CN1438257A - Acrylic polyurethane copolymer emulsion, its preparation method and use - Google Patents
Acrylic polyurethane copolymer emulsion, its preparation method and use Download PDFInfo
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Abstract
The invention refers to a kind of acrylic acid polyurethane copolymer latex, the making method and the application to carpentry dope. It adopts technique of seed-latex polymerization, selects end-sealing agent, and adopts self cross-linking acrylate monomer to make the excellent-capability epoxy cross-linked denaturing copolymer latex. The diameter of particles of the latex is small and distributes evenly. The painting film made of it has excelelnt water-resistant, solvent resistance, high rigidity and better appearance.
Description
Technical field
The present invention relates to the acroleic acid polyurethane copolymer emulsion.
The invention still further relates to the preparation method of described acroleic acid polyurethane copolymer emulsion.
The invention still further relates to the application of described acroleic acid polyurethane copolymer emulsion in the preparation woodwork coating.
Technical background
Along with the enhancing, particularly various countries' environmental law of people's environmental protection, energy consciousness strictness restriction, promoted that water-borne coatings is the development of the low-contamination type coating of representative to volatile organic compounds in the coating system (VOC) content.Urethane (PU) emulsion and polyacrylic ester (PA) emulsion have been widely used as the base-material of coating, printing ink and glue paste, and its performance is difficult to match in excellence or beauty with corresponding solvent type resin usually, because preparation the time will be introduced hydrophilic radical or emulsifying agent.Yet the performance of PU and PA two class emulsions has very strong complementarity, have excellent solvent resistance, wear resistance, scratch resistance and snappiness and elasticity etc. preferably as the PU emulsion film, but in stability, unsatisfactory from aspects such as thickening property, solid 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 effective ways that improve emulsion property are with two or more latex composite compoundings, make it to have complementary advantages.Main preparation method has physical blending and chemical copolymerization.Domestic and international numerous scientific workers carry out modification to aqueous polyurethane emulsion, comprise cross-linking modified, organic-silicon-modified and acrylic acid modified.The method of acrylic acid modified polyurethane emulsion has physical blending method and chemical copolymerization method.Though physical blending can improve the performance of polyaminoester emulsion, there are problems affect appearance of films such as comixing compatibility difference; The chemical copolymerization products therefrom is acrylate-urethane (PUA) composite emulsion, and it films more superior than physical blending thing film performance.The preparation method of PUA composite emulsion comprises seed emulsion polymerization, situ aggregation method and solution polymerization phase inversion process.Seed emulsion polymerization process stabilizing, quality product are easy to control, but film performance is not very good.Situ aggregation method is primary solvent with the vinyl monomer, and hydrophilic PU prepolymer of preparation and acrylate monomer blend are disperseed in water then earlier, carry out letex polymerization again.The less use of this technology or not with an organic solvent, the PUA compound emulsion film performance of preparation is good, it is lower to have a cost, but processing condition are wayward, is disperseing and the letex polymerization stage is prone to gel; Above-mentioned two kinds of methods prepare the PUA emulsion, submitting connection except that small part PU micelle is combined with polyacrylic ester (PA) molecular chain, major part still exists with simple PU and PA form, and the resin of this compound state is after film forming, and its over-all properties still can not be given full play to the advantage separately of PU and PA resin.The solution polymerization phase inversion process is to prepare hydrophilic PUA compound resin earlier in organic solvent, adds water-dispersion generation inversion of phases then, obtains the PUA composite emulsion.This technology can significantly improve the percentage of grafting of acrylate monomer and PU, but the phase transition behavior complexity, the difficult control of processing condition, and need use and reclaim a large amount of solvents, cost height.U.S. Pat P6462127 (2002,10.8) prepares the acroleic acid polyurethane composite emulsion of oxidation drying under the room temperature by the siccative oil polyvalent alcohol, this preparation technology length consuming time, and raw material is rare, and the transformation efficiency of Acrylic Acid Monomer is low.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, there is complicated process of preparation equally, store instability under the composite emulsion room temperature, need add emulsifying agent; We pass through after the lot of experiments to above-mentioned processing method, obtained to remedy the insufficient processing method of aforesaid method, this is that seed emulsion polymerization and in-situ polymerization are combined, in preparation process, utilize hydroxyl and ethylene linkage bifunctional material as PU and PA grafted bridge, preparation has the acroleic acid polyurethane composite emulsion of graft copolymer, this technology can not only improve the transformation efficiency and the percentage of grafting of acrylate monomer, and carry out cross-linking modified with Resins, epoxy, realized that the nucleocapsid between the acroleic acid polyurethane emulsion is crosslinked, make that the emulsion particle diameter of preparation is little, size distribution is even, filming of its preparation has excellent in water resistance, solvent resistance, high rigidity and appearance of film preferably, show this process stabilizing through pilot scale research, quality product is easy to control.
