CN101792570A - Hydroxyl-containing crylic acid polyurethane aqueous dispersion body and application - Google Patents
Hydroxyl-containing crylic acid polyurethane aqueous dispersion body and application Download PDFInfo
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- CN101792570A CN101792570A CN 201010112179 CN201010112179A CN101792570A CN 101792570 A CN101792570 A CN 101792570A CN 201010112179 CN201010112179 CN 201010112179 CN 201010112179 A CN201010112179 A CN 201010112179A CN 101792570 A CN101792570 A CN 101792570A
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- 239000006185 dispersion Substances 0.000 title claims abstract description 33
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 26
- 239000004814 polyurethane Substances 0.000 title claims abstract description 26
- 125000002887 hydroxy group Chemical group [H]O* 0.000 title claims abstract description 25
- 239000002253 acid Substances 0.000 title claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000002966 varnish Substances 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 239000012153 distilled water Substances 0.000 claims abstract description 18
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 17
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 15
- 239000000178 monomer Substances 0.000 claims abstract description 13
- 238000002360 preparation method Methods 0.000 claims abstract description 12
- -1 hydroxyl acrylic ester Chemical class 0.000 claims abstract description 8
- 239000003999 initiator Substances 0.000 claims abstract description 8
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 8
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 6
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 6
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 3
- 229920000642 polymer Polymers 0.000 claims description 20
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 14
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 238000013019 agitation Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 238000012986 modification Methods 0.000 claims description 12
- 230000004048 modification Effects 0.000 claims description 12
- 238000010792 warming Methods 0.000 claims description 12
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 10
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 238000004945 emulsification Methods 0.000 claims description 6
- 238000009775 high-speed stirring Methods 0.000 claims description 6
- 239000012948 isocyanate Substances 0.000 claims description 6
- 150000002513 isocyanates Chemical class 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical class OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 claims description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 5
- 239000013530 defoamer Substances 0.000 claims description 5
- 239000002270 dispersing agent Substances 0.000 claims description 5
- 230000008719 thickening Effects 0.000 claims description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 claims description 4
- 239000004970 Chain extender Substances 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 150000002148 esters Chemical class 0.000 claims description 4
- VLCAYQIMSMPEBW-UHFFFAOYSA-N methyl 3-hydroxy-2-methylidenebutanoate Chemical compound COC(=O)C(=C)C(C)O VLCAYQIMSMPEBW-UHFFFAOYSA-N 0.000 claims description 4
- 230000003472 neutralizing effect Effects 0.000 claims description 4
- 229920005862 polyol Polymers 0.000 claims description 4
- 150000003077 polyols Chemical class 0.000 claims description 4
- 150000003384 small molecules Chemical class 0.000 claims description 4
- MMCOUVMKNAHQOY-UHFFFAOYSA-N carbonoperoxoic acid Chemical class OOC(O)=O MMCOUVMKNAHQOY-UHFFFAOYSA-N 0.000 claims description 3
- ZMARGGQEAJXRFP-UHFFFAOYSA-N 1-hydroxypropan-2-yl 2-methylprop-2-enoate Chemical compound OCC(C)OC(=O)C(C)=C ZMARGGQEAJXRFP-UHFFFAOYSA-N 0.000 claims description 2
- DNXHEGUUPJUMQT-CBZIJGRNSA-N Estrone Chemical compound OC1=CC=C2[C@H]3CC[C@](C)(C(CC4)=O)[C@@H]4[C@@H]3CCC2=C1 DNXHEGUUPJUMQT-CBZIJGRNSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000523 sample Substances 0.000 description 20
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 15
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 14
- 239000000243 solution Substances 0.000 description 14
- 238000012360 testing method Methods 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 10
- 238000004448 titration Methods 0.000 description 10
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 7
- 239000003973 paint Substances 0.000 description 7
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 description 6
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000005484 gravity Effects 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 239000012975 dibutyltin dilaurate Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 229920003180 amino resin Polymers 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- ZLLVNPWAUPIQPX-UHFFFAOYSA-N 2-(dihydroxymethyl)pentanoic acid Chemical compound CCCC(C(O)O)C(O)=O ZLLVNPWAUPIQPX-UHFFFAOYSA-N 0.000 description 1
- 239000004160 Ammonium persulphate Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical class CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical group CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004159 Potassium persulphate Substances 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 235000019395 ammonium persulphate Nutrition 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 231100001010 corrosive Toxicity 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 125000005442 diisocyanate group Chemical group 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920003009 polyurethane dispersion Polymers 0.000 description 1
