DE4441760A1 - Vinyl] copolymer for use as binders in water-dispersible coating compsns. - Google Patents

Abstract

A vinyl copolymer (I) comprises the reaction prod. of (a) 1-99.9 wt.% vinyl monomer(s), (b) 0-98.9 wt.% mono-unsatd. monomer(s) other than (a) and (c) 0.1-99 wt.% mono-unsatd. macromonomer, comprising the reaction prod. (MM) of styrene/maleic anhydride copolymer (SMA) and hydroxyethyl acrylate (HEA), or a hydrolysed deriv. of MM, or a mixt. of either of these with the reaction prod. of trimellitic anhydride (TMA) and HEA. Also claimed are (1) a water-dispersible compsn. (II) contg. the reaction prod. of 50-95 wt.% (a), 0-20 wt.% (b) and 5-40 wt.% (c), the vinyl copolymer being dispersible in aq. media after neutralisation of the COOH gps. with base; (2) the water-dispersible salt-contg. compsn. thus obtd.; (3) hardenable mixts. contg. compsn (II) and a crosslinker (III), and hardenable mixts. in aq. dispersion, contg. relatively large amts. of water and small amts. of (II) and (III); and (4) macromonomers and macromonomer mixts. as above. Pref. (I) is the reaction prod. of vinyl chloride, vinyl acetate, hydroxyalkyl (meth)acrylate and macromonomer as above.

Description

The present invention relates to (i) macromonomers enthal Tende vinyl copolymers and process for the preparation dersel (ii) water-dispersible vinyl copolymer coating Compositions and processes for their preparation and (iii) Macromonomers and macromonomer mixtures and methods for Production of the same.

It is well known in the art in the formation of Coat organic polymers, which in organic Lösungsmit are dissolved or dispersed, use. The education of coatings using such solvents or Dispersions involve the removal of large quantities of orga niche solvents and especially in recent years is such solvent removal from ecological and environmental considerations considered undesirable Service. Accordingly, an increasing interest in Be coating compositions in which the organic polymer in a medium consisting mainly of water disper greed or dissolved.

Some water-dispersible vinyl copolymers can by a Processes are prepared which the dissolution of hydroxyl containing vinyl resin in acetone, the addition of styrene / Ma A maleic anhydride oligomer and the grafting of the latter on the former includes. The excess anhydride groups are then reacted with water and neutralized with amine, around pervious polar charged groups from the vinyl head Chain removed, creating sufficient hydrophilicity is generated to render the vinyl copolymer water-dispersible do. Unfortunately, this procedure is quite costly play, making the final product too expensive for many applications in the price is. A better and less expensive way to educate The same result would be the incorporation of a suitable polar group-containing monomers in a Vi nyl copolymer during the polymerization.  

Numerous attempts to find the right monomer to achieve the find above result, have not been successful exposed. Common problems are either a vinyl copo lymer which precipitates or coagulates after the addition of water liert and gelled or a vinyl copolymer, which is under Formation of a viscous solution and an unusable one dissolves water-sensitive film in water. It turned out to be quite difficult to find the right balance hold true.

The present invention relates in one aspect to vinyl Copolymers comprising the reaction product of:

• (a) about 1-99.9, preferably about 10-90, wt% one or more vinyl-containing monomers, more typical example of vinyl chloride and / or vinyl acetate;
• (b) about 0-98.9, preferably about 0-25, wt% one or more monoethylenically unsaturated monomers, which are different from component (a), typically from Hydroxyalkyl (meth) acrylate; and
• (c) about 0.1-99, preferably about 5-60, wt% one or more monoethylenically unsaturated macromonomes rer, typically a monoethylenically unsaturated macro monomer which is the reaction product of styrene / maleic acid hydride copolymer and hydroxyethyl acrylate or the hydrolyzate te derivative of this reaction product comprises, or a Mi Scheme of monoethylenically unsaturated macromonomers, the (i) a macromonomer which is the reaction product of trimellit acid anhydride and hydroxyethyl acrylate, and (ii) a Macromonomer, which is the reaction product of styrene / maleic acid anhydride copolymer and hydroxyethyl acrylate or the hydroly derived derivative of this reaction product comprises comprises.

The invention also relates to a further aspect Process for the preparation of vinyl copolymers, which um summarizes:

• (a) the formation of a reaction mixture comprising (i) about 1-99.9, preferably about 10-90, wt .-% of one or several vinyl-containing monomers, typically vinyl chloride and / or vinyl acetate; (ii) about 0-98.9, preferably about 0-25, wt .-% of one or more monoethylenically unge saturated monomers other than component (i), typically of hydroxyalkyl (meth) acrylate and (iii) about 0.1-99, preferably 5-60, wt .-% of one or more monoethylenically unsaturated macromonomer, typically a monoethylenically unsaturated macromonomer comprising the reaction product of styrene / maleic anhydride copolymer and hydroxyethyl acrylate or the hydrolyzed derivative of this Reaction product, or a mixture of monoethylenic unsaturated macromonomers which comprise (i) a macromol nomer, which is the reaction product of trimellitic anhydride and Hydroxyethyl acrylate, and (ii) a macromonomer containing the Reaction product of styrene / maleic anhydride copolymer and Hydroxyethyl acrylate or the hydrolyzed derivative of this Reaction product; and
• (b) the reaction of the reaction mixture of (a) under Polymerization conditions sufficient to remove these vinyl To produce copolymers.

The present invention further relates to water dispersants bare coating compositions containing the vinyl copolymers of the present invention, in which the weight fractions of components (a), (b) and (c) in the range of may be about 50-95%, 0-20% and 5-40% respectively, and these Vinyl copolymers after the neutralization of at least some Carboxylic acid groups with a base in a mainly aqueous medium medium are dispersible.

This invention relates in still another aspect Process for the preparation of water-dispersible coating compositions, which comprises:

• (a) the formation of a reaction mixture comprising (i) about 50-95, preferably about 60-90, wt .-% of one or  several vinyl-containing monomers, typically vinyl chloride and / or vinyl acetate; (ii) about 0-20, preferably about 5-15, wt .-% of one or more monoethylenically unge saturated monomers other than component (i), typically of hydroxyalkyl (meth) acrylate, and (iii) about 5-40, preferably 10-25, wt .-% of one or more mono ethylenically unsaturated macromonomer, typically one monoethylenically unsaturated macromonomer comprising the reaction product of styrene / maleic anhydride copolymer and hydroxyethyl acrylate or the hydrolyzed derivative of this Reaction product, or a mixture of monoethylenically un saturated macromonomers which comprise (i) a macromol nomer, which is the reaction product of trimellitic anhydride and hydroxyethyl acrylate, and (ii) a macromonomer the reaction product of styrene / maleic anhydride copolymer and hydroxyethyl acrylate or the hydrolyzed derivative of this Reaction product; and
• (b) the reaction of the reaction mixture of (a), wherein the implementation is carried out to the extent that is to produce a film-forming composition len after neutralization of at least a few car Bonsäuregruppen with a base in a mainly aqueous Medium is dispersible.