Summary of the invention
The objective of the invention is to problem, a kind of preparation method of acroleic acid polyurethane copolymer emulsion is provided at the prior art existence.
The present invention also aims to provide the acroleic acid polyurethane copolymer emulsion of described method preparation.
The present invention also aims to provide the application of described acroleic acid polyurethane copolymer emulsion in the preparation woodwork coating.
The present invention adopts seeded emulsion polymerization technology, selects the end-capping reagent with two functionalities for use, the acroleic acid polyurethane copolymer emulsion of the cross linking of epoxy resin modification of the acrylate monomer processability excellence of employing energy self-crosslinking; Raw materials used and proportioning is as follows:
---polyhydric alcohol polymer, number average relative molecular mass are 300-3000, and hydroxyl value is 50-200mgKOH/g, and its consumption is a total mass fractional 10～40%;
---diisocyanate monomer, consumption are 20～40% of monomer total mass;
---small molecule chain extender, consumption are the 3%-10% of total raw material;
---Resins, epoxy, consumption are the 1.0-10% of total solids quality;
---two functionality encapsulants, consumption are the 1-5% of total solids quality;
---acrylate monomer, consumption are the 20-60% of total solids quality;
---neutralizing agent is a basic cpd, and its consumption is the 50-120% of carboxyl consumption;
Acroleic acid polyurethane copolymer emulsion of the present invention preparation method more specifically comprises the steps:
1) raw-material preparation and processing: be that 90-120 ℃, vacuum tightness are vacuum hydro-extraction 1.0-2.0h under the 0.05-0.1Mpa with polyhydric alcohol polymer in temperature in reactor, it is standby to lower the temperature then; Solvent and chainextender etc. are handled by molecular sieve dehydration;
2) preparation of base polyurethane prepolymer for use as: in the reactor that stirring arm, thermometer and condenser are housed, add polyhydric alcohol polymer, Resins, epoxy and diisocyanate monomer, be warming up to 60-90 ℃, be incubated 1.0-2.0 hour, the content of NCO group in the analytical reaction thing is when reaching prescribed value, add small molecules dibasic alcohol chainextender, react to the NCO group content at 70-80 ℃ and to reach prescribed value, add hydrophilic chain extender, 60-70 ℃ react to NCO base content when constant till.Add two functionality materials and carry out end capping, dilute the reduction reactant viscosity, obtain end group and contain the two key polyurethane prepolymers of C=C with acrylate monomer;
3) above-mentioned polyurethane prepolymer is cooled to about 30-60 ℃, add in the neutralizing agent stirring of measuring and after 5-30 minute, neutralized reaction product is moved in the emulsification still, quantitative deionized water is joined the emulsification of emulsification still high speed, add amine chain extender simultaneously and carry out chain extension, obtain acrylate monomer swollen aqueous polyurethane emulsion;
4) with the above-mentioned emulsion heat temperature raising to 50-80 ℃, the insulation 0.5-1.5h.Drip initiator then, every 1h drips once in batches, drips off for 2-5 time, dropwise, and insulation 1-3h, cooling filtration discharging obtains the acroleic acid polyurethane graft copolymer emulsion.
