing solution. In another aspect, the present invention discloses a polyurethane / polyvinyl hybrid latex, and a method for making the same through seed emulsion polymerization. The hybrid latex comprises the seed polymerization reaction of: a) at least one sulfonated polyurethane dispersion, the polyurethane serving as a seed; b) at least one pre-emulsion of an ethylenically unsaturated aqueous monomer, comprising at least one ethylenically unsaturated monomer, and c) at least one free radical initiator. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a graph showing the distribution of seed polyurethane particle (dotted line) as a function of the particle distribution of the final hybrid latex (solid line) for latex (water-based sulfonated polymer composition) prepared in Example 6. Figure 2 is a graph showing the particle size distribution of seed polyurethane (dotted line) as a function of the final hybrid latex particle distribution (FIG. solid line), for the latex (sulfonated water-based polymer composition) prepared in Example 7.

The sulfonated polymer compositions have improved mechanical and adhesion properties compared to their corresponding water-based sulfonated polyurethane-urea polymers, aqueous polyvinyl dispersions and their simple mixtures. For the purposes of the present application, polyvinyl dispersions include dispersions of addition polymerization products of ethylenically unsaturated monomers including, but not limited to, methacrylate monomers. Polyurethane also refers in the present application to a polymer that contains more than one urethane group and is intended to include polyurethanes containing urea groups as well as (polyurethanes-ureas). It is summarized that some of these unique properties can be attributed to the formation of interpenetrating polymer networks. The term "interpenetrating polymer network" is defined as an interlaced and / or semi-entangled system comprising at least two unequal or different polymers. IPNs are also described in "Handbook of Adhesives", Irving Skeist, 3a. edition, chapter 1, page 18, Van Nostrand, NY, 1990. For the purposes of the present application "hybrids" means a polymer composed of two or more different polymers. The different polymers may or may not be covalently linked.

In the present invention, when isocyanate terminated polyurethane prepolymers are dispersed in aqueous polyvinyl dispersions, which may contain active hydrogen atoms such as primary amines, secondary amines, primary hydroxyl groups and secondary hydroxyl groups, the dispersions of polyurethane prepolymer Isocyanate-terminated interact with aqueous polyvinyl dispersions to form IPN and interlaced networks. The frequency of said interactions can be influenced by the amount of isocyanate and active hydrogen atoms present in the respective polymer dispersions. It is possible to increase the interlacing density using a structured aqueous polyvinyl dispersion, where active hydrogen atoms are distributed on the surface of the particle. A structured particle can be generated when ethylenically unsaturated monomers, containing active hydrogen atoms, are added at the end of the free radical emulsion polymerization process. It is believed that said particle morphology improves the collision frequency of the isocyanate / active hydrogen atom reaction to increase the crosslinking density of the composition. The dispersed particles may contain a complex mixture of polymers consisting of sulfonated polyurethane-urea polymers, polyvinyl polymers and sulfonated polyurethane-vinyl polymers. Complex particle mixtures can be formed when substantially unequal or substantially different polymers diffuse and interact or intertwine with adjacent particles. Such diffusion processes can generate particles having polymers within the particle that are different when compared with polymers on the surface of the particle. Examples include particles having substantially polyvinyl based polymers on the surface of predominantly polyurethane-urea based or substantially polyurethane-urea based polymers on the surface of predominantly polyvinyl based particles. Said surface layers may be continuous or non-continuous and may be several in thickness. If a particle surface layer has a substantial thickness, as long as it is continuous, then the particle approaches a core-shell type structure. The isocyanate terminated polyurethane prepolymers of the present invention can be formed using onisocyanates and polyisocyanates. The isocyanates can be linear aliphatics, cyclic aliphatics, aromatics and mixtures thereof. Examples of commercially available polyisocyanates include Vestanat® IPDI which is isophorone diisocyanate from HÜLS America Inc. (Psicataway, NJ), TMXDT® which is tetramethylxylene diisocyanate from Cyanamid (Wayne, NJ), Luxate® HM which is diisocyanate from hexamethylene from Olin Corporation (Stamford, CN), diphenylmethane diisocyanate from Upjohn Polymer Chemicals (Kalamazoo, MI), Desmodur® which is 4,4'-dicyclohexylmethane diisocyanate from Bayer Corporation (Pittsburg, PA) and toluene diisocyanate (TDI) ). Preferred diisocyanates are hexamethylene diisocyanate, isophorone diisocyanate and mixtures thereof. If desired, small amounts of polyisocyanates, which have an isocyanate content greater than 2.1, can be used. In addition, modified polyisocyanates, which are prepared from hexamethylene diisocyanate, isophorone diisocyanate and toluene diisocyanate, can also be used. Said polyisocyanates may have functionalities including urethanes, uretdiones, isocyanurates, biurets and mixtures thereof. The polyester polyol component used in the preparation of the isocyanate-terminated polyurethane prepolymer may have hydroxyl number, as determined by ASTM designation E-222-67 (Method B), on the scale of about 20 to about 140, and preferably about 40 to 110. The polyols can be formed with components such as diacids, diols, sulfonates, diols and diacid sulfonates. Said polyols and their preparation are further described in U.S. Patent No. 5,334,690, incorporated herein by reference. The preferred sulfonated polyester polyols are based on the monosodium salt of 5-sulfoisophthalic acid, adipic acid and 1,6-hexanediol and / or diethylene glycol. It is believed that the sulfonate character, which is present in the polyol segment improves the dispersibility of the polymer and the stability thereof at a reduced pH. Optionally, non-sulfonated polymeric diols can be used in combination with the sulfonated polyester polyols. Such polyols may have hydroxyl numbers in the range from about 20 to about 140, and preferably from about 40 to about 110. The non-sulfonated polymer polyols may include polyester polyols, polyether polyols, polycarbonate polyols, polyurethane polyols, polyacetal polyols, polyacrylate polyols, polycaprolactone polyols, polyesteramine polyols, polythioethers polyols, and mixtures thereof. Alkylene diols can also be used in the preparation of finished polymers of isocyanate. The alkylene diols may have hydroxyl numbers in the range of about 130 to about 1250, and preferably about 950 to 1250. Preferred alkylene diols include 1,4-butanediol, 1,6-hexanediol and 2-methyl-1, 3-propanediol and may be present in the isocyanate terminated polyurethane prepolymer on a scale from about 0.1 wt% to about 10.0 wt%, and preferably about 0.5 wt% to 5.0 wt%, based on 100 parts of total pre-polymer solids. Higher functional polyols can be used in the preparation of polyurethane-urea polymers. Suitable examples include glycerol, trimethylolpropane, 1,2,4-butane triol, 1,2,6-nexane triol and mixtures thereof. The preferred top functional polyol is trimethylolpropane. Said polyols may be present in the range of about 0.1 wt% to about 1.0 wt%, and preferably about 0.3% to about 0.7 wt%, based on 100 parts of the total isocyanate-terminated polyurethane prepolymer solids. Optionally, dihydroxy carboxylic acids can be used when preparing the isocyanate-terminated polyurethane pre-polymer. A preferred dihydroxy carboxylic acid is dimethylolpropionic acid. The dihydroxycarboxylic acid component may be present in the range from about 0.05 wt% to about 1.0 wt%, and preferably from about 0.2 wt% to about 0.5 wt%, based on 100 parts of solid from above. Total polyurethane polymer. The neutralization of the dihydroxy carboxylic acid groups can be achieved with compounds such as alkali metal hydroxyl, organic tertiary amines, ammonia and mixtures thereof. Preferred neutralizing agents are sodium hydroxide and triethylamine. The conversion of the acid groups to ionic groups (salts) can be achieved before, or at the same time, that the isocyanate terminated polyurethane prepolymer has been dispersed in the polyvinyl dispersion mixture. The isocyanate-terminated polyurethane prepolymer is prepared by reacting a stoichiometric excess of polyisocyanate with said polyol components. The reagents are in such proportions that the resulting isocyanate percentage can be in the range of about 1.0% by weight to about 10.0% by weight, and preferably about 2.0% by weight to 5.0% by weight, based on 100 parts of the polyurethane pre-polymer solids finished in total isocyanate. The prepolymers can be processed at temperatures in the range of about 30 ° C to about 110 ° C, and preferably around 65 ° C to 85 ° C. In addition, small amounts of catalysts can be used to accelerate the hydroxy / isocyanate reaction. The catalysts may be present in the range of about 0.05 wt% to about 2.0 wt%, and preferably about 0.13 wt% to about 0.15 wt%, based on 100 parts of finished polyurethane pre-polymer solids in total isocyanate, one example includes Metacure ™ T-12 which is an organic tin compound from Air Products and Chemicals, Inc. (Allentown, PA). The ethylenically unsaturated monomers can include monounsaturated monomers, polyunsaturated monomers and mixtures thereof. Examples include methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate, n-propyl acrylate, iso-propyl acrylate, methyl methacrylate, butyl methacrylate, vinyl acetate, vinyl propionate, ethers vinyl, ethylenically unsaturated fumerate, ethylenically unsaturated maleate, styrene, acrylonitrile, acrylamides, butanediol diacrylate, hexanediol diacrylate, ethylene glycol dimethacrylate, trimethylol propane triacylate and pentaerythritol triacylate. Ethylenically unsaturated monomers containing anionic and / or ionic groups can be used. Examples of such monomers include acrylic acid, methacrylic acid, fumaric acid, crotonic acid, itaconic acid, mesaconic acid, maleic acid, citraconic acid, and / or their corresponding ionic groups. Such monomers may be in the range of about 0.1 wt% to about 25.0 wt%, and preferably about 0.1 wt% to about 10.0 wt%, based on 100 parts of total composition solids. Ethylenically unsaturated monomers containing active hydrogen atoms can also be used. The term "active hydrogen atoms" refers to hydrogens that display activity against the Zerewitinoff test as described by Kohlerin, J. Am Chem. Soc., 49.3181 (1927). Examples include hydroxyethyl acrylate, allyl alcohol, allyl amine, N-methylol acrylamide, monoacrylic acid esters of glycols, monoacrylic acid of glycols, itaconic acid and methyl 3-aminocrotonate. Functional amine and hydroxyl protective colloids can be used to prepare the aqueous polyvinyl dispersion of the present invention. Suitable examples include the water-dispersible polyvinyl alcohol-copoly (vinyl amine) polymers described in EP 0599245 assigned to Air Products and Chemicals, Inc.

