WO1997023519A1 - Synthese de polymeres d'acrylate amines, anioniques et aqueux - Google Patents

Synthese de polymeres d'acrylate amines, anioniques et aqueux Download PDF

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Publication number
WO1997023519A1
WO1997023519A1 PCT/US1996/018586 US9618586W WO9723519A1 WO 1997023519 A1 WO1997023519 A1 WO 1997023519A1 US 9618586 W US9618586 W US 9618586W WO 9723519 A1 WO9723519 A1 WO 9723519A1
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amino
polymer
coating composition
water
available
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PCT/US1996/018586
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English (en)
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Suryya K. Das
Soner Kilic
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Ppg Industries, Inc.
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Publication of WO1997023519A1 publication Critical patent/WO1997023519A1/fr

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    • 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
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/34—Esters containing nitrogen, e.g. N,N-dimethylaminoethyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C09D133/04—Homopolymers or copolymers of esters
    • C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09D133/062—Copolymers with monomers not covered by C09D133/06

Definitions

  • This invention relates to synthesis of amino acrylate polymers in water.
  • Acrylate polymers with amine functionality have various uses, particularly in coating compositions in which they may be crosslinked by means of polyisocyanate compositions. Since water based coatings are often preferred over organic solvent based coatings for the sake of environmental considerations, it is desirable to provide waterborne polymers that contain groups that are reactive with crosslinking agents such as polyisocyanates.
  • the present invention is directed to aqueous, anionic amino polymers that are the polymerization products of olefinically unsaturated compounds, including compounds containing primary amine groups and or secondary amine groups.
  • the amino polymer is an amino acrylate.
  • the amino polymers ofthe present invention are synthesized in water in the presence of an emulsifier. Neutralization of amine groups with acid is not involved. Accordingly, the dispersed polymer product has pH greater than 7.0. Furthermore, the amino polymers ofthe present invention do not require acrylic acid to be included among the copolymerization monomers; preferably there is no deliberate addition of acid group containing monomers.
  • azo type initiators having carboxy functionality to initiate free radical polymerization ofthe monomers that constitute the amino polymers.
  • the carboxy functionality is neutralized with a base to render the initiator soluble in water.
  • the amino polymer is formed from olefinically unsaturated monomers containing primary and/or secondary amino groups. These amino groups serve as curing sites for reaction with the polyisocyanate to form urea linkages.
  • the amino polymers may also include hydroxyl groups, which upon curing with the isocyanate groups form urethane linkages.
  • the amino group-containing polymers have a number average molecular weight (M n ), as determined by gel permeation chromatography, of about 500 to 50,000, preferably about 1,000 to 10,000.
  • M n number average molecular weight
  • the amine content ofthe amino polymer is preferably 0.05 to 2.70 milliequivalents per gram, most preferably 0.25 to 1.62 milliequivalents per gram.
  • amino polymer component ofthe coating compositions ofthe present invention are provided in an aqueous medium in amounts of 10 to 50 percent by weight resin solids, preferably 20 to 40 percent by weight, and has a pH value of 7.0 to 10 preferably 7.5 to 9.5.
  • suitable amino comonomers are any olefinically unsaturated, polymerizable compounds which contain at least one primary or secondary amino group, e.g.: amino acrylates and amino methacrylates such as tert- butylaminoethyl methacrylate or meta-isopropenyl- ⁇ , ⁇ -dimethylbenzylamine.
  • Amino groups can also be obtained by the reaction of acid polymers with aziridines such as ethylene imine, or by the reaction of epoxy and blocked ketimines, as well as other techniques known for adding amine functionality to polymers.
  • Monomers containing hydroxyl groups are not required in the present invention, but when used, may be included in the monomer mixture in such quantities that the hydroxyl group-containing monomers are used in quantities of about 0 to 30 percent by weight, preferably 0 to 10 percent by weight based on the total weight of monomers used to copolymerize the amino polymer.
  • Suitable monomers containing hydroxyl groups include, in particular, hydroxyalkyi esters of acrylic acid or methacrylic acid preferably containing 2 to 4 carbon atoms in the alkyl radical such as 2-hydroxyethyl acrylate or methacrylate, 2- or 3 -hydroxypropyl acrylate or methacrylate, the isomeric hydroxybutyl acrylates or methacrylates and mixtures of such monomers.
