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WO1997028199A1 - Latex a petites particules - Google Patents

Latex a petites particules Download PDF

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Publication number
WO1997028199A1
WO1997028199A1 PCT/US1997/000912 US9700912W WO9728199A1 WO 1997028199 A1 WO1997028199 A1 WO 1997028199A1 US 9700912 W US9700912 W US 9700912W WO 9728199 A1 WO9728199 A1 WO 9728199A1
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WO
WIPO (PCT)
Prior art keywords
polyester
water
acid
monomer
group
Prior art date
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PCT/US1997/000912
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English (en)
Inventor
Linda Jane Adams
Mark Dwight Clark
Chih-Herng James Su
Original Assignee
Eastman Chemical Company
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Publication date
Application filed by Eastman Chemical Company filed Critical Eastman Chemical Company
Priority to AU17516/97A priority Critical patent/AU1751697A/en
Publication of WO1997028199A1 publication Critical patent/WO1997028199A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/44—Polyester-amides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
    • C08F2/26—Emulsion polymerisation with the aid of emulsifying agents anionic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
    • C08G63/6884—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/6886—Dicarboxylic acids and dihydroxy compounds

Definitions

  • This invention belongs to the field of polymer chemistry.
  • it relates to small particle size latexes obtained by emulsion polymerization.
  • the particle size of a latex can often have a direct impact on the performance of a coating prepared from that latex.
  • properties that can be affected are gloss, clarity, film formation, and substrate penetration (i.e., for porous substrates). In a very general sense, a smaller particle size will have a positive effect on such properties.
  • Small particle sizes are most often achieved by using relatively high levels (2—4 wt%)of small molecule, typically anionic, surfactants such as AEROSOL-OT, sodium dioctyl sulfosuccinate and AEROSOL NPES 2030, ammonium nonylphenoxy polyethoxy ethanol sulfate, which are anionic surfactants sold by Cytec Industries, Inc.
  • anionic surfactants such as AEROSOL-OT, sodium dioctyl sulfosuccinate and AEROSOL NPES 2030, ammonium nonylphenoxy polyethoxy ethanol sulfate, which are anionic surfactants sold by Cytec Industries, Inc.
  • small particle size and the properties directly affected by it are not, the only important properties in water—based coatings. Of primary importance is the water—resistance/sensitivity of the final film.
  • the high level of anionic surfactant the very component in the latex which gives the small particle size and all of its concommitant advantages,
  • 5,342,877 describes a method for preparing small particle size latexes via copoly erization of hydroxyalkyl (meth) acrylates (15—40 weight percent based on total latex solids) and other vinyl/acrylic monomers (particularly styrene) in the presence of water-dispersible polyesters.
  • U.S. Patent No. 4,939,233 describes a method for preparing water-dispersible polyester/vinyl acetate copolymer blends via emulsion polymerization using sulfonated polyesters as stabilizers in the reaction.
  • U.S. Patent Nos. 4,946,932 and 5,277,978 describe a method for preparing water dispersible polyester/— acrylic copolymer blends via emulsion polymerization in the presence of sulfonated polyesters as stabilizers.
  • U.S. Patent No. 5,156,651 describes water dispersible polyester/vinyl aromatic latexes for textile sizing applications.
  • U.S. Patent No. 4,839,413 describes the use of low molecular weight (i.e., less than 20,000) alkali-soluble resins as "support resins" in emulsion polymerization.
  • the support resin is formed via non—aqueous polymeriza ⁇ tion methods and is subsequently dispersed/dissolved in alkaline solution.