(Allentown, PA). Said protective colloids may have an amine content in the range of approximately 0.5 meq. amine / grain at approximately 3.5 meq. amine / gram, and preferably from about 10 meq, amine / gram to about 3.0 meq amine / gram. The number average molecular weight can be on the scale of approximately 10,000 grams / mol. at about 350,000 grams / mol., and preferably about 30,000 grams / mol. to approximately 250,000 grams / mol. Such colloids may be present on a scale of about 0.1 wt% to about 20.0 wt%, and preferably about 0.5 wt% to about 5.0 wt%, based on 100 parts of total polyacrylic solids. It is assumed that grafting reactions occur during the emulsion polymerization process. The graft copolymerization process is further described in "Polyvinyl Alcohol Developments", edited by C.A. Finch, John Wiley & Sons, New York, 1992, p. 449-453. Specialty monomers may also be incorporated into the aqueous polyvinyl dispersions and include the amino / organosilane coupling agents described in U.S. Patent No. 4,745,028 (PPG) and U.S. Patent No. 5,236,982, (Owens-Conrning), the monomers of adhesion in functional numbers of imidazolidinone described in U.S. Patent No. 5,496,907, (HB Fuller Co., St. Paul, MN) and the monomer VinamerDEF, which is N-ethynylformamide from Air Products Chemicals, Inc. (Alletown, PA ). When Vinamer EF monomers are incorporated into the aqueous polyvinyl dispersions, the attached formamide group can be hydrolyzed to a primary amine using catalysts such as bases or acids including sodium hydroxide, hydrochloric acid and sulfuric acid. The resultant functional amine polyvinyl can then be used as a reactive component in the process of the present invention. Aqueous polyvinyls can be formed using free radical polymerization materials and processes known in the art. For example, the free radical initiators, further used in the polymerization process, can be water soluble, oil soluble mixtures, or mixtures thereof. Examples include hydrogen peroxide, sodium persulfate, potassium persulfate, ammonium persulfate, 2,2-azobis (2,4-dimethylpentanenitrile), 2,2-azobis (2-methylpropanentryl), and mixtures such as hydroperoxide. -butyl, Fe-EDTA and isoascorbic acid. Such initiators may be present in amounts of about 0.05% by weight to about 1.5% by weight, and preferably about 0.1% by weight to about 0.5% by weight, based on 100 parts of total solids. Oxidation agents can also be used independently or in combination with reducing agents such as sodium formaldehyde sulfixilate, ferrous salts, sodium dithionite, sodium acid sulfite, sodium sulfite and sodium triosulfate. The redox catalysts may be present in amounts, from about 0.05 wt% to about 1.5 wt%, preferably about 0.1 wt .-% to 0.5 wt%, based on 100 parts of total solids. The ethylenically unsaturated monomers are polymerized using free radical polymerization techniques known in the art. Free radical initiators can also be added all at once, slowly for a while or as a partial initial charge and the rest being added slowly over time. The free radical polymerization can be conducted at temperatures on a scale from about 5 ° C to about 85 ° C, and preferably around 25 ° C to about 80 ° C. The water-based sulfonated polymer compositions of the present invention are formed using a method, wherein isocyanate-terminated polyurethane prepolymers are dispersed in an aqueous polyvinyl dispersion, which may contain primary amines, secondary amines, hydroxyl groups primary, secondary hydroxyl groups and formamide groups. It is also possible to disperse the isocyanate-terminated polyurethane prepolymer in water and then immediately mix it with an aqueous polyvinyl dispersion. Optionally, the aqueous polyvinyl dispersion can be added to a net isocyanate terminated polyurethane pre-polymer or dispersed in water. The unequal polymers are conveniently combined at a temperature in the range from about 25 ° C to about 85 ° C, preferably around 45 ° C to about 75 ° C. If amine-functional aqueous polyvinyl dispersions are used, the polyvinyl components can be mixed using an amine isocyanate active hydrogen equivalence ratio in the range of about 1:10 to about 10: 5, and preferably about 1: 5 to about 5: 1. If desired, water-soluble compounds containing primary and / or secondary amines can be reacted with the polymer blend of the invention. Suitable examples include monoethanolamine, ethylene diamine, diethylene triamine and ammonia. Water-based sulfonated polymer compositions can have viscosities at about 10 mPa.s to about 1,000 mPa.s, and preferably about 10 mPa.s to about 500 mPa. s. The particle size distribution can be monomodal and multimodal and will generally have a mean diameter on the scale of about 0.01 microns to about 2.0 microns. The water-based sulfonated polymer compositions may have a solids content in the range from about 20% by weight to about 70% by weight, and preferably about 35% by weight to 55% by weight of the total composition. The dried sulfonated polymer compositions can have single or multiple glass transition temperatures (Tg.) In the range from about -100 ° C to about + 200 ° C. The present invention is also directed to a sulfonated water-based polymer composition, which can be used, among other things, for sizing glass fiber and a method for making same. The water-based sulfonated polyurethane-polyvinyl hybrid latex of the present invention comprises the reaction product of at least one sulfonated polyurethane dispersion, at least one pre-emulsion of an ethylenically unsaturated aqueous monomer comprising at least one ethylenically active monomer unsaturated and at least one free radical initiator, such as those described above. The invention is also directed to a water-based sulfonated polymer composition comprising particles, the particles comprising a core and a surface wherein the core and the surface comprise substantially different polymers, the core comprising at least one selected polymer of the group consisting of sulfonated polyurethane polymers and sulfonated polyurethane-urea polymers and mixtures thereof, the surface comprising predominantly polyvinyl polymers. The composition can be formed from the free radical seed emulsion polymerization of at least one ethylenically unsaturated monomer in the presence of a sulfonated polyurethane or polyurethane-urea dispersion, the polyurethane serving as a seed. The sulfonated polyurethane dispersions are like those described in US Pat. No. 5, 608,000 (Duan et al.), U.S. Patent No. 5,610,323 (Duan et al.) And are suitable for use in the present invention. Two sulfonated polyurethane dispersions which are embodiments of the above inventions, NP-4062-M or NP-4073, both are produced by H.B. Fuller Company, are particularly suitable for use in the present invention although other sulfonated polyurethane dispersions may be used as well as include sulfonated polyurethane-urea dispersions. The aqueous ethylenically unsaturated monomer will preferably be selected from acrylate monomers, methacrylate monomers, methacrylic monomers, vinyl monomers, allylic monomers, acrylamine monomers or mixtures thereof. Examples include methyl acrylate, ethyl acrylate, isobutyl acrylate, n-propyl acrylate, iso-propyl acrylate, butyl methacrylate, hexanediol diacrylate, ethylene glycol dimethacrylate, trimethylol propane diacrylate and pentaerythritol triacrylate and mixtures thereof. Preferably, the emulsion comprising the monomer will comprise methyl methacrylate, n-butyl acrylate, hydroxyethyl methacrylate, and mixtures thereof. However, any of the ethylenically unsaturated monomers mentioned above such as ethylenically unsaturated monomers comprising anionic and / or ionic groups, or ethylenically unsaturated monomer containing active hydrogen atoms, may also be used. A suitable surfactant such as Pluronic L64 (manufactured by BASF) or a combination of surfactants can be used to prepare the pre-emulsion. In one embodiment, the ratio of sulfonated polyurethane solids to polyvinyl solids is from about 9: 1 to about 1: 9. Preferably, the ratio is from about 4: 1 to about 1: 4, and most preferably the ratio from about 4: 1 to about 2: 1. The present invention is also directed to a water-based sulphonated polyurethane-polyurethane hybrid latex comprising polyurethane-polyvinyl particles wherein the average particle size is at least 200 nm.

