CN101481451B - High solid content latent curing polyurethane acroleic acid hybrid emulsion - Google Patents

High solid content latent curing polyurethane acroleic acid hybrid emulsion Download PDF

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CN101481451B
CN101481451B CN200910036941XA CN200910036941A CN101481451B CN 101481451 B CN101481451 B CN 101481451B CN 200910036941X A CN200910036941X A CN 200910036941XA CN 200910036941 A CN200910036941 A CN 200910036941A CN 101481451 B CN101481451 B CN 101481451B
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emulsion
solid content
latex
latent curing
polyurethane
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CN101481451A (en
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瞿金清
黎永津
黄洪
陈焕钦
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South China University of Technology SCUT
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South China University of Technology SCUT
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Abstract

The invention relates to a method for preparing a high solid content latent cured polyurethane acrylic acid heterozygous latex and an application thereof. The preparation method comprises the following steps: pre-polymerizing polyester polyalcohol, hydrophilic chain extender and diisocyanate monomer to obtain the polyurethane prepolymer containing a hydrophilic group (carboxyl or sulfo group) and a terminal NCO group; then, neutralizing the polymer into salt and dispersing the salt in water to prepare the polyurethane water dispersoid; finally, using the dispersoid as macro molecular emulsifying agent and reactant to emulsify and disperse the acrylic ester monomer, initiating the polymerization by heating, dropping initiator to perform the latex polymerization, and regulating the pH of the latex by adding a latent curing agent to obtain the high solid content latent cured polyurethane acrylic acid heterozygous latex. The high solid content latent cured polyurethane acrylic acid heterozygous latex has a solid content of above 45%; the storage of the high solid content latent cured polyurethane acrylic acid heterozygous latex is stable; and high hardness film coating can be formed at the room temperature. Compared with acrylic acid latex and polyurethane latex, the high solid content latent cured polyurethane acrylic acid heterozygous latex has better film forming performance, water resistance, alcohol resistance, pollution resistance, dry/wet cleaning resistance and chemical solvent resistance, as well as high hardness.

Description

High solid content latent curing polyurethane acroleic acid hybrid emulsion
Technical field
The present invention relates to high solid content latent curing polyurethane acroleic acid hybrid emulsion.
Technical background
Along with the appearance of resource and energy dilemma and 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 woodwork coatings such as polyacrylic ester (PA) emulsion, urethane (PU) water dispersion and acroleic acid polyurethane compound (PUA) emulsion.The PU emulsion film has excellent solvent resistance, wear resistance, scratch resistance and snappiness and elasticity etc. preferably, but in stability, not fully up to expectations from aspects such as thickening property, solids content, gloss, costs; The advantage of PA emulsion film is big, good with outward appearance and the relative low cost of weathering resistance of hardness, but snappiness, wear resistance, chemical-resistant are relatively poor.The PUA emulsion makes it two kinds of emulsion combinations have complementary advantages.By chemical copolymerization gained polyacrylic ester-urethane (PUA) composite emulsion, it is filmed than the superior performance of physical blending thing.The preparation method of PUA composite emulsion comprises seed emulsion polymerization, situ aggregation method and solution polymerization phase inversion process.The resulting PUA emulsion solids of aforesaid method content low (30-35%), appearance of film is bad, and gloss is lower, and because the feasible cross-linking density of filming of preparation method's limitation is low, water-fast, anti-alcohol, alkaline-resisting and stain resistance is bad, hardness is not high yet, can't compare with the solvent-borne type woodwork coating.Though the physical blending method can to a certain degree improve the solids content of emulsion, can reduce the physical and mechanical properties of filming.The amount of solid content that improves the PUA emulsion does not at present also have method preferably, yet rarer pertinent literature report.On the other hand, adopt cross-linking modified chemical-resistant, hardness and the cross-linking density of filming that improve.Cross-linking modified comprising: based on cross-linking systems such as Michael reaction, aziridine or carbonization imines/carboxylic acid, siloxanes hydrolytic condensation, acetoacetyl/polyamine, active carbonyl/hydrazides (ketone hydrazine) and cyclic carbonate/amidos; but for the PUA system, all can cause the package stability of emulsion to descend; increase the emulsion cost; maybe can improve the content of volatile organic compound of emulsion, perhaps adopt bi-component package to make troubles for the application and construction of woodwork coating.U.S. Pat P6063861 (2000.5.16) is seed emulsion with the aqueous polyurethane emulsion, adopt the polyurethane acroleic acid emulsion of monomer such as the acrylamide and the vinylformic acid acetate acetyl triethyl prepared in reaction energy self-crosslinking of energy self-crosslinking, store unstable under its room temperature; We are by analyzing the structure of PUA emulsion, advantage in conjunction with ACRYLIC EMULSION, adopt self-emulsification aqueous polyaminoester emulsion as macromole emulsifying agent and reactant, earlier acrylate monomer being carried out emulsification disperses, improve the solids content of emulsion, adopt the thermal-initiated polymerization of acrylate monomer and initiator initiated polymerization to combine simultaneously.This technology can improve acrylate monomer stability of emulsion polymerization and solids content; Add the influence that latent curing agent is eliminated the hydrophilic radical on the PUA molecular chain by the back, improve the cross-linking density and the hardness of film of filming.Filming of this emulsion preparation has excellent in water resistance, solvent resistance, high rigidity and appearance of film preferably.
