WO2002031021A1 - Dispersions de compose organique faiblement volatile d'alkyde polyol et dispersions de polyurethanne - Google Patents

Dispersions de compose organique faiblement volatile d'alkyde polyol et dispersions de polyurethanne Download PDF

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WO2002031021A1
WO2002031021A1 PCT/SG2001/000192 SG0100192W WO0231021A1 WO 2002031021 A1 WO2002031021 A1 WO 2002031021A1 SG 0100192 W SG0100192 W SG 0100192W WO 0231021 A1 WO0231021 A1 WO 0231021A1
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dispersion
range
temperature
resin
amine
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PCT/SG2001/000192
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English (en)
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Zeling Dou
Paul Shau Lung Chan
Peter Ping Kwong Chan
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Polymer Coating Technologies Of Singapore Pte Ltd.
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Priority to AU2001296200A priority Critical patent/AU2001296200A1/en
Publication of WO2002031021A1 publication Critical patent/WO2002031021A1/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
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4288—Polycondensates having carboxylic or carbonic ester groups in the main chain modified by higher fatty oils or their acids or by resin acids
    • 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
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/46—Polyesters chemically modified by esterification
    • C08G63/48—Polyesters chemically modified by esterification by unsaturated higher fatty oils or their acids; by resin acids
    • 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
    • C08G63/66—Polyesters containing oxygen in the form of ether groups
    • C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/06—Polyurethanes from polyesters

Definitions

  • THE PRESENT INVENTION relates to low voi?iive organic compound (VOC) polyol alkyd dispersions and polyurethane dispersions, methods for their production, and coatings produced therefrom.
  • VOC voi?iive organic compound
  • Waterborne polyurethane coatings are an important part of this new development effort. Waterborne polyurethane dispersions are non-toxic, non-flammable and do not pollute air or water, and they have potential for use in the coatings industry. As polyurethane coatings have advantageous properties, such as superior abrasion resistance, toughness, chemical resistance, corrosion resistance and a wide range of mechanical strengths, they have attracted more attention than other systems.
  • dispersions are obtained by incorporation of an ionic group from a salt (ionomer dispersion), and/or a hydrophilic side group, into the polymer structure.
  • Most of the current commercial polyurethane dispersions (PUDs) coating systems are prepared by one of the following two approaches. Either the polyurethane is polymerized in a solvent, then dispersed in water; or an isocyanate-teiminated pre-polymer is prepared in a melt or in an aprotic solvent, and is then chain extended with a diamine in the water phase, in the presence of a neutralizing tertiary amine, (J. Polym. Sci., Polym. Chem., 1996, Vol 34, 1095-1104).
  • the acetone process (US 4820762) is widely used in preparing polyurethane dispersions, wherein the polyurethane polymer is synthesized as a solution in acetone. After thinning with water, the organic solvent is distilled off, with the hydrophobic polymer being precipitated during distillation. As a suitable counter ion must be added to ensure the stability of the dispersion as it forms, some co-solvent and surfactant must be added, making it difficult to lower the VOC content in the final coating system. Although this process is suitable for reliably producing a broad range of chemical structures of PUDs, it can only be used to produce PUDs which are soluble in acetone. Consequently, the resulting polyurethane paint films are not very solvent resistant.
  • the ketimine and ketazine process can yield high quality polyurethane dispersions by dispersing hydrophilic isocyanate (NCO) prepolymers with polyketimine or ketazines in water.
  • NCO hydrophilic isocyanate
  • a hydrophilically modified prepolymer is mixed with water, then reacted with a diamine. If the reaction is controlled carefully, the reaction of the NCO groups with the diamine dorriinates over the reaction with water. In order to control the viscosity of the prepolymer, a small amount of solvent must be added, which remains as a co- solvent in the dispersion.
  • the polyurethane prepolymer is synthesized in low solvent content medium. This process can ensure a suitable viscosity of the polyurethane prepolymer, which can make dispersion and chain extension proceed smoothly. However, it is subject to the compatability of the polyurethane prepolymer with water and chain extender, and usually requires the use of some co-solvent and surfactants to achieve a stable dispersion.
  • the particle size of the dispersions obtained from the above processes is related to the stirring rate.