Water-based sulfonated polymer compositions formed through seed emulsion polymerization are characterized by high resistances of shear stress of at least about 24605 kg / cm2 (350 psi). The present invention is also directed to a method for preparing the aforementioned polyurethane-polyvinyl latex hybrid. The method comprises the steps of forming an aqueous pre-emulsion comprising at least one ethylenically unsaturated monomer, the pre-emulsion comprising at least one acrylate and optionally a surfactant and reacting the pre-emulsion with at least one Sulfonated polyurethane dispersion in the presence of at least one radically free initiator. The aqueous polyvinyl pre-emulsion can be formed by dispersing ethylenically unsaturated mohomers in water, with a surfactant and stirring the mixture. The dispersion of the polyurethane-polyvinyl latex is then formed by adding an initiator solution such as t-butyl acid peroxide, a reducing solution such as hydrosulfite and the pre-emulsion to a polyurethane dispersion. Alternatively, the initiator may already be present in the pre-emulsion or in the polyurethane dispersion. The mixture is allowed to react for a period at a temperature between 50 ° C and 100 ° C, preferably at 65 ° C. The characteristics of the water-based sulfonated polymer compositions can be modified through the addition of compounds including surfactants, defoaming agents, coalescence aids, fungicides, bactericides, polyfunctional crosslinking agents, plasticizers, thickening agents, fillers, pigments, reactive pigments, dispersing agents for pigments, colors, perfume type materials, UV stabilizers, sequestering agents, waxes, oils, flame retardants, and organic solvents. Said materials can be introduced at any stage of the production process. The present invention is further illustrated through the following examples. EXAMPLES In the examples, the following test methods were used. Stress Resistance and Elongation The polymer dispersions were cast to dry films generated having a thickness in the scale from about 508 microns (20 mils) to about 1016 microns (40 mils.). Type "dog bones" of type V were cut with a die of Dewes Gu bs and conditioned for at least 24 hours in an environment having a relative humidity of 50% at 23 ° C. The samples were operated using ASTDM-638 at a head speed of 5.0 cm / min. Resistance to Shear Stress: The polymer dispersions were coated in steel, acrylonitrile-butadiene-styrene (ABS) and glass, then dried for 24 hours. Similar substrates were then matched using manual pressure after being heat activated at 70 ° C for 30 minutes. The samples, which have a joint area of 1.27 x 2.57 cm (0.5 x 1.0 inches), were operated using ASTM-D-1002 at a head speed of 1.27 cm / min. Peel Resistance: Peel strength was measured as follows. A pre-cut sheet (26.67 x 32.38 cm) of polished, compressed PVC, with a thickness of 254 microns (10 mil) was cleaned with isopropyl alcohol and placed on a glass or aluminum plate containing a small amount of isopropyl alcohol. The excess isopropyl alcohol was removed to produce a good seal. The exposed PVC surface is cleaned with isopropyl alcohol. A film of adhesive, stocked from a film applicator set at 127 microns (5 mil), was cast on slit onto the PVC sheet according to the specification of ASTM D32-87. The adhesive was allowed to dry at room temperature. A second PCV sheet, similarly cleaned as the first sheet, was applied onto the first coated PVC sheet. The PVC adhesive sandwich was cut into 2.54 cm (1 inch) strips and allowed to dry for 2 hours. The strips were placed in a heat sealer with the uncoated PVC in contact with the top plate, the upper stage having been preheated to 87.7 ° C (190 ° F) and with a pressure setting of 3,519 kg / cm2 (50 psi). After a resting time of 30 seconds, the temperature at the junction line of 71.1 ° C (160 ° F). A minimum of six joints per strip was heat sealed with a total bond area of 2.54 x 17.78 cm (1 by 7 inches) with 3.81 cm (1.5 inches) of joint at both ends. The joints were allowed to age at room temperature for 1 to 2 hours and 1 week before the test. The test was performed on the Thwing Albert Intellect 500 with a head speed of 30.48 cm (12 inches) per minute, and a pre-release of 2.54 cm and 7.62 cm (1 to 3 inches) of recorded detachment. Resistance to Turning Cutting Effort The sample was placed as a coating on the glass and allowed to dry overnight. The joint area was 1.61"x 6.45 cm2 0.5x1.0 in2.) The spin shear test was maintained at 71.1 ° C (160 ° F) for 30 minutes.The shear shear strength afterwards was measured using ASTM D-1002 with a head speed of 1.27 cm / minute (9.5 in / minute) The measurement was made under an ambient of 505 relative humidity at a temperature of 23 ° C. Example 1: This example describes the preparation of a water-based sulfonated vinyl polyurethane polymer composition The composition and its properties are compared to its corresponding polymer components Compound 1 Compound 1A is an aqueous polyvinyl dispersion prepared with a reactive emulsifying agent which it is polyvinyl alcohol / polyvinyl / amine copolymer (PVOH-PVAM) by Air Products & Chemicals, Inc. (Allentown, PA). (1) Reactor Load Grams PVOH / PVAM (6% vinyl amide, medium M.W). 1 . 50 Deionized water / acetic acid 350. 00 Acetic acid 0. 30 (2) Pre-emulsion Methyl methacrylate 155.00 N-butyl acrylate 145.00 Methacrylic Acid 3.90 Thiolacetic Acid 0.10 (3) Delayed Feeding of T-Det Tensoactive Agent 0-407 of Harcros 7.50 Deionized water 30.00 (4) Starter feed T-butyl hydroperoxide 1.28 Deionized water 20.00 (5) Reducer feed Formaldehyde-sodium sulfoxide 0.92 Deionized water 20.00 A reactor charge (1) was added to a reactor equipped with an agitator, thermometer, condenser and nitrogen flea. The mixture was heated to 65 ° C and stirred for minutes. While maintaining the reaction temperature at 65 ° C, the pre-emulsion (2) and the surfactant feed (3) were added over a period of 3 hours. The initiator feed (4) and the reducer feed (5) were added over a period of 3.5 hours. Once all the materials were added, the dispersion was heated for an additional 30 minutes. The polymer had a solids content of 33.2% and a pH of 2.65. Compound IB Compound IB is a sulfonated water-based polyurethane-urea polymer. A reactor was charged with 4.5 grams (0.099 equivalence of hydroxyl) of 2-methyl-1,3-propanediol and 95.4 grams (0.093 equivalents of hydroxyl) of molten Rucoflex®. XS-5570-55, which is a sulphonated polyol of Ruco. Polymer Corporation based on monosodium salt of 5-sulfoisophthalic acid - (4% by weight), adipic acid and diethylene glycol. The mixture was charged with 39.96 grams of isoporane isocyanate, one drop of dibutyltin dilaurate, and heated at 80 ° C for 2 hours to produce an isocyanate-terminated polyurethane pre-polymer. The resulting isocyanate-terminated polyurethane prepolymer was dispersed in 247.0 grams of deionized water at 70 ° C, using moderate agitation, and heated for a further 2 hours at 65 ° C. Compound IC The compound IC is a water-based sulfonated polyurethane-vinyl polymer. 139.86 grams of an isocyanate-terminated polyurethane prepolymer (prepared in the form of Compound IB) were dispersed. it had a temperature of 80 ° C, in 139.86 grams of de-ionized water and it was stirred for 5 minutes. The dispersed pre-polymer was charged with 341.5 grams of a functional hydroxyl-polyvinyl dispersion (compound IA). The mixture was stirred and heated at 65 ° C for 2 hours. The water-based sulfonated polyurethane-vinyl polymer had a solids content of 40.2% and a pH of 6.4.

