CA2061445A1 - Non-aqueous dispersion - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
Disclosed herein is a non-aqueous dispersion of an addition polymer in an alkyd medium. The alkyd has a z-average molecular weight (Mz) of greater than about 150,000 and an NVM
of less than about 70%. The addition polymer is produced by polymerizing two or more monomers in the presence of the alkyd by a radical addition polymerization. At least one of the monomers is (meth)acrylonitrile, hydroxyethyl (meth)acrylate, methyl (meth)acrylate, (meth)acrylamide, vinyl chloride, vinylidene chloride, (meth)acrylic acid, itaconic acid, maleic acid or fumaric acid. At least one of the monomers has a hydroxy-functionality. The polymerization is conducted in the presence of a chain transfer agent. The non-aqueous dispersion is particularly suitable for interior or exterior applications in the architectural industrial maintenance and traffic paint and coating industries.

Description

2~

IMPROVED NON-AQUEOUS DISPERSIONS

R~ Tomko M. Rao D. Sayre BACKGROUND OF THE INVENTION
Non~aqueous dispersions (NAD's) are well known in the art and typically consist of dispersions of addition polymers in a relatively non-polar non-aqueous liquid containing a steric stabilizing agent having dual a~finity to both the dispersing and the dispersed media. For example, U.S. Patent 3,198,759 teaches dispersions of addition polymers in a hydrocarbon medium. The hydrocarbon medium contains one or more aliphatic hydrocarbons containing dissolved therein an alkyd formed ~y either the direct esterification of a drying oil *atty acid with a diaarboxylic acid and a polyhydric alcohol or the indirect esterification of a drying oil by first alcoholization with a polyhydric alcohol and second esterification with a polybasic acid. European Patent Application 0 310 331 A2 teaches a non-a~ueous di~persion of a soluble low molecular weight non-alkyd polymer which i8 attached or adsor~ed onto a second non-soluble alkyd-~ree polymer. U.S. Patent 4,530,957 teaches non-aqueous dispersions based on crosslinked acrylic polymar particles dispersed in a non-aqueous medium having a polymeric dispersion stabilizer. The polymeric dispersion stabilizer can be an alkyd which is formed by the self condensation of 12-hydroxystearic acid follow2d by a capping reaction with glycidyl methacrylate. U.S. Patent 4,206,099 teaches non-aqueous dispersions of crosslinked polymer particles in a non-aqueous medium having an amphipathic steric stabilizing agent. The steric stabilizing agent can be a graft copolymer obtained by reacting a low molecular weight carboxyl group terminated condensate of linseed oil fatty acids and 12-hydroxystearic acid with acrylic copolymers. U.S. Pa~ent 3,77~,977 teaches non-aqueous dispersions of an acrylonitrile copolymer in a liquid butadiene homopolymer or copolymer in a non-polar organic hydrocarbon liquid.
Previous work of ours has shown that selecting alkyds which have speci~ic properties for use as the steric stabilizing media for an NAD can lead to high solids, low VOC stable NAD's which exhibit acceptable viscosities. In the present invention, we have found a means ~or producing NAD's which utilize conventional, lower solids alkyds as the steric stabilizing media. our present NAD's have excellent stability, filterability, gloss, low grit, viscosity and tack-free and dry hard times when formulated as air dry coatiny compositions. Surprisingly, when produced at the same solids content as the alkyd used to make the NAD's, they exhibit substantially equivalant or lower viscosity than that alkyd. Thus, the potential ~or lowering the VOC o~ the coating exists. The NADIs of this invention also air dry ~aster than the alkyds used to make the NAD.
These NAD's-utilize conventional, traditional alkyds as the dispersing media and steric stabilizer. These NAD's require a specific selection process wherein certain aritical parameters, described fully below, must be observed in order to improve the coating.