  • the third group of olefinically unsaturated monomers which may be used for the production ofthe amino polymers are olefinically unsaturated compounds which contain neither amino nor hydroxyl groups.
  • polyfunctional materials may be included, such as ethylene glycol dimethacrylate or allyl methacrylate.
  • the monomers of this third group are used in quantities of 50 to 90 percent by weight, preferably about 40 to 80 percent by weight, based on the total weight ofthe monomers used.
  • the amino polymers are synthesized in water in the presence of an emulsifier. Details of such a polymerization process are well known to those of skill in the art.
  • a novel feature ofthe polymerization is the selection of initiators.
  • the polymerization reaction is free radically initiated when the monomer mixture is added together with an initiator mixture over a period of about 1 to 10 hours, preferably about 3 to 6 hours, at reaction temperature. Thereafter, more initiator may optionally be added to take the polymerization to a conversion of at least 99 percent.
  • Emulsifiers suitable for use in the polymerization include anionic, nonionic, and amphoteric (if non-ionic) emulsifiers. Many such emulsifiers are commercially available, several of which are disclosed in the examples herein.
  • the choice ofthe initiator compound used in the polymerization is important in the present invention.
  • azo type initiators which have carboxy groups are used.
  • An initiator of this type is 4,4'- azobis(4-cyanovaleric acid), commercially available as "V-501" initiator from Wako Chemicals USA, Inc.
  • the initiators are used in quantities of about 0.05 to 10 percent by weight, based on the total quantity of monomers.
  • the polymerization reaction takes place at temperatures in the range previously set forth, preferably at a temperature of about 50 to 100 °C under atmospheric pressure. The exact polymerization temperature is determined by the initiator used.
  • the molecular weight ofthe polymers may be regulated by standard regulators such as n-dodecylmercaptan, diisopropyl xanthogene disulfide, di- (methylene-trimethylolpropane)-xanthogene disulfide and thioglycol. They may be added in quantities of up to about 10 percent by weight, based on the monomer mixture.
  • the coating compositions according to the invention thus obtained are suitable for virtually any applications where high performance is desired. They are particularly useful for coating of metal surfaces and various plastic surfaces.
  • Methyl methacrylate 179.2 Tert-butylaminoethyl methacrylate 160.0
  • Aqueous ammonia (29.7 %) 7.0 Deionized water 296.6 Ammonium salt of sulfated nonylphenoxypoly(ethyleneoxy) ethanol (30 % active), available from Rhone-Poulenc, USA.
  • the initial charge was heated to a temperature of 80°C with agitation in a reaction vessel suitable for aqueous emulsion polymerization.
  • 40 grams of Feed 1 were added to the reaction vessel and held about 5 minutes for regaining the temperature, followed by the addition of 40 grams of Feed 2 and holding the reaction mixture temperature at 80°C. for 30 minutes. Then the temperature was raised to 85°C, and the reaction mixture was held for 30 minutes at this temperature.
  • the remaining portions of Feed 1 and 2 were added to the reaction mixture simultaneously over a 3 -hour period while maintaining the reaction mixture temperature at about 85°C. At the completion of the additions, the reaction mixture was held for 2 hours at 85°C. to complete the polymerization.
  • the product was filtered to yield a dispersion with a resin content of 40.6 percent determined at 110°C. for one hour and a pH of 9.27.
  • Aqueous ammonia (29.7 %) 3.5
  • Deionized water 148.3 The initial charge was heated to a temperature of 85°C. with agitation in a reaction vessel suitable for aqueous emulsion polymerization. 25 grams of Feed 1 was added to the reaction vessel and held about 10 minutes for regaining the temperature, followed by the addition of 25 grams of Feed 2 and holding the reaction mixture temperature at 85°C. for 30 minutes. Then the remaining portions of Feed 1 and 2 were added to the reaction mixture simultaneously over a 3 -hour period while maintaining the reaction mixture temperature at about 85°C. At the completion ofthe additions, the reaction mixture was held for 2 hours at 85°C. to complete the polymerization. The product was filtered to yield a dispersion with a resin content of 40.2 percent determined at 110°C. for one hour and a pH of 8.8.
  • a secondary amine functional polymer was prepared in the same manner as disclosed in Example 5 of U.S. Patent No. 5,225,505.
  • a mixture of 54 grams of methyl methacrylate, 50 grams of tert-butylaminoethyl methacrylate, 94 grams of n-butyl acrylate and 2 grams of acrylic acid was polymerized batchwise in an emulsion in 300 grams of deionized water in the presence of 0.7 grams of ammonium persulphate and 0.7 grams of sodium metabisulphite as initiators, and in the presence of 20 grams of AB EX- 120 (30 percent active) as surfactant.
