The invention relates to water-dissipatable, lipophilic polymers comprising pendant sulfonic acid salt groups, methods of making such water- dissipatable polymers and the use of such polymers in aqueous systems, including aqueous coating compositions

As used herein, "water-dissipatable", "dissipated in water", and other grammatical forms of such terms are meant to include all forms of one or more substances in water, that is, a solution and/or a colloidal system, including but not limited to solutions, dispersions, suspensions, emulsions, etc

As used herein, "lipophilic polymers" means polymers that are non- dissiDatable, or substantially noπ-dissipatable in water The polymer, however, may contain components, or be the polymerization product of monomers, which in and of themselves are water-dissipatable, as long as the polymer is not Further, the term "polymer" is intended to include oligomers unless otherwise stated Any " popholic polymer" is contemplated herein, however, in general, the lipophilic polymer possess an Mn in the range of about 300 to about 100,000, more preferably about 1000 to about 50,000 and especially about 1000 to about 20,000

As used herein, "aqueous system" means a system wherein one or more substances are dissipated in water

Organic carriers, solvents, emulsifiers, dispersing agents, etc have historically been used to dissipate generally lipophttic polymers

(sometimes also referred to as "resins") in coatings, adhesives, sealants,

film forming products, etc The desire to reduce the use of the above- mentioned organic carriers, solvents, etc in polymer systems has lead to the search for alternatives One of those is using water as the carrier for polymers ultimately dried, cured and/or reacted with other components to produce coatings, adhesives, sealants, etc As noted, for example, in WO- A-92/07010, various options have been pursued to dissipate in water otherwise water-incompatible lipophilic polymers in order to form stable aqueous systems

EP-A-543228 (US-A-5336711 ) discloses, in part, an aqueous binder composition wherein a polyisocyanate component is emulsified in an aqueous solution or dispersion of water-dilutabie organic polyols containing at least one polyester resin having carboxylate and hydroxyl groups and grafted with vinyl monomers That patent publication also teaches preparation of carboxylate groups by at least partially neutralizing carboxyl groups with a base, preferably ammonia or dimethyl ethanol amine However, if such aqueous organic polyol systems are used with polyisoyanates the presence of organic amines can catalyze the undesired reaction between water and isocyanate This produces carbon dioxide which can foam, leading to undesirable effects, such as imperfections in a coating layer Aqueous organic polyol systems requiring little or no organic amme are therefore desirable Further, if such aqueous organic polyol systems are used in coating compositions comprising aminopiasts, such organic amines can retard the curing reaction of the polyol and the aminoplast

Aqueous systems of organic polyols having sulfonate groups are generally known from, for example, EP-A-537568 (US-A-5344873) and EP-A-542105 (US-A-5331039). EP-A-537568 discloses generally an aqueous binder composition containing (A) an aqueous solution or dispersion of a water- dilutable organic polyol component containing at least one water-dilutable

polyester resin requiring, among other things, 4 to 70 mil equivalent sulfonate groups per 100 g polyester resin, and (B) a polyisocyanate component emulsified in the aqueous solution or dispersion (A) EP-A- 537568 prefers sulfonate groups that are obtained from aromatic sulfocarboxylic acids having a molecular weight of 224 to 360 Also among the sulfonate groups specifically mentioned as suitable synthesis components are sulfonate diols such as those described in DE-OS-2 446 440 (US-A-4 08814) However, the sulfonate diols disclosed there are difficult to prepare

Difunctional monomers containing a -S0 ₃ M group attached to an aromatic nucleus wherein M is hydrogen or a metal ion are known from US-A- 4973656 Use in polyester water-dissipated resins is also disclosed There is, however, little flexibility in the configuration of the compounds disclosed in US-A-4973656, and thus insufficient capability to adapt the compounds to various systems and situations

EP-A-542105 may be summarized as disclosing a water-based binder composition wherein a polyisocyanate component is emulsified in an aqueous solution or dispersion of a water-dilutable organic polyol component which is a mixture of at least 5 wt % of each of at least two hydroxy-functional polymers selected from a group of five classes or types of resins, designated as A1 through A5 in EP-A-542105 Among the hydroxy-functional polymers possible in A1 through A5 are polyester resins having sulfonate groups (A3 and A4) and acrylate-grafted polyester resins having sulfonate groups (A5) In addition to the inconvenince and cost of preparing and/or obtaining two polyols, the binder compositions of EP-A- 542105 also risk incompatibility and/or colloidal instability due to the presence of two of the polyols mentioned in that publication

Consequently, the search for water-dissipatable polymers are sought which overcome these and other problems found with current technology

In one embodiment, the current invention relates to lipophilic polymers having pendant sulfonic acid salt groups of the following formula (Formula

1 )

-N-R ² -SO ₃ M

R ¹

wherein

R ¹ is selected from the group (a) hydrogen, (b) Ci to C ₂ o alkyl, (c) substituted Ci to C ₂₀ alkyl and (d) the following formula (Formula 2)

R ³ R ⁴

I I _ ^. c - c — x

I I H OH

wherein R ³ and R ⁴ are independently selected from the group hydrogen and methyl, and

X is the residue of a monoepoxy-containing compound,

R ² is selected from the group d to C ₆ alkylene and Ci to C ₆ substituted alkylene, and

M is a cation.

In a specific variation of this embodiment the lipophilic polymers further compπse pendant Ci to C ₄ alkoxy polyalkoxy alkylene groups

In a preferred embodiment of the current invention the lipophilic polymer is a polyol, preferably an addition polymer polyol

Another embodiment of the current invention comprises an at least partially unsaturated polymer to which has been grafted an addition polymer of the above-descnbed type

The invention also comprises methods of preparing the above-described polymers

The invention further comprises aqueous systems, and in particular aqueous coating compositions comprising the above-described polymers wherein the polymers serve as binders, emulsifying agents and/or dispersing agents

According to the present invention, the " lipophilic polymer" may be based upon any number of the well-known vaπety of polymer systems As examples thereof may be mentioned polyesters and alkyds, poiyepoxyesters, polyethers, polyurethanes, cellulose-based polymers, polycarbonates, polyacrylates, polyvinyls, polyamides, polyacetats, etc.