  • the emulsion polymerization is then carried out, at high pH, in the presence of this dissolved support resin and an additional costabilizer (surfactant) .
  • a pH of greater than 8 is taught to be necessary.
  • U.S. Patent No. 5,258,355 describes a dye element for thermosublimation printing comprising a support and a dye acceptor layer containing a graft copolymer of an unsaturated copolyester as the graft base and a vinyl copolymer as the graft shell.
  • JP 73 102887 describes the emulsion polymerization of vinyl bromide in the presence of catalysts consisting of peroxides and heavy metal salts.
  • U.S. Patent No. 4,543,401 describes a process for the suspension polymerization of vinyl chloride, in the presence of a redox catalyst system consisting of a peroxyester or diacyl peroxide and isoascorbic acid.
  • WO 95/01381 describes polymer blends comprising water-dispersible sulfonate group—containing polyester or polyester—amides, styrene polymers, and either a different water-dispersible sulfonate group containing polyester or polyester amide or a nonylphenol ethoxylated surfactant.
  • WO 95/01399 describes blends of water-dispersible sulfonate group—containing polyester or polyester—amides and styrene polymers. Summary of the Invention
  • This invention provides certain water-dispersible polyesters which are useful in preparing polyester/acrylic hybrid latexes.
  • the polyesters of the invention are particularly effective stabilizers for vinyl and acrylic latex emulsion preparation, thereby providing emulsions with high solids content without the formation of significant amounts of coagulum.
  • the latexes of the invention have a particle size of less than lOOn and are useful in coatings compositions, in inks, and in adhesive compositions.
  • the present invention provides a polyester/acrylic hybrid latex having a particle size diameter of less than about lOOnm, prepared by the emulsion polymerization of ethylenically unsaturated monomers in the presence of a polyester stabilizer, wherein said polyester stabilizer is a water-dispersible polyester comprised of:
  • X SO_X 3 wherein X is Na + , K + , or Li + ;
  • weight percent of —S0 3 X groups is about 7 to 8%, and the sum of the weight percent of —S0 3 X groups and oxygen, excluding the oxygen in said —S0 3 X groups, in said polyester is about 30 to 32%.
  • Preferred latexes and polyesters are those in which the weight percentage of —S0 3 X groups in the water— disperisible polyesters is between 7.5 and 8. In these ranges, the range is based on the case where X is Na + ; thus, if X is K + or Li + , the ranges will be changed accordingly.
  • the aromatic diacids are preferably selected from the group consisting of terephthalic acid, isophthalic acid, and phthalic acid.
  • the aliphatic diacids are preferably chosen from those having the general formula H00C-(CH 2 ) n -C00H, wherein n is an integer of from 1 to 12 , or are selected from the group consisting of 1,2-, 1,3-, and 1,4- cyclohexanedicarboxylic acid, aleic acid, fumaric acid, and 5 (6) carboxy—4—hexyl—2—cyclohexene—1—octanoic acid.
  • the combination of aromatic diacids and difunctional sulfomonomers comprise about 50 to 100 mole percent of the total dicarboxylic acid moieties.
  • the aliphatic dicarboxylic acids thus comprise the remainder of the dicarboxylic acid moieties.
  • the glycol residues are preferably comprised of residues of one or more ethylene, diethylene, triethylene, tetraethylene, propylene, and dipropylene glycols and cyclohexanedimethanol. It is further preferred that ethylene glycol comprises less than 75 mole % of the total glycols and that cyclohexanedi—methanol comprises greater than about 25 mole % of the total glycols.
  • the water dispersible polyesters and polyester- amides are, for the most part, water-dispersible because they form electrostatically—stabilized colloids when mixed with water.
  • the colloid particle size varies with the polymer composition but has been shown by light diffraction studies and transmission electron microscopy to be mostly 200—800 A in diameter.