The present invention further relates to a monoethyle unsaturated macromonomer, which comprises the reac tion product of styrene / maleic anhydride copolymer and Hydroxyethyl acrylate or the hydrolyzed derivative of this Reaction product, or a mixture of monoethylenic unsaturated macromonomer comprising (i) a macromonomer, the reaction product of trimellitic anhydride and Hy and (ii) a macromonomer containing the Reaction product of styrene / maleic anhydride copolymer and Hydroxyethyl acrylate or the hydrolyzed derivative of this Reaction product includes.  

The present invention also relates to a method for Preparation of a macromonomer mixture comprising:

• (a) the reaction of dissolved in a solvent Trimellitic anhydride with a molar excess of hydroxy ethyl acrylate;
• (b) the reaction of dissolved in a solvent Styrene / maleic anhydride copolymer with the molar excess Hydroxyethyl acrylate from step (a),
• (c) optionally, the incorporation of water, the is reactive with anhydride groups in the reaction; and
• (d) obtaining the macromonomer mixture which comprises (i) a macromonomer which is the reaction product of trimellit acid anhydride and hydroxyethyl acrylate, and (ii) a Macromonomer, which is the reaction product of styrene / maleic acid anhydride copolymer and hydroxyethyl acrylate or the hydroly derived derivative of this reaction product.

The present invention provides economical vinyl copoly mer resins which are dispersible for use in water Baren coating compositions are suitable. The vinyl Copolymer resins provided by the present invention are formed by the copolymerization a monomer mixture comprising (i) about 0.1-99.9, preferably about 10-90% by weight of one or more vinyls containing monomer, typically vinyl chloride and / or vinyl acetate; and (ii) about 0-98.9, preferably 0-25, Wt .-% of one or more monoethylenically unsaturated Mak romonomers other than (i), typically from Hydroxyalkyl (meth) acrylate; and (iii) about 0.1-99, preferably Example, about 5-60, wt .-%, of one or more monoethylenic unsaturated macromonomer, typically a monoethyle unsaturated macromonomer which comprises the reac tion product of styrene / maleic anhydride copolymer and Hydroxyethyl acrylate or the hydrolyzed derivative of this Reaction product, or a mixture of monoethylenic unsaturated macromonomer comprising (i) a macromonomer, the reaction product of trimellitic anhydride and Hy  and (ii) a macromonomer containing the Reaction product of styrene / maleic anhydride copolymer and Hydroxyethyl acrylate or the hydrolyzed derivative of this Reaction product includes.

The vinyl copolymer resins are preferably composed from monomer units which include (i) a first mono vinyl chloride unit of the formula -CH₂-CHCl-, (ii) a second monomer unit of vinyl acetate of the formula -CH₂-CH (O-CO-CH₃) -, (iii) a third monomer unit from Hy hydroxypropyl acrylate and (iv) a fourth monomer unit a monoethylenically unsaturated macromonomer which comprises the reaction product of styrene / maleic anhydride Copolymer and hydroxyethyl acrylate or the hydrolyzed Deri vat this reaction product, or a mixture of mono ethylenically unsaturated macromonomer comprising (1) Macromonomer, which is the reaction product of trimellitic anhydride and hydroxyethyl acrylate, and (2) a macromonomer, the reaction product of styrene / maleic anhydride copo lymer and hydroxyethyl acrylate or the hydrolyzed derivative this reaction product comprises. The weight fractions the These preferred monomer units can be in the range of 1-99.9% for (i) and (ii), 0-98.9% for (iii) and 0.1 to 99% for (iv) lie. It is also preferred that the copolymer an average logarithmic viscosity number in Be has from 0.1 to 0.5 in methyl ethyl ketone.

The copolymerization reaction of the comonomers can be described by ir a known method can be carried out Lich the methods of emulsion polymerization, Lösungspolyme and the like. The vinyl acetate unit in the copolymer can if desired by vinyl propionate or another Vi nylester a lower carboxylic acid are replaced. The Vi nyl copolymers of the present invention are described by Copo lymerisation of the monomers described above in a mixture obtained a copolymer with an average log  arithmetic viscosity number of 0.1 to 0.5 in methyl ethyl ketone to give tone.

Conventional solution polymerization techniques may be desirable valued, as discussed below, to prepare the vinyl copolymers of the invention. Similar For example, other polymerization techniques such as conventional emulsion polymerization also used become. Thus, the process used to prepare the Vi nyl copolymers of the present invention is used, not critical, and such a technology is the subject man well known.

In general, and as an illustrative example, may prepared the vinyl copolymers of the present invention be by using solution polymerization, wherein a solvent for the resulting copolymer and also the used various components. suitable Solvents include, for example, the conventional ones Ketone solvents such as acetone, methyl ethyl ketone clay, methyl n-butyl ketone, methyl isopropyl ketone and the like finally, mixtures of such ketone solvents with Alko such as methanol, ethanol and isopropanol. Illustrate vinyl copolymer polymerizations of the present invention are described in detail in Examples 5-7 below.

The polymerization can be either batchwise or continuous be carried out. Typically, the behavior varies solvent / monomer from about 0.3 / 1 to 4/1, depending on the desired molecular weight. The selected temperature can from about 35 ° C to about 80 ° C, depending on the ge desired reaction rate and the desired molecule large weight of the copolymer. It can be any oil-soluble free Radical catalyst can be used in an amount ranging from from about 0.01 to about 3.0%, based on the weight of the monomer ren, varies. Suitable catalysts include as veran Illustrative examples dibenzoyl peroxide, dilauroyl peroxide,  Azobisisobutyronitrile and diisopropyl peroxydicarbonate. It can any pressure above the vapor pressure of the components of the Sy Stems are used, wherein pressures of about 30 to 100 psi typical.

The relative amounts of components (a), (b) and (c) used in the vinyl copolymers of the invention are present are not critical in the narrow sense. Components (a) and (b) are present in a crowd that is sufficient to ensure that the vinyl copolymer is capable of satisfying to form a coating on a substrate, and component (c) is present in an amount sufficient to ensure safety len that the vinyl copolymer after the neutralization of min at least some of the carboxylic acid groups with a base in one mainly aqueous medium is dispersible. Preferably For example, the vinyl copolymer contains a weight ratio of Kom components (a) and (b) to component (c) of about 1: 0.01 to 1: 1, and more preferably from 1: 0.15 to 1: 0.4. Appropriate quantities the components (a), (b) and (c) are in the inventive Process for the preparation of these vinyl copolymers used.

The vinyl copolymers according to the invention are film-forming. As as used herein means a "film-forming" material Material that is capable of forming a continuous dry, dry film on a solid substrate to become. Such a plot will usually be works by taking a film from a solution of the material in pour a suitable solvent and dry the film leaves. Film-forming materials are too under-material Separate the liquid films or discontinuous, solid Particles under conditions form the film-forming materia induce the formation of films.

Vinyl copolymers prepared from components (a) and (b) are not dispersible in water. Vinyl copolymers made from Components (a), (b) and (c) are made according to Um conversion into salts dispersible in water. The vinyl copolymer  Ren of the present invention are after neutralization of at least some of the carboxylic acid groups with a base in aqueous media dispersible.