  • the polymerization was carried out at 72°C for about 3 hours, resulting in an unstable dispersion. An exotherm was observed after further addition of 0.7 grams of ammonium persulphate dissolved in 10 grams of deionized water and 0.7 grams of sodium metabisulphite dissolved in 10 grams of deionized water and raising the reaction temperature to 85°C. The reaction mixture was held about one hour at 85°C. The resultant dispersion was full of grit, and after filtration gave a dispersion having 31.4 percent solids determined at 110°C for one hour. The product was unsuitable for use in a coating composition.
  • the aqueous anionic amino polymers ofthe present invention may constitute film forming resins in coating compositions when formulated with curing agents such as polyisocyanates or polyepoxides.
  • Aqueous, polyisocyanate-cured, anionic coatings containing the amino polymers ofthe present invention are the subject matter of commonly owned U.S. Patent Application Serial No. titled "Aqueous, Anionic, Amino Acrylate Coating Compositions" filed on even date herewith by Suryya Das, Soner Kilic, Robert E. Jennings, and James A. Claar.
  • the polyisocyanate component is emulsified in the aqueous amino group-containing polymer component.
  • the dissolved or dispersed polymer simultaneously serves as an emulsifier for the polyisocyanate added.
  • dispersion ofthe polyisocyanate component may be assisted by a separate surfactant.
  • the polyisocyanate component may be any polyisocyanate containing aliphatically, cycloaliphatically, araliphatically and/or aromatically bound isocyanate groups which are liquid at room temperature.
  • the polyisocyanate component may optionally be modified to be water dispersible or soluble.
  • the polyisocyanate component is preferably a polyisocyanate or polyisocyanate mixture exclusively containing aliphatically and/or cycloaliphatically bound isocyanate groups and having an average NCO functionality of about 2.0 to 5.0.
  • Suitable polyisocyanates include those containing aromatically or (cyclo)aliphatically bound isocyanate groups, (cyclo)aliphatic polyisocyanates being particularly preferred. Particularly suitable are polyisocyanates based on hexamethylene diisocyanate, l-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl cydohexane (IPDI) and/or bis-(isocyanatocyclohexyl)-methane, particularly those based on hexamethylene diisocyanate.
  • IPDI l-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl cydohexane
  • bis-(isocyanatocyclohexyl)-methane particularly those based on hexamethylene diisocyanate.
  • suitable polyisocyanates based on these diisocyanates may include the biuret, urethane, uretdione and/or isocyanurate derivatives of these diisocyanates which, after their production, have been freed in the known manner, preferably by distillation, from excess starting diisocyanate to a residual content of less than 0.5 percent by weight.
  • Aliphatic polyisocyanates for use in accordance with the invention include biuret polyisocyanates based on hexamethylene which are based on mixtures of N,N',N"-tris-(6- isocyanatohexyl)biuret with small quantities of its higher homologs. These polyisocyanates may be obtained by the processes according to U.S.
  • Examples A, B, and C are coating compositions formulated with the anionic amino polymers of Examples 1 and 2.
  • the pH of each of the compositions was greater than 7.0.
  • TAMOL 850 Aqueous pigment dispersant available from Union Carbide Chemicals & Plastic Company, Industrial Chemicals Div., Danbury, Connecticut.
  • PGNP-15 Polyproxylated nonyl phenol, nonionic surfactant produced by PPG Industries, Pittsburgh, Pennsylvania.
  • TRITON GR-7M - Anionic surfactant available form Union Carbide Chemicals & Plastic Company, Industrial Chemicals Div., Danbury, Connecticut.
  • TI-PURE R902-38 Titanium dioxide pigment available from E.I. du Pont de Nemours & Co., Wilmington, Delaware.
  • Anionic isocyanate made by the following reaction. Isophorone diisocyanate (318.2 grams, 2.88 NCO equivalents), DESMODUR W (188.6 grams, 1.44 NCO equivalents), and propoxylated 1 ,4-butanediol sodium sulfonate (244.7 grams, 1.03 OH equivalents) were placed into a one liter, four-neck, round bottom flask. The flask was heated to 90°C and a nitrogen blanket was applied throughout the reaction.. The flask was kept at 90°C until the isocyanate equivalent weight reached 225. The propoxylated 1 ,4-butanediol sodium sulfonate was prepared in accordance with British Patent No.
  • Emulsifier - A nonionic surfactant containing 62.3% T-l 890 (an IPDI isocyanurate from Huls America, Inc., Piscataway, NJ 08855), 28.8% CARBOWAX 750ME (a monofunctional polyether surfactant available from Union Carbide 25 Chemicals & Plastics Co., Inc., S. Washington, WV 25303), 16.9% diethylamine (secondary amine available from Union Carbide, S.
  • DESMODUR N 3400 A trimer isocyanate available from Bayer Corporation, Pittsburgh, Pennsylvania.