  • the aqueous colloid dispersions exhibit a minimum precipitation of solid material with time, in the temperature range of 0.1—99.9°C because the relationship between the particle densities and viscosities (very similar to those of water when concentrations are less than 30 weight percent) are such that thermal energy expressed as Brownian motion is sufficient to keep the particles suspended in water.
  • the water-dispersible polyesters have an inherent viscosity of at least 0.1 dL/g, preferably about 0.20—0.38 dL/g, when determined at 25°C using 0.25 g polymer per 100 ml of a solvent consisting of 60 parts by weight phenol and 40 parts by weight tetrachloro- ethane.
  • the sulfonate-containing, water-dispersible, linear polymers thus comprise polyesters, including polyester- amides, consisting of repeating, alternating residues of (1) one or more dicarboxylic acids and (2) one or more diols or a combination of one or more diols and one or more diamines where, in the preceding definition, the mole percentages are based on 100 mole percent dicarboxylic acid residues and 100 mole percent diol or diol and diamine residues.
  • the polymers may include residues of monomers having mixed functionality such as hydroxycarboxylic acids, aminocarboxylic acids and/or aminoalkanols.
  • the polyester or polyester- amide is preferably present in about 1 to 20 weight percent, based on the total weight of solids, more preferably 1 to 10 weight percent, and most preferably 1 to 6 weight percent.
  • ethylenically unsaturated species which can be utilized include, for example, acrylic monomers such as methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, isopropyl acrylate, isopropyl methacrylate, butyl acrylate, butyl methacrylate, isobutyl acrylate, isobutyl methacrylate, ethylhexyl acrylate, ethylhexyl methacrylate, octyl acrylate, hydroxyethyl methacrylate, alkenyl aromatic compounds (e.g., styrene, a—methyl styrene, vinyl n
  • R 4 is independently hydrogen or methyl and R 5 is C-—C 12 alkyl; acetoacetoxyethyl methacrylate, acetoacetoxyethyl acrylate, acetoacetoxy(methyl) ethyl acrylate, acetoacetoxypropyl acrylate, and acetoacetoxybutyl acrylate.
  • Such compounds provide a polymer with pendant acetoacetoxy groups which may optionally treated with ammonia or a primary or secondary amine to provide an enamine group as taught in EP 492 847.
  • Further ethylenically unsaturated compounds include t— utylaminoethyl methacrylate, N,N—dimethylaminoethyl methacrylate, N—dimethylaminopropyl methacrylamide, 2—t— butylaminoethyl methacrylate, and N,N—dimethylaminoethyl acrylate.
  • Especially preferred compounds of Formula (2) include t—butylaminoethyl methacrylate and N,N— dimethylaminoethyl methacrylate.
  • Preferred ethylenically unsaturated compounds include the following:
  • CH 2 CH-C-0-CH 2 -CH-CH 2 CH 2 CH-CH 3
  • CH 2 CH-C-0-CH 2 -CH 3 ; CH ⁇ CH-C-O-CH CH-CH ⁇ CH- ; and
  • alkyl and alkylene groups may be straight or branched chain.
  • the polymers may further be prepared from known wet adhesion—promoting monomers, including methacrylamido— ethylethyleneurea and/or N-(2-methylacryloyloxyeth- yl)ethylene urea.
  • any number of free radical initiators can be used to generate small particle size latexes.
  • Typical initiators include hydrogen peroxide, potassium or ammonium peroxydisulfate, dibenzoyl peroxide, lauryl peroxide, ditertiary butyl peroxide, 2,2'—azobisiso— butyronitrile, t—butyl hydroperoxide, benzoyl peroxide, and the like.
  • Suitable reducing agents are those which increase the rate of polymerization and include for example, sodium bisulfite, sodium hydrosulfite, sodium formaldehyde sulfoxylate, ascorbic acid, isoascorbic acid, and mixtures thereof.
  • Suitable catalysts are those compounds which increase the rate of polymerization and which, in combination with the above described reducing agents, promote decomposition of the polymerization initiator under the reaction conditions.
  • Suitable catalysts include transition metal compounds such as, for example, ferrous sulfate heptahydrate, ferrous chloride, cupric sulfate, cupric chloride, cobalt acetate, cobaltous sulfate, and mixtures thereof.