  • the present invention seeks to provide stable, low VOC, polyethylene glycol (PEG) modified, aqueous polyol alkyd dispersions (PADs) which can be used in two component (2K) coating systems, and also aqueous polyurethane dispersions (PUDs) which can be used in one component (IK) coating systems, and their methods of production.
  • PEG polyethylene glycol
  • PLDs aqueous polyol alkyd dispersions
  • IK one component
  • the present inventions seeks to provide a new method for the preparation of low VOC polyurethane dispersions combining ionic and non- ionic groups into the polymer structure, and also products that can be self- emulsified without co-solvent and external stabilizers, to form stable dispersions.
  • the present invention seeks to provide a simple and efficient method for the preparation of polyurethane dispersions, especially on a large scale, and also to provide polyurethane dispersion coatings, paint and binder compositions which possess a wide range of properties including solvent resistance, good adhesion, hardness, flexibility, scrub resistance, and good color retention.
  • the invention allows the use of polyethylene glycol (PEG) in the preparation of alkyd resins.
  • PEG polyethylene glycol
  • alkyd resin synthesis allows a combination of ionic and non-ionic groups into the polymer structure.
  • the resultant resin may be self-emulsified, without co-solvent and external stabilizers, to form stable polyol alkyd dispersions.
  • low VOC ( ⁇ 50g/l) aqueous dispersions may be obtained.
  • the PEG-modified PADs of the present invention exhibit good reactivity with some crosslinkable monomers and polymers, and may be used in IK or 2K coating systems. As these dispersions and their derivative products have low VOC content ( ⁇ 50g/l), they can meet increasingly stringent government regulations on VOC and thus have great commercial value.
  • PADs of the present invention and their similar products can also be used in processes of making low VOC baking-type coating systems and non- isocyanate (NCO group free) crosslinking type coating systems.
  • low VOC PADs of the present invention can also be applied in making low VOC polyester dispersions which can be used in making a wide range of low VOC coating systems.
  • the low VOC PADs of the present invention and their similar products, are stable over a wide range of temperatures (from 20° to 35°C) and pH (from pH 6.5 to 9.0). 6)
  • the dispersion process of the present invention can also be applied to prepare low NOC aqueous dispersions containing ionic and non-ionic groups in the polymer structure.
  • a method of making a polyol alkyd resin comprising an alcoholysis step of reacting polyethylene glycol (PEG), an oil and a polyhydroxy compound; followed by an esterification step of reacting the resultant mixture from the alcoholysis step with an acid and/or an acid anhydride, and a polyhydric alcohol with the esterification step being terminated on reaching a predetermined acid value or predetermined viscosity.
  • PEG polyethylene glycol
  • the oil is safflower oil.
  • the oil is soybean oil.
  • polyhydric alcohol and/or the polyhydroxy compound is pentaerythritol.
  • the acid is p-t-butyl benzoic acid or benzoic acid.
  • the acid is, or the acid anhydride corresponds to, a polybasic acid.
  • the acid is isophthalic acid.
  • the acid anhydride is phthalic anhydride.
  • the PEG has a molecular weight in the range of 3000-3700.
  • a method of making an aqueous polyol alkyd resin dispersion, comprising the steps of heating in a reactor a predetermined amount of water, and a predetermined amount of an amine, to a dispersing temperature, and pouring into the reactor, with stirring, a polyol alkyd resin, which has been heated to a melt state, at such a rate that the temperature of the mix in the reactor is no more than about 5°C above the dispersing temperature, with the temperature in the reactor being held at about the dispersing temperature for a period of time after the addition of the resin
  • PAD aqueous polyol alkyd resin dispersion
  • the method further comprises the step of cooling the mix to room temperature and adjusting the pH and/or solids content of the dispersion.
  • the amine is triemylamine, 2-amino-2-methyl-l-propanol, dimethylethanol amine (DMEA) or ammonia solution.
  • DMEA dimethylethanol amine
  • the dispersing temperature is in the range of 55°-70°C.
  • the dispersing temperature is in the range of 60°-65°C.
  • the amine is added in a mole ratio amount in the range of 0.3-1.0:1.0 with respect to the resin.
