CN104250360B - Preparation and purposes of a kind of imido- with hydroxyl composite aqueous polyurethane dispersion - Google Patents
Preparation and purposes of a kind of imido- with hydroxyl composite aqueous polyurethane dispersion Download PDFInfo
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- CN104250360B CN104250360B CN201410453995.7A CN201410453995A CN104250360B CN 104250360 B CN104250360 B CN 104250360B CN 201410453995 A CN201410453995 A CN 201410453995A CN 104250360 B CN104250360 B CN 104250360B
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000002131 composite material Substances 0.000 title claims abstract description 14
- 229920003009 polyurethane dispersion Polymers 0.000 title description 4
- 239000004814 polyurethane Substances 0.000 claims abstract description 37
- 229920000642 polymer Polymers 0.000 claims abstract description 29
- 239000006185 dispersion Substances 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229920002635 polyurethane Polymers 0.000 claims abstract description 27
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 25
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 25
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 17
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 10
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002585 base Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 239000000178 monomer Substances 0.000 claims description 10
- -1 propylene acetoacetic ester Chemical compound 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 150000002148 esters Chemical class 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 8
- 239000002202 Polyethylene glycol Substances 0.000 claims description 7
- 229920001223 polyethylene glycol Polymers 0.000 claims description 7
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 5
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 5
- 229920005862 polyol Polymers 0.000 claims description 5
- 150000003077 polyols Chemical class 0.000 claims description 5
- 229920001451 polypropylene glycol Polymers 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 5
- 239000004970 Chain extender Substances 0.000 claims description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 4
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 4
- 239000003112 inhibitor Substances 0.000 claims description 4
- 239000003999 initiator Substances 0.000 claims description 4
- 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 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 4
- 235000019394 potassium persulphate Nutrition 0.000 claims description 4
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- GTACSIONMHMRPD-UHFFFAOYSA-N 2-[4-[2-(benzenesulfonamido)ethylsulfanyl]-2,6-difluorophenoxy]acetamide Chemical compound C1=C(F)C(OCC(=O)N)=C(F)C=C1SCCNS(=O)(=O)C1=CC=CC=C1 GTACSIONMHMRPD-UHFFFAOYSA-N 0.000 claims description 3
- 101710130081 Aspergillopepsin-1 Proteins 0.000 claims description 3
- 102100031007 Cytosolic non-specific dipeptidase Human genes 0.000 claims description 3
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- 229960002887 deanol Drugs 0.000 claims description 3
- 239000012972 dimethylethanolamine Substances 0.000 claims description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 3
- 150000003384 small molecules Chemical group 0.000 claims description 3
- 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
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 2
- 210000000481 breast Anatomy 0.000 claims description 2
- MMCOUVMKNAHQOY-UHFFFAOYSA-N carbonoperoxoic acid Chemical class OOC(O)=O MMCOUVMKNAHQOY-UHFFFAOYSA-N 0.000 claims description 2
- 239000000284 extract Substances 0.000 claims description 2
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical compound OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims 2
- 229930192474 thiophene Natural products 0.000 claims 1
- 239000003973 paint Substances 0.000 abstract description 23
- 238000001035 drying Methods 0.000 abstract description 15
- 230000000694 effects Effects 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000010276 construction Methods 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000003960 organic solvent Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 2
- 230000009286 beneficial effect Effects 0.000 abstract 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 41
- 239000000523 sample Substances 0.000 description 30
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 25
- 239000000243 solution Substances 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 238000000576 coating method Methods 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 239000011248 coating agent Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 238000004448 titration Methods 0.000 description 8
- 210000003298 dental enamel Anatomy 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 230000005484 gravity Effects 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 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 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000004703 alkoxides Chemical class 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 125000001841 imino group Chemical group [H]N=* 0.000 description 3
- 239000012948 isocyanate Substances 0.000 description 3
- 150000002513 isocyanates Chemical class 0.000 description 3
- 238000010422 painting Methods 0.000 description 3
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 description 2
- 230000000875 corresponding effect Effects 0.000 description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 description 2
- 125000005442 diisocyanate group Chemical group 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 description 2