  • transition metal compounds such as, for example, ferrous sulfate heptahydrate, ferrous chloride, cupric sulfate, cupric chloride, cobalt acetate, cobaltous sulfate, and mixtures thereof.
  • the preferred initiator as part of a redox pair, is t—butyl hydroperoxide (TBHP) .
  • the preferred reductants for redox system used in this invention are sodium formaldehyde sulfoxylate (SFS) , isoascorbic acid (IAsA) and ascorbic acid (AsA) with the most preferred reductant being isoascorbic acid.
  • chain transfer agents such as mercaptans may be used to control the molecular weights of the seed and/or any or all of the subsequent polymerization stages.
  • Exemplary chain transfer agents are butyl mercaptan, mercaptopropionic acid, 2—ethylhexyl
  • One process for preparing these polymers involves charging the water-dispersible polyester or polyester— amide to a reactor, feeding in the monomers for the first stage of the latex under monomer starved conditions.
  • starved—feed or “monomer starved” refers to a process where a mixture of the monomers and separately the initiator are fed into the preheated reaction mixture over a period of time.
  • This process results in better compositional control of the copolymers since a high conversion of monomer to polymer is maintained in the reaction vessel.
  • This process also results in better temperature control of the polymerization.
  • the addition rate and process temperature is optimized for the initiator used.
  • the reaction is preferably conducted at about 65°C under an inert gas such as nitrogen, and the polymerization is initiated using a free radical redox initiator such as t-butyl peroxide/isoascorbic acid.
  • a mixture of monomers comprised of, for example, styrene, butyl acrylate, and the monomers of which define the second stage are fed into the reactor.
  • a latex coating composition which comprises the polyester/acrylic hybrid latex polymers as described above, further comprising one or more leveling, rheology, and flow control agents such as silicones, fluorocarbons or cellulosics; extenders; reactive coalescing aids such as those described in U.S. Patent No.
  • plasticizers plasticizers; flatting agents; pigment wetting and dispersing agents and surfactants; ultraviolet (UV) absorbers; UV light stabilizers; tinting pigments; extenders; defoaming and antifoaming agents; anti- settling, anti—sag and bodying agents; anti—skinning agents; anti—flooding and anti—floating agents; fungicides and mildewcides; corrosion inhibitors; thickening agents; or coalescing agents.
  • UV absorbers ultraviolet (UV) absorbers
  • UV light stabilizers tinting pigments
  • extenders defoaming and antifoaming agents
  • anti- settling anti—sag and bodying agents
  • anti—skinning agents anti—flooding and anti—floating agents
  • fungicides and mildewcides corrosion inhibitors
  • thickening agents or coalescing agents.
  • additives can be found in Raw Materials Index, published by the National Paint & Coatings Association, 1500 Rhode Island Avenue, N.W., Washington, D.C. 20005. Further examples of such additives and emulsion polymerization methodology may be found in U.S. Patent No. 5,371,148, incorporated herein by reference.
  • flatting agents examples include synthetic silica, available from the Davison Chemical Division of W.R. Grace & Company under the trademark SYLOID ® ; polypropylene, available from Hercules Inc. , under the trademark HERCOFLAT ® ; synthetic silicate, available from J.M. Huber Corporation under the trademark ZEOLEX ® .
  • dispersing agents and surfactants include sodium bis(tridecyl) sulfosuccinnate, di(2-ethyl hexyl) sodium sulfosuccinnate, sodium dihexylsulfo— succinnate, sodium dicyclohexyl sulfosuccinnate, diamyl sodium sulfosuccinnate, sodium diisobutyl sulfo— succinnate, disodium iso—decyl sulfosuccinnate, disodium ethoxylated alcohol half ester of sulfosuccinnic acid, disodium alkyl amido polyethoxy sulfosuccinnate, tetra— sodium N—(1,2—dicarboxyethyl)—N—octadecyl sulfo— succinnamate, disodium N—octasulfosuccinnamate, sulfated ethoxylated nonylphenol