The compounds were tested for tensile strength, elongation and shear strength on glass, steel and acrylonitrile-butadiene-styrene (ABS) copolymers. The results are presented in Table 1 below. Table 1. Resistance to tension, elongation and shear strength.

The data shows the sulfonated polyurethane-vinyl polymer (Compound IC) which has improved mechanical properties compared to the mixture of Compound 1A and IB. The data also shows that Compound IA has improved adhesion properties compared to Compound IA, Compound IB and in its 50/50 blend, thus showing the utility of the invention. Example 2: This example describes the preparation of a water-based sulfonated polyurethane-vinyl polymer using vinyl acetate. The polymer properties of the invention are compared with their corresponding polymer components. Compound 2A Compound 2A is a dispersion of aqueous polyvinyl acetate using a reactive emulsifying agent, which is polyvinyl alcohol-polyvinyl amine copolymer (PVOH-PVAM), from Air Products & Chemicals, Inc. (Allentown, PA). The polymer was prepared as described in Example 1 (Compound 1A) except that the pre-emulsion contained 265 grams of vinyl acetate, 35.0 grams of n-butyl acrylate, 3.9 grams of methacrylic acid and 0.10 grams of thiolacetic acid. The resulting polymer dispersion has a solid dispersion of 33.6% and a pH of 2.5. Compound 2B Compound 2B is a sulfonated polyurethane polymer. The polymer was prepared exactly as described in Example 1 (compound IB). Compound 2C Compound 2C is a sulfonated water-based polyurethane-vinyl acetate polymer. 139.86 grams of an isocyanate-terminated polyurethane pre-polymer were dispersed, prepared in the form of Compound IB, but before dispersion, which had a temperature of 80 ° C, in 247 grams of deionized water (70 ° C). ) and stirred for about 10 minutes. The dispersed prepolymer was charged with 341.5 grams of the polyvinyl amino and hydroxyl functional dispersion described as Compound 2A. The mixture was stirred moderately and heated at 65 ° C for 2 hours. The water-based sulfonated polyurethane-vinyl acetate polymer composition had a solids content of 35.5 and a pH of 6.5. The compounds were tested for tensile strength, elongation and shear strength on glass, steel and acrylonitrile-butadiene-styrene (ABS) copolymers. The results are given in Table 2.

Table 2. Resistance to stress, elongation and shear strength.

The data shows that the sulfonated polyurethane-vinyl acetate polymer (Compound 2C) has improved mechanical properties compared to the mixture of Compounds 2A and 2B. The data also shows that Compound 2C has improved adhesion properties compared to Compound 2A and Compound 2B thus showing the utility of the invention. Example 3: This example describes the preparation of a sulfonated water-based polyurethane-vinyl polymer, wherein the polyvinyl amide functional dispersion is formed using the Vinamer EF monomer, which the N-ethenylformamide from Air Products & Chemicals, Inc. (Alletown, PA). Compound 3A Compound 3A is a functional polyvinyl amine dispersion using N-ethynylformamide. (1) Reactor Loading Grams Deionized water 295.0 Potassium persulfate 0.42 Deionized water 20.0 (2) Pre-emulsion Deionized water 80.0 T-Det 0-407 (Harcros) 8.86 Foamaster 111 0.325 Potassium persulfate 0.55 Methyl methacrylate 155.0 Acrylate N-Butyl 155.0 Methacrylic Acid 0.5 (3) Initiator Feeding Deionized Water 20.0 Potassium Persulfate 0.42 (4) Feeding Vinamer Monomer EF 3.1 The pre-emulsion (2) was prepared using the following procedure. The water, surfactant, defoamer and initiator were combined and stirred for 15 minutes. The monomers were added to this mixture over a period of 30 minutes, using agitation, to form a white milky pre-emulsion. The reactor charge (1) was added to a reactor equipped with a stirrer, thermometer, condenser and nitrogen purge. The materials were heated to approximately 80 ° C and loaded with 2% of the total pre-emulsion (2) after being stirred for a further 15 minutes. While maintaining a reaction temperature of 80 ° C, the pre-emulsion (2) was added over a period of 3 hours. The monomer feed (4) was added approximately 1.5 hours after the initial pre-emulsion feed. Once all the materials were added, the reaction mixture was heated 30 minutes more. The dispersion was charged with 3.1 grams of Igepal CO-710, which is an Rhone-Poulenc surfactant, and the reaction mixture was heated an additional hour to allow complete polymerization of the free radical of said monomers. The Vinamer EF monomer was then hydrolyzed to a primary amine. This was achieved by adding 17.5 grams of a 5% sodium hydroxide solution and heating an additional 2 hours at 80 ° C. Compound 3B Compound 3B is a sulfonated water-based polyurethane-vinyl polymer. 95.4 grams were charged to a reaction flask (0.093 hydroxyl equivalents) of Rucoflex® XS-5570-55 and 4.5 grams of 2-methyl-1,3-propanediol. The materials were heated to 50 ° C and then loaded with 39.96 grams of isophorone diisocyanate and one drop of dibutyltin dilaurate. The mixture was heated for a further 2 hours at 80 ° C. The resulting isocyanate-terminated polyurethane prepolymer was dispersed in a solution containing 315 grams of a functional polyvinyl amine polymer (Compound 3A) and 244 grams of deionized water. The dispersion was stirred for 2 hours at 60 ° C.

The mechanical and addition properties of the compounds are presented in Table 3. Table 3. Resistance to stress, elongation and resistance to shear stress.