Illustrative of the ethylenically unsaturated monomers, as components (a) and (b) in the vinyl copolymers of are useful in the present invention are one or more Vinyl-containing monomers and one or more ethylenic unsaturated monomers having a hydroxyl group or an in have a hydroxyl group convertible group. Typical for such monomers are hydrolyzed vinyl acetate, hydroxyal alkyl acrylates or methacrylates having 2 to about 6 carbon atoms in the alkyl groups (eg, hydroxyethyl acrylate, hydroxy ethyl methacrylate, hydroxypropyl acrylate and hydroxypropyl meth acrylate), alkenols (eg allyl alcohol), alkenyl acetals (eg. Vinyl formal) and the like. Typical other monomers are vinyl halo genicides (eg vinyl chloride), vinyl esters (eg vinyl acetate), α- Olefins having 2 to 4 carbon atoms (eg, ethylene and propy len), alkyl acrylates and methacrylates with 1 to 18 carbon atoms atoms in the alkyl moiety (eg, methyl and ethyl acrylate and methacrylate), acrylic acid and methacrylic acid, alkenyl substituted aromatic compounds (eg styrene and α- Methylstyrene), alkenylalkyl ethers (e.g., methyl vinyl ether and Octadecyl vinyl ether) and the like. The preferred monomers which as components (a) and (b) are useful vinylchlo chloride / vinyl acetate / hydroxyalkyl acrylate or methacrylate terpo polymers having from 2 to about 6 carbon atoms in the hydroxyalkyl unit. The most preferred member of this class is a Vinyl chloride / vinyl acetate / hydroxypropyl acrylate copolymer.

Other monoethylenically unsaturated monomers known as compo nenten (a) and (b) in the vinyl copolymers of the present For example, the invention includes vinyl esters of carboxylic acids such as vinyl propionate and VYNATE® Vinyl Ester Monomers, available from Union Carbide Chemicals and Plastics Company Inc. are available; Vinyl ethers like  Methyl vinyl ether, isobutyl vinyl ether and cetyl vinyl ether; Vinylidene halides such as vinylidene chloride and vinylidene fluoride; unsaturated carboxylic acids such as acrylic acid, methacrylic acid, Maleic acid and itaconic acid; unsaturated carboxylic acid anhydrides such as maleic anhydride; Esters of unsaturated carboxylic acids such as diethyl maleate, butylbenzyl maleate, dimethyl itaconate, β- Carboxyethyl acrylate, methyl (meth) acrylate, ethyl (meth) acrylate and lauryl (meth) acrylate; unsaturated nitriles such as (meth) acrylic nitrile; and aromatic vinyl compounds such as styrene, α-Me methylstyrene and p-methylstyrene.

Suitable macromonomers used as component (c) in the inventions vinyl copolymers of the invention are useful are of ethy derived from unsaturated monomers, the Anhydridgrup pen, such as maleic anhydride, trimel Litsäureanhydrid, phenylmaleic anhydride, chloromaleic acid anhydride, dichloromaleic anhydride, itaconic anhydride and Aconitic. The anhydride-containing monomers are usually with another ethylenically unsaturated mono as indicated above, copolymerized. Preferably the component (c) is a monoethylenically unsaturated Ma cromonomer, which is the reaction product of styrene / maleic acid hydride copolymer and hydroxyethyl acrylate or the hydrolyzate te derivative of this reaction product comprises, or a mixture of monoethylenically unsaturated macromonomers comprising (i) a macromonomer which is the reaction product of trimellit acid anhydride and hydroxyethyl acrylate and (ii) a Macromonomer, which is the reaction product of styrene / maleic acid anhydride copolymer and hydroxyethyl acrylate or the hydroly derived derivative of this reaction product.

For the water-dispersible coating compositions of the present invention, the hydroxyalkyl (meth) acrylate as Component (b), component (c) is preferably (i) the hydrolyzed derivative of the reaction product of Sty rol / maleic anhydride copolymer and hydroxyethyl acrylate or (ii) a mixture of (1) the reaction product of trimellit  acid anhydride and hydroxyethyl acrylate and (2) the hydroly derived derivative of the reaction product of styrene / maleic acid anhydride copolymer and hydroxyethyl acrylate. For the water dispersible coating compositions of the present the invention, the no hydroxyalkyl (meth) acrylate as Kom component (b), component (c) is preferably one monoethylenically unsaturated macromonomer comprising Reaction product of styrene / maleic anhydride copolymer and Hydroxyethyl acrylate or the hydrolyzed derivative of this Reaction product, or a mixture of monoethylenic unsaturated macromonomer comprising (i) a macromonomer, the reaction product of trimellitic anhydride and Hy and (ii) a macromonomer containing the Reaction product of styrene / maleic anhydride copolymer and Hydroxyethyl acrylate or the hydrolyzed derivative of this Reaction product includes.

The reaction product of styrene / maleic anhydride copolymer and hydroxyethyl acrylate or the hydrolyzed derivative of this Reaction product contains hydroxyethyl acrylate: styrene / maleic acid anhydride copolymer in a molar ratio of about 0.4: 1 to 1.4: 1. The reaction product of trimellitic anhydride and Hydroxyethyl acrylate contains hydroxyethyl acrylate: trimellit acid anhydride in a molar ratio of about 0.8: 1 to 1: 1. If component (c) is a mixture, the weight may be Ratio of the reaction product of styrene / Maleinsäureanhy drid copolymer and hydroxyethyl acrylate or hydrolyzed Derivatives of this reaction product to the reaction product of Trimellitic anhydride and hydroxyethyl acrylate in the range of about 1: 10 to 99: 1 or larger. Illustrative Macromonomer production process of the present invention are detailed in the following Examples 1, 3 and 4 give.

In the reaction mixtures used in the Ver driving is preferably an organic one Reaction solvent present. Suitable solvents  include ketones, alcohols, esters, chlorinated hydrocarbons substances and the like. The preferred reaction solvents are saturated aliphatic ketones of 2 to about 4 carbons atoms in each aliphatic moiety. exemplary Ketones include acetone, methyl ethyl ketone, ethyl propyl ketone and methyl butyl ketone, ethyl butyl ketone and the like. The ver solvent used is preferably acetone or another Solvent having the following properties:

• (1) it boils at a low temperature, causing the thermal decomposition of the reactants is minimized;
• (2) It can be easily obtained from the inventive composition deducted;
• (3) It is incorporated in the present invention Reaction mixtures did not react (with the exception of as a chain transfer agent); and
• (4) it is water-soluble.

Suitable amounts of reaction solvents are 75 to 500 Parts by weight of solvent per 100 parts by weight of the components (a), (b) and (c). When a reaction solvent is invented The process according to the invention is used, the product is a Solution of the composition according to the invention in an organi solvent. These solutions ("paints") are new and also form part of the present invention.