Summary of the invention
The invention provides the preparation method of latent curing polyurethane acroleic acid hybrid emulsion
A further object of the invention is that high solid content latent curing polyurethane acroleic acid hybrid emulsion of the present invention is used as woodwork coating.
The present invention adopts the self-emulsifying polyaminoester emulsion as macromole emulsifying agent and reactant, adopt the thermal-initiated polymerization and the initiator initiated polymerization of Acrylic Acid Monomer to combine, add the high solid content latent curing polyurethane acroleic acid hybrid emulsion of latent curing agent processability excellence.
High solid content latent curing polyurethane acroleic acid hybrid emulsion of the present invention, it is prepared by following feed composition:
---polyvalent alcohol, number average relative molecular mass are 30-10000, and hydroxyl value is 15-500mgKOH/g, and consumption is the 5-70% of total solids quality;
---diisocyanate monomer, consumption are the 15-65% of total solids quality;
---hydrophilic chain extender, consumption are the 1-15% of total solids quality;
---small molecule chain extender, consumption are the 0.1%-20% of total raw material;
---amine chain extender, consumption are the 0.1-15% of total solids quality;
---latent curing agent, consumption are the 0.1-15% of total solids quality.
---acrylate monomer, consumption are the 5-60% of total solids quality.
---neutralizing agent is a basic cpd, the 1-10% of its consumption total solids quality.
The present invention's preparation earlier contains the polyurethane prepolymer of hydrophilic radical (carboxyl and sulfonic group) and end NCO base, in prepare aqueous polyurethane emulsion with emulsification.Then by the emulsion polymerization prepared high solid content latent curing polyurethane acroleic acid hybrid emulsion.Its concrete step comprises:
1) raw-material preparation and processing: be that 70-120 ℃, vacuum tightness are vacuum hydro-extraction 1.0-4.0h under the 0.05-0.12Mpa with polyvalent alcohol in temperature in reactor, it is standby to lower the temperature then; Solvent and chainextender etc. make its water content less than 0.05% by processed.
2) preparation of base polyurethane prepolymer for use as: in the reactor that thermometer, agitator, condenser and nitrogen protection device are housed, add polyvalent alcohol, hydrophilic chain extender, small molecule chain extender and solvent, be warming up to 60 ℃ and open to stir and make it become homogeneous system.Slowly add diisocyanate monomer and catalyzer to reaction system then, be warming up to 60-120 ℃, be incubated 3.0-7.0 hour, the content of NCO group in the analytical reaction thing, when reaching prescribed value, cooling obtains containing the polyurethane prepolymer that hydrophilic radical and end group contain the NCO base.
3) above-mentioned polyurethane prepolymer is cooled to about 30-60 ℃, add in the neutralizing agent stirring of measuring and after 1-60 minute, neutralized reaction product is moved in the emulsification still, the base polyurethane prepolymer for use as high speed emulsification of becoming reconciled in joining quantitative deionized water, add amine chain extender after emulsification is finished and carried out chain extension 3-60 minute, obtain aqueous polyurethane emulsion.
4) with above-mentioned aqueous polyurethane emulsion as macromole emulsifying agent emulsion acrylic ester monomer, the mass ratio of macromole emulsifying agent and acrylate monomer is 1: 0.1-5.0, add an amount of water according to system viscosity in the emulsion process and be prepared into urethane (PU)/monomer (M) emulsion.
5) above-mentioned PU/M emulsion is carried out thermopolymerization 1-4h at 40-90 ℃.Dropwise addition of acrylic acid ester monomer mass fractional 0.5-3.0% initiator solution then, 2-4h drips off, dropwise, insulation 0.5-3h, adopt thin-film evaporator or step-down distillation to remove low boiling point solvent, be cooled to 30-50 ℃, add latent curing agent, the pH value of adjusting emulsion is filtered discharging then and is obtained high solid content latent curing polyurethane acroleic acid hybrid emulsion between 6.5-11.5.