Preferably, the polymers contain essentially ester and/or addition polymer linkages such as, for example, polyesters (including alkyds), poiyepoxyesters and polymers produced via free-radical addition polymerization. These preferred polymers may also contain minor amounts of other types of linkages such as, for example, urethane (e.g., from chain extension of a polyol with a diisocyanate), ether (e g., chain extension of a polyol with a diepoxide) and others well-known to those skilled in the

relevant art Further, if the lipophilic polymers are grafted with an addition polymer comprising suifonic acid salt groups, the lipophilic polymer must be at least partially unsaturated to enable grafting of the addition polymer The compositions of a number of suitable lipophilic polymers are also discussed in further detail below

As noted above, addition polymers according to the current invention are a preferred embodiment, more particularly, addition polymer polyols Addition polymer polyols, in general, that is, polyols formed by addition polymerization of monomers, are well-known to those skilled in the art and need not be described in detail here All such addition polymers are suitable for use in the current invention Non-limiting examples of free- radically polymerizable monomers suitable for producing addition polymers of the invention are (cyclo)alkyl (meth)acrylates having one to about 12, preferably about 1 to about 6, carbon atoms in the (cyclo)alkyl group, such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, isobornyl (meth)acrylate, dodecyl (meth)acrylate and cyclohexyl (meth)acrylate, (cyclo)alkyl esters of dicarboxylic acids with one to about 12, preferably about 1 to about 6 carbon atoms in the (cycio)alkyl groups, such as dimethyl maleate and diethyl maleate, alkoxy polyalkoxy alkylene (meth)acrylates, such as methoxy polyethylene glycol (meth)acrylates (also referred to as "MPEG (meth)acrylates", typically having a molecular weight from about 300 to about 2000), other (meth)acrylates with ether groups, such as 2-methoxy-ethyl methacrylate, 2-ethoxy-ethyl methacrylate and 3-methoxy-propyl (meth)acryiate, hydroxyalkyl (meth)acrylates, such as 2-hydroxy ethyl (meth)acrylate, 2- hydroxy propyl (meth)acrylate, 4-hydroxy butyl acrylate, 6-hydroxy hexyl acrylate, p-hydroxy polypropylene glycol (meth)acrylate, and alkoxy derivatives thereof; monovinyl aromatic compounds, such as styrene, vinyl toluene, α-methyl styrene and vinyl napthalene, other substituted

(meth)acrylιc compounds such as (meth)acrylamιde, (meth)acrylonιtrιle, N- methylol (meth)acrylamιde and N-alkyl (meth)acrylamιdes, other mono unsaturated compounds such vinyl chloride, vinyl acetate, vinyl propionate and vinyl pyrrolidone, and unsaturated monoepoxides, such as glycidyl (meth)acrylate and glycidyl allyl ether

Monomers suitable for providing pendant sulfonic acid salt groups of Formula 1 generally are free-radically polymerizable monomers having at least one terminal group of Formula 1 Non-limiting examples of such monomers are styrene sulfonic acid, 2-acrylamιdo-2-methyl-propane sulfonic acid, amino ethane sulfonic acid and the salts of such acids, and sodium dodecyl allyl sulfosucciante Other examples of these monomers are monomers which are the reaction product of (a) free-radically polymerizable monomers having an isocyanate group, for non-limiting example, dimethyl-m-isopropenyl benzyl isocyanate, and isocyanato-ethyl methacrylate, and (b) alkali metal tauπnates (in particular, sodium tauπnate), salts of N-(alkyl)tauπnates (especially the sodium salts thereof), and adducts comprising the reaction product of monoepoxy-containing compounds and alkali metal tauπnates, in particular sodium tauπnates Regarding such adducts, reference is made to Formula 2 above "X" in Formula 2 is determined by the monoepoxy-containing compound selected to react with alkali metal tauπnates Examples of such compounds are given below

In pπnciple, any monoepoxy-containing compound is suitable for preparation of the above-described adduct of tauπnate and monoepoxy-containing compound Particularly suitable epoxy-containing compounds are mono glycidyl ethers, such as alkyl glycidyl ethers, for example, butyl glycidyl ether and 2-ethylhexyl glycidyl ether; mono glycidyl esters, including glycidyl esters of carboxylic acids, for example, glycidyl esters of α, α-dimethyl

octanoic acid (available under the trademark CarduraΘE from Shell Chemical Corporation, Houston, Texas, the glycidyl ester of Versatic acid (available as CarduraΘE- 10 from Shell Chemical Corporation, Houston, Texas), etc In one method of preparing such adducts the reactants are brought together in mixtures of water and organic solvent, preferably, water- miscible solvents, for non-limiting example, the water-miscible solvents mentioned below for addition polymerization, and particularly, methoxy ethanol, methoxy propanol and ethanol The ratio of monoepoxy-containing compound to the monomer supplying sulfonic acid or sulfonic acid salt depends on the polymer to which the adduct is ultimately attached and the use made of that polymer (e g , reactive polyol, emulsifier, dispersing agent etc ) However, generally, a suitable ratio is about 0 8 to 1 6, preferably about 1 to about 1 4

Pendant, nonionic stabilizing moieties can be provided by copolymerization with other monomers during polymer formation For example, such pendant nonionic groups may be provided to addition polymers by monomers comprising both unsaturated groups capable of addition polymerization and one or more nonionic groups, such as alkoxy polyalkoxy alkylene (meth)acrylate, preferably the so-called "MPEG- (meth)acrylates" in molecular weight ranges of about 350 to about 2000 Other nonionic monomers which may be copolymerized during addition polymerization are the reaction products of dimethyl-m-isopropenyl benzyl isocyanate and either poiyether amines or adducts which are the reaction product of polyether amme and a monoepoxide. Polyether amines (also referred to as alkoxy polyalkoxy alkylene monoamines) can be prepared by polymerization of monoalcohol with ethylene oxide (EO), propylene oxide (PO) or mixtures of EO and PO The polymerization is carried out in the presence of an initiator such as methanol. After polymerization the end- group is converted to an amme by conventional methods. Polyether

amines are commercially available as Jeffamιne®M from Huntsman Corporation, Zaventem, Belgium