As indicated above, those caused by the reaction of the components th (a), (b) and (c) produced vinyl copolymers only What water-dispersible when a sufficient portion of the carboxylic acid groups in the vinyl copolymers into more hydrophilic groups (For example, salt groups produced by the reaction of the carboxylic acid groups formed with a base), was converted. Such salt formation can be effected by adding the polymerization reaction uses an excess of base. Preferably, the amount of base added is sufficient to provide the Make the composition water-dispersible. suitable Bases include, for example, triethylamine, ammonia, dime  thylethanolamine and the like. The neutralized together Compositions are the novel salts of the present invention.

The vinyl copolymers of the invention may be used with others Copolymers can be dispersed together and as such or mixed (alloyed) with alkyd, polyurethane, epoxy or Latex polymers used to form mixtures who those useful as coatings, paints and adhesives are.

The vinyl copolymers of the invention are also with Vor part in coating applications in the form of salts in main aqueous dispersions (i.e., dispersions in which the continuous phase consists mainly of water) used. Such dispersions preferably contain 15 to 55% by weight (more preferably 20 to 45% by weight) of a salt of a vinyl copolymer according to the invention, 40 to 84% by weight (more preferably 50 to 70% by weight) of water and 0 to 35% by weight (More preferably, 0 to 10% by weight) of an organic solvent (eg, the reaction solvent described above). typi scherweise the aqueous dispersions by addition of Base, then adding water and then stripping off the Formed solvent. The base neutralizes the carboxylic acid in the vinyl copolymer and forms a salt, the Water-dispersible.

The aqueous dispersions of the invention may be more typical be prepared in the following manner. The Copolymer varnish, dissolved in acetone and isopropanol, is placed in a provided with stirrer provided vessel. Triethylamine is in Added to an amount that is about half the stoichiometry amount, based on carboxylic acid in the polymer corresponds, followed by deionized water. The triethylamine and the Water is stirred slowly with good stirring where to form a fine dispersion through them. From the dispersion the solvent is removed under vacuum at a jacket temperature subtracted from up to about 100 ° C, whereby one in wesentli  solvent-free dispersion containing non-aqueous Volatile constituents of about 36 to 40 wt .-% produces. The pH of the withdrawn dispersion is typically between about 6.0 and 7.0. The withdrawn dispersion is typi preferably with ammonium hydroxide to a pH of about 8.5 to 9,0 post-neutralized. An antifoam can be used before the Ab optionally be added. Illustrative Manufacturing process for aqueous dispersions are detail described in the following examples 8-10.

Aqueous produced by the process according to the invention Dispersions remain provided the pH is not too low rig, liquid and uniform at 50 ° C for at least 2 months, d. H. free from gel, coagulum, sediment or grains. The aq rigen dispersions of the present invention can be described as Kom components of industrial coatings, paints, binders and the like can be used. The aqueous according to the invention Dispersions are shear stable. Accordingly, the pigments directly producing pigmented coatings and Far be ground into the water-based dispersion.

In order to support the film formation, may optionally coalescing solvent can be used. Typical co Solvents include, for example, monobutyl ethylene glycol, monopropyl ethylene glycol, monoethyl ethylene glycol, mono methylethylene glycol, monomethyl diethylene glycol, monoethyl diet ethylene glycol, monopropyldiethylene glycol, monobutyldiethylene glycol and the like (and corresponding solvents on propylene oxide basis). If enough co-solvent is added, dry the applied aqueous dispersions to clear shiny films. The unmodified films are thermo plastic.

The aqueous dispersions may optionally be crosslinked agents that are reactive with hydroxy or carboxy groups, be added to thermosetting binders and over produce trains. Polyaziridines and polycarbodiimides are  typical carboxyl-reactive crosslinkers. Amino-formaldehyde resins and polyfunctional isocyanates are typical hydroxy functionality nelle crosslinking agents.

The aqueous dispersions of the invention can be used with others Water-based carriers to form polymer alloys be mixed. These include, for example, a water reducible alkyds, alkali-soluble or -dispersible Acrylic and styrene-acrylic copolymers, polyurethane dispersions, conventional latexes and the like. The aqueous dispersions can optionally modified with plasticizers to the Improve film flexibility.

Made from the vinyl copolymers of the invention Coatings, as well as general coatings, are made from vinyl copoly mers are made, a good balance of chemi shear resistance, flexibility and hardness. The properties the cured coatings of various aqueous Dispersio salts of the vinyl copolymers of the present invention were in the same range as vinyl chloride / vinyl acetate / Hy droxypropylacrylate terpolymers in solvent. Clear, gehär tete coatings of aqueous dispersions of salts of the inventions Vinyl copolymers according to the invention on solid substrates such as For example, metal substrates including aluminum or Steel are made from curable mixtures of the present invention made of the salt-containing vinyl copolymers of present invention and crosslinking agents. The curable mixtures contain compared to the amount of salt containing composition of the present invention, a rela tively small amount of crosslinking agent. Preferably included the curable mixtures about 10 to 20 parts by weight curing average per 100 parts by weight of the salt-containing composition of the present invention. Preferably, the curable Mixtures made by mixing a crosslinking agent and one of the above-described aqueous dispersions of present invention, and in such a case is the curable mixture is a curable aqueous dispersion containing a  larger amount of water, a smaller amount of salt-containing Vinyl copolymer of the present invention, a smaller one Amount of crosslinking agent and optionally a smaller one Contains amount of organic solvent. Hardened over Trains are made of the curable composition of the invention tongues on solid substrates by known crosslinking and Coating process produced. If desired, you can the substrates before application of the curable composition primed by known methods. Preferably the crosslinking agents melamine-formaldehyde resins (eg hexa methoxymethylmelamine), urea-formaldehyde resins, polyaziri din resins or polycarbodiimide resins. Curable mixtures of Vinyl copolymer coating compositions of the present invention (or salts thereof) and crosslinking agents new and also form part of the present invention like the process for coating substrates with it and the coated substrates thus prepared.

For purposes of the present invention, the hydroly derived derivative of the reaction product of styrene / maleic acid hydride copolymer and hydroxyethyl acrylate, that at least one ge, preferably virtually all and most preferably all, unreacted maleic anhydride groups in the reaction hydrolyzed product.

The invention is further ver through the following examples anschaulicht.

used abbreviations

In the following examples, the following abbreviations were used used:

Explanation of the properties in Table I Gel-free paint

"GOOD" means that the solvent-based paint practically free of gel particles larger than about 1 μm. Prior to its inversion in water, the copolymer was dissolved diluted with acetone and poured onto a glass plate. The dried film was examined under a microscope.

Shelf Life

"GOOD" means that the aqueous dispersions are at least 2 months at 50 ° C were stable. With "GOOD" judged Disper have a predicted storage stability of minde at least 1 year at 25 ° C. Stable means that the dispersio remain liquid and practically free of sediment or koa gulum are.

Initial dispersion stability

"GOOD" indicates that the amine-modified reactor paint with moderate stirring readily dispersed in water who which was able to make a uniform dispersion with a through  average particle size below about 0.3 μm. The resulting dispersion was virtually free of sediment, gel or grains and remained during the removal of the solvent stable.

Solids / viscosity

"GOOD" indicates that the final withdrawn aqueous Dispersion has a solids content of over 35 wt .-% at a Viscosity of less than about 300 centipoise.

