CN105061665B - A kind of hydroxy polyacrylate lotion and preparation method and application - Google Patents

A kind of hydroxy polyacrylate lotion and preparation method and application Download PDF

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CN105061665B
CN105061665B CN201510468212.7A CN201510468212A CN105061665B CN 105061665 B CN105061665 B CN 105061665B CN 201510468212 A CN201510468212 A CN 201510468212A CN 105061665 B CN105061665 B CN 105061665B
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hydroxy
lotion
parts
hydroxy polyacrylate
acrylate
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CN201510468212.7A
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CN105061665A (en
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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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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00Processes of polymerisation
    • C08F2/12Polymerisation in non-solvents
    • C08F2/16Aqueous medium
    • C08F2/22Emulsion polymerisation
    • C08F2/24Emulsion polymerisation with the aid of emulsifying agents
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F212/00Copolymers 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
    • C08F212/02Monomers containing only one unsaturated aliphatic radical
    • C08F212/04Monomers containing only one unsaturated aliphatic radical containing one ring
    • C08F212/06Hydrocarbons
    • C08F212/08Styrene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers 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
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04Acids; Metal salts or ammonium salts thereof
    • C08F220/06Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers 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
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10Esters
    • C08F220/12Esters of monohydric alcohols or phenols
    • C08F220/14Methyl esters, e.g. methyl (meth)acrylate
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers 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
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10Esters
    • C08F220/12Esters of monohydric alcohols or phenols
    • C08F220/16Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers 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
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10Esters
    • C08F220/26Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00Copolymers 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
    • C08F220/02Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52Amides or imides
    • C08F220/54Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/56Acrylamide; Methacrylamide
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING 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
    • C09D175/00Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04Polyurethanes

Abstract

The invention discloses a kind of hydroxy polyacrylate lotions and preparation method and application, the preparation method is to weigh acrylate monomer and/or methacrylate monomers, hydroxy-acrylate monomer, acrylic monomers, acrylate functional monomer, hydroxyl oligomer, it is uniformly mixed and prepares monomer mixture, 10 15% monomer mixture is taken with emulsifier to prepare seed pre-emulsion spare;Emulsifier, sodium bicarbonate and deionized water are added in reaction kettle, it opens stirring and increases the temperature of reaction system, add in initiator, stablize, seed pre-emulsion is dripped, stablizes, residual monomer mixture and remaining initiator is being dripped off, heating, cooling, neutralizes curing, and cooling discharge obtains hydroxy polyacrylate lotion after heat preservation;The film for the aqueous double-component polyurethane coating that the hydroxy polyacrylate lotion is prepared with aqueous polyisocyanate curing agent has high rigidity, high glaze and excellent chemical resistance.

Description

A kind of hydroxy polyacrylate lotion and preparation method and application

Technical field

The present invention relates to aqueous double-component polyurethane coating, and in particular to a kind of hydroxy polyacrylate lotion and its preparation Method and application.

Background technology

Existing woodwork coating is mostly solvent based coating, and containing the organic solvent for having more than more than 50%, these solvents are being constructed It can evaporate into air in the process and pollute environment, also damage health, and organic solvent can be brought in itself as burnt, exploding Etc. security risks.Therefore, the Water-borne modification of woodwork coating is the trend of international coatings development.Water-borne wood coating include one-component and Double-component aqueous woodwork coating.The paint film property of wherein single-component water-based woodwork coating includes water resistance, chemical-resistant and hard Degree etc. is bad, larger with oil paint gap, seriously limits the popularization and application of water-borne wood coating.Double-component aqueous wood The mechanical performance of device coating, water resistance and chemical-resistant are suitable with solvent wood coatings, can overcome one-component well The shortcomings that water-borne wood coating.In January, 2015, China was issued about the decree that the consumption tax is imposed to solvent based coating so that Double-component aqueous woodwork coating will be as the first choice of high-grade water-borne wood coating.

There is double-component waterborne polyurethane coating excellent film performance widely to be studied and applied, it is by aqueous poly- Object polyalcohol and aqueous polyisocyanate curing agent composition are closed, is separately packed, when use mixes in proportion.Wherein waterborne polymeric Polyalcohol include water polyacrylic acid polyalcohol, aqueous polyurethane polyalcohol, waterborne polyester polyalcohol and polyether polyol with And polyols blend.Wherein water polyacrylic acid polyalcohol has excellent guarantor's color, protects light and weatherability, cheap, and The advantages that molecular weight, glass transition temperature (Tg) and hydroxy radical content can easily be accommodated is current double-component waterborne polyurethane coating The first choice of middle waterborne polymeric polyalcohol.Two class polyacrylate of emulsion-type and dispersion type can be made using different polymerization techniques Polyalcohol.The hydroxy radical content of water polyacrylic acid dispersion is higher, and the film of preparation has excellent water resistance and chemically-resistant Moral character is deposited in process of production using a large amount of organic solvents, and product solid content is relatively low, generally 30%-40%, and paint film is done It is fast slow, it is of high cost the shortcomings of.In contrast, emulsion-type polyacrylate polyol (also referred to as hydroxy polyacrylate lotion) production It is simple for process, Gu containing up to more than 50%, it is at low cost, and drying speed.Therefore, double groups of hydroxy polyacrylate lotion preparation Part polyurethane coating occupies the market space of larger aqueous double-component coating.

