CN101481451A - High solid content latent curing polyurethane acroleic acid hybrid emulsion - Google Patents
High solid content latent curing polyurethane acroleic acid hybrid emulsion Download PDFInfo
- Publication number
- CN101481451A CN101481451A CNA200910036941XA CN200910036941A CN101481451A CN 101481451 A CN101481451 A CN 101481451A CN A200910036941X A CNA200910036941X A CN A200910036941XA CN 200910036941 A CN200910036941 A CN 200910036941A CN 101481451 A CN101481451 A CN 101481451A
- Authority
- CN
- China
- Prior art keywords
- emulsion
- solid content
- latent curing
- latex
- polyurethane
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Paints Or Removers (AREA)
- Polyurethanes Or Polyureas (AREA)
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
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 5-70% of a total solids quality;
---diisocyanate monomer, consumption are 15-65% of total solids quality;
---hydrophilic chain extender, consumption are 1-15% of total solids quality;
---small molecule chain extender, consumption are 0.1%-20% of total raw material;
---amine chain extender, consumption are 0.1-15% of total solids quality;
---latent curing agent, consumption are 0.1-15% of total solids quality.
---acrylate monomer, consumption are 5-60% of total solids quality.
---neutralizing agent is a basic cpd, 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 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 hours, 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 minutes, 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, adds an amount of water according to system viscosity in the emulsion process and is 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.
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
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/mins; Emulsification times is 5-60 minutes;
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, advance-go on foot to 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)△E * | ≤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
The drying nitrogen protection down; 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 2-No. 9 raw materials are joined in the stirring tank, disperseed 10-30 minutes with high speed dispersor, then the PUA emulsion is slowly joined in the stirring tank, middling speed stirred 30-60 minutes, the pH value of regulating coating with AMP-95 is as pH〉filtration 7.0 time, 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
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 2-No. 8 raw materials are joined in the stirring tank, disperseed 10-30 minutes 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 minutes, 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.The woodenware film performance:
Pencil hardness: H films; 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 2-No. 9 raw materials are joined in the stirring tank, disperseed 10-30 minutes with high speed dispersor, then the vinylformic acid microemulsion is slowly joined in the stirring tank, middling speed stirred 30-60 minutes, 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
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 (10)
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 5-70% of a total solids quality;
---diisocyanate monomer, consumption are 15-65% of total solids quality;
---hydrophilic chain extender, consumption are 1-15% of total solids quality;
---small molecule chain extender, consumption are 0.1%-20% of total raw material;
---amine chain extender, consumption are 0.1-15% of total solids quality;
---latent curing agent, consumption are 0.1-15% of total solids quality.
---acrylate monomer, consumption are 5-60% of total solids quality.
---neutralizing agent is a basic cpd, 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 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 hours, 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 minutes, 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 macromole emulsifying agent emulsion acrylic ester monomer, the mass ratio of macromole emulsifying agent and acrylate monomer is 1:0.1-5.0, adds water in the emulsion process and is 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 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.
2. method according to claim 1 is characterized in that described polyvalent alcohol is one or more mixtures in 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, the poly-terminal hydroxy group dimethylsilane.
3. method according to claim 1 and 2, it is characterized in that described vulcabond is a 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), the mixture of one or more in the xylylene diisocyanate.
4. method according to claim 3 is characterized in that described small molecules diol chain-extension agent is 1, the 4-butyleneglycol, 1, the 6-hexylene glycol, 1,4-cyclohexanediol, ethylene glycol, propylene glycol, Diethylene Glycol, glycol ether equimolecular quantity are less than one or more the mixture in 500 the dibasic alcohol.
5. method according to claim 4, it is characterized in that 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.
6. method according to claim 5, 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 the compound of epoxy group(ing), aziridine and nitrogenize imines and active ketone diazanyl group, and such latent curing agent is one or more mixtures in the siloxanes (1-4) that contains epoxy group(ing), many aziridine, the poly-nitrogenize diimine.
7. method according to claim 6 is characterized in that 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.