End-use behavior

"GOOD" indicates that the final withdrawn aqueous Dispersion made a clear, grain-free film when using a suitable coalescing solvent such as EGME was modified and poured onto glass. The Dis Persians were under high shear mixing conditions stable and could formu to colors, cover covers and the like be liert.

example 1 Preparation of SMA / HEA macromonomer

In a 2 liter flask equipped with a heating mantle, cooler, Stirrer and an air inlet tube were added 550 g MIBK and 1.6 g of methoxyphenol. This mixture was Added 450 g of SMA and the resulting reaction mixture was heated to 80 ° C to 100 ° C to dissolve the SMA. The Mixture was then cooled to 75 ° C and a mixture of 33 g of HEA and 33 g of MIBK were added dropwise. The mixture was Heated to reflux for 8 hours, then abge to 75-80 ° C abge cooled and 150 g of water was added over 20 minutes drips. The temperature was refluxed for 2-3 hours temperature (about 88 ° C) raised. The resulting solution Can be as it is as a feed to the below discussed Polymerization can be used, or it can be desired if solvent-exchanged with EGME.  

The solvent exchange with the above product he became reaches, by putting on the flask a vacuum distillation set up equipment and an addition funnel, so that MIBK from could be distilled while added EGME has been.

Example 2 Preparation of TMA / HEA macromonomer

A 1 liter round bottom flask was equipped with heating mantle, stirrer, condenser, Air blubber tube and thermocouple equipped. The piston was charged with 384 g TMA, 232 g HEA, 100 g acetone, 0.15 g methoxy phenol and 0.01 g of phenothiazine. The mixture was heated to 60 ° C, a slow flow of air was started and 2.0 g TEA was added. After 4 hours of reaction was the mixture was cooled, 200 g of EGME were added and the Mixture was placed in a rotary evaporator where the Acetone and the triethylamine under vacuum at 50 ° C deducted were.

Example 3 Preparation of a mixture of TMA / HEA and SMA / HEA Macromonomers in MIBK solvent

A 3 liter round bottom flask equipped with heating mantle, stirrer, condenser and Air inlet tube was charged with 500 g of MIBK, 0.6 g of meth oxyphenol and 82 g TMA fed. The mix was for short Time heated to 80 ° C-100 ° C to dissolve the TMA, then on cooled to about 50 ° C, and 124 g HEA mixed with 100 g MIBK were added. The reaction mixture was then heated to 111 ° C. Heated to 112 ° C, while maintaining a slow flow of air was. The reaction mixture was allowed to stand for 7 hours Temperature maintained. The mixture was then lowered to 40 ° C cooled, 500 g MIBK was added, and then 636 g SMA added with stirring. The temperature was then raised to 80 ° C raised until the entire SMA had dissolved, then 3 Increased to 111 ° C-112 ° C for hours. At the end of this time span, the mixture was cooled to 80 ° C-84 ° C, 200 g Water was added and the mixture was stirred for another 1½  Heated for hours. This final mix was on Raumtem cooled, diluted with about 700 g of acetone and as Be used for the polymerization discussed below.

Example 4 Preparation of a mixture of TMA / HEA and SMA / HEA Macromonomers in acetone

One with outside heating, inside cooling coils, magnetic Stirrer and various sampling opening equipped 2 liter stainless steel high pressure reactor was used for this synthesis used. 220 g of acetone, 0.44 g of methoxyphenol, 55 g of TMA and 81.4 g of HEA were added to the open reactor, which was then was assembled. The mixture was heated to 120 ° C for 8 hours heated and then cooled to room temperature. Then 420 became g SMA dissolved in 440 g of acetone added. The reaction Mi The mixture was again heated at 120 ° C for 4 hours, then cooled and 132 g of water were added. The reactor was heated again to 120 ° C for an additional hour, whereupon the final reaction mixture cooled to room temperature and was drained from the reactor.

Examples 5-7 and Control Examples A-E

In a continuous 3 liter filled with liquid Cylindrical loop reactor polymerizations were durchge leads. There were two or three separate feed streams to Reactor. A charge, d. H. Monomer feed 1, contained Vinyl chloride, vinyl acetate, acetone and optionally additional reagents. A second load, d. H. Feed 2, contained IPP polymerization initiator in acetone. A third Feeding, d. H. Monomer feed 3, if available, ent held a second monomer solution in acetone.

The reactor was operated under continuous feed until the appropriate resin solids content was achieved, which detected by densitometer reading and sampling has been. The IPP rate was adjusted so that the desired Solid content was obtained. Only if the solids in the  were desired area became representative resin varnish for processing into a water-based prototype product collected. The collected varnish was batched under Ver deducted from a vacuum pump to unreacted Vinyl chloride and some acetone and vinyl acetate to remove.

Example 5 Monomer feed 1: VCl 7 900 g VAc 1 400 g acetone 4,800 g isopropanol 1 600 g HPA  320 g 16 020 g

Monomer feed 3:
prepared as in Example 3, 95 g / 1000 g Monomerbeschickung

Feed 2:
5 wt% IPP in acetone, about 50 g / hour / about 2000 g / hour monomer feed

Resin solids: 15-17% by weight
Temperature: 60 ° C

Example 6 Monomer feed 1: VCl 6 600 g VAc 1 150 g acetone 3 200 g isopropanol 3 100 g HPA  280 g 14 330 g

Monomer feed 3:
prepared as in Example 4, 96 g / 1000 g Monomerbeschickung

Feed 2:
2.5 wt% IPP in acetone, about 45 g / hr / about 1300 g / hr monomer feed

Resin solids: 16% by weight
Temperature: 59 ° C

Example 7 Monomer feed 1: VCl 5 100 g VAc 600 g acetone 7 560 g HPA  280 g 13 540 g

Monomer feed 3:
prepared as in Example 1, 140 g / 1000 g Monomerbeschickung

Feed 2:
10 wt% IPP in acetone, about 55 g / hr / about 1300 g / hr monomer feed

Resin solids: 16-17 wt%
Temperature: 59 ° C

Control Example A Monomer feed 1: VCl 5 350 g VAc 330 g acetone 9 200 g HPA / TMA solution *)  450 g 15 330 g

*) Prepared in a similar manner as in Example 2.