The paint film that existing hydroxy polyacrylate lotion and aqueous polyisocyanate curing agent are prepared still have poor appearance, The problems such as chemical-resistant is poor, hardness is low.The main of paint film appearance difference is presented with the paint film transparency is poor, and gloss is low etc., mainly The reason is that hydroxy polyacrylate lotion is bad to the emulsion dispersion energy force difference of curing agent and with the compatibility of curing agent.To ensure Paint film high rigidity and during the Tg higher of polyacrylate designed, and the compatibility of curing agent is bad causes paint film appearance poor.Paint The crosslink density of film is higher, and chemical-resistant is better, and the polyacrylate of high hydroxyl content can obtain the paint of high crosslink density Film.But the polymerization stability of the polyacrylate dispersion of conventional high hydroxyl content is poor, and industrialized production is unstable.In addition, Emulsifier or emulsifier mismatch is excessively used can reduce the gloss and chemical-resistant of paint film in emulsion polymerization.At present, It is hard that aqueous double-component polyurethane paint film is improved by improving glass transition temperature and the hydroxy radical content of hydroxy polyacrylate lotion Degree and chemical resistance, also result in needed during with paint more organic molecule coalescents and curing agent (Gu Often contain a certain amount of cosolvent in agent), increase volatile organic compounds (VOC) content in coating, also result in coating Cost increase.Therefore, the more difficult poor appearance for improving hydroxy polyacrylate emulsion-type two-component paint film of conventional method, chemically-resistant The problems such as moral character is poor, hardness is low.

Chinese invention patent application CN103059210 is by adding the fluoro-acrylate monomer of 2%-5% come modified hydroxyl Polyacrylate dispersion, though the water resistance and chemical-resistant of two-component paint film can be slightly improved, due to fluorinated acrylate The characteristic of the hydrophobic oleophobic of monomer makes the conversion ratio of its polymerisation not high, easily causes a large amount of residuals of fluorochemical monomer, also makes Into paint film ply adhesion it is poor the problems such as, and fluorinated acrylate monomer is expensive causes polymer emulsion cost drastically Rise etc..

Invention content

The object of the present invention is to overcome the problems of the prior art, provides a kind of realization hydroxy polyacrylate lotion The easy adjusting of hydroxy radical content makes different structure, different molecular weight, a variety of hydroxy resins of different glass temperature and curing dosage form Hydroxy polyacrylate lotion into multiple cross-linked structure and preparation method thereof.

Another object of the present invention is to provide the hydroxy polyacrylate lotion in aqueous double-component polyurethane coating Application so that the hardness of film of double-component polyurethane coating reaches H, and gloss (60 °) reaches 83%, have it is excellent it is water-fast/ Alcohol performance, also with good dry heat resistance.

The present invention adds high hydroxyl in view of the deficiencies of the prior art, using in hydroxy polyacrylate emulsion polymerization process China and foreign countries The technique of the oligomer of base content, prepares the appropriate hydroxy polyacrylate lotion of hydroxy radical content, which not only realizes hydroxyl The easy adjusting of polyacrylate dispersion hydroxy radical content, and make a variety of hydroxy resins of different structure, different molecular weight, difference Tg Multiple cross-linked structure is formed with curing agent.Compared with the conventional emulsions of identical hydroxy radical content for not adding hydroxyl oligomer, greatly Improve paint film appearance, improve hardness of paint film, solve the problems such as chemicals-resistant difference.Meanwhile ensureing emulsion polymerization stabilization Under the premise of property and high monomer conversion ratio, the adjustable extent of the hydroxy radical content of hydroxy polyacrylate lotion of the present invention is wider, makes The hydroxy polyacrylate lotion of high hydroxyl content easily realizes large-scale industrial production.In addition, the present invention uses special propylene Acid monomers, such as (methyl) isobornyl acrylate, improve hydroxy polyacrylate lotion and the compatibility of curing agent, so as to improve Paint film appearance.