Pendant nonionic groups may also be provided by grafting onto an already formed polymer backbone via appropriate reactive groups before, simultaneously, or after modification with the sulfonate adduct The already discussed polyether amines and their adducts prepared from the reaction product of polyther amine and a monoepoxide are perferably used

Methods for preparing addition polymers, and in particular addition polymer polyols, are well-known to the skilled artisan Accordingly such polymerization need not be described in detail here but will be discussed in general terms

Addition polymerization reactions are usually carried out under inert atmosphere (e g , nitrogen) Polymerization temperatures are generally from about 60°C to about 200°C, preferably about 100°C to about 160°C at atmospheric pressure Reaction at elevated pressure (typically about 1 5 to about 10 bar) is also possible The reaction is also conducted in the presence of a radical initiator A non-limiting list of suitable radical initiators includes dibenzoyl peroxide, dicumyl peroxide, t-butyl-2-ethyl hexanoate, t-butyl perbenzoate, t-butyl cumyl peroxide, methyl ethyl ketone peroxide, di-t-butyl peroxy-3,5,5- trimethyl cyclohexane, di-t-butyl peroxide, 1 ,3-bιs(t-butyl)peroxy isopropyl benzene and mixtures thereof The radical initiators are typically used in amounts from about 0 05 wt % to about 10 wt %, perferably from about 1 wt % to about 5 wt %, based on the weight of the monomer mixture Optionally, chain regulators may be used, such as for non-limiting example, n-octyl mercaptan, dodecyl mercaptan and alkyl mercapto propionates, such as butyl mercapto propionate

Addition polymerization reactions preferably take place in about 5 to about 30 wt % organic solvent, preferably water-miscible organic solvent Non- limiting examples are glycol ethers and propylene glycol ether, such as methoxy propanol, butyoxy ethanol, isopropoxy propanol, n-propoxy propanol, diethylene glycol mono- and di-methyl ether and dipropylene glycol mono-and di-methyl ether Small amounts (e g , less than about 10- 20 wt %) non-water-miscible organic solvents may also be used Larger amounts of non-water-miscible solvents may also be used but they typically require removal, e g by standard distillation techniques

Various processes can be used to carry out addition polymerization For non-limiting example, one homogeneous monomer mixture can be reacted, the monomers and/or monomer mixtures can be sequentially dosed and reacted, some or all monomers can be continuously introduced while varying the concentration of such monomers (see generally, for example, the process disclosed in US-A-3804481 ), etc

In one embodiment of the current invention, an addition polymer comprising sulfonate adducts and optionally nonionic adducts are grafted to an at least partially unsaturated polymer, preferably an at least partially unsaturated polyester However, other at least partially unsaturated polymers can be used, for non-limiting example, polyepoxyester, polyether, polyurethane, etc. and mixtures thereof In a preferred embodiment, the at least partially unsaturated polymers are polymer polyols In a particularly preferred embodiment, the at least partially unsaturated polymer is a polyester polyol.

The preparation of polyols, and especially polyester polyols, is well-known

(see, for example, Surface Coatings, S. Paul, John Wiley & Sons, 1985) and need not be described in detail here Generally, polyester can be prepared from aliphatic, cycloaliphatic or aromatic monocarboxylic acids,

for non-limiting example, benzoic acid, t-butyl benzoic acid, saturated fatty acids (such as isononanoic acid), 2-ethyl hexanoic acid, unsaturated fatty acids (such as soya fatty acid, dehydrated castor oil fatty acid, sorbic acid, etc ) and mixtures, polycarboxylic acids, their esters and anydπdes, for non-limiting example, hexahydrophthalic acid, isophthalic acid, phthalic acid, maleic acid, terephthalic acid, itaconic acid, adipic acid, dimer fatty acids, trimellitic acid, pyromellitic acid and mixtures, aliphatic, cycloaliphatic or araliphatic monofunctional alcohols, for noniimiting example, decanol, n-hexanol, cyclohexanol and mixtures, hydroxy carboxylic acids, for non-limiting example, dimethylol propionic acid, castor oil fatty acid, hydroxy caproic acid and mixtures, and polyols, for non- limiting example, ethylene glycol, propane dιol-1 ,2, neopentyl glycol, butane diol, tπmethylol propane, tπmethylol ethane, 1 ,4-cyctohexane dimethanol, glycerol, pentaerythritol, di-tπmethylol propane, di- pentaerythritol and mixtures.

Polyesters useful in the current invention can be prepared by well-known processes, for non-limiting example, the melt process or the azeotropic process If necessary or desirable, a catalyst can be employed Reaction temperature is typically about 150°C to about 250°C If transesterification is involved, produced alcohol is typically removed (e g., methanol when dimethyl terephthalate is employed)

An unsaturated site for grafting can be provided, in principle, by any copolymerizable monomer having unsaturation. Particularly preferred unsaturated monomers are maleic anhydride, itaconic acid and unsaturated fatty acids, in particular, conjugated unsaturated fatty acids Unsaturation may also be provided after polymer formation by an unsaturated moπoisocyanate, for non-limiting example, dimethyl-m- isopropenylbenzyl isocyanate. A polyester polyol grafted with an addition polyol can be prepared by free-radical addition polymerization in the

presence of an at least partly unsaturated polyol The free-radical addition polymerization can be carried out according to the methods described above

A polymer of the current invention comprising pendant sulfonic acid salt groups, and optionally pendant nonionic groups, is readily dissipatable in an aqueous medium by conventional means, e g stirring, high shear, etc If the polymer is an organic polyol, it is preferably dissipated at temperatures between about 50°C and about 100°C Typically, an aqueous dispersion made according to the current invention comprises a solids content of from about 30 wt % to about 60 wt %, preferably from about 35 wt % to about 55 wt %

Sulfonic acid salt groups of the current invention need to be present in amounts sufficient to render the lipophilic polymer water-dissipatable The amount of sulfonic acid salt groups necessary will vary with the type of lipophilic polymer, but is readily determined by a skilled artisan based on the hydrophobic character of the polymer and the further teachings found herein

