CN101481437B - Preparation of high closeness polyacrylacid ester dispersion - Google Patents
Preparation of high closeness polyacrylacid ester dispersion Download PDFInfo
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Abstract
The invention relates to a high-sealing polyacrylic ester dispersoid and a preparation method thereof; a multi-element emulsifier system which consists of an anionic emulsifier and a compound non-ionic emulsifier is adopted for controlling the charging process and components of the emulsifier in different polymerization periods, and the room-temperature self-crosslinking high-sealing polyacrylic ester dispersoid is prepared by a semi-continuous seeding emulsion polymerization process. The dispersoid has small particle size, good electrolyte-resistance (calcium ion) stability and high tolerance to various film forming accessory ingredients (various organic solvents with high boiling point). The dispersoid is used as seal coat of water-based wood coating and has good sealing performance to various woods; harmful volatile organic compounds (VOC) such as formaldehyde, and the like sealed against escaping from plates to pollute indoor environment, and the colored compounds such as turpentine, pine oil and tannin and the like are sealed against dissolving out of the plates to pollute pure top coating and white top coating of a water-based wooden ware; and in addition, the dispersoid can be used in water-based leather finishing agents.
Description
Technical field
The present invention relates to a kind of high closeness polyacrylacid ester dispersion and preparation method thereof.
The invention still further relates to the application of high closeness polyacrylacid ester dispersion in the preparation water-borne wood coating of described method preparation.
Background technology
Along with the continuous enhancing of people's environment and health perception, water-borne wood coating comes into one's own day by day.Existing water-borne wood coating comprises resins such as polyacrylate dispersion, polyurethane aqueous dispersion body and polyurethane acroleic acid dispersion, wherein polyacrylate dispersion has hardness height, weather resisteant and reaches the low advantage of cost well, but has shortcomings such as hot sticky cold crisp, anti-solvent and poor water resistance.
The room-temperature self crosslinking modification can overcome above-mentioned shortcoming, comprises based on cross-linking systems such as Michael reaction, many aziridine or poly-carbonization imines/carboxylic acid, siloxanes hydrolytic condensation, acetoacetyl/polyamine, active carbonyl/hydrazides (ketone hydrazine) and cyclic carbonate/amidos.U.S. Pat P425150 (2003.04.29) and USP246929 (2005.10.07) have reported room-temperature self crosslinking type acrylic acid dispersion, the cross-linking monomer of introducing ketocarbonyl-containing to the polymer segment as active sites, change the back in the pH value that becomes mem stage because of system and crosslinking reaction takes place form crosslinking polymer network, but have cross-linking monomer content height (reach total monomer amount 25%), cost height and cause that stability of emulsion polymerization is poor, the storage period of polymer emulsion shortcoming such as weak point; U.S. Pat P887626 (2004.07.09) reported to adopt and contained the active two component blend of differential responses, and introduces the 3rd component and control reaction process between two components, synthesized a kind of self-crosslinking aqueous coating.Because this system contains two above components, the construction technology complexity exists the construction time limit short, defectives such as construction cost height.The problem of at present cross-linking modified following several respects of polyacrylate dispersion ubiquity: (1) dispersion solid content is low, generally all at 20-40%; (2) the electrolyte-resistant stability of dispersion is not good, and the tolerance of formulation for coating material is narrow; (3) the not high and cross-linking system instability of the degree of crosslinking of self-cross linking type dispersion, rate of drying is slow, does not almost have sealing effect, can't seal the harmful VOC gas evolution such as formaldehyde that contain in the sheet material and pollute indoor environment.Because timber particularly pine and Black walnut contains sylvic acid, Weibull, rosin and other colored compound, easily separate out and pollute aqueous wooden ware white finish paint and clear finish, need the good aqueous wooden ware priming paint decontamination of closure.Existing watersoluble closed priming paint can't solve " yellowing " problem that the water-based white paint causes because of separating out of colored compounds such as Weibull.
Summary of the invention
Indoor environment is polluted in the effusion that the objective of the invention is to can not to seal at current water-borne wood coating the harmful VOC gas that contains in the sheet material such as formaldehyde etc., simultaneously water-borne wood coating runs into " yellowing ", " bleeding " and an easy difficult problem such as adhesion in construction process, provide a kind of closure by force, the high closeness polyacrylacid ester dispersion of antiblocking and excellent combination property and preparation method thereof.