  • the amine is added in a mole ratio amount in the range of 0.6- 0.95: 1.0 with respect to the resin.
  • the solids content of the dispersion is in the range of 35-45%.
  • the solids content of the dispersion is in the range of 38-40%.
  • PAD aqueous polyol alkyd resin dispersion
  • a method of making an aqueous polyurethane dispersion (PUD) from a polyol alkyd dispersion (PAD) comprising the steps of heating in a reactor a predetermined amount of water, and a predeteimined amount of an amine, to a dispersing temperature, and pouring into the reactor, with stirring, a polyol alkyd resin, which has been heated to a melt state, at such a rate that the temperature of the mix in the reactor is no more than about 5°C above the dispersing temperature, with the temperature in the reactor being held at about the dispersing temperature for a period of time after the addition of the resin, followed by reaction with an isocyanate chain extender.
  • the method further comprises the step of cooling the mix to room temperature and adjusting the pH and/or solids content of the dispersion.
  • the amine is triethylamine, 2-amino-2-methyl-I-propanol, dimethylethanolamine (DMEA) or ammonia solution.
  • the dispersing temperature is in the range of 55°-70°C.
  • the dispersing temperature is in the range of 60°-65°C.
  • the amine is added in a mole ratio amount in the range of 0.3-1.0: 1.0 with respect to the resin.
  • the amine is added in a mole ratio amount in the range of 0.6- 0.95: 1.0 with respect to the resin.
  • the solids content of the dispersion is in the range of 35-45%.
  • the solids content of the dispersion is in the range of 38-40%.
  • the chain extender is an isocyanate-containing compound.
  • the isocyanate-containing compound is an aliphatic compound.
  • the isocyanate-containing compound is isophorone di-isocyanate.
  • the isocyanate-containing compound is an aromatic compound.
  • the isocyanate containing compound is a di-isocyanate.
  • the chain extender is an aziridine-containing compound.
  • the range of equivalents of the chain extender to the solids content of the polyol alkyd dispersion is in the range of between 10:90 and 30:70.
  • the range of equivalents of the chain extender to the solids content of the polyol alkyd dispersion is in the range of between 10:90 and 20:80.
  • the range of equivalents of the chain extender to the solids content of the polyol alkyd dispersion is about 15:85.
  • reaction is performed in the temperature range of from about 25°C to about 30°C.
  • a one component (IK) or a two component (2K) coating system comprising the dispersion of the present invention.
  • the coating system is a room temperature cure or a baking-type coating system.
  • FIGURE 1 is a graph showing the stability of viscosity with time for examples of PADs
  • FIGURE 2 is a graph showing the change in viscosity with time for the examples of PADs of Figure 1;
  • FIGURE 3 is a graph showing the change in pH over six months for examples of PUDs
  • FIGURE 4 is a graph showing the change in viscosity over six months for the examples of PUDs of Figure 3;
  • FIGURE 5 is a graph showing the change in pH over six months for further examples of PUDs.
  • FIGURE 6 is a graph showing the change in viscosity over six months for the further examples of PUDs of Figure 5.
  • the present invention is directed to methods of making stable low VOC ( ⁇ 50g/l) waterborne polyol alkyd dispersions (PADs).
  • PEG polyethylene glycol
  • the polyol alkyd dispersions also can be crosslinked by reaction with polyisocyanates, polyfunctional aziridines and otl er crosslinkers to give low VOC binders in 2K coating systems.
  • the invention also has the advantages of using PEG as a non-ionic part of raw materials for making alkyd dispersions; using isophorone diisocyanate as a reactant to obtain IK waterborne PUD systems; and using an aliphatic polyisocyanate as a crosslinker to achieve 2K waterborne PUD finishings.
  • the invention also relates to coatings making use of these dispersions. Coatings made from these dispersions are particularly suitable for uses on surfaces such as wood, metal, glass, plastic and other substrates where traditional solvent-based polyurethanes are used.
  • the alkyd resin of the present invention is a PEG modified solvent free, short oil alkyd resin with certain chemical structures.
  • short oil denotes a level of less than 40% oil in solids.