8. method according to claim 7 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 such as sodium bisulfite-Potassium Persulphate, hydrogen peroxide-iron protochloride, Potassium Persulphate-iron protochloride or isopropyl benzene hydroperoxide-iron protochloride.
9. method according to claim 8 is characterized in that the described emulsification rotating speed of step (4) is at 1000-10000 rev/mins; Emulsification times is 5-60 minutes; 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 30-5000 nanometers.
10. the application of high solid content latent curing polyurethane acroleic acid hybrid emulsion in the preparation water-borne wood coating of the described method preparation of one of claim 1-10.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910036941XA CN101481451B (en) | 2009-01-23 | 2009-01-23 | High solid content latent curing polyurethane acroleic acid hybrid emulsion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200910036941XA CN101481451B (en) | 2009-01-23 | 2009-01-23 | High solid content latent curing polyurethane acroleic acid hybrid emulsion |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101481451A true CN101481451A (en) | 2009-07-15 |
| CN101481451B CN101481451B (en) | 2011-06-08 |
Family
ID=40878751
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200910036941XA Expired - Fee Related CN101481451B (en) | 2009-01-23 | 2009-01-23 | High solid content latent curing polyurethane acroleic acid hybrid emulsion |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101481451B (en) |
Cited By (44)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101805514A (en) * | 2010-03-17 | 2010-08-18 | 上海大学 | Castor oil type polyurethane/acrylic resin double-component damping material and preparation method thereof |
| CN101962524A (en) * | 2010-09-29 | 2011-02-02 | 江苏力合粘合剂有限公司 | Waterborne polyurethane adhesive and preparation method thereof |
| CN102093534A (en) * | 2010-12-26 | 2011-06-15 | 华南理工大学 | Preparation method of polyurethane aqueous dispersion and waterborne polyurethane paint containing polyurethane aqueous dispersion |
| CN102363702A (en) * | 2011-06-30 | 2012-02-29 | 成都倍大涂料有限公司 | Aqueous mono-component matte varnish and preparation method thereof |
| CN102367358A (en) * | 2011-06-30 | 2012-03-07 | 成都倍大涂料有限公司 | Waterborne single-component full-glossy white finish and preparation method thereof |
| CN102432795A (en) * | 2011-08-30 | 2012-05-02 | 华南理工大学 | Sulfonic acid type aqueous UV polyurethane modified epoxy acrylic emulsion and preparation method thereof |
| CN102516465A (en) * | 2011-11-19 | 2012-06-27 | 烟台万华聚氨酯股份有限公司 | High-elasticity waterborne polyurethane-acrylate composite resin, and preparation method and application thereof |
| CN102533184A (en) * | 2011-12-15 | 2012-07-04 | 广东达美新材料有限公司 | Water-based pressure-sensitive adhesive of polyethylene protective film and preparation method thereof |
| CN102887985A (en) * | 2011-07-19 | 2013-01-23 | 中科华宇(福建)科技发展有限公司 | Waterborne polyurethane resin production method without wastewater discharge |
| CN102952041A (en) * | 2011-08-25 | 2013-03-06 | 山东轻工业学院 | Polyurethane cross-linked and modified acrylate elastic emulsion and preparation method |
| CN103059230A (en) * | 2013-01-30 | 2013-04-24 | 广东银洋树脂有限公司 | Acrylate modified aqueous polyurethane and preparation method and application thereof |
| WO2013139019A1 (en) * | 2012-03-22 | 2013-09-26 | Dow Global Technologies Llc | Polyurethane/acrylic hybrid dispersions for roof coatings and their preparation |
| CN104530962A (en) * | 2014-12-17 | 2015-04-22 | 宜兴市宁沪精细化工厂 | Waterborne UV wood paint coating and preparation method thereof |