A further object of the invention is that high closeness polyacrylacid ester dispersion of the present invention is used to prepare water-borne wood coating.
The preparation method of high closeness polyacrylacid ester dispersion of the present invention is the emulsifier system that adopts anionic emulsifier and compound nonionic emulsifier to form, and has introduced the room-temperature self crosslinking system, and its acrylate monomer is composed as follows:
---alkyl acrylate, alkyl carbon atoms number are 1～20, and consumption is 10～50% of a monomer total mass;
---alkyl methacrylate, alkyl carbon atoms number are 1～25, and consumption is 10～60% of a monomer total mass;
---acrylic acid hydroxy alkyl ester, alkyl carbon atoms number are 1～15, and consumption is 0.1～15% of a monomer total mass;
---alkyl acrylic, alkyl carbon atoms number are 1～10, and consumption is 0.1～20% of a monomer total mass;
---other acrylate functional monomer, consumption are 0.1～15% of monomer total mass;
---vinyl aromatic compound, consumption are 1～60% of monomer total mass;
Described alkyl acrylate is one or more mixtures in methyl acrylate, ethyl propenoate, butyl acrylate, vinylformic acid pentyl ester, Ethyl acrylate, 2-EHA, the isobornyl acrylate;
Described alkyl methacrylate is one or more mixtures in methyl methacrylate, Jia Jibingxisuanyizhi, methacrylic ester propyl ester, butyl methacrylate, methacrylic acid pentyl ester, N-Hexyl methacrylate, n octyl methacrylate, Isooctyl methacrylate, the isobornyl methacrylate;
Described acrylic acid hydroxy alkyl ester is one or more mixtures in 2-Hydroxy ethyl acrylate, vinylformic acid-3-hydroxy propyl ester, the vinylformic acid-own ester of 6-carboxyl, methacrylic acid-2-hydroxy methacrylate, the methacrylic acid-2-hydroxy propyl ester;
Described thiazolinyl carboxylic acid is one or more mixtures in vinylformic acid, methacrylic acid, methylene-succinic acid, the octadecenic acid;
Described vinyl aromatic compounds is one or more mixtures in vinylbenzene, alpha-methyl styrene, 2-chlorostyrene, 3-t-butyl styrene, 3, the 4-dimethyl styrene;
Described other acrylate functional monomer is acrylamide, diacetone-acryloamide(DAA), N hydroxymethyl acrylamide, Methacrylamide, N, N-DMAA, methacrylic acid tert-butyl amine base ethyl ester, Dimethylaminoethyl Methacrylate, glycidyl methacrylate, methacrylic acid tetrahydrofuran ester, ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1, one or more mixtures in the 6-hexylene glycol acrylate.
Specifically comprise the steps:
(1) preparation seed dispersion: with deionized water, emulsifier system and buffer reagent join in the reactor, under 50 ℃ of water bath condition, stirred 30 minutes, add described acrylate monomer blend then, be warmed up to simultaneously more than 82 ℃, slowly drip initiator solution, insulation 30min in back is standby mutually to treat seed dispersion to be indigo plant; The seed dispersion weight proportion is as follows:
Water 30-80 part
Emulsifier system (1) 2-10 part
Buffer reagent 0.1-5.0 part
Acrylate monomer blend 5-40 part
Initiator 0.1-5.0 part;
(2) drip the nuclear layer monomer pre-emulsion: constant speed drips alkyl methacrylate, alkyl acrylate, alkyl acrylic and the monomeric pre-emulsion of acrylate functional in above-mentioned seed dispersion in 1.5 hours, keep suitable initiator rate of addition simultaneously, temperature of reaction is controlled at 82-85 ℃; Nuclear layer monomer pre-emulsion weight proportion is as follows:
Water 10-80 part
Emulsifier system (2) 1-10 part
Alkyl methacrylate, alkyl acrylate and alkyl acrylic mixture 80-200 part
Acrylate functional monomer 0.1-10 part
Initiator (massfraction is 1.0%) 0.1-2.0 part;
(3) drip the shell monomers pre-emulsion: treat that the dispersion nuclear monomer dropwises, insulation half an hour begin to drip the shell monomer pre-emulsion, dripped off with interior in 2 hours, constant speed drips initiator solution simultaneously, and control reaction temperature is 82-85 ℃; Shell monomers pre-emulsion weight proportion is as follows:
Water 20-80 part
Emulsifier system (3) 1-5 part
Alkyl acrylate 100-150 part
Alkyl acrylic 1-3 part
Acrylate functional monomer 2-15 part
Neutralizing agent 2-6 part
Initiator (massfraction is 1.0%) 0.5-2.0 part;
(4) treat that the shell monomer pre-emulsion dropwises, add an amount of initiator, reaction system is warmed up to 85 ℃ continues reaction 2 hours, cool to 50 ℃, regulate the pH value to 8.0-10.0, the discharging packing with neutralizing agent;
The polyacrylate dispersion number-average molecular weight that obtains is 10
3-10
6, molecular weight distribution is 1.0-50, and latex particle size is in 300 nanometers, and the dispersion solids content is more than 45%, the second-order transition temperature of polymkeric substance-20～80 ℃.