Example 4: Example 4 describes the preparation of water-based compositions, wherein the sulfonated polyurethane prepolymers terminated in isocyanate are dispersed in hydroxy-functional water-based polyacrylic dispersions. Compound 4A Compound 4A is a polyacrylic hydroxyl functional dispersion, wherein the hydroxyl groups are within the latex particle. (1) Reactor Loading Grams Deionized water 275.0 Methacrylic acid 1.0 (2) Pre-emulsion Des-ionized water 80.0 T-Det 0-407 (Harcros) 8.86 Methyl methacrylate 155.0 N-butyl acrylate 155.0 Hydroxy ethyl acrylate 10.85 N -dodecil mercaptan 0.31 (3) Initifier feed Deionized water 20.0 t-Butyl hydroperoxide 1.37 (4) Reducer feed Deionized water 20.0 Formaldehyde-sodium sulfoxide 0.97 The load was added to a reactor equipped with an agitator, thermometer, condenser and nitrogen purge of the reactor (1). The water was heated to about 65 ° C and then charged with 3% of the total pre-emulsion. While maintaining a reaction temperature of 65 ° C, the pre-emulsion (2) was added over a period of 3 hours, while the initiator feed (3) and the reducer feed (4) were added over a period of 4 hours. The reaction mixture was charged with 10.85 grams of hydroxyethyl acrylate after the addition of about 75% of the pre-emulsion. Once all the materials were added, the reaction mixture was heated 1 hour more. The dispersion had a solids content of 45.2%, a pH of 2.65 and an average particle size diameter of 443 nanometers. Compound B Compound 4B is a polyacrylic hydroxyl functional dispersion, wherein a portion of the hydroxyl groups are distributed on the surface of the particle. (1) Reactor Loading Grams Deionized water 275.0 Methacrylic acid 1.0 (2) Pre-emulsion Deionized water 80.0 T-Det 0-407 (Harcros) 8.86 Methyl methacrylate 155.0 N-butyl acrylate 155.0 N-dodecyl mercaptan 0.31 (3) Initiator feed Deionized water 20.0 t-Butyl hydroperoxide 1.37 (4) Reducer feed Deionized water 20.0 Formaldehyde-sodium sulfoxide 0.97 The reactor charge was added to a reactor equipped with an agitator, thermometer, condenser and nitrogen purge ( 1) . The water was heated to about 65 ° C and then charged with 3% of the total pre-emulsion (2). While maintaining a reaction temperature of 65 ° C, the pre-emulsion (2) was added over a period of 3 hours, while the initiator feed (3) and the feed reducer (4) were added over a period of time. 4 hours The reaction mixture was charged with 10.85 grams of hydroxyethyl acrylate after the addition of about 75% of the pre-emulsion. Once all the materials were added, the reaction mixture was heated 1 hour more. The dispersion had a solids content of 45.2%, a pH of 2.65 and an average particle size diameter of 443 nanometers. Compound 4C Compound 4C is a sulfonated polyurethane pre-polymer. One reactor was charged with 4.5 grams (0.099 hydroxyl equivalents) 2-methyl-1,3-propanediol and 95.4 grams (0.093 hydroxyl equivalency) of molten Rucoflex® XS-5570-55, which is a sulfonated polyol of RUCO Polymer Corporation based on the monosodium salt of 5-sulfoisophthalic acid (4% by weight), adipic acid and diethylene glycol. The mixture was charged with 39.96 grams of isophorone diisocyanate, one drop of dibutyl tin dilaurate and heated at 80 ° C for 2 hours. Compound 4D Compound 4D is a sulfonated water-based polyurethane-urea polymer. 139.86 grams of the pre-polymer (80 ° C) described as Compound 4C was charged with 629.3 grams of de-ionized water (65 ° C) and stirred for 2 hours keeping the temperature below 65 ° C. Compound 4E Compound 4E is a sulfonated water based acrylic-polyurethane polymer composition. 139.86 grams of the pre-polymer were dispersed (80 ° C) described as Compound 4C with 309.4 grams of a polyacrylic and oxy functional dispersion (65 ° C) as described as compound 4k. The dispersion mixture was stirred for 5 minutes and then loaded with 250.0 grams of deionized water (65 ° C). The materials were heated an additional 2 hours at 65 ° C to generate a polymer composition having a solid content of 40.2% and a pH of 6.5. Compound 4F Compound 4F was similarly prepared as described in compound 4E with the exception that 312.2 grams of the polyacrylic hydroxyl functional dispersion described as compound 4B was used. the polymer composition had a solids content of 40% and a pH of 6.5.

The mechanical properties of the compounds are presented below in Table 4.