- 229920005749 polyurethane resin Polymers 0.000 description 1
- IWZKICVEHNUQTL-UHFFFAOYSA-M potassium hydrogen phthalate Chemical compound [K+].OC(=O)C1=CC=CC=C1C([O-])=O IWZKICVEHNUQTL-UHFFFAOYSA-M 0.000 description 1
- 235000019394 potassium persulphate Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229960004418 trolamine Drugs 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Abstract
The invention provides a preparation method of hydroxyl-containing crylic acid polyurethane aqueous dispersion body, comprising the following steps: (1) hydroxyl-containing terminal isocyanate group polyurethane prepolymer is obtained by reaction; (2) hydroxyl acrylic ester monomer is added in the obtained polyurethane prepolymer in the step (1) for further reaction, so as to obtain a molecular chain hydroxyl-containing terminal ethenyl containing polyurethane prepolymer; (3) neutralizer is added in the polyurethane prepolymer obtained in the step (2), the pH of the system reaches 7-8, and then distilled water is added to disperse the prepolymer, so as to obtain the dispersion-type polyurethane prepolymer; and (4) vinyl monomers and chain transfer agent are added in the step (3), and then the solution formed by radical initiators and distilled water is dropwise added, so as to obtain the hydroxyl-containing crylic acid polyurethane aqueous dispersion body by reaction; the invention further provides aqueous finish varnish for vehicle, which is formed by aqueous dispersion body and polyisocyanate curing agent.
Description
Technical field
The present invention relates to a kind of based finish varnish for vehicles, relate in particular to a kind of crylic acid polyurethane aqueous dispersion body preparation by hydroxyl, general water-based finish varnish for vehicles is mended in former repair in shop.
Background technology
Based finish varnish for vehicles is the outermost one deck coating of automobile, and it is applied on the metal flash paint, and the weather resistance that improves paint film, scratch resistance, erosion resistance etc. are played an important role.
Coating varnish product in the market is based on solvent-borne type, and based on solvent-type acrylic aminoresin, then lay equal stress on acrylic-amino resin and acrylated polyurethane resin in Europe and North America as Japan.This series products is harmful, and VOC quantity discharged height is unfavorable for environment protection.
For adapting to environmental protection requirement, the research of based finish varnish for vehicles at present concentrates on powder coating varnish and two aspects of water-based finishing varnish.Existing many documents and patent report about the preparation of water-based finish varnish for vehicles.But because the preparation technology of water-based finish varnish for vehicles is still immature, the performance of prepared product such as gloss, weathering resistance, erosion resistance etc. remain in defective, and its practical application is restricted.And do not appear in the newspapers as yet about the preparation that can realize the water-based finish varnish for vehicles that former repair in shop benefit is general.
Summary of the invention
The objective of the invention is to solve the deficiency on the prior art, the crylic acid polyurethane aqueous dispersion body of the hydroxyl of synthetic a kind of excellent performance, and prepare a kind of original factory of vehicle by it and repair general water-based finishing varnish.
The invention provides a kind of preparation method of crylic acid polyurethane aqueous dispersion body of hydroxyl, this method may further comprise the steps:
1), carboxylic isocyanate terminated based polyurethanes performed polymer is synthetic
Under nitrogen protection, with 30～50 weight parts (preferred 35～45, more preferably 38-42) methyl methacrylate is a solvent, with 120～160 weight parts (preferred 130～150, more preferably 135～145) oligomer polyol (average functionality 2～2.5, preferred 2.1～2.3, number-average molecular weight 500～3000, preferred 1000～2000), 20～60 weight parts (preferred 25-55, more preferably 30-50, more preferably 35-45 again) aliphatics or alicyclic diisocyanate (for example hexamethylene diisocyanate HDI or isophorone diisocyanate IPDI), 5～10 weight parts (preferred 6-9, the urea Alkanizing catalyst of hydrophilic small molecules chainextender more preferably 7-8) and 1～2 weight part (preferred 1.2-1.8) adds in the reactor, under agitation be warming up to 70～80 ℃, reaction 1～2h obtains carboxylic isocyanate terminated based polyurethanes performed polymer;
2), the end-vinyl base polyurethane prepolymer for use as is synthetic
The hydroxy acrylate monomer that adds 10～30 weight parts (preferred 15～25, more preferably 18～22) in step (1) in the base polyurethane prepolymer for use as of gained at 80～90 ℃ of reaction 1～2h down, obtains the base polyurethane prepolymer for use as that molecular chain contains carboxyl and contains end-vinyl;
3), the water dispersant type polyaminoester performed polymer is synthetic
In step (2) gained base polyurethane prepolymer for use as, add 5～10 weight parts (preferred 6-9, more preferably 6.5-8.5) neutralizing agent, the system pH of making reaches 7～8, and the distilled water that under agitation adds 200～300 weight parts then disperses performed polymer, obtains the water dispersant type polyaminoester performed polymer.