- 238000004945 emulsification Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000009775 high-speed stirring Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 235000015927 pasta Nutrition 0.000 description 2
- 239000005056 polyisocyanate Substances 0.000 description 2
- 229920001228 polyisocyanate Polymers 0.000 description 2
- IWZKICVEHNUQTL-UHFFFAOYSA-M potassium hydrogen phthalate Chemical compound [K+].OC(=O)C1=CC=CC=C1C([O-])=O IWZKICVEHNUQTL-UHFFFAOYSA-M 0.000 description 2
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000000205 computational method Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 239000013530 defoamer Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000011010 flushing procedure Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- GAPYKZAARZMMGP-UHFFFAOYSA-N pyridin-1-ium;acetate Chemical compound CC(O)=O.C1=CC=NC=C1 GAPYKZAARZMMGP-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
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- 230000009257 reactivity Effects 0.000 description 1
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- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Landscapes
- Polyurethanes Or Polyureas (AREA)
Abstract
The present invention relates to the preparation of a kind of imido- and hydroxyl composite water soluble acrylic PU dispersion, it is adaptable to enterprise of car paint system.It discloses the synthesis of hydrophilic modifying terminal isocyanate group base polyurethane prepolymer for use as, the synthesis of imido- performed polymer, the synthesis of end-vinyl base polyurethane prepolymer for use as, the synthesis of water-dispersible polyurethane performed polymer, the synthesis of acroleic acid polyurethane water-borne dispersions.Activity of curing reaction of the present invention is high, can meet construction quick-drying, and appearance property can be made outstanding, and resistance to all kinds of chemical mediators are strong, considerably reduce organic solvent and use, it is ensured that production and construction safety, and are very beneficial for environmental protection.
Description
Technical field
The present invention relates to a kind of aqueous automobile paint, more particularly to one kind is by imido- and hydroxyl composite aqueous polyurethane
The preparation of dispersion, further relates to the preparation method that genuine repairs general aqueous quick-drying solid color enamel.
Background technology
1) car paint, which is meant, is painted on all kinds such as car, jeep, motor bus, truck body of a motor car and zero
Coating general name on part, requirement based on auto industry to car paint performance is high, wide in variety, consumption is big, and needs to have
Unique workability and coating performance, therefore, car paint turn into a kind of special coating already.Automobile is used as national economy
Pillar industry, is rapidly developed in recent years, and present China has been the big producer of world car first.But with Chinese vapour
The fast development of turner industry, the environmental protection pressure faced is also increasing, and domestic automobile industry is generally used in vehicle painting
Be traditional solvent based coating.VOC content is high, and serious environmental pollution is caused in production and coating process, endangers the mankind
Health.VOC emission of the car paint in production and application is reduced, environment-friendly type coating must be just used, wherein aqueous apply
Material replaces organic solvent with substantial amounts of water, and the volatile quantity of organic solvent is greatly reduced in production and work progress, is environmentally friendly painting
One important development direction of material, research and development water paint is imperative, with far-reaching environment protection significance.
2) car paint uses the coating system of classical acroleic acid polyurethane.Current most domestic automobile repairing paint
The 2K systems of manufactory nearly all use acroleic acid polyurethane (PU).Two-component PU coating is the principal item of low-temperature setting class,
Either acroleic acid polyurethane or polyester-polyurethane be main resin containing OH with the isocyanate curing agent compounding containing NCO and
Into.Such PU because its remarkable dicoration, resistance to ag(e)ing, resistance to all kinds of media and by the popular welcome in market.But, it is such
System is the cross-linking reaction based on OH and NCO due to its curing mechanism, and its rate of drying is necessarily restricted, more and more fuller
The not current rhythm of life increasingly accelerated of foot.People also just have increasingly urgent need to environmentally friendly quick-drying.
The content of the invention：
In order to overcome the shortcomings of present technology, the present invention provides a kind of imido- and gathered with the water soluble acrylic acid that hydroxyl is combined
Urethane dispersion and the aqueous automobile paint prepared using it, using Isocyanates curing agent, it is possible to use imino group is exceedingly fast
Cross-linking reaction speed, obtain ultrafast dry promising result, meanwhile, the cross-linking reaction of hydroxyl ensure that in the same of ultrafast dry effect
When, it can guarantee that the paint film to be formed has excellent ornamental and resistance to all kinds of medium effects.Successfully solve curing rate and paint
The contradiction of film properties effect, has set up the ultrafast dry system of an environment-friendly and high-performance.