Described emulsifying agent is the polynary emulsifier system of anion surfactant and multiple nonionic surface active agent, and described anionic emulsifier is a kind of in Sodium dodecylbenzene sulfonate (SDBS), sodium lauryl sulphate (SDS), alkyl diphenyl ether disodium sulfonate salt (DSB), dodecylbenzene phenyl ether sodium disulfonate (DowFax2A-1), oxyethyl group disodium sulfosuccinate (A-102), sodium vinyl sulfonate (SVS), alkyl amido sodium vinyl sulfonate (DNS-86) and the alkylaryl sulphonate and more than one mixture; Described nonionic surface active agent is the CO-893 of alkylphenol and ethylene oxide condensate (NP-40), glycol fatty acid ester, propylene glycol fatty acid ester, nonyl phenol polyethoxy ether (OP-10), polyoxyethylene nonylphenol ether (OP-40), sorbitan monostearate, polyoxyethylene sorbitan Triolein, polyoxyethylene 20 sorbitan monolaurate, TX-100, Rohdia company, one or more the mixture among the CO-897; The mass ratio of total anion surfactant and nonionic surface active agent is 1-4: 2-10.The moon/the nonsurfactant ratio is 1: 0.1-4 in the emulsifier system (1); The moon/the nonsurfactant ratio is 1: 0.1-3 in the emulsifier system (2); The moon/the nonsurfactant ratio is 1: 0.1-10 in the emulsifier system (3).
Described initiator is Potassium Persulphate, ammonium persulphate, sodium bisulfite-Potassium Persulphate, hydrogen peroxide-iron protochloride, Potassium Persulphate-iron protochloride, isopropyl benzene hydroperoxide-iron protochloride or its compound system.
Described neutralizing agent is N, the mixture of one or more in N-dimethylethanolamine (DMEA), ammoniacal liquor, triethylamine, sodium hydroxide, the potassium hydroxide.
Described buffer reagent is wherein one or more a mixture such as sodium bicarbonate, sodium bisulfite, sodium pyrosulfate, SODIUM PHOSPHATE, MONOBASIC.
The polynary emulsifier system that the present invention adopts anionic and compound nonionic emulsifier to be combined into, adjust the reasonable distribution of emulsifier system at different polymerization stages, carry out the letex polymerization of acrylate, the gel fraction that this emulsification system has emulsifying agent addition little (monomer total mass 1.5-3.5%), monomer conversion height, emulsion polymerization systems is low, dispersion particle diameters is little and be evenly distributed, dispersion electrolyte-resistant (calcium ion) good stability, to film coalescence aid tolerance height.Advantages such as the excellent storage stability of emulsion.
But the group of introducing room-temperature self crosslinking of the present invention such as hydroxyl, amino, N-methylol, glycidyl or epoxy group(ing), acetyl oxyethyl group, amide group, alkylsiloxane, diacetone-acryloamide(DAA) base etc., in the dispersion film process, continuous volatilization along with moisture, the pH value of system reduces, rely on the chemical reaction between group to obtain having filming of crosslinking structure, improve the water tolerance and the solvent resistance of filming.The characteristics of this self-crosslinking woodwork coating are fast dryings, and the transparency is good, the chemical-resistant excellence, and have good low-temperature snappiness, high closeness and resistance to blocking.