One preferred embodiment of the current invention is an addition polymer polyol which comprises pendant sulfonic acid salt groups, perferably about 0 01 to about 0 4 meq/g sulfonic acid salt groups, most preferably about 0 07 to about 0.25 meq/g and, optionally, nonionic stabilizing groups, the nonionic stabilizing groups preferably 0 01 to about 10 wt %, most preferably about 0 5 to about 3 wt % of the polyol Such an addition polymer polyol typically has a molecular weight of about 100 to about 50,000 preferably about 100 to about 40,000, more preferably about 1000 to about 20,000, most preferably, about 1000 to about 10,000 and an OH number of about 20 to about 300 The nonionic stabilizing groups are

typically alkoxy polyalkoxy alkylene groups, preferably having 1 to 4 carbon atoms per group

Another perferred embodiment compπses an organic polyol comprising an at least partially unsaturated polyol having a molecular weight of about 300 to about 3000, an OH number of about 20 to about 300 and an acid number of less than 5 which has been grafted with an addition polymer polyol having an molecular weight of about 1000 to about 50,000 preferably about 100 to about 40,000, more preferably about 1000 to about 20,000, most preferably about 1000 to about 10,000 and an OH number of about 20 to 300 The organic polyol further comprises about 0 01 to about 0 4 meq/g sulfonic acid salt groups, most preferably about 0 01 to about 0 25 meq/g and, optionally nonionic stabilizing groups, the nonionic stabilizing groups preferably being 0 1 to about 10 wt %, most preferably about 0 5 to about 3 wt % (based on solids) of the organic polyol The nonionic stabilizing groups are typically alkoxy polyalkoxy alkylene groups, preferably having 1 to 4 carbon atoms per group

A preferred use of aqueous systems according to the current invention is in coating compositions One particularly preferred coating composition compπses a polyol according to the instant invention and a curing agent for the hydroxyl groups of the polyol Such hydroxyl-reactive curing agents are well-known in the art and need not be fully described here. Preferred classes of hydroxyl-reactive curing agents are N-methylol-contaimng aminoplasts, N-methylol ether-containing aminoplasts and polyisocyanates, more particularly, water-dispersible isocyanates and blocked isocyanates (blocked, e g , with methyl ethyl ketoxime )

Particularly preferred aminoplasts are methylol melamines comprising about 4 to about 6 methylol groups per molecule, wherein at least about 3 of the methylol groups have been etheπfied with methanol, butanol and/or

a methanol or butanol condensation product of formaldehyde and N,N'- ethylene diurea. The preferred ratio of hydroxyl groups provided by the polyol to hydroxyl-reactive groups in the aminoplast is about 0.7 to about 1.5.

Water-dispersable polyisocyanates are well-known and need not be described here in detail. Water-dispersible polyisocyanates particularly suitable for use in the current invention include, but are not limited to tolylene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HMDI), 1 -isocyanate-3,3,5-trimethyl-5- isocyaπatomethylcyclohexane (IPDI), bis-(isocyanatocyclohexyl)methane, etc. The ratio of hydroxyl groups provided by the polyol to hydroxyl- reactive groups of the polyisocyanate is typically about 0.5 to about 5, preferably about 0.9 to about 2.

The coating compositions of the current invention can further comprise other components and additives conventionally present in coating compositions, for non-limiting example, pigments, coloring agents, pigment dispersing agents, thixotropic and other rheological agents, accelerators (e.g., tin catalysts, p-toluene sulfonic acid and blocked derivatives thereof, etc.).

The coating compositions can be applied to any substrate; that is, wood, metal, plastic and other synthetic materials, etc. Further, the aqueous dispersions of the instant invention can be employed in all types of coating compositions particularly, paints. They are especially useful as clear coats and pigmented top coats for metal surfaces (particularly automotive and transportation vehicle coatings and more particularly refinishing). These applications make use of the fact that the current invetion provides stable, aqueous coating compositions (typically "paints") which, when cured, provide high quality coatings. These coatings have high asesthetic

qualities (e.g. high gloss ( > 70 at 20°) and lack of haziness) without sacrificing technical characteristics, such as hardness, solvent resistance and water resistance. They are thus particularly suitable for coatings that are "finishes"; that is, visible coatings that must provide aesthetic appeal, such as clear coats and pigmented top coats on vehicles, appliances, etc. and indeed, any consumer product.

Any known methods for applying coating compositions can also be used. Non-limiting examples of such application methods are spreading (e.g. brushing, rolling, by paint pad or doctor blade), spraying (e.g., airfed spray, airless spray, hot spray and electrostatic spray), flow coating (e.g. dipping, curtain coating, roller coating and reverse roller coating) and electrodeposition. (See generally, Paint and Surface Coatings: Theory and Practice, R. Lambourne, Editor, Ellis Horwood, 1987, page 39 et seq.) Coating compositions of the instant invention can be formulated to accommodate drying and curing at ambient temperature and elevated temperature (e.g. about 60°C to about 160°C ).

In addition to being used as the binder or resin component in a coating composition, the polymers of the current invention can also be employed in aqueous systems, particularly coating compositions, as a polymeric emulsifying agent or dispersing agent for other polymers in the aqueous system, especially those which do not have sulfonate and/or nonionic groups. The other polymer present in the aqueous system is typically a polyol, for non- limiting example, polyester polyol, polyepoxyester polyol, polyether polyol, polyurethane polyol, polyacrylate polyol, etc. and mixtures thereof. However, the polymers of the current invention can also be used as an emulsifying and/or dispersing agent for other polymers, such as alkyds. Polymers of the current invention can also be used as a dispersing agent for pigments.

