CN105601885A - Ultraviolet curing water-based urethane acrylate and preparation method thereof - Google Patents
Ultraviolet curing water-based urethane acrylate and preparation method thereof Download PDFInfo
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- CN105601885A CN105601885A CN201511020225.4A CN201511020225A CN105601885A CN 105601885 A CN105601885 A CN 105601885A CN 201511020225 A CN201511020225 A CN 201511020225A CN 105601885 A CN105601885 A CN 105601885A
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- hydroxy
- vulcabond
- reactant liquor
- ultraviolet light
- polyurethane acrylate
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 title abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 52
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 30
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical compound OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000003112 inhibitor Substances 0.000 claims abstract description 25
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- 239000003607 modifier Substances 0.000 claims abstract description 17
- 239000008367 deionised water Substances 0.000 claims abstract description 11
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- 239000000376 reactant Substances 0.000 claims description 60
- 239000004814 polyurethane Substances 0.000 claims description 54
- 229920002635 polyurethane Polymers 0.000 claims description 54
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 51
- 230000004048 modification Effects 0.000 claims description 42
- 238000012986 modification Methods 0.000 claims description 42
- 238000003756 stirring Methods 0.000 claims description 34
- 239000002253 acid Substances 0.000 claims description 33
- 150000001298 alcohols Chemical class 0.000 claims description 32
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 30
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 10
- 150000002148 esters Chemical class 0.000 claims description 10
- 238000010792 warming Methods 0.000 claims description 9
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical group C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 8
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical group CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 230000001804 emulsifying effect Effects 0.000 claims description 7
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical group COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 7
- 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
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 5
- 230000002045 lasting effect Effects 0.000 claims description 5
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 4
- 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
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical group CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 4
- 229940106691 bisphenol a Drugs 0.000 claims description 4
- 229920000570 polyether Polymers 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 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
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 150000002334 glycols Chemical class 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
- 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 3
- 229920001610 polycaprolactone Polymers 0.000 claims description 3
- 239000004632 polycaprolactone Substances 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
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 claims 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 2
- 125000005442 diisocyanate group Chemical group 0.000 abstract 3
- DSKYSDCYIODJPC-UHFFFAOYSA-N 2-butyl-2-ethylpropane-1,3-diol Chemical compound CCCCC(CC)(CO)CO DSKYSDCYIODJPC-UHFFFAOYSA-N 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 8
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 6
- 238000000034 method Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 230000020477 pH reduction Effects 0.000 description 5
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 description 4
- 239000012295 chemical reaction liquid Substances 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- FEWFXBUNENSNBQ-UHFFFAOYSA-N 2-hydroxyacrylic acid Chemical compound OC(=C)C(O)=O FEWFXBUNENSNBQ-UHFFFAOYSA-N 0.000 description 2
- 239000004970 Chain extender Substances 0.000 description 2
- 238000003848 UV Light-Curing Methods 0.000 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 description 2
- 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 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000003973 paint 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
- 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
- 230000033228 biological regulation Effects 0.000 description 1
- 150000004651 carbonic acid esters Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- -1 ester acrylate Chemical class 0.000 description 1
- JZTLWHBTNKUQME-UHFFFAOYSA-N ethyl carbamate;prop-1-ene Chemical group CC=C.CCOC(N)=O JZTLWHBTNKUQME-UHFFFAOYSA-N 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
Classifications
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
- C08G18/8006—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32
- C08G18/8009—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203
- C08G18/8012—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203 with diols
- C08G18/8016—Masked aliphatic or cycloaliphatic polyisocyanates
-
- 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
-
- 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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
- C08G18/80—Masked polyisocyanates
- C08G18/8003—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen
- C08G18/8006—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32
- C08G18/8009—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203
- C08G18/8012—Masked polyisocyanates masked with compounds having at least two groups containing active hydrogen with compounds of C08G18/32 with compounds of C08G18/3203 with diols
- C08G18/8019—Masked aromatic polyisocyanates
-
- 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
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 ultraviolet curing water-based urethane acrylate and a preparation method thereof. The preparation method of the ultraviolet curing water-based urethane acrylate comprises the following steps: enabling diisocyanate and a modifier to react to obtain modified diisocyanate; enabling the modified diisocyanate and dihydric alcohol to react to obtain a first reaction solution; adding multi-hydroxyl carboxylic acid and a catalyst to the first reaction solution to react to obtain a second reaction solution, and adding 2-butyl-2-ethyl-1, 3-propylene glycol to the second reaction solution to react to obtain a third reaction solution; adding hydroxyl acrylate and a polymerization inhibitor to the third reaction solution to react to obtain a fourth reaction solution, and adding triethylamine to the fourth reaction solution to react to obtain a urethane acrylate prepolymer; adding deionized water to the urethane acrylate prepolymer to prepare the ultraviolet curing water-based urethane acrylate. The ultraviolet curing water-based urethane acrylate prepared by the preparation method disclosed by the invention is novel urethane acrylate.