4), crylic acid polyurethane aqueous dispersion body is synthetic
In step (3), add 30～60 weight parts (preferred 35～55 in the gained performed polymer, more preferably 40～50) the vinyl monomer and the chain-transfer agent of 0.5～1 weight part (preferred 0.6～0.8), high-speed stirring emulsification, be warming up to 80～90 ℃, the solution that dropping is made up of the distilled water of the initiator of 0.5～1 weight part and 60～80 weight parts, reaction 3～4h is incubated 1h after reaction is finished, and obtains the crylic acid polyurethane aqueous dispersion body of hydroxyl.
As oligomer polyol, preferably use polyether glycol, more preferably use polyoxyethylene glycol, polypropylene glycol and/or polyoxyethylene-propylene oxide glycol.
Generally, the hydrophilic small molecules chainextender be selected from dihydroxy carboxylic acids, dihydroxyl half ester or the dihydroxyl sulfonate one or both or multiple.Wherein dihydroxy carboxylic acids is dimethylol propionic acid, dimethylolpropionic acid or dihydroxymethyl valeric acid.
The urea Alkanizing catalyst is selected from the catalyzer of organic amine or organic tin.
Generally, the hydroxy acrylate monomer be selected from Hydroxyethyl acrylate, hydroxyethyl methylacrylate, Propylene glycol monoacrylate, Rocryl 410, vinylformic acid hydroxy butyl ester or the methacrylic acid hydroxy butyl ester one or both or multiple.
Generally, vinyl monomer be selected from esters of acrylic acid, methyl acrylic ester, vinylbenzene and the hydroxy acrylate class etc. one or both or multiple.For example, vinyl monomer comprises three kinds of butyl acrylate, n-BMA and hydroxyethyl methylacrylates in a specific embodiment; Vinyl monomer comprises four kinds of methyl methacrylate, butyl acrylate, n-BMA and Hydroxyethyl acrylates in another specific embodiment.
Neutralizing agent is triethylamine, trolamine or ammoniacal liquor etc.
4) initiator that uses in the step is ammonium persulphate or Potassium Persulphate etc.
In another embodiment of the invention, a kind of preparation method of automobile-used water-based finishing varnish is provided, it comprises:
1) in above-mentioned water dispersion, add flow agent, defoamer, water and optional thickening material, obtain component A, wherein the addition of each component following (is 100 parts in water dispersion weight):
Water dispersion: 100
Flow agent: 1-5
Defoamer: 0.2-1, preferred 0.2-0.6
Water: 20-70, preferred 30-60
Thickening material: 0-0.8, preferred 0.2-0.5
2) will be as the polyisocyanates of curing agent component B and component A according to A: B=2.5-3.5: the part by weight of 1 (preferred about 3: 1) mixes, and can make automobile-used water-based finishing varnish.Wherein polyisocyanates is selected from HDI, IPDI, and modification HDI, modification IPDI, or modification HDI+ modification IPDI (presses 3-6: any the mixture of 1 weight ratio).
Preferably, modification HDI is the Bayhydur 304 of Beyer Co., Ltd and the Bayhydur 401-70 that modification IPDI is Beyer Co., Ltd.
Positively effect of the present invention is embodied in:
1, the general water-based finishing varnish of finished product of preparing a kind of water-based acrylic acid polyurethane dispersions of water-based finish varnish for vehicles and being deployed into.
2, utilize the crosslinking and curing agent of modified water-soluble end-sealed type polyisocyanates as water-based finishing varnish, make it can be complete when high temperature (180 ℃-220 ℃) at the 30-45min dry solidification, reach ideal hardness of paint film and various physical and chemical performance after the cooling, again can be when repairing (80 ℃), after adding the wetting ability solubility promoter, after the baking of 45-60min, obtain the ideal paint film.
3, use a kind of multifunctional aqueous auxiliary agent, it can the effective clarity that must improve paint film, reduces the mist shadow.Anti scuffing performance and water resistance to paint film is significantly improved simultaneously.
4, by adjusting construction technology the construction adaptability of water-based finishing varnish can be improved greatly, promote for the water-based finishing varnish big area and established solid basis.
5, no matter this water-based finishing varnish product is to be used for former factory, still is used to repair its VOC content and all is lower than 21%.Do not contain simultaneously corrosives, very friendly to environment, greatly alleviated use and dependence simultaneously to organic solvent, saved the energy effectively.
Illustrate below by embodiment.
Embodiment
(1) raw material that uses in an embodiment:
The raw material that uses among the embodiment only is for example, should not be considered as to limit the scope of the invention.In an embodiment:
As oligomer polyol, the polyoxypropyleneglycol ether PPG-220 (number-average molecular weight is 2000, and the average hydroxy functionality 2) that uses Shanghai Gaoqiao petrochemical corporation (complex) to produce;
Vulcabond is aliphatic diisocyanate HDI or alicyclic diisocyanate IPDI;
(2) performance of aqueous dispersion and testing method
The hydroxy acryl acid polyurethane aqueous dispersion body is the filmogen of coating, and its performance has determined the performance of the finished product.The performance index of institute's synthetic water dispersion are all within the following table scope in the following illustrated embodiment.
The concrete testing method of every performance is as follows:
1) mensuration of non-volatile component
Get the flat ware of glass of a cleaning, claim its quality.Take a morsel and (1 ± 0.1g) testing sample in the flat ware of the glass of cleaning, be transferred in 125 ℃ the baking oven, keep 60min.Ware is transferred to makes it to be cooled to room temperature in the moisture eliminator, its quality of weighing.Calculate the ratio that remaining solid part accounts for the sample total mass.Carry out twice replicate(determination), average.
2) mensuration of acid number
Take by weighing sample 2.5g and put into the 250ml Erlenmeyer flask, be accurate to 1mg, add 50ml mixing solutions (by 2 parts of toluene and 1 part of volume fraction is that 95% ethanol is made into by volume, and neutralizing with potassium hydroxide solution before using changes mixed solvent) dissolved samples.(concentration is 10g/L to add 2～8 phenolphthalein indicator solution in sample solution, by volume fraction is that 95% ethanol, methyl alcohol or the configuration of 2-propyl alcohol form), (with volume fraction is that 95% ethanol or methyl alcohol are mixed with the solution that concentration is 0.1mol/L to use potassium hydroxide solution immediately, and deviate from carbonate, demarcate its concentration with Potassium Hydrogen Phthalate) extremely appearance is red in titration, at least 10s does not disappear and is terminal point, writes down the potassium hydroxide solution milliliter number that is consumed.With measure the parallel blank test of carrying out, testing sequence is the same.
Be calculated as follows acid number A:
In the formula:
A---acid number is with the milligram number scale of every gram sample consumption KOH;
V
0---the volume (ml) of potassium hydroxide that blank test consumes;
V
1---measure the volume (ml) of potassium hydroxide solution that sample consumes;
C---the titration actual concentrations (mol/L) of potassium hydroxide solution;
The quality of m---sample (g);
NV---measure the non-volatile content of sample, represent with mass percent.
3) mensuration of viscosity
The sample of an amount of inorganics impurity is placed beaker, remove air filled cavity.Cover watch-glass, be placed in 25 ± 0.1 ℃ of waters bath with thermostatic control, intermittently stirring sample (but not introducing bubble) reaches evenly constant until specimen temperature.Select suitable rotor and rotating speed according to sample viscosity size.Install instrument, rotor is immersed in the sample, make sample reach the last graticule of rotor.Behind 25 ± 0.1 ℃ of constant 10min, unclamp the viscometer control lever, open motor rotor rotated continuously, treat that pointer is stable after, press the pointer control lever, close motor simultaneously, read reading to a decimal on the dish at quarter.Same sample repeats twice reading under same rotating speed.
The viscosity of sample is calculated as follows:
η＝K·a
In the formula:
The viscosity of η---sample (mPas);
K---instrument parameter (mPas);
A---the arithmetical av of twice reading on the viscometer scale card.
4) mensuration of pH
Soak glass electrode and rectify an instrument by the specification sheets of acidometer.Measure in about 50mL water dispersion impouring beaker as sample with graduated cylinder, and beaker put into 23 ± 1 ℃ thermostatic bath, after the temperature for the treatment of specimen temperature and thermostatic bath reaches balance, to wash and insert in the beaker with distillation with the electrode that softish thieving paper is dried, measure behind the vibrational stabilization a little, getting continuous three mensuration fixed values is pH pH-value determination pH value, gets first of decimal.Same method is measured all the other two samples, makes the difference of pH value of three samples be not more than 0.3.The arithmetical av of getting three sample measured values is as net result.
5) mensuration of density
Under (23 ± 0.5) ℃, the weighing specific gravity flask also writes down its quality m
1Sample is filled with specific gravity flask, wipe with spongy material and overflow material, with rayon balls wiping gently, and the quality m of test product specific gravity flask filled with in record
2
The method of calculation of density are as follows:
In the formula, m
1---the quality of empty specific gravity flask, g;
m
2---fill the quality of the specific gravity flask of sample, g;
V
t---the volume of specific gravity flask, mL.
6) mensuration of hydroxyl value
To Erlenmeyer flask, the test portion quality is m with syringe sampling.In each test portion and blank Erlenmeyer flask, accurately pipette 25mL phthalic acid anhydridization reagent.Shake bottle to test portion and dissolve, each Erlenmeyer flask connects air set pipe, is placed on 30min in (115 ± 2) ℃ oil bath.To install and from oil bath, take out and be cooled to room temperature.Solution is quantitatively transferred in the 250ml beaker.
Beaker is placed on the autotitrator, uses magnetic stirrer.The titration apparatus electrode is immersed solution, and the sodium hydroxide standard titration solution titration of usefulness 0.5mol/L to terminal.
Hydroxyl value OHV shows with the potassium hydroxide milligram numerical table of every gram sample consumption, is calculated as follows:
In the formula:
V
3---the volume of the sodium hydroxide standard titration solution that the titration test portion consumes, mL;
V
4---the volume of the blank sodium hydroxide standard titration solution that consumes of titration, mL;
C---the concentration of sodium hydroxide standard titration solution, mol/L;
The quality of m---test portion, g.
In the present invention, when water dispersion synthetic directly with Acrylic Acid Monomer as solvent, and make solvent participate in polymerization in the reaction later stage, further reduced the VOC content of product, and better with the isocyanate curing agent consistency, help the dispersion of solidifying agent.
(3) specific embodiment
The preparation embodiment of embodiment 1-product
Under nitrogen protection, methyl methacrylate with 30g is a solvent, (Shanghai Gaoqiao chemical company produces with 120g PPG-220, number-average molecular weight 2000, the average hydroxy functionality 2), 20g hexamethylene diisocyanate, 6g dimethylol propionic acid and 1g dibutyl tin dilaurate add in the reactor, under agitation be warming up to 80 ℃, reaction 1.5h obtains carboxylic isocyanate terminated based polyurethanes performed polymer; In this performed polymer, add the 10g hydroxyethyl methylacrylate, react 1h down, obtain the base polyurethane prepolymer for use as that molecular chain contains carboxyl and contains end-vinyl at 85 ℃; In performed polymer, add triethylamine and make pH=7, thereby make in the carboxyl and salify, under agitation add 250g distilled water then performed polymer is disperseed, obtain the water dispersant type polyaminoester performed polymer; Add 15g butyl acrylate, 5g n-BMA, 10g hydroxyethyl methylacrylate and 0.5g Dodecyl Mercaptan, high-speed stirring emulsification, be warming up to 85 ℃, the solution that dropping is made up of 0.5g initiator potassium persulfate and 60g distilled water, reaction 3h, be incubated 1h after reaction is finished, obtain the crylic acid polyurethane aqueous dispersion body of hydroxyl.