Achieve the object of the present invention used technical solution:

The preparation method of hydroxy polyacrylate lotion, comprises the following steps:

In terms of mass fraction, acrylate monomer and/or 30~45 parts of methacrylate monomers, hydroxy acrylic acid are weighed 5~15 parts of ester monomer, 1.0~3.0 parts of acrylic monomers, 0.5~3.0 part of acrylate functional monomer, hydroxyl oligomer 0.5~ It 3 parts, is uniformly mixed and prepares monomer mixture, the monomer mixture of 10-15% is taken to prepare the pre- breast of seed with 1-2 parts of emulsifiers It is spare to change liquid;

1~2 part of emulsifier, 0.05-0.2 parts of sodium bicarbonates and 20~30 parts of deionized waters are added in reaction kettle, opens and stirs The temperature of reaction system is mixed and increased, the initiator of 10-15% is added in after temperature reaches 78-83 DEG C, after stablizing 5-15 minutes, It dripped seed pre-emulsion in 15-30 minutes, stablizes 15-30 minutes, by residual monomer mixture and with 10~20 parts of water It dissolves remaining initiator to drip off in 3-4 hours, is warming up to 80-85 DEG C and cures 1-2 hours, be cooled to 40-60 DEG C, with 3~ 10 parts of water dilute 0.3~0.6 part of neutralizer and neutralize, and cooling discharge obtains hydroxy polyacrylate lotion after heat preservation 15-30 minutes;

The hydroxy-acrylate monomer is hydroxy-ethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and first Base hydroxypropyl acrylate it is one or more;

The hydroxy-acrylate monomer is hydroxy-ethyl acrylate, hydroxypropyl acrylate, metering system hydroxyl ethyl ester and methyl Hydroxypropyl acrylate it is one or more.

The acrylic monomers for acrylic acid, methacrylic acid it is one or more.

The acrylate functional monomer is acrylamide, isobornyl methacrylate, methyl propenoic acid glycidyl Ester, acetoacetoxyethyl methacrylate it is one or more.

Urea formaldehyde A81 of the hydroxyl oligomer for BASF AG, the aldehyde ketone resin of Changsha Chang Tai Industrial Co., Ltd.s KR-80F, KR-120, KR120B, KR-120W, UK-100, UK-300, UK-500, Ba Ling stone of Weng Kaier companies aldehyde ketone resin Change the one or more of YHKR-1210, YHKR-1218 of aldehyde ketone resin.

The emulsifier for isomeric alcohol polyethenoxy ether (EH-9), end Dicon A/S ADEKA REASOAP series it is non-from Sub (ER-30) and anion (SR-10) emulsifier, 2- acrylamide-2-methylpro panesulfonic acids sodium (COPS-2), fatty alcohol polyoxy It is one or more in ethylene ether ammonium sulfate (KL-525), lauryl sodium sulfate (SDS).

The initiator for potassium peroxydisulfate, ammonium persulfate it is one or more.

A kind of hydroxy polyacrylate lotion, is made by above-mentioned preparation method.The hydroxy polyacrylate lotion grain of gained Diameter < 300nm, solid content 45-52%, hydroxyl value 40-150mgKOH/g, Tg are 10-80 DEG C.

Hydroxy polyacrylate lotion of the present invention, which is mainly used in, prepares aqueous double-component polyurethane coating.

Hydroxy polyacrylate lotion is added in stirred tank, in terms of mass fraction, 1-10 parts of coalescents of addition, 0.05-1.5 parts of antifoaming agent, 0.05-0.2 parts of thickeners, 0.05-0.3 parts of wetting agents and 0.05-0.1 parts of neutralizers disperse 10- 30 minutes, filtering and discharging, the coating that hydroxy polyacrylate lotion is prepared;

The coalescents are propylene glycol monomethyl ether, propandiol butyl ether, dipropylene glycol methyl ether, it is a kind of in dipropylene or It is a variety of.

The antifoaming agent is polyether siloxane copolymer antifoaming agent TEGO-800, TEGO-805, TEGO- of TEGO companies 815th, modified polyorganosiloxane copolymer solution B YK-019, BYK-020 of TEGO-825 and BYK companies is one or more.

The thickener is swollen association for non-ionic polyurethane association thickener RM-8W, the hydrophobically-modified alkali of DOW companies Type thickener TT-935, alkali soluble is swollen non-association thickener ASE-60 and the non-ionic associative type thickener TEGO of TEGO companies ViscoPlus 3000, TEGO ViscoPlus 3030, TEGO ViscoPlus 3060 it is one or more.

The wetting agent is polyether siloxane copolymer TEGO-245, the nonionic organic surfactant of TEGO companies The Siloxane-Oxyalkylene Copolymers solution B YK-346's of TEGO-500 and BYK companies is one or more.

Told neutralizer for triethylamine, dimethylethanolamine it is one or more.

The polyisocyanate curing agent includes the hexa-methylene two or two of sulfonate, carboxylate and alkoxy hydrophilic modifying Isocyanates (HDI) is one or more.

Gained aqueous double-component polyurethane film has high glaze, the high grade of transparency, water-fast and excellent chemical resistance, height Crosslink density and high rigidity, anti scuffing and it is wear-resisting the advantages that.It can be applied to high-grade woodwork coating, car paint, anti-corrosion of metal Coating and other industrial protection coating.