- i ~ 2~ 5 SUMMARY OF THE INVENTION
This invention relates to improved non-aqueous dispersions (NAD's) and a process for producing these improved non-aqueous dispersions. The improved NAD's of this invention comprise a conventional alkyd as the dispersing medium and steric stabilizer for the polymerization product of specific monomers, which polymers are predominantly non soluble in the alkyd medium. The improved NAD's of this invention are the product of a process which utilizes a conventional alkyd steric stabilizer in the dispersing media, a combination of monomers wherein at least one monomer is selected from the group consisting of acrylonitrile, methacrylonitrile, hydroxy ethyl acrylate and methacrylate, methyl acrylate and methacrylate, acrylamide, methacrylamide, vinyl chloride, vinylidene chloride, acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, the methyl esters of itaconic, maleic and fumaric acid, and mixtures thereof, wherein at least one monomer is a hydroxy-functional free radical addition monomer, and wherein the polymerization is conducted in the presence of a chain transfer agent. ThiG yields NADIs which ara particularly suited for interior and exterior applications in the architectural, industrial maintenance, and traffic paint and coatings industries.
The process for producing the NAD's of this invention comprises using an alkyd meeting the criteria established herein as the dispersing medium, either alone or in combination with some minor amount of hydrocarbon, aromatic, polar, ketone, ester, or alcohol solvent, or in combinatio~ with other minor amounts of other alkyd, modified-alkyd, or hydrocarbon disp~rsing media, for the polymerization of monomers, which polymers are predominantly insoluble in the alkyd medium. The particular means for the production of the alkyd are not o~ import to this invention. Thus, the alkyd can be produced according to any of the traditional processes for the production of alkyds which are readily available from the art. However, as a conventional alkyd, thP alkyd stabilizer has an Mz of greater than about 150,000,`an NVM solids content of less than about 70%, more preferably of between about 40~ and about 70%, and a viscosity in the above NVM range and at 25 degrees C of no greater than about lO,000 cps.
The alkyd serves as the dispersing medium and steric stabilizer for the reaction of free radical addition monomers which produce a polymer which is predominantly insoluble in the alkyd medium. The monomers are polymerized in the presence of the alkyd to produce the novel NAD's of this invention. A critical parameter which must be followed is that at least one monomer must be selected from the group consi~ting of acrylonitrile, methacrylonitrile, hydroxy ethyl acrylate and methacrylate, methyl acrylate and methacrylate, acrylamide, methacrylamide, vinyl chloride, vinylidene chloride, acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, the methyl esters of itaconic, maleic and fumaric acid, and mixtures thereof. A second critical parameter is that at least one monomer must have hydroxy-functionality. A third critical parameter which must ~e ~ollowed ~ 5 is that the polymerization must take place i~ the presence of a chain transfer agent.
We have ~ound that by following these key critical parameters, explained in more detail below! one can formulate an NAD which is stable, non-gritty, filterable, with a substantially equal or lower viscosity at the same solids level than the alkyd which was used to make the NAD and which dries fas~er than that alkyd. We have found that failure to ~ollow these key critical parameters when using a conventional alkyd as the dispersing media re~ults in NADIs which do not exhibit the equivalence or improvements in viscosity or dry time vis-a-vis the alkyd used to make them and/or are unstable, gritty, non-filterable or have excessively low conversions.
Accordingly, it is an object of this invention to teach improved non-aqueous dispersions which utilize conventional alkyds as the dispersing medla.
It $s another object of this invantion to teach a non-aqueous dispersion having improved air dry times.
It is a further ob;ect o~ this invention to teach a process for producing non-aqueous dispersions havinq improved air dry times.
It is a further ob;ect o~ this invention to teach coating compositions containing the non aqueous dispersions of this invention.
DETAILED D~SCRIPTION OF THE INVENTION
As stated above, the process for pxoducing the NAD's of this invention comprises selecting a conventional alkyd; and using this alkyd as the dispersing medium, either alone or in combination with some minor amount o~ solvent or other dispersi~g ~edia, for the polymerization of monomers, which polymers are predominantly insoluble in the alkyd medium. The alkyd used in these NAD's is formed by any of the traditional processes such as fatty acid esterification or alcoholysis of a drying oil with later reaction with a di- or tri- basic acid. The alkyds of this invention are selected from conventional alkyds for the paint `and coatings industry. Conventional alkyds are defined herein as alkyds having a z-average molecular weight greater than about 150,000, preferably between about 250,000 and about 1,000,000, and an NVM solids content of less than about 70~, preferably between about 40% and about 70%.
Typical raw materials for the ~ormation of alkyds include triglyceride oils or t~e fatty acids thereof. These can be selected from the group consisting of linseed oil, soya oil, coconut oil, cottonseed oil, peanut oil, canola oil, corn oil, safflower oil, sunflower oil, dehydrated castor oil, fish oil, perilla, lard, walnut oil, tung oil, tall oil, the fatty acids thereof and mixtures thereof. Particularly preferred are thosè
oils and acids containing unsaturation in the glycexide chains.
Particularly preferred are soya oil, dehydrated castor oil and linseed oil and the fatty acids thereof.
Multi-functional alcohols, and mixtures thereof, are al80 common raw materials for the production of alkyds. one suitable b. ~ '~5 ~ ~.