The invention is further described and illustrated by the examples which follow

EXAMPLES

In the Examples which follow, the compositions listed below are available as indicated

i 1 -Methoxy propanol-2 is available as "Dowaπol PM" from Dow Chemicals, Midland, Michigan

II T-butyl peroxy-2-ethyl hexanoate is available as "Tπgonox®21 S from Akzo Nobel Chemicals, Amersfoort, the Netherlands

In the Examples which follow, the commercial products listed below have the compositions indicated and are available from the suppliers named

i Cardura®E-10, the glycidyl ester of Verstic acid, is available from either Shell Chemical Corpoaration,

Houston, Texas

n Jeffamιne®M-1000, a polyether amme having an EO/PO ratio of approximately 19/3 and an Mn of about 1100, is available from Huntsman Corporation,

Zaveπtem, Belgium

Preparation of Polymers and Agueous Dispersions

Reaction Product A

Low MW Unsaturated Polyester A

The components listed below were weighed into a 3-neck 6-lιter round- bottom flask fitted with a stirrer, a thermometer, a Dean- Stark apparatus and a reflux condenser tπmethylol propane 1608.00 parts itaconic acid 104 00 parts isononanoic acid 1264.00 parts hexahydrophthalic anhydride 1108 80 parts o-phosphoπc acid catalyst 1 00 part o-xylene 200 00 parts

After the Dean-Stark apparatus was filled with o-xylene, the reaction flask was evacuated and the air replaced with nitrogen This procedure was repeated twice The contents of the flask were heated until the formed water was trapped by the Dean-Stark apparatus (azeotropic distillation with xylene) The temperature was increased gradually to 250°C and the water collected After 15 hours, 315 parts of water were collected. The reaction product had an acid value of 1 05 mg KOH/g. The reactor was cooled to 180°C and the xylene and remaining water removed at reduced pressure by distillation The end product had an acid value of 0 83 mg KOH/g

The polyester was cooled to 120°C and diluted with 418 parts -methoxy propanol-2 to a solids content of 90% by weight. The polyester solution was then cooled to room temperature

Reaction Product B

Adduct of Sodium Tauπne and Glycidyl Ester of Versatic Acid

The components listed below were weighed into a 3-neck 2-lιter round- bottom flask fitted with a stirrer, a thermometer, a dropping funnel and a reflux condenser tauπne (2-amιnoethane sulfonic acid) 187 50 parts sodium hydroxide 60 00 parts demineralized water 149.00 parts

1 - methoxy propaπol-2 704.00 parts

The dropping funnel was filled with 450 parts Cardura®E-10 glycidyl ester After a vacuum/nitrogen flushing procedure (3 times) the reactor was heated to 10OX.

The Cardura E-10 glycidyl ester was added in 2 hrs to the reactor while the contents of the reactor were stirred. The system was initially heterogeneous, but after circa 35 minutes a homogeneous solution was obtained Post-reaction conditions were continued until the conversion of the Cardura E-10 glycidyl ester was complete (5-10 minutes after the end of the dosage).

The water was removed by distillation under reduced pressure. The maximum temperature of the solution was 105°C and the lowest pressure circa 15 mm Hg.

Enough 1 -methoxy propanol-2 was added to obtain a product with a solids content of 66.5 wt.%. The product was easily handled at room temperature.

Reaction Product C

Adduct of Polyether Amine and Glycidyl Ester of Versatic Acid

Eight hundred (800) parts Jeffamine M-1000 polyether amme were weighed into a 3-neck 2-liter round-bottom flask fitted with a stirrer, a thermometer, a dropping funnel and a reflux condenser.

The dropping funnel was filled with 200 parts Cardura E-10 glycidyl ester. After a vacuum/nitrogen flushing procedure (3 times) the reactor was heated to 120°C and the Cardura E-10 giycidyl ester was added. The reaction was continued until the conversion of the Cardura E- 0 glycidyl ester was complete. The reaction product was cooled to 60° C and stored at room temperature.

Reaction Product D

Low MW Unsaturated Polyester D

Reaction Product D is identical to Reaction Product A except it has a solids content of 68.3 wt.%.

Reaction Product E

Low MW Unsaturated Polyester E

Reaction Product E is identical to Reaction Product A except it has a solids content of 87 wt.%.

20 Reaction Product F

Acrylic Polymer

Three hundred fifty (350 0) parts 1 -methoxy propanol-2 were weighed into a 3-neck 2-lιter round-bottom flask fitted with a stirrer, a thermometer, two dropping funnels and a reflux condenser

Dropping Funnel A was filled with a homogeneous mixture of the following components

2-hydroxyethyl methacrylate 447 23 parts butyl acrylate 314 20 parts methyl methacrylate 49045 parts gylcidyl methacrylate 190 31 parts

Dropping Funnel B was filled with a homogeneous mixture of the following components

t-butyl peroxy-2-ethyl hexanoate 57 59 parts 1 - methoxy propanol-2 25 00 parts

The flask was evacuated and the air replaced with nitrogen three (3) times The contents of the flask were heated to reflux and contents of the funnels were added according to the scheme detailed below.

Time (hrs) Remarks

0 start Dropping Funnels A and B

3 stop Dropping Funnel A, continue B 4 stop Dropping Funnel B

After the addition of Dropping Funnel B was completed, the temperature was kept at refiux (approximately 125°C) for another 2 hours. The polymer solution was then allowed to cool to room temperature.

Example 1 : Sulfonate Stabilization

The following component was weighed into a 3-neck 2-liter round-bottom flask fitted with a stirrer, a thermometer, three dropping funnels and a reflux condenser.

Reaction Product A 311.11 parts

Dropping Funnel A was filled with a homogeneous mixture of the following components:

2-hydroxy ethyl methacrylate 53.23 parts butyl acrylate 41.21 parts methyi methacrylate 77.26 parts dodecyl mercaptan 3.43 parts

Dropping Funnel B was filled with a homogeneous mixture of the following components:

2-hydroxy ethyl methacryalte 63.20 parts butyl acrylate 45.88 parts methyl methacrylate 81.07 parts glycidyl methacrylate 13.70 parts dodecyl mercaptan 4.08 parts

1 - methoxy propanol-2 14.75 parts

22 Dropping Funnel C was filled with a homogeneous mixture of the following components:

t-butyl peroxy-2-ethyl hexanoate 15.03 parts 1 - methoxy propanol-2 25.00 parts

After a vacuum/nitrogen flushing procedure (3 times) the contents of the reactor were heated to 120°C and the contents of the dropping funnels were added according the scheme detailed below

Time (hrs) Remarks

0 start Dropping Funnels A and C 1.5 stop Dropping Funnel A, start B and continue C 3.0 stop Dropping Funnel B, continue C

4 0 stop Dropping Funnel C

After the addition of Dropping Funnel C was completed, the temperature was kept at 120°C for another 2 hours.