Relative to the prior art, the invention has the advantages that:

The chemical resistance of aqueous double-component polyurethane coating film is determined by film crosslink density, by hydroxyl polypropylene The OH bases content and NCO of acid esters lotion regulate and control with OH molar ratios;Appearance of film and decoration performance determined by group partition inter-capacitive, phase The structure of capacitive and water-based hydroxyl resin, particle structure with form, it is related to the emulsifying capacity and emulsifier content of curing agent.This For invention hydroxy polyacrylate lotion using polyacrylate polyol as main components, hydroxyl oligomer is auxiliary hydroxyl group Part.First with the suitable hydroxyl oligomer of monomer dissolved mixture, pre-emulsification is carried out to it with suitable emulsifier, take part or Person's whole pre-emulsion prepares seed, and hydroxy polyacrylate breast is can be prepared by using the technique of pre-emulsification seeded emulsion polymerization Liquid.Present invention obviates hydroxy-acrylate monomer additive amount it is excessive caused by polymerization stability drastically reduce the problem of, therefore Lotion hydroxyl value and adjustment hydroxyl structure can be greatly improved by adjusting the type and additive amount of hydroxyl oligomer, so as to improve double groups The mechanically and chemically performance of part film.Meanwhile the hydroxyl oligomer of introducing has the characteristics that high glaze, the high grade of transparency in itself, it can Further improve the appearance of film and decoration performance.The hydroxy polyacrylate lotion of the present invention cures with aqueous polyisocyanates The film for the aqueous double-component polyurethane coating that agent is prepared has high rigidity, high glaze and excellent chemical resistance, solves Traditional hydroxy polyacrylate lotion due to hydroxyl value is low and caused by paint film mechanically and chemically poor performance problem, overcome with The problems such as mating gloss of film obtained of aqueous polyisocyanate curing agent is low, poor transparency.

Specific embodiment

With reference to specific embodiment, the invention will be further described, but the implementation of the present invention is not limited to this, right In especially not dated technological parameter, routine techniques progress can refer to.

The related detection method of example below is as follows:

Basic performance test includes:Hydroxy polyacrylate lotion is with reference to GB/T11175-2002《Synthetic resin emulsion tries Proved recipe method》It is tested, tests appearance, pH, solid content, the viscosity of lotion.Paint film property is with reference to GB/T23999-2009《Room Interior trim finishing water-borne wood coating》It is tested, test gloss, hardness, water resistance, dry heat resistance, alcohol resistance.Lotion is put down Equal grain size is measured using nano-particle size analysis instrument (ZS Nano S).

Embodiment 1

(1) preparation of hydroxy polyacrylate lotion:(hydroxyl value=65mgKOH/g) formula of hydroxy polyacrylate lotion Such as table 1a:

Table 1a

Preparation process:1-9 is mixed with monomer mixture, take 10% monomer mixture with 0.05 part of emulsifier (wherein 0.025 part of KL-525 and 0.025 part of COPS-2) and 2.75 parts of water to its pre-emulsification as seed pre-emulsion.Residue is emulsified Agent, sodium bicarbonate, 0.1 part of initiator (potassium peroxydisulfate), 25 parts of deionized waters are added in reaction kettle, are warming up to 78 DEG C, stirring 15 Minute, seed pre-emulsion in 20 minutes was at the uniform velocity dripped off, emulsion-stabilizing half an hour is treated, obtains seed emulsion.Keep reaction System temperature is 80 DEG C.Remaining mix monomer with remaining monomer is mixed, is then added dropwise into seed emulsion, while be added dropwise with 15 The aqueous solution of part 0.15 part of initiator (potassium peroxydisulfate) of water dissolution, drips off in 3.5h or so.85 DEG C are warming up to after dripping, heat preservation 1.5h.55 DEG C are cooled to, adds in and neutralizes after 5.5 parts of water and neutralizer triethylamine are mixed, keep the temperature 0.25h, cooling discharge obtains Milky white semi-transparent hydroxy polyacrylate lotion.

(2) performance of hydroxy polyacrylate lotion:The lotion average grain diameter 128nm prepared, viscosity:535cps, pH =7.0, solid content:48.3%.

(3) preparation of high-performance water-based double-component polyurethane coating:Formula such as table 1b:

Table 1b

NCO group and the molar ratio 1.8 of OH groups in hydroxy polyacrylate lotion wherein in curing agent:1.

Preparation method is as follows:Lotion is added in stirred tank, rotating speed is 700 turns/min, by 10 parts of water and coalescents It is added in lotion after premix, sequentially adds 5-9 raw materials, disperseed 20 minutes, filtering and discharging.During construction, by aqueous polyisocyanic acid Ester curing agent is added in the coating that above-mentioned hydroxy polyacrylate lotion is prepared, and is stirred 6 minutes, is obtained the poly- ammonia of aqueous double-component Ester paint.