hexafunctional alcohol includes dipentaerythritol~ One suitable tetrafunctional alcohol includes pentaerythritol. Suitable tri~unctional alcohols include the group con6isting of trimethylol propane, trimethylol ethane, glycerine, tris hydroxyethyl isocyanurate, and mixtures thereof, either alone or in combination with a difunctional alcohol selected from the group consisting of ethylene glycol, propylene glycol, cyclohexane dimethanol, and mixtures thereof. Addition~lly, dimethyl~l propionic acid can be used in combination with the trifunctional alcohol. Multi-~unctional alcohols, trifunctional alcohols, and mixtures thereof are particularly preferred due to the degree o~ branching they allow. Difunctional alcohols, if used, are preferably u~ed as a minor component in combination with tri~unctional alcohols. A
portion of monofunctional alcohol, or monobasic acid such as soya fatty acid, linseed oil fatty acid, ben~oic acid or crotonic acid, up to about 20~ by weight of the total alkyd can be added with the multifunctional alcohol to control molecular weight and act as a chain stopper.
Another typical raw material used in the f ormation of alkyds iB multi-functional carboxylic acids or anhydrides. Suitable trl~unctional carboxylic acids include trlmelletic acid, trimesic acid, 1,3,5-pentane tricarboxylic acid, citric acid and others whereas suitable trifunctional anhydrides include trimelletic anhydride, pyromelletic anhydride and others. Di~unctional carboxylic acids include phthalic acid, isophthalic acid, terephthalic acid,-maleic acid and fumaric acid and mixture~

