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WO2017020513A1 - 一种羟基聚丙烯酸酯乳液及其制备方法与应用 - Google Patents

一种羟基聚丙烯酸酯乳液及其制备方法与应用 Download PDF

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Publication number
WO2017020513A1
WO2017020513A1 PCT/CN2015/099289 CN2015099289W WO2017020513A1 WO 2017020513 A1 WO2017020513 A1 WO 2017020513A1 CN 2015099289 W CN2015099289 W CN 2015099289W WO 2017020513 A1 WO2017020513 A1 WO 2017020513A1
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Prior art keywords
parts
emulsion
hydroxy
monomer
polyacrylate emulsion
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Ceased
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PCT/CN2015/099289
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English (en)
French (fr)
Inventor
瞿金清
段晓俊
朱延安
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CARPOLY CHEMICAL GROUP Co Ltd
South China University of Technology SCUT
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CARPOLY CHEMICAL GROUP Co Ltd
South China University of Technology SCUT
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Publication of WO2017020513A1 publication Critical patent/WO2017020513A1/zh
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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
    • 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
    • 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
    • C08F212/00—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 an aromatic carbocyclic ring
    • C08F212/02—Monomers containing only one unsaturated aliphatic radical
    • C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06—Hydrocarbons
    • C08F212/08—Styrene
    • 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
    • C08F220/00—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
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • 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
    • C08F220/00—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
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • 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
    • C08F220/00—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
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/56—Acrylamide; Methacrylamide
    • 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
    • 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
    • C08F220/00—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
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • 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
    • C08F220/00—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
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/283—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing one or more carboxylic moiety in the chain, e.g. acetoacetoxyethyl(meth)acrylate

Definitions

  • the invention relates to an aqueous two-component polyurethane coating, in particular to a hydroxy polyacrylate emulsion and a preparation method and application thereof.
  • Waterborne wood coatings include one-component and two-component waterborne wood coatings. Among them, the paint properties of single-component waterborne wood coatings include poor water resistance, chemical resistance and hardness, and the gap with oily coatings is large, which severely limits the promotion and application of waterborne wood coatings.
  • the mechanical properties, water resistance and chemical resistance of the two-component waterborne wood coating are comparable to those of the solvent-based wood coating, which can overcome the shortcomings of the one-component waterborne wood coating.
  • China has issued a decree on the consumption tax on solvent-based coatings, making two-component waterborne wood coatings the first choice for high-grade waterborne wood coatings.
  • Two-component waterborne polyurethane coatings have been widely studied and applied for their excellent film properties. They are composed of an aqueous polymer polyol and an aqueous polyisocyanate curing agent, which are packaged separately and mixed in proportion when used.
  • the aqueous polymer polyol includes an aqueous polyacrylate polyol, an aqueous polyurethane polyol, an aqueous polyester polyol and a polyether polyol, and a mixed polyol.
  • water-based polyacrylate polyol has excellent color retention, gloss retention and weather resistance, low cost, and easy to adjust molecular weight, glass transition temperature (Tg) and hydroxyl content, and is currently water-based in two-component waterborne polyurethane coatings.
  • the first choice for polymer polyols Two types of polyacrylate polyols, emulsion type and dispersion type, can be obtained by different polymerization processes.
  • the aqueous polyacrylate dispersion has a high hydroxyl content, and the formulated coating film has excellent water resistance and chemical resistance. A large amount of organic solvent is used in the production process, and the solid content of the product is low, generally 30% to 40%. And the paint film has a slow dry speed and high cost.
  • emulsion polyacrylate polyols also known as hydroxy polyacrylate emulsions
  • emulsion polyacrylate polyols have a simple production process with a solid content of up to 50%, low cost, and fast dry speed. Therefore, the two-component polyurethane coating formulated with the hydroxy polyacrylate emulsion occupies a large market space for the aqueous two-component coating.
  • the paint film prepared by the existing hydroxy polyacrylate emulsion and the aqueous polyisocyanate curing agent still has problems of poor appearance, poor chemical resistance, and low hardness.
  • the main performance of the paint film is poor in transparency and low gloss of the paint film.
  • the main reason is that the hydroxypolyacrylate emulsion has poor emulsifying and dispersing ability to the curing agent and poor compatibility with the curing agent.
  • the compatibility with the curing agent is poor, resulting in poor appearance of the paint film.
  • the conventional high hydroxyl content polyacrylate emulsion has poor polymerization stability and is unstable in industrial production.
  • excessive use of an emulsifier or an emulsifier in an emulsion polymerization may reduce the gloss and chemical resistance of the paint film.
  • improving the hardness and chemical resistance of aqueous two-component polyurethane paint film by increasing the glass transition temperature and hydroxyl content of the hydroxy polyacrylate emulsion, and also requiring more organic small molecule film formation in the paint process.
  • Agents and curing agents the curing agent often contains a certain amount of co-solvent
  • increasing the volatile organic compound (VOC) content in the coating will also lead to an increase in coating costs. Therefore, the conventional method is difficult to improve the poor appearance of the hydroxy polyacrylate emulsion type two-component paint film, poor chemical resistance, and low hardness.
  • Chinese invention patent application CN103059210 modified hydroxy polyacrylate emulsion by adding 2%-5% fluorine-containing acrylic acid monomer, which slightly improved the water resistance and chemical resistance of the two-component paint film due to fluorine-containing acrylic acid
  • the hydrophobic oleophobic property of the ester monomer makes the conversion rate of the polymerization reaction not high, and it is easy to cause a large amount of residual fluorine-containing monomer, and also causes problems such as poor interlayer adhesion of the paint film, and the fluorine-containing acrylate monomer.
  • the high price causes the polymer emulsion cost to rise sharply.
  • the object of the present invention is to overcome the problems existing in the prior art and to provide an easy adjustment of the hydroxyl content of the hydroxy polyacrylate emulsion, so that a plurality of hydroxy resins of different structures, different molecular weights and different glass transition temperatures form a multiple crossover with the curing agent.
  • Linked hydroxy polyacrylate emulsion and preparation method thereof are provided.
  • Another object of the present invention is to provide the use of the hydroxy polyacrylate emulsion in an aqueous two-component polyurethane coating, so that the coating hardness of the two-component polyurethane coating reaches H, and the gloss (60 0 ) reaches 83%, which is excellent. Water/ethanol resistance and good dry heat resistance.
  • the invention aims at the deficiencies of the prior art, and adopts a process of adding a high hydroxyl content oligomer in the process of hydroxypolyacrylate emulsion polymerization to prepare a hydroxy polyacrylate emulsion having a suitable hydroxyl content, which not only realizes a hydroxy polyacrylate emulsion.
  • the hydroxyl group content is easily adjusted, and a plurality of hydroxy resins having different structures, different molecular weights and different Tg and the curing agent form a multiple crosslinked structure.
  • the appearance of the paint film is greatly improved, the hardness of the paint film is improved, and the problem of poor chemical resistance is solved.
  • the hydroxyl group content of the hydroxy polyacrylate emulsion of the invention can be adjusted wider, and the high hydroxyl content hydroxy polyacrylate emulsion is easy to realize large-scale industrialization. produce.
  • the present invention employs a special acrylic monomer such as isobornyl (meth)acrylate to improve the compatibility of the hydroxypolyacrylate emulsion with the curing agent, thereby improving the appearance of the paint film.