The preparation of aqueous wooden ware seal coat: above-mentioned high closeness polyacrylacid ester dispersion is joined in the dispersion cylinder, under the middling speed agitation condition, wetting agent, cosolvent, defoamer and thickening material are slowly joined in the differential prose style free from parallelism, stir discharging behind the 30-60min, filter, be packaged to be water-borne wood coating.
Above-mentioned wetting agent can be the TEGO245 and the TEGO500 of Di Gao company, and serial wetting agents such as the BYK-346 of BYK company etc. are one or more mixtures wherein.
Above-mentioned cosolvent can be a high boiling solvent, as one or more mixtures wherein such as ethylene glycol ethyl ether, butyl glycol ether, Diethylene Glycol butyl ether, propylene glycol monomethyl ether, propylene glycol butyl ether, dipropylene glycol methyl ether.
Above-mentioned defoamer: can be TEGO-800, TEGO-805, TEGO-810, TEGO-815, the TEGO-825 of TEGO company, also BYK-019, the BYK-020 etc. of BYK company one or more mixtures wherein.
Above-mentioned thickening material can be fiber disposition such as Natvosol, wherein a kind of and more than one mixture such as alkali swelling acrylate type such as RM-2020 and polyurethane associative thickener such as SN-612 etc.
Ultimate principle of the present invention: the polynary emulsifier system of selecting for use (as SDBS, DowFax2A-1, OP-10 and EP110 etc.), utilized the sterically hindered effect of negatively charged ion and non-ionic type compound emulsifying agent to produce synergistic effect, improve the stability of dispersion polymerization, effectively controlled the particle diameter and the distribution of dispersion.Utilize the compatibility of different chain length nonionic emulsifier, the hydrophile-lipophile balance value (HLB value) of regulation and control emulsifier system makes it to meet the HLB value of reaction system, make the polymerization system that contains high hydrophilic monomer have the high emulsion polymerization stability, the freeze thaw stability that makes polymeric dispersions have excellence simultaneously reaches the high tolerance to film coalescence aid.The present invention adopts functional self-cross linking monomer, and with the shell (surface of latex particle) of self-crosslinking acrylic ester monomer distribution at latex particle, in film process, because the neutralizing agent volatilization changes system pH, crosslinked group increases in the concentration that is coated with membrane interface, and the speed of crosslinking reaction improves, and films and forms the polymer coating film of solid space network structure at the interface easily, make polymer coating film not only have the high closeness energy, and have excellent physical and mechanical performance and chemical mediator-resitant property.
The high closeness polyacrylacid ester dispersion of the present invention's preparation characterizes with the following method: the particle diameter of dispersion and the employing nano particle size analyser (ZS Nano S) that distributes are measured; Polymer architecture is measured with Fourier infrared spectrograph (FTIR); Second-order transition temperature is measured with the minimum film-forming temperature instrument with differential scanning calorimeter (DSC), minimum film-forming temperature; The latex particle form of dispersion is measured with scanning electron microscope (TEM).Film performance can characterize with the following method: be coated with film dynamic performance and test with the Instron electronic tension tester; The latex film cross-linking density is measured by MEK (methyl ethyl ketone) reflux method of extraction; The pendulum-rocker hardness of filming is measured by GB/T1730-93; Sticking power is pressed GB/T9286-88 cross cross-hatching and is measured; The test of chemical solvent resistance (MEK) is to use by the saturated non-woven paper of MEK to come and go scouring film coated surface, the scouring number of times that record is filmed and just frayed; The closed performance testing method is that the high closeness polyacrylacid dispersion is brushed in black walnut timber surface, drying at room temperature at film coated surface brushing water-based white paint, was observed the yellowing on white paint surface or the closure that the bleeding degree is measured dispersion after one day behind the dried coating film; Thermogravimetic analysis (TGA) adopts thermal gravimetric analyzer (NETZSCH STA 499C) to measure.