Described polyhydric alcohol polymer can be polyester polyol, polyether glycol, Viscotrol C.It can be one or more mixture of polyester-polyether glycol, polycarbonate polyol, polytetrahydrofuran polyvalent alcohol, polyurethane polyol, polyacrylate polyol, polyolefin polyhydric alcohol (polybutadiene polyol), polycaprolactone (PCL) polyvalent alcohol.
Described vulcabond can be tolylene diisocyanate (TDI), diphenylmethanediisocyanate (MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI) and six cyclohexyl diisocyanate (H
6MDI), one or more mixture of xylylene diisocyanate.
Described Resins, epoxy can be bisphenol A type epoxy resin such as E12, E20, E44, E51, also the suitable Resins, epoxy of oxirane value of Ciba company.
Described small molecules diol chain-extension agent can be ethylene glycol, propylene glycol, 1,4 butyleneglycol, 1,6 hexylene glycol, one or more mixture such as 1,4 cyclohexanediol, Diethylene Glycol, glycol ether.
Described hydrophilic chain extender is the dihydroxyl alkyl acid, can be dihydroxymethyl acetate, dimethylol propionic acid (DMPA), dimethylolpropionic acid (DMBA), one or more mixtures of dihydroxymethyl valeric acid and sulfonate.
Described two functionality materials can be one or more mixtures such as hydroxyethyl methylacrylate, Propylene glycol monoacrylate, Jia base Bing Xi Suan Shrink water glyceryl ester.
Described acrylate monomer can be one or more mixtures such as methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate, methyl acrylate, ethyl propenoate, butyl acrylate, vinylbenzene, vinyl toluene.
Described initiator can be an oil-soluble initiator, and as Diisopropyl azodicarboxylate, benzoyl peroxide, tert-butyl peroxide etc. also can be water soluble starter such as Potassium Persulphate, ammonium persulphate; Also the oxidation-reduction type initiator as or redox system such as sodium bisulfite-Potassium Persulphate, hydrogen peroxide-iron protochloride, Potassium Persulphate-iron protochloride, isopropyl benzene hydroperoxide-iron protochloride etc.
Described emulsion polymerization technique is that segmentation drips initiator technology, also acrylate monomer and initiator can be dripped respectively simultaneously, also can will drip simultaneously with initiator after the pre-emulsification of monomer.
Ultimate principle of the present invention: at abundant research polymer progressively on the polymeric basis, the present invention selects for use polymer polyatomic alcohol, Resins, epoxy and polyisocyanates prepared in reaction to contain the polyurethane prepolymer of carboxyl and the two keys of end C=C, the dilution of employing acrylate monomer, in and emulsification preparation contain the aqueous polyurethane emulsion of the two keys of C=C, the method that adopts radical polymerization to drip initiator step by step prepares epoxy resin modification acroleic acid polyurethane copolymer emulsion.So acroleic acid polyurethane graft copolymer emulsion of the present invention's preparation, has the nucleocapsid crosslinking structure, 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, anti stickness power, degree of crosslinking, sticking power, be widely used in high-grade water-borne wood coating, waterproof paint and waterborne metallic paint and aqueous adhesive and printing ink etc.
Self-crosslinking modified polyurethane emulsion of the present invention compared with prior art has the following advantages:
1, 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 HBC12-2002 standard, belong to Green Product.
2, by radical polymerization acrylic ester polymer is grafted on the polyurethane molecular chain, has shell nuclear nucleocapsid structure, it is crosslinked that graft copolymer plays nucleocapsid, this graft copolymer helps increasing the consistency between acrylic ester polymer and urethane, improves the film-forming properties and the appearance of film of emulsion film.Core-shell structure makes that the film performance of the performance of emulsion film and polyaminoester emulsion is close.
3, initiator adopts the substep adding technology, both can guarantee the stability of letex polymerization, can improve the transformation efficiency of acrylate monomer again, guarantees the package stability of emulsion.
4, adopt the end NCO base of two functionality materials sealing polyurethane prepolymer, guarantee that the two keys of C=C are at polyurethane molecular amount end group, the reactive behavior that helps the two keys of C=C in the graft polymerization process, improve the percentage of grafting (the actual measurement percentage of grafting surpasses 50%) of acrylic ester polymer, help improving the outward appearance and the physical and chemical performance of filming.