Table 4. Resistance to Stress and Elongation The data shows that the polymer compositions of the invention (Compounds 4E and 4F) have an improved tensile strength compared to Compound 4A, Compound 4B, Compound 4D, the 50/50 mixture of Compound 4A and 4D and the mixture of Compound 4B and 4D. Example 5: This example describes the preparation of a sulfonated water-based polyurethane-urea / polyvinyl polymer and its properties compared to its corresponding polyvinyl components. Compound 5A Compound 5A describes the preparation of a polyvinyl dispersion, which is free of active hydrogen atoms. (1) Reactor Load Grams Deionized water 290.0 (2) Pre-emulsion Deionized water 90.0 T-Det 0-407 (Harcros) 15.0 Methyl methacrylate 170.0 N-butyl acrylate 180.0 7.0 Methacrylic acid N-dodecyl mercaptan 7.0 (3) Initiator Feeding Deionized water 30.0 t-Butyl hydroperoxide 2.15. (4) Deionized Water Reducer Feed 30.0 Formaldehyde-Sodium Sulfoxide 2.10 To a reactor equipped with a stirrer, thermometer, condenser and nitrogen purge was added (1) the reactor charge. The water heated to approximately 65 ° C and then charged with 3% by weight of the total pre-emulsion (2). While maintaining a reaction temperature of 65 ° C, the pre-emulsion (2), the initiator feed (3), feed reducer (4) were added over a period of 3 hours. Once all the materials were added, the dispersion was heated an additional hour. Compound 5B Compound 5B is a sulfonated water-based polyurethane-urea polymer. One reactor was charged 95.4 grams (0.0093 equivalents of hydroxyl) Rucoflex® XS-5570-55 and 4.5 grams of 2-methyl-l, 3-propanediol. The mixture was heated to 50 ° C, then 39.96 grams of isophorone diisocyanate and one drop of dibutyltin dilaurate were charged. The mixture was heated at 80 ° C for 2 hours using moderate agitation. The isocyanate-terminated polyurethane prepolymer was then dispersed in 339.4 grams of de-ionized water and charged with a solution containing 2.88 grams of ethylene amine, 1.09 of diethylene triamine and 20 grams of deionized water. Compound 5C Compound 5CB is a sulfonated polyurethane-urea / polyvinyl dispersion based on water. To a reaction vessel were charged 95.4 grams (0.093 equivalents of hydroxyl) of Rucoflex® XS-5570-55 and 4.5 grams of 2-methyl-1,3-propanediol. The mixture was heated to 50 ° C, then charged with 39.96 grams of isophorone diisocyanate and one drop of dibutyltin dilaurate. The mixture was heated at 80 ° C for about 2 hours using moderate agitation to give an isocyanate-terminated polyurethane pre-polymer. The isocyanate-terminated polyurethane prepolymer was then dispersed in a mixture containing 339.4 grams of de-ionized water and 969.3 grams of the polyacrylic dispersion, Compound 5A whose mixture was adjusted to a pH of 9.3, using a hydroxyl mixture of 10% sodium / water, before the dispersion procedure. The resulting isocyanate / polyvinyl-terminated polyurethane prepolymer dispersion was charged with a solution containing 2.88 grams of ethylene diamine, 1.09 grams of diethylene triamine and 20 grams of deionized water. The polyurethane-urea / sulfonated polyvinyl-based water polymer had a solids content of 35% and a pH of 9.0. The compounds described above were tested for shear strength on glass, steel and acrylonitrile-butadiene-styrene (ABS) copolymers. The results are presented in Table 5 below. Table 5. Shear Strength Resistance The data shows that the polymer of the invention (Compound 5C) has an increased shear strength compared to Compound 5A, Compound 5B and the 50/50 mixture of Compound 5A and Compound 5B showing the utility of the invention. Examples 6 and 7 relate to the formation of water-based sulfonated polymer compositions, wherein a polyurethane dispersion was used as a seed to polymerize methacrylic monomers. The water-based sulfonated polymer composition can be used to size glass fiber. As used herein, acrylic denotes acrylate, methacrylic acid and acrylamide. Example 6. Synthesis of acrylic hybrid latex of polyurethane dispersion. Example '6 describes the preparation of a water-based sulfonated polymer composition through seed emulsion polymerization and its properties purchased with the corresponding polymer mixture. Compound 6A Compound 6A is a pre-emulsion of polyacrylate (1) Charge of Grams Reactor Deionised Water 90. 8 Pluronic L64 (a surface active agent, BASF) 9.08 (2) Mixture of methyl methacrylate monomer (ICI) 159.6 N-butyl acrylate (Hoechst Celanese) 163.5 Hydroxy ethyl methacrylate (Rohm & amp;; Hass) 6.49 The reactor charge (1) was added to a vessel with an agitator and mixed for 10 minutes at a temperature of 25 ° C. The monomer mixture (2) was then added over a period of 30 minutes under agitation to the vessel. The mixture was combined for a further 10 minutes at a temperature of 25 ° C. The resulting pre-emulsion was transferred to a feed tank. Compound 6B Compound 6B is a polyurethane dispersion for use in the preparation of the compositions of the invention. (1) Reactor Charge Grams Deionized Water 181.7 Thiolactic Acid (Evans) 0.065 AWC Hydrosulfite (Henkel) 0.065 Hamp-0 14.5% Iron (Hapshire) 0.039 Reactor charge (1) was added to a clean jacketed reaction vessel equipped with an agitator, thermometer, condenser and nitrogen purge and mixed well. 332.3 grams of NP-4062-M (a polyurethane dispersion, H.B. Fuller Company) were added to the mixture. The reactor, under the nitrogen purge, was stirred and the temperature was raised to 65 ° C. Compound 6C Compound 6C is a water-based sulfonated polymer composition prepared through seed emulsion polymerization. During a 4.5 hour period, the polyacrylate pre-emulsion (Compound 6A), an initiator solution containing 1.95 grams of hydrogenated t-butyl peroxide (Akzo) and 19.5 grams of de-ionized water, a reducing solution containing 0.91 grams of AWC hydrosulfite (Henkel) and 19.5 grams of de-ionized water is fed to a clean jacketed reaction vessel equipped with a stirrer, thermometer, condenser and nitrogen purge containing the polyurethane dispersion mixture (Compound 6B). After completing the feeds, the mixture was kept at a constant temperature for another hour to allow the total conversion of the monomers. The reactor was then cooled to room temperature and the resulting latex was filtered through a 200 mesh filter. A stable latex with 45% solids, pH of 7.35 and a viscosity of 316 cps was obtained.

Additional compounds were prepared similarly to Compound 6C by varying the amount of compound 6B resulting in a water-based sulfonated polymer composition with different polyurethane / polyacrylate (PU / PA) ratios. Compound 6C and similarly prepared compounds with different polyurethane / polyacrylic ratios, and mixtures of compounds 6A and 6B (absent initiator and reductant solutions) were tested for tensile strength and elongation, peel strength (using a foil) of transparent PVC and a white one as substrates) and the resistance of shear stress. The results are given in Tables 6-9. Note that the ratio of polyurethane to polyacrylate is based on the solids content of polyurethane and polyacrylate. In this way, a PU / PA ratio of 75/25 indicates that there are 3 parts of polyurethane solids for each part of polyacrylate solids. It is also noted that "hybrid" presented in Table 9 was prepared as Compound 6C with a PU / PA ratio of 25/75. The mixture in Table 9 has a PU / PA ratio of 25/75. Table 6. Stress resistance and elongation Table 7 Resistance to detachment. PCV movie tr nspare te Table 8. Peel strength, white PCV film: (Hybrid prepared with Example 6) Table 9. Resistance to the Turning Cutting Effort: (glass to glass).