  • the preparation method of the hydroxy polyacrylate emulsion comprises the following steps:
  • the hydroxy acrylate monomer is one or more of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate;
  • the hydroxy acrylate monomer is one or more of hydroxyethyl acrylate, hydroxypropyl acrylate, methacrylic acid hydroxyethyl ester and hydroxypropyl methacrylate.
  • the acrylic monomer is one or more of acrylic acid and methacrylic acid.
  • the acrylate functional monomer is one or more of acrylamide, isobornyl methacrylate, glycidyl methacrylate, and acetoacetoxyethyl methacrylate.
  • the hydroxy oligomer is BASF's aldehyde resin A81, Changsha Zhengtai Industrial Co., Ltd. aldehyde ketone resin KR-80F, KR-120, KR120B, KR-120W, Wenkel's aldehyde-ketone resin UK-100, One or more of YHKR-1210 and YHKR-1218 of UK-300, UK-500, Baling Petrochemical aldehyde and ketone resin.
  • the emulsifier is an isomeric alcohol polyoxyethylene ether (EH-9), Adeco's ADEKA REASOAP series of nonionic (ER-30) and anionic (SR-10) emulsifiers, 2-acrylamido-2 - one or more of sodium methylpropane sulfonate (COPS-2), fatty alcohol polyoxyethylene ether ammonium sulfate (KL-525), sodium dodecyl sulfate (SDS).
  • EH-9 isomeric alcohol polyoxyethylene ether
  • ER-30 Adeco's ADEKA REASOAP series of nonionic
  • SR-10 anionic emulsifiers
  • COPS-2 2-acrylamido-2 - one or more of sodium methylpropane sulfonate
  • KL-525 fatty alcohol polyoxyethylene ether ammonium sulfate
  • SDS sodium dodecyl sulfate
  • the initiator is one or more of potassium persulfate and ammonium persulfate.
  • a hydroxy polyacrylate emulsion prepared by the above preparation method had a particle size of ⁇ 300 nm, a solid content of 45-52%, a hydroxyl value of 40-150 mgKOH/g, and a Tg of 10-80 °C.
  • the hydroxy polyacrylate emulsion of the invention is mainly used for preparing an aqueous two-component polyurethane coating.
  • Adding the hydroxy polyacrylate emulsion to the stirred tank adding 1-10 parts of film-forming auxiliary, 0.05-1.5 parts of antifoaming agent, 0.05-0.2 part thickener, 0.05-0.3 part by weight, in parts by mass And 0.05-0.1 parts neutralizer, dispersed for 10-30 minutes, filtered Discharge, a coating prepared from a hydroxy polyacrylate emulsion;
  • the film forming aid is one or more of propylene glycol methyl ether, propylene glycol butyl ether, dipropylene glycol methyl ether, and dipropylene glycol butyl ether.
  • the antifoaming agent is TEGO's polyether siloxane copolymer defoamer TEGO-800, TEGO-805, TEGO-815, TEGO-825 and BYK modified polysiloxane copolymer solution BYK-019 One or more of BYK-020.
  • the thickener is DOW's nonionic polyurethane associative thickener RM-8W, hydrophobically modified alkali swellable associative thickener TT-935, alkali swollen non-associative thickener ASE-60 and One or more of TEGO's nonionic associative thickeners TEGO ViscoPlus 3000, TEGO Visco Plus 3030, TEGO Visco Plus 3060.
  • the wetting agent is one or more of TEGO's polyether siloxane copolymer TEGO-245, nonionic organic surfactant TEGO-500 and BYK's polyether modified polysiloxane solution BYK-346.
  • TEGO's polyether siloxane copolymer TEGO-245 nonionic organic surfactant TEGO-500
  • BYK's polyether modified polysiloxane solution BYK-346 BYK's polyether modified polysiloxane solution BYK-346.
  • the neutralizing agent is one or more of triethylamine and dimethylethanolamine.
  • the polyisocyanate curing agent includes one or more of a sulfonate, a carboxylate, and an alkoxy hydrophilically modified hexamethylene diisocyanate (HDI).
  • a sulfonate a carboxylate
  • HDI alkoxy hydrophilically modified hexamethylene diisocyanate
  • the obtained aqueous two-component polyurethane coating film has the advantages of high gloss, high transparency, excellent water and chemical resistance, high crosslink density, high hardness, scratch resistance and abrasion resistance. Can be applied to high-grade wood coatings, automotive coatings, metal anti-corrosion coatings and other industrial protective coatings.
  • the present invention has the following advantages:
  • the chemical resistance of the aqueous two-component polyurethane coating film is determined by the cross-linking density of the coating film, which is controlled by the OH group content of the hydroxy polyacrylate emulsion and the molar ratio of NCO to OH; the appearance and decorative properties of the coating film are determined by the inter-component phase.
  • the compatibility determines that the compatibility is related to the structure, particle structure and morphology of the aqueous hydroxy resin, the emulsifying ability of the curing agent, and the emulsifier content.
  • the hydroxy polyacrylate emulsion of the present invention has a polyacrylate polyol as a main hydroxyl component and a hydroxy oligomer as an auxiliary hydroxyl component.
  • a proper amount of hydroxy oligomer is dissolved by a monomer mixture, pre-emulsified with an appropriate amount of an emulsifier, and some or all of the pre-emulsion is used to prepare seeds, and a hydroxy polyacrylate can be obtained by a pre-emulsified seed emulsion polymerization process.
  • Emulsion. The invention avoids the problem that the polymerization stability caused by the excessive addition of the hydroxy acrylate monomer is drastically reduced. Therefore, by adjusting the kind and the amount of the hydroxy oligomer, the hydroxyl value of the emulsion can be greatly increased and the hydroxyl structure can be adjusted, thereby improving the double The mechanical and chemical properties of the component coating.
  • the introduced hydroxy oligomer itself has the characteristics of high gloss and high transparency, and can further improve the appearance and decorative properties of the coating film.
  • the coating film of the aqueous two-component polyurethane coating prepared by the hydroxy polyacrylate emulsion of the invention and the aqueous polyisocyanate curing agent has high hardness, high gloss and excellent chemical resistance, and solves the problem of the traditional hydroxy polyacrylate emulsion due to the hydroxyl value. Overcoming the problem of poor mechanical and chemical properties of the paint film, overcoming the problem
  • the paint film prepared with the aqueous polyisocyanate curing agent has low gloss and poor transparency.
  • the basic performance test includes: the hydroxy polyacrylate emulsion is tested according to GB/T11175-2002 "Test Method for Synthetic Resin Emulsion” to test the appearance, pH, solid content and viscosity of the emulsion.
  • the performance of the paint film is tested according to GB/T23999-2009 "Water-based wood coating for interior decoration and decoration", and the gloss, hardness, water resistance, dry heat resistance and alcohol resistance are tested.
  • the average particle size of the emulsion was measured using a nanoparticle size analyzer (ZS Nano S).
  • Preparation process Mixing 1-9 to prepare a monomer mixture, pre-emulsification of 10% monomer mixture with 0.05 parts of emulsifier (0.025 parts of KL-525 and 0.025 parts of COPS-2) and 2.75 parts of water as seed pre-emulsified liquid. Add the remaining emulsifier, sodium bicarbonate, 0.1 part initiator (potassium persulfate), 25 parts deionized water to the reaction kettle, raise the temperature to 78 ° C, stir for 15 minutes, and spray the seed pre-emulsion at a constant rate within 20 minutes. After the emulsion was stabilized for half an hour, a seed emulsion was obtained. Guarantee The temperature of the reaction system was 80 °C.