Dropping Funnel D was filled with 32.93 parts Reaction Product B.

Dropping Funnel D was fitted on the reactor and its contents added over a 15 minute period. After completion the contents of the reactor were heated to 140°C.

After 4 hours the contents of the reactor were cooled to less than 100°C and 490.85 parts demineralized water were added gradually (circa 3 hours) to

23 the reactor The temperature of the contents of the reactor was maintained at 60°C.

The end product, a fine waterbome dispersion, was cooled to room temperature The solids content was 55% by weight and the average particle size 247 nm (measured with QELS Quasi Elastic Light Scattering) The dispersion was still stable after 4 weeks at 35°C

Example 2 Sodium Sulfonate and Nonionic Stabilization

Reaction Product A (311 11 parts) was weighed into a 3-neck 2-liter round- bottom flask fitted with a stirrer, a thermometer, three dropping funnels and a reflux condenser.

Dropping Funnel A was filled with a homogeneous mixture of the following components

2-hydroxy ethyl methacrylate 53.23 parts butyl acrylate 41.21 parts methyl methacrylate 77.26 parts dodecyl mercaptan 3 43 parts

Dropping Funnel B was filled with a homogeneous mixture of the following components:

2-hydroxy ethyl methacrylate 60.65 parts butyl acrylate 46.66 parts methyl methacrylate 72.37 parts glycidyl methacrylate 15.93 parts dodecyl mercaptan 3.92 parts

1 -methoxy propanol-2 14.75 parts

Dropping Funnel C was filled with a homogeneous mixture of the following components:

t-butylxperoxy-2 -ethyl hexanoate 14.69 parts

1 -methoxy propanol-2 25.00 parts

After a vacuum/nitrogen flushing procedure (3 times) the reactor was heated to 120°C and the contents of the dropping funnels were added according the following scheme:

Time (hrs) Remarks

0 start Dropping Funnels A and C 1.5 stop Dropping Funnel A, start B and continue C 3.0 stop Dropping Funnel B, continue C

4.0 stop Dropping Funnel C

After the addition of Dropping Funnel C was completed, the temperature was kept at 120°C for another 2 hours.

Dropping Funnel D was filled with a warm, homogeneous mixture of the following components:

Reaction Product B 32.93 parts

Reaction Product C 8.75 parts

Dropping Funnel D was fitted on the reactor and its contents added over a 15 minute period. After completion of the addition, the contents of the reactor were heated to 140°C.

After 4 hours the contents of the reactor were cooled to below 100°C and 618.09 parts demineralized water were added gradually (circa 3 hours) to the reactor. The temperature of the contents of the reactor was maintained at 60°C. The end product, a fine waterbome dispersion, was cooled to room temperature. The solids content was 50% by weight and the average particle size 186 nm (measured with QELS: Quasi Elastic Light Scattering). The dispersion was still stable after 4 weeks at 35°C.

Example 3 Sulphonate Stabilization

Reaction Product A (311.11 parts) was weighed into a 3-neck 2-iιter round- bottom flask fitted with a stirrer, a thermometer, three dropping funnels and a reflux condenser.

Dropping Funnel A was filled with a homogeneous mixture of the following components:

2-hydroxy ethyl methacrylate 53.23 parts butyl acrylate 41.22 parts methyl methacrylate 77.26 parts dodecyl mercaptan 3.43 parts

Dropping Funnel B was filled with a homogeneous mixture of the following components:

2-hydroxy ethyl methacrylate 61.85 parts butyl acrylate 47.25 parts methyl methacrylate 73.38 parts glycidyl methacrylate 16.95 parts dodecyl mercaptan 3.99 parts

1 -methoxy propanol-2 12.55 parts

26 Dropping Funnel C was filled with a homogeneous mixture of the following components: t-butyl peroxy-2-ethyl hexanoate 14.85 parts

1 -methoxy propanol-2 25.00 parts

After a vacuum/nitrogen flushing procedure (3 times) the contents of the reactor were heated to 120° C and the contents of the dropping funnels was added according the scheme described in Example 2.

After the addition of Dropping Funnel C, the temperature was kept at 120° C for another 2 hours.

Dropping Funnel D was filled with 38.95 parts Reaction Product B.

Dropping Funnel D was fitted on the reactor and its contents added over a 15 minute period. After completion of the addition, the contents of the reactor were heated to 140°C.

After 4 hours the contents of the reactor were cooled to below 100°C and 619.00 parts demineralized water were added gradually (circa 3 hours) to the reactor. The temperature of the contents of the reactor was maintained at 60°C.

The end product, a fine waterbome dispersion, was cooled to room temperature. The solids content was 50% by weight and the average particle size 153 nm (measured with QELS: Quasi Elastic Light Scattering). The dispersion was still stable after 4 weeks at 35°C.

Example 4: External Emulsifier

Five hundred (500) parts Reaction Product F were weighed into a 3-neck 2- liter round-bottom flask fitted with a stirrer, a thermometer, two dropping funnels and a reflux condenser.

Dropping Funnel A was filled with 16.90 Reaction Product C and Dropping Funnel B was filled with 61.86 parts Reaction Product D.

The reactor was evacuated then nitrogen-flushed three times. The reaction was heated to reflux (about 126°C) and the contents of the dropping funnels were added according to the following scheme.

Time (hrs. min) Remarks

0.00 start Dropping Funnel A

0.10 stop Dropping Funnel A

2.10 start Dropping Funnel B

2.20 stop Dropping Funnel B

After addition of Dropping Funnel B was completed, the temperature was kept at reflux (about 123° ) for another 3 hours. The emulsifier solution was then allowed to cool to room temperature.

Example 5: Polyol Dispersion Having External Emulsifier

The following components were weighed into a flask fitted with a stirrer, a thermometer and a reflux condenser. (The "high solids polyester polyol solution" had a solids content of 90 wt.% in 1 -methoxy propanol-2, a calculated MW of 1200 and an OH number of 160 mg KOH/g solids.)