thereo~. Mixtures of such acids and anhydrides are also acceptable.
The amounts of oil, acid and alcohol used should be such that the resulting alkyd has a high degree of branching, a z-average molecular weight, Mz, greater than about 150,000, pre~erably between about 250,000 and a~out l,OOo,000. It should be appreciated that the longer these materials are allowed to react, the greater the resultant molecular weight of the alkyd. The alkyd should have an oil length o~ between about ~0% and 75%, an acid value less than about 20, and a hydroxyl number less than 100, preferably between about 40 and about ~0. The NVM should be below about 70%, preferably between about 40% and about 70%.
If desired, a reaction catalyst such as lithium hydroxide monohydrate, barium hydroxide, or di-butyl tin oxide can be added in an amount of approximately 0O02% by weight of oil.
The NAD's made according to this invention typically have Brookfield LVT #3 (6/12 rpm) viscosities less than about 10,000 cps at 25 degrees C, preferably lees than about 7,000 cps. They can easily be formulated to have volatile organic contents less than 400 g/l, many times less than 380 g/l, and exhibit excellent air dry times using conventional drier compounds. Interestingly, the NADIs o~ this invention, at the same solid~ level, exhibit viscosities substantially equal to or lower than the alkyds used to prepare them. They also hava very ~ast dry times when compared to thP alkyds used to prepare them.
As stated above, any-conventional alkyd as herein de~ined can s be used in thi~ invention. Particularly suitable commercially available alkyds for use in this invention include the alkyds available from Cargill, Inc. such as 5070 (soya oil alkyd), 5054 (linseed oil alkyd), 5091 (tall oil fatty acid alkyd), 5076 (soya oil in odorless mineral spirits alkyd), and 5074 (isophthalic soya oil alkyd). One particularly preferred alkyd is the reaction product of soya oil, pentaerythritol, maleic anhydride and phthalic anhydride as shown in Example I, below.
When preparing non-aqueous dispersions accor~ing to this invention, the monomers should be selected from monomers which would produce a polymer via the free radical addition reaction mechanism, which polymer is predominantly insoluble in the alkyd medium. It is essential that at least one of the monomers be selected from the group con~isting of acrylonitrile, methacrylonitrile, hydroxy ethyl acrylate and methacrylate, methyl acrylate and methacrylate, acrylamid~, methacrylamide, vinyl chloride, vinylidene chlorideJ acrylic acid, methacrylic acid, itaconi¢ acid, maleic acld, fumaric acid, the methyl es~ers of itaconic, maleic and fumaric acid, and mixtures thereof. It is also essential that at least one of the monomers have hydroxy functionality. More pre~erably, between about 5% and 35% by weight o~ the total reactor solids comprises hydroxy functional monomers.
Most preferably, between about 10% and about 25% by weight of the total reactor solids comprises a hydroxy ~unctional monomer such as hydroxy ethyl acrylate or hydroxy ethyl methacrylate.
In addition to pure monomer~, pre~ormed polymer~, polymeric intermediates, multifunctional epoxides, melamines and isocyanates, can be included in the reactor charge.
Most preferred is a combination of methyl methacrylate and hydroxy ethyl acrylate wherein the methyl methacrylate is present in an amount of between abouti20 and 40~, and the hydroxy ethyl acrylate is present in an amount o~ between about 10 and 25%, by weight of total reactor solids.
Additional monomers selected ~rom the group consisting of hydroxy propyl acrylate and methacrylate, ethyl acrylate and methacrylate, butyl acrylate and methacrylate, lauryl acrylate and methacrylate, and the like, trimethylol propane triacrylate and trimethacrylate, hexanediol diacrylate, Tone M-100 (caprolactone modified hydroxy ethyl acrylate), polyethylene oxide acrylate and methacrylate, polypropylene oxide acrylate and methacrylate, allyl alcohol, can be included in the reactor charge in relatively minor amounts, so long as they are not added in percentages sufficient to adversely affect the viscosity and/or odor of the NAD. Certain monomers are to ba avoided such as styrene because of an unacceptable resultant increase in NAD viscosity. Also to be avoided are divinyl benzene, vinyl naphthalene, and vlnyl toluene because these are generally soluble in alkyds. Vinyl acetate is unacceptable for inclusion as it does not polymerize under the conditions taught herein~ These monomers have been found to cont~ibute to a decrease in yield, additional grit, and/or a lessening.of stability over time.
To prepàre the NAD's of this invention, the alkyd disper~ing a ~ 1~ 2 ~ J ~ ~ ~ 5 medium is used as the polymerization medium ~or the monomer charge.
The alkyd medium can be diluted with mineral spirits or other solvent if desired, with ~he primary limitation being concern for the VOC of the composition and the viscosity increase which accompanies the swelling and solubilization of the dispersed phase in stronger solvents.
The total~amount of alkyd contained in the reaction vessel, including any alkyd which may be added with the monomer charge, should comprise between about 35% to about 75~, p~efera~ly from about 40% to about 60%, by weight of the total reactor solids. The ~ree radical addition monomer charge should, after completely added to the reaction vessel, account for approximately 65% to about 25%, preferably between about 60% to about 40~, by weight of the total reactor solids.