  • Emulsifier - A nonionic surfactant containing 75% T-l 890 (an IPDI isocyanurate available from Huls America, Inc., Piscataway, NJ 08855) and 25% CARBOWAX 750ME (a monofunctional polyether surfactant available from Union Carbide Chemicals & Plastic Co., Inc., Solvents & Coatings Materials Div., S. Washington, WV 25303), prepared in methyl ethyl ketone and PROGLYDE DMM
  • the coating compositions of Examples A through C were prepared in the following manner. In a grinding vessel under high speed agitation with a Cowles blade, the pigments were sifted into the other components ofthe grind paste (except the thickener). After stirring for 5 minutes the Cowles blade was replaced with an Impeller blade, and zircoa beads were then added. This mix was stirred at high speed for one hour, after which the beads were separated from the grind paste. The thickener (DSX- 1514) was then added to the grind paste and stirred at high speed for five minutes, after which the grind paste was diluted with the let-down ingredients. The isocyanate portions ofthe Examples were prepared and added to the other ingredients as described below. In Example A, the anionic isocyanate was diluted with EXXATE 900 to 70% solids, further diluted to 35% solids with deionized water, and then immediately stirred with moderate agitation into the container holding the remainder ofthe ingredients.
  • Example B 75% isophorone diisocyanate was blended with 25% of the isocyanate emulsifier. This combination was stirred with moderate agitation into the container holding the remainder ofthe ingredients.
  • Example C the isocyanate emulsifier was blended with SILQUEST Y-9669 at 1 part isocyanate to 1 part amine by equivalents. After a 24 hour induction, 25% ofthe blend was mixed with DESMODUR N 3400 isocyanate. This isocyanate combination was stirred with moderate agitation into the container holding the remainder ofthe ingredients.
  • each ofthe coating formulations of Examples A, B, and C was tested for performance by application onto a substrate prepared as follows.
  • the substrate for each example was 32 gauge, unpolished, cold rolled steel (available from Advanced Coating Technologies, Inc., Hillsdale, Michigan, as code: APR10288) sanded with P180 grit sandpaper (Pl 80-216U, Production RN FRE-CUT, Paper A weight, open coat, available from 3M, St. Paul, MN).
  • the substrate was washed with Acryli-Clean or DX-330 (available from PPG Industries, Pittsburgh, PA as a wax and grease remover) and wiped with a lintless tissue (available from Scott Paper Company, Philadelphia, Pennsylvania, as Scott Precision Wipes).
  • each ofthe compositions ofthe examples was applied by air-atomized spray at 45 psi. over the previously prepared substrates.
  • Each coated substrate was air-dried under ambient conditions for 1 hour.
  • P400 grit sandpaper P400-213Q, Imperial Wetordry production paper, "A" weight, available from 3M, St. Paul, Minnesota
  • each example composition approximately 85 to 100 grams was sealed in a 1/2 pint container. Each sample container was stored at room temperature for two months, reopened, and observed for fluidity at one month intervals.
  • a "fail” rating under SANDING indicated fouling ofthe sandpaper due to embedment of the coating into the sandpaper's grit.
  • a "fail” rating under ADHESION indicated a less than 95% adhesion ofthe example coating over the substrate.
  • a "fail” rating under FLUIDITY indicated an example coating with an unsprayable viscosity, even when diluted with water.
  • Examples 4 and 5 relate to amino polymers employed in the coating formulations of Examples D and E.
  • V-501 initiator 16.0 Aqueous ammonia (29.7 %>) 7.0
  • the polymerization was conducted under the same procedure as described above in Example 1.
  • the product was filtered to yield a dispersion with a resin content of 41.5 percent determined at 110°C. for one hour and a pH of 9.33.
  • EXAMPLE 5 The following initial charge and feeds were used in the preparation of aqueous secondary amine functional acrylic polymer via emulsion polymerization technique.
  • Aqueous ammonia (29.7 %) 3.5
  • Deionized water 148.3
  • the initial charge was heated to a temperature of 85°C. with agitation in a reaction vessel suitable for aqueous emulsion polymerization.
  • 25 grams of Feed 1 was added to the reaction vessel and held about 10 minutes for regaining the temperature, followed by the addition of 25 grams of Feed 2 and holding the reaction mixture temperature at 85°C. for 30 minutes.
  • the remaining portions of Feed 1 and 2 were added to the reaction mixture simultaneously over a 3-hour period while maintaining the reaction mixture temperature at about 85°C.
  • the reaction mixture was held for 2 hours at 85°C. to complete the polymerization.
  • the product was filtered to yield a dispersion with a resin content of 40.2 percent determined at 110°C. for one hour and a pH of 8.8.
  • NALZI T 2 - Anticorrosive pigment available from Rheox, Inc., P.O. Box 700, Hightstown, NJ.
  • the coating compositions of Examples A and B were prepared as two- package compositions with the amino acrylate, pigments, and additives in one package (Package 1 ) and the isocyanate and isocyanate emulsifier in a second package (Package 2).