5, adopt acrylate monomer to replace acetone or butanone to make thinner dilution polyurethane prepolymer, the polyurethane acroleic acid emulsion of preparation does not need organic solvent, and the reaction later stage need not remove and reclaim operations such as organic solvent, saves cost, helps environmental protection.
6, emulsion particle diameter very little (less than 60nm), and surface tension is very low, emulsion has bilayer structure, moisture content is contained in emulsion particle inside, and moisture content has plastification, can help polyaminoester emulsion Cheng Mo, so they have fabulous film-forming properties, perviousness, wettability and levelling property, can infiltrate in atomic thin bump maps line, the fine capillary channel and the unusual complicated matrix surface of geometrical shape, can improve coating film gloss and improve the outward appearance of filming, have the ornamental of excellence.
7, has lower minimum film-forming temperature, thereby has a good film forming properties, when the preparation water-borne wood coating, only need add a small amount of solubility promoter and get final product film forming, reduced raw materials cost, reduce volatile organic compounds (VOC) content of coating, improve the mechanical property of filming again and particularly improved hardness of film, increased the contamination resistance of filming.
8, acroleic acid polyurethane graft copolymer 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 following table of acroleic acid polyurethane graft copolymer emulsion woodwork coating of the present invention:
Table 1 water-borne wood coating performance index
The smooth 60 ° of gloss of project performance index flat appearance, %＞95 surface drying times, h 1 does solid work the time, h 4 pendulum-rocker hardnesss＞0.65 sticking power＜2 impact resistances, kg.cm 50 water tolerance 48h do not have the considerable change alkali resistance and are dipped in the 10%NaOH solution 24h and do not have the considerable change water-intake rate of filming, and % films the water-intake rate of 48h less than 10%
Performance to the microemulsion of the present invention preparation can characterize with following main method: particle size of emulsion size and distribute and adopt the automatic particle diameter instrument mensuration of Autosizer Lo-c; Being coated with film dynamic performance tests with the Instron electronic tension tester; The emulsion polymer structure 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; The latex particle form of emulsion has scanning electron microscope (TEM) to measure; The emulsion latex film is crosslinked to be measured by MEK (methyl ethyl ketone) reflux method of extraction; 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
Embodiment 1
Adopt cross linking of epoxy resin modified acrylic polyurethane copolymer emulsion, its recipe ingredient is listed in table 2.
Table 2 acroleic acid polyurethane graftomer emulsion
Constituent mass 1 PPG (N210) 252 epoxy resin (E20) 133 toluene di-isocyanate(TDI)s (TDI) 404 dihydromethyl propionic acids (DMPA) 7.55 diethylene glycol (DEG)s (DEG) 66 trihydroxy methyl propionic acid (TMP) 2.07 triethylamines (TEA) 4.08 ethylenediamines (EDA) 0.89 methyl methacrylates (MMA) 3510 initators 0.0511 deionized water 150.0
Under the drying nitrogen protection; the polyether glycol N210 that dewatered and Resins, epoxy and TDI are joined in the 1000ml four-hole boiling flask that thermometer, whipping appts and reflux exchanger are housed; 70 ℃-80 ℃ reactions 2 hours; add glycol ether then 70 ℃-80 ℃ reactions 1 hour, judge reaction end with the n-butylamine titration method.Add the nmp solution that is dissolved with dimethylol propionic acid (DMPA) after reaching terminal point, react to the NCO base at 60 ℃-65 ℃ and to reach prescribed value, add Rocryl 410, react to NCO base content at 60 ℃ and to reach theoretical value, be cooled to 40 ℃ then, add the triethylamine neutralization, add the acrylate monomer dilution, the quadrol chain extension is used in emulsification in normal-temperature water, obtains aqueous polyurethane dispersion (WPU).This emulsion is at 70-75 ℃ of insulation 0.5-1.0h, and substep drips initiator emulsion, divides three dropping, and every 1h drips 1 time, dropwises insulation 1h, treats that the acrylate monomer transformation efficiency reaches 98% when above, lowers the temperature, and filtration, packages spare at discharging.This emulsion 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 2
Use the cross linking of epoxy resin modified acroleic acid ester polyurethane microemulsion 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 | Microemulsion in the example 1 | 85 |
| ?2 | Wetting agent (TEGO-245) | 0.2 |
| ?3 | Defoamer (TEGO-805) | 0.05 |
| ?4 | Flow agent (BYK-330) | 0.1 |
| ?5 | Thickening material (SN-612) | 0.15 |
| ?6 | Deionized water | 14.5 |
| Amount to | 100.0 |
The preparation method is as follows: earlier the 2-6 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 35-40%, viscosity 30-200cps.Woodenware film performance: the pencil hardness of filming: H; Water tolerance: immersion 48h does not have considerable change; Sticking power: 1 grade; Impact strength: 50kg.cm; Snappiness: 1 grade.