| CN104672395A (en) * | 2015-03-19 | 2015-06-03 | 苏州嘉祥树脂有限公司 | Waterborne composite resin emulsion for fabric slurry |
| CN104725570A (en) * | 2015-01-26 | 2015-06-24 | 陈维林 | Latex and preparation method thereof |
| CN104762014A (en) * | 2015-03-30 | 2015-07-08 | 广西吉宽太阳能设备有限公司 | Polyurethane waterproof mildew-resistant paint and preparation method thereof |
| CN104805995A (en) * | 2015-04-27 | 2015-07-29 | 安徽美祥实业有限公司 | Production process of rubber floorboard |
| CN105218755A (en) * | 2015-10-30 | 2016-01-06 | 江门市珍图新材料有限公司 | A kind of preparation method of the new modified resin being used for making digital ink |
| CN105283527A (en) * | 2013-04-02 | 2016-01-27 | 英派尔科技开发有限公司 | Photo-responsive hydrophilic coating |
| CN105330796A (en) * | 2015-12-16 | 2016-02-17 | 江南大学 | Method for preparing super-hydrophilicity two-component polyurethane modified acrylic resins |
| CN105906771A (en) * | 2016-02-02 | 2016-08-31 | 广东多正化工科技有限公司 | Waterborne polyurethane-acrylate interpenetrating polymer network copolymer emulsion continuous production method and device |
| CN106065060A (en) * | 2016-06-13 | 2016-11-02 | 珠海长先新材料科技股份有限公司 | A kind of high-performance water-based polyurethane resin and preparation method thereof |
| CN106318192A (en) * | 2016-09-12 | 2017-01-11 | 广东玉兰集团股份有限公司 | Water-based waterproof base film for wallpaper and preparation method of water-based waterproof base film |
| CN106400583A (en) * | 2016-08-30 | 2017-02-15 | 成都金箭桥包装材料有限公司 | Post-crosslinked elastic transfer film emulsion and preparation method thereof |
| CN106478958A (en) * | 2016-10-11 | 2017-03-08 | 西北工业大学 | A kind of preparation method of mechanical response latex particle |
| CN106519133A (en) * | 2016-11-10 | 2017-03-22 | 万华化学集团股份有限公司 | Sulfonic acid type waterborne polyurethane-acrylate self extinction resin and preparation method and application thereof |
| CN108102061A (en) * | 2017-11-24 | 2018-06-01 | 南雄市金鸿泰化工新材料有限公司 | A kind of synthetic method of aqueous three-proofing coating polyurethane |
| CN108473650A (en) * | 2015-12-15 | 2018-08-31 | 巴斯夫欧洲公司 | aqueous polymer dispersions for adhesive compounds |
| CN108485510A (en) * | 2018-05-02 | 2018-09-04 | 广东海顺新材料科技有限公司 | A kind of air-dry water-based sealer of woodenware one-component and preparation method thereof |
| CN109054354A (en) * | 2018-07-25 | 2018-12-21 | 佛山皖阳生物科技有限公司 | A kind of preparation method of artificial tree tree bark materials |
| CN109251715A (en) * | 2018-09-20 | 2019-01-22 | 江苏理工学院 | A kind of latent curing type one-pack polyurethane adhesive and preparation method thereof |
| CN109563232A (en) * | 2016-08-03 | 2019-04-02 | Sika技术股份公司 | With the mechanical performance not being affected by temperature substantially and high-intensitive two component polyurethane adhesive |
| CN109642006A (en) * | 2016-08-25 | 2019-04-16 | 巴斯夫欧洲公司 | Polyurethane material with high temperature resistance |
| CN110003397A (en) * | 2019-04-12 | 2019-07-12 | 舟山恒丽新型材料技术有限公司 | Polyurethane-modified resin of large arch dam and preparation method thereof |
| CN110128932A (en) * | 2019-04-30 | 2019-08-16 | 中国人民解放军陆军军事交通学院 | A kind of rubber tyre ageing-proof coating |
| CN110951003A (en) * | 2018-09-27 | 2020-04-03 | 南亚塑胶工业股份有限公司 | Waterborne polyurethane and preparation method thereof |
| CN112080197A (en) * | 2014-12-23 | 2020-12-15 | 帝斯曼知识产权资产管理有限公司 | Aqueous coating composition having soft touch after drying |
| CN113105577A (en) * | 2021-03-23 | 2021-07-13 | 商洛学院 | Repairing agent for heavy metal pollution control and ecological restoration and preparation method thereof |