  • viscosity, suspension, and flow control agents examples include polyaminoamide phosphate, high molecular weight carboxylic acid salts of polyamine amides, and alkylene amine salts of an unsaturated fatty acid, all available from BYK Che ie U.S.A. under the trademark ANTI TERRA ® .
  • Further examples include polysiloxane copolymers, polyacrylate solution, cellulose esters, hydroxyethyl cellulose, hydrophobically—modified hydroxyethyl cellulose, hydroxypropyl cellulose, poly— amide wax, polyolefin wax, carboxymethyl cellulose, ammonium polyacrylate, sodium polyacrylate, and poly ⁇ ethylene oxide.
  • thickeners include the methylene/ethylene oxide associative thickeners and water soluble carboxylated thickeners, for example, those sold under the UCAR POLYPHOBE trademark by
  • fungicides examples include 4,4—dimethyloxazolidine, 3,4, 4—trimethyl— oxazolidine, modified barium metaborate, potassium N— hydroxy—methyl—N—methyldithiocarbamate, 2—(thiocyano— methylthio) benzothiazole, potassium dimethyl dithio— carbamate, adamantane, N—(trichloromethylthio) phthalimide, 2,4,5,6—tetrachloroisophthalonitrile, orthophenyl phenol, 2,4,5—trichlorophenol, dehydroacetic acid, copper naphthenate, copper octoate, organic arsenic, tributyl tin oxide, zinc naphthenate, and copper 8—quinolinate.
  • U.V. absorbers and U.V. light stabilizers include substituted benzophenone, substituted benzotriazoles, hindered amines, and hindered benzoates, available from American Cyanamid Company under the trademark CYASORB UV, and diethyl—3- acetyl—4—hydroxy—benzyl—phosphonate, 4—dodecyloxy—2— hydroxy benzophenone, and resorcinol monobenzoate.
  • a coating composition optionally containing one or more of the above—described additives. It may also be desirable to utilize a water—miscible organic solvent and/or coalescing agent.
  • solvents and coalescing agents are well known and include ethanol, n— propanol, isopropanol, n-butanol, sec—butanol, iso- butanol, ethylene glycol monobutyl ether, propylene glycol n—butyl ether, propylene glycol methyl ether, propylene glycol monopropyl ether, dipropylene glycol methyl ether, diacetone alcohol, TEXANOL ® ester alcohol (Eastman Chemical Company) , and the like.
  • solvents and coalescing aids may also include reactive solvents and coalescing aids such as diallyl phthalate, SANTOLINK XI-100 ® polyglycidyl allyl ether from Monsanto, and others as described in U.S. Patent Nos. 5,349,026 and 5,371,148, incorporated herein by reference.
  • a coating composition as set forth above, further comprising one or more pigments and ⁇ or fillers in a concentration of about 1 to about 70 weight percent, preferably about 30 to about 60 weight percent, based on the total weight of the solids in the composi ⁇ tion.
  • Pigments suitable for use in the coating composi ⁇ tions envisioned by the present invention are the typical organic and inorganic pigments, well—known to one of ordinary skill in the art of surface coatings, especially those set forth by the Colour Index, 3d Ed. , 2d Rev., 1982, published by the Society of Dyers and Colourists in association with the American Association of Textile Chemists and Colorists. Examples include, but are not limited to the following: Cl Pigment
  • the coating compositions is then applied to the desired substrate or article, e.g., steel, aluminum, wood, gypsum board, or galvanized sheeting (either primed or unprimed) , and allowed to air dry.
  • the desired substrate or article e.g., steel, aluminum, wood, gypsum board, or galvanized sheeting (either primed or unprimed) , and allowed to air dry.
  • Any coating composition designed for industrial coatings, textile coatings, ink coatings, adhesives, or coatings for plastics are within the scope of the present invention and is included in the term "article".
  • an article which has been coated with the coating compositions of the present invention and dried.
  • the latex compositions of the present invention may be used alone or in combination with other waterborne coating compositions in the form of a blend.