  • Package 1 was prepared by mixing the pigments into a surfactant, defoamer, and water mix. After stirring for 5 minutes the Cowles blade was replaced with an Impeller blade, and zircoa beads were then added. This mix was stirred at high speed for one hour, after which the beads were separated from the grind paste.
  • the thickener (DSX-1514) was added to the grind paste and stirred at high speed for five minutes. An appropriate amount of this grind paste was then added to the amino acrylate and water.
  • each of the coating formulations of Examples D and E was tested for performance by application onto a substrate prepared in the same manner as described above in connection with Examples A, B, and C.
  • Package 2 was added to Package 1 for each example, with moderate and constant agitation.
  • Each ofthe compositions ofthe examples was applied by air-atomized spray at 45 psi. over the previously prepared substrates.
  • Each coated substrate was air-dried under ambient conditions for 1 hour. Then each was dry-sanded with P400 grit sandpaper (P400-213Q, Imperial Wetordry production paper, "A" weight, available form 3M, St. Paul, Minnesota) immediately and, if necessary, at every succeeding hour interval.
  • P400 grit sandpaper P400-213Q, Imperial Wetordry production paper, "A" weight, available form 3M, St. Paul, Minnesota
  • Each two-component coating composition example was additionally subjected to a test for gassing potential. Immediately after each spray application, the remaining portion of each blended composition, approximately 85 to 100 grams, was sealed in a 1/2 pint container. Each sample container was opened at 1 hour intervals and was evaluated for gas-pressure buildup by listening for an audible hissing of pressurized gas, an audible popping ofthe lid, or observing bubbling or foaming of the wet sample.
  • a "fail” rating under ADHESION indicated a less than 95% adhesion ofthe example coating over the substrate
  • a "fail" rating under GASSING indicated bubbling of the wet sample due to gas evolvement.
  • the initial charge was heated to a temperature of 80°C. with agitation in a reaction vessel suitable for aqueous emulsion polymerization.
  • 40 Grams of Feed 1 was added to the reaction vessel and held about 5 minutes for regaining the temperature followed by the addition of 40 grams of Feed 2 and holding the reaction mixture temperature at 80°C. for 30 minutes. Then the temperature raised to 85°C. and the reaction mixture was held 30 minutes at this temperature.
  • the remaining of Feed 1 and 2 were added to the reaction mixture simultaneously over a 3 -hour period while maintaining the reaction mixture temperature at about 85°C. At the completion of addition the reaction mixture was held for 2 hours at 85°C. to complete the polymerization.
  • the product was filtered to yield a dispersion with a resin content of 41.6 percent determined at 110°C. for one hour and a pH of 9.31.
  • EXAMPLE 7 The following initial charge and feeds were used to prepare an aqueous secondary amine functional acrylic polymer using phosphate containing surfactant.
  • Aqueous ammonia (29.7 %) 7.0 Deionized water 296.6
  • the initial charge was heated to a temperature of 85°C. with agitation in a reaction vessel suitable for aqueous emulsion polymerization.
  • 40 Grams of Feed 1 was added to the reaction vessel and held about 10 minutes for regaining the temperature followed by the addition of 40 grams of Feed 2 and holding the reaction mixture temperature at 85°C. for 30 minutes.
  • the remaining portions of Feed 1 and 2 were added to the reaction mixture simultaneously over a 3 -hour period while maintaining the reaction temperature at about 85°C.
  • the reaction mixture was held for 2 hours at 85°C. to complete the polymerization.
  • the product was filtered to yield a dispersion with a resin content of 62.5 percent determined at 110°C. for one hour and a pH of 8.84.
  • the initial charge was heated to a temperature of 90°C. with agitation in a reaction vessel suitable for aqueous emulsion polymerization.
  • the Feeds 1 and 2 were added to the reaction mixture simultaneously over a 3 -hour period while maintaining the reaction temperature at about 90°C.
  • the reaction mixture was held for 2 hours at 90°C. to complete the polymerization.
  • the product was filtered to yield a dispersion with a resin content of 43.1 percent determined at 110°C. for one hour and a pH of 9.25.
  • the initial charge was heated to a temperature of 90°C. with agitation in a reaction vessel suitable for aqueous emulsion polymerization.
  • Feeding of Feed 1 and 3 was initiated at the same time.
  • the Feed 1 was added over 45 minutes and Feed 3 was added to a 3-hour period while maintaining the reaction temperature at about 90°C.
  • the Feed 2 addition was initiated and added over 2 hours and 15 minutes.
  • the reaction mixture was held for 2 hours at 90°C. to complete the polymerization.
  • the product was filtered to yield a dispersion with a resin content of 42.4 percent determined at 110°C. for one hour and a pH of9.0.