Monomer feed 3: none

Feed 2:
10 wt% IPP in acetone, about 25 g / hr / about 1900 g / hr monomer feed

Resin solids: 10% by weight
Temperature: 60 ° C

Control Example B Monomer feed 1: VCl 4,800 g VAc 300 g acetone 9 100 g maleic 31 g water 24 g HPA  245 g 14 500 g

Monomer feed 3: none

Feed 2:
10 wt% IPP in acetone, about 45 g / hour / about 2000 g / hour monomer feed

Resin solids: 11-13% by weight
Temperature: 60 ° C

Control Example C Monomer feed 1: VCl 5 400 g VAc 300 g acetone 9,700 g CEA 225 g HPA  245 g 15,835 g

Monomer feed 3: none

Feed 2:
20 wt% IPP in acetone, about 20 g / hr / about 1400 g / hr monomer feed

Resin solids: 11-12% by weight
Temperature: 60 ° C

Control Example D Monomer feed 1: VCl 6 350 g VAc 390 g acetone 8 400 g itaconic 175 g HPA  270 g 15 595 g

Monomer feed 3: none

Feed 2:
10 wt% IPP in acetone, about 80 g / hr / about 2100 g / hr monomer feed

Resin solids: 14-15 wt%
Temperature: 60 ° C

Control Example E Monomer feed 1: VCl 6 025 g VAc 590 g acetone 8 950 g HPA  435 g 16,000 g

Monomer feed 3:
17.6 wt .-% acrylic acid in acetone, fed with 250 g / 1500 g monomer charge alternately with no charge for the next 1500 g monomer charge

Feed 2:
10 wt% IPP in acetone, about 150 g / hr / about 2600 g / hr monomer feed

Resin solids: 15-17% by weight
Temperature: 59 ° C

Example 8 Preparation of a water-based vinyl dispersion

This example illustrates the superiority of the mix of SMA / HEA and TMA / HEA macromonomers at the same time Achieving small particle size and good storage stability ness.

The polymer solution (varnish) in acetone described in example 5 was stirred in amine to neutralize some of the Acid groups in the polymer in a substantially solvent converted free aqueous dispersion. Water was then turned on stirred, whereby the aqueous dispersion was formed. When Next, the remaining solvent was removed.

Finally, additional amine was added to adjust the pH deliver.

In this example, the polymer had the following estimated Composition (in% by weight) on: VCl 66 / VAc 6.6 / HPA 10 / SMA: HEA: H₂O adduct 14.7 / TMA: HEA adduct 2.7. The mix of SMA / HEA and TMA / HEA macromonomers were prepared as in Example 3 in a one-pot reaction in MIBK. The acid number of Polymer solids was 70 (about 60 derived from SMA and about 10 derived from TMA). The logarithmic viscosity number of the polymer was 0.25. The polymer solution had a Non-volatile content of 28% by weight.

595.9 g of the described paint were in a mixing vessel given with a high-speed disperser was equipped with sawtooth mixing blade. The leaf was so large that a good vortex at low and high Viskosi  was maintained to a viscosity drop in the Adding water. 9.61 g TEA were added with stirring, followed by distilled 313.9 g Water. The water was over a period of about 30 - 90 seconds added. After the addition of the water was the pH 6.7. About 50% of the theoretical acid groups were neutral Siert.

The resulting dispersion was poured into a 2 liter neck transferred and put on a rotary evaporator, equipped with hot water, radiator and vacuum pump was. The dispersion was taken at 100 ml vacuum and a water Bath temperature of 95 ° C-99 ° C virtually free of solvent and remaining monomers. The temperature of the abgezo gene was 63 ° C at 100 mm vacuum. The pH of withdrawn dispersion was 5.6. The withdrawn dispersion was cooled to room temperature and with 28% ammonium hydroxide adjusted to pH 9.6. The final dispersion was a uniform germ-free liquid, with an appearance and a viscosity similar to that of or de-skimmed milk. The total solids content was 40% by weight. The average particle size was 0.08 μm, with 90% of the Particles were below 0.17 microns. The dispersion was 3 months long stable at room temperature and 50 ° C. The properties of Water-based vinyl dispersion are in the following table I indicated.

The water-based dispersion was treated with 50 phr of EGME, a coalescing solvent, modified. A 1 mil thicker wet film was poured on a glass plate. The dried one Film was clear, colorless and germ-free. The foaming tendency of Dispersion during stripping was generally low. If necessary, the foam was added by adding 0.1 % By weight of an antifoam agent, d. H. Colloids 770, receives by Rhone-Poulenc, based on polymer solids, regulated.  

Example 9 Preparation of water-based vinyl dispersion

This example illustrates the superiority of the mix of SMA / HEA and TMA / HEA macromonomers at the same time Achieving a small particle size and a good bearing stability.

The polymer solution (paint) described in Example 6 in acetone was stirred by stirring in order to neutralize some the acid groups in the polymer in a substantially solution converted medium-free, aqueous dispersion. Then what became stirred in, whereby the aqueous dispersion was formed. Next, the remaining solvent was removed. Finally, additional amine was added to adjust the pH deliver.

In this example, the polymer had the following estimated value composition (in% by weight): VCl 66 / VAc 6.6 / HPA 10 / SMA: HEA: H 2 O- Adduct 14.7 / TMA: HEA adduct 2.7. The mix of SMA / HEA and TMA / HEA macromonomer was as in Example 4 in an on pot reaction in acetone. The acid number of the poly mer solids was 70 (about 60 derived from SMA and about 10 derived from TMA). The logarithmic viscosity number of the polymer was 0.21. The polymer solution had a content to non-volatiles of 28% by weight.

555.6 g of the described paint were in one with a high Speed dispersing device with sawtooth mixing blade equipped mixing vessel given. The leaf had one Size that a good vortex at low and high viscosity was maintained to reduce the viscosity at the water. 10.78 g of TEA were added Stirring was added, followed by 320.0 g of distilled water. The water was over a period of about 30-90 seconds the added. 0.156 g of an antifoam agent (Colloids 770)  were stirred. After the addition of the water, the pH was 8.2. About 55% of the theoretical acid groups were neutral Siert.

The resulting dispersion was poured into a 2 liter neck transferred and placed on a rotary evaporator, the equipped with hot water, radiator and vacuum pump. The Dispersion was at 100 mm vacuum and a water bath temperature of 95 ° C-99 ° C substantially free of solvent and made of remaining monomers. The temperature of the withdrawn Dispersion was about 63 ° C at 100 mm vacuum. The pH of withdrawn dispersion was 6.3. The withdrawn dispersion was cooled to room temperature and treated with 4.0 g of 28% Ammonium hydroxide adjusted to pH 9.3. The final dis persion was a uniform germ-free liquid with one Appearance and a viscosity similar to that or those of skimmed milk. The total solids content was 39% by weight. and the viscosity was 148 centipoise. The average Particle size was 0.08 μm. The dispersion had a bearing Stability similar to that of the dispersion of Example 8 on. The properties of vinyl dispersion based on water are given in Table I.

The water-based dispersion was made with 50 phr of EGME, a coalescing solvent, modified. A 1-mil thicker wet film was poured on a glass plate. The dried one Film was clear, colorless and grain free.

Example 10 Preparation of water-based vinyl dispersion

This example illustrates that water-based vinyls with small particle size and good storage stability by direct polymerization using a HEA / SMA monome can be prepared in the monomer mixture. gel part in the paint, on polyfunctional fractions in HEA / SMA Ma recycled, however, require a filtration  or centrifuging before the varnish inverts in water can be.

The polymer solution (lacquer) in acetone described in Example 7, was stirred by stirring in order to neutralize some the acid groups in the polymer in a substantially solution converted medium-free, aqueous dispersion. Water became then stirred, whereby the aqueous dispersion wur formed de. Next, the remaining solvent was removed Finally, additional amine was added to adjust the pH adjust.