  • the remaining mixed monomer was mixed with the remaining monomers, and then added dropwise to the seed emulsion while dropwise adding an aqueous solution of 0.15 parts of an initiator (potassium persulfate) with 15 parts of water, and dropping was carried out at about 3.5 hours.
  • an initiator potassium persulfate
  • the temperature was raised to 85 ° C and kept for 1.5 h.
  • the temperature was lowered to 55 ° C, 5.5 parts of water and the neutralizing agent triethylamine were mixed, neutralized, and incubated for 0.25 h, and the temperature was discharged to obtain a milky white semipermeable hydroxy polyacrylate emulsion.
  • the molar ratio of the NCO group in the curing agent to the OH group in the hydroxy polyacrylate emulsion is 1.8:1.
  • the preparation method is as follows: the emulsion is added to the stirred tank at a rotation speed of 700 rpm, 10 parts of water is premixed with the film forming aid, and then added to the emulsion, and the raw materials of No. 5-9 are sequentially added, dispersed for 20 minutes, and the material is filtered. .
  • an aqueous polyisocyanate curing agent was added to the coating prepared by the above hydroxypolyacrylate emulsion, and stirred for 6 minutes to obtain an aqueous two-component polyurethane coating.
  • a hydroxy oligomer A81 is added to a hydroxy polyacrylate emulsion having a lower hydroxyl content, and the emulsified seed emulsion is prepared by dissolving the monomer and pre-emulsification, and preparing a hydroxy polyacrylate emulsion on the basis of the seed emulsion.
  • the method ensures that the hydroxy oligomer is stably dispersed in the hydroxy polyacrylate emulsion, mainly in the latex particles, and the acrylate monomer is polymerized in the hydroxy oligomer to form an interpenetrating polymer of the polyacrylate and the hydroxy oligomer.
  • the network ensures thorough mixing between the hydroxy oligomer and the acrylic polymer.
  • a small amount of acrylic polymer may be grafted onto the hydroxy oligomer, and the graft polymer provides a polymer-compatible bridge.
  • the addition of the hydroxy oligomer increases the hydroxyl content of the hydroxy polyacrylate emulsion, ensures the polymerization stability of the hydroxy polyacrylate emulsion, and makes the two-component coating film hardness H, gloss (60 0 ) 83%, excellent
  • the water/ethanol resistance and the good dry heat resistance, the hydroxy polyacrylate emulsion prepared by the method overcomes the shortcomings of the conventional hydroxy polyacrylate emulsion to prepare the two-component polyurethane coating.
  • Preparation method mixing 1-8 to prepare a monomer mixture, taking 15% monomer mixture dissolved in 0.1 part emulsifier (0.05 parts of SR-10 and ER-30 each) and 3 parts of water to pre-emulsifie it as seed pre-emulsified liquid. Add the remaining emulsifier, sodium bicarbonate, 0.1 part initiator (ammonium persulfate), 30 parts deionized water to the reaction kettle, raise the temperature to 80 ° C, stir for 30 minutes, The seed pre-emulsion was continuously sprayed in 30 minutes, and the emulsion was stabilized for half an hour to obtain a seed emulsion. The temperature of the reaction system was maintained at 80 °C.
  • the remaining monomer mixture was added dropwise to the seed emulsion while an aqueous solution of 0.2 part of an initiator (ammonium persulfate) dissolved in 20 parts of water was added dropwise, and the mixture was dropped over 4 hours.
  • an initiator ammonium persulfate
  • the temperature was raised to 82 ° C and kept for 2 h.
  • the temperature was lowered to 45 ° C, 10 parts of water and N,N-dimethylethanolamine were mixed, neutralized, and incubated for 0.25 h, and the temperature was lowered to obtain a milky white semipermeable hydroxy polyacrylate emulsion.
  • the molar ratio of the NCO group in the curing agent to the OH group in the hydroxy polyacrylate emulsion is 1.5:1.
  • the preparation method is as follows: the emulsion is added to the stirred tank at a rotation speed of 700 rpm, 10 parts of water is premixed with the film forming aid, and then added to the emulsion, and the raw materials of No. 5-9 are sequentially added, dispersed for 10 minutes, and the material is filtered. .
  • an aqueous polyisocyanate curing agent was added to the coating prepared by the above hydroxy polyacrylate emulsion, and stirred for 5 minutes to obtain an aqueous two-component polyurethane coating.
  • Two-component coating performance The paint film obtained by the aqueous two-component polyurethane coating was cured and dried at room temperature for 7 days, and its properties are as follows:
  • a monomer mixture was prepared by mixing 1-8, and 12% of the monomer mixture was pre-emulsified as a seed pre-emulsion with 0.1 part of an emulsifier (0.05 parts each of two emulsifiers) and 3 parts of water.
  • the remaining emulsifier, sodium hydrogencarbonate, 0.1 part initiator (KPS), 20 parts of deionized water were added to the reaction kettle, the temperature was raised to 82 ° C, stirred for 15 minutes, and the seed pre-emulsion was continuously sprayed in 15 minutes.
  • the emulsion was stabilized for half an hour to give a seed emulsion.
  • the temperature of the reaction system was maintained at 82 °C.
  • the remaining monomer mixture was mixed with the remaining monomers, and then added dropwise to the seed emulsion, while an aqueous solution of 0.2 part of initiator (KPS) dissolved in 10 parts of water was added dropwise, and the mixture was dropped over 3 hours.
  • KPS initiator
  • the temperature was raised to 85 ° C and kept for 1 h.
  • the temperature was lowered to 60 ° C, 5.9 parts of water and triethylamine were mixed, neutralized, and kept for 30 minutes, and the temperature was discharged to obtain a milky white semipermeable hydroxy polyacrylate emulsion.
  • the molar ratio of the NCO group in the curing agent to the OH group in the hydroxy polyacrylate emulsion is 1.2:1.
  • the preparation method is as follows: the emulsion is added to the stirred tank at a rotation speed of 700 rpm, 10 parts of water is premixed with the film forming aid, and then added to the emulsion, and the raw materials of No. 5-9 are sequentially added, dispersed for 10 minutes, and the material is filtered. .
  • an aqueous polyisocyanate curing agent was added to the coating prepared by the above hydroxy polyacrylate emulsion, and stirred for 8 minutes to obtain an aqueous two-component polyurethane coating.
  • a monomer mixture was prepared by uniformly mixing 1-8, and 14 parts of the monomer mixture was pre-emulsified as a seed pre-emulsion with 0.1 part of an emulsifier (0.05 parts each of two emulsifiers) and 3.35 parts of water.
  • the remaining emulsifier, sodium bicarbonate, 0.1 part initiator, 25 parts deionized water was added to the reaction kettle, the temperature was raised to 75 ° C, and stirred for 15 minutes.
  • the seed pre-emulsion was continuously dropped in 20 minutes, and the emulsion was stabilized for half. In hours, a seed emulsion is obtained.
  • the temperature of the reaction system was maintained at 80 °C.
  • the remaining monomer mixture was added dropwise to the seed emulsion while dropwise adding an aqueous solution of 0.2 part of the initiator with 15 parts of water, and dropping was carried out at about 3.5 hours. After the addition was completed, the temperature was raised to 85 ° C and kept for 1.5 h. The temperature was lowered to 55 ° C, 6 parts of water and N,N-dimethylethanolamine were mixed, neutralized, and incubated for 0.25 h, and the mixture was cooled to obtain a milky white semipermeable hydroxy polyacrylate emulsion.
  • the molar ratio of the NCO group in the curing agent to the OH group in the hydroxy polyacrylate emulsion is 1.8:1.