(4) film performance:Paint film is made in aqueous double-component polyurethane coating and cures 7 days dry, performance at normal temperatures It is as follows:

The comprehensive performance of the high-performance water-based double-component polyurethane coatings of table 1c

The present embodiment adds hydroxyl oligomer A81 in the hydroxy polyacrylate lotion of relatively low hydroxy radical content, passes through list Body dissolves, and pre-emulsification, prepares emulsification seed emulsion, hydroxy polyacrylate lotion is prepared on the basis of seed emulsion.It should Method ensures in hydroxyl oligomer stable dispersion to hydroxy polyacrylate lotion, is primarily present in inside latex particle, acrylic acid Ester monomer polymerize in hydroxyl oligomer, forms the interpenetrating polymer networks of polyacrylate and hydroxyl oligomer, on the one hand protects It is sufficiently mixed between card hydroxyl oligomer and acrylate copolymer, on the other hand, it is understood that there may be a small amount of acrylate copolymer is grafted to On hydroxyl oligomer, graft polymers provides the bridge of polymer-compatible.The addition of hydroxyl oligomer improves hydroxyl polypropylene The hydroxy radical content of acid esters lotion ensures the polymerization stability of hydroxy polyacrylate lotion so that two-component hardness of film reaches H, (60 °) of gloss are 83%, have excellent water-fast/alcohol performance, the hydroxyl also prepared with good dry heat resistance, this method The shortcomings that based polyacrylic acid ester lotion overcomes traditional hydroxy polyacrylate lotion to prepare double-component polyurethane coating.

Embodiment 2

(1) preparation of hydroxy polyacrylate lotion:Hydroxy polyacrylate lotion (hydroxyl value=65mgKOH/g) is formulated such as Table 2a:

Table 2a

Preparation method:1-8 is mixed with monomer mixture, take 15% monomer mixture molten (is with 0.1 part of emulsifier Each 0.05 part of SR-10 and ER-30) and 3 parts of water to its pre-emulsification as seed pre-emulsion.By residual emulsifier, sodium bicarbonate, 0.1 part of initiator (ammonium persulfate), 30 parts of deionized waters are added in reaction kettle, are warming up to 80 DEG C, are stirred 30 minutes, and seed is pre- Emulsion at the uniform velocity dripped off in 30 minutes, treats emulsion-stabilizing half an hour, obtains seed emulsion.It is 80 to keep temperature of reaction system ℃.Residual monomer mixture into seed emulsion is added dropwise, while is added dropwise with 20 parts of water dissolutions, 0.2 part of initiator (ammonium persulfate) Aqueous solution, dripped off in 4h or so.82 DEG C are warming up to after dripping, keeps the temperature 2h.45 DEG C are cooled to, by 10 parts of water and N, N- diformazan It adds in and neutralizes after ethylethanolamine mixing, keep the temperature 0.25h, cooling discharge obtains milky white semi-transparent hydroxy polyacrylate lotion.

(2) performance of hydroxy polyacrylate lotion:The lotion average grain diameter 135nm prepared, viscosity:573cps, pH =7.0, solid content:48.5%.

(3) preparation of high-performance water-based double-component polyurethane coating:Formula such as table 2b:

Table 2b

NCO group and the molar ratio 1.5 of OH groups in hydroxy polyacrylate lotion wherein in curing agent:1.

Preparation method is as follows:Lotion is added in stirred tank, rotating speed is 700 turns/min, by 10 parts of water and coalescents It is added in lotion after premix, sequentially adds 5-9 raw materials, disperseed 10 minutes, filtering and discharging.During construction, by aqueous polyisocyanic acid Ester curing agent is added in the coating that above-mentioned hydroxy polyacrylate lotion is prepared, and is stirred 5 minutes, is obtained the poly- ammonia of aqueous double-component Ester paint.

(4) dual-component coating performance:Paint film is made in aqueous double-component polyurethane coating and cures drying 7 days at normal temperatures, Its performance is as follows:

The comprehensive performance of the high-performance water-based double-component polyurethane coatings of table 2c

Embodiment 3

(1) preparation of hydroxy polyacrylate lotion:Hydroxy polyacrylate lotion (hydroxyl value=70mgKOH/g) is formulated such as Table 3a:

Table 3a

Preparation process:1-8 is mixed with monomer mixture, takes 12% monomer mixture, 0.1 part of emulsifier (two kinds of breasts Each 0.05 part of agent) and 3 parts of water to its pre-emulsification as seed pre-emulsion.Residual emulsifier, sodium bicarbonate, 0.1 part are drawn It sends out in agent (KPS), 20 parts of deionized waters addition reaction kettles, is warming up to 82 DEG C, stirs 15 minutes, by seed pre-emulsion at 15 points It is at the uniform velocity dripped off in clock, treats emulsion-stabilizing half an hour, obtain seed emulsion.It is 82 DEG C to keep temperature of reaction system.By residual monomer Mixture is mixed with remaining monomer, is then added dropwise into seed emulsion, while is added dropwise with 10 parts of water dissolutions, 0.2 part of initiator (KPS) aqueous solution, drips off in 3h or so.85 DEG C are warming up to after dripping, keeps the temperature 1h.60 DEG C are cooled to, by 5.9 parts of water and three It adds in and neutralizes after ethamine mixing, keep the temperature 30min, cooling discharge obtains milky white semi-transparent hydroxy polyacrylate lotion.