A mercaptan-containing chain transfer agent such as methyl mercaptopropionate, dodecyl mercaptan, thioglycolic acid, or 2-mercapto ethanol must also be added to the vessel in an amount from about 0.1% to about 6.0~ by weight of total reactor 601ids. Most preferred is 2-mercapto ethanol.
An initiator which will not oxidize the chain transfer agent is selected from the group consisting o~ organic peroxides such as benzoyl peroxide, iauroyl peroxide, di-t-butyl peroxide, acetyl peroxide, t-butyl peroctoate, t amyl peroctoate, and t-butyl perbenzoate, or selected from the group consisting of nitrile initiators such as a,a~-azobisisobutyronitrile, and mixtures therèof and i8 also added in an amount up ko about 3% by weight of L ~ ~ 5 the total monomer charge.
All free radical addition reactants are preferably added via dropwise addition over a period of time to the alkyd dispersing medium. The monomer charge can be added pure, or, in a preferred embodiment, the monomers can be dispersed in an amount of the alkyd prior to addition to the dispersing medium. The amount of alkyd used for such a dispersion should be included in the calculation of the overall amount of alkyd present in the reaction vessel. Any additional ingredients such as acrylic polymers and copolymers, macromonomers, silicones, XI-loo from Monsanto (poly allyl glycidyl ether), alkyds, uralkyds, urethane-modified oils, polyesters, and epoxy esters can be included in the reactor charge provided they are solubilized in either the monomer charge or the alkyd dispersing media.
The temperature of the contents of the reaction vessel should be maintained between about 200~F and 250aF for the entire period that monomer charge is being added. A nitrogen blanket i5 also highly preferred. Upon completion o~ the monomer addition, up to about 0.1~ by weight of total reactor charge an activator selected fro~ the group consisting of the iron, copper, vanadium, cobalt and manganese naphthenates, octoates, hexanates and iæodecanoates is added to the reactor vessel and from about 0.5% to about 5.0~ by weight of total reactor solids of a hydroperoxide chaser composition selected ~rom the group consisting o~ cumene hydroperoxide,-t-butyl hydroperoxide/ t-amyl hydroperoxide, and the like is added dropwise over a period o~ about 90 minutes. The r 2q ~ 9 5 hydroperoxide chasers are preferred because they oxidize the remaining mercaptan from the chain transfer agent and thus eliminate the odor from the sulfur. Upon completion of the chase, the temperature should be maintained between 200~F and 2~0~F for approximately one hour. At the end of that hour, the heat is removed and the contents of the vessel are filtered.
Tha non-aqueous dispersions o~ this invention can be used alone as coating compositions. Or, they can be blended or used in combination with other alkyds or NAD~s. They can be combined with other film-forming compositions such as acrylic polymers and copolymers, macromonomers, silicone alkyds, XI-100 from ~onsanto, alkyds, uralkyds, urethane-modified oils, polyesters, epoxy esters, polybutadiene, and polyallyl glycidyl ether. They can be formulated with other readily available, standard paint ingredients and components such as crosslinking agents, catalysts, rheology modifiers, thixotropes, extenders, colors and pigments, solvents, anti-skinning agents, drying agents, dispersants and surfactants, fungicides, mildewcides, preservatives, W absorbers, anti-marring agents, anti-cratering agents, flow and leveling agents, fragrances, defoaming a~ents, chelating agents, flattening agents, and anti-rusting agents.
Suitable rheology modifiers are well known in the art and can comprise organoclays, fumed silica, dehydrated castor oil organic derivatives texemplary tradenames: Thixatrol (~), NL Industries;
Flowtone (R), English China Clay), polyamides, polyamide modi~ied alkyds, MPSA-60, Rheox, alkylbenzene sulphonate derivatives, ~_ - ` 2~'$~ ~5 aluminum, calcium and zinc stearates, calcium soyate, and the like.
Suitable extenders are also well known in the art and can comprise amorphous, diatomaceous, ~umed, quartz and crystalline silica, clays, aluminum silicates, magnesium aluminum silicates, talc, mica, delaminated clays, calcium carbonates and silicates, gypsum, barium sul~ate, zinc, calcium zinc molybdates, zinc oxide, phosphosilicates and borosilicates of calcium, barium and strontium, barium metaborate monohydrate, and the like.
Suitable colors and pigments are well known in the .art and can comprise for example, titanium dioxide, carbon black, graphite, ceramic black, antimony sulfide, black iron oxide, aluminum pastes, yellow iron oxide, red iron oxide, iron blue, phthalo blue, nickel titanate, dianisidine orange, dinitroaniline orange, imidazole orange, quinacridone red, violet and magenta, toluidine red, molybdate orange, and the like.
Suitable solvents can comprise propylene and ethylene glycol ethers and acetates, alcohols, ketones, aliphatic and aromatic hydrocarbons and naphthas, petroleum and wood distillates, turpentine, pine oil, and the like. Solvent seleation iæ limit~d primarily by the desire to maintain the overall VOC level of the coating composition as low as possible without resulting in an unacceptable increase in viscosity.
Anti-skinning agents such as methyl ethyl ketoxime, o-cresol, and hydroquinone can b.e included.
Drying agents can comprise standard metallic and rare earth driers such as cobalt, calcium, potassium, barium, zinc, manganese, - z~ 5 _~"~ ' ~. ~?` - ~