  • the alkyd dispersion (PAD) is prepared by dispersing the above resin in water with an amine neutralizer in the absence of other solvents. This process produces a stable, fine particle size and low VOC content ( ⁇ 50 g/1) waterborne polyol alkyd dispersion.
  • the waterborne polyurethane dispersions (PUDs) for IK system are obtained by performing a urethane reaction of a polyol alkyd dispersion (PAD) with a di-isocyanate.
  • the waterborne polyurethane dispersions (PUDs) for 2K system are obtained by crosslinking the polyol alkyd dispersion (PAD) with a polyisocyanate or other crosslinker.
  • the amount of cross-linker may be calculated by the following formula: Isocyanate cross-linker needed 247 x (%OH in resin) for equivalence of 100 pbw OH resin
  • the resultant dispersions have low VOC content ( ⁇ 50 g/1) and fine particle size, are cosolvent-free, and surfactant-free, and are physically and chemically stable.
  • the solvent-free alkyd resin is prepared from monomers by a two step process; alcoholysis, followed by esterification.
  • a small amount of solvent for example, butyl cellosolve
  • Termination of the reaction is controlled by achieving an predetermined acid value and viscosity.
  • the reaction time and temperature for obtaining the proper degree of alcoholysis in the first step is about 3 hours at 250°C.
  • the esterification is carried out at 230°C.
  • the raw materials requirements for the resin may include the following:
  • ALCOHOLS pentaerythritol, glycerine, trimethylol propane, trimethylol ethane, ethylene glycol, neopentyl glycol, propylene glycol, cyclohexanedimethanol,
  • ACIDS AND ACID ANHYDRIDES benzoic acid, p-t-butyl benzoic acid, capric acid, castor fatty acid, coconut fatty acid, dimethylol propionic acid, 2-ethyl butyric acid, lauric fatty acid, linseed fatty acid, myristic acid, oleic acid, palargonic acid, soya fatty acid, stearic acid, tall oil fatty acid, adipic acid, azelaic acid, fumaric acid, isophthalic acid, maleic anhydride, phthalic anhydride, terephthalic acid, trimellitic anhydride,
  • OILS soybean oil, castor oil, coconut oil, dehydrated castor oil, linseed oil, safflower oil, rung oil.
  • the molecular weight of the PEG is preferably from 3000 to 3700.
  • Safflower oil and soybean oil are both suitable for the reaction, but safflower oil is preferred.
  • Benzoic acid which is usually used in alkyd preparation, can also be applied in this alkyd resin, but p-t-butylbenzoic acid is preferred.
  • the color and viscosity of alkyd resin at 60% in xylene may range from 3 to 7 for color and from V to Z5 for viscosity, but preferably with the range from 3 to 5 for color, and X to Z for viscosity.
  • the acid value of the alkyd resin may range from 12 to 25, but preferably within the range from 12 to 15.
  • the molecular weight (Mw) of the resins typically range from about 3,000 up to 14,000, but preferably within the range from 4,000 to 10,000. High molecular weight resins tend to be very viscous and difficult to disperse.
  • the alkyd resins exhibit good stability, and are ready to use.
  • the surface of resin might form an elastic membrane. This membrane may originate from the air- oxidation of the resin, and will affect the quality of the subsequent alkyd dispersion. In order to rriinimize this effect on the dispersing process, it is preferable to discard the membrane.
  • Polyol alkyd dispersions are prepared by pouring a pre-heated alkyd resin into water with mild stirring. A general procedure is discussed below.
  • the alkyd resin is heated to a melt state. Meanwhile, the calculated amount of de-ionized water is heated to the dispersing temperature in an emulsion reactor fitted with an anchor stirrer. (The amount of water is based on the desired NVM% of the final product).
  • a calculated amount of an amine for example triethylamine, TEA
  • TEA triethylamine
  • the amount of amine may be calculated as follows:
  • the emulsion reactor After complete addition of the resin, the emulsion reactor is maintained at about the dispersing temperature for some time in order to cure the dispersion. The reactor is then cooled to room temperature, the pH adjusted to neutral and the solids content adjusted to the required value. Characteristics of the resulting dispersion are shown below:
  • a pre-heated alkyd resin is added to a mixture of water and amine, at 55-70°C, with mild stiiring, in an amount sufficient to obtain a dispersion of about 35-45 weight percent solids, following by curing, and adjustment of the pH to a desired value to obtain a suitable viscosity.