External Emulsifier from Example 4 300 01 parts high solids polyester polyol solution 513 33 parts

The contents of the reactor were heated to 80°C under good mixing Over a period of approximately 3 hours, 615 26 parts demineralized water were added During water addition, the reactor was gradually cooled to 60° C then held at that temperature for the remainder of the water addition

The end product, a fine waterbome dispersion, was cooled to room temperature The solids content was 49% by weight and the average particle size 288 nm (measured with QELS Quasi Elastic Light Scattering) The OH number of the dispersion was 152 7 mg KOH/g solids The dispersion was still stable after 4 weeks at 35°C

Comparative Example 6- Carboxylate Stabilization with Amme Neutralization

Reaction Product E (275.90 parts) was weighed into the flask of an apparatus configuration of the type described in Example 1

Dropping Funnel A was filled with a homogeneous mixture of the following components.

2-hydroxyethyl methacrylate 44.57 parts butyl acrylate 35.66 parts methyl methacrylate 68.34 parts dodecyl mercaptan 2.97 parts

Dropping Funnel B was filled with a homogeneous mixture of the following components.

2-hydroxyethyl methacrylate 58.29 parts butyl acrylate 60.61 parts methyl methacrylate 53.43 parts methacrylic acid 1.96 parts dodecyl mercaptan 3.88 parts

1 -methoxy propanol-2 9.50 parts

Dropping Funnel C was filled with a homogeneous mixture of the following components.

t-butyl peroxy-2-ethylhexanoate 10.30 parts

1 -methyloxy propaπol-2 25.00 parts

The reactor was evacuated and flushed with nitrogen three (3) times. The contents of the reactor were heated to 120°C. The contents of the dropping

30 funnels were added according to the scheme descπbed in Example 2 After addition of the contents of Dropping Funnel C the temperature was held at 120°C for another 2 hours THe contents of the reactor were then cooled to 108°C

Dropping Funnel D was filled with 17 02 parts N,N-dιmethylethanol amine It was fitted on the reactor and the contents were added over a period of 15 minutes The contents of the reactor were cooled to about 100°C and 747 50 parts demineralized water were added gradually (about 3 hours) to the reactor During water addition the reactor contents were allowed to cool to 80°C, and then held at that temperature

The end product, a fine waterbome dispersion, was cooled to room temperature The solids content was 43 wt % and the average particle size 150 nm (measured with QELS Quasi Elastic light Scattering) The OH number of the dispersion was 145 mg KOH/g solids (corrected for the OH originating from N.N-dimethylethanol amine 158 KOH/g)

Comparative Example 7 Carboxylate Stabilization with NaOH Neutralization

Reaction Product E (275 90 parts) was weighed into the flask of an apparatus configuration of the type described in Example 1

Dropping Funnel A was filled with a homogeneous mixture of the following components

2-hydroxy ethyl methacrylate 44 57 parts butyl acrylate 35 66 parts methyl methacrylate 68 34 parts dodecyl mercaptan 2 97 parts

Dropping Funnel B was filled with a homogeneous mixture of the following components

2-hydroxy ethyl methacrylate 58 29 parts butyl acrylate 60 61 parts methyl methacrylate 53 43 parts methacrylic acid 21 96 parts dodecyl mercaptan 3 88 parts

1 -methoxy propanol-2 9 50 parts

Dropping Funnel C was filled with a homogeneous mixture of the following components

t-butyl peroxy-2-ethyl hexanoate 10 30 parts 1 -methyloxy propanol-2 25 00 parts

The reactor was evacuated and flushed with nitrogen three (3) times The contents of the reactor were heated to 120°C The contents of the dropping funnels were added according to the scheme described in Example 2 After addition of the contents of Dropping Funnel C the temperature was held at 120°C for another 2 hours The contents of the reactor were then cooled to 105°C

Dropping Funnel D was filled with a homogeneous solution of 7 65 parts sodium hydroxide and 12 parts demineralized water It was fitted on the reactor and the contents were added over a period of 15 minutes The contents of the reactor were cooled to about 100°C and 698 58 parts demineralized water were added gradually (about 3 hours) to the reactor During water addition the reactor contents were allowed to cool to 80°C, and then held at that temperature

The end product, a fine waterbome dispersion, was cooled to room temperature The solids content was 43 wt % and the average particle size 206 nm (measured with QELS Quasi Elastic Light Scattering) The OH number of the dispersion was 143 mg KOH/g solids

Preparation of Coating Compositions and Films

In the following Examples 8-13, unpigmented coating compositions in accordance with the present invention were prepared by homogeneously mixing the dispersion, the polyisocyanate, and methoxypropanol acetate, commercially available as Dowanol PMA from Dow, Midland, Michigan Demineralized water was added as needed to adjust for application viscosity (between about 0 5 and about 1 0 Pa-sec)

The polyisocyanate used in Examples 8-13 is the polyisocyanate resm commercially available as Bayhydur LS 2032 from Bayer, Leverkussen Germany It was diluted before mixing with methoxypropanol acetate to 80% solids contents

The coating compositions of Examples 8-13 were applied to a zinc phosphate pretreated steel panel (Bonder 26 60 OC) and cured at room temperature The hardness, gloss, organic solvent resistance and water resistance were measured after 1 week curing. Organic solvent resistance and water resistance were also measured after 2 days curing.

The Persoz hardness was determined in accordance with French industπal standard NF T30-016, and the results are expressed in seconds An acceptable minimum for automotive and car refinish coating is about 180 seconds

The gloss of the coating was determined in accordance with U.S industrial standard ASTM D-523 at 60° and 20° A gloss value on a steel substrate of above 80 at 60° and of above 70 at 20° is considered high.