| CN114015344A (en) * | 2021-11-09 | 2022-02-08 | 上海金狮化工有限公司 | Self-crosslinking aqueous polyurethane-acrylic acid hybrid emulsion and preparation method and application thereof |
| CN114044873A (en) * | 2021-12-13 | 2022-02-15 | 嘉宝莉化工集团股份有限公司 | Polyurethane acrylate dispersion and preparation method thereof, and high-performance water-based wood coating and preparation method thereof |
| CN114058316A (en) * | 2020-08-03 | 2022-02-18 | 浙江卫星石化股份有限公司 | Waterborne polyurethane dispersion with good wettability and preparation method thereof |
| CN115304979A (en) * | 2022-08-25 | 2022-11-08 | 鹤山市君子兰涂料有限公司 | Preparation method of water-based single-component white finish for manually sprayed window blinds |
| CN116285637A (en) * | 2023-04-10 | 2023-06-23 | 齐鲁工业大学(山东省科学院) | High-strength anticorrosion aqueous polyurethane, anticorrosion material and application |
| CN116640514A (en) * | 2023-07-26 | 2023-08-25 | 山东康展新能源有限公司 | Preparation method and construction method of ecological anti-skid pavement paint |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3094109B2 (en) * | 1990-08-22 | 2000-10-03 | 関西ペイント株式会社 | Water-based paint and coating method using the same |
| DE10331484A1 (en) * | 2003-07-11 | 2005-03-03 | Construction Research & Technology Gmbh | Polyurethane-polymer hybrid dispersion with improved surface properties, process for their preparation and their use |
| CN1257228C (en) * | 2003-12-31 | 2006-05-24 | 中国化工建设总公司常州涂料化工研究院 | Polyurethane-acrylate water dispersion resin and its preparation |
| CN100392017C (en) * | 2005-10-12 | 2008-06-04 | 中国化工建设总公司常州涂料化工研究院 | Acrylate polyurethane water-dispersed resin and its making method |
-
2009
- 2009-01-23 CN CN200910036941XA patent/CN101481451B/en not_active Expired - Fee Related
Cited By (62)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101805514B (en) * | 2010-03-17 | 2012-01-04 | 上海大学 | Castor oil type polyurethane/acrylic resin double-component damping material and preparation method thereof |
| CN101805514A (en) * | 2010-03-17 | 2010-08-18 | 上海大学 | Castor oil type polyurethane/acrylic resin double-component damping material and preparation method thereof |
| CN101962524A (en) * | 2010-09-29 | 2011-02-02 | 江苏力合粘合剂有限公司 | Waterborne polyurethane adhesive and preparation method thereof |
| CN102093534B (en) * | 2010-12-26 | 2012-08-08 | 华南理工大学 | Preparation method of polyurethane aqueous dispersion and waterborne polyurethane paint containing polyurethane aqueous dispersion |
| CN102093534A (en) * | 2010-12-26 | 2011-06-15 | 华南理工大学 | Preparation method of polyurethane aqueous dispersion and waterborne polyurethane paint containing polyurethane aqueous dispersion |
| CN102363702A (en) * | 2011-06-30 | 2012-02-29 | 成都倍大涂料有限公司 | Aqueous mono-component matte varnish and preparation method thereof |
| CN102367358A (en) * | 2011-06-30 | 2012-03-07 | 成都倍大涂料有限公司 | Waterborne single-component full-glossy white finish and preparation method thereof |
| CN102887985A (en) * | 2011-07-19 | 2013-01-23 | 中科华宇(福建)科技发展有限公司 | Waterborne polyurethane resin production method without wastewater discharge |
| CN102952041A (en) * | 2011-08-25 | 2013-03-06 | 山东轻工业学院 | Polyurethane cross-linked and modified acrylate elastic emulsion and preparation method |
| CN102952041B (en) * | 2011-08-25 | 2014-07-30 | 山东轻工业学院 | Polyurethane cross-linked and modified acrylate elastic emulsion and preparation method |
| CN102432795A (en) * | 2011-08-30 | 2012-05-02 | 华南理工大学 | Sulfonic acid type aqueous UV polyurethane modified epoxy acrylic emulsion and preparation method thereof |