  • the preparation method is as follows: the emulsion is added to the stirred tank at a rotation speed of 700 rpm, 10 parts of water is premixed with the film forming aid, and then added to the emulsion, and the raw materials of No. 5-9 are sequentially added, dispersed for 25 minutes, and the material is filtered. .
  • an aqueous polyisocyanate curing agent was added to the coating prepared by the above hydroxypolyacrylate emulsion, and stirred for 7 minutes to obtain an aqueous two-component polyurethane coating.
  • a monomer mixture was prepared by uniformly mixing 1-7, and 13 parts of the monomer mixture was pre-emulsified as a seed pre-emulsion with 0.1 part of an emulsifier (0.05 parts each of two emulsifiers) and 4 parts of water. The remaining emulsifier, sodium bicarbonate, 0.1 part initiator, 25 parts deionized water was added to the reaction kettle, the temperature was raised to 75 ° C, and stirred for 15 minutes. The seed pre-emulsion was continuously dropped in 20 minutes, and the emulsion was stabilized for half. In hours, a seed emulsion is obtained. The temperature of the reaction system was maintained at 80 °C.
  • the remaining monomer mixture was added dropwise to the seed emulsion while dropwise adding an aqueous solution of 0.2 part of the initiator with 15 parts of water, and dropping was carried out at about 3.5 hours. After the addition was completed, the temperature was raised to 85 ° C and kept for 1.5 h. The temperature was lowered to 55 ° C, 5.9 parts of water and triethylamine were mixed, neutralized, and incubated for 0.25 h, and the temperature was discharged to obtain a milky white semipermeable hydroxy polyacrylate emulsion.
  • the molar ratio of the NCO group in the curing agent to the OH group in the hydroxy polyacrylate emulsion is 1.5:1.
  • the preparation method is as follows: the emulsion is added to the stirring kettle at a rotation speed of 700 rpm, 10 parts of water is premixed with the film forming aid, and then added to the emulsion, and the raw materials of No. 5-9 are sequentially added, dispersed for 30 minutes, and the material is filtered. .
  • an aqueous polyisocyanate curing agent was added to the coating prepared by the above hydroxypolyacrylate emulsion, and stirred for 6 minutes to obtain an aqueous two-component polyurethane coating.
  • a monomer mixture was prepared by uniformly mixing 1-7, and a 10% monomer mixture was pre-emulsified as a seed pre-emulsion with 0.1 part of an emulsifier (0.05 parts each of two emulsifiers) and 4.5 parts of water.
  • the remaining emulsifier, sodium bicarbonate, 0.1 part initiator, 25 parts deionized water was added to the reaction kettle, the temperature was raised to 75 ° C, and stirred for 15 minutes.
  • the seed pre-emulsion was continuously dropped in 20 minutes, and the emulsion was stabilized for half. In hours, a seed emulsion is obtained.
  • the temperature of the reaction system was maintained at 80 °C.