Embodiment 3
Use the pure and mild aliphatic diisocyanate prepared in reaction of polyester polyols acroleic acid polyurethane graft copolymer emulsion, used starting material are listed in table 4.
Table 4 self-crosslinking remodeling aqueous polyurethane emulsion
Constituent mass 1 PEPA (T1136) 37.22 epoxy resin E51 6.33 different phorone vulcabond (IPDI) 37.84 butanediols (BDO) 6.05 dihydromethyl propionic acids (DMPA) 7.06 N methyl pyrrolidones, 10.07 triethylamines (TEA) 4.08 ethylenediamines (EDA) 0.89 styrene (ST) 5510 initators 0.0811 deionized water 170.0
Under the drying nitrogen protection; polyester glycol, Resins, epoxy and the IPDI that dewatered joined in the 1000ml four-hole boiling flask that thermometer, whipping appts and reflux exchanger are housed; 70 ℃-90 ℃ reactions 2 hours; add butyleneglycol then 70 ℃-80 ℃ reactions 1 hour, judge reaction end with the n-butylamine titration method.Add the nmp solution that is dissolved with dimethylol propionic acid (DMPA) after reaching terminal point, react to the NC0 base at 60 ℃-65 ℃ and to reach prescribed value, add Propylene glycol monoacrylate, react to NCO base content at 60 ℃ and to reach prescribed value, be cooled to 40 ℃ then, add the triethylamine neutralization, add the vinylbenzene dilution, emulsification in normal-temperature water obtains aqueous polyurethane dispersion (WPU) with the quadrol chain extension.This emulsion is at 70 ℃ of insulation 1.0h, and substep drips initiator emulsion, divides three dropping, and every 1h dropping 1 time dropwises and is incubated 1h, treats that the styrene monomer conversion rate reaches 98% when above, cooling, filtration, discharging, packages spare.This emulsion is mixed with leather gloss agent, advantage such as have that feel nature, winter hardiness are good, the anti-bending of folding, water-fast and anti-doing/wet rubbing are good.