A kind of preparation method for the Aqueous acrylic urethane's dispersion being combined the invention provides imido- and hydroxyl：
1) synthesis of hydrophilic modifying terminal isocyanate group base polyurethane prepolymer for use as
In a nitrogen environment, using 35-40 parts by weight of methylmethacrylate and 1-5 parts by weight propylene acetoacetic ester as solvent,
By the oligomer polyol (average functionality 2-2.3, molecular weight 1000-2000) of 130-145 parts by weight, 35-50 parts by weight
Aliphatic or alicyclic diisocyanate (HDI or IPDI), 7-8 part by weight of hydrophilic small molecule chain extender and 1.5 parts by weight
Catalyst is added in reactor, and 70 DEG C -80 DEG C are heated under stirring, is reacted 1-2h, is obtained hydrophilic modifying isocyanate terminated
Based polyurethanes performed polymer；
2) synthesis of imido- performed polymer
Choose 25-40 weight parts of methacrylic acid ethyl ester and 6-10 parts by weight N, N '-tert-butyl group hydroxyl butylimine are added to
In reaction vessel equipped with condensing unit, then into reaction vessel add 0.1-0.15 weight parts of polymer inhibitor 7- diaminourea
12 tungstophosphoric acid alkali salts of phenthazine and 0.1-0.2 parts by weight alkaline-earth alkoxides, 2.5- is stirred at 60 DEG C -70 DEG C
3.5h carries out ester exchange reaction, then extracts the performed polymer for obtaining imido- by being evaporated in vacuo；
3) synthesis of end-vinyl base polyurethane prepolymer for use as
To step 1) in obtained by base polyurethane prepolymer for use as in add 60-70 parts by weight hydroxy-acrylate monomer and 8-
15 parts by weight steps 2) obtained by imido- performed polymer, at 80 DEG C -90 DEG C, lower reaction 1-2h obtains strand containing imido
Base and the hydrophilic polyurethane performed polymer containing vinyl；
4) synthesis of water-dispersible polyurethane performed polymer
To step 3) the middle nertralizer for adding 6-8 parts by weight, system pH is reached 7-8, then added under stirring
The distilled water of 200-300 parts by weight makes performed polymer be uniformly dispersed, and obtains water-dispersible polyurethane performed polymer；
5) synthesis of acroleic acid polyurethane water-borne dispersions
To step 4) in add 40-50 parts by weight vinyl monomer and 0.5-1 parts by weight chain-transferring agent, high-speed stirring
Mix emulsification, be warming up to 80-90 DEG C, be added dropwise by the initiator of 0.5-1 parts by weight and the distilled water of 60-80 parts by weight constituted it is molten
Liquid, reacts 3-4h, 1h is incubated after reaction, obtains Aqueous acrylic urethane's dispersion that imido- is combined with hydroxyl.
Oligomer polyol described above is PEPA or PPG, preferably polyethylene glycol, polypropylene glycol
Or polyethylene glycol oxide-propylene oxide glycol.
Above-mentioned polyisocyanates is IPDI or '-diphenylmethane diisocyanate or toluene diisocyanate
Acid esters or hexamethylene diisocyanate.
Above-mentioned hydrophilic chain extender elects dihydroxy carboxylic acids, dicarboxyl half ester or one kind or many in dicarboxyl sulfonate as
Kind.
Above-mentioned catalyst is selected from organic amine or organic tin.
Above-mentioned nertralizer is N- ethyl diisopropyl amines or triethylamine or dimethylethanolamine.
Above-mentioned initiator is ammonium persulfate or potassium peroxydisulfate etc..
The positive effect of the present invention is embodied in three below advantage：
(1) present invention has synthesized the acroleic acid polyurethane water-borne dispersions that imino group is combined with hydroxyl, prepares a kind of solid
Change reactivity height, the aqueous quick-drying solid color enamel of excellent combination property, requirement of the modern society for quick-drying, and energy can be met
Ensure the appearance property (gloss is high, and hardness is high) and resistance to all kinds of media (water, acid, gasoline) performance of film.
(2) VOC content for the aqueous quick-drying solid color enamel that the present invention is prepared is reduced within 10%, is reduced to organic molten
The use of agent, effectively reduces cost, while the danger of coating material production storage and haulage time is reduced, and greatly
The real color finish paint of aqueous automobile VOC in work progress discharge capacity is reduced, it is extremely friendly to environment.
(3) the aqueous quick-drying solid color enamel that the present invention is prepared has good dispersiveness and application property, application method and biography
Solvent-borne type finish paint of uniting is consistent, with wide applicability.
Illustrated below by embodiment：
(1) material therefor in embodiment
Material therefor is only citing in embodiment, it should not be assumed that limit the scope of the present invention.
Oligomer polyol used：Polyethylene glycol PEG2000.
Diisocyanate is aliphatic diisocyanate HDI or alicyclic diisocyanate IPDI.
(2) performance and method of testing of water-borne dispersions：
Imido- is determined most with the main film forming substance that hydroxyl polyurethane water-borne dispersions are car paints, its performance
The performance of finished product.The performance of water-borne dispersions synthesized in example is within the scope of following table below.
The water-borne dispersions performance indications of table one
The specific method of testing of properties is as follows：
1) measure of non-volatile component
A clean flat ware of glass is taken, claims its quality.Take a small amount of (1 ± 0.1g) testing sample flat in clean glass
In ware, in the baking oven for being transferred to 125 DEG C, keep taking out out of baking oven after 2h, stir sample with glass bar, surface skining is subject to
It is broken, then ware is put back into baking oven.It is allowed to be cooled to room temperature after ware is transferred in drier after sample constant weight, weighs its quality,
It is accurate to 1mg.Calculate the ratio that remaining solid part accounts for sample gross mass.Parallel determination twice is carried out, is averaged.
The content (V) of volatile matter or the content (N V) of nonvolatile matter are calculated, calculation formula with test product mass fraction
It is as follows：
In formula：
m1--- the quality of sample, mg before heating；
m2--- the quality of sample, mg after heating under the conditions of defined；
The content of V --- volatile matter, is represented with mass percent；
The content of NV --- volatile matter, is represented with mass percent.
2) measure of viscosity
The sample of proper amount of inorganic matter impurity is placed in beaker, air bubble is removed.Cap upper surface ware, is placed on 25 ± 0.1 DEG C
In water bath with thermostatic control, intermittent stirring sample (but not introducing bubble) is until specimen temperature reaches homogeneous constant.It is big according to sample viscosity
Small selection appropriate rotor and rotating speed.Instrument is installed, rotor is immersed in sample, sample is reached the upper graticule of rotor.
After 25 ± 0.1 DEG C of constant 10min, viscosimeter control-rod is unclamped, opening motor makes rotor continuously rotate, and after pointer is stable, presses
Lower finger needle control lever, simultaneously closes off motor, reads reading in dish to a decimal.Same sample is repeated under same rotating speed
Reading twice.
The viscosity of sample is calculated as follows：
η=Ka
In formula：
The viscosity of η --- sample, mPas；
K --- instrument parameter, mPas；
A --- the arithmetic mean of instantaneous value of reading twice on viscometer dial.
3) pH measure
Glass electrode is soaked by the specification of acidometer and is rectified an instrument.About 50mL imido- acrylic acid is measured with graduated cylinder
Resin is poured into as sample in beaker, and beaker is put into 23 ± 1 DEG C of constant temperature bath, treats the temperature of specimen temperature and constant temperature bath
Reach after balance, by with distilling in electrode insertion beaker that is water washed and being dried with soft blotting paper, slightly after vibrational stabilization
It is measured, takes continuous three times and determine fixed value for pH value measured value, get decimal first.Same method determine remaining two
Individual sample so that the difference of the pH value of three samples is not more than 0.3.The arithmetic mean of instantaneous value of three Specimen Determination values is taken as final
As a result.
4) measure of density
At (23 ± 0.5) DEG C, weigh specific gravity bottle and simultaneously record its quality m1；Sample is filled into specific gravity bottle, with there is suction
Aqueous material wipes spilling material, is gently wiped with rayon balls, and records the quality m for filling test product specific gravity bottle2。
The computational methods of density are as follows：
In formula, m1--- the quality of empty specific gravity bottle, g；
m2--- fill the quality of the specific gravity bottle of sample, g；
Vt--- the volume of specific gravity bottle, mL.
5) measure of acid number
Weigh sample 2.5g (being accurate to 0.2mg) to be put into 250ml conical flasks, add 50ml mixed solutions (by 2 parts of toluene
It is made into by volume for 95% ethanol with 1 part of volume fraction, shaking conical flask is completely dissolved sample, can heat if necessary.
4~10 drop phenolphthalein indicator solutions are added into sample solution, and (concentration is 10g/L, ethanol, methanol by volume fraction for 95%
Or the configuration of 2- propyl alcohol is formed), (prepared immediately with standard potassium hydroxide volumetric soiutions with volume fraction for 95% ethanol or methanol
Into the solution that concentration is 0.1mol/L, and deviate from carbonate, its concentration demarcated with Potassium Hydrogen Phthalate) to be titrated to appearance micro- red
Color, it is terminal to keep 30s colour-fast, writes down consumed potassium hydroxide solution milliliter number.Make line blank test simultaneously.
Acid number A is calculated as follows：
In formula：
A --- acid number, KOH milligram number scale is consumed with every gram of sample；
V1--- ethanolic potassium hydroxide standard titration solution consumption, mL during titration sample；
V2--- ethanolic potassium hydroxide standard titration solution consumption, mL during blank test；
C --- the concentration of ethanolic potassium hydroxide standard titration solution, mol/L；
The quality of m --- sample, g；
56.10 --- the molal weight of potassium hydroxide, g/mol.
6) measure of hydroxyl value
Weigh sample 2.5g (being accurate to 0.2mg) to be put into 250ml conical flasks, add 25ml pyridinium acetate solution and (press body
Product is than being 1：23 prepare), reflux condensation mode bottle is installed rapidly, taper is slowly shaken, and is completely dissolved sample.Conical flask is dipped into
In oil bath, sample page is set to be located under the pasta of oil bath, in 115 ± 5 DEG C of constant temperature backflow 1h.Conical flask is proposed into pasta, from cold
Solidifying tube top portion adds 10ml water, and then conical flask is dipped into oil bath and reacts 10min, and is constantly shaken.Reflux is taken out, it is cold
15ml n-butanols flushing rinse condenser pipe inwall and conical flask are added to room temperature, then at the top of condenser pipe, 2~8 drop phenolphthalein is added and indicates
Liquid, with standard potassium hydroxide volumetric soiutions, (it is 0.1mol/L's that the ethanol or methanol for being 95% with volume fraction, which are configured to concentration,
Solution, and deviate from carbonate, its concentration is demarcated with Potassium Hydrogen Phthalate) it is titrated to and blush occurs, keep 30s colour-fast i.e.
For terminal, consumed potassium hydroxide solution milliliter number is write down.Make line blank test simultaneously.
Hydroxyl value is calculated as follows：
In formula：
OHV --- hydroxyl value, with the suitable potassium hydroxide milligram number scale of hydroxy radical content in every gram of sample；
V1--- ethanolic potassium hydroxide standard titration solution consumption, mL during blank test；
V2--- ethanolic potassium hydroxide standard titration solution consumption, mL during titration sample；
C --- the concentration of ethanolic potassium hydroxide standard titration solution, mol/L；
The quality of m --- sample, g；
56.10 --- the molal weight of potassium hydroxide, g/mol；
A --- acid number, KOH milligram number scale is consumed with every gram of sample.
The embodiment 1 of the present invention：
1) synthesis of hydrophilic modifying terminal isocyanate group base polyurethane prepolymer for use as
In a nitrogen environment, using 35 parts by weight of methylmethacrylate and 3 parts by weight propylene acetoacetic esters as solvent, by 140
The polyethylene glycol PEG2000 of parts by weight, the hexamethylene diisocyanate of 36 parts by weight, the dihydromethyl propionic acid of 7 parts by weight and
The dibutyl tin dilaurate of 1.5 parts by weight is added in reactor, and 70 DEG C -80 DEG C are heated under stirring, is reacted 1-2h, is obtained
To hydrophilic modifying terminal isocyanate group base polyurethane prepolymer for use as.
2) synthesis of imido- acrylic monomers
Choose 38 weight parts of methacrylic acid ethyl esters and 10 parts by weight N, N '-tert-butyl group hydroxyl butylimine is added to equipped with cold
In the reaction vessel of solidifying device, then add into reaction vessel 0.15 weight parts of polymer inhibitor 7- diaminophenothiazines and
12 tungstophosphoric acid alkali salts of 0.15 parts by weight alkaline-earth alkoxides, stir 3h progress ester exchange reactions, so at 65 DEG C
Afterwards corresponding imido- acrylic monomers is obtained by the way that extraction is evaporated in vacuo.
3) synthesis of end-vinyl base polyurethane prepolymer for use as
To step 1) in obtained by base polyurethane prepolymer for use as in add the hydroxyethyl methacrylate and 10 weights of 65 parts by weight
Measure part step 2) obtained by imido- acrylic monomers, react 2h at 80 DEG C, obtain strand imido- and containing second
The hydrophilic polyurethane performed polymer of alkenyl.
4) synthesis of water-dispersible polyurethane performed polymer
To step 3) the middle triethylamine for adding 6 parts by weight, system pH is reached 7.5, then add 260 under stirring
The distilled water of parts by weight makes performed polymer be uniformly dispersed, and obtains water-dispersible polyurethane performed polymer.
5) synthesis of acroleic acid polyurethane water-borne dispersions
To step 4) in add 42 parts by weight butyl acrylate and 0.6 parts by weight lauryl mercaptan, high-speed stirred breast
Change, be warming up to 80 DEG C, the solution being made up of the potassium peroxydisulfate of 0.5 parts by weight and the distilled water of 80 parts by weight is added dropwise, react 3h,
1h is incubated after reaction, Aqueous acrylic urethane's dispersion that imido- is combined with hydroxyl is obtained.
The embodiment 2 of the present invention：
1) synthesis of hydrophilic modifying terminal isocyanate group base polyurethane prepolymer for use as
In a nitrogen environment, using 38 parts by weight of methylmethacrylate and 5 parts by weight propylene acetoacetic esters as solvent, by 135
The polyethylene glycol PEG2000 of parts by weight, the IPDI diisocyanate of 40 parts by weight, the dihydroxy of 8 parts by weight
Methylbutanoic acid and the dibutyl tin dilaurate of 1.5 parts by weight are added in reactor, and 78 DEG C, reaction are heated under stirring
2h, obtains hydrophilic modifying terminal isocyanate group base polyurethane prepolymer for use as.
2) synthesis of imido- acrylic monomers
Choose 38 weight parts of methacrylic acid ethyl esters and 10 parts by weight N, N '-tert-butyl group hydroxyl butylimine is added to equipped with cold
In the reaction vessel of solidifying device, then add into reaction vessel 0.15 weight parts of polymer inhibitor 7- diaminophenothiazines and
12 tungstophosphoric acid alkali salts of 0.15 parts by weight alkaline-earth alkoxides, stir 3h progress ester exchange reactions, so at 65 DEG C
Afterwards corresponding imido- acrylic monomers is obtained by the way that extraction is evaporated in vacuo.
3) synthesis of end-vinyl base polyurethane prepolymer for use as
To step 1) in obtained by base polyurethane prepolymer for use as in add the hydroxy-ethyl acrylate and 12 parts by weight of 67 parts by weight
Step 2) obtained by imido- acrylic monomers, react 2h at 80 DEG C, obtain strand imido- and containing vinyl
Hydrophilic polyurethane performed polymer.
4) synthesis of water-dispersible polyurethane performed polymer
To step 3) the middle dimethylethanolamine for adding 8 parts by weight, system pH is reached 7.8, then under stirring
Adding the distilled water of 248 parts by weight makes performed polymer be uniformly dispersed, and obtains water-dispersible polyurethane performed polymer.
5) synthesis of acroleic acid polyurethane water-borne dispersions
To step 4) in add 46 parts by weight butyl methacrylate and 0.6 parts by weight lauryl mercaptan, high-speed stirring
Emulsification is mixed, 80-90 DEG C is warming up to, the solution being made up of the potassium peroxydisulfate of 0.5 parts by weight and the distilled water of 80 parts by weight is added dropwise,
3h is reacted, 1h is incubated after reaction, Aqueous acrylic urethane's dispersion that imido- is combined with hydroxyl is obtained.
The purposes (Application Example) of the embodiment 3- products of the present invention：
The system of general aqueous quick-drying solid color enamel is repaired in another embodiment in the present invention there is provided a kind of genuine
Preparation Method, it includes：
The preparation method of aqueous quick-drying solid color enamel, preparation process is included (by taking yellow as an example)：
1) in above-mentioned aqueous dispersion add dispersant, levelling agent, defoamer, wetting dispersing agent, organic yellow uitramarine,
Water, obtains component A, and the addition of wherein each component is as follows：
Table two：Basic components (by taking yellow as an example)
Above raw material are to be slowly added under stirring state, and are uniformly dispersed, and the aqueous quick-drying needed for finally obtaining is real
Colored paint finished product, i.e. component A.
Using component A with as component B hydrophilic modifying polyisocyanates according to A:B：Water=4：1：1 part by weight is mixed
Close uniform, you can carry out construction spraying.
Using common testing methods in paint field, it is as shown in the table for the correlated performance of the aqueous quick-drying yellow paint of acquisition：
Table three：The performance indications of aqueous quick-drying yellow paint
Present invention design has synthesized a kind of imido- and hydroxyl composite aqueous polyurethane dispersion, the friendship that imino group is exceedingly fast
Join reaction speed, ultrafast dry promising result can be obtained, meanwhile, the cross-linking reaction of hydroxyl ensure that in the same of ultrafast dry effect
When, it can make the paint film to be formed that there are excellent ornamental and resistance to all kinds of media, successfully solve curing rate and paint film property
The contradiction of effect, has set up the ultrafast dry system of an environment-friendly and high-performance.The real color of aqueous quick-drying prepared using the dispersion
The characteristics of paint has high activity of curing reaction, excellent combination property, while VOC content is reduced within 10%, the feature of environmental protection is extremely
Substantially, constructing operation is simple, and the development for promoting water paint is significant.The present invention relates to a kind of painting of aqueous automobile
Material, more particularly to a kind of preparation by imido- and hydroxyl composite aqueous polyurethane dispersion, further relate to genuine repairing general
Aqueous quick-drying solid color enamel preparation method.
Claims (8)
1. the preparation method of a kind of imido- and hydroxyl composite water soluble acrylic PU dispersion, it is characterized in that：
1) synthesis of hydrophilic modifying terminal isocyanate group base polyurethane prepolymer for use as
In a nitrogen environment, will using 35-40 parts by weight of methylmethacrylate and 1-5 parts by weight propylene acetoacetic ester as solvent
The average functionality 2-2.3 of 130-145 parts by weight, molecular weight 1000-2000 oligomer polyols, the fat of 35-50 parts by weight
The catalyst of race or alicyclic diisocyanate, 7-8 part by weight of hydrophilic small molecule chain extender and 1.5 parts by weight adds reactor
In, 70 DEG C -80 DEG C are heated under stirring, 1-2h is reacted, obtains hydrophilic modifying terminal isocyanate group base polyurethane prepolymer for use as；
2) synthesis of imido- performed polymer
Selection 25-40 weight parts of methacrylic acid ethyl ester and 6-10 parts by weight N, N '-tert-butyl group hydroxyl butylimine, which are added to, to be equipped with
In the reaction vessel of condensing unit, then into reaction vessel add 0.1-0.15 weight parts of polymer inhibitor 7- diaminourea fen thiophenes
Piperazine and the tungstophosphoric acid alkali salt of 0.1-0.2 parts by weight 12, stir 2.5-3.5h progress ester exchanges anti-at 60 DEG C -70 DEG C
Should, then extract the performed polymer for obtaining imido- by being evaporated in vacuo；
3) synthesis of end-vinyl base polyurethane prepolymer for use as
To step 1) in obtained by base polyurethane prepolymer for use as in add 60-70 parts by weight hydroxy-acrylate monomer and 8-15 weight
Measure part step 2) obtained by imido- performed polymer, at 80 DEG C -90 DEG C, lower reaction 1-2h, obtain strand imido- and
Hydrophilic polyurethane performed polymer containing vinyl；
4) synthesis of water-dispersible polyurethane performed polymer
To step 3) the middle nertralizer for adding 6-8 parts by weight, system pH is reached 7-8, then add 200- under stirring
The distilled water of 300 parts by weight makes performed polymer be uniformly dispersed, and obtains water-dispersible polyurethane performed polymer；
5) synthesis of acroleic acid polyurethane water-borne dispersions
To step 4) in add 40-50 parts by weight vinyl monomer and 0.5-1 parts by weight chain-transferring agent, high-speed stirred breast
Change, be warming up to 80-90 DEG C, the solution being made up of the initiator of 0.5-1 parts by weight and the distilled water of 60-80 parts by weight is added dropwise,
3-4h is reacted, 1h is incubated after reaction, Aqueous acrylic urethane's dispersion that imido- is combined with hydroxyl is obtained.
2. the preparation side of a kind of imido- according to claim 1 and hydroxyl composite water soluble acrylic PU dispersion
Method, it is characterized in that oligomer polyol is PEPA or PPG.
3. the preparation side of a kind of imido- according to claim 2 and hydroxyl composite water soluble acrylic PU dispersion
Method, it is characterized in that PEPA or PPG are polyethylene glycol, polypropylene glycol or polyethylene glycol oxide-propylene oxide two
Alcohol.
4. the preparation side of a kind of imido- according to claim 1 and hydroxyl composite water soluble acrylic PU dispersion
Method, it is characterized in that aliphatic or alicyclic diisocyanate are IPDI or hexamethylene diisocyanate.
5. the preparation side of a kind of imido- according to claim 1 and hydroxyl composite water soluble acrylic PU dispersion
Method, it is characterized in that hydrophilic small molecules chain extender elects one kind in dihydroxy carboxylic acids, dicarboxyl half ester or dicarboxyl sulfonate as
Or it is a variety of.
6. the preparation side of a kind of imido- according to claim 1 and hydroxyl composite water soluble acrylic PU dispersion
Method, it is characterized in that catalyst is selected from organic amine or organic tin.
7. the preparation side of a kind of imido- according to claim 1 and hydroxyl composite water soluble acrylic PU dispersion
Method, it is characterized in that nertralizer is N- ethyl diisopropyl amines or triethylamine or dimethylethanolamine.
8. the preparation side of a kind of imido- according to claim 1 and hydroxyl composite water soluble acrylic PU dispersion
Method, it is characterized in that initiator is ammonium persulfate or potassium peroxydisulfate.
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| CN101148562A (en) * | 2007-10-26 | 2008-03-26 | 苏州巨峰绝缘材料有限公司 | Environment-friendly acrylic polyurethane two-component surface enamel |
| CN101792570A (en) * | 2010-02-10 | 2010-08-04 | 汤汉良 | Hydroxyl-containing crylic acid polyurethane aqueous dispersion body and application |
| CN102020917A (en) * | 2010-11-18 | 2011-04-20 | 青岛德鑫汽车涂料有限公司 | Water-based two-component acrylic acid polyurethane automobile paint and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101148562A (en) * | 2007-10-26 | 2008-03-26 | 苏州巨峰绝缘材料有限公司 | Environment-friendly acrylic polyurethane two-component surface enamel |
| CN101792570A (en) * | 2010-02-10 | 2010-08-04 | 汤汉良 | Hydroxyl-containing crylic acid polyurethane aqueous dispersion body and application |
| CN102020917A (en) * | 2010-11-18 | 2011-04-20 | 青岛德鑫汽车涂料有限公司 | Water-based two-component acrylic acid polyurethane automobile paint and preparation method thereof |
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| Title |
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| 低温快固化丙烯酸聚氨酯涂料的发展现状;王淑娟等;《涂料工业》;20111201;第41卷(第12期);第67页左栏第1-3行和右栏第8-9行，第68页第2.1.1节 * |
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