(2) performance of hydroxy polyacrylate lotion:The lotion average grain diameter 123nm prepared, viscosity:617cps, pH =7.0, solid content:48.0%.

(3) preparation of high-performance water-based double-component polyurethane coating:Formula such as table 3b:

Table 3b

NCO group and the molar ratio 1.2 of OH groups in hydroxy polyacrylate lotion wherein in curing agent:1.

Preparation method is as follows:Lotion is added in stirred tank, rotating speed is 700 turns/min, by 10 parts of water and coalescents It is added in lotion after premix, sequentially adds 5-9 raw materials, disperseed 10 minutes, filtering and discharging.During construction, by aqueous polyisocyanic acid Ester curing agent is added in the coating that above-mentioned hydroxy polyacrylate lotion is prepared, and is stirred 8 minutes, is obtained the poly- ammonia of aqueous double-component Ester paint.

(4) by the paint film property of aqueous double-component polyurethane coating:Obtained paint film cures 7 days dry, property at normal temperatures It can be as follows:

The comprehensive performance of the high-performance water-based double-component polyurethane coatings of table 3c

Embodiment 4

(1) preparation of hydroxy polyacrylate lotion:Hydroxy polyacrylate lotion (hydroxyl value=79mgKOH/g) is formulated such as Table 4a:

Table 4a

Preparation process:1-8 is uniformly mixed and prepares monomer mixture, takes 14 parts of monomer mixtures with 0.1 part of emulsifier (two Kind of each 0.05 part of emulsifier) and 3.35 parts of water to its pre-emulsification as seed pre-emulsion.By residual emulsifier, sodium bicarbonate, 0.1 part of initiator, 25 parts of deionized waters are added in reaction kettle, are warming up to 75 DEG C, are stirred 15 minutes, by seed pre-emulsion 20 It is at the uniform velocity dripped off in minute, treats emulsion-stabilizing half an hour, obtain seed emulsion.It is 80 DEG C to keep temperature of reaction system.It will be remaining single Body mixture is added dropwise into seed emulsion, while the aqueous solution with 15 parts of water dissolutions, 0.2 part of initiator is added dropwise, in 3.5h or so drops It is complete.85 DEG C are warming up to after dripping, keeps the temperature 1.5h.55 DEG C are cooled to, 6 parts of water and N add after N-dimethylethanolamine mixing Enter to neutralize, keep the temperature 0.25h, cooling discharge obtains milky white semi-transparent hydroxy polyacrylate lotion.

(2) performance of hydroxy polyacrylate lotion:The lotion average grain diameter 119nm prepared, viscosity:820cps, pH =7.0, solid content:47.7%.

(3) preparation of high-performance water-based double-component polyurethane coating:Formula such as table 4b:

Table 4b

NCO group and the molar ratio 1.8 of OH groups in hydroxy polyacrylate lotion wherein in curing agent:1.

Preparation method is as follows:Lotion is added in stirred tank, rotating speed is 700 turns/min, by 10 parts of water and coalescents It is added in lotion after premix, sequentially adds 5-9 raw materials, disperseed 25 minutes, filtering and discharging.During construction, by aqueous polyisocyanic acid Ester curing agent is added in the coating that above-mentioned hydroxy polyacrylate lotion is prepared, and is stirred 7 minutes, is obtained the poly- ammonia of aqueous double-component Ester paint.

(4) film performance of aqueous double-component polyurethane coating:Paint film is made normal in aqueous double-component polyurethane coating The lower curing of temperature is 7 days dry, and performance is as follows:

The comprehensive performance of the high-performance water-based double-component polyurethane coatings of table 4c

Embodiment 5

(1) preparation of hydroxy polyacrylate lotion:Hydroxy polyacrylate lotion (hydroxyl value=95mgKOH/g) is formulated such as Table 5a:

Table 5a

Preparation process:1-7 is uniformly mixed and prepares monomer mixture, takes 13 parts of monomer mixtures with 0.1 part of emulsifier (two Kind of each 0.05 part of emulsifier) and 4 parts of water to its pre-emulsification as seed pre-emulsion.By residual emulsifier, sodium bicarbonate, 0.1 Part initiator, 25 parts of deionized waters are added in reaction kettles, are warming up to 75 DEG C, are stirred 15 minutes, by seed pre-emulsion at 20 points It is at the uniform velocity dripped off in clock, treats emulsion-stabilizing half an hour, obtain seed emulsion.It is 80 DEG C to keep temperature of reaction system.By residual monomer Mixture is added dropwise into seed emulsion, while the aqueous solution with 15 parts of water dissolutions, 0.2 part of initiator is added dropwise, in 3.5h or so drops It is complete.85 DEG C are warming up to after dripping, keeps the temperature 1.5h.55 DEG C are cooled to, adds in and neutralizes after 5.9 parts of water and triethylamine are mixed, protect Warm 0.25h, cooling discharge obtain milky white semi-transparent hydroxy polyacrylate lotion.