Embodiment 4
Use the microemulsion 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 | Vinylformic acid microemulsion in the example 1 | 80 |
| ?2 | The propylene glycol butyl ether | 5 |
| ?3 | Wetting agent (TEGO-245) | 0.2 |
| ?4 | Defoamer (THGO-805) | 0.05 |
| ?5 | Flow agent (BYK-330) | 0.1 |
| ?6 | Thickening material (SN-612) | 0.15 |
| ?7 | Deionized water | 14.5 |
| Amount to | 100.0 |
The preparation method is as follows: earlier the 2-7 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 35-40%, viscosity 30-200cps.Woodenware film performance: the pencil hardness of filming: 2H; Water tolerance: immersion 48h does not have considerable change; 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 Viscotrol C | 30.0 |
| 2 Resins, epoxy E44 | 5.0 |
| 3 diphenylmethanediisocyanates (MDI) | 42.0 |
| 4 hexylene glycols (HDO) | 45.0 |
| 5 dimethylol propionic acids (DMPA) | 6.0 |
| 6 triethylamines (TEA) | 4.0 |
| 7 quadrols (EDA) | 0.8 |
| 8 methyl methacrylates (MMA) | 20.0 |
| 9 vinylbenzene (ST) | 15.0 |
| 10 butyl acrylates | 20.0 |
| 11 initiators | 0.10 |
| 12 deionized waters | 200.0 |
Under the drying nitrogen protection; Viscotrol C, Resins, epoxy and the MDI that dewatered joined in the 1000ml four-hole boiling flask that thermometer, whipping appts and reflux exchanger are housed; 70 ℃-80 ℃ reactions 2 hours; add hexylene glycol then 70 ℃-80 ℃ reactions 1 hour, judge reaction end with the n-butylamine titration method.Add nmp solution and the TriMethylolPropane(TMP) that is dissolved with dimethylol propionic acid (DMPA) after reaching terminal point, react to the NCO base at 60 ℃-65 ℃ and to reach prescribed value, add Propylene glycol monoacrylate, react to NCO base content at 60 ℃ and to reach prescribed value, be cooled to 40 ℃ then, add the triethylamine neutralization, add the vinylbenzene dilution, emulsification in normal-temperature water obtains aqueous polyurethane dispersion (WPU) with the quadrol chain extension.This emulsion is at 70 ℃ of insulation 1.0h, and substep drips initiator emulsion, divides three dropping, and every 1h dropping 1 time dropwises and is incubated 1h, treats that the styrene monomer conversion rate reaches 98% when above, cooling, filtration, discharging, packages spare.This emulsion of acroleic acid polyurethane graft copolymer emulsion 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 | Microemulsion in the example 5 | 80 |
| ?2 | The propylene glycol butyl ether | 5 |
| ?3 | Wetting agent (TEGO-245) | 0.2 |
| ?4 | Defoamer (TEGO-805) | 0.05 |
| ?5 | Flow agent (BYK-330) | 0.1 |
| ?6 | Thickening material (SN-612) | 0.15 |
| ?7 | Deionized water | 14.5 |
| Amount to | 100.0 |
The preparation method is as follows: earlier the 2-7 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 35-40%, viscosity 30-200cps.Woodenware film performance: the pencil hardness of filming: H; Water tolerance: immersion 48h 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 is test item HG/T3608-embodiment 2 embodiment 4 embodiment 6 relatively
1999 outward appearance uniform liquids, no uniform liquid, uniform liquid, evenly liquid
Condensation product does not have condensation product and does not have the cohesion object, does not have and coagulates
Polymers pH value--8.0 8.0 8.0 solid contents, 45.0 36.5 38.5 40.0105 ℃ ± 2 ℃ of % (being not less than), the 4h cross cut test, level, (not 1111 greater than) 60 ° of gloss, %, 95 96 95 93 snappinesies, mm 2111 pencil hardness H H 2H 2H alcohol resistances (wiping of volume fraction wiping loss of gloss do not lose wiping not the loss of gloss wiping do not lose 50% ethanol) light light shock-resistance, (90 1111 ℃ of kg.cm 45 50 50 50 dry heat resistances, 15min), the level free TDI content, % 2.0 0.0 0.0 0.0
The highly filled self-crosslinking acrylic microemulsion woodwork coating of table 8 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, a kind of preparation method of acroleic acid polyurethane copolymer emulsion is characterized in that adopting seeded emulsion polymerization technology, selects the end-capping reagent with two functionalities for use, adopt can self-crosslinking the acrylate monomer preparation, raw materials used and proportioning is as follows:
---polyhydric alcohol polymer, number average relative molecular mass are 300-3000, and hydroxyl value is 50-200mgKOH/g, and its consumption is a total mass fractional 10～40%;
---diisocyanate monomer, consumption are 20～40% of monomer total mass;
---small molecule chain extender, consumption are the 3%-10% of total raw material;
---Resins, epoxy, consumption are the 1.0-10% of total solids quality;
---two functionality encapsulants, consumption are the 1-5% of total solids quality;
---acrylate monomer, consumption are the 20-60% of total solids quality;
---neutralizing agent is a basic cpd, and its consumption is the 50-120% of carboxyl consumption.