  • the remaining monomer mixture mixture was added dropwise to the seed emulsion while dropwise adding an aqueous solution of 0.2 part of the initiator with 15 parts of water, and dropping was carried out for about 3.5 hours. After the addition was completed, the temperature was raised to 85 ° C and kept for 1.5 h. The temperature was lowered to 55 ° C, and 5.55 parts of water and N,N-dimethylethanolamine were mixed, neutralized, and incubated for 0.25 h, and the mixture was cooled to obtain a milky white semipermeable hydroxy polyacrylate emulsion.
  • the molar ratio of the NCO group in the curing agent to the OH group in the hydroxy polyacrylate emulsion is 1.0:1.
  • the preparation method is as follows: the emulsion is added to the stirred tank at a rotation speed of 700 rpm, 10 parts of water is premixed with the film forming aid, and then added to the emulsion, and the raw materials of No. 5-9 are sequentially added, dispersed for 20 minutes, and the material is filtered. .
  • an aqueous polyisocyanate curing agent was added to the coating prepared by the above hydroxy polyacrylate emulsion, and stirred for 5 minutes to obtain an aqueous two-component polyurethane coating.

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Abstract

本发明公开了一种羟基聚丙烯酸酯乳液及其制备方法与应用，该制备方法是称取丙烯酸酯单体和/或甲基丙烯酸酯单体、羟基丙烯酸酯单体、丙烯酸单体，丙烯酸酯功能单体，羟基低聚物，混合均匀制备单体混合物，取10-15％的单体混合物用乳化剂乳化制备种子预乳化液备用；将乳化剂、碳酸氢钠和去离子水加入反应釜中，开搅拌并升高反应体系的温度，加入引发剂，稳定，滴加完种子预乳化液，稳定，将剩余单体混合物和剩余的引发剂在滴完，升温、熟化、降温、中和，保温后降温出料得羟基聚丙烯酸酯乳液；该羟基聚丙烯酸酯乳液与水性多异氰酸酯固化剂配制的水性双组份聚氨酯涂料的涂膜具有高硬度、高光泽和优异的耐化学品性能。

Description

一种羟基聚丙烯酸酯乳液及其制备方法与应用 技术领域
本发明涉及水性双组份聚氨酯涂料，具体涉及一种羟基聚丙烯酸酯乳液及其制备方法与应用。
背景技术
现有木器涂料多为溶剂型涂料，含有超过50％以上的有机溶剂，这些溶剂在施工过程中会挥发到大气中污染环境，还损害人体健康，并且有机溶剂本身会带来如燃烧、爆炸等安全隐患。因此，木器涂料的水性化是国际涂料发展的趋势。水性木器涂料包括单组份和双组份水性木器涂料。其中单组份水性木器涂料的漆膜性能包括耐水性、耐化学品性及硬度等方面不好，与油性涂料差距较大，严重限制了水性木器涂料的推广应用。双组份水性木器涂料的机械性能、耐水性和耐化学品性与溶剂型木器涂料相当，能很好的克服了单组份水性木器涂料的缺点。2015年1月我国已发布了关于对溶剂型涂料征收消费税的法令，使得双组份水性木器涂料将成为高档水性木器涂料的首选。
双组份水性聚氨酯涂料具有优异的涂膜性能得到广泛的研究和应用，它由水性聚合物多元醇和水性多异氰酸酯固化剂组成，分开包装，使用时按比例混合。其中水性聚合物多元醇包括水性聚丙烯酸酯多元醇、水性聚氨酯多元醇、水性聚酯多元醇和聚醚多元醇以及混合多元醇。其中水性聚丙烯酸酯多元醇具有优异的保色、保光和耐候性，价格便宜，且分子量、玻璃化转变温度(Tg)和羟基含量易于调节等优点，是目前双组份水性聚氨酯涂料中水性聚合物多元醇的首选。采用不同聚合工艺可制得乳液型和分散体型两类聚丙烯酸酯多元醇。水性聚丙烯酸酯分散体的羟基含量较高，配制的涂膜具有优异的耐水性及耐化学品性，存在生产过程中使用大量有机溶剂，产品固体含量较低，一般为30％-40％，且漆膜干速慢，成本高等缺点。相比之下，乳液型聚丙烯酸酯多元醇(也称羟基聚丙烯酸酯乳液)生产工艺简单，固含可高达50％以上，成本低，且干速快。因此，羟基聚丙烯酸酯乳液配制的双组份聚氨酯涂料占有较大的水性双组份涂料的市场空间。
现有羟基聚丙烯酸酯乳液与水性多异氰酸酯固化剂配制的漆膜仍然存在外观差、耐化学品性差、硬度低等问题。漆膜外观差的主要表现有漆膜透明性差，光泽低等，其主要原因是羟基聚丙烯酸酯乳液对固化剂的乳化分散能力差及与固化剂的相容性不好。为保证漆 膜高硬度而设计的聚丙烯酸酯的Tg较高时，与固化剂的相容性不好导致漆膜外观差。漆膜的交联密度越高，其耐化学品性越好，高羟基含量的聚丙烯酸酯可得到高交联密度的漆膜。但常规的高羟基含量的聚丙烯酸酯乳液的聚合稳定性较差，工业化生产不稳定。另外，乳液聚合中的过量使用乳化剂或乳化剂搭配不当会降低漆膜的光泽和耐化学品性。目前，通过提高羟基聚丙烯酸酯乳液的玻璃化温度和羟基含量来提高水性双组份聚氨酯漆膜硬度和耐化学品性能，还会导致在配漆过程中需要更多的有机小分子成膜助剂和固化剂(固化剂中常含有一定量的助溶剂)，增加涂料中挥发性有机化合物(VOC)含量，也会导致涂料成本上升。因此，常规的方法较难改善羟基聚丙烯酸酯乳液型双组份漆膜的外观差、耐化学品性差、硬度低等问题。
中国发明专利申请CN103059210通过添加2％-5％的含氟丙烯酸单体来改性羟基聚丙烯酸酯乳液，虽会稍微改善了双组份漆膜的耐水性和耐化学品性，由于含氟丙烯酸酯单体的疏水疏油的特性使其聚合反应的转化率不高，易造成有含氟单体的大量残留，还造成漆膜的层间附着力差等问题，而且含氟丙烯酸酯单体价格昂贵造成聚合物乳液成本急剧上升等。
发明内容
本发明的目的在于克服现有技术存在的问题，提供一种实现羟基聚丙烯酸酯乳液羟基含量的易调节，使不同结构、不同分子量、不同玻璃化温度的多种羟基树脂与固化剂形成多重交联结构的羟基聚丙烯酸酯乳液及其制备方法。
本发明另一目的在于提供所述羟基聚丙烯酸酯乳液在水性双组份聚氨酯涂料中的应用，使得双组份聚氨酯涂料的涂膜硬度达到H，光泽(600)达到83％，具有优异的耐水/乙醇性能，还具有良好的耐干热性。
本发明针对现有技术的不足，采用在羟基聚丙烯酸酯乳液聚合过程中外添加高羟基含量的低聚物的工艺，制备羟基含量适当的羟基聚丙烯酸酯乳液，该工艺不仅实现羟基聚丙烯酸酯乳液羟基含量的易调节，而且使不同结构、不同分子量、不同Tg的多种羟基树脂与固化剂形成多重交联结构。与不添加羟基低聚物的相同羟基含量的常规乳液相比，极大的改善了漆膜外观，提高了漆膜硬度，解决耐化学品差等难题。同时，在保证乳液聚合稳定性及高单体转化率的前提下，本发明羟基聚丙烯酸酯乳液的羟基含量的可调范围更广，使高羟基含量的羟基聚丙烯酸酯乳液易实现大规模工业化生产。另外，本发明采用特殊丙烯酸单体，如(甲基)丙烯酸异冰片酯，改善羟基聚丙烯酸酯乳液与固化剂的相容性，从而改善漆膜外观。
实现本发明的目的所采用的技术方案：