  • a waterborne coating composition comprising a blend of the hybrid latexes of the present invention and a water-dispersible polymer selected from the group consisting of alkyds, polyesters, polyester—amides, cellulose esters, polyurethanes, polyethers, acrylics, and vinyl polymers.
  • Other polyesters were prepared similarly.
  • This example illustrates the preparation of aqueous dispersions of one of the polyesters used in the process of this invention.
  • Deionized water 70 g was heated to 90°C, stirred vigorously, and 30 g of the polymer of Example 1 was added in 7.5 g increments, with a 15 min interval between additions.
  • the dispersion was stirred for an additional 1 hr at 90°C, then cooled to room temperature and filtered through 2 layers of cheese cloth.
  • the resulting clear, light yellow dispersion contained 31.35% solids; the pH was 5.7, and the viscosity was 42.1 cps (60 rpm, #2 spindle, Brookfield viscometer) .
  • This example illustrates the preparation of the latex of Example 1 in Table I.
  • AMPS sodium carbonate
  • Latex Preparation II illustrates the preparation of the latex of Example 2 in Table I. Latex Preparation II
  • Latex Preparation (Example III) was followed except that 14.86 g of polyester dispersion (30.29% solids) was added initially, and the water in solution III was 229.99 g.
  • the polyester was 77% isophthalate, 23% 5—sodiosulfoisophthalate, 77% diethylene glycol, and 23% 1,4 cyclohexanedimethanol.
  • the final latex had pH of 7.2, % solids of 38.17, and dry scrap of 18.5 g (Table 1, Ex. 3) .
  • This example illustrates the preparation of another polyester stabilizer of the present invention.
  • the flask and contents were placed under a N2 purge and then inserted into a Belmont metal bath with a temperature controller.
  • a Heller stirrer/motor assembly was used for agitation.
  • the chemicals were reacted, with stirring, at 200°C for 1 hour with removal of water/methanol; the temperature was increased to 220°C and the reaction product stirred an hour at this temperature with removal of additional water/methanol and other volatiles.
  • the temperature was increased to 250°C and held for 30 minutes; a clear melt was obtained.
  • the temperature was increased to 275°C and the system was placed under vacuum using an oil—based electrical pump.
  • the reaction was stirred under a 0.2 mm vacuum for - 1 hour with removal of additional water/methanol and excess diethylene glycol.
  • a clear, viscous, light yellow melt was obtained.
  • the polymer was removed from the bath, cooled, and isolated.
  • a polyester with an I.V. of 0.315, 2nd cycle Tg of 80°C, and composition by NMR of 77.6 mol % isophthalate, 22.4 mol % 5—sodiosulfoisophthalate, 77.6 mole % 1,4— cyclohexanedimethanol, and 22.4 mol % diethylene glycol was obtained. (The acid components are calculated to equal 100 mol % and the glycol components are calculated to equal 100 mole %) .
  • polyester compositions can be prepared in a similar fashion either on a small scale in the lab, in the pilot plant batch or continuous equipment, or by scale—up to commercial scale in either batch or continuous units.
  • the polymers may be prepared from the diacids, diesters, or anhydrides with Ti or other suitable known esterification, ester—exchange, and/or polycondensation catalysts.
  • aqueous polymer dispersion (16.88 g of a 30.6% solids dispersion of polyester of Example V) were placed in a 3—necked round bottom flask which was equipped with a mechanical stirrer and flushed with nitrogen. The mixture was stirred, and 1.0 g of a 1% solution of ammonium iron sulfate and a solution of 0.25 g of isoascorbic acid in 2.0 g water was added.
  • This example illustrates the preparation of latex from the stabilizer of Example VII.
  • Example VII Weights of materials used and the procedure were identical to that shown in Latex Preparation of Example VI above.
  • the polymer composition is shown in Polymer Prep III (Example VII) above.