  • Triemylamine, 2-amino-2- methyl- 1-propanol, dimethylethanol amine (DMEA) and ammonia solution can be used as neutralizing reagents, (AMP95 is proprietary 2-amine-2-methyl-l- propanol supplied by ANGUS Chemie GMBH).
  • the amount of neutralizer used during the dispersing process is in the range of 0.3- 1.0:1.0 (mole ratio), more preferably in the range of 0.6-0.95: 1.0.
  • the particle size, and particle size distribution (PSD), may be measured using light diffraction techniques known in the art.
  • the obtained alkyd dispersions have excellent storage stability and a solid content of about 39 ⁇ 1% by weight.
  • the paiticle size is generally smaller than 5 micron, preferably from 0.01 to 1.0 micron.
  • the small particle size enhances the stability of the dispersed particles and also leads to the production of films with high surface gloss.
  • the alkyd dispersions have good stability in particle size of over 6 months at room temperature. However, the pH value and viscosity of the dispersions decrease as the storage period is prolonged.
  • the polyol alkyd dispersions (PADs) of the present invention can be reacted with a di-isocyanate, such as isophorone diisocyanate (IPDI), to give stable, fine particle size, and low VOC content waterborne polyurethane dispersions (PUDs).
  • a di-isocyanate such as isophorone diisocyanate (IPDI)
  • IPDI isophorone diisocyanate
  • the range of equivalents of isophorone di-isocyanate (IPDI) to the solids of the alkyd dispersions ratio is between 10:90 and 30:70, more preferably 10:90, 15:85, and 20:80.
  • the recommended optimal temperature range for PUD preparation in the method of the present invention is between 25 and 30°C.
  • the polyurethane dispersions (PUDs) of the present invention have relatively good appearance stability at room temperature. After 6 months of storage, the PUDs exhibit good stability in particle size, with only a slight increase in pH value and a slight decrease in viscosity.
  • the polyol alkyd dispersions can be crosslinked by reaction with crosslinkers to give a type of low VOC binders in 2K coating systems.
  • the crosslinkers used in 2K systems may be aliphatic or aromatic polyisocyanates, aliphatic polyisocyanates, polyfunctional aziridines or other crosslinkers.
  • the method of making low VOC polyol alkyd dispersions of the present invention can also be applied to make low VOC polyester dispersions that can be applied to make a wide range of low VOC coating systems.
  • the polyol alkyd dispersions (PADs) of the present invention and their similar products can also be used in processes of making low VOC baking type coating systems and non-isocyanate (NCO group free) crosslinking type coating systems.
  • Films can be made from these dispersions by methods known in the art.
  • the dispersions could be formulated with other components to achieve desired properties of the coating systems and also to obtain desired film properties.
  • the dispersions can be applied by casting, spraying, brushing or rolling.
  • the PUD coatings can be used on wood, glass, metal, plastic and other surfaces.
  • the polyol alkyd dispersions performed very well when cross-linked with polyisocyanate.
  • the resultant film has excellent gloss, good DOI, excellent flow and levelling, and good solvent resistance properties.
  • Table 5 presents some properties of alkyd resins prepared according to this method. (The molecular weight of the polymers is measured using Gel Permeation Chromatography, GPC).
  • PADs Low VOC Waterborne Alkyd Dispersion
  • the calculated amount of alkyd dispersion (PAD:REA-1 162 or REA-1165) is charged into an emulsion reactor with a thermocouple, agitator and kept efficiently stirred.
  • Each of the alkyd dispersions (PADs) and IK alkyd polyurethane dispersions (PUDs) were examined for changes in viscosity, pH and particle size at room temperature for up to 6 months.
  • Appearance stability of the dispersions of the present invention at room temperature and high temperature (50°C) were also tested, using the following methods: Room temperature: a) Check appearance and test pH, viscosity and particle size of the dispersion every week for the first two months, and then every two weeks thereafter until 6 months. Record the time when t s deposition of the dispersions appeared and when it cannot be reversed through efficiently stirring, and record the pH, viscosity and particle size data. b) Adjust the pH value of the dispersion to the fixed value and record the change of the status, viscosity and particle size of the dispersion every week for the first two months and then every two weeks thereafter until 6 months.