Described polyvalent alcohol can be wherein one or more mixtures such as polyester polyol, polyether glycol, Viscotrol C, Resins, epoxy, epoxidized vegetable oil, polycarbonate polyol, polytetrahydrofuran polyvalent alcohol, polyurethane polyol, polyacrylate polyol, polyolefin polyhydric alcohol (polybutadiene polyol), polycaprolactone (PCL) polyvalent alcohol and poly-terminal hydroxy group dimethylsilane.
Described vulcabond, it can be tolylene diisocyanate (TDI) (2,4-TDI/2,6-TDI=100/0,80/20 and 60/40), diphenylmethanediisocyanate (MDI) (solid or liquid), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI) and six cyclohexyl diisocyanate (H 6MDI), one or more mixture wherein such as xylylene diisocyanate.
Described small molecules diol chain-extension agent can be 1, the 4-butyleneglycol, and 1, the 6-hexylene glycol, 1,4-cyclohexanediol, ethylene glycol, propylene glycol, Diethylene Glycol, glycol ether equimolecular quantity are less than one or more mixture wherein such as dibasic alcohol of 500.
Described hydrophilic chain extender is dihydroxyl alkyl acid/sulfonate or diamines yl carboxylic acid/sulfonate, can be dihydroxymethyl acetate, dimethylol propionic acid (DMPA), dimethylolpropionic acid (DMBA), dihydroxymethyl valeric acid/sulfonate etc. are one or more mixtures wherein.
Described latent curing agent, it is characterized in that this solidifying agent contain at least can with the group of carboxylic acid or amido reaction, and this reaction can be subjected to the control of pH value, o'clock just react in pH<7.0, this class group comprises the compound of epoxy group(ing), aziridine and groups such as nitrogenize imines and active ketone hydrazine, and such latent curing agent can be wherein one or more mixtures such as the siloxanes (1-4) that contains epoxy group(ing) (structure as shown in the formula), many aziridine, poly-nitrogenize diimine.
Figure G200910036941XD00051
γ-glycidyl alkyltrialkoxysilaneand γ-glycidyl alkyl dialkoxy alkyl silane
Figure G200910036941XD00052
β-(3,4-epoxy group(ing) cyclohexyl) alkyltrialkoxysilaneand β-(3,4-epoxy group(ing) cyclohexyl) alkyl dialkoxy alkyl silane
n=0-10 R=-CH 3,-C 2H 5,-(n?or?i)C 3H 7,-(n?or?i)C 4H 10
Described acrylate monomer can be wherein one or more mixtures such as methyl acrylate, ethyl propenoate, Propylene glycol monoacrylate, propyl acrylate, butyl acrylate, methyl methacrylate, Jia Jibingxisuanyizhi, hydroxyethyl methylacrylate, butyl methacrylate, vinylbenzene, vinyl toluene, isobornyl acrylate, the different new ester of vinylformic acid.
Described initiator can be an oil-soluble initiator, can be Diisopropyl azodicarboxylate, benzoyl peroxide, and tert-butyl peroxide etc. also can be water soluble starter such as Potassium Persulphate, ammonium persulphate; Also redox system such as sodium bisulfite-Potassium Persulphate, hydrogen peroxide-iron protochloride, Potassium Persulphate-iron protochloride, isopropyl benzene hydroperoxide-iron protochloride etc.
Described aqueous polyurethane emulsion carries out emulsification as macromole emulsifying agent to acrylate monomer, and its emulsification rotating speed is at 1000-10000 rev/min; Emulsification times is 5-60 minute;
Described emulsion polymerization technique is the segmentation emulsion polymerization technique: promptly earlier at 40-90 ℃ thermal-initiated polymerization is arranged; Be the initiator initiated polymerization then.Dropping initiator technology can be to drip promptly continuously to drip continuously in 2-5 hour, also can be that intermittently segmentation dropping was promptly only per hour dripping in 2-5 hour in preceding 10 minutes.
Described high solid content latent curing polyurethane acroleic acid hybrid emulsion is as the application of water-borne wood coating.