High closeness polyacrylacid ester dispersion of the present invention compared with prior art, the polynary emulsification system that the present invention adopts anionic emulsifier and compound nonionic emulsifier to form, the control emulsifying agent has synthesized the room-temperature self crosslinking high closeness polyacrylacid ester dispersion at the charging technology of different polymerization stages by semi-continuous seed emulsion polymerization technology.This dispersion particle diameters is little, electrolyte-resistant (calcium ion) excellent in stability, tolerance height to various film coalescence aid (all kinds of high boiling organic solvent), as the water-borne wood coating seal coat, various timber are comprised three-ply wood, composition board, pine, Black walnuts etc. have excellent closed performance, can closed methanal and other VOC gas from sheet material, overflow, also can seal rosin, colored compound such as pine tar and Weibull is separated out from sheet material and is polluted aqueous woodware varnish lacquer and white finish paint, have excellent physics and chemical property simultaneously, comprise the cross-linking density height of filming, the hardness height, chemical mediator-resitant property is good, Heat stability is good, advantages such as the fast and easy polishing of rate of drying, can be used as the seal coat and the finish paint of the water-borne wood coating of various sheet materials, also can make the water-based hide finishes, have good market outlook.Have the following advantages:
(1) the polynary emulsification system that has adopted anionic emulsifier and compound non-ionic type type emulsifying agent to form has been controlled the reasonable distribution of emulsifying agent at different polymerization stages, has improved monomer conversion and polymerization stability.This dispersion particle diameters is little, electrolyte-resistant (calcium ion) excellent in stability and to the tolerance height of various film coalescence aid (all kinds of high boiling organic solvent).
(2) this dispersion is as the water-borne wood coating seal coat, various timber are comprised that three-ply wood, composition board, pine, Black walnut etc. have excellent closed performance, can closed methanal and other VOC gas from sheet material, overflow and pollute indoor environment, also can seal colored compounds such as rosin, pine tar and Weibull and from sheet material, separate out pollution aqueous woodware varnish lacquer and white finish paint, can solve " yellowing " and " bleeding " problem of water-based white paint.
(3) this dispersion has excellent physics and chemical property, comprise advantages such as cross-linking density height, hardness height, the chemical mediator-resitant property of filming are good, Heat stability is good, the fast and easy polishing of rate of drying, can be used as the seal coat and the finish paint of the water-borne wood coating of various sheet materials, also can make the water-based hide finishes.
(4) the high closeness acrylate dispersoid of the present invention preparation has that emulsifier content is low, solids content is high, at room temperature can the self-crosslinking film forming, have good film-forming properties, excellent in water resistance, scrub resistance and contamination resistance.
(5) polymer emulsion is nontoxic, and is nonflammable.The compound that does not have artificial interpolation halohydrocarbon, benzene,toluene,xylene, formaldehyde and polymkeric substance thereof and heavy metal lead, cadmium chromium, mercury.The content of total volatile organic compound (TVOC) is less than 50g/L in the product.Satisfy the environmental labelling product authentication techniques fully and require water-borne coatings HJ/T201-2005 standard, belong to Green Product.
Embodiment
Embodiment 1
Set of monomers becomes butyl acrylate, methyl methacrylate, methacrylic acid, diacetone-acryloamide(DAA), methacrylic acid ethylidene-urea ethoxylated ester, and its component such as table 1 are listed.
Table 1 polyacrylate dispersion prescription
With 2.7 parts of mixed emulsifiers, buffer reagent, 32.92 part deionized water adds in the reactor, high-speed stirring 20 minutes, and be warming up to 55 ℃, drip 0.4 part of methacrylic acid in 20 minutes, 8.4 part butyl acrylate, the mix monomer of 16 parts of methyl methacrylates, temperature of reaction kettle is risen to 82 ℃, slowly drip the part initiator solution, treat that seed dispersion is blue and also stablizes half an hour mutually, 1.5 drip the good nuclear monomer of pre-emulsification in hour, continue in 2 hours, to drip pre-emulsified shell monomer at interval after 20 minutes, add 4 part 10% initiator solution after all monomer dropping finishes, be warming up to 85 ℃ of slakings 1 hour, cooling, add 10%N, the N-dimethylethanolamine is regulated pH value to 7.5～8.5, and the cold filtration discharging promptly gets translucent polyacrylate dispersion.