tin, aiuminum, zirconium and vanadium napthenates, octoates, hexanate~, and isodecanoates. A particularly preferred dri~r c~mpoSition iS a combination of cobalt, calcium~ and zirconiu~
driers present in an amount from about 0.1% to about 2.5% by waight of the coating composition.
Suitable dispersants and surfactants can comprise any of the readily available dispersants and surfactants to the coatings industry, including the anionlc and nonionic sur~actants, soya lecithin, alkyl ammonium salts oP fatty acids, amine salts of alkyl aryl sulfonates, unsaturated organic acids, sulfonated castor oil, mixtures of high boiling point aromatic and ester solvents, sodium salts of aryl sulfonic acid, Solsperse from ICI, and the like.
The following examples will demonstrate various embodiments of this invention.

` ~ EXAMPLE I: PREPARATION OF ALKYD
Charge a reactor equipped with inert gas, mechanical stirrer, and condenser with 2591 lbs alkali refined ~oybean oil and 753 lbs of pentaerythritol. Heat to 400 degrees F under inert gas blanket. ~dd 5.1 lbs of lithium hydroxide catalyst and heat to 470 degrees F. Hold ~or approximately two hours untll clear. Add 1133 lbs of soybean oil and cool to 390 degreeff F. Add 28 lb~ of maleic anhydride, 1375 lbs of phthalic anhydride and 144 lbs o~
xylene. Heat to 490 degrees F and hold for a ~iscosity of Z-Z2 using the Gardner-Holdt method and an acid value of les~ than about 10 at 70~ NVM in mineral spirits. Cut with 2300 lbs-of mineral 2~ 5 i ` ,.

spirits to produce a 70% Nv~ alkyd.
The resulting alkyd should have an Mz of between about 250,000 to about 1,000,000, an NVM of about 70% and a viscosity of about 5700 to 5900 Cp6 at 25 degrees C.
The following procedure was used to make the NAD's of Examples A through ~ from the alkyd of Example I:
Charge about 1/2 of the alkyd to a reactor equipped with a mechanical stirrer. Heat to 100C. Disperse the monomer/chain transfer agent solution in the remainder of the alkyd along with an initiator solution comprising t-butyl peroctoate and begin a three hour dropwise addition of the solution to the reactor. Upon completion of the addition of the solutions, hold for approximately one hour and then add vanadium naphthenate to the reactor. Begin a 90 minute addition of a "chase" comprising mineral spirits and cumene hydroperoxide. Hold the temperature at lOO~C for approximately ~ to 1 hour after the chase has been completely added. Shut off heat and filter the contents of the reactor through a 15 micron polyester filter bag.
The following N~D's were made according to the above procedure (parts by weight), with the following properties reeulting t~erefrom. The Hegman scale is used to measure the level of grittiness of the NAD priox to filtration, with a value of "8"
representing no grit and a value of "0" representing all grit.
Viscosities were measured using the Brookfield Viscometer LVT #3 spindle at 12 rpm.