2, the preparation method of acroleic acid polyurethane copolymer emulsion according to claim 1 is characterized in that comprising the steps:
1) raw-material preparation and processing: be that 90-120 ℃, vacuum tightness are vacuum hydro-extraction 1.0-2.0h under the 0.05-0.1Mpa with polyhydric alcohol polymer in temperature in reactor, it is standby to lower the temperature then; Solvent and chainextender etc. are handled by molecular sieve dehydration;
2) preparation of base polyurethane prepolymer for use as: in the reactor that stirring arm, thermometer and condenser are housed, add polyhydric alcohol polymer, Resins, epoxy and diisocyanate monomer, be warming up to 60-90 ℃, be incubated 1.0-2.0 hour, the content of NCO group in the analytical reaction thing is when reaching prescribed value, add small molecules dibasic alcohol chainextender, react to the NCO group content at 70-80 ℃ and to reach prescribed value, add hydrophilic chain extender, 60-70 ℃ react to NCO base content when constant till; Add two functionality materials and carry out end capping, dilute the reduction reactant viscosity, obtain end group and contain the two key polyurethane prepolymers of C=C with acrylate monomer;
3) above-mentioned polyurethane prepolymer is cooled to about 30-60 ℃, add in the neutralizing agent stirring of measuring and after 5-30 minute, neutralized reaction product is moved in the emulsification still, quantitative deionized water is joined the emulsification of emulsification still high speed, add amine chain extender simultaneously and carry out chain extension, obtain acrylate monomer swollen aqueous polyurethane emulsion;
4) with the above-mentioned emulsion heat temperature raising to 50-80 ℃, the insulation 0.5-1.5h; Drip initiator then, every 1h drips once in batches, drips off for 2-5 time, dropwise, and insulation 1-3h, cooling filtration discharging obtains the acroleic acid polyurethane graft copolymer emulsion.
3, the preparation method of acroleic acid polyurethane copolymer emulsion according to claim 1 and 2 is characterized in that described polyhydric alcohol polymer is wherein one or more a mixture of polyester polyol, polyether glycol, Viscotrol C, polyester-polyether glycol, polycarbonate polyol, polytetrahydrofuran polyvalent alcohol, polyurethane polyol, polyacrylate polyol, polyolefin polyhydric alcohol, polycaprolactone polyol.
4, the preparation method of acroleic acid polyurethane copolymer emulsion according to claim 1 and 2 is characterized in that described vulcabond is wherein one or more a mixture of tolylene diisocyanate, diphenylmethanediisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, six cyclohexyl diisocyanate, xylylene diisocyanate; Described Resins, epoxy is bisphenol A type epoxy resin.
5, the preparation method of acroleic acid polyurethane copolymer emulsion according to claim 1 and 2, it is characterized in that described small molecules diol chain-extension agent is ethylene glycol, propylene glycol, 1,4 butyleneglycols, 1,6 hexylene glycols, 1,4 cyclohexanediol, Diethylene Glycol, glycol ether be one or more mixture wherein.
6, the preparation method of acroleic acid polyurethane copolymer emulsion according to claim 1 and 2 is characterized in that described hydrophilic chain extender is wherein one or more mixtures of dihydroxymethyl acetate, dimethylol propionic acid, dimethylolpropionic acid, dihydroxymethyl valeric acid and sulfonate.
7, the preparation method of acroleic acid polyurethane copolymer emulsion according to claim 1 and 2 is characterized in that described two functionality materials are wherein one or more mixtures of hydroxyethyl methylacrylate, Propylene glycol monoacrylate, Jia base Bing Xi Suan Shrink water glyceryl ester.
8, the preparation method of acroleic acid polyurethane copolymer emulsion according to claim 1 and 2 is characterized in that described acrylate monomer is wherein one or more mixtures of methyl methacrylate, Jia Jibingxisuanyizhi, butyl methacrylate, methyl acrylate, ethyl propenoate, butyl acrylate, vinylbenzene, vinyl toluene.
9, the acroleic acid polyurethane copolymer emulsion of the described method preparation of claim 1.
10, the application of the described acroleic acid polyurethane copolymer emulsion of claim 10 in the preparation woodwork coating.
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