CN105602439A - Water-based ultraviolet curing coating and preparation method thereof - Google Patents
Water-based ultraviolet curing coating and preparation method thereof Download PDFInfo
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- CN105602439A CN105602439A CN201511019509.1A CN201511019509A CN105602439A CN 105602439 A CN105602439 A CN 105602439A CN 201511019509 A CN201511019509 A CN 201511019509A CN 105602439 A CN105602439 A CN 105602439A
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- preparation
- waterborne coatings
- curable waterborne
- vulcabond
- stirring
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- 238000000576 coating method Methods 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 239000011248 coating agent Substances 0.000 title abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 58
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 51
- 238000003756 stirring Methods 0.000 claims abstract description 45
- 150000001336 alkenes Chemical class 0.000 claims abstract description 30
- 239000004970 Chain extender Substances 0.000 claims abstract description 28
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 22
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 21
- 239000003112 inhibitor Substances 0.000 claims abstract description 20
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 19
- 239000006185 dispersion Substances 0.000 claims abstract description 19
- 239000008367 deionised water Substances 0.000 claims abstract description 15
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 15
- 239000000376 reactant Substances 0.000 claims description 41
- 150000001298 alcohols Chemical class 0.000 claims description 39
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 34
- MMCOUVMKNAHQOY-UHFFFAOYSA-N carbonoperoxoic acid Chemical class OOC(O)=O MMCOUVMKNAHQOY-UHFFFAOYSA-N 0.000 claims description 29
- 239000003153 chemical reaction reagent Substances 0.000 claims description 28
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims description 21
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 19
- 239000004814 polyurethane Substances 0.000 claims description 19
- 229920002635 polyurethane Polymers 0.000 claims description 19
- 239000013530 defoamer Substances 0.000 claims description 17
- 239000000945 filler Substances 0.000 claims description 15
- -1 isocyano ion Chemical class 0.000 claims description 15
- 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
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 13
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 12
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 12
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical group COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 230000001804 emulsifying effect Effects 0.000 claims description 7
- 239000005543 nano-size silicon particle Substances 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 235000019260 propionic acid Nutrition 0.000 claims description 6
- 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 claims description 6
- 229920001610 polycaprolactone Polymers 0.000 claims description 5
- 239000004632 polycaprolactone Substances 0.000 claims description 5
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 4
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 4
- 150000002334 glycols Chemical class 0.000 claims description 4
- 229920000570 polyether Polymers 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 3
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 3
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- TUOBEAZXHLTYLF-UHFFFAOYSA-N [2-(hydroxymethyl)-2-(prop-2-enoyloxymethyl)butyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(CC)COC(=O)C=C TUOBEAZXHLTYLF-UHFFFAOYSA-N 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- 230000002045 lasting effect Effects 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 claims description 2
- BRWZYZWZBMGMMG-UHFFFAOYSA-J dodecanoate tin(4+) Chemical compound [Sn+4].CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O.CCCCCCCCCCCC([O-])=O BRWZYZWZBMGMMG-UHFFFAOYSA-J 0.000 claims 1
- 238000001723 curing Methods 0.000 abstract description 8
- 238000002156 mixing Methods 0.000 abstract description 4
- 125000005442 diisocyanate group Chemical group 0.000 abstract description 2
- 239000000243 solution Substances 0.000 abstract 7
- 239000002518 antifoaming agent Substances 0.000 abstract 1
- 150000007942 carboxylates Chemical class 0.000 abstract 1
- 150000002009 diols Chemical class 0.000 abstract 1
- 239000000839 emulsion Substances 0.000 abstract 1
- 239000011259 mixed solution Substances 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 239000003973 paint Substances 0.000 description 7
- 239000000178 monomer Substances 0.000 description 6
- 150000002148 esters Chemical class 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 125000002462 isocyano group Chemical group *[N+]#[C-] 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- AYOHIQLKSOJJQH-UHFFFAOYSA-N dibutyltin Chemical compound CCCC[Sn]CCCC AYOHIQLKSOJJQH-UHFFFAOYSA-N 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 238000003848 UV Light-Curing Methods 0.000 description 2
- 125000004494 ethyl ester group Chemical group 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- WWSNKXVETXETTP-UHFFFAOYSA-N 3,3-dihydroxyprop-2-enoic acid Chemical compound OC(O)=CC(O)=O WWSNKXVETXETTP-UHFFFAOYSA-N 0.000 description 1
- JRCGLALFKDKSAN-UHFFFAOYSA-N 3-hydroxybutyl prop-2-enoate Chemical group CC(O)CCOC(=O)C=C JRCGLALFKDKSAN-UHFFFAOYSA-N 0.000 description 1
- XCHLRFRZJLYDOF-UHFFFAOYSA-N CCC.OC(=O)C=C.OC(=O)C=C Chemical compound CCC.OC(=O)C=C.OC(=O)C=C XCHLRFRZJLYDOF-UHFFFAOYSA-N 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- XXKOQQBKBHUATC-UHFFFAOYSA-N cyclohexylmethylcyclohexane Chemical compound C1CCCCC1CC1CCCCC1 XXKOQQBKBHUATC-UHFFFAOYSA-N 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 1
- 238000006253 efflorescence Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 206010037844 rash Diseases 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
- C08G18/348—Hydroxycarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
- C08G18/673—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen containing two or more acrylate or alkylacrylate ester groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Polyurethanes Or Polyureas (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention relates to a water-based ultraviolet curing coating and a preparation method thereof. The preparation method for the water-based ultraviolet curing coating comprises the following steps: mixing diisocyanate and diol and reacting to obtain a first reaction solution; adding dyhydroxyl carboxylate and a catalyst to the first reaction solution and reacting to obtain a second reaction solution, and mixing the second reaction solution and a chain extender and reacting to obtain a third reaction solution; adding an alkene end-capping agent and a polymerization inhibitor to the third mixed solution and reacting to obtain a fourth reaction solution, and adding triethylamine to the fourth reaction solution and reacting to obtain a urethane acrylate prepolymer; adding deionized water to the urethane acrylate prepolymer, carrying out emulsion dispersion to obtain an urethane acrylate dispersoid, mixing the urethane acrylate dispersoid, a photoinitiator, a defoaming agent and a leveling agent, and carrying out stirring dispersion for 15 to 30 minutes to obtain the water-based ultraviolet curing coating. The water-based ultraviolet curing coating prepared by the preparation method disclosed by the invention has relatively higher performances.
Description
Technical field
The present invention relates to paint field, particularly a kind of UV-curable waterborne coatings and preparation method thereof.
Background technology
That water paint has is nontoxic, pollution-free, non-stimulated, film performance is good, save the energy, produce peaceCongruence advantage, has responded 21st century efficient, energy-conservation, green and the themes of the times of environmental protection. At present, waterProperty coating adopts linear polymer as main material mostly, and linear polymer has the performance of many excellences,But there is the slow shortcoming of curing rate.
Water paint and photocureable coating technology are combined, can effectively utilize photocuring technology to solidify speedSpend fast advantage, obtain preferably UV-curable waterborne coatings of easy construction, properties.
But existing UV-curable waterborne coatings is because of under exposure in sunshine out of doors, the very fast xanthochromia of paint film,Efflorescence; If at architectural use UV-curable waterborne coatings, also can cause the exposed corrosion of building surface, fromAnd the durability of reduction building.
Summary of the invention
Based on this, be necessary to provide a kind of side of the UV-curable waterborne coatings that can prepare better performancesMethod.
In addition, also provide a kind of UV-curable waterborne coatings.
A preparation method for UV-curable waterborne coatings, comprises the steps:
Under the environment of protective gas, be that 1:0.2～0.6 is by mixed to vulcabond and dihydroxylic alcohols according to mol ratioClose, in 70～90 DEG C of stirring reactions 1～3 hour, obtain the first reactant liquor;
In described the first reactant liquor, add dihydroxy carboxylic acids and catalyst, in 70～80 DEG C of stirring reactions 1～2Hour, obtain the second reactant liquor, wherein, the mol ratio of described dihydroxy carboxylic acids and described vulcabond is0.1～0.5:1；
Under the condition of 50～60 DEG C, described the second reactant liquor and chain extender are mixed, carry out chain extending reaction 2～3Hour, obtain the 3rd reactant liquor;
Under the condition of 50～60 DEG C, in described the 3rd mixed liquor, add alkene class end-capping reagent and polymerization inhibitor, reactionAfter 1 hour, be warming up to 75～85 DEG C, be adjusted to appropriate viscosity extremely with acetone, continue reaction 2 hours, obtainThe 4th reactant liquor, wherein, the mol ratio of described alkene class end-capping reagent and described vulcabond is 0.1～0.6:1;
Under the condition of 40～50 DEG C, in described the 4th reactant liquor, add triethylamine, react 0.5～1.0 hour,Obtain polyurethane acrylate prepolymer, wherein, the mol ratio of described triethylamine and described dihydroxy carboxylic acids is1～1.5:1；
Under the lasting condition stirring, deionized water is joined in described polyurethane acrylate prepolymer,Continue stirring and emulsifying and disperse 30～40 minutes, through cooling, obtain urethane acrylate dispersoid, wherein,The mass ratio of described polyurethane acrylate prepolymer and described deionized water is 30～50:40～60;
Comprise following component according to mass fraction: 65～90 parts of described urethane acrylate dispersoids, filler3～6 parts of 5～30 parts, 0.1～1 part of levelling agent, 0.1～1 part of defoamer and light triggers, wherein, described fillerBeing selected from mass fraction is 30% nano silicon aqueous dispersions, the nanometer titanium dioxide that mass fraction is 20%Titanium aqueous dispersions and mass fraction are at least one in 20% nano-aluminium oxide aqueous dispersions; And
By described urethane acrylate dispersoid, described filler, described light trigger, described defoamer andDescribed levelling agent mixes, and dispersed with stirring 15～30 minutes, obtains UV-curable waterborne coatings.
In an embodiment, described vulcabond is selected from XDI, dicyclohexyl thereinMethane diisocyanate, '-diphenylmethane diisocyanate, terephthalylidene vulcabond, oneself two isocyanidesAt least one in acid esters and IPDI
In an embodiment, described dihydroxylic alcohols is selected from polyether Glycols, polycaprolactone dihydroxylic alcohols and poly-thereinAt least one in carbonic ester dihydroxylic alcohols.
Therein in an embodiment, the molecular weight of described dihydroxylic alcohols be 500g/mol, 600g/mol or1000g/mol。
In an embodiment, described dihydroxy carboxylic acids is in dihydromethyl propionic acid and dimethylolpropionic acid thereinAt least one; Described catalyst is dibutyl tin laurate; Wherein, described catalyst and described dihydroxyThe mass ratio of yl carboxylic acid is 0.1～1:2～10.
In an embodiment, described alkene class end-capping reagent is selected from first hydroxyethyl methacrylate, acrylic acid thereinHydroxyl ethyl ester, pentaerythritol triacrylate, hydroxy propyl methacrylate, hydroxypropyl acrylate, trihydroxy methylAt least one in propane diacrylate; Described polymerization inhibitor is p methoxy phenol, wherein said polymerization inhibitorWith the mass ratio of described alkene class end-capping reagent be 0.1～0.5:8～60.
In an embodiment, also comprise the preparation process of described chain extender therein:
Pentaerythritol triacrylate, metoxyphenol and acetone are mixed, under the condition of 45 DEG C, addIPDI and dibutyl tin laurate, then rise to 40～60 DEG C of reactions until isocyanoThe content of ion is 8%, obtains the first mixed liquor wherein; Described in the acetone soln of trimethylolpropane is addedIn the first mixed liquor, react until isocyano ion isocyano ion disappears, described in obtaining in 60～75 DEG CChain extender, wherein, described pentaerythritol triacrylate, described IPDI and described threeThe mol ratio of hydroxymethyl-propane is 1:1:1.
Therein in an embodiment, by described urethane acrylate dispersoid, described filler, described lightInitator, described defoamer and described levelling agent mix, after the dispersed with stirring step of 15～30 minutes, alsoComprise the step of described UV-curable waterborne coatings being crossed to 200～400 mesh sieves.
A kind of UV-curable waterborne being prepared by the preparation method of above-mentioned UV-curable waterborne coatingsCoating.
The preparation method of above-mentioned UV-curable waterborne coatings is simple to operate, is easy to suitability for industrialized production. Above-mentioned waterProperty ultraviolet-curing paint adopts with vulcabond, dihydroxylic alcohols, dihydroxy carboxylic acids, chain extender, hydroxyl thirdOlefin(e) acid ester and triethylamine are that primary raw material has been prepared polyurethane acrylate prepolymer, by containing two key dihydroxylic alcoholsIntroduce UV curing groups at molecular backbone side group, prepared and obtained UV-curable waterborne coatings.
Brief description of the drawings
Fig. 1 is the preparation method's of the UV-curable waterborne coatings of an embodiment flow chart.
Detailed description of the invention
Mainly in conjunction with the drawings and the specific embodiments UV-curable waterborne coatings and preparation method thereof is done belowFurther detailed explanation.
As shown in Figure 1, the preparation method of the UV-curable waterborne coatings of an embodiment, comprises following stepRapid:
Step S110: under the environment of protective gas, be that 1:0.2～0.6 is by vulcabond according to mol ratioMix with dihydroxylic alcohols, in 70～90 DEG C of stirring reactions 1～3 hour, obtain the first reactant liquor.
Wherein, protective gas can be nitrogen or inert gas.
Wherein, vulcabond is selected from XDI, dicyclohexyl methyl hydride diisocyanate, twoPhenylmethane vulcabond, terephthalylidene vulcabond, hexamethylene diisocyanate and isophorone two are differentAt least one in cyanate.
Wherein, dihydroxylic alcohols is selected from polyether Glycols, polycaprolactone dihydroxylic alcohols and PCDL extremelyFew a kind of. And the molecular weight of dihydroxylic alcohols is 500g/mol, 600g/mol or 1000g/mol.
Step S120: add dihydroxy carboxylic acids and catalyst in the first reactant liquor, stir anti-in 70～80 DEG CAnswer 1～2 hour, obtain the second reactant liquor.
Wherein, the mol ratio of dihydroxy carboxylic acids and vulcabond is 0.1～0.5:1.
Wherein, dihydroxy carboxylic acids is at least one in dihydromethyl propionic acid and dimethylolpropionic acid.
Wherein, catalyst is dibutyl tin laurate. Wherein, the mass ratio of catalyst and dihydroxy carboxylic acidsBe 0.1～1:2～10.
Step S130: under the condition of 50～60 DEG C, the second reactant liquor and chain extender are mixed, carry out chain extensionReact 2～3 hours, obtain the 3rd reactant liquor.
Wherein, chain extender is double bond containing dihydroxylic alcohols monomer.
Concrete, chain extender can prepare by being prepared as follows step: by pentaerythritol triacrylate,Metoxyphenol and acetone mix, and under the condition of 45 DEG C, add IPDI (IDPI)And dibutyl tin laurate (DBTAL), then rise to 40～60 DEG C of reactions until the containing of isocyano ionAmount is 8%, obtains the first mixed liquor wherein; The acetone soln of trimethylolpropane (TMP) is added to firstIn mixed liquor, until isocyano ion isocyano ion disappears, obtain double bond containing in 60～75 DEG C of reactionsDihydroxylic alcohols monomer. Wherein, pentaerythritol triacrylate, IPDI and trihydroxy methyl thirdThe mol ratio of alkane is 1:1:1.
Wherein, the quality of metoxyphenol and the mass ratio of pentaerythritol triacrylate are 0.5:100.
Wherein, the mass ratio of dibutyl tin laurate and IPDI is 0.08:100.
Wherein, the mol ratio of chain extender and vulcabond is 0.1～0.3:1.
Step S140: under the condition of 50～60 DEG C, add alkene class end-capping reagent and inhibition in the 3rd mixed liquorAgent, reacted after 1 hour, was warming up to 75～85 DEG C, was adjusted to appropriate viscosity with acetone, continued reaction 2 hours,Obtain the 4th reactant liquor.
Wherein, the mol ratio of alkene class end-capping reagent and vulcabond is 0.1～0.6:1.
Wherein, alkene class end-capping reagent is selected from hydroxyethyl methacrylate, hydroxy-ethyl acrylate, pentaerythrite 3 thirdIn olefin(e) acid ester, hydroxy propyl methacrylate, hydroxypropyl acrylate, trimethylolpropane diacrylate extremelyFew a kind of.
Wherein, polymerization inhibitor is p methoxy phenol.
Wherein, the mass ratio of polymerization inhibitor and alkene class end-capping reagent is 0.1～0.5:8～60.
Step S150: under the condition of 40～50 DEG C, add triethylamine in the 4th reactant liquor, reaction 0.5～1.0Hour, obtain polyurethane acrylate prepolymer.
Wherein, the mol ratio of triethylamine and dihydroxy carboxylic acids is 1～1.5:1.
Step S160: continuing under the condition stirring, deionized water is being joined to polyurethane acrylate prepolymer poly-In body, continue stirring and emulsifying and disperse 30～40 minutes, through cooling, obtain urethane acrylate dispersoid.
Wherein, the mass ratio of polyurethane acrylate prepolymer and deionized water is 30～50:40～60.
In step S160, it is 300～400 revs/min in the speed that continues the condition stirring; Continue stirring and emulsifyingThe mixing speed of disperseing 30～40 minutes is 400～600 revs/min.
Step S170: comprise following component according to mass fraction: 65～90 parts of urethane acrylate dispersoids,3～6 parts of 5～30 parts of fillers, 0.1～1 part of levelling agent, 0.1～1 part of defoamer and light triggers.
Wherein, to be selected from mass fraction be 30% nano silicon aqueous dispersions, mass fraction to described fillerIt is the nano-aluminium oxide aqueous dispersions that 20% nano titanium dioxide water-dispersion liquid and mass fraction are 20%In at least one.
Wherein, levelling agent is selected from least one in BYK346, BYK333, BYK301 and BYK307.Defoamer is the conventional defoamer in this area, defoamer be selected from BYK024, BYK028, BYK022 andAt least one in BYK093.
Wherein, light trigger is selected from least one in 907,184,1173,2959 and 754.
Step S180: by urethane acrylate dispersoid, filler, light trigger, defoamer and levelling agentMix, dispersed with stirring 15～30 minutes, obtains UV-curable waterborne coatings.
Wherein, urethane acrylate dispersoid, filler, light trigger, defoamer and levelling agent are mixed,After the dispersed with stirring step of 15～30 minutes, also comprise UV-curable waterborne coatings is crossed to 200～400 ordersThe step of sieve.
The preparation method of above-mentioned UV-curable waterborne coatings is simple to operate, is easy to suitability for industrialized production. Above-mentioned waterProperty ultraviolet-curing paint adopts with vulcabond, dihydroxylic alcohols, dihydroxy carboxylic acids, chain extender, dihydroxyAcrylic acid and triethylamine are that primary raw material has been prepared polyurethane acrylate prepolymer, by containing two key dihydroxylic alcoholsIntroduce UV curing groups at molecular backbone side group, prepared high performance UV-curable waterborne coatings.
A kind of UV-curable waterborne being prepared by the preparation method of above-mentioned UV-curable waterborne coatingsCoating. Prepare because this UV-curable waterborne coatings adopts above-mentioned preparation method, make above-mentioned water-basedUltraviolet-curing paint has high performance.
Be below specific embodiment part:
Embodiment 1
The preparation process of the UV-curable waterborne coatings of the present embodiment is as follows:
(1) preparation of chain extender: pentaerythritol triacrylate and metoxyphenol (MEHQ) are used to 10gAcetone proceed in the there-necked flask that thermometer, condenser pipe and agitator are housed, wherein, metoxyphenolThe mass ratio of quality and pentaerythritol triacrylate is 0.5:100; Then be placed in 45 DEG C of waters bath with thermostatic control,Utilize constant pressure funnel that IPDI is dropwise joined in there-necked flask, add two bays simultaneouslyAcid dibutyl tin (DBTAL) carries out catalysis, then rises to 55 DEG C of reaction 2h, to the isocyano in systemThe content of ion is 8%. Trimethylolpropane constant voltage is splashed in reaction system, add in right amount acetone, heat upTo 65 DEG C of reaction 3h, the isocyano ion in question response system disappears, and discharging, obtains colourless or pale yellowThe double bond containing dihydroxylic alcohols monomer of look, is chain extender, wherein, and dibutyl tin laurate and isophoroneThe mass ratio of vulcabond is 0.08:100; Pentaerythritol triacrylate, IPDI andThe mol ratio of trimethylolpropane is 1:1:1.
(2) preparation of urethane acrylate dispersoid:
1, under logical nitrogen protection condition, to the four-hole circle reaction bulb that is placed with thermometer, condenser pipe, stirring rodIn, add vulcabond and dihydroxylic alcohols, 70 DEG C of stirring reactions 3 hours, obtain the first reactant liquor, itsIn, the mol ratio of vulcabond and dihydroxylic alcohols is 1:0.6, vulcabond is selected from dimethylbenzene two isocyanic acidsEster; Dihydroxylic alcohols is selected from polyether Glycols; The molecular weight of dihydroxylic alcohols is 500g/mol.
2, in the first reactant liquor, add dihydroxy carboxylic acids and catalyst, in 70 DEG C of stirring reactions 2 hours,To the second reactant liquor. Wherein, the mol ratio of dihydroxy carboxylic acids and vulcabond is 0.1:1, dihydroxy carboxylic acidsFor dihydromethyl propionic acid, catalyst is dibutyl tin laurate, the mass ratio of catalyst and dihydroxy carboxylic acidsFor 0.1:2.
3, be cooled to 50 DEG C, adopt constant pressure funnel chain extender prepared by step (1) to add second anti-Answer in liquid, carry out chain extending reaction 2 hours, obtain the 3rd reactant liquor. Wherein, chain extender and vulcabondMol ratio be 0.1:1.
4, under the condition of 50 DEG C, in the 3rd mixed liquor, add alkene class end-capping reagent and polymerization inhibitor, reaction 1 is littleShi Hou, is warming up to 75 DEG C, is adjusted to appropriate viscosity with acetone, continues reaction 2 hours, obtains the 4th reactionLiquid. Wherein, the mol ratio of alkene class end-capping reagent and vulcabond is 0.1:1; Alkene class end-capping reagent is selected from methyl-propOlefin(e) acid hydroxyl ethyl ester; Polymerization inhibitor is p methoxy phenol; The mass ratio of polymerization inhibitor and alkene class end-capping reagent is 0.1:8.
5, under the condition of 40 DEG C, in described the 4th reactant liquor, add triethylamine, react 0.5 hour,To transparent polyurethane acrylate prepolymer. Wherein, the mol ratio of triethylamine and dihydroxy carboxylic acids is 1:1.
6, under 300 revs/min of conditions that continue to stir, deionized water is joined to polyurethane acrylate prepolymerIn aggressiveness, continue to disperse 30 minutes with the speed stirring and emulsifying of 400 revs/min, through cooling, obtain polyurethaneAcrylate dispersoid.
(3) preparation of filler: under room temperature condition, nano silicon is mixed to dispersion with deionized water,To dispersion liquid.
(4) preparation of UV-curable waterborne coatings:
1, take following component according to mass fraction:
2, according to said ratio, urethane acrylate dispersoid, step (3) prepared by step (2)Filler, light trigger, defoamer and the levelling agent of preparation adds and disperses to mix in cylinder, dispersed with stirring 15 minutes,Cross 200 mesh sieves, obtain UV-curable waterborne coatings. Wherein, levelling agent be selected from BYK346. Light-initiatedAgent is selected from 907.
Test the performance of the UV-curable waterborne coatings of the present embodiment, obtain the aquosity ultraviolet light of the present embodimentCoating material solidified performance is in table 1.
Embodiment 2
The preparation process of the UV-curable waterborne coatings of the present embodiment is as follows:
(1) preparation of chain extender: pentaerythritol triacrylate and metoxyphenol (MEHQ) are used to 10gAcetone proceed in the there-necked flask that thermometer, condenser pipe and agitator are housed, wherein, metoxyphenolThe mass ratio of quality and pentaerythritol triacrylate is 0.5:100; Then be placed in 45 DEG C of waters bath with thermostatic control,Utilize constant pressure funnel that IPDI is dropwise joined in there-necked flask, add two bays simultaneouslyAcid dibutyl tin (DBTAL) carries out catalysis, then rises to 55 DEG C of reaction 2h, to the isocyano in systemThe content of ion is 8%, and trimethylolpropane constant voltage is splashed in reaction system, adds in right amount acetone, heats upTo 65 DEG C of reaction 3h, the isocyano ion isocyano ion in question response system disappears, and discharging, obtainsColourless or lurid double bond containing dihydroxylic alcohols monomer, is chain extender, wherein, and di lauric dibutylThe mass ratio of tin and IPDI is 0.08:100; Pentaerythritol triacrylate, isophoroneThe mol ratio of vulcabond and trimethylolpropane is 1:1:1.
(2) preparation of urethane acrylate dispersoid:
1, under logical nitrogen protection condition, to the four-hole circle reaction bulb that is placed with thermometer, condenser pipe, stirring rodIn, add vulcabond and dihydroxylic alcohols, 90 DEG C of stirring reactions 1 hour, obtain the first reactant liquor, itsIn, the mol ratio of vulcabond and dihydroxylic alcohols is 1:0.3, vulcabond is selected from dicyclohexyl methyl hydride twoIsocyanates; Dihydroxylic alcohols is selected from polycaprolactone dihydroxylic alcohols; The molecular weight of dihydroxylic alcohols is 600g/mol.
2, in the first reactant liquor, add dihydroxy carboxylic acids and catalyst, in 80 DEG C of stirring reactions 1 hour,To the second reactant liquor. Wherein, the mol ratio of dihydroxy carboxylic acids and vulcabond is 0.4:1, dihydroxy carboxylic acidsIn dimethylolpropionic acid, catalyst is dibutyl tin laurate, the quality of catalyst and dihydroxy carboxylic acidsThan being 1:10.
3, be cooled to 60 DEG C, adopt constant pressure funnel chain extender prepared by step (1) to add second anti-Answer in liquid, carry out chain extending reaction 3 hours, obtain the 3rd reactant liquor. Wherein, chain extender and vulcabondMol ratio be 0.3:1.
4, under the condition of 60 DEG C, in the 3rd mixed liquor, add alkene class end-capping reagent and polymerization inhibitor, reaction 1 is littleShi Hou, is warming up to 85 DEG C, is adjusted to applicable viscosity with acetone, continues reaction 2 hours, obtains the 4th reactionLiquid. Wherein, the mol ratio of alkene class end-capping reagent and vulcabond is 0.1:1; Alkene class end-capping reagent is selected from acrylic acidHydroxyl ethyl ester; Polymerization inhibitor is p methoxy phenol; The mass ratio of polymerization inhibitor and alkene class end-capping reagent is 0.5:80.
5, under the condition of 50 DEG C, in described the 4th reactant liquor, add triethylamine, react 1.0 hours,To transparent polyurethane acrylate prepolymer. Wherein, the mol ratio of triethylamine and dihydroxy carboxylic acids is 1.5:1.
6, under 400 revs/min of conditions that continue to stir, deionized water is joined to polyurethane acrylate prepolymerIn aggressiveness, continue to disperse 40 minutes with the speed stirring and emulsifying of 600 revs/min, through cooling, obtain polyurethaneAcrylate dispersoid.
(3) preparation of filler: under room temperature condition, by nano silicon, nano titanium oxide and nanometer threeAt least one in Al 2 O mixed dispersion with deionized water, obtain dispersion liquid.
(4) preparation of UV-curable waterborne coatings:
1, take following component according to mass fraction:
2, according to said ratio, urethane acrylate dispersoid, step (3) prepared by step (2)Filler, light trigger, defoamer and the levelling agent of preparation adds and disperses to mix in cylinder, dispersed with stirring 30 minutes,Cross 200 mesh sieves, obtain UV-curable waterborne coatings. Wherein, levelling agent is selected from BYK333. DefoamerBe selected from BYK024. Light trigger is selected from 184.
Adopt the identical method of testing of embodiment 1 to obtain the property of the purple UV-curable waterborne coatings of the present embodimentCan be in table 1.
Embodiment 3
The preparation process of the UV-curable waterborne coatings of the present embodiment is as follows:
(1) preparation of chain extender: pentaerythritol triacrylate and metoxyphenol (MEHQ) are used to 10gAcetone proceed in the there-necked flask that thermometer, condenser pipe and agitator are housed, wherein, metoxyphenolThe mass ratio of quality and pentaerythritol triacrylate is 0.5:100; Then be placed in 45 DEG C of waters bath with thermostatic control,Utilize constant pressure funnel that IPDI is dropwise joined in there-necked flask, add two bays simultaneouslyAcid dibutyl tin (DBTAL) carries out catalysis, then rises to 55 DEG C of reaction 2h, to the isocyano in systemThe content of ion is 8%. Trimethylolpropane constant voltage is splashed in reaction system, add in right amount acetone, heat upTo 65 DEG C of reaction 3h, the isocyano ion in question response system disappears, and discharging, obtains colourless or pale yellowThe double bond containing dihydroxylic alcohols monomer of look, is chain extender, wherein, and dibutyl tin laurate and isophoroneThe mass ratio of vulcabond is 0.08:100; Pentaerythritol triacrylate, IPDI andThe mol ratio of trimethylolpropane is 1:1:1.
(2) preparation of urethane acrylate dispersoid:
1, under logical nitrogen protection condition, to the four-hole circle reaction bulb that is placed with thermometer, condenser pipe, stirring rodIn, add vulcabond and dihydroxylic alcohols, 80 DEG C of stirring reactions 2 hours, obtain the first reactant liquor, itsIn, the mol ratio of vulcabond and dihydroxylic alcohols is 1:0.2, vulcabond is selected from diphenyl-methane two isocyanidesAcid esters; Dihydroxylic alcohols is selected from polycaprolactone dihydroxylic alcohols; The molecular weight of dihydroxylic alcohols is 1000g/mol.
2, in the first reactant liquor, add dihydroxy carboxylic acids and catalyst, in 75 DEG C of stirring reactions 1.5 hours,Obtain the second reactant liquor. Wherein, the mol ratio of dihydroxy carboxylic acids and vulcabond is 0.3:1, dihydroxy carboxylicAcid is dihydromethyl propionic acid, and catalyst is dibutyl tin laurate, the quality of catalyst and dihydroxy carboxylic acidsThan being 0.5:8.
3, be cooled to 55 DEG C, adopt constant pressure funnel chain extender prepared by step (1) to add second anti-Answer in liquid, carry out chain extending reaction 3 hours, obtain the 3rd reactant liquor. Wherein, chain extender and vulcabondMol ratio be 0.2:1.
4, under the condition of 55 DEG C, in the 3rd mixed liquor, add alkene class end-capping reagent and polymerization inhibitor, reaction 1 is littleShi Hou, is warming up to 80 DEG C, to suitable, continues reaction 2 hours with acetone adjusting viscosity, obtains the 4th reactionLiquid. Wherein, the mol ratio of alkene class end-capping reagent and vulcabond is 0.4:1; Alkene class end-capping reagent is selected from season pentaTetrol diacrylate; Polymerization inhibitor is p methoxy phenol; The mass ratio of polymerization inhibitor and alkene class end-capping reagent is 0.3:40。
5, under the condition of 45 DEG C, in described the 4th reactant liquor, add triethylamine, react 0.6 hour,To transparent polyurethane acrylate prepolymer. Wherein, the mol ratio of triethylamine and dihydroxy carboxylic acids is 1.2:1.
6, under 350 revs/min of conditions that continue to stir, deionized water is joined to polyurethane acrylate prepolymerIn aggressiveness, continue to disperse 35 minutes with the speed stirring and emulsifying of 500 revs/min, through cooling, obtain polyurethaneAcrylate dispersoid.
(3) preparation of filler: under room temperature condition, by nano silicon, nano titanium oxide and nanometer threeAt least one in Al 2 O mixed dispersion with deionized water, obtain dispersion liquid.
(4) preparation of UV-curable waterborne coatings:
1, take following component according to mass fraction:
2, according to said ratio, urethane acrylate dispersoid, step (3) prepared by step (2)Filler, light trigger, defoamer and the levelling agent of preparation adds and disperses to mix in cylinder, dispersed with stirring 20 minutes,Cross 300 mesh sieves, obtain UV-curable waterborne coatings. Wherein, levelling agent is selected from BYK307. DefoamerBe selected from BYK022. Light trigger is selected from 2959. Adopt the identical method of testing of embodiment 1 to obtain this enforcementThe performance of the purple UV-curable waterborne coatings of example is in table 1.
Embodiment 4
The preparation process of the UV-curable waterborne coatings of the present embodiment is as follows:
(1) preparation of chain extender: pentaerythritol triacrylate and metoxyphenol (MEHQ) are used to 10gAcetone proceed in the there-necked flask that thermometer, condenser pipe and agitator are housed, wherein, metoxyphenolThe mass ratio of quality and pentaerythritol triacrylate is 0.5:100; Then be placed in 45 DEG C of waters bath with thermostatic control,Utilize constant pressure funnel that IPDI is dropwise joined in there-necked flask, add two bays simultaneouslyAcid dibutyl tin (DBTAL) carries out catalysis, then rises to 55 DEG C of reaction 2h, to the isocyano in systemThe content of ion is 8%. Trimethylolpropane constant voltage is splashed in reaction system, add in right amount acetone, heat upTo 65 DEG C of reaction 3h, the isocyano ion in question response system disappears, and discharging, obtains colourless or pale yellowThe double bond containing dihydroxylic alcohols monomer of look, is chain extender, wherein, and dibutyl tin laurate and isophoroneThe mass ratio of vulcabond is 0.08:100; Pentaerythritol triacrylate, IPDI andThe mol ratio of trimethylolpropane is 1:1:1.
(2) preparation of urethane acrylate dispersoid:
1, under logical nitrogen protection condition, to the four-hole circle reaction bulb that is placed with thermometer, condenser pipe, stirring rodIn, add vulcabond and dihydroxylic alcohols, 85 DEG C of stirring reactions 1.5 hours, obtain the first reactant liquor,Wherein, the mol ratio of vulcabond and dihydroxylic alcohols is 1:0.2, the vulcabond isophorone two of selecting oneselfIsocyanates; Dihydroxylic alcohols is selected from PCDL; The molecular weight of dihydroxylic alcohols is 1000g/mol.
2, in the first reactant liquor, add dihydroxy carboxylic acids and catalyst, in 75 DEG C of stirring reactions 1.2 hours,Obtain the second reactant liquor. Wherein, the mol ratio of dihydroxy carboxylic acids and vulcabond is 0.3:1, dihydroxy carboxylicAcid is dihydromethyl propionic acid, and catalyst is dibutyl tin laurate, the quality of catalyst and dihydroxy carboxylic acidsThan being 0.6:7.
3, be cooled to 60 DEG C, adopt constant pressure funnel chain extender prepared by step (1) to add second anti-Answer in liquid, carry out chain extending reaction 3 hours, obtain the 3rd reactant liquor. Wherein, chain extender and vulcabondMol ratio be 0.2:1.
4, under the condition of 60 DEG C, in the 3rd mixed liquor, add alkene class end-capping reagent and polymerization inhibitor, reaction 1 is littleShi Hou, is warming up to 85 DEG C, is adjusted to appropriate viscosity extremely with acetone, continues reaction 2 hours, obtains the 4th anti-Answer liquid. Wherein, the mol ratio of alkene class end-capping reagent and vulcabond is 0.6:1; Alkene class end-capping reagent is selected from methylHydroxypropyl acrylate; Polymerization inhibitor is p methoxy phenol; The mass ratio of polymerization inhibitor and alkene class end-capping reagent is 0.5:80.
5, under the condition of 40 DEG C, in described the 4th reactant liquor, add triethylamine, react 0.5 hour,To transparent polyurethane acrylate prepolymer. Wherein, the mol ratio of triethylamine and dihydroxy carboxylic acids is 1.5:1.
6, under 400 revs/min of conditions that continue to stir, deionized water is joined to polyurethane acrylate prepolymerIn aggressiveness, continue to disperse 40 minutes with the speed stirring and emulsifying of 600 revs/min, through cooling, obtain polyurethaneAcrylate dispersoid.
(3) preparation of filler: under room temperature condition, by nano silicon, nano titanium oxide and nanometer threeAt least one in Al 2 O mixed dispersion with deionized water, obtain dispersion liquid.
(4) preparation of UV-curable waterborne coatings:
1, take following component according to mass fraction:
2, according to said ratio, urethane acrylate dispersoid, step (3) prepared by step (2)Filler, light trigger, defoamer and the levelling agent of preparation adds and disperses to mix in cylinder, dispersed with stirring 25 minutes,Cross 400 mesh sieves, obtain UV-curable waterborne coatings. Wherein, levelling agent be selected from BYK346, BYK333,At least one in BYK301 and BYK307. Defoamer is selected from BYK093. Light trigger is selected from 2959.
Adopt the identical method of testing of embodiment 1 to obtain the property of the purple UV-curable waterborne coatings of the present embodimentCan be in table 1.
What table 1 represented is the performance of the UV-curable waterborne coatings of embodiment 1～4.
Table 1
Obvious above-mentioned UV-curable waterborne coatings possesses good performance.
The above embodiment has only expressed several embodiment of the present invention, and it describes comparatively concrete and detailed,But can not therefore be interpreted as the restriction to the scope of the claims of the present invention. It should be pointed out that for this areaThose of ordinary skill, without departing from the inventive concept of the premise, can also make some distortion andImprove, these all belong to protection scope of the present invention. Therefore, the protection domain of patent of the present invention should be with appendedClaim is as the criterion.
Claims (9)
1. a preparation method for UV-curable waterborne coatings, is characterized in that, comprises the steps:
Under the environment of protective gas, be that 1:0.2～0.6 is by mixed to vulcabond and dihydroxylic alcohols according to mol ratioClose, in 70～90 DEG C of stirring reactions 1～3 hour, obtain the first reactant liquor;
In described the first reactant liquor, add dihydroxy carboxylic acids and catalyst, in 70～80 DEG C of stirring reactions 1～2Hour, obtain the second reactant liquor, wherein, the mol ratio of described dihydroxy carboxylic acids and described vulcabond is0.1～0.5:1；
Under the condition of 50～60 DEG C, described the second reactant liquor and chain extender are mixed, carry out chain extending reaction 2～3Hour, obtain the 3rd reactant liquor;
Under the condition of 50～60 DEG C, in described the 3rd mixed liquor, add alkene class end-capping reagent and polymerization inhibitor, reactionAfter 1 hour, be warming up to 75～85 DEG C, be adjusted to appropriate viscosity with acetone, continue reaction 2 hours, obtain theFour reactant liquors, wherein, the mol ratio of described alkene class end-capping reagent and described vulcabond is 0.1～0.6:1;
Under the condition of 40～50 DEG C, in described the 4th reactant liquor, add triethylamine, react 0.5～1.0 hour,Obtain polyurethane acrylate prepolymer, wherein, the mol ratio of described triethylamine and described dihydroxy carboxylic acids is1～1.5:1；
Under the lasting condition stirring, deionized water is joined in described polyurethane acrylate prepolymer,Continue stirring and emulsifying and disperse 30～40 minutes, through cooling, obtain urethane acrylate dispersoid, wherein,The mass ratio of described polyurethane acrylate prepolymer and described deionized water is 30～50:40～60;
Comprise following component according to mass fraction: 65～90 parts of described urethane acrylate dispersoids, filler3～6 parts of 5～30 parts, 0.1～1 part of levelling agent, 0.1～1 part of defoamer and light triggers, wherein, described fillerBeing selected from mass fraction is 30% nano silicon aqueous dispersions, the nanometer titanium dioxide that mass fraction is 20%Titanium aqueous dispersions and mass fraction are at least one in 20% nano-aluminium oxide aqueous dispersions; And
By described urethane acrylate dispersoid, described filler, described light trigger, described defoamer andDescribed levelling agent mixes, and dispersed with stirring 15～30 minutes, obtains UV-curable waterborne coatings.
2. the preparation method of UV-curable waterborne coatings according to claim 1, is characterized in that,Described vulcabond is selected from XDI, dicyclohexyl methyl hydride diisocyanate, diphenyl-methaneVulcabond, terephthalylidene vulcabond, hexamethylene diisocyanate and IPDIIn at least one.
3. the preparation method of UV-curable waterborne coatings according to claim 1, is characterized in that,Described dihydroxylic alcohols is selected from least one in polyether Glycols, polycaprolactone dihydroxylic alcohols and PCDL.
4. the preparation method of UV-curable waterborne coatings according to claim 1, is characterized in that,The molecular weight of described dihydroxylic alcohols is 500g/mol, 600g/mol or 1000g/mol.
5. the preparation method of UV-curable waterborne coatings according to claim 1, is characterized in that,Described dihydroxy carboxylic acids is at least one in dihydromethyl propionic acid and dimethylolpropionic acid; Described catalyst isDibutyl tin laurate; Wherein, the mass ratio of described catalyst and described dihydroxy carboxylic acids is 0.1～1:2～10.
6. the preparation method of UV-curable waterborne coatings according to claim 1, is characterized in that,Described alkene class end-capping reagent be selected from hydroxyethyl methacrylate, hydroxy-ethyl acrylate, pentaerythritol triacrylate,At least one in hydroxy propyl methacrylate, hydroxypropyl acrylate, trimethylolpropane diacrylate;Described polymerization inhibitor is p methoxy phenol, and the mass ratio of wherein said polymerization inhibitor and described alkene class end-capping reagent is0.1～0.5:8～60。
7. the preparation method of UV-curable waterborne coatings according to claim 1, is characterized in that,Also comprise the preparation process of described chain extender:
Pentaerythritol triacrylate, metoxyphenol and acetone are mixed, under the condition of 45 DEG C, addIPDI and dibutyl tin laurate, then rise to 50～60 DEG C of reactions until isocyanoContent be 8%, obtain the first mixed liquor wherein; The acetone soln of trimethylolpropane is added to described firstIn mixed liquor, until different isocyano ion disappears, obtain described chain extender in 60～75 DEG C of reactions, wherein,Rubbing of described pentaerythritol triacrylate, described IPDI and described trimethylolpropaneYou are than being 1:1:1.
8. the preparation method of UV-curable waterborne coatings according to claim 1, is characterized in that,By described urethane acrylate dispersoid, described filler, described light trigger, described defoamer and described inLevelling agent mixes, and after the dispersed with stirring step of 15～30 minutes, also comprises described UV-curable waterborneCoating is crossed the step of 200～400 mesh sieves.
9. the preparation method of the UV-curable waterborne coatings as described in claim 1～8 any oneThe UV-curable waterborne coatings preparing.
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| CN113416486A (en) * | 2021-07-02 | 2021-09-21 | 衡阳师范学院 | Waterborne polyurethane wood paint coating and preparation method and application thereof |
| CN113861833A (en) * | 2021-10-22 | 2021-12-31 | 浙江奋飞科技有限公司 | Ultraviolet curing coating suitable for surface treatment of rubber conveying belt and application thereof |
| CN115745799A (en) * | 2022-11-25 | 2023-03-07 | 科顺民用建材有限公司 | Glycerol trimethacrylate, waterproof coating composition, waterproof coating and preparation method thereof |
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| CN101423677A (en) * | 2008-12-18 | 2009-05-06 | 江南大学 | Method for preparing transparent and heat insulating water ultraviolet curing coating |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101423677A (en) * | 2008-12-18 | 2009-05-06 | 江南大学 | Method for preparing transparent and heat insulating water ultraviolet curing coating |
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|---|---|---|---|---|
| CN107254250A (en) * | 2017-07-10 | 2017-10-17 | 湖南邦弗特新材料技术有限公司 | A kind of aqueous UV urethane acrylate dispersoids of high glaze and preparation method thereof |
| CN107254250B (en) * | 2017-07-10 | 2019-09-03 | 湖南邦弗特新材料技术有限公司 | A kind of aqueous UV urethane acrylate dispersoid of high glaze and preparation method thereof |
| CN109135549A (en) * | 2018-07-19 | 2019-01-04 | 宁波帝杨电子科技有限公司 | A kind of ultraviolet solidified aqueous coating and preparation method thereof |
| CN111234685A (en) * | 2020-03-04 | 2020-06-05 | 浙江理工大学 | Photo-curing textile coating agent with anti-oxidation resistance characteristic and processing method of imitation leather coating thereof |
| CN113416486A (en) * | 2021-07-02 | 2021-09-21 | 衡阳师范学院 | Waterborne polyurethane wood paint coating and preparation method and application thereof |
| CN113861833A (en) * | 2021-10-22 | 2021-12-31 | 浙江奋飞科技有限公司 | Ultraviolet curing coating suitable for surface treatment of rubber conveying belt and application thereof |
| CN113861833B (en) * | 2021-10-22 | 2022-06-10 | 浙江奋飞科技有限公司 | Ultraviolet curing coating suitable for surface treatment of rubber conveying belt and application thereof |
| CN115745799A (en) * | 2022-11-25 | 2023-03-07 | 科顺民用建材有限公司 | Glycerol trimethacrylate, waterproof coating composition, waterproof coating and preparation method thereof |
| CN115745799B (en) * | 2022-11-25 | 2024-01-26 | 科顺民用建材有限公司 | Glycerol trimethyl acrylate, waterproof coating composition, waterproof coating and preparation method thereof |
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| Publication number | Publication date |
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| CN105602439B (en) | 2018-06-22 |
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