  • High temperature (50°C) a) Check appearance and test pH, viscosity and particle size of the dispersion every day. Record the time when the deposition of the dispersions appeared and when it cannot be reversed and record the pH, viscosity and particle size data. b) Adjust the pH value of the dispersion to the fixed value and record the change of status, viscosity and particle size of the dispersion every day until it cannot be recovered.
  • Figure 1 and Figure 2 show viscosity change with respect to storage period at a fixed pH value, for examples of PADs, (alkyd dispersion (PADs): (REA- 1165-02), A008EA).
  • PADs alkyd dispersion
  • REA- 1165-02 alkyd dispersion
  • A008EA alkyd dispersion
  • Table 12 shows the deposition formation time.
  • the homogeneous status of alkyd dispersions (PADs) may be recovered through efficient stirring.
  • Table 12 The status change for alkyd dispersions ⁇ REA- 1165-02, A008EA & REA- 1167-01. A004EA ⁇
  • a IK PUD gloss clear coat was formulated based on alkyd polyurethane dispersion (PUD-II-1).
  • the coating composition comprised the following ingredients:
  • a IK PUD low gloss clear coat was formulated based on alkyd polyurethane dispersion (PUD-II-3).
  • the coating composition comprised the following ingredients:
  • the additives were added and mixed efficiently.
  • the sample was then drawn on the substrate - glass, paper, wood, tin and alumieriirm, at a wet thickness of about 3mm. All panels were cured at room temperature for 7 days before being subjected to physical testing in accordance with the ASTM methods.
  • a IK PUD low gloss clear coat was formulated based on alkyd polyurethane dispersion (PUD-II-2).
  • the coating composition comprises the following ingredients:
  • the additives were added and mixed efficiently.
  • the sample was then drawn on the substrate - glass, paper, wood, tin and aluminanium, at a wet thickness of about 3mm. All panels were cured at room temperature for 7 days.
  • the film is clear, hard and flexible, and has a gloss appearance between those of examples 1 and 2 above.
  • a IK PUD white paint was formulated based on alkyd polyurethane dispersion (PUD-II-1,3). The formula and procedure are shown below:
  • the additives were added and mixed efficiently.
  • the sample was then reduced to a proper application viscosity with deionized (DI) water and drawn on the substrate - glass, paper, wood, tin and aluminium. All panels were cured at room temperature for 7 days before being subjected to physical testing in accordance with the ASTM methods.
  • DI deionized
  • a IK PUD white paint was formulated based on alkyd polyurethane dispersion (PUD-II-1). The formula and procedure are set out below:
  • a IK PUD white paint was formulated based on alkyd polyurethane dispersion (PUD-II-3). The formula and procedure are set out below:
  • the additives were added and mixed efficiently.
  • the sample was then reduced to a proper application viscosity with DI water and drawn on the substrate - glass, pape , wood, tin and aluminium. All panels were cured at room temperature for 7 days before being subjected to physical testing in accordance with the ASTM methods.
  • a 2K high gloss varnish was formulated based on polyol alkyd dispersion.
  • the crosslinker for the system was RHODOCOAT WT-2102, an aliphatic polyisocyanate from CRHODIA.
  • the ratio of NCO/OH was 1.1/1.
  • the part 1 and part 2 were added and hand mixed.
  • the sample were then reduced to a proper application viscosity (62 Kus) with DI water and drawn on Q panels for testing. All panels were cured at room temperature for 7 days before being subjected to the physical testing in accordance with the ASTM methods. Coating Characteristics and Dry Film Properties.