(2) performance of hydroxy polyacrylate lotion:The lotion average grain diameter 132nm prepared, viscosity:673cps, pH =7.0, solid content:48.2%.

(3) preparation of high-performance water-based double-component polyurethane coating:Formula such as table 5b:

Table 5b

NCO group and the molar ratio 1.5 of OH groups in hydroxy polyacrylate lotion wherein in curing agent:1.

Preparation method is as follows:Lotion is added in stirred tank, rotating speed is 700 turns/min, by 10 parts of water and coalescents It is added in lotion after premix, sequentially adds 5-9 raw materials, disperseed 30 minutes, filtering and discharging.During construction, by aqueous polyisocyanic acid Ester curing agent is added in the coating that above-mentioned hydroxy polyacrylate lotion is prepared, and is stirred 6 minutes, is obtained the poly- ammonia of aqueous double-component Ester paint.

(4) film performance of aqueous double-component polyurethane coating:Paint film is made normal in aqueous double-component polyurethane coating The lower curing of temperature is 7 days dry, and performance is as follows:

The comprehensive performance of the high-performance water-based double-component polyurethane coatings of table 5c

Embodiment 6

(1) preparation of hydroxy polyacrylate lotion:Hydroxy polyacrylate lotion (hydroxyl value=110mgKOH/g) is formulated Such as table 6a:

Table 6a

Preparation process:1-7 is uniformly mixed and prepares monomer mixture, takes 10% monomer mixture with 0.1 part of emulsifier (two Kind of each 0.05 part of emulsifier) and 4.5 parts of water to its pre-emulsification as seed pre-emulsion.By residual emulsifier, sodium bicarbonate, 0.1 part of initiator, 25 parts of deionized waters are added in reaction kettle, are warming up to 75 DEG C, are stirred 15 minutes, by seed pre-emulsion 20 It is at the uniform velocity dripped off in minute, treats emulsion-stabilizing half an hour, obtain seed emulsion.It is 80 DEG C to keep temperature of reaction system.It will be remaining single Body blend mixture is added dropwise into seed emulsion, while the aqueous solution with 15 parts of water dissolutions, 0.2 part of initiator is added dropwise, on a 3.5h left sides The right side drips off.85 DEG C are warming up to after dripping, keeps the temperature 1.5h.55 DEG C are cooled to, by 5.55 parts of water and N, N-dimethylethanolamine mixes It adds in and neutralizes after conjunction, keep the temperature 0.25h, cooling discharge obtains milky white semi-transparent hydroxy polyacrylate lotion.

(2) performance of hydroxy polyacrylate lotion:The lotion average grain diameter 125nm prepared, viscosity:725cps, pH =7.0, solid content:47.6%.

(3) preparation of high-performance water-based double-component polyurethane coating:Formula such as table 6b:

Table 6b

NCO group and the molar ratio 1.0 of OH groups in hydroxy polyacrylate lotion wherein in curing agent:1.

Preparation method is as follows:Lotion is added in stirred tank, rotating speed is 700 turns/min, by 10 parts of water and coalescents It is added in lotion after premix, sequentially adds 5-9 raw materials, disperseed 20 minutes, filtering and discharging.During construction, by aqueous polyisocyanic acid Ester curing agent is added in the coating that above-mentioned hydroxy polyacrylate lotion is prepared, and is stirred 5 minutes, is obtained the poly- ammonia of aqueous double-component Ester paint.

(4) film performance of aqueous double-component polyurethane coating:Paint film is made normal in aqueous double-component polyurethane coating The lower curing of temperature is 7 days dry, and performance is as follows:

The comprehensive performance of the high-performance water-based double-component polyurethane coatings of table 6c

Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification, Equivalent substitute mode is should be, is included within protection scope of the present invention.

Claims (8)