羟基聚丙烯酸酯乳液的制备方法，包含如下步骤：
以质量份数计，称取丙烯酸酯单体和/或甲基丙烯酸酯单体30～45份、羟基丙烯酸酯单体5～15份、丙烯酸单体1.0～3.0份，丙烯酸酯功能单体0.5～3.0份，羟基低聚物0.5～3份，混合均匀制备单体混合物，取10-15％的单体混合物用1-2份乳化剂乳化制备种子预乳化液备用；
将1～2份乳化剂、0.05-0.2份碳酸氢钠和20～30份去离子水加入反应釜中，开搅拌并升高反应体系的温度，当温度达到78-83℃后加入10-15％的引发剂，稳定5-15分钟后，在15-30分钟内滴加完种子预乳化液，稳定15-30分钟，将剩余单体混合物和用10～20份水溶解剩余的引发剂在3-4小时内滴完，升温至80-85℃熟化1-2小时，降温至40-60℃，用3～10份水稀释0.3～0.6份中和剂中和，保温15-30分钟后降温出料得羟基聚丙烯酸酯乳液；
所述羟基丙烯酸酯单体为丙烯酸羟乙酯、丙烯酸羟丙酯、甲基丙烯酸羟乙酯和甲基丙烯酸羟丙酯的一种或多种；
所述羟基丙烯酸酯单体为丙烯酸羟乙酯、丙烯酸羟丙酯、甲基丙烯羟乙酯和甲基丙烯酸羟丙酯的一种或多种。
所述丙烯酸单体为丙烯酸、甲基丙烯酸的一种或多种。
所述丙烯酸酯功能单体为丙烯酰胺、甲基丙烯酸异冰片酯、甲基丙烯酸缩水甘油酯、甲基丙烯酸乙酰乙酰氧基乙酯的一种或多种。
所述羟基低聚物为巴斯夫公司的醛树脂A81，长沙倡泰实业有限公司的醛酮树脂KR-80F、KR-120、KR120B、KR-120W，翁开尔公司醛酮树脂的UK-100、UK-300、UK-500、巴陵石化醛酮树脂的YHKR-1210、YHKR-1218的一种或多种。
所述乳化剂为异构醇聚氧乙烯醚(EH-9)、艾迪科公司的ADEKA REASOAP系列非离子(ER-30)和阴离子(SR-10)乳化剂、2-丙烯酰胺基-2-甲基丙磺酸钠(COPS-2)、脂肪醇聚氧乙烯醚硫酸铵(KL-525)、十二烷基硫酸钠(SDS)中的一种或多种。
所述引发剂为过硫酸钾、过硫酸铵的一种或多种。
一种羟基聚丙烯酸酯乳液，由上述制备方法制得。所得的羟基聚丙烯酸酯乳液粒径＜300nm，固体含量45-52％，羟值为40-150mgKOH/g，Tg为10-80℃。
本发明羟基聚丙烯酸酯乳液主要应用于制备水性双组份聚氨酯涂料。
将羟基聚丙烯酸酯乳液加入到搅拌釜中，以质量份数计，加入1-10份成膜助剂、0.05-1.5份消泡剂、0.05-0.2份增稠剂、0.05-0.3份润湿剂和0.05-0.1份中和剂，分散10-30分钟，过滤 出料，羟基聚丙烯酸酯乳液配制的涂料；
所述成膜助剂为丙二醇甲醚、丙二醇丁醚、二丙二醇甲醚、二丙二醇丁醚中一种或多种。
所述消泡剂为TEGO公司的聚醚硅氧烷共聚物消泡剂TEGO-800、TEGO-805、TEGO-815、TEGO-825和BYK公司的改性聚硅氧烷共聚体溶液BYK-019、BYK-020的一种或多种。
所述增稠剂为DOW公司的非离子聚氨酯缔合型增稠剂RM-8W、疏水改性碱溶胀缔合型增稠剂TT-935、碱溶胀非缔合型增稠剂ASE-60和TEGO公司的非离子缔合型增稠剂TEGO ViscoPlus 3000、TEGO ViscoPlus 3030、TEGO ViscoPlus 3060的一种或多种。
所述润湿剂为TEGO公司的聚醚硅氧烷共聚物TEGO-245、非离子有机表面活性剂TEGO-500和BYK公司的聚醚改性聚硅氧烷溶液BYK-346的一种或多种。
所诉中和剂为三乙胺、二甲基乙醇胺的一种或多种。
所述的多异氰酸酯固化剂包括磺酸盐、羧酸盐及烷氧基亲水改性的六亚甲基二二异氰酸酯(HDI)一种或多种。
所得水性双组份聚氨酯涂膜具有高光泽、高透明度、耐水和耐化学品性能优异、高交联密度以及高硬度、抗刮伤且耐磨等优点。可应用于高档木器涂料、汽车涂料、金属防腐涂料及其它工业防护涂料。
相对于现有技术，本发明具有如下优点：
水性双组份聚氨酯涂料涂膜的耐化学品性能由涂膜交联密度决定，由羟基聚丙烯酸酯乳液的OH基含量和NCO与OH摩尔比调控；涂膜外观和装饰性能由组分间相容性决定，相容性与水性羟基树脂的结构、粒子结构与形态、对固化剂的乳化能力及乳化剂含量有关。本发明羟基聚丙烯酸酯乳液以聚丙烯酸酯多元醇为主要羟基组份，羟基低聚物为辅助羟基组份。首先用单体混合物溶解适量的羟基低聚物，用适量的乳化剂对其进行预乳化，取部分或者全部预乳化液制备种子，采用预乳化种子乳液聚合的工艺即可制得羟基聚丙烯酸酯乳液。本发明避开了羟基丙烯酸酯单体添加量过大造成的聚合稳定性急剧降低的问题，因此通过调整羟基低聚物的种类和添加量可大幅提高乳液羟值和调整羟基结构，从而改善双组份涂膜的机械和化学性能。同时，引入的羟基低聚物本身具有高光泽、高透明度等特点，可进一步改善涂膜的外观和装饰性能。本发明的羟基聚丙烯酸酯乳液与水性多异氰酸酯固化剂配制的水性双组份聚氨酯涂料的涂膜具有高硬度、高光泽和优异的耐化学品性能，解决了传统羟基聚丙烯酸酯乳液由于羟值低而造成的漆膜机械和化学性能差的难题，克服了 与水性多异氰酸酯固化剂配套制得的漆膜光泽低、透明度差等问题。
具体实施例
下面结合具体实施例对本发明作进一步描述，但本发明的实施方式不限于此，对于未特别注明的工艺参数，可参照常规技术进行。
下面实施例有关检测方法如下：
基本性能测试包括：羟基聚丙烯酸酯乳液参照GB/T11175-2002《合成树脂乳液试验方法》进行测试，测试乳液的外观、pH、固体含量、粘度。漆膜性能参照GB/T23999-2009《室内装饰装修用水性木器涂料》进行测试，测试光泽、硬度、耐水性、耐干热、耐醇性。乳液的平均粒径采用纳米粒度分析仪(ZS Nano S)测定。
实施例1
(1)羟基聚丙烯酸酯乳液的制备：羟基聚丙烯酸酯乳液的(羟值＝65mgKOH/g)配方如表1a：
表1a
Figure PCTCN2015099289-appb-000001
制备工艺：将1-9混合制备单体混合物，取10％单体混合物用0.05份乳化剂(其中0.025份KL-525和0.025份COPS-2)和2.75份水对其预乳化作为种子预乳化液。将剩余乳化剂、碳酸氢钠、0.1份引发剂(过硫酸钾)、25份去离子水加入反应釜中，升温至78℃，搅拌15分钟，将种子预乳化液在20分钟内匀速滴完，待乳液稳定半小时，得到种子乳液。保 持反应体系温度为80℃。将剩余混合单体与其余单体混合，然后向种子乳液中滴加，同时滴加用15份水溶解0.15份引发剂(过硫酸钾)的水溶液，在3.5h左右滴完。滴加完后升温至85℃，保温1.5h。降温至55℃，将5.5份水和中和剂三乙胺混合后加入中和，保温0.25h，降温出料得到乳白半透的羟基聚丙烯酸酯乳液。
(2)羟基聚丙烯酸酯乳液的性能：制备出的乳液平均粒径128nm，粘度：535cps，pH＝7.0，固体含量：48.3％。
(3)高性能水性双组份聚氨酯涂料的配制：配方如表1b：
表1b
Figure PCTCN2015099289-appb-000002
其中固化剂中NCO基团与羟基聚丙烯酸酯乳液中OH基团的摩尔比1.8:1。
制备方法如下：将乳液加入到搅拌釜中，转速为700转/min，将10份水与成膜助剂预混后加入乳液中，依次加入5-9号原料，分散20分钟，过滤出料。施工时，将水性多异氰酸酯固化剂加入到上述羟基聚丙烯酸酯乳液配制的涂料中，搅拌6分钟，得到水性双组份聚氨酯涂料。
(4)涂膜性能：将水性双组份聚氨酯涂料制得漆膜在常温下固化干燥7天，其性能如下所示：
表1c 高性能水性双组份聚氨酯涂料的综合性能
Figure PCTCN2015099289-appb-000003
Figure PCTCN2015099289-appb-000004