Abstract

L'invention concerne un procédé de préparation de dispersions aqueuses de polymère, à teneur stable en composé organique faiblement volatile (VOC) et en particules fines. Ce procédé permet d'obtenir des dispersions aqueuses d'alkyde polyol (PAD) à VOC et des dispersions de polyuréthanne d'alkyde (PUD). Les dispersions de polyuréthanne d'alkyde (PUD) peuvent être obtenues à partir de dispersions d'alkyde polyol (PAD) qui sont polyéthylène glycol (PEG) modifié et sans solvant. Les dispersions de polyuréthanne d'alkyde (PUD), qui sont stables et qui ont un VOC, peuvent être réalisées par réaction d'un di-isocyanate (IPDI) avec la dispersion d'alkyde et appliquées dans un système de revêtement à un composant (1K). La dispersion aqueuse de polyol d'alkyde (PAD) peut également être appliquée dans un système de revêtement à deux composants (2K) par réaction avec un agent de réticulation poly-isocyanate ou d'autres agents de réticulation pour obtenir des systèmes de revêtement aqueux à composé organique faiblement volatile, VOC. Les revêtements comportant des dispersions polyuréthanne à teneur en composé organique faiblement volatile, VOC, peuvent être utilisés sur la surface d'objets en métal, en bois, en verre ou en matière plastique.
PCT/SG2001/000192 2000-10-10 2001-09-27 Dispersions de compose organique faiblement volatile d'alkyde polyol et dispersions de polyurethanne WO2002031021A1 (fr)

Priority Applications (1)

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WO2002079296A2 (fr) * 2001-03-30 2002-10-10 Ashland-Südchemie-Kernfest GmbH Emulsion de resine de polyester et peinture aqueuse a deux composants
WO2003080752A1 (fr) * 2002-03-25 2003-10-02 Bayer Materialscience Ag Systemes pur a deux composantes aqueux
US6734251B2 (en) 1998-09-25 2004-05-11 Eastman Chemical Company Stable aqueous polymer dispersions and a process for their preparation
US6849682B2 (en) 2002-09-30 2005-02-01 Omnova Solutions Inc. VOC containment coating, methods and articles
EP1869101A1 (fr) * 2005-04-14 2007-12-26 Perstorp Specialty Chemicals AB Polymere sechant a l'air
WO2008005483A2 (fr) * 2006-07-05 2008-01-10 Valspar Sourcing, Inc. Polymère de polyuréthane dispersable dans l'eau
US7462679B1 (en) 2002-11-27 2008-12-09 Han Xiong Xiao Process for preparing functionalized oils; adhesives and coatings and interpenetrating polymer networks prepared from the functionalized oils
US7776956B2 (en) 2006-08-04 2010-08-17 Ndsu Research Foundation Water dispersible epoxy urethane compounds and coating compositions
US9051413B2 (en) 2007-09-28 2015-06-09 Ndsu Research Foundation Modified glycidyl carbamate resins
US9676895B2 (en) 2006-08-04 2017-06-13 Ndsu Research Foundation Water dispersible epoxy urethane compounds and coating compositions
CN110713592A (zh) * 2018-07-11 2020-01-21 广东华润涂料有限公司 包含聚醚改性聚酯的高固低粘树脂组合物
CN111040141A (zh) * 2019-11-22 2020-04-21 山东齐鲁漆业有限公司 一种水性醇酸树脂及其应用
US10899944B2 (en) 2018-10-29 2021-01-26 Lake Region Manufacturing, Inc. Polyurethane urea-containing adipic acid dihydrazide where active hydrogens react with the epoxy group found on glycidol to form a diol
FR3109583A1 (fr) 2020-04-28 2021-10-29 Arkema France Dispersion aqueuse de poly(ester-uréthane) ou de poly(ester-urée-uréthane)
CN114656623A (zh) * 2022-03-07 2022-06-24 广东睿鹏材料科学有限公司 一种基于全生物质基酸-醇体系一步制备可回收聚酯的方法

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DD299467A7 (de) * 1972-10-03 1992-04-23 Lackkunstharz Und Lackfabrik Z Verfahren zur herstellung von alkydharzen