| CN102432795B (en) * | 2011-08-30 | 2013-07-24 | 华南理工大学 | Sulfonated aqueous UV polyurethane modified epoxy acrylate emulsion and its preparation method |
| CN102516465A (en) * | 2011-11-19 | 2012-06-27 | 烟台万华聚氨酯股份有限公司 | High-elasticity waterborne polyurethane-acrylate composite resin, and preparation method and application thereof |
| CN102516465B (en) * | 2011-11-19 | 2014-10-29 | 万华化学（广东）有限公司 | High-elasticity waterborne polyurethane-acrylate composite resin, and preparation method and application thereof |
| CN102533184A (en) * | 2011-12-15 | 2012-07-04 | 广东达美新材料有限公司 | Water-based pressure-sensitive adhesive of polyethylene protective film and preparation method thereof |
| CN102533184B (en) * | 2011-12-15 | 2014-10-15 | 广东达美新材料有限公司 | Water-based pressure-sensitive adhesive of polyethylene protective film and preparation method thereof |
| WO2013139019A1 (en) * | 2012-03-22 | 2013-09-26 | Dow Global Technologies Llc | Polyurethane/acrylic hybrid dispersions for roof coatings and their preparation |
| CN103059230A (en) * | 2013-01-30 | 2013-04-24 | 广东银洋树脂有限公司 | Acrylate modified aqueous polyurethane and preparation method and application thereof |
| CN103059230B (en) * | 2013-01-30 | 2015-04-15 | 广东银洋树脂有限公司 | Acrylate modified aqueous polyurethane and preparation method and application thereof |
| CN105283527A (en) * | 2013-04-02 | 2016-01-27 | 英派尔科技开发有限公司 | Photo-responsive hydrophilic coating |
| CN104530962A (en) * | 2014-12-17 | 2015-04-22 | 宜兴市宁沪精细化工厂 | Waterborne UV wood paint coating and preparation method thereof |
| CN112080197A (en) * | 2014-12-23 | 2020-12-15 | 帝斯曼知识产权资产管理有限公司 | Aqueous coating composition having soft touch after drying |
| CN112080197B (en) * | 2014-12-23 | 2022-09-20 | 科思创(荷兰)有限公司 | Aqueous coating composition having soft touch after drying |
| CN104725570A (en) * | 2015-01-26 | 2015-06-24 | 陈维林 | Latex and preparation method thereof |
| CN104672395A (en) * | 2015-03-19 | 2015-06-03 | 苏州嘉祥树脂有限公司 | Waterborne composite resin emulsion for fabric slurry |
| CN104762014A (en) * | 2015-03-30 | 2015-07-08 | 广西吉宽太阳能设备有限公司 | Polyurethane waterproof mildew-resistant paint and preparation method thereof |
| CN104805995A (en) * | 2015-04-27 | 2015-07-29 | 安徽美祥实业有限公司 | Production process of rubber floorboard |
| CN105218755A (en) * | 2015-10-30 | 2016-01-06 | 江门市珍图新材料有限公司 | A kind of preparation method of the new modified resin being used for making digital ink |
| CN108473650A (en) * | 2015-12-15 | 2018-08-31 | 巴斯夫欧洲公司 | aqueous polymer dispersions for adhesive compounds |
| CN105330796A (en) * | 2015-12-16 | 2016-02-17 | 江南大学 | Method for preparing super-hydrophilicity two-component polyurethane modified acrylic resins |
| CN105906771A (en) * | 2016-02-02 | 2016-08-31 | 广东多正化工科技有限公司 | Waterborne polyurethane-acrylate interpenetrating polymer network copolymer emulsion continuous production method and device |
| CN105906771B (en) * | 2016-02-02 | 2019-01-25 | 广东多正树脂科技有限公司 | Aqueous polyurethane acrylate interpenetrating polymer networks copolymer emulsion continuous producing method and equipment |
| CN106065060A (en) * | 2016-06-13 | 2016-11-02 | 珠海长先新材料科技股份有限公司 | A kind of high-performance water-based polyurethane resin and preparation method thereof |
| CN106065060B (en) * | 2016-06-13 | 2018-12-18 | 珠海长先新材料科技股份有限公司 | A kind of high-performance water-based polyurethane resin and preparation method thereof |
| CN109563232B (en) * | 2016-08-03 | 2022-04-12 | Sika技术股份公司 | Two-component polyurethane adhesive with mechanical properties substantially unaffected by temperature and high strength |