  • the polyester dispersion contained 29.9% solids and had a pH of 6.17.
  • the resulting latex had a pH of 4.70, % solids of 39.50, and a large amount of scrap. (Ex. 15, Table I).
  • lattices were prepared with 8.1 and 5.3% polyester stabilizer (with no added surfactant) with the polymer and dispersion of Polymer Preparation II (Example V) (High SIP) .
  • other polyesters evaluated were AQ-29 (89% isophthalate, 11% 5-sodio- sulfoisophthalate and 100% diethylene glycol) ;
  • AQ—38 (89% isophthalate, 11% 5—sodiosulfoisophthalate, 78% diethylene glycol, and 22% 1, 4—cyclohexanedimethanol) ;
  • AQ—55 (82% isophthalate, 18% 5—sodiosulfoisophthalate, 54% diethylene glycol, and 46% 1,4—cyclohexane ⁇ dimethanol) ;
  • LB 89% isophthalate, 11% 5—sodio ⁇ sulfoisophthalate, 72 mole % diethylene glycol
  • Reaction Conditions Initial charge materials were weighed and transferred to the kettle. A slow nitrogen purge was used during the reaction and the water bath was set to the desired temperature. The kettle was purged with N2 at least 10 minutes before any kicker, initiators, or monomers were fed into the system. Kickers were fed into the system just before the initiator and monomer feeds were started.
  • Initiators/reductants and monomers were weighed into Erlenmeyer flasks, feed rates were calibrated, and then these materials were fed at specified rates into the reaction kettle. After all the material had been fed into the kettle, the pumps were turned off and the system was stirred at the set temperature for 30—90 minutes, normally for 60 minutes. The contents of the reaction kettle were cooled with stirring to ⁇ room temperature by circulating cold water through the jacket. The agitator was stopped and the latex was filtered through a preweighed wire mesh screen (100 mm) to capture any scrap. Scrap was also carefully removed from the agitator blades and shaft. The scrap was air dried for 24 hours and reweighed. Percent solids and particle size were determined on the filtered latex.
  • Polyester Composition b a Acids Particle
  • Aerosol OT surfactant 0.40 g ammonium carbonate and the following vinyl/acrylic monomers
  • the monomer weights were based upon a total of 100 g of monomers (acrylic/vinyl + AQ polyester.
  • the first set of experiments (as shown in table 2 below) used the following conditions: 8.11% polyester
  • the initiator feed was 0.576 g t—butyl hydroperoxide and 0.387 g ammonium carbonate in 35.0 g demineralized H 2 0 (feed rate of 0.288 g/min) and the reductant was 0.570 g isoascorbic acid in 35 g demineralized H 2 0 (feed rate of 0.285 g/min).
  • a 75/25 styrene/methylmethacrylate monomer solution (194.33 g styrene/64.78 g MMA) was fed at 2.16 g/min.
  • the experiment was repeated with 25/75 styrene/methylmethacrylate monomer solution (64.78 g styrene/194.33 g MMA) .
  • the total batch size was 800 g and the theoretical % solids was 35%.
  • %Scrap is based on the g scrap/g theoretical monomer X100. Particle Size is in nm and was measured on a Brookhaven BI—90.
  • Table 3 shows the results for Experiment 2 which used an initiator/reductant system of ammonium persulfate/sodium bisulfite at 75/25 styrene/— ethylmethacrylate and a polyester concentration of 5.26%.
  • a second set of experiments used the following conditions: 5.26% polyester (376.53 g demineralized H 2 0, 43.60 g polyester dispersion - except for AQ—55 which used 380.49 g H 2 0 and 39.64 g dispersion); kicker added was 0.45 g of 1% ammonium iron sulfate solution; the initiator was 0.453 g ammonium persulfate in 40.0 g demineralized H 0 at 0.270 g/min; reductant was 0.264 g/min; monomer was a 75/25 styrene/MMA solution (187.06 g/62.35 g) at a feed rate of 1.66 g/min. In some instances ammonium carbonate (0.218 g) was added with the initiator. The total batch size was 750 g and the theoretical % solids was 35%. The temperature was 55°C.
  • % Scrap is based on the g scrap/g theoretical monomer X100. Particle Size is in nm and was measured on a Brookhaven BI-90.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Paints Or Removers (AREA)