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Abstract

Cette invention se rapporte à un procédé pour produire des polymères aminés anioniques aqueux dans de l'eau, à partir de monomères à insaturation oléfinique contenant des monomères à teneur en amines, mais pratiquement sans inclusion de monomères à teneur en groupes acides. La polymérisation du polymère anionique est effectuée en présence d'un initiateur azo fonctionnel carboxy dissous dans de l'eau par neutralisation des groupes acides présents sur l'initiateur. Ce polymère est utile dans des compositions de revêtements monocouches ou bicouches ayant un pH supérieur à 7,0, qui peuvent être durcies avec des polyisocyanates ou des polyépoxydes.
PCT/US1996/018586 1995-12-21 1996-11-19 Synthese de polymeres d'acrylate amines, anioniques et aqueux WO1997023519A1 (fr)

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US57756695A 1995-12-21 1995-12-21
US08/577,566 1995-12-21

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6262176B1 (en) 1998-05-14 2001-07-17 Basf Aktiengesellschaft Crosslinked water-soluble or water-dispersible polyurethanes

Citations (4)

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Publication number Priority date Publication date Assignee Title
US4306045A (en) * 1979-06-13 1981-12-15 Nitto Chemical Industry Co., Ltd. Process for producing acrylamide polymers
US5075370A (en) * 1988-09-01 1991-12-24 Bayer Aktiengesellschaft Aqueous coating composition based on specific two-component polyurethanes and to a process for its production
US5225505A (en) * 1989-12-21 1993-07-06 Atochem Acrylic copolymers and their use as coatings
WO1996018668A1 (fr) * 1994-12-16 1996-06-20 Ppg Industries, Inc. Enduits aqueux durcissant a temperature ambiante a base de resines de polycarbamide

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4306045A (en) * 1979-06-13 1981-12-15 Nitto Chemical Industry Co., Ltd. Process for producing acrylamide polymers
US5075370A (en) * 1988-09-01 1991-12-24 Bayer Aktiengesellschaft Aqueous coating composition based on specific two-component polyurethanes and to a process for its production
US5225505A (en) * 1989-12-21 1993-07-06 Atochem Acrylic copolymers and their use as coatings
WO1996018668A1 (fr) * 1994-12-16 1996-06-20 Ppg Industries, Inc. Enduits aqueux durcissant a temperature ambiante a base de resines de polycarbamide

Non-Patent Citations (1)

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Title
DATABASE "CHEMICAL ABSTRACTS" (HOST: STN);Abs. 108: 168 158, Colombus, OH, USA; & JP-A-62 243 607 (SOKEN CHEM.ENG.CO.,Ltd)24 October 1987 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6262176B1 (en) 1998-05-14 2001-07-17 Basf Aktiengesellschaft Crosslinked water-soluble or water-dispersible polyurethanes
US6489397B2 (en) 1998-05-14 2002-12-03 Basf Aktiengesellschaft Crosslinked, water-soluble or water-dispersible polyurethanes
USRE39936E1 (en) 1998-05-14 2007-12-04 Basf Aktiengesellschaft Crosslinked, water-soluble or water-dispersible polyurethanes
USRE41615E1 (en) 1998-05-14 2010-08-31 Basf Se Crosslinked, water-soluble or water-dispersible polyurethanes

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