2 ~ x 5 EXAMPLE A
50 parts alkyd 35 parts methyl methacrylate 15 parts hydr~xy ethyl acrylate 0.28 parts 2-mercapto ethanol NVM: 6~.1%
Visc: 2850 cps Hegman: 8 EXAMPLE B
~0 parts alkyd . 50 parts methyl methacrylate 0 parts OH-functional monomer 0.28 parts 2-mercapto ethanol NVM: 71.0%
Visc: 186,000 cps Hegman: 2 EXAMPLE C
50 parts alkyd 35 parts methyl methacrylate 15 parts hydroxy ethyl acrylate 0 parts chain transfer agent NVM: 68.3%
Visc: 2000 cps ~egman: 2 EXANPLE D
50 parts alkyd 50 parts mathyl methacrylate 0 parts OH-functional monomer 0 parts chain transfer agent NVM: 67.1~
Visc: 15,800 cps Hegman:
EXANPLE E
50 parts alkyd O parts methyl methacrylate 50 parts hydroxy ethyl methacrylate 0.28 parts chain transfer. agent 2~

NVM: 71.5%
Visc: 10,400 cps Hegman: 8 EXAMPLE F
50 parts alkyd 35 parts methyl methacrylate ; 15 parts ethyl acrylate o parts OH-functional monomer 0.28 parts chain transfer agent ` Result: Paste EXAMPLE G
50 parts alkyd 45 parts methyl methacrylate 5 parts acrylic acid O parts OH-functional monomer 0.28 parts chain transfer agent NVM: 6~.0~
Visc: 7,000 cps Hegman: 8 EXAMPLE H
50 parts alkyd 35 parts methyl methacrylate 15 parts styrene O parts OH-functional monomer 0.28 parts chain transfer agent NVM: 67.7~
Visc: 18,300 cps Hegman: 4.5 Paint compositions were made from the alkyd of Example I and from the NAD o~ Example ~ as follows:
EXAMPLE II--PAIN~ CON~AINING ALKYD OE EXAMPLE I
Add 246.23 lbs of alkyd from Example I to a mixing vessel.
Begin the grind phase by adding 11.38 lbs of aliphatic naptha and 3.64 lbs o~ soya lecithin. Start the mill and add 111.50 lbs of rutile titanium dioxide ~nd 5.00 lbs of organophilic clay. Run on high for l minutes. Reduce the speed of the mill and stabilize with 45.20 lbs of aliphatic naptha and 29.49 lbs of alkyd from Example I. Add 0.64 lbs 12% cobalt catalyst, 3.83 lbs 18~
zir~onium 2-ethylhexanoate and 1.38 lbs 10% calcium driers. Add l.Oo lbs of methyl ethyl ketoxime and 11.74 lbs of aliphatic naptha.
The resultant paint has KU and ICI viscosities at 25 degrees C of 80 and 4.4, respectively. The "dry-to-set" time, as measured by the ~yk-Gardner circular drytime recorder, at 25 degrees c and 50% relative humidity, is approximately 2.5 hours. The "surface-dry" time, as measured the same instrument under the same conditions i~ approximately 2.25 hours. The "thru-dry" time, as measured by the same instrument under the same conditions is greater than 12 hours. The "dry-hard" time, as measured by the same instrument under the same conditions is greater than 12 hours.