In this example, the polymer had the following estimated Composition (in% by weight) on: VCl 65 / VAc 5 / HPA 10 / SMA: HEA: (H₂O) 20. The macromonomer was prepared as in Example 1 herge provides. The acid number of the polymer solids was 87, all from SMA. The logarithmic viscosity number of the poly meren was 0.15. The polymer solution had a content non-volatiles of 33% by weight and was trü be. A glass cast film showed very fine insoluble Particles. The paint was acetone to 10% solids ge cut and filtered. The resulting clear varnish was concentrated to 23% solids and disperse in water as follows alternates:

6.9 g of the described paint were gege in a mixing vessel ben, with a high-speed disperser equipped with sawtooth mixing blade. The sheet was like that great, that a good vortex at low and high viscosity was maintained to a viscosity drop in the Zu water. 4.21 g of TEA were added Stirring was added followed by 76.5 g of distilled water. The water was over a period of about 30-90 seconds added. After the addition of the water, the pH was 10.5. 100% of the theoretical acid groups were neutralized.  

The resulting dispersion was poured into a 1 liter neck given and hung on a rotary evaporator, the equipped with hot water, cooler and vacuum pump. The dispersion was vacuumed at 20 mm and a water bath temperature of 60 ° C deducted. The pH of the withdrawn Disper was 8.9. The final dispersion was one unit grain-free liquid with a look and a viscous similar to that of skimmed milk. The Total solids content was 28% by weight.

The water-based dispersion was made with 50 phr of EGME, a coalescing solvent, modified. A 1 mil thicker wet film was poured on a glass plate. The dried one Film was clear, colorless and free of grains.

The dispersion was at 50 ° C for about 90 days and at room temperature stable for 400 days. The properties of vinyl-Disper water-based are given in Table I.

Control Example F Preparation of a water-based vinyl dispersion

This example illustrates that vinyl copolymers, the Trimellitic anhydride, to smaller dispersions Particle size and low storage stability lead.

The polymer solution (lacquer) described in Control Example A was stirred by stirring in order to neutralize the Säu groups in the polymer into a substantially solvent converted free, aqueous dispersion. Then water came in stirred, whereby the aqueous dispersion was formed. When Next, the remaining solvent was removed. Finally, additional amine was added to adjust the pH deliver.

In this example, the polymer has the following estimated Composition (in% by weight) on: VCl 77 / VAc 3 / HPA 10 / HPA: TMA Adduct 10. The HPA / TMA macromonomer was similarly  as prepared in Example 2 in DMF. The acid number of the poly mer solids was 37, all from TMA. The logarith mixing viscosity number of the polymer was 0.28. The polymer Solution in acetone was by precipitation in cold water / Iso propanol, followed by washing in cold water and drying in a vacuum oven overnight, of residual monomer cleans. The dry resin was redissolved in acetone to a non-volatile content of 23% by weight to surrender.

116.9 g of the described paint were in a mixing vessel given with a high-speed disperser was equipped with sawtooth mixing blade. The sheet had such a size that a good vertebra at both low and at high viscosity was maintained to the Viscosity drop in the addition of water to meet. 2.15 g TEA was added with stirring, followed by 76.5 g distilled water. The water was over a period of time of about 30-90 seconds added. After the addition of what The pH was 10.0. 100% of the theoretical acid groups were neutralized.

The resulting dispersion was poured into a 1 liter neck given and hung on a rotary evaporator, the equipped with hot water, radiator and vacuum pump. The Dispersion was at 20 mm vacuum and a water bath temperature subtracted from 60 ° C. The pH of the withdrawn dispersion was 8.1. The withdrawn dispersion was one of granules free liquid with low viscosity and a cloudy / translucent appearance, giving an approximate particle size of about 0.1 microns indicated. The total solids content was about 30-35% by weight.

The water-based dispersion was mixed with 50 phr of EMGE, a coalescing solvent, modified. A 1 mil thicker wet film was poured on a glass plate. The dried one Film was clear, colorless and free from germs.  

The dispersion was at 50 ° C for about 5 days and at room temperature stable for about 40 days. The properties of vinyl dis water-based persistence are given in Table I.

Control Example G Preparation of a water-based vinyl dispersion

This example illustrates that unstable or qua result in low-grade dispersions based on water, when vinyl copolymers of conventional carboxylic acid functio vinyl monomers, VCl, VAc and HPA from acetone solution in Water / amine are dispersed.

In this example, the polymer had the following estimated Composition (in% by weight): VCl 81 / VAc 3 / HPA 13 / male acid 3. The calculated acid number of the polymer solids be was 29. The logarithmic viscosity number of the polymer was 0.27. The polymer solution in acetone was as follows in Water dispersed:

370.2 g of the paint described in Control Example B, the Contained 79.5 g of polymer solids were placed in a mixing vessel given out with a high-speed mixing blade was equipped. 7.92 g of TEA were added with stirring, followed of 230.0 g of distilled water. The water was over one Time span of about 30-90 seconds added. It made no dispersion; the polymer coagulated. The pH was 9.8. 100% of the theoretical acid groups were neutralized. The properties of the vinyl dispersion are water-based in Table I.

Control Example H Preparation of a water-based vinyl dispersion

This example illustrates that unstable or qualitative inferior water-based dispersions will result if Vinyl copolymers of conventional carboxylic acid-functional  Vinyl monomers, VCl, VAc and HPA from acetone solution in water / Amine be dispersed.

The polymer solution (lacquer) described in Control Example C in acetone was stirred by stirring in amine for neutralization tion of the acid groups in the polymer in an aqueous dispersion transformed. Then water was stirred in, whereby the aqueous Dispersion was formed. Next was the remaining one Solvent deducted.

In this example, the polymer had the following estimated Composition (in% by weight) on: VCl 74 / VAc 3 / HPA 11 / CEA 12. The acid number of the polymer solids was 47. The logarith mixing viscosity number of the polymer was 0.26. The polymer Solution in acetone was by precipitation in cold water / Iso propanol, followed by cold water, and drying in one Vacuum oven overnight, freed of residual monomer. The dry resin was again dissolved in acetone to a content to give non-volatiles of 23%. The resulting polymer solution was dispersed in water as follows yaws.

155.8 g of the described paint were in a mixing vessel given with a high-speed disperser was equipped with saw blade mixing blade. The sheet had Such a size that both high and low Viscosity a good vortex was maintained to one Viscosity drop in the addition of water to meet. 3.03 g TEA was added with stirring, followed by 102.0 g of distilled water. The water was over a period of time of about 30-90 seconds added. After the addition of what The pH was 9.9. 100% of the theoretical acid groups were neutralized. The resulting dispersion of fine Particle particles were transferred to a 1 liter one-necked flask leads and added to a rotary evaporator with warm water bath, cooler and vacuum pump was equipped. The Disper sion was at 20 mm vacuum and a water bath temperature of  Subtracted 60 ° C. The dispersion became unstable and coagulated, after less than half of the acetone has been subtracted was. The properties of vinyl dispersion based on water are given in Table I.

The partially withdrawn dispersion had a pH of 9.3.