Wherein, the preparation method of pre-emulsification nuclear monomer is: add 17.95 parts of deionized waters in Erlenmeyer flask, 0.6 part Sodium dodecylbenzene sulfonate, 0.3 part nonyl phenol polyethoxy ether (OP-10), the high speed magnetic agitation slowly drips 0.9 part of methacrylic acid after 20 minutes, 40.9 part butyl acrylate, 40.9 parts of mix monomers that methyl methacrylate is formed.
The preparation method of pre-emulsification shell monomer is: with 27.95 parts of deionized waters, 0.8 part Sodium dodecylbenzene sulfonate, 0.4 part OP-10 and 1.6 parts of NP-40 join in the Erlenmeyer flask, the high speed magnetic agitation slowly drips 1.0 parts of methacrylic acids after 20 minutes, 24.4 part butyl acrylate, 44.5 part methyl methacrylate, the mix monomer that 5.2 parts of diacetone-acryloamide(DAA)s (DAAM) and 4.0 parts of methacrylic acid ethylidene-urea ethoxylated esters (50%) are formed.
The acrylate differential prose style free from parallelism median size 150nm for preparing, molecular weight 10
5, viscosity: 120cps, pH=8.4, solids content: 45.3%.
Embodiment 2
Use the acrylate dispersoid of preparation among the embodiment 1, preparation woodwork coating prescription such as following table 2.
Table 2 water-borne wood coating prescription
The preparation method is as follows: earlier the 2-8 raw material is joined in the stirring tank, disperseed 10-30 minute with high speed dispersor, then acrylic acid dispersion is slowly joined in the stirring tank, middling speed stirred 30-60 minute, with the pH value of ammoniacal liquor adjusting coating, when the qualified after-filtration of pH value, discharging, packing.The woodwork coating performance of preparing: outward appearance: milky white sub-translucent liquid, do not have mechanical impurity; PH=7-9; Solids content 35-40%, viscosity 30-200cps.Woodenware film performance: the pencil hardness of filming: HB; Water tolerance: immersion 48h does not have considerable change; Sticking power: 1 grade; Snappiness: 1 grade; The closure excellence; Antiblocking: A level.
Embodiment 3
Set of monomers becomes butyl acrylate, methyl methacrylate, methacrylic acid, diacetone-acryloamide(DAA), the methacrylic acid acid amides, and its component is filled a prescription as table 3:
Table 3 polyacrylate dispersion prescription
With 4.0 parts of mixed emulsifiers, buffer reagent, 51.92 part deionized water adds in the reactor, high-speed stirring 20 minutes, and be warming up to 55 ℃, drip 0.5 part of methacrylic acid in 20 minutes, 10.5 part vinylbenzene, 22.5 the mix monomer of part butyl methacrylate, temperature of reaction kettle is warming up to 82 ℃, slowly drip the part initiator solution, treat that seed dispersion is blue and also stablizes half an hour mutually, 1.5 drip the good nuclear monomer of pre-emulsification in hour, continue in 2 hours, to drip pre-emulsified shell monomer at interval after 20 minutes, add 4 part 10% initiator solution after all monomer dropping finishes, be warming up to 85 ℃ of slakings 1 hour, cooling adds triethylamine and regulates pH value to 7.5～8.5, the cold filtration discharging promptly gets translucent acrylate dispersoid.
Wherein, the preparation method of pre-emulsification nuclear monomer is: add 79.5 parts of deionized waters in Erlenmeyer flask, 2 parts of Dowfax 2A-1,1 part of nonyl phenol polyethoxy ether (OP-10), the high speed magnetic agitation slowly drips 3 parts of methacrylic acids after 20 minutes, 87 parts of vinylbenzene, 113 parts of mix monomers that the butyl methacrylate ester is formed.
The preparation method of pre-emulsification shell monomer is: with 79.5 parts of deionized waters, 2 parts of Dowfax 2A-1,1 part of nonyl phenol polyethoxy ether (OP-10) and 4 parts of NP-40 join in the Erlenmeyer flask, the high speed magnetic agitation slowly drips 3 parts of methacrylic acids after 20 minutes, 50 parts of vinylbenzene, 100 parts of butyl methacrylate, 10 parts of diacetone-acryloamide(DAA)s (DAAM) and 5.0 parts of mix monomers that Methacrylamide is formed.
The polyacrylate dispersion median size 130nm for preparing, molecular weight 10
5, viscosity: 90cps, pH=8.0, solids content: 45.7%.