本实施例在较低羟基含量的羟基聚丙烯酸酯乳液中添加羟基低聚物A81，通过单体溶解，并预乳化，制备乳化种子乳液，在种子乳液的基础上制备羟基聚丙烯酸酯乳液。该法保证羟基低聚物稳定分散到羟基聚丙烯酸酯乳液中，主要存在于乳胶粒子内部，丙烯酸酯单体在羟基低聚物中聚合，形成聚丙烯酸酯与羟基低聚物的互穿聚合物网络，一方面保证羟基低聚物与丙烯酸聚合物间充分混合，另一方面，可能存在少量丙烯酸聚合物接枝到羟基低聚物上，接枝聚合物提供聚合物相容的桥梁。羟基低聚物的添加，提高了羟基聚丙烯酸酯乳液的羟基含量，保证羟基聚丙烯酸酯乳液的聚合稳定性，使得双组份涂膜硬度达到H，光泽(600)为83％，具有优异的耐水/乙醇性能，还具有良好的耐干热性，该方法制备的羟基聚丙烯酸酯乳液克服传统羟基聚丙烯酸酯乳液制备双组份聚氨酯涂料的缺点。
实施例2
(1)羟基聚丙烯酸酯乳液的制备：羟基聚丙烯酸酯乳液(羟值＝65mgKOH/g)配方如表2a：
表2a
Figure PCTCN2015099289-appb-000005
制备方法：将1-8混合制备单体混合物，取15％单体混合物溶用0.1份乳化剂(是SR-10和ER-30各0.05份)和3份水对其预乳化作为种子预乳化液。将剩余乳化剂、碳酸氢钠、0.1份引发剂(过硫酸铵)、30份去离子水加入反应釜中，升温至80℃，搅拌30分钟，将 种子预乳化液在30分钟内匀速滴完，待乳液稳定半小时，得到种子乳液。保持反应体系温度为80℃。将剩余单体混合物向种子乳液中滴加，同时滴加用20份水溶解0.2份引发剂(过硫酸铵)的水溶液，在4h左右滴完。滴加完后升温至82℃，保温2h。降温至45℃，将10份水和N,N-二甲基乙醇胺混合后加入中和，保温0.25h，降温出料得到乳白半透的羟基聚丙烯酸酯乳液。
(2)羟基聚丙烯酸酯乳液的性能：制备出的乳液平均粒径135nm，粘度：573cps，pH＝7.0，固体含量：48.5％。
(3)高性能水性双组份聚氨酯涂料的配制：配方如表2b：
表2b
Figure PCTCN2015099289-appb-000006
其中固化剂中NCO基团与羟基聚丙烯酸酯乳液中OH基团的摩尔比1.5:1。
制备方法如下：将乳液加入到搅拌釜中，转速为700转/min，将10份水与成膜助剂预混后加入乳液中，依次加入5-9号原料，分散10分钟，过滤出料。施工时，将水性多异氰酸酯固化剂加入到上述羟基聚丙烯酸酯乳液配制的涂料中，搅拌5分钟，得到水性双组份聚氨酯涂料。
(4)双组份涂料性能：将水性双组份聚氨酯涂料制得漆膜在常温下固化干燥7天，其性能如下所示：
表2c 高性能水性双组份聚氨酯涂料的综合性能
Figure PCTCN2015099289-appb-000007
Figure PCTCN2015099289-appb-000008
实施例3
(1)羟基聚丙烯酸酯乳液的制备：羟基聚丙烯酸酯乳液(羟值＝70mgKOH/g)配方如表3a：
表3a
Figure PCTCN2015099289-appb-000009
制备工艺：将1-8混合制备单体混合物，取12％单体混合物用0.1份乳化剂(两种乳化剂各0.05份)和3份水对其预乳化作为种子预乳化液。将剩余乳化剂、碳酸氢钠、0.1份引发剂(KPS)、20份去离子水加入反应釜中，升温至82℃，搅拌15分钟，将种子预乳化液在15分钟内匀速滴完，待乳液稳定半小时，得到种子乳液。保持反应体系温度为82℃。将剩余单体混合物与其余单体混合，然后向种子乳液中滴加，同时滴加用10份水溶解0.2份引发剂(KPS)的水溶液，在3h左右滴完。滴加完后升温至85℃，保温1h。降温至60℃，将5.9份水和三乙胺混合后加入中和，保温30min，降温出料得到乳白半透的羟基聚丙烯酸酯乳液。
(2)羟基聚丙烯酸酯乳液的性能：制备出的乳液平均粒径123nm，粘度：617cps，pH＝7.0，固体含量：48.0％。
(3)高性能水性双组份聚氨酯涂料的制备：配方如表3b：
表3b
Figure PCTCN2015099289-appb-000010
其中固化剂中NCO基团与羟基聚丙烯酸酯乳液中OH基团的摩尔比1.2:1。
制备方法如下：将乳液加入到搅拌釜中，转速为700转/min，将10份水与成膜助剂预混后加入乳液中，依次加入5-9号原料，分散10分钟，过滤出料。施工时，将水性多异氰酸酯固化剂加入到上述羟基聚丙烯酸酯乳液配制的涂料中，搅拌8分钟，得到水性双组份聚氨酯涂料。
(4)将水性双组份聚氨酯涂料的漆膜性能：制得漆膜在常温下固化干燥7天，其性能如下所示：
表3c 高性能水性双组份聚氨酯涂料的综合性能
Figure PCTCN2015099289-appb-000011
实施例4
(1)羟基聚丙烯酸酯乳液的制备：羟基聚丙烯酸酯乳液(羟值＝79mgKOH/g)配方如表4a：
表4a
Figure PCTCN2015099289-appb-000012
Figure PCTCN2015099289-appb-000013
制备工艺：将1-8混合均匀制备单体混合物，取14份单体混合物用0.1份乳化剂(两种乳化剂各0.05份)和3.35份水对其预乳化作为种子预乳化液。将剩余乳化剂、碳酸氢钠、0.1份引发剂、25份去离子水加入反应釜中，升温至75℃，搅拌15分钟，将种子预乳化液在20分钟内匀速滴完，待乳液稳定半小时，得到种子乳液。保持反应体系温度为80℃。将剩余单体混合物向种子乳液中滴加，同时滴加用15份水溶解0.2份引发剂的水溶液，在3.5h左右滴完。滴加完后升温至85℃，保温1.5h。降温至55℃，将6份水和N,N—二甲基乙醇胺混合后加入中和，保温0.25h，降温出料得到乳白半透的羟基聚丙烯酸酯乳液。
(2)羟基聚丙烯酸酯乳液的性能：制备出的乳液平均粒径119nm，粘度：820cps，pH＝7.0，固体含量：47.7％。
(3)高性能水性双组份聚氨酯涂料的配制：配方如表4b：
表4b
Figure PCTCN2015099289-appb-000014
Figure PCTCN2015099289-appb-000015
其中固化剂中NCO基团与羟基聚丙烯酸酯乳液中OH基团的摩尔比1.8:1。
制备方法如下：将乳液加入到搅拌釜中，转速为700转/min，将10份水与成膜助剂预混后加入乳液中，依次加入5-9号原料，分散25分钟，过滤出料。施工时，将水性多异氰酸酯固化剂加入到上述羟基聚丙烯酸酯乳液配制的涂料中，搅拌7分钟，得到水性双组份聚氨酯涂料。
(4)水性双组份聚氨酯涂料的涂膜性能：将水性双组份聚氨酯涂料制得漆膜在常温下固化干燥7天，其性能如下所示：
表4c 高性能水性双组份聚氨酯涂料的综合性能
Figure PCTCN2015099289-appb-000016
实施例5
(1)羟基聚丙烯酸酯乳液的制备：羟基聚丙烯酸酯乳液(羟值＝95mgKOH/g)配方如表5a：
表5a
Figure PCTCN2015099289-appb-000017
Figure PCTCN2015099289-appb-000018
制备工艺：将1-7混合均匀制备单体混合物，取13份单体混合物用0.1份乳化剂(两种乳化剂各0.05份)和4份水对其预乳化作为种子预乳化液。将剩余乳化剂、碳酸氢钠、0.1份引发剂、25份去离子水加入反应釜中，升温至75℃，搅拌15分钟，将种子预乳化液在20分钟内匀速滴完，待乳液稳定半小时，得到种子乳液。保持反应体系温度为80℃。将剩余单体混合物向种子乳液中滴加，同时滴加用15份水溶解0.2份引发剂的水溶液，在3.5h左右滴完。滴加完后升温至85℃，保温1.5h。降温至55℃，将5.9份水和三乙胺混合后加入中和，保温0.25h，降温出料得到乳白半透的羟基聚丙烯酸酯乳液。