Ultimate principle of the present invention: the present invention selects for use aqueous polyurethane emulsion as macromole emulsifying agent and reactant, comes the emulsion acrylic esters monomer with it, improves the solids content of final polymer emulsion; PU also can carry out graft polymerization reaction with acrylic ester monomer simultaneously, the performance of improving the PUA emulsion and filming.In emulsion polymerization process, adopt thermal-initiated polymerization and initiator initiated polymerization to combine, guarantee stability of emulsion polymerization and package stability.On the other hand, contain hydrophilic radical such as amido and carboxyl on the PUA molecular chain, the hydrophilic radical that remains on the polymeric film can reduce resistant to chemical media and stain resistances such as polymer emulsion water tolerance, alcohol resistance, by adding latent curing agent, in the emulsion storage process,, guarantee the shelf-stable of emulsion because pH value higher (greater than 7.0) latent curing agent can not react with hydrophilic radical; In the polymer emulsion film process because the volatilization of neutralizing agent, the pH value of film forming system reduces, and causes latent curing agent generation crosslinking reaction, comprises carboxyl on the PUA molecular chain and the epoxy reaction on the latent curing agent, latent curing agent is incorporated on the PUA molecular chain, eliminates the influence of hydrophilic radical; Hydrolysis-condensation reaction can take place in the siloxanes of latent curing agent under low pH value simultaneously, improves relative molecular mass and the cross-linking density of PUA, thereby improves the physical and chemical performance of filming.So high solid content latent curing polyurethane acroleic acid hybrid emulsion of the present invention's preparation, be have highly filled, do not contain the outer emulsifying agent that adds, at room temperature can the self-crosslinking film forming, have good film-forming properties, excellent in water resistance, scrub resistance, chemical solvent resistance, contamination resistance and anti stickness power, the cross-linking density height of filming, sticking power is good, can be widely used in binder resins such as high-grade water-borne wood coating, waterproof paint and waterborne metallic paint and aqueous adhesive and printing ink.
High solid content latent curing polyurethane acroleic acid hybrid emulsion of the present invention compared with prior art has the following advantages:
1. the solids content height of emulsion, the resulting PUA emulsion solids of the present invention content reaches more than 45% (massfraction), substantially exceeds the solids content (30-35%) of conventional PUA emulsion.Adopt the woodwork coating of emulsion preparation of the present invention to be easy to prepare filming of high gloss, the fullness ratio height of filming, outward appearance is good; Adopt the high solid coating of emulsion preparation of the present invention simultaneously, can reduce construction times, save construction cost.
2. 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.
3. adopting the self-emulsifying polyaminoester emulsion is macromole emulsifying agent and reactant, in whole emulsion preparation process, do not add and comprise the low molecular tensio-active agent of OP-10 class, avoid using deleterious polyoxyethylene nonylphenol ether series products, but, improve the final solids content of PUA emulsion by macromole emulsifying agent emulsion acrylic esters monomer.
4. the polymerization technique that adopts thermal-initiated polymerization and initiator initiated polymerization to combine in the polymerization process adopts initiator to drip technology flexibly, improves monomeric transformation efficiency, guarantees the polymerization stability and the package stability of PUA emulsion.
5. adding latent curing agent by the back makes emulsion that crosslinking reaction take place in film process, hydrophilic radical during elimination PUA films, improve the relative molecular mass of film-forming polymer and the cross-linking density of filming, further improve water tolerance, alcohol resistance and anti-other chemical mediator performance of filming.
6. this technology synthetic is to be shell with urethane, and polyacrylic ester is the hud typed PUA emulsion of nuclear.Combine the good physical and mechanical properties of the excellent film-forming properties and the acrylic ester emulsion of polyaminoester emulsion, this nucleocapsid structure can improve the film-forming properties of emulsion, reduce the usage quantity of film coalescence aid and the content of volatile organic compound of water-borne wood coating, improve the mechanical property of filming simultaneously and particularly improved hardness of film, increased the contamination resistance of filming.
7. high solid content latent curing polyurethane acroleic acid hybrid emulsion of the present invention than the polyaminoester emulsion under the similarity condition have more superior water tolerance, scrub resistance, chemical solvent resistance, weathering resistance, contamination resistance, anti-stickly put forth effort, degree of crosslinking, sticking power, hardness and tensile strength, be widely used in that high-grade water-borne wood coating, waterproof paint and the decoration of metal alloy sheet material are coated with and aqueous adhesive etc.The coating performance index such as the table 1 of acroleic acid polyurethane graft copolymer emulsion woodwork coating of the present invention.