Example 7. Synthesis of Sulfonated Polymer Composition based on Extended Chain Water-Water. With the sample procedure of Example 6, another water-based sulfonated polymer composition was prepared in the form of Example 6C, except that the polyurethane dispersion NP-4062 used to prepare Compound 6B was replaced by NP-4073 (a sulfonate polyurethane dispersion, HB Fuller Company, Capillary Hydrodynamic Fractionation was used to verify the latex particle growth in Examples 6 and 7. Figures 1 and 2 present the polyurethane particle size distribution (dotted line) as a fraction of the final hybrid latex particle distribution (solid line), for the latex (sulfonated polymer composition based on water) prepared in Examples 6 and 7. Both figures show that no new population of acrylic particles was generated, implying that a polycarbonate core polyacrylic shell hybrid structure was formed, the only hybrid morphology of the latex The water-based sulfonated polymer position in this description leads to superior physical properties compared to the corresponding mixture or a common alloy. '

Claims (13)

1. CLAIMS 1. A water-based sulfonated polymer composition characterized in that it comprises a sulfonated polyurethane-vinyl polymer comprising the reaction product of: A) at least one polymer comprising the product of the reaction of: I) minus one polyisocyanate; and II) at least one sulfonated polyol polyester, wherein the sulfo groups are present in the form of alkali metal salts; and B) at least one polyvinyl dispersion comprising the radically free polymerized product of; I) at least one ethylenically unsaturated monomer; and II) optionally, at least one radically reactive protective colloid comprising active hydrogen atoms. 2. A water based sulfonated polymer composition characterized in that it comprises: A) at least one polymer comprising the reaction product of; I) at least one polyisocyanate; and II) at least one sulfonated polyol polyester, wherein the sulfo groups are present in the form of alkali metal salts; B) at least one polyvinyl dispersion comprising the radically free polymerized product of; I) at least one ethylenically unsaturated monomer; and II) optionally, at least one protective colloid comprising active hydrogen atoms; Y
2. C) a polyurethane-vinyl polymer comprising the reaction product of; I) at least one isocyanate-terminated sulfonated polyurethane prepolymer comprising the reaction product of; a) at least one polyisocyanate; and b) at least one sulfonated polyol polyester, wherein the sulfo groups are present in the form of alkali metal salts; with II) at least one polyvinyl dispersion comprising a reaction product of; a) at least one ethylenically unsaturated monomer; and b) optionally at least one protective colloid comprising active hydrogen atoms.
3. 3. A water based sulfonated polymer composition characterized in that it comprises the reaction product of: A) at least one free radical initiator; B) at least one pre-emulsion comprising; I) at least one ethylenically unsaturated monomer; II) water; III) optionally at least one surfactant; and C) at least one water-based polyurethane dispersion comprising the reaction product of: I) at least one polyisocyanate; and II) at least one sulfonated polyol polyester wherein the sulfo groups are present in the form of alkali metal salts; wherein said dispersion is used as a seed during the free radical polymerization of the emulsion.
4. 4. A fiberglass sizing composition characterized in that it comprises the composition described in any of the preceding claims.
5. 5. A water-based sulfonated polymer composition characterized in that it comprises the reaction product of: a) at least one sulfonated polyurethane dispersion; b) at least one pre-emulsion, the pre-emulsion comprising at least one ethylenically unsaturated monomer, water and surfactant; c) at least one free radical initiator; wherein the dispersion is used as a seed for the polymerization of the ethylenically unsaturated monomer and the free radical initiator initiates the polymerization of the ethylenically unsaturated monomer.
6. 6. The water-based sulfonated polymer composition according to any of claims 1, 2, 3 and 5, characterized in that the composition exhibits a shear shear strength of at least about 24605 kg / cm2. A water-based sulfonated polyurethane composition characterized comprising: a) at least one sulfonated polyurethane-urea polymer comprising the reaction product of: I) at least one polyisocyanate; II) at least one dihydroxy carboxylic acid; and III) at least one sulfonated polyol polyester wherein the sulfo groups are present in the form of alkali metal salts; b) at least one aqueous vinyl polymer dispersion comprising the radically free polymerized product of: I) at least one ethylenically unsaturated monomer; and II) at least one radically free reactive protective colloid comprising active hydrogen atoms; and c) at least one water-based sulfonated polymer composition comprising the reaction product of: I) at least one isocyanate-terminated sulfonated polyurethane prepolymer comprising the reaction product of: i) by at least one polyisocyanate; ii) at least one dihydroxy carboxylic acid; and iii) at least one sulfonated polyol polyester wherein the sulfo groups are present in the form of alkali metal salts; with II) at least one dispersion of aqueous vinyl polymer comprising the reaction product of: i) at least one ethylenically unsaturated monomer; and ii) at least one radically free reactive protective colloid comprising active hydrogen atoms. 8. The composition according to any of claims 1, 2 or 7, characterized in that at least one sulfonated polymer further comprises at least one non sulfonated polymer diol. The composition according to any one of claims 1, 2, 7 or 8, wherein at least one sulfonated polyurethane pre-polymer further comprises at least one non-sulfonated polymer diol. 10. The composition according to claim 1, characterized in that the protective colloid has active hydrogen atoms comprising amines. 11. A method for the preparation of sulfonated polymer compositions based on water through seed emulsion polymerization characterized in that it comprises the steps of: A) provide at least one free radical initiator; B) forming at least one pre-emulsion comprising; I) at least one ethylenically unsaturated monomer; II) water; and III) optionally at least one surfactant; C) providing a water-based polyurethane comprising the reaction product of: I) at least one polyisocyanate; and II) at least one sulfonated polyol polyester wherein the sulfo groups are present in the form of alkali metal salts; so D) add A) and B) to C) after starting the polymerization of free radical using heat, the polyurethane serving as the seed. 12. The method according to claim 1, characterized in that the free radical initiator is present in the pre-emulsion. A method for the preparation of water-based sulfonated polyurethane-polyvinyl hybrid latex according to claim 11 or 12, characterized in that it comprises the steps of forming an aqueous pre-emulsion comprising at least one pre-emulsion of ethylenically unsaturated monomer, the pre-emulsion comprising at least one acrylate and optionally a surfactant, and reacting the aqueous pre-emulsion with at least one sulfonated polyurethane dispersion in the presence of an initiator.