(2)羟基聚丙烯酸酯乳液的性能：制备出的乳液平均粒径132nm，粘度：673cps，pH＝7.0，固体含量：48.2％。
(3)高性能水性双组份聚氨酯涂料的制备：配方如表5b：
表5b
Figure PCTCN2015099289-appb-000019
其中固化剂中NCO基团与羟基聚丙烯酸酯乳液中OH基团的摩尔比1.5:1。
制备方法如下：将乳液加入到搅拌釜中，转速为700转/min，将10份水与成膜助剂预混后加入乳液中，依次加入5-9号原料，分散30分钟，过滤出料。施工时，将水性多异氰酸酯固化剂加入到上述羟基聚丙烯酸酯乳液配制的涂料中，搅拌6分钟，得到水性双组份聚氨酯涂料。
(4)水性双组份聚氨酯涂料的涂膜性能：将水性双组份聚氨酯涂料制得漆膜在常温下固化干燥7天，其性能如下所示：
表5c 高性能水性双组份聚氨酯涂料的综合性能
Figure PCTCN2015099289-appb-000020
实施例6
(1)羟基聚丙烯酸酯乳液的制备：羟基聚丙烯酸酯乳液(羟值＝110mgKOH/g)配方如表6a：
表6a
Figure PCTCN2015099289-appb-000021
制备工艺：将1-7混合均匀制备单体混合物，取10％单体混合物用0.1份乳化剂(两种乳化剂各0.05份)和4.5份水对其预乳化作为种子预乳化液。将剩余乳化剂、碳酸氢钠、0.1份引发剂、25份去离子水加入反应釜中，升温至75℃，搅拌15分钟，将种子预乳化液在20分钟内匀速滴完，待乳液稳定半小时，得到种子乳液。保持反应体系温度为80℃。将剩余单体混合混合物向种子乳液中滴加，同时滴加用15份水溶解0.2份引发剂的水溶液，在3.5h左右滴完。滴加完后升温至85℃，保温1.5h。降温至55℃，将5.55份水和N,N—二甲基乙醇胺混合后加入中和，保温0.25h，降温出料得到乳白半透的羟基聚丙烯酸酯乳液。
(2)羟基聚丙烯酸酯乳液的性能：制备出的乳液平均粒径125nm，粘度：725cps，pH ＝7.0，固体含量：47.6％。
(3)高性能水性双组份聚氨酯涂料的制备：配方如表6b：
表6b
Figure PCTCN2015099289-appb-000022
其中固化剂中NCO基团与羟基聚丙烯酸酯乳液中OH基团的摩尔比1.0:1。
制备方法如下：将乳液加入到搅拌釜中，转速为700转/min，将10份水与成膜助剂预混后加入乳液中，依次加入5-9号原料，分散20分钟，过滤出料。施工时，将水性多异氰酸酯固化剂加入到上述羟基聚丙烯酸酯乳液配制的涂料中，搅拌5分钟，得到水性双组份聚氨酯涂料。
(4)水性双组份聚氨酯涂料的涂膜性能：将水性双组份聚氨酯涂料制得漆膜在常温下固化干燥7天，其性能如下所示：
表6c 高性能水性双组份聚氨酯涂料的综合性能
Figure PCTCN2015099289-appb-000023
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。

Claims (8)

  1. 一种羟基聚丙烯酸酯的制备方法，其特征在于包含如下步骤，
    1)以质量份数计，称取丙烯酸酯单体和/或甲基丙烯酸酯单体30～45份、羟基丙烯酸酯单体5～15份、丙烯酸单体1.0～3.0份，丙烯酸酯功能单体0.5～3.0份，羟基低聚物0.5～3份，混合均匀制备单体混合物，取10-15％的单体混合物用1-2份乳化剂乳化制备种子预乳化液备用；
    2)以质量份数计，将1～2份乳化剂、0.05-0.2份碳酸氢钠和20～30份去离子水加入反应釜中，开搅拌并升高反应体系的温度，当温度达到78-83℃后加入10-15％的引发剂，稳定5-15分钟后，在15-30分钟内滴加完种子预乳化液，稳定15-30分钟，将剩余单体混合物和用10～20份水溶解剩余的引发剂在3-4小时内滴完，升温至80-85℃熟化1-2小时，降温至40-60℃，用3～10份水稀释0.3～0.6份中和剂中和，保温15-30分钟后降温出料得羟基聚丙烯酸酯乳液；
    所述丙烯酸酯单体和/或甲基丙烯酸酯单体为甲基丙烯酸甲酯、丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸丁酯、丙烯酸丁酯和苯乙烯的一种或多种；
    所述羟基丙烯酸酯单体为丙烯酸羟乙酯、丙烯酸羟丙酯、甲基丙烯酸羟乙酯和甲基丙烯酸羟丙酯的一种或多种；
    所述丙烯酸单体为丙烯酸和/或甲基丙烯酸；
    所述丙烯酸酯功能单体为丙烯酰胺、甲基丙烯酸异冰片酯、甲基丙烯酸缩水甘油酯、甲基丙烯酸乙酰乙酰氧基乙酯的一种或多种；
    所述羟基低聚物为醛树脂A81、醛酮树脂KR-80F、KR-120、KR120B、KR-120W、醛酮树脂UK-100、UK-300、UK-500、醛酮树脂的YHKR-1210和YHKR-1218的一种或多种；
    所述乳化剂为异构醇聚氧乙烯醚、可聚合乳化剂ADEKA REASOAP系列非离子ER-30和阴离子SR-10乳化剂、2-丙烯酰胺基-2-甲基丙磺酸钠、脂肪醇聚氧乙烯醚硫酸铵和十二烷基硫酸钠的一种或多种；
    所述引发剂为过硫酸钾、过硫酸铵的一种或多种。
  2. 根据权利要求1所述的羟基聚丙烯酸酯乳液的制备方法，其特征在于，所述中和剂为三乙胺、氨水和二甲基乙醇胺中的一种或多种。
  3. 根据权利要求1所述的羟基聚丙烯酸酯乳液的制备方法，其特征在于，所述羟基聚 丙烯酸酯乳液的羟值为40-150mgKOH/g(以固体树脂计)。
  4. 根据权利要求1所述的羟基聚丙烯酸酯乳液的制备方法，其特征在于，所述羟基聚丙烯酸酯乳液的玻璃转化温度为10-80℃。
  5. 一种羟基聚丙烯酸酯乳液，其所述特征在于，其由权利要求1-4任一项所述制备方法制得。
  6. 权利要求5所述羟基聚丙烯酸酯乳液在水性双组份聚氨酯涂料中的应用。
  7. 根据6所述羟基聚丙烯酸酯乳液在水性双组份聚氨酯涂料中的应用，其特征在于包括如下步骤：
    1)将羟基聚丙烯酸酯乳液加入到搅拌釜中，以质量份数计，加入1-10份成膜助剂、0.05-1.5份消泡剂、0.05-0.2份增稠剂、0.05-0.3份润湿剂和0.05-0.1份中和剂，分散10-30分钟，过滤出料，羟基聚丙烯酸酯乳液配制的涂料；
    2)施工时，将水性多异氰酸酯固化剂按照NCO/OH摩尔比为1.0-1.8加入到所述羟基聚丙烯酸酯乳液配制的涂料中，搅拌5-8分钟，得到水性双组份聚氨酯涂料。
  8. 根据7所述羟基聚丙烯酸酯乳液在水性双组份聚氨酯涂料中的应用，其特征在于，所述成膜助剂为丙二醇甲醚、丙二醇丁醚、二丙二醇甲醚和二丙二醇丁醚的一种或多种；
    所述消泡剂为聚醚硅氧烷共聚物消泡剂TEGO-800、TEGO-805、TEGO-815、TEGO-825、改性聚硅氧烷共聚体溶液BYK-019和BYK-020的一种或多种；
    所述增稠剂为非离子聚氨酯缔合型增稠剂RM-8W、疏水改性碱溶胀缔合型增稠剂TT-935、碱溶胀非缔合型增稠剂ASE-60、非离子缔合型增稠剂TEGO ViscoPlus 3000、TEGO ViscoPlus 3030和TEGO ViscoPlus 3060的一种或多种；
    所述润湿剂为聚醚硅氧烷共聚物TEGO-245、非离子有机表面活性剂TEGO-500和聚醚改性聚硅氧烷溶液BYK-346的一种或多种；
    所述中和剂为三乙胺、氨水和二甲基乙醇胺中的一种或多种；
    所述的多异氰酸酯固化剂包括磺酸盐、羧酸盐及烷氧基亲水改性的六亚甲基二异氰酸酯中的一种或多种。
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