Embodiment 4
Use the acrylate dispersoid of preparation among the embodiment 3, preparation woodwork coating prescription such as following table 4.
Table 4 water-borne wood coating prescription
The preparation method is as follows: earlier the 2-8 raw material is joined in the stirring tank, disperseed 10-30 minute with high speed dispersor, then acrylic acid dispersion is slowly joined in the stirring tank, middling speed stirred 30-60 minute, with the pH value of ammoniacal liquor adjusting coating, when the qualified after-filtration of pH value, discharging, packing.The woodwork coating performance of preparing: outward appearance: milky white sub-translucent liquid, do not have mechanical impurity; PH=7-9; Solids content 35-40%, viscosity 30-200cps.Woodenware film performance: the pencil hardness of filming: HB; Water tolerance: immersion 48h does not have considerable change; Sticking power: 1 grade; Snappiness: 1 grade; The closure excellence; Antiblocking: A level.
Performance relatively
The performance of the woodenware use seal coat of the polyacrylate dispersion of embodiment 1 and 3 and embodiment 2 and 4 is compared with pure-acrylic emulsion and film performance thereof respectively, and testing data is listed in table 5.
Table 5 high closeness polyacrylacid ester dispersion and the over-all properties of filming
Table 5 explanation the present invention prepares the high closeness polyacrylacid ester dispersion woodwork coating and compares with the pure acrylic acid woodwork coating, the hardness of filming, degree of crosslinking, medium-resistance closure and antiblocking performance all improve a lot, can be widely used in the water-borne wood coating industry, solve the pollution of ground, have bigger industrial application value and market outlook aqueous pigmented finish paint.
Claims (6)
1. the preparation method of a high closeness polyacrylacid ester dispersion is characterized in that its acrylate monomer is composed as follows:
---alkyl acrylate, consumption are 10～50% of monomer total mass;
---alkyl methacrylate, consumption are 10～60% of monomer total mass;
---acrylic acid hydroxy alkyl ester, consumption are 0.1～15% of monomer total mass;
---alkyl acrylic, consumption are 0.1～20% of monomer total mass;
---other acrylate functional monomer, consumption are 0.1～15% of monomer total mass;
---vinyl aromatic compound, consumption are 1～60% of monomer total mass;
Described alkyl acrylate is one or more mixtures in methyl acrylate, ethyl propenoate, butyl acrylate, vinylformic acid pentyl ester, Ethyl acrylate, the 2-EHA;
Described alkyl methacrylate is one or more mixtures in methyl methacrylate, Jia Jibingxisuanyizhi, methacrylic ester propyl ester, butyl methacrylate, methacrylic acid pentyl ester, N-Hexyl methacrylate, n octyl methacrylate, the Isooctyl methacrylate;
Described acrylic acid hydroxy alkyl ester is one or more mixtures in 2-Hydroxy ethyl acrylate, vinylformic acid-3-hydroxy propyl ester, methacrylic acid-2-hydroxy methacrylate, the methacrylic acid-2-hydroxy propyl ester;
Described thiazolinyl carboxylic acid is one or both the mixture in the acrylic or methacrylic acid;
Described vinyl aromatic compounds is one or more mixtures in vinylbenzene, alpha-methyl styrene, 2-chlorostyrene, 3-t-butyl styrene, 3, the 4-dimethyl styrene;
Described other acrylate functional monomer is acrylamide, diacetone-acryloamide(DAA), N hydroxymethyl acrylamide, Methacrylamide, N, N-DMAA, methacrylic acid tert-butyl amine base ethyl ester, Dimethylaminoethyl Methacrylate, glycidyl methacrylate, methacrylic acid tetrahydrofuran ester, ethylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, 1, one or more mixtures in the 6-hexylene glycol acrylate;
Comprise the steps:
(1) preparation seed dispersion: with deionized water, emulsifier system and buffer reagent join in the reactor, under 50 ℃ of water bath condition, stirred 30 minutes, add described acrylate monomer blend then, be warmed up to simultaneously more than 82 ℃, slowly drip initiator solution, insulation 30min in back is standby mutually to treat seed dispersion to be indigo plant; The seed dispersion weight proportion is as follows:
Water 30-80 part
Emulsifier system (1) 2-10 part
Buffer reagent 0.1-5.0 part
Acrylate monomer blend 5-40 part
Initiator 0.1-5.0 part;
(2) drip the nuclear layer monomer pre-emulsion: constant speed drips alkyl methacrylate, alkyl acrylate, alkyl acrylic and the monomeric pre-emulsion of acrylate functional in above-mentioned seed dispersion in 1.5 hours, keep suitable initiator rate of addition simultaneously, temperature of reaction is controlled at 82-85 ℃; Nuclear layer monomer pre-emulsion weight proportion is as follows:
Water 10-80 part
Emulsifier system (2) 1-10 part
Alkyl methacrylate, alkyl acrylate and alkyl acrylic mixture 80-200 part
Acrylate functional monomer 0.1-10 part
The initiator massfraction is 1.0% 0.1-2.0 part;
(3) drip the shell monomers pre-emulsion: treat that the dispersion nuclear monomer dropwises, insulation half an hour begin to drip the shell monomer pre-emulsion, dripped off with interior in 2 hours, constant speed drips initiator solution simultaneously, and control reaction temperature is 82-85 ℃; Shell monomers pre-emulsion weight proportion is as follows:
Water 20-80 part
Emulsifier system (3) 1-5 part
Alkyl acrylate 100-150 part
Alkyl acrylic 1-3 part
Acrylate functional monomer 2-15 part
Neutralizing agent 2-6 part
The initiator massfraction is 1.0% 0.5-2.0 part;
(4) treat that the shell monomer pre-emulsion dropwises, add an amount of initiator, reaction system is warmed up to 85 ℃ continues reaction 2 hours, cool to 50 ℃, regulate the pH value to 8.0-10.0, the discharging packing with neutralizing agent;
The polyacrylate dispersion number-average molecular weight that obtains is 10
3-10
6, molecular weight distribution is 1.0-50, and latex particle size is in 300 nanometers, and the dispersion solids content is more than 45%, the second-order transition temperature of polymkeric substance-20～80 ℃;
Described emulsifier system is the polynary emulsifier system of anion surfactant and multiple nonionic surface active agent, and described anionic emulsifier is a kind of in Sodium dodecylbenzene sulfonate, sodium lauryl sulphate, alkyl diphenyl ether disodium sulfonate salt, dodecylbenzene phenyl ether sodium disulfonate, oxyethyl group disodium sulfosuccinate, sodium vinyl sulfonate, alkyl amido sodium vinyl sulfonate and the alkylaryl sulphonate and more than one mixture; Described nonionic surface active agent is one or more the mixture among alkylphenol and ethylene oxide condensate, glycol fatty acid ester, propylene glycol fatty acid ester, nonyl phenol polyethoxy ether, polyoxyethylene nonylphenol ether, sorbitan monostearate, polyoxyethylene sorbitan Triolein, polyoxyethylene 20 sorbitan monolaurate, the TX-100; The mass ratio of total anion surfactant and nonionic surface active agent is 1-4: 2-10; The moon/the nonsurfactant ratio is 1: 0.1-4 in the emulsifier system (1); The moon/the nonsurfactant ratio is 1: 0.1-3 in the emulsifier system (2); The moon/the nonsurfactant ratio is 1: 0.1-10 in the emulsifier system (3).
2. method according to claim 1 is characterized in that described initiator is Potassium Persulphate, ammonium persulphate, sodium bisulfite-Potassium Persulphate, hydrogen peroxide-iron protochloride, Potassium Persulphate-iron protochloride, isopropyl benzene hydroperoxide-iron protochloride or its compound system.
3. method according to claim 2 is characterized in that described neutralizing agent is N, the mixture of one or more in N-dimethylethanolamine, ammoniacal liquor, triethylamine, sodium hydroxide, the potassium hydroxide.
4. method according to claim 3 is characterized in that described buffer reagent is wherein one or more a mixture of sodium bicarbonate, sodium bisulfite, sodium pyrosulfate, SODIUM PHOSPHATE, MONOBASIC.
5. the high closeness polyacrylacid ester dispersion of the described method of one of claim 1-4 preparation.
6. the application of high closeness polyacrylacid ester dispersion in the preparation water-borne wood coating of the described method preparation of one of claim 1-4.
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