Abstract

L'invention concerne certains polyesters susceptibles d'être dispersés dans l'eau qui sont utiles comme stabilisants dans la préparation de latex vinyliques et acryliques. Les latex hybrides polyester/acrylique ainsi obtenus ont une teneur élevée en matières solides et contiennent beaucoup moins de matières coagulées.
PCT/US1997/000912 1996-01-31 1997-01-17 Latex a petites particules WO1997028199A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU17516/97A AU1751697A (en) 1996-01-31 1997-01-17 Small particle size latexes

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US59455396A 1996-01-31 1996-01-31
US08/594,553 1996-01-31

Publications (1)

Publication Number Publication Date
WO1997028199A1 true WO1997028199A1 (fr) 1997-08-07

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1997/000912 WO1997028199A1 (fr) 1996-01-31 1997-01-17 Latex a petites particules

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AU (1) AU1751697A (fr)
WO (1) WO1997028199A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001025304A1 (fr) * 1999-10-01 2001-04-12 Eastman Chemical Company Polymeres sulfones en tant que stabilisateurs d'emulsion presentant un meilleur niveau de coagulum
WO2001027177A1 (fr) * 1999-10-12 2001-04-19 Eastman Chemical Company Preparation de latex en milieu reactif alcalin et leurs applications dans la formation de melanges de polyesters
US6699931B2 (en) 2001-04-09 2004-03-02 Eastman Chemical Company Modified alkyd compositions comprising diol latex compositions and processes of making the same
US6844390B2 (en) 2001-04-09 2005-01-18 Eastman Chemical Company Modified alkyd compositions comprising polyol latex compositions and processes of making them
WO2014193643A1 (fr) * 2013-05-29 2014-12-04 Eastman Chemical Company Sulfopolyester présentant une densité de charge supérieure à un et produits à base de celui-ci

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1991008237A1 (fr) * 1989-12-02 1991-06-13 Henkel Kommanditgesellschaft Auf Aktien Stabilisants polymeres pour la polymerisation d'une emulsion
US5342877A (en) * 1992-07-06 1994-08-30 Eastman Chemical Company Blends of polyesters and alkylhydroxy (meth)acrylate compounds
WO1995001382A1 (fr) * 1993-06-29 1995-01-12 Eastman Chemical Company Melanges de polymeres produisant un brillant intense
WO1995005413A1 (fr) * 1993-08-12 1995-02-23 Eastman Chemical Company Resines polyester acrylique modifie dispersibles dans l'eau utilisees dans des enduits, et procede pour leur fabrication

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1991008237A1 (fr) * 1989-12-02 1991-06-13 Henkel Kommanditgesellschaft Auf Aktien Stabilisants polymeres pour la polymerisation d'une emulsion
US5342877A (en) * 1992-07-06 1994-08-30 Eastman Chemical Company Blends of polyesters and alkylhydroxy (meth)acrylate compounds
WO1995001382A1 (fr) * 1993-06-29 1995-01-12 Eastman Chemical Company Melanges de polymeres produisant un brillant intense
WO1995005413A1 (fr) * 1993-08-12 1995-02-23 Eastman Chemical Company Resines polyester acrylique modifie dispersibles dans l'eau utilisees dans des enduits, et procede pour leur fabrication

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001025304A1 (fr) * 1999-10-01 2001-04-12 Eastman Chemical Company Polymeres sulfones en tant que stabilisateurs d'emulsion presentant un meilleur niveau de coagulum
US6255366B1 (en) 1999-10-01 2001-07-03 Eastman Chemical Company Sulfopolymers as emulsion stabilizers with improved coagulum level
WO2001027177A1 (fr) * 1999-10-12 2001-04-19 Eastman Chemical Company Preparation de latex en milieu reactif alcalin et leurs applications dans la formation de melanges de polyesters
US6462109B1 (en) 1999-10-12 2002-10-08 Eastman Chemical Company Surfactantless latex compositions and methods of making polymer blends using these compositions
US6699931B2 (en) 2001-04-09 2004-03-02 Eastman Chemical Company Modified alkyd compositions comprising diol latex compositions and processes of making the same
US6844390B2 (en) 2001-04-09 2005-01-18 Eastman Chemical Company Modified alkyd compositions comprising polyol latex compositions and processes of making them
WO2014193643A1 (fr) * 2013-05-29 2014-12-04 Eastman Chemical Company Sulfopolyester présentant une densité de charge supérieure à un et produits à base de celui-ci
CN105229051A (zh) * 2013-05-29 2016-01-06 伊士曼化工公司 具有大于1的电荷密度的磺基聚酯及由其制造的产品

Also Published As

Publication number Publication date
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