WO2017020513A1 - Émulsion à base d'hydroxyl polyacrylate et procédé de préparation et application associés - Google Patents

Émulsion à base d'hydroxyl polyacrylate et procédé de préparation et application associés 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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parts
emulsion
hydroxy
monomer
polyacrylate emulsion
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PCT/CN2015/099289
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English (en)
Chinese (zh)
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瞿金清
段晓俊
朱延安
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华南理工大学
嘉宝莉化工集团股份有限公司
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Publication of WO2017020513A1 publication Critical patent/WO2017020513A1/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
    • 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

La présente invention concerne une émulsion à base d'hydroxyl polyacrylate, ainsi qu'un procédé de préparation et une application associés. Le procédé de préparation comprend : la pesée d'un monomère d'acrylate et/ou d'un monomère de méthacrylate, d'un monomère d'hydroxyl acrylate, d'un monomère d'acide acrylique, d'un monomère à fonction acrylate et d'un oligomère d'hydroxyle, le mélange uniforme pour préparer un mélange monomère, et le prélèvement de 10 à 15 % du mélange monomère pour émulsifier avec un émulsifiant, de manière à préparer une pré-émulsion d'ensemencement; l'ajout de l'émulsifiant, de bicarbonate de sodium et d'eau désionisée dans un réacteur, l'agitation, l'augmentation de la température du système réactionnel, l'ajout d'un initiateur, la stabilisation, l'ajout de toute la pré-émulsion d'ensemencement goutte-à-goutte, la stabilisation, l'ajout du reste de mélange monomère et d'initiateur goutte-à-goutte, l'augmentation de la température, le vieillissement, l'abaissement de la température, la neutralisation, le maintien de la température, puis le refroidissement pour obtenir l'émulsion d'hydroxyl polyacrylate. Un film de revêtement d'un revêtement de polyuréthane aqueux à deux composants préparé à partir de l'émulsion d'hydroxyl polyacrylate et d'un agent de durcissement polyisocyanate aqueux a une dureté, un éclat et une durabilité supérieurs aux produits chimiques.
PCT/CN2015/099289 2015-07-31 2015-12-28 Émulsion à base d'hydroxyl polyacrylate et procédé de préparation et application associés WO2017020513A1 (fr)

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