Control Example I Preparation of a water-based vinyl dispersion

This example illustrates that unstable or qualitative resulting in water-based inferior dispersions, when vinyl copolymers of conventional carboxylic acid funktio vinyl monomers, VCl, VAc and HPA from acetone solution in Water / amine are dispersed.

In this example, the polymer had the following estimated Composition (in% by weight): VCl 80 / VAc 3 / HPA 10 / Itacon acid 7. The calculated acid number of the polymer solids was 61. The logarithmic viscosity number of the polymer was 0.23. The polymer solution in acetone was as follows in Water dispersed:

90.9 g of the paint described in Control Example D, 20.9 g polymer solids containing, were in a mixing vessel given out with a high-speed mixing blade was equipped. 2.53 g of TEA were added with stirring, followed of 59.5 g of distilled water. The water was over one Time span of 30-90 seconds added. 100% of the theory acid groups were neutralized. When adding Water formed a uniform cloudy-translucent Dispersion, but the dispersion coagulated after 1 hour.

The pH of the unstripped dispersion was 9.2. The Dis persion was too unstable for peeling. The properties The water-based vinyl dispersion are listed in Table I. give.  

Control Example J Preparation of a water-based vinyl dispersion

This example illustrates that unstable or qualitative inferior water-based dispersions will result if Vinyl copolymers of conventional carboxylic acid-functional Vinyl monomers, VCl, VAc and HPA from acetone solution in water / Amine be dispersed.

In this example, the polymer had the following estimated Composition (in% by weight): VCl 72.8 / VAc 4.5 / HPA 13.6 / Acrylic acid 9.1. The acrylic acid monomer was pulsed and introduced into the reactor to a block-like Create structure in which the acid groups in the form of Clusters. The calculated acid number of the polymer Solid basis was 61. The logarithmic viscosity number of the polymer was 0.2. The polymer solution in acetone was like follows dispersed in water:

129.9 g of the paint described in Control Example E, 29.9 g polymer solids containing, were in a mixing vessel given out with a high-speed mixing blade was equipped. 3.82 g of TEA were added with stirring, followed of 60.0 g of distilled water. The water was over one Time span of about 30-90 seconds added. 100% of theo Retic acid groups were neutralized. At the addition Water formed a coarse, unstable dispersion. The pH of the non-withdrawn dispersion was 9.9. , The own properties of the vinyl dispersion based on water are shown in Table I indicated.

Claims (12)

A vinyl copolymer comprising the reaction product of:

• (a) about 1-99.9 weight percent of one or more vinyl halous monomers;
• (b) about 0-98.9% by weight of one or more monoethylenically unsaturated monomers other than component (a); and
• (c) about 0.1 to 99% by weight of a monoethylenically unsaturated macromonomer comprising the reaction product of styrene / maleic anhydride copolymer and hydroxyethyl acrylate or the hydrolyzed derivative of this reaction product, or a mixture of monoethylenically unsaturated macromonomers; which comprises (i) a macromonomer comprising the reaction product of trimellitic anhydride and hydroxyethyl acrylate, and (ii) a macromonomer comprising the reaction product of styrene / maleic anhydride copolymer and hydroxyethyl acrylate or the hydrolyzed derivative of this reaction product.

2. Vinyl copolymer according to claim 1, comprising the reaction product of:

• (a) vinyl chloride;
• (b) vinyl acetate;
• (c) hydroxyalkyl (meth) acrylate; and
• (d) a monoethylenically unsaturated macromonomer comprising the reaction product of styrene / maleic anhydride copolymer and hydroxyethyl acrylate or the hydrolyzed derivative of this reaction product, or a mixture of monoethylenically unsaturated macromonomers comprising (i) a macromonomer which is the reaction product of Trimellitic anhydride and hydroxyethyl acrylate, and (ii) a macromonomer comprising the reaction product of styrene / maleic anhydride copolymer and hydroxyethyl acrylate or the hydrolyzed derivative of this reaction product.

A water-dispersible coating composition comprising a vinyl copolymer comprising the reaction product of:

• (a) about 50-95% by weight of one or more vinyl halous monomers;
• (b) about 0-20% by weight of one or more monoethylenically unsaturated monomers other than component (a), and
• (c) about 5-40% by weight of a monoethylenically unsaturated macromonomer comprising the hydrolyzed derivative of the reaction product of styrene / maleic anhydride copolymer and hydroxyethyl acrylate or a mixture of monoethylenically unsaturated macromonomers comprising (i) a macro monomer comprising the reaction product of trimellitic anhydride and hydroxyethyl acrylate, and (ii) a macromonomer comprising the hydrolyzed derivative of the reaction product of styrene / maleic anhydride copolymer and hydroxyethyl acrylate;

wherein the vinyl copolymer after neutralization at least some carboxylic acid groups with a base in a main aqueous medium is dispersible. 4. The composition of claim 3 comprising the reaction product of:

• (a) vinyl chloride;
• (b) vinyl acetate;
• (c) hydroxyalkyl (meth) acrylate; and
• (d) a monoethylenically unsaturated macromonomer comprising the hydrolyzed derivative of the styrene / maleic anhydride copolymer reaction product and hydroxyethyl acrylate or a mixture of monoethylenically unsaturated macromonomers comprising (i) a macromonomer comprising the reaction product of trimellitic anhydride and hydroxyethyl acrylate and (ii) a macromonomer comprising the hydrolyzed derivative of the reaction product of styrene / maleic anhydride copolymer and hydroxyethyl acrylate.

5. Water-dispersible salt-containing coating composition comprise a vinyl copolymer comprising the reaction product of:

• (a) about 50-95% by weight of one or more vinyl halous monomers;
• (b) about 0-20% by weight of one or more monoethylenically unsaturated monomers other than component (a); and
• (c) about 5-40% by weight of a monoethylenically unsaturated macromonomer comprising the hydrolyzed derivative of the reaction product of styrene / maleic anhydride copolymer and hydroxyethyl acrylate or a mixture of monoethylenically unsaturated macromonomers comprising (i) a macro monomer comprising the reaction product of trimellitic anhydride and hydroxyethyl acrylate, and (ii) a macromonomer comprising the hydrolyzed derivative of the reaction product of styrene / maleic anhydride copolymer and hydroxyethyl acrylate;

wherein the vinyl copolymer has at least some salt groups comprising the reaction of carboxylic acid groups and come from a base. 6. An aqueous dispersion comprising a major amount of what and a smaller amount of composition according to Claim 5. 7. A curable composition comprising the composition according to Claim 5 and a crosslinking agent. 8. Hardenable mixture, which is present in aqueous dispersion and a larger amount of water and a smaller amount of  A composition according to claim 5 and a crosslinking agent includes. 9. macromonomer comprising the reaction product of styrene / Maleic anhydride copolymer and hydroxyethyl acrylate or the hydrolyzed derivative of this reaction product. A macromonomer mixture comprising (i) a macromonomer, the reaction product of trimellitic anhydride and Hydroxyethyl acrylate, and (ii) a macromonomer, the reaction product of styrene / maleic anhydride Copolymer and hydroxyethyl acrylate or the hydrolyzed Derivative of this reaction product.