Description
Technical field
The present invention relates to paint field, particularly a kind of ultraviolet light solidfication water polyurethane acrylate andPreparation method.
Background technology
Traditional solvent-borne type UV-cured polyurethane acrylate, in application, need to add esters of acrylic acidReactive diluent regulates the viscosity of oligomer resin, and these reactive diluents have certain skin conventionallyExcitant and volatility, after ultraviolet light polymerization, the complete little molecule of unreacted evaporate into can be to construction in airPersonnel, user and environment all cause serious harm. Along with the raising of people's environmental consciousness and various countries are to volatilizationProperty organic compound (VOC) containing quantitative limitation, develop the water-based UV curing urethane propylene of low pollution environment-friendly typeAcid esters product has become everybody common recognition.
Aquosity ultraviolet light (UV) curing system combines the many excellent of traditional photocureable coating and water paintPoint, with viscosity and the rheological property of water replacement reactive diluent regulation system, has nonflammable, process operationThe advantages such as convenience. But the solid content of the water borne UV curing resin of report only has 30-50% at present, is admittedly containingAmount is 50% when above, and viscosity sharply increases, and the performance of resin and film sharply reduces. And the many collection of researchIn in aqueous dispersion or emulsion system, this type of water paint is due to washiness in system, moreover evaporation of water enthalpy isHeight, volatilization process is very slow, and too much water makes must be dry faster as cost exchanges for to sacrifice the energyDry and solidification rate, this has increased energy consumption and time undoubtedly, and hardness is lower.
Summary of the invention
Based on this, be necessary to provide a kind of and can prepare a kind of novel ultraviolet light solidfication water polyurethane propyleneThe method of acid esters.
In addition, also provide a kind of novel ultraviolet light solidfication water polyurethane acrylate.
A preparation method for ultraviolet light solidfication water polyurethane acrylate, comprises the steps:
Under the environment of protective gas, vulcabond is mixed with modifier, in 60～85 DEG C of reactions 1～3Hour, obtain the vulcabond of modification, wherein, the mol ratio of described modifier and described vulcabondIt is 1: 2;
In the vulcabond of described modification, add dihydroxylic alcohols, in 60～80 DEG C of stirring reactions 2～4 hours,To the first reactant liquor, wherein, the mol ratio of the described vulcabond of described dihydroxylic alcohols and modification is 1: 2～6;
In described the first reactant liquor, add multi-hydroxy carboxy acid and catalyst, in 70～80 DEG C of stirring reactions 1～2Hour, obtain the second reactant liquor, wherein, the rubbing of described multi-hydroxy carboxy acid and described modifying diisocyanatesYou are than being 0.1～0.3: 1;
Under the condition of 50～60 DEG C, in described the second reactant liquor, add 2-butyl-2-ethyl-1,3-PD,Chain extending reaction 2～3 hours, obtains the 3rd reactant liquor, wherein, described 2-butyl-2-ethyl-1,3-PD withThe mol ratio of the vulcabond of described modification is 0.1～0.3: 1;
Under the condition of 50～60 DEG C, in described the 3rd reactant liquor, add hydroxy acrylate and polymerization inhibitor to carry outEnd-blocking, reacted after 1 hour, was warming up to 70～85 DEG C, then added acetone, continued reaction 2 hours, obtainedThe 4th reactant liquor; Wherein, the mol ratio of the vulcabond of described hydroxy acrylate and described modification is0.2～0.6: 1; And
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, described triethylamine and described multi-hydroxy carboxy acid's mol ratio is1～1.5: 1; And
Under the condition that continues to stir, deionized water is joined in described polyurethane acrylate prepolymer, continueContinuous stirring and emulsifying is disperseed 30～40 minutes, through cooling, obtains ultraviolet light solidfication water polyurethane acrylate,Wherein, the mass ratio of described polyurethane acrylate prepolymer and described deionized water is 30～50: 40～60.
In an embodiment, described vulcabond is selected from dicyclohexyl methyl hydride diisocyanate, two thereinPhenylmethane vulcabond, terephthalylidene vulcabond, hexamethylene diisocyanate and isophorone two are differentAt least one in cyanate.
In an embodiment, described dihydroxylic alcohols is selected from polyether Glycols, polycaprolactone dihydroxylic alcohols and poly-thereinAt least one in carbonic ester dihydroxylic alcohols.
In an embodiment, described multi-hydroxy carboxy acid is in dihydromethyl propionic acid and dimethylolpropionic acid thereinAt least one.
In an embodiment, described catalyst is dibutyl tin laurate therein; Wherein, described catalysisThe quality of agent be the quality of described multi-hydroxy carboxy acid and described the first reactant liquor summation 0.1%～1%.
In an embodiment, described hydroxy acrylate is selected from hydroxyethyl methacrylate, acrylic acid thereinHydroxyl ethyl ester, pentaerythritol triacrylate, hydroxy propyl methacrylate, hydroxypropyl acrylate and trihydroxy methylAt least one in propane diacrylate.
In an embodiment, described polymerization inhibitor is p methoxy phenol therein, described polymerization inhibitor and described hydroxylThe mass ratio of base acrylate is 0.1～0.5: 20～60.
In an embodiment, described modifier is selected from bisphenol-A, 1 therein, 3-adamantane glycol, 1,3-bis-(4-Hydroxy benzenes) at least one in adamantane and Isosorbide-5-Nitrae-cyclohexyl dimethanol.
Therein in an embodiment, be set forth under the condition of 50～60 DEG C, in described the 3rd reactant liquor, addDescribed hydroxy acrylate and described polymerization inhibitor carry out end-blocking, react after 1 hour, are warming up to 70～85 DEG C, soAfter add in the step of described acetone, the quality of described acetone is described the 3rd reactant liquor, described hydroxyl propylene5～10% of the gross mass of acid esters and described polymerization inhibitor.
A kind of ultraviolet light being prepared by the preparation method of above-mentioned ultraviolet light solidfication water polyurethane acrylateSolidfication water polyurethane acrylate.
The preparation method of above-mentioned ultraviolet light solidfication water polyurethane acrylate is simple to operate, is easy to industrialization rawProduce. Above-mentioned ultraviolet light solidfication water polyurethane acrylate passes through to introduce modifier to vulcabond modification,Continuation and dihydroxylic alcohols, multi-hydroxy carboxy acid, and functional dihydroxylic alcohols chain extender, hydroxy acrylic acid monomer reaction,Synthesize a kind of novel urethane acrylate.
Brief description of the drawings
Fig. 1 is the preparation method's of the ultraviolet light solidfication water polyurethane acrylate of an embodiment flow chart.
Detailed description of the invention
Below mainly in conjunction with the drawings and the specific embodiments to ultraviolet light solidfication water polyurethane acrylate and system thereofPreparation Method is described in further detail.
As shown in Figure 1, the preparation method of the ultraviolet light solidfication water polyurethane acrylate of an embodiment,Comprise the steps:
Step S110: under the environment of protective gas, vulcabond is mixed with modifier, in 60～85 DEG CReact 1～3 hour, obtain the vulcabond of modification.
Wherein, the mol ratio of modifier and vulcabond is 1: 2.
Wherein, protective gas can be nitrogen or inert gas.
Wherein, vulcabond be selected from dicyclohexyl methyl hydride diisocyanate, '-diphenylmethane diisocyanate,At least one in terephthalylidene vulcabond, hexamethylene diisocyanate and IPDI.
Wherein, modifier is selected from bisphenol-A, 1,3-adamantane glycol, 1,3-bis-(4-hydroxy benzenes) adamantane andAt least one in Isosorbide-5-Nitrae-cyclohexyl dimethanol.
Step S120: add dihydroxylic alcohols in the vulcabond of modification, in 60～80 DEG C of stirring reactions 2～4Hour, obtain the first reactant liquor.
Wherein, dihydroxylic alcohols is selected from polyether Glycols, polycaprolactone dihydroxylic alcohols and PCDL extremelyFew a kind of.
Wherein, the mol ratio of the vulcabond of dihydroxylic alcohols and modification is 1: 2～6.
Step S130: add multi-hydroxy carboxy acid 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 the vulcabond of multi-hydroxy carboxy acid and modification is 0.1～0.3: 1.
Wherein, multi-hydroxy carboxy acid is selected from least one in dihydromethyl propionic acid and dimethylolpropionic acid.
Wherein, catalyst is dibutyl tin laurate. Wherein, the quality of catalyst be multi-hydroxy carboxy acid and0.1%～1% of the summation of the quality of the first reactant liquor.
Step S140: under the condition of 50～60 DEG C, add 2-butyl-2-ethyl-1 in the second reactant liquor, 3-Propane diols, chain extending reaction 2～3 hours, obtains the 3rd reactant liquor.
Wherein, the mol ratio of the vulcabond of 2-butyl-2-ethyl-1,3-PD and modification is 0.1～0.3: 1.
Step S150: under the condition of 50～60 DEG C, add hydroxy acrylate and resistance in the 3rd reactant liquorEnd-blocking is carried out in poly-agent, reacts after 1 hour, is warming up to 70～85 DEG C, then adds acetone, continues reaction 2 littleTime, obtain the 4th reactant liquor.
Wherein, the mol ratio of the vulcabond of described hydroxy acrylate and described modification be 0.2～0.6: 1 itsIn, hydroxy acrylate is selected from hydroxyethyl methacrylate, hydroxy-ethyl acrylate, pentaerythrite three acrylic acidAt least one in ester, hydroxy propyl methacrylate, hydroxypropyl acrylate and trimethylolpropane diacrylateKind.
Wherein, polymerization inhibitor is p methoxy phenol. The mass ratio of polymerization inhibitor and hydroxy acrylate is 0.1～0.5: 20～60。
Wherein, in step S150, the quality of acetone is the total of the second reactant liquor, hydroxy acrylate and polymerization inhibitor5～10% of quality.
Step S160: 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, triethylamine and multi-hydroxy carboxy acid's mol ratio is 1～1.5: 1.
Step S170: 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 ultraviolet light solidfication water polyurethane thirdOlefin(e) acid ester.
Wherein, the mass ratio of polyurethane acrylate prepolymer and deionized water is 30～50: 40～60.
In step S170, 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.
The preparation method of above-mentioned ultraviolet light solidfication water polyurethane acrylate is simple to operate, is easy to industrialization rawProduce. Above-mentioned ultraviolet light solidfication water polyurethane acrylate, continues vulcabond modification by modifierWith dihydroxylic alcohols, multi-hydroxy carboxy acid, and functional dihydroxylic alcohols chain extender, hydroxy acrylic acid monomer reaction, syntheticA kind of novel urethane acrylate.
A kind of ultraviolet light being prepared by the preparation method of above-mentioned ultraviolet light solidfication water polyurethane acrylateSolidfication water polyurethane acrylate, this ultraviolet light solidfication water polyurethane acrylate is a kind of novel gatheringAmmonia ester acrylate, can be used in ultraviolet light coating, so that contain this ultraviolet light solidfication water polyurethane propyleneThe coating of acid esters has good performance.
Be below specific embodiment part:
Embodiment 1
The preparation process of the ultraviolet light solidfication water polyurethane acrylate of the present embodiment is as follows:
1, under logical nitrogen protection condition, to the four-hole circle reaction bulb that is placed with thermometer, condenser pipe, stirring rodIn, add vulcabond, be placed in the water bath with thermostatic control of 60 DEG C, utilize constant pressure funnel that modifier is drippedBe added in four-hole reaction bulb, insulation reaction 3 hours, obtains the vulcabond of modification. Wherein, modifierWith the mol ratio of vulcabond be 1: 2. Vulcabond is selected from dicyclohexyl methyl hydride diisocyanate. ModificationAgent is selected from bisphenol-A, 1,3-adamantane glycol.
2, in the vulcabond of modification, add dihydroxylic alcohols, in 60 DEG C of stirring reactions 4 hours, obtain firstReactant liquor. Wherein, the mol ratio of the vulcabond of dihydroxylic alcohols and modification is 1: 2. Dihydroxylic alcohols is selected from polyethersDihydroxylic alcohols.
3, in the first reactant liquor, add multi-hydroxy carboxy acid and catalyst, in 70 DEG C of stirring reactions 2 hours,To the second reactant liquor. Wherein, the mol ratio of the vulcabond of multi-hydroxy carboxy acid and modification is 0.1: 1, many hydroxylsYl carboxylic acid is dihydromethyl propionic acid, and catalyst is dibutyl tin laurate, and the quality of catalyst is polyhydroxy0.1% of the summation of the quality of carboxylic acid and the first reactant liquor.
4, be cooled to 50 DEG C, adopt constant pressure funnel that 2-butyl-2-ethyl-1,3-PD is added second anti-Answer in liquid, chain extending reaction 2 hours, obtains the 3rd reactant liquor. Wherein, 2-butyl-2-ethyl-1,3-PD withThe mol ratio of the vulcabond of modification is 0.1: 1.
5, under the condition of 50 DEG C, in the 3rd reactant liquor, add hydroxy acrylate and polymerization inhibitor to carry out end-blocking,React after 1 hour, be warming up to 70 DEG C, then add acetone, continue reaction 2 hours, obtain the 4th reactionLiquid. Wherein, the mol ratio of the vulcabond of hydroxy acrylate and modification is 0.2: 1. Hydroxy acrylateBe selected from hydroxyethyl methacrylate. Polymerization inhibitor is p methoxy phenol. The matter of polymerization inhibitor and hydroxy acrylateAmount is than being 1: 20. The quality of acetone be the second reactant liquor, hydroxy acrylate and polymerization inhibitor gross mass 5%.
6, under the condition of 40 DEG C, in the 4th reactant liquor, add triethylamine, react 0.5 hour, obtainBright polyurethane acrylate prepolymer. Wherein, triethylamine and multi-hydroxy carboxy acid's mol ratio is 1: 1.
7, under the condition of the lasting stirring of 300 revs/min, deionized water is joined to urethane acrylateIn performed polymer, continue to disperse 30 minutes with the speed stirring and emulsifying of 400 revs/min, through cooling, obtain ultravioletPhotocuring aqueous polyurethane acrylate.
Embodiment 2
The preparation process of the ultraviolet light solidfication water polyurethane acrylate of the present embodiment is as follows:
1, under logical nitrogen protection condition, to the four-hole circle reaction bulb that is placed with thermometer, condenser pipe, stirring rodIn, add vulcabond, be placed in the water bath with thermostatic control of 85 DEG C, utilize constant pressure funnel that modifier is drippedBe added in four-hole reaction bulb, insulation reaction 1 hour, obtains the vulcabond of modification. Wherein, modifierWith the mol ratio of vulcabond be 1: 2. Vulcabond is selected from '-diphenylmethane diisocyanate. Modifier choosingFrom 1,3-adamantane glycol.
2, in the vulcabond of modification, add dihydroxylic alcohols, in 80 DEG C of stirring reactions 2 hours, obtain firstReactant liquor. Wherein, the mol ratio of the vulcabond of dihydroxylic alcohols and modification is 1: 6. Dihydroxylic alcohols is selected from and gathers in oneselfEster dihydroxylic alcohols.
3, in the first reactant liquor, add multi-hydroxy carboxy acid and catalyst, in 70 DEG C of stirring reactions 2 hours,To the second reactant liquor. Wherein, the mol ratio of the vulcabond of multi-hydroxy carboxy acid and modification is 0.3: 1, many hydroxylsYl carboxylic acid is dihydromethyl propionic acid, and catalyst is dibutyl tin laurate, and the quality of catalyst is polyhydroxy1% of the summation of the quality of carboxylic acid and the first reactant liquor.
4, be cooled to 60 DEG C, adopt constant pressure funnel that 2-butyl-2-ethyl-1,3-PD is added second anti-Answer in liquid, chain extending reaction 3 hours, obtains the 3rd reactant liquor. Wherein, 2-butyl-2-ethyl-1,3-PD withThe mol ratio of the vulcabond of modification is 0.3: 1.
5, under the condition of 60 DEG C, in the 3rd reactant liquor, add hydroxy acrylate and polymerization inhibitor to carry out end-blocking,React after 1 hour, be warming up to 85 DEG C, then add acetone, continue reaction 2 hours, obtain the 4th reactionLiquid. Wherein, the mol ratio of the vulcabond of hydroxy acrylate and modification is 0.6: 1. Hydroxy acrylateBe selected from pentaerythritol triacrylate. Polymerization inhibitor is p methoxy phenol. Polymerization inhibitor and hydroxy acrylateMass ratio is 0.5: 60. The quality of acetone is the gross mass of the second reactant liquor, hydroxy acrylate and polymerization inhibitor15％。
6, under the condition of 50 DEG C, in the 4th reactant liquor, add triethylamine, react 1.0 hours, obtainBright polyurethane acrylate prepolymer. Wherein, triethylamine and multi-hydroxy carboxy acid's mol ratio is 1.5: 1.
7, under the condition of the lasting stirring of 400 revs/min, deionized water is joined to urethane acrylateIn performed polymer, continue to disperse 40 minutes with the speed stirring and emulsifying of 600 revs/min, through cooling, obtain ultravioletPhotocuring aqueous polyurethane acrylate.
Embodiment 3
The preparation process of the ultraviolet light solidfication water polyurethane acrylate of the present embodiment is as follows:
1, under logical nitrogen protection condition, to the four-hole circle reaction bulb that is placed with thermometer, condenser pipe, stirring rodIn, add vulcabond, be placed in the water bath with thermostatic control of 85 DEG C, utilize constant pressure funnel that modifier is drippedBe added in four-hole reaction bulb, insulation reaction 2 hours, obtains the vulcabond of modification. Wherein, modifierWith the mol ratio of vulcabond be 1: 2. Vulcabond is selected from terephthalylidene vulcabond. ModificationAgent is selected from Isosorbide-5-Nitrae-cyclohexyl dimethanol.
2, in the vulcabond of modification, add dihydroxylic alcohols, in 70 DEG C of stirring reactions 3 hours, obtain firstReactant liquor. Wherein, the mol ratio of the vulcabond of dihydroxylic alcohols and modification is 1: 4. Dihydroxylic alcohols is selected from poly-carbonic acidEster dihydroxylic alcohols.
3, in the first reactant liquor, add multi-hydroxy carboxy acid and catalyst, in 80 DEG C of stirring reactions 1 hour,To the second reactant liquor. Wherein, the mol ratio of the vulcabond of multi-hydroxy carboxy acid and modification is 0.2: 1, many hydroxylsYl carboxylic acid is dimethylolpropionic acid, and catalyst is dibutyl tin laurate, and the quality of catalyst is polyhydroxy0.5% of the summation of the quality of carboxylic acid and the first reactant liquor.
4, be cooled to 55 DEG C, adopt constant pressure funnel that 2-butyl-2-ethyl-1,3-PD is added second anti-Answer in liquid, chain extending reaction 2.5 hours, obtains the 3rd reactant liquor. Wherein, 2-butyl-2-ethyl-1,3-PDWith the mol ratio of the vulcabond of modification be 0.2: 1.
5, under the condition of 60 DEG C, in the 3rd reactant liquor, add hydroxy acrylate and polymerization inhibitor to carry out end-blocking,React after 1 hour, be warming up to 85 DEG C, then add acetone, continue reaction 2 hours, obtain the 4th reactionLiquid. Wherein, the mol ratio of the vulcabond of hydroxy acrylate and modification is 0.4: 1. Hydroxy acrylateBe selected from trimethylolpropane diacrylate. Polymerization inhibitor is p methoxy phenol. Polymerization inhibitor and hydroxy acrylic acidThe mass ratio of ester is 0.8: 30. The quality of acetone is total matter of the second reactant liquor, hydroxy acrylate and polymerization inhibitor10% of amount.
6, under the condition of 50 DEG C, in the 4th reactant liquor, add triethylamine, react 0.5～1.0 hour,To transparent polyurethane acrylate prepolymer. Wherein, triethylamine and multi-hydroxy carboxy acid's mol ratio is 1.5: 1.
7, under the condition of the lasting stirring of 400 revs/min, the deionized water of 50 DEG C is joined to polyurethaneIn acrylate performed polymer, continue to disperse 35 minutes with the speed stirring and emulsifying of 500 revs/min, through cooling,Obtain ultraviolet light solidfication water polyurethane acrylate.
Embodiment 4
The preparation process of the ultraviolet light solidfication water polyurethane acrylate of the present embodiment is as follows:
1, under logical nitrogen protection condition, to the four-hole circle reaction bulb that is placed with thermometer, condenser pipe, stirring rodIn, add vulcabond, be placed in the water bath with thermostatic control of 80 DEG C, utilize constant pressure funnel that modifier is drippedBe added in four-hole reaction bulb, insulation reaction 2 hours, obtains the vulcabond of modification. Wherein, modifierWith the mol ratio of vulcabond be 1: 2. Vulcabond is selected from IPDI. Modifier choosingFrom Isosorbide-5-Nitrae-cyclohexyl dimethanol.
2, in the vulcabond of modification, add dihydroxylic alcohols, in 60 DEG C of stirring reactions 4 hours, obtain firstReactant liquor. Wherein, the mol ratio of the vulcabond of dihydroxylic alcohols and modification is 1: 4. Dihydroxylic alcohols is selected from polyethers twoUnit's alcohol.
3, in the first reactant liquor, add multi-hydroxy carboxy acid and catalyst, in 80 DEG C of stirring reactions 1 hour,To the second reactant liquor. Wherein, the mol ratio of the vulcabond of multi-hydroxy carboxy acid and modification is 0.2: 1, many hydroxylsYl carboxylic acid is dihydromethyl propionic acid, and catalyst is dibutyl tin laurate, and the quality of catalyst is polyhydroxy0.5% of the summation of the quality of carboxylic acid and the first reactant liquor.
4, be cooled to 60 DEG C, adopt constant pressure funnel that 2-butyl-2-ethyl-1,3-PD is added second anti-Answer in liquid, chain extending reaction 2.5 hours, obtains the 3rd reactant liquor. Wherein, 2-butyl-2-ethyl-1,3-PDWith the mol ratio of the vulcabond of modification be 0.2: 1.
5, under the condition of 55 DEG C, in the 3rd reactant liquor, add hydroxy acrylate and polymerization inhibitor to carry out end-blocking,React after 1 hour, be warming up to 75 DEG C, then add acetone, continue reaction 2 hours, obtain the 4th reactionLiquid. Wherein, the mol ratio of the isocyanates of hydroxy acrylate and modification is 0.6: 1. Hydroxy acrylate choosingFrom trimethylolpropane diacrylate. Polymerization inhibitor is p methoxy phenol. Polymerization inhibitor and hydroxy acrylateMass ratio be 0.6: 40. The quality of acetone is the gross mass of the second reactant liquor, hydroxy acrylate and polymerization inhibitor10%.
6, under the condition of 45 DEG C, in the 4th reactant liquor, add triethylamine, react 0.5～1.0 hour,To transparent polyurethane acrylate prepolymer. Wherein, triethylamine and multi-hydroxy carboxy acid's mol ratio is 1.2: 1.
7, under the condition of the lasting stirring of 350 revs/min, deionized water is joined to urethane acrylateIn performed polymer, continue to disperse 35 minutes with the speed stirring and emulsifying of 500 revs/min, through cooling, obtain ultravioletPhotocuring aqueous polyurethane acrylate.
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 (10)
1. a preparation method for ultraviolet light solidfication water polyurethane acrylate, is characterized in that, comprise asLower step:
Under the environment of protective gas, vulcabond is mixed with modifier, in 60～85 DEG C of reactions 1～3Hour, obtain the vulcabond of modification, wherein, the mol ratio of described modifier and described vulcabondIt is 1: 2;
In the vulcabond of described modification, add dihydroxylic alcohols, in 60～80 DEG C of stirring reactions 2～4 hours,To the first reactant liquor, wherein, the mol ratio of the vulcabond of described dihydroxylic alcohols and described modification is 1: 2～6;
In described the first reactant liquor, add multi-hydroxy carboxy acid and catalyst, in 70～80 DEG C of stirring reactions 1～2Hour, obtain the second reactant liquor, wherein, the rubbing of the vulcabond of described multi-hydroxy carboxy acid and described modificationYou are than being 0.1～0.3: 1;
Under the condition of 50～60 DEG C, in described the second reactant liquor, add 2-butyl-2-ethyl-1,3-PD,Chain extending reaction 2～3 hours, obtains the 3rd reactant liquor, wherein, described 2-butyl-2-ethyl-1,3-PD withThe mol ratio of the vulcabond of described modification is 0.1～0.3: 1;
Under the condition of 50～60 DEG C, in described the 3rd reactant liquor, add hydroxy acrylate and polymerization inhibitor to carry outEnd-blocking, reacted after 1 hour, was warming up to 70～85 DEG C, then added acetone, continued reaction 2 hours, obtainedThe 4th reactant liquor; Wherein, the mol ratio of the vulcabond of described hydroxy acrylate and described modification is0.2～0.6: 1; And
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, described triethylamine and described multi-hydroxy carboxy acid's mol ratio is1～1.5: 1; And
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 ultraviolet light solidfication water polyurethane acrylate,Wherein, the mass ratio of described polyurethane acrylate prepolymer and described deionized water is 30～50: 40～60.
2. the preparation method of ultraviolet light solidfication water polyurethane acrylate according to claim 1, itsBe characterised in that, described vulcabond is selected from dicyclohexyl methyl hydride diisocyanate, diphenyl-methane two isocyanic acidsIn ester, terephthalylidene vulcabond, hexamethylene diisocyanate and IPDI at leastA kind of.
3. the preparation method of ultraviolet light solidfication water polyurethane acrylate according to claim 1, itsBe characterised in that, described dihydroxylic alcohols is selected from polyether Glycols, polycaprolactone dihydroxylic alcohols and PCDLAt least one.
4. the preparation method of ultraviolet light solidfication water polyurethane acrylate according to claim 1, itsBe characterised in that, described multi-hydroxy carboxy acid is at least one in dihydromethyl propionic acid and dimethylolpropionic acid.
5. according to the preparation method of the ultraviolet light solidfication water polyurethane acrylate described in claim 1 or 4,It is characterized in that, described catalyst is dibutyl tin laurate; Wherein, the quality of described catalyst is instituteState the quality of multi-hydroxy carboxy acid and described the first reactant liquor summation 0.1%～1%.
6. the preparation method of ultraviolet light solidfication water polyurethane acrylate according to claim 1, itsBe characterised in that, described hydroxy acrylate is selected from hydroxyethyl methacrylate, hydroxy-ethyl acrylate, Ji WusiAlcohol triacrylate, hydroxy propyl methacrylate, hydroxypropyl acrylate and trimethylolpropane diacrylateIn at least one.
7. according to the preparation method of the ultraviolet light solidfication water polyurethane acrylate described in claim 1 or 6,It is characterized in that, described polymerization inhibitor is p methoxy phenol, described polymerization inhibitor and described hydroxy acrylateMass ratio is 0.1～0.5: 20～60.
8. the preparation method of ultraviolet light solidfication water polyurethane acrylate according to claim 1, itsBe characterised in that, described modifier is selected from bisphenol-A, 1,3-adamantane glycol, 1,3-bis-(4-hydroxy benzenes) Buddha's warrior attendantAt least one in alkane and Isosorbide-5-Nitrae-cyclohexyl dimethanol.
9. the preparation method of ultraviolet light solidfication water polyurethane acrylate according to claim 1, itsBe characterised in that, be set forth under the condition of 50～60 DEG C, in described the 3rd reactant liquor, add described hydroxy acrylic acidEster and described polymerization inhibitor carry out end-blocking, react after 1 hour, are warming up to 70～85 DEG C, then add described acetoneStep in, the quality of described acetone is described the 3rd reactant liquor, described hydroxy acrylate and described inhibition5～10% of the gross mass of agent.
10. a ultraviolet light solidfication water polyurethane acrylate as claimed in any one of claims 1 to 9 whereinThe ultraviolet light solidfication water polyurethane acrylate for preparing of preparation method.
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| CN105001396A (en) * | 2015-07-08 | 2015-10-28 | 华南理工大学 | 80-95% solid content waterborne UV-curable urethane acrylate and preparation method |
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