Embodiment 2
Under nitrogen protection, methyl methacrylate with 30g is a solvent, with 120g PPG-220 (high bridge Chemical Manufacture, number-average molecular weight 2000,), 25g isophorone diisocyanate, 8g dimethylol propionic acid and 1g dibutyl tin dilaurate add in the reactor, under agitation be warming up to 80 ℃, reaction 1.5h; Add the 10g Hydroxyethyl acrylate, react 1h down, obtain the base polyurethane prepolymer for use as that molecular chain contains carboxyl and contains end-vinyl at 85 ℃; Add triethylamine and make pH=7, thereby make in the carboxyl and salify, under agitation add 250g distilled water then performed polymer is disperseed; Add 10g butyl acrylate, 20g n-BMA, 10g Hydroxyethyl acrylate and 0.5g Dodecyl Mercaptan and 30g distilled water, high-speed stirring emulsification, be warming up to 85 ℃, the solution that dropping is made up of 0.5g initiator ammonium persulfate and 30g distilled water, reaction 3h, be incubated 1h after reaction is finished, obtain the crylic acid polyurethane aqueous dispersion body of hydroxyl.
Embodiment 3
Under nitrogen protection, methyl methacrylate with 30g is a solvent, with 120gPPG-220 (high bridge Chemical Manufacture, number-average molecular weight 2000), 25g isophorone diisocyanate, 9g dimethylol propionic acid and 1g dibutyl tin dilaurate add in the reactor, under agitation be warming up to 80 ℃, reaction 1.5h; Add the 15g Propylene glycol monoacrylate, react 1h down, obtain the base polyurethane prepolymer for use as that molecular chain contains carboxyl and contains end-vinyl at 85 ℃; Add the 10g triethylamine and make pH=7, thereby make in the carboxyl and salify, under agitation add 250g distilled water then performed polymer is disperseed; Add 20g butyl acrylate, 10g n-BMA, 10g Hydroxyethyl acrylate and 20g distilled water, high-speed stirring emulsification, be warming up to 85 ℃, the solution that dropping is made up of 0.5g initiator potassium persulfate and 40g distilled water, reaction 3h, be incubated 1h after reaction is finished, obtain the crylic acid polyurethane aqueous dispersion body of hydroxyl.
Embodiment 4
Under nitrogen protection, mixed solution with 20g methyl methacrylate and 10g butyl acrylate is a solvent, with 120g PPG-220 (high bridge Chemical Manufacture, number-average molecular weight 2000), 30g hexamethylene diisocyanate, 10g dimethylol propionic acid and 1g dibutyl tin dilaurate add in the reactor, under agitation be warming up to 80 ℃, reaction 1.5h; Add the 12g Propylene glycol monoacrylate, react 1h down, obtain the base polyurethane prepolymer for use as that molecular chain contains carboxyl and contains end-vinyl at 85 ℃; Add triethylamine and make pH=7, thereby make in the carboxyl and salify, under agitation add 250g distilled water then performed polymer is disperseed; Add 10g methyl methacrylate, 10g butyl acrylate, 10g n-BMA, 10g Hydroxyethyl acrylate and 30g distilled water, high-speed stirring emulsification, be warming up to 85 ℃, the solution that dropping is made up of 0.5g initiator potassium persulfate and 30g distilled water, reaction 3h, be incubated 1h after reaction is finished, obtain the crylic acid polyurethane aqueous dispersion body of hydroxyl.
The purposes (Application Example) of embodiment 5-product
Get the prepared crylic acid polyurethane aqueous dispersion body of 45.0g embodiment 1 as hydroxy-containing component, add 1.0g flow agent BYK346 (by Bi Ke company produce and market), 0.1g thickening material Borchi Gel PW-25 (by German Borchers company produce and market), 0.2g defoamer BYK028 (by Bi Ke company produce and market) and 28.7g distilled water, stirring is mixed with hydroxy-containing component A.
Get 20.1g Bayhydur 304 (by Beyer Co., Ltd's produce and market, hydrophilic modifying HDI) (70%MPA) and 4.9g Bayhydur 401-70 (by Beyer Co., Ltd's produce and market, hydrophilic modifying IPDI), stir, be mixed with and contain the isocyanate group B component.
Component A and B are mixed with 3: 1 part by weight, can make automobile-used water-based finishing varnish.
Use common testing methods in the paint field, it is as follows to obtain this varnish correlated performance.
Water dispersion with other embodiment prepares varnish, obtains similar result.
Claims (10)
1. the preparation method of the crylic acid polyurethane aqueous dispersion body of a hydroxyl, this method may further comprise the steps:
1), carboxylic isocyanate terminated based polyurethanes performed polymer is synthetic
Under nitrogen protection, methyl methacrylate with 30～50 weight parts is a solvent, with the average functionality 2～2.5 of 120～160 weight parts, the oligomer polyol of number-average molecular weight 500～3000, the aliphatics of 20～60 weight parts or alicyclic diisocyanate, the hydrophilic small molecules chainextender of 5～10 weight parts and the urea Alkanizing catalyst of 1～2 weight part add in the reactor, under agitation be warming up to 70～80 ℃, reaction 1～2h obtains carboxylic isocyanate terminated based polyurethanes performed polymer;
2), the end-vinyl base polyurethane prepolymer for use as is synthetic
The hydroxy acrylate class monomer that adds 10～30 weight parts in step (1) in the base polyurethane prepolymer for use as of gained reacts 1～2h down at 80～90 ℃, obtains the base polyurethane prepolymer for use as that molecular chain contains carboxyl and contains end-vinyl;
3), the water dispersant type polyaminoester performed polymer is synthetic
Add the neutralizing agent of 5～10 weight parts in step (2) gained base polyurethane prepolymer for use as, the system pH of making reaches 7～8, and the distilled water that under agitation adds 200～300 weight parts then disperses performed polymer, obtains the water dispersant type polyaminoester performed polymer; With
4), crylic acid polyurethane aqueous dispersion body is synthetic
In step (3), add the vinyl monomer of 30～60 weight parts and the chain-transfer agent of 0.5～1 weight part in the gained performed polymer, high-speed stirring emulsification, be warming up to 80～90 ℃, the solution that dropping is made up of the distilled water of the initiator of 0.5～1 weight part and 60～80 weight parts, reaction 3～4h, be incubated 1h after reaction is finished, obtain the crylic acid polyurethane aqueous dispersion body of hydroxyl.
According to the process of claim 1 wherein the hydrophilic small molecules chainextender be selected from dihydroxy carboxylic acids, dihydroxyl half ester or the dihydroxyl sulfonate one or both or multiple.
3. according to the process of claim 1 wherein that the urea Alkanizing catalyst is selected from the catalyzer of organic amine or organic tin.
According to the process of claim 1 wherein hydroxy acrylate class monomer be selected from Hydroxyethyl acrylate, hydroxyethyl methylacrylate, Propylene glycol monoacrylate, Rocryl 410, vinylformic acid hydroxy butyl ester or the methacrylic acid hydroxy butyl ester one or both or multiple.
According to the process of claim 1 wherein vinyl monomer be selected from esters of acrylic acid, methyl acrylic ester, vinylbenzene and the hydroxy acrylate class etc. one or both or multiple.
6. by the crylic acid polyurethane aqueous dispersion body of the hydroxyl of the method for claim 1 preparation.
7. the preparation method of an automobile-used water-based finishing varnish, it comprises:
1), in the crylic acid polyurethane aqueous dispersion body of the prepared hydroxyl of claim 1 or in the crylic acid polyurethane aqueous dispersion body of the hydroxyl of claim 6, adds flow agent, defoamer, water and optional thickening material, obtain component A, wherein the addition of each component following (is 100 parts in water dispersion weight):
Water dispersion: 100 weight parts,
Flow agent: the 1-5 weight part,
Defoamer: the 0.2-1 weight part,
Water: the 20-70 weight part,
Thickening material: the 0-0.8 weight part,
2), will be as the polyisocyanates of curing agent component B and component A according to A: B=2.5-3.5: 1 part by weight mixes, and can make automobile-used water-based finishing varnish.
8. according to the method for claim 7, wherein the polyisocyanates as curing agent component B is selected from HDI, IPDI, modification HDI, modification IPDI, or modification HDI+ modification IPDI presses 3-6: any in the mixture of 1 weight ratio.
9. method according to Claim 8, wherein modification HDI is the Bayhydur 304 of Beyer Co., Ltd and the Bayhydur 401-70 that modification IPDI is Beyer Co., Ltd.
10. the automobile-used water-based finishing varnish that obtains by the method for claim 7.
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