Table 1. water-borne wood coating performance index
Project Technical indicator The water-based matte varnish The bright clear finish of water-based jade-like stone The water-based light white finish paint of making mute
At condition in container Stir evenly no lump of back Meet Meet Meet
Fineness/μ m ≤50 35 35 40
Non-volatile matter/% ≥30 40 41 58
Surface drying time/min ≤30 Meet Meet Meet
Do solid work time/h ≤6 Meet Meet Meet
Package stability ((50 ± 2) ℃/7d) No abnormal Meet Meet Meet
Freeze-thaw resistance a Never degenerate Meet Meet Meet
Appearance of film Normally Meet Meet Meet
Gloss (60 °) 28.4 98 21.0
Grinability Good Good Good
Hardness (scratch) ≥B H H 2H
Sticking power (drawing compartment)/level apart from 2mm ≤1 0 0 0
Shock-resistance Film not have and come off, do not have cracking Meet Meet Meet
Resistance to blocking (500g, (50 ± 2) ℃/4h) MM:A-0 MB:A-0 MM:A -0 MM:A -0 MM:A-0 MB:A-0
MB:A -0 MB:A -0
Wear resistance (750g/500r)/g ≤0.030 0.006 0.006 0.006
Scratch resistance (100g) Do not scratch Meet Meet Meet
Water tolerance (96h) No abnormal Meet Meet Meet
Resistance to boiling water (15min) No abnormal Meet Meet Meet
Alkali resistance (50g/L NaHCO 3,1h) No abnormal Meet Meet Meet
Alcohol resistance (50%, 1h) No abnormal Meet Meet Meet
Anti-vinegar No abnormal Meet Meet Meet
Anti-green tea No abnormal Meet Meet Meet
Dry heat resistance/level [(70 ± 2) ℃, 15min, level ≤2 1 1 1
Yellowing resistance b(168h)ΔE * ≤3.0 -- -- 2.4
Benzene,toluene,xylene, ethylbenzene summation, mg/kg ≤500 5.0 3.8 2.7
Halohydrocarbon, mg/kg ≤500 8.5 8.5 8.5
Formaldehyde and yuban, mg/kg ≤100 40 40 40
Total volatile organic compound (TVOC)/(g/L) ≤300 62 56 74
Heavy metal/(mg/kg) (except the varnish)
Dissoluble lead ≤90 Do not detect Do not detect Do not detect
Soluble cadmium ≤75 Do not detect Do not detect Do not detect
Soluble chromium ≤60 Do not detect Do not detect Do not detect
Soluble mercury ≤60 Do not detect Do not detect Do not detect
PUA emulsion property to the present invention's preparation can characterize with the following method: the emulsion particle diameter and the automatic particle diameter instrument of employing Autosizer Lo-c that distributes are measured; Being coated with film dynamic performance tests with the Instron electronic tension tester; Polymer architecture is measured with Fourier infrared spectrograph (FTIR); The emulsion second-order transition temperature is measured with the minimum film-forming temperature instrument with differential scanning calorimeter (DSC), minimum film-forming temperature; Latex particle form (nucleocapsid structure) is measured with scanning electron microscope (TEM); The cross-linking density of filming is measured by the method for Soxhlet extractor (methyl ethyl ketone is a solvent); The pencil hardness of filming is measured by ASTM-3364; 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.
Embodiment
Below be specific embodiments of the invention, but be not limited to described embodiment.
Embodiment 1
Adopt high solid content latent curing polyurethane acroleic acid hybrid emulsion, its recipe ingredient is listed in table 2.
Table 2 high solid content latent curing polyurethane acroleic acid hybrid emulsion
Under the drying nitrogen protection; polyether glycol N210, N220, BDO and the DMPA that dewatered joined in the 1000ml four-hole boiling flask that thermometer, whipping appts and reflux exchanger are housed; add minor N-methyl-2-pyrrolidone; be warming up to 60 ℃ and open stirring; begin to drip TDI when reaction system becomes when transparent, dripped off in 1 hour.70 ℃-80 ℃ reactions 3-5 hour, judge reaction end with the n-butylamine titration method.Be cooled to 40 ℃ after reaching terminal point, add the triethylamine neutralization, add acetone diluted, the quadrol chain extension is used in emulsification in normal-temperature water, obtains aqueous polyurethane dispersion (PUD).
Under high-speed stirring, in the dispersion bucket that above-mentioned polyaminoester emulsion is housed, slowly add acrylic ester monomer, high speed dispersion is 20 minutes then, this emulsion is joined in the 1000ml four-hole boiling flask that thermometer, whipping appts and reflux exchanger are housed, at 70-75 ℃ of insulation 1.0-2.0h, substep drips initiator emulsion, divide and drip for three times, every 1h drips 1 time, dropwise insulation 1h, treat that the acrylate monomer transformation efficiency reaches 98% when above, cool to 50 ℃, interpolation contains epoxysilicone (1), regulates more than the pH value to 7.0 of emulsion.Discharging, filter, package spare.This emulsion solids content 45% has fabulous stability to hydrolysis and package stability.Hardness of film is higher, water-tolerant, solvent resistance are good, can be used as various water-borne wood coatings.
Embodiment 2
Use the high solid content latent curing polyurethane acroleic acid hybrid emulsion of preparation among the embodiment 1, preparation woodwork coating prescription such as following table 3.
Table 3 water-borne wood coating prescription
Sequence number Form Mass percent, %
1 PUA emulsion in the example 1 88
2 Deionized water 8.1
3 Film coalescence aid (dipropylene glycol butyl ether) 3.0
4 Wetting agent (TEGO-245) 0.2
5 Defoamer (TEGO-805) 0.05
6 Flow agent (BYK-330) 0.1
7 Thickening material (RM2020) 0.15
8 PH value conditioning agent (AMP-95) 0.20
9 Mould inhibitor 0.20
Amount to 100
The preparation method is as follows: earlier the 2-9 raw material is joined in the stirring tank, disperseed 10-30 minute with high speed dispersor, then the PUA emulsion is slowly joined in the stirring tank, middling speed stirred 30-60 minute, the pH value of regulating coating with AMP-95, filtration when pH>7.0, 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 35-42%, viscosity 30-200cps.Woodenware film performance: the pencil hardness of filming: H; Water tolerance: immersion 96h does not have considerable change; Sticking power: 1 grade; Impact strength: 50kg.cm; Snappiness: 1 grade;
Example 3
Use the pure and mild aliphatic diisocyanate prepared in reaction of polyester binary high solid content latent curing polyurethane acroleic acid hybrid emulsion, used starting material are listed in table 4.
Table 4 high solid content latent curing polyurethane acroleic acid hybrid emulsion
Figure G200910036941XD00121
Figure G200910036941XD00131
Under the drying nitrogen protection; polyether glycol N210, T1136, BDO and the DMPA that dewatered joined in the 1000ml four-hole boiling flask that thermometer, whipping appts and reflux exchanger are housed; add minor N-methyl-2-pyrrolidone; be warming up to 60 ℃ and open stirring; begin to drip IPDI when reaction system becomes when transparent, dripped off in 1 hour, add catalyzer then; 70 ℃-80 ℃ reactions 3-5 hour, judge reaction end with the n-butylamine titration method.Be cooled to 40 ℃ after reaching terminal point, add the triethylamine neutralization, add acetone diluted, the quadrol chain extension is used in emulsification in normal-temperature water, obtains aqueous polyurethane dispersion (PUD).
Under high-speed stirring, in the dispersion bucket that above-mentioned polyaminoester emulsion is housed, slowly add acrylic ester monomer, high speed dispersion is 20 minutes then, this emulsion is joined in the 1000ml four-hole boiling flask that thermometer, whipping appts and reflux exchanger are housed, at 70-75 ℃ of insulation 1.0-2.0h, drip initiator solution in three hours continuously, dropwise insulation 1h, treat that the acrylate monomer transformation efficiency reaches 98% when above, cool to 50 ℃, add epoxysilicone (3), regulate more than the pH value to 7.0 of emulsion.Discharging, filter, package spare.This emulsion solids content 45% is mixed with water-borne wood coating, advantage such as have feel nature, winter hardiness is good, water-fast and anti-doing/wet rubbing is good.
Embodiment 2
Use the emulsion of preparation among the embodiment 3, preparation woodwork coating prescription such as following table 5.
Table 5 water-borne wood coating prescription
Sequence number Form Mass percent, %
1 High solid content latent curing polyurethane acroleic acid hybrid emulsion in the example 1 85
2 The dipropylene glycol butyl ether 4
3 Wetting agent (BYK-346) 0.25
4 Defoamer (TEGO-805) 0.25
5 Flow agent (BYK-330) 0.15
6 Thickening material (SN-612) 0.15
7 Surface slip agent (TEGO-440) 0.20
8 Deionized water 9.8
9 Mould inhibitor 0.2
Amount to 100
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, slowly join high solid content latent curing polyurethane acroleic acid hybrid emulsion in the stirring tank then, 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 38-42%, viscosity 30-200cps.Woodenware film performance: the pencil hardness of filming: H; Water tolerance: immersion 96 no considerable changes; Sticking power: 1 grade; Impact strength: 50kg.cm; Snappiness: 1 grade;
Example 5
Adopt Viscotrol C and MDI prepared in reaction acroleic acid polyurethane graft copolymer emulsion.Raw materials used and component is listed in table 6.
Table 6 acroleic acid polyurethane graft copolymer emulsion
Component Massfraction
1 hexylene glycol (HDO) 8.0
2 polyester polyols (T1136) 10
3 dimethylol propionic acids (DMPA) 6.5
4 Viscotrol C 30.0
5 diphenylmethanediisocyanates (MDI) 60.0
6 triethylamines (TEA) 4.0
7 quadrols (EDA) 0.8
8 methyl methacrylates (MMA) 40.0
9 vinylbenzene (ST) 30.0
10 butyl acrylates 25.0
11 initiators (AIBN) 0.10
12 epoxysilicones (4) n=2, R=-iC 3H 7 2.0
13 deionized waters 200.0
Under the drying nitrogen protection; Viscotrol C, T1136, BDO and the DMPA that dewatered joined in the 1000ml four-hole boiling flask that thermometer, whipping appts and reflux exchanger are housed; add minor N-methyl-2-pyrrolidone; be warming up to 60 ℃ and open stirring; begin to drip liquefied mdi when reaction system becomes when transparent, dripped off in 1 hour, add catalyzer then; 70 ℃-80 ℃ reactions 3-5 hour, judge reaction end with the n-butylamine titration method.Be cooled to 40 ℃ after reaching terminal point, add the triethylamine neutralization, add acetone diluted, the quadrol chain extension is used in emulsification in normal-temperature water, obtains aqueous polyurethane dispersion (PUD).
Under high-speed stirring, in the dispersion bucket that above-mentioned polyaminoester emulsion is housed, slowly add acrylic ester monomer, high speed dispersion is 20 minutes then, this emulsion is joined in the 1000ml four-hole boiling flask that thermometer, whipping appts and reflux exchanger are housed, at 70-75 ℃ of insulation 1.0-2.0h, substep drips initiator emulsion, divide and drip for three times, every 1h drips 1 time, dropwise insulation 1h, treat that the acrylate monomer transformation efficiency reaches 98% when above, cool to 50 ℃, interpolation contains epoxysilicone (4), regulates more than the pH value to 7.0 of emulsion.Discharging, filter, package spare.Emulsion solids content 45% has fabulous stability to hydrolysis and package stability.Hardness of film is higher, water-tolerant, solvent resistance are good, can be used as water-borne wood coating.
Embodiment 6
Use the microemulsion of preparation among the embodiment 5, preparation woodwork coating prescription such as following table 7.
Table 7 water-borne wood coating prescription
Sequence number Form Mass percent, %
1 PUA emulsion in the example 5 88.5
2 Dipropylene glycol methyl ether 4.5
3 Wetting agent (TEGO-245) 0.2
4 Defoamer (TEGO-805) 0.05
5 Flow agent (BYK-330) 0.1
6 Thickening material (RM2020) 0.15
7 Thickening material (RM8W) 0.10
8 Grinding auxiliary agent 0.15
9 Deionized water 6.25
Amount to 100
The preparation method is as follows: earlier the 2-9 raw material is joined in the stirring tank, disperseed 10-30 minute with high speed dispersor, then the vinylformic acid microemulsion 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 35-45%, viscosity 30-200cps.Woodenware film performance: the pencil hardness of filming: H; Water tolerance: immersion 96h does not have considerable change; Sticking power: 1 grade; Impact strength: 50kg.cm; Snappiness: 1 grade;
Performance relatively
The performance of embodiment 2, embodiment 4 and the water-borne wood coating of embodiment 6 is compared with HG/T3608-1999 solvent-borne type polyester-polyurethane wood lacquer standard, and testing data is listed in table 8.
The performance of table 8 water-borne wood coating relatively
Figure G200910036941XD00171
The high solid content latent curing vinylformic acid microemulsion woodwork coating of table 7 explanation the present invention preparation is compared with solvent-borne type polyester-polyurethane woodwork coating (HG/T3608-1999), the hardness of filming, water tolerance, appearance of film are suitable with the solvent-borne type polyester polyurethane coating, can replace the solvent borne polyester polyurethane coating fully, have bigger prospects for commercial application.

Claims (6)

1. the preparation method of a high solid content latent curing polyurethane acroleic acid hybrid emulsion is characterized in that it is prepared by following feed composition:
---polyvalent alcohol, number average relative molecular mass are 30-10000, and hydroxyl value is 15-500mgKOH/g, and consumption is the 5-70% of total solids quality;
---diisocyanate monomer, consumption are the 15-65% of total solids quality;
---hydrophilic chain extender, consumption are the 1-15% of total solids quality;
---small molecule chain extender, consumption are the 0.1%-20% of total raw material;
---amine chain extender, consumption are the 0.1-15% of total solids quality;
---latent curing agent, consumption are the 0.1-15% of total solids quality.
---in acrylate monomer, vinylbenzene or the vinyl toluene one or more, consumption is the 5-60% of total solids quality.
---neutralizing agent is a basic cpd, the 1-10% of its consumption total solids quality;
Preparation earlier contains the polyurethane prepolymer of hydrophilic radical carboxyl and sulfonic group and end NCO base, in and emulsification prepare aqueous polyurethane emulsion; Then by the emulsion polymerization prepared high solid content latent curing polyurethane acroleic acid hybrid emulsion; Its preparation method comprises the steps:
1) raw-material preparation and processing: be that 70-120 ℃, vacuum tightness are vacuum hydro-extraction 1.0-4.0h under the 0.05-0.12Mpa with polyvalent alcohol in temperature in reactor, it is standby to lower the temperature then; Solvent and chainextender make its water content less than 0.05% quality by processed;
2) preparation of base polyurethane prepolymer for use as: in the reactor that thermometer, agitator, condenser and nitrogen protection device are housed, add polyvalent alcohol, hydrophilic chain extender, small molecule chain extender and solvent, be warming up to 60 ℃ and open to stir and make it become homogeneous system; Slowly add diisocyanate monomer and catalyzer to reaction system then, be warming up to 60-120 ℃, be incubated 3.0-7.0 hour, cooling obtains containing the polyurethane prepolymer that hydrophilic radical and end group contain the NCO base;
3) above-mentioned polyurethane prepolymer is cooled to 30-60 ℃, add in the neutralizing agent stirring of measuring and after 1-60 minute, neutralized reaction product is moved in the emulsification still, the base polyurethane prepolymer for use as high speed emulsification of becoming reconciled in joining deionized water, add amine chain extender after emulsification is finished and carried out chain extension 3-60 minute, obtain aqueous polyurethane emulsion;
4) with above-mentioned aqueous polyurethane emulsion as in macromole emulsifying agent emulsion acrylic ester monomer, vinylbenzene or the vinyl toluene one or more, the mass ratio of one or more in macromole emulsifying agent and acrylate monomer, vinylbenzene or the vinyl toluene is 1: 0.1-5.0, add water and be prepared into urethane (PU)/monomer (M) emulsion in the emulsion process;
5) above-mentioned PU/M emulsion is carried out thermopolymerization 1-4h at 40-90 ℃; The 0.5-3.0% initiator solution of one or more massfractions in dropwise addition of acrylic acid ester monomer, vinylbenzene or the vinyl toluene then, 2-4h drips off, dropwise, insulation 0.5-3h, adopt thin-film evaporator or underpressure distillation to remove low boiling point solvent, be cooled to 30-50 ℃, add latent curing agent, the pH value of regulating emulsion is filtered discharging then between 6.5-11.5;
Described small molecule chain extender is 1,4-butyleneglycol, 1,6-hexylene glycol, 1, the mixture of one or more in 4-cyclohexanediol, ethylene glycol, propylene glycol, Diethylene Glycol, the glycol ether;
Described hydrophilic chain extender is dihydroxyl alkyl acid/sulfonate or diamines yl carboxylic acid/sulfonate, promptly be dihydroxymethyl acetate, dimethylol propionic acid (DMPA), dimethylolpropionic acid (DMBA), one or more mixtures in dihydroxymethyl valeric acid/sulfonate;
Described amine chain extender is a quadrol;
Described acrylate monomer is one or more mixtures in methyl acrylate, ethyl propenoate, Propylene glycol monoacrylate, propyl acrylate, butyl acrylate, methyl methacrylate, Jia Jibingxisuanyizhi, hydroxyethyl methylacrylate, butyl methacrylate, vinylbenzene, vinyl toluene, isobornyl acrylate, the different new ester of vinylformic acid.
2. method according to claim 1 is characterized in that described polyvalent alcohol is one or more mixtures in polyester polyol, polyether glycol, Resins, epoxy, epoxidized vegetable oil, polycarbonate polyol, polyurethane polyol, polyolefin polyhydric alcohol, the poly-terminal hydroxy group dimethylsilane.
3. method according to claim 1 and 2 is characterized in that described vulcabond is tolylene diisocyanate (TDI), diphenylmethanediisocyanate (MDI) solid or liquid, hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI) and six cyclohexyl diisocyanate (H 6MDI), the mixture of one or more in the xylylene diisocyanate.
4. method according to claim 3, it is characterized in that described latent curing agent contain at least can with the group of carboxylic acid or amido reaction, and this reaction can be subjected to the control of pH value, o'clock just react in pH<7.0, this class group comprises epoxy group(ing), the compound of aziridine and nitrogenize imines and active ketone diazanyl group, such latent curing agent is γ-glycidyl alkyltrialkoxysilaneand, γ-glycidyl alkyl dialkoxy alkyl silane, β-(3,4-epoxy group(ing) cyclohexyl) alkyltrialkoxysilaneand, β-(3,4-epoxy group(ing) cyclohexyl) alkyl dialkoxy alkyl silane, many aziridine, one or more mixtures in the poly-nitrogenize diimine.
5. method according to claim 4 is characterized in that described initiator oil-soluble initiator Diisopropyl azodicarboxylate, benzoyl peroxide or tert-butyl peroxide, or water soluble starter Potassium Persulphate or ammonium persulphate; Or redox system.
6. method according to claim 5 is characterized in that the described emulsification rotating speed of step (4) is at 1000-10000 rev/min; Emulsification times is 5-60 minute; The described dropping initiator of step (5) is to drip continuously in 2-5 hour or dripped in 50 minutes at interval in 2-5 hour; The polymkeric substance number-average molecular weight is 10 in the emulsion that obtains 4-10 7, molecular weight distribution is 1.0-200.0, emulsion particle diameter is the 30-5000 nanometer.
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