EXAMPLE III--PAIN~ CON~AINING N~D OF ~XAMPLE A
Add 294.90 lbs of an NAD (composition of 45 parts by weight alkyd of Example I, 40 parts methyl methacrylate, 15 parts hydroxy ethyl acrylate and 0.28 parts 2-mercapto ethanol, produced according to the procedure used ~or Examples A-H, above) to a mixing vessel. Begin the grind phase by adding 21.45 lbs of aliphatic naptha and 7.28 lbs of soya lecithin. Start the mill and add 223.00 lbs of rutile titanium dioxld~ and 10.00 lbs of organophilic clay. Xun on high for 15 minutes. Reduce the ~peed 2~ 5 of the mill and stabilize with 109.01 lbs of aliphatic nap~-ha and 260.79 lbs of NAD. Add 0.92 lbs 12% cobalt catalyst and 9.18 lbs 10% calcium driers. Add 2.00 lbs of methyl ethyl ketoxime and 23.47 lbs of aliphatic naptha.
The resultant paint has KU and ICI viscosities at 25 degrees ~ of 86 and 2.7, respectively. The "dry-to-set" time, as measured by the syk-Gardner circular drytime recorder, at 25 degrees C and 50~ relative humidity, is approximately 0.75 hours. The "surface-dry" time, as measured the same instrument u~der the same conditions is approximately 1.0 hours. The "thru-dry" time, as measured by the same instrument under the same conditions is approximately 1.5 hours. The "dry-hard" time, as measured by the same instrument under the same conditions is approximately 3.5.

Claims (6)

1. In a non-aqueous dispersion of addition polymers in an alkyd medium, wherein said alkyd has a z-average molecular weight of greater than about 150,000, and an NVM of less than about 70%, the improvement comprising polymerizing two or more monomers in the presence of said alkyd via the free radical addition mechanism; wherein at least one of said monomers is selected from the group consisting of acrylonitrile, methacrylonitrile, hydroxy ethyl acrylate and methacrylate, methyl acrylate and methacrylate, acrylamide, methacrylamide, vinyl chloride, vinylidene chloride, acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, the methyl esters of itaconic, maleic and fumaric acid, and mixtures thereof; wherein at least one of said monomers has hydroxy-functionality; and wherein said polymerization is conducted in the presence of a chain transfer agent.

2. The composition of Claim 1 wherein between about 5% and 35%
by weight of the reactor solids comprises at least one monomer having hydroxy functionality.

3. The composition of Claim 2 wherein said hydroxy functional monomer is selected from the group consisting of hydroxy ethyl acrylate and hydroxy ethyl methacrylate, and mixtures thereof.

4. The composition of Claim 3 wherein said monomer charge comprises methyl methacrylate and hydroxy ethyl acrylate.

5. The composition of Claim 4 wherein said chain transfer agent is selected from the group consisting of methyl mercaptopropionate, dodecyl mercaptan and 2-mercapto ethanol.

6. In a coating composition comprising a non-aqueous dispersion of addition polymers in an alkyd medium and at least one other paint ingredient or component selected from the groups such as crosslinking agents, catalysts, rheology modifiers, thixotropes, extenders, colors and pigments, solvents, anti-skinning agents, drying agents, dispersants and surfactants, fungicides, mildewcides, preservatives, W absorbers, anti-marring agents, anti-cratering agents, flow and leveling agents, fragrances, defoaming agents, chelating agents, flattening agents, anti-rusting agents and mixtures thereof;
wherein said alkyd has a z-average molecular weight of greater than about 150,000, and an NVM of less than about 70%, the improvement comprising polymerizing two or more monomers in the presence of said alkyd via the free radical addition mechanism; wherein at least one of said monomers is selected from the group consisting of acrylonitrile, methacrylonitrile, hydroxy ethyl acrylate and methacrylate, methyl acrylate and methacrylate, acrylamide, methacrylamide, vinyl chloride, vinylidena chloride, acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, the methyl esters of itaconic, maleic and fumaric acid, and mixtures thereof;
wherein at least one of said monomers has hydroxy-functionality; and wherein said polymerization is conducted in the prsence of a chain transfer agent.