1. a kind of preparation method of hydroxy polyacrylate lotion, it is characterised in that it comprises the following steps,
1) in terms of mass fraction, acrylate monomer and/or 30~45 parts of methacrylate monomers, hydroxy acrylate are weighed 5~15 parts of monomer, 1.0~3.0 parts of acrylic monomers, 0.5~3.0 part of acrylate functional monomer, hydroxyl oligomer 0.5~3 Part, it is uniformly mixed and prepares monomer mixture, the monomer mixture of 10-15% is taken to prepare the pre- breast of seed with 1-2 parts of emulsifiers It is spare to change liquid;
2) in terms of mass fraction, 1~2 part of emulsifier, 0.05-0.2 parts of sodium bicarbonates and 20~30 parts of deionized waters are added in anti- It answers in kettle, open stirring and increases the temperature of reaction system, the initiator of 10-15% is added in after temperature reaches 78-83 DEG C, stablize After 5-15 minutes, seed pre-emulsion was dripped in 15-30 minutes, is stablized 15-30 minutes, by residual monomer mixture and use 10~20 parts of remaining initiators of water dissolution dripped off in 3-4 hours, were warming up to 80-85 DEG C and cured 1-2 hours, are cooled to 40- It 60 DEG C, dilutes 0.3~0.6 part of neutralizer with 3~10 parts of water and neutralizes, cooling discharge obtains hydroxyl polypropylene after heat preservation 15-30 minutes Acid esters lotion;
The acrylate monomer and/or methacrylate monomers are methyl methacrylate, methyl acrylate, acrylic acid second Ester, butyl methacrylate and butyl acrylate it is one or more;
The hydroxy-acrylate monomer is hydroxy-ethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and methyl-prop Olefin(e) acid hydroxypropyl acrylate it is one or more;
The acrylic monomers is acrylic acid and/or methacrylic acid;
The acrylate functional monomer is isobornyl methacrylate, glycidyl methacrylate and methacrylic acid Acetoacetoxyethyl it is one or more;
The hydroxyl oligomer is urea formaldehyde A81, aldehyde ketone resin KR-80F, KR-120, KR120B, KR-120W, aldehyde ketone resin UK-100, UK-300, UK-500, aldehyde ketone resin YHKR-1210 and YHKR-1218 it is one or more;
The emulsifier is isomeric alcohol polyethenoxy ether, polymerisable emulsifier ADEKAREASOAP series non-ionics ER-30 and the moon Ion SR-10 emulsifiers, 2- acrylamide-2-methylpro panesulfonic acids sodium, fatty alcohol polyoxyethylene ether ammonium sulfate and dodecyl Sodium sulphate it is one or more;
The initiator for potassium peroxydisulfate, ammonium persulfate it is one or more.
2. the preparation method of hydroxy polyacrylate lotion according to claim 1, which is characterized in that the neutralizer is It is one or more in triethylamine, ammonium hydroxide and dimethylethanolamine.
3. the preparation method of hydroxy polyacrylate lotion according to claim 1, which is characterized in that with hard resin Meter, the hydroxyl value of the hydroxy polyacrylate lotion is 40-150mgKOH/g.
4. the preparation method of hydroxy polyacrylate lotion according to claim 1, which is characterized in that the hydroxyl poly- third The glass transition temperature of olefin(e) acid ester lotion is 10-80 DEG C.
5. a kind of hydroxy polyacrylate lotion, described in be characterized in that, by any one of the claim 1-4 preparation methods It is made.
6. application of the hydroxy polyacrylate lotion in aqueous double-component polyurethane coating described in claim 5.
7. application of the hydroxy polyacrylate lotion in aqueous double-component polyurethane coating according to claim 6, special Sign is to include the following steps:
1) hydroxy polyacrylate lotion is added in stirred tank, in terms of mass fraction, 1-10 parts of coalescents of addition, 0.05-1.5 parts of antifoaming agent, 0.05-0.2 parts of thickeners, 0.05-0.3 parts of wetting agents and 0.05-0.1 parts of neutralizers disperse 10- 30 minutes, filtering and discharging obtained the coating of hydroxy polyacrylate lotion preparation;
2) when constructing, aqueous polyisocyanate curing agent is added to the hydroxyl for 1.0-1.8 according to NCO/OH molar ratios and is gathered In the coating that acrylic acid ester emulsion is prepared, stir 5-8 minutes, obtain aqueous double-component polyurethane coating.
8. application of the hydroxy polyacrylate lotion in aqueous double-component polyurethane coating according to claim 7, special Sign is, the coalescents are propylene glycol monomethyl ether, one kind of propandiol butyl ether, dipropylene glycol methyl ether and dipropylene or It is a variety of;
The antifoaming agent is polyether siloxane copolymer antifoaming agent TEGO-800, TEGO-805, TEGO-815, TEGO-825, changes Property polysiloxanes copolymer solution B YK-019's and BYK-020 is one or more;
The thickener is non-ionic polyurethane association thickener RM-8W, hydrophobically-modified alkali is swollen association thickener TT- 935th, the swollen non-association thickener ASE-60 of alkali soluble, non-ionic associative type thickener TEGO ViscoPlus 3000, TEGO ViscoPlus's 3030 and TEGO ViscoPlus 3060 is one or more;
The wetting agent changes for polyether siloxane copolymer TEGO-245, nonionic organic surfactant TEGO-500 and polyethers Property polysiloxane solution BYK-346's is one or more;
The neutralizer is one or more in triethylamine, ammonium hydroxide and dimethylethanolamine;
The polyisocyanate curing agent includes the hexa-methylene diisocyanate of sulfonate, carboxylate and alkoxy hydrophilic modifying It is one or more in ester.
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