| CN109563232A (en) * | 2016-08-03 | 2019-04-02 | Sika技术股份公司 | With the mechanical performance not being affected by temperature substantially and high-intensitive two component polyurethane adhesive |
| CN109642006B (en) * | 2016-08-25 | 2022-05-10 | 巴斯夫欧洲公司 | Polyurethane material with high temperature resistance |
| CN109642006A (en) * | 2016-08-25 | 2019-04-16 | 巴斯夫欧洲公司 | Polyurethane material with high temperature resistance |
| CN106400583A (en) * | 2016-08-30 | 2017-02-15 | 成都金箭桥包装材料有限公司 | Post-crosslinked elastic transfer film emulsion and preparation method thereof |
| CN106400583B (en) * | 2016-08-30 | 2019-05-14 | 成都金箭桥包装材料有限公司 | Post-crosslinking elasticity transfer membrane latex solution and preparation method thereof |
| CN106318192A (en) * | 2016-09-12 | 2017-01-11 | 广东玉兰集团股份有限公司 | Water-based waterproof base film for wallpaper and preparation method of water-based waterproof base film |
| CN106478958A (en) * | 2016-10-11 | 2017-03-08 | 西北工业大学 | A kind of preparation method of mechanical response latex particle |
| CN106478958B (en) * | 2016-10-11 | 2019-08-09 | 西北工业大学 | A kind of preparation method of mechanical response latex particle |
| CN106519133A (en) * | 2016-11-10 | 2017-03-22 | 万华化学集团股份有限公司 | Sulfonic acid type waterborne polyurethane-acrylate self extinction resin and preparation method and application thereof |
| CN108102061A (en) * | 2017-11-24 | 2018-06-01 | 南雄市金鸿泰化工新材料有限公司 | A kind of synthetic method of aqueous three-proofing coating polyurethane |
| CN108102061B (en) * | 2017-11-24 | 2020-04-28 | 广东金鸿泰化工新材料有限公司 | Synthetic method of polyurethane for water-based conformal coating |
| CN108485510A (en) * | 2018-05-02 | 2018-09-04 | 广东海顺新材料科技有限公司 | A kind of air-dry water-based sealer of woodenware one-component and preparation method thereof |
| CN109054354A (en) * | 2018-07-25 | 2018-12-21 | 佛山皖阳生物科技有限公司 | A kind of preparation method of artificial tree tree bark materials |
| CN109251715A (en) * | 2018-09-20 | 2019-01-22 | 江苏理工学院 | A kind of latent curing type one-pack polyurethane adhesive and preparation method thereof |
| CN110951003A (en) * | 2018-09-27 | 2020-04-03 | 南亚塑胶工业股份有限公司 | Waterborne polyurethane and preparation method thereof |
| US11053336B2 (en) * | 2018-09-27 | 2021-07-06 | Nan Ya Plastics Corporation | High heat resistant and high scratch resistant water-based polyurethane and manufacturing method thereof |
| CN110003397A (en) * | 2019-04-12 | 2019-07-12 | 舟山恒丽新型材料技术有限公司 | Polyurethane-modified resin of large arch dam and preparation method thereof |
| CN110128932A (en) * | 2019-04-30 | 2019-08-16 | 中国人民解放军陆军军事交通学院 | A kind of rubber tyre ageing-proof coating |
| CN114058316A (en) * | 2020-08-03 | 2022-02-18 | 浙江卫星石化股份有限公司 | Waterborne polyurethane dispersion with good wettability and preparation method thereof |
| CN114058316B (en) * | 2020-08-03 | 2023-08-25 | 卫星化学股份有限公司 | Aqueous polyurethane dispersion liquid with good wettability and preparation method thereof |
| CN113105577A (en) * | 2021-03-23 | 2021-07-13 | 商洛学院 | Repairing agent for heavy metal pollution control and ecological restoration and preparation method thereof |
| CN114015344A (en) * | 2021-11-09 | 2022-02-08 | 上海金狮化工有限公司 | Self-crosslinking aqueous polyurethane-acrylic acid hybrid emulsion and preparation method and application thereof |
| CN114044873A (en) * | 2021-12-13 | 2022-02-15 | 嘉宝莉化工集团股份有限公司 | Polyurethane acrylate dispersion and preparation method thereof, and high-performance water-based wood coating and preparation method thereof |