Tests

Water resistance was tested by putting a piece of water-soaked cottonwool on the coating After one hour the wet cotton-wool was removed and the panel was wiped dry. Appearance was noted. The scratch resistance was tested by rubbing the treated area with a finger nail. Test results are reported on a scale from 0 to 10, where 0 is very bad and 10 is very good An acceptable minimum is generally considered to be 8

The solvent resistance to gasoline and methyl ethyl ketone was tested. The test was similar to the water resistance test, but the cotton-wool was removed after 1 minute instead of 1 hour. An acceptable minimum for gasoline resistance is generally considered to be 8 and for methyl ethyl ketone resistance 5.

Tests for both water resistance and solvent resistance were carried out after two days and after one week.

Example 8

The following components were added sequentially to 90.9 parts by wt. (pbw) of the dispersion from Example 1.

15.0 pbw methoxy propanol acetate

61.6 pbw Bayhydur LS 2032 solution in methoxypropanol acetate (solids content = 80%)

The resulting coating composition was diluted with demineralized water to application viscosity

A doctor blade was used to coat (100-200 μm thick, wet) a Bonder 26 60 OC steel panel with the coating composition After 1 week curing at room temperature the resulting film had a Persoz hardness of 253 seconds and showed high gloss (> 75 at 20° and > 85 at 60° ) The solvent and water resistance test results are reported in Table I

The coating composition was also applied as a top coat to both a waterbome basecoat and a solvent borne base coat, available commercially, respectively as Autowave® basecoat and Autobase® basecoat, Akzo Nobel Coatings, Sassenheim, the Netherlands

The resulting test panels had a good metallic appearance and high gloss after cure

Example 9

The following components were added sequentially to 104 2 parts by wt (pbw) of the dispersion from Example 2

14 9 pbw methoxy propanol acetate

61 3 pbw Bayhydur LS 2032 solution in methoxypropanol acetate (solids content = 80%)

The resulting coating composition was diluted with demineralized water to application viscosity

A doctor blade was used to coat (100-200 μm thick, wet) a Bonder 26 60 OC steel panel with the coating composition After 1 week curing at room temperature the resulting film had a Persoz hardness of 230 seconds and showed high gloss (> 75 at 20° and > 85 at 60° ) The solvent and water resistance test results are reported in Table I

The coating composition was also applied as a top coat to both a waterbome basecoat and a solvent borne basecoat, available commercially, respectively as Autowave® basecoat and Autobase® basecoat, Akzo Nobel Coatings, Sassenheim, the Netherlands.

The resulting test panels had a good metallic appearance and high gloss after cure.

Example 10

The following components were added sequentially to 100 0 parts by wt (pbw) of the dispersion from Example 3

15.0 pbw methoxy propanol acetate

61.8 pbw Bayhydur LS 2032 solution in methoxypropanol acetate (solids content is 80%)

The resulting coating composition was diluted with demineralized water to application viscosity.

A doctor blade was used to coat (100-200 μm thick, wet) a Bonder 26 60 OC steel panel with the coating composition. After 1 week curing at room temperature the resulting film had a Persoz hardness of 255 seconds and

showed high gloss (> 75 at 20° and > 85 at 60° ) The solvent and water resistance test results are reported in Table I

The coating composition was also applied as a top coat to both a waterbome basecoat and a solvent borne base coat, available commercially, respectively as Autowave® basecoat and Autobase® basecoat, Akzo Nobel Coatings, Sassenheim, the Netherlands

The resulting test panels had a good metallic appearance and high gloss after cure

Example 11

The following components were added sequentially to 102 parts by wt (pbw) of the dispersion from Example 5

12 6 pbw methoxy propanol acetate

60 8 pbw Bayhydur LS 2032 solution in methoxypropanol acetate

(solids content = 80%)

The resulting coating composition was diluted with demineralized water to application viscosity A doctor blade was used to coat (100-200 μm thick, wet) a Bonder 26 60 OC steel panel with the coating composition After 1 week curing at room temperature the resulting film had a Persoz hardness of 269 seconds and showed high gloss (> 75 at 20° and > 85 at 60° ) The solvent and water resistance test results are reported in Table I

The coating composition was also applied as a top coat to both a waterbome basecoat and a solvent borne basecoat, available commercially, respectively as Autowave® basecoat and Autobase® basecoat, Akzo Nobel Coatings, Sassenheim, the Netherlands

The resulting test panels had a good metallic appearance and high gloss after cure.

Example 12 (Comparative Example)

The following components were added sequentially to 100.0 parts by wt. (pbw) of the dispersion from Example 6.

13.0 pbw methoxy propanol acetate

55.4 pbw Bayhydur LS 2032 solution in methoxypropanol acetate (solids content = 80%)

The resulting coating composition was diluted with demineralized water to application viscosity.

A doctor blade was used to coat (100-200 μm thick, wet) a Bonder 26 60 OC steel panel with the coating composition. After 1 week curing at room temperature the resulting film had a Persoz hardness of 250 seconds and showed high gloss (> 75 at 20° and > 85 at 60° ). The solvent and water resistance test results are reported in Table I.

The coating composition was also applied as a top coat to both a waterbome basecoat and a solvent borne basecoat, available commercially, respectively as Autowave® basecoat and Autobase® basecoat, Akzo Nobel Coatings, Sassenheim, the Netherlands. The gloss of both panels was unacceptable due to foam formation in the top coat.

Example 13 (Comparative Example)

The following components were added sequentially to 100 0 parts by wt (pbw) of the dispersion from Example 7

12 6 pbw methoxy propanol acetate

50 1 pbw Bayhydur LS 2032 solution in methoxypropanol acetate (solids content = 80%)

The resulting coating composition was diluted with demineralized water to application viscosity

A doctor blade was used to coat (100-200 μm thick, wet) a Bonder 26 60 OC steel panel with the coating composition Solvent and water resistance test results are reported in Table I

After one week curing at room temperature the film was hazy Testing was stopped

Table

Resistance Tests (after 2 days/1 week)

Example Water Gasoline Methyl ethyl ketone

8 9/10 10 7/8

9 9/10 10 7/8

10 9/10 10 7/8

11 9/10 10 7/8

12 (comparative) 9/9 9/9 7/8

13 (comparative) 5(*)/7( ^* *) 9/9 7/8

( ^* ) white s pot and loss of adhesion or

(* ^* ) loss of adhesion on steel