JPS5852370A (ja) * 1981-09-21 1983-03-28 Dainippon Toryo Co Ltd 水系塗料被覆組成物
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Cited By (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6734251B2 (en) 1998-09-25 2004-05-11 Eastman Chemical Company Stable aqueous polymer dispersions and a process for their preparation
WO2002079296A3 (fr) * 2001-03-30 2002-12-27 Ashland Suedchemie Kernfest Emulsion de resine de polyester et peinture aqueuse a deux composants
US7262255B2 (en) 2001-03-30 2007-08-28 Ashland-Sudchemie-Kernfest Gmbh Polyester resin emulsion and two-component aqueous paint
WO2002079296A2 (fr) * 2001-03-30 2002-10-10 Ashland-Südchemie-Kernfest GmbH Emulsion de resine de polyester et peinture aqueuse a deux composants
WO2003080752A1 (fr) * 2002-03-25 2003-10-02 Bayer Materialscience Ag Systemes pur a deux composantes aqueux
US7005470B2 (en) 2002-03-25 2006-02-28 Bayer Aktiengesellschaft Aqueous 2K PUR systems
US6849682B2 (en) 2002-09-30 2005-02-01 Omnova Solutions Inc. VOC containment coating, methods and articles
US7462679B1 (en) 2002-11-27 2008-12-09 Han Xiong Xiao Process for preparing functionalized oils; adhesives and coatings and interpenetrating polymer networks prepared from the functionalized oils
EP1869101A1 (fr) * 2005-04-14 2007-12-26 Perstorp Specialty Chemicals AB Polymere sechant a l'air
EP1869101A4 (fr) * 2005-04-14 2011-11-02 Perstorp Specialty Chem Ab Polymere sechant a l'air
US8466230B2 (en) 2006-07-05 2013-06-18 Valspar Sourcing, Inc. Water-dispersible polyurethane polymer
US9873760B2 (en) 2006-07-05 2018-01-23 Valspar Sourcing, Inc. Water-dispersible polyurethane polymer
WO2008005483A3 (fr) * 2006-07-05 2008-03-27 Valspar Sourcing Inc Polymère de polyuréthane dispersable dans l'eau
CN101484490B (zh) * 2006-07-05 2012-10-03 威士伯采购公司 水分散性聚氨酯聚合物
WO2008005483A2 (fr) * 2006-07-05 2008-01-10 Valspar Sourcing, Inc. Polymère de polyuréthane dispersable dans l'eau
US9045666B2 (en) 2006-07-05 2015-06-02 Valspar Sourcing, Inc. Water-dispersible polyurethane polymer
US9676895B2 (en) 2006-08-04 2017-06-13 Ndsu Research Foundation Water dispersible epoxy urethane compounds and coating compositions
US7776956B2 (en) 2006-08-04 2010-08-17 Ndsu Research Foundation Water dispersible epoxy urethane compounds and coating compositions
US9051413B2 (en) 2007-09-28 2015-06-09 Ndsu Research Foundation Modified glycidyl carbamate resins
US9593258B2 (en) 2007-09-28 2017-03-14 Ndsu Research Foundation Modified glycidyl carbamate resins
CN110713592A (zh) * 2018-07-11 2020-01-21 广东华润涂料有限公司 包含聚醚改性聚酯的高固低粘树脂组合物
US10899944B2 (en) 2018-10-29 2021-01-26 Lake Region Manufacturing, Inc. Polyurethane urea-containing adipic acid dihydrazide where active hydrogens react with the epoxy group found on glycidol to form a diol
US11421129B2 (en) 2018-10-29 2022-08-23 Lake Region Manufacturing, Inc. Polyurethane urea-containing adipic acid dihydrazide coating where active hydrogens react with the glycidol epoxy group to form a diol
CN111040141A (zh) * 2019-11-22 2020-04-21 山东齐鲁漆业有限公司 一种水性醇酸树脂及其应用
CN111040141B (zh) * 2019-11-22 2022-04-19 山东齐鲁漆业有限公司 一种水性醇酸树脂及其应用
FR3109583A1 (fr) 2020-04-28 2021-10-29 Arkema France Dispersion aqueuse de poly(ester-uréthane) ou de poly(ester-urée-uréthane)
WO2021219760A1 (fr) 2020-04-28 2021-11-04 Arkema France Dispersion aqueuse de poly(ester-uréthane) ou de poly(ester-urée-uréthane)
CN114656623A (zh) * 2022-03-07 2022-06-24 广东睿鹏材料科学有限公司 一种基于全生物质基酸-醇体系一步制备可回收聚酯的方法

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