| CN115304979A (en) * | 2022-08-25 | 2022-11-08 | 鹤山市君子兰涂料有限公司 | Preparation method of water-based single-component white finish for manually sprayed window blinds |
| CN116285637A (en) * | 2023-04-10 | 2023-06-23 | 齐鲁工业大学(山东省科学院) | High-strength anticorrosion aqueous polyurethane, anticorrosion material and application |
| CN116285637B (en) * | 2023-04-10 | 2024-01-16 | 齐鲁工业大学(山东省科学院) | High-strength anticorrosion aqueous polyurethane, anticorrosion material and application |
| CN116640514A (en) * | 2023-07-26 | 2023-08-25 | 山东康展新能源有限公司 | Preparation method and construction method of ecological anti-skid pavement paint |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101481451B (en) | 2011-06-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101481451B (en) | High solid content latent curing polyurethane acroleic acid hybrid emulsion | |
| CN100443539C (en) | Room temperature crosslinking curing polyurethane-polyacrylic ester composite aqueous emulsion and preparing method thereof | |
| CN1218981C (en) | Acrylic polyurethane copolymer emulsion, its preparation method and use | |
| CN104559617B (en) | A kind of application type aqueous dual-component fluorocarbon coating and its preparation and application | |
| CN101696262B (en) | Preparation method and application of modified polyurethane aqueous dispersions of polyisocyanate curing agents | |
| CN101497687B (en) | Anti-scratch aqueous polyurethane disperse system with high hygrometric state adhesive force and use thereof | |
| CN101357978B (en) | Waterborne polyurethane-polyacrylate emulsion and preparation method thereof | |
| CN101235148B (en) | Multiple crosslinking ultraviolet light solidifying water polyurethane dispersoid and its preparation method and application | |
| KR100942404B1 (en) | Two-component curable aqueous urethane-alkyd resin composition and use thereof | |
| CN110300771B (en) | Aqueous coating composition | |
| CN103403049A (en) | Method for producing polyurethane polyacrylate hybrid dispersions | |
| US20150045491A1 (en) | Polyurethane/acrylic hybrid dispersions for roof coatings and their preparation | |
| AU2011384369B2 (en) | Process for preparing polyurethane/acrylic hybrid dispersions | |
| CN103319680B (en) | Preparation method of composite emulsion of cation-nonionic waterborne polyurethane-polyacrylate | |
| DE102006048926A1 (en) | Aqueous coating agent based on a binder mixture as a basecoat | |
| CN1527865A (en) | Energy curable polymeric ink compositions | |
| CN103724574A (en) | Preparation method of non-ionic waterborne polyurethane-polyacrylate composite emulsion for leather finishing | |
| CN102675553A (en) | Method for preparing polyurethane/polyacrylate core-shell emulsion | |
| CN106414630B (en) | The water-based composition of elongation at break with raising | |
| CN104211878A (en) | Preparation method of polyurethane epoxy resin acrylate ternary polymerization resin nano aqueous dispersion | |
| CN107936814A (en) | The net taste woodcare paint of high hardness polyurethane that a kind of POSS is modified | |
| CN104341572A (en) | Preparation method of solvent-free water-based polyurethane resin | |
| CN100392017C (en) | Acrylate polyurethane water-dispersed resin and its making method | |
| JP5411018B2 (en) | Method for producing aqueous urethane-modified (meth) acrylic resin dispersion | |
| CN111620984A (en) | Modified polyurethane resin and preparation method thereof, water-based paint and coating product |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20110608 Termination date: 20180123 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |