CN105542121A - Ultraviolet-curing polyurethane acrylate and preparation method thereof - Google Patents
Ultraviolet-curing polyurethane acrylate and preparation method thereof Download PDFInfo
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- CN105542121A CN105542121A CN201511026141.1A CN201511026141A CN105542121A CN 105542121 A CN105542121 A CN 105542121A CN 201511026141 A CN201511026141 A CN 201511026141A CN 105542121 A CN105542121 A CN 105542121A
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- polyurethane acrylate
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- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title claims abstract description 56
- 239000004814 polyurethane Substances 0.000 title claims abstract description 54
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 93
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 45
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 34
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical compound OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 claims abstract description 33
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000003756 stirring Methods 0.000 claims abstract description 20
- 239000002253 acid Substances 0.000 claims description 37
- 230000004048 modification Effects 0.000 claims description 30
- 238000012986 modification Methods 0.000 claims description 30
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 claims description 16
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 10
- 238000010792 warming Methods 0.000 claims description 9
- 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
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical group COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 7
- VLCAYQIMSMPEBW-UHFFFAOYSA-N methyl 3-hydroxy-2-methylidenebutanoate Chemical compound COC(=O)C(=C)C(C)O VLCAYQIMSMPEBW-UHFFFAOYSA-N 0.000 claims description 6
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 5
- 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 5
- ZMARGGQEAJXRFP-UHFFFAOYSA-N 1-hydroxypropan-2-yl 2-methylprop-2-enoate Chemical compound OCC(C)OC(=O)C(C)=C ZMARGGQEAJXRFP-UHFFFAOYSA-N 0.000 claims description 4
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 4
- KXBFLNPZHXDQLV-UHFFFAOYSA-N [cyclohexyl(diisocyanato)methyl]cyclohexane Chemical compound C1CCCCC1C(N=C=O)(N=C=O)C1CCCCC1 KXBFLNPZHXDQLV-UHFFFAOYSA-N 0.000 claims description 4
- 150000002009 diols Chemical class 0.000 claims description 4
- 150000002334 glycols Chemical class 0.000 claims description 4
- 229920001610 polycaprolactone Polymers 0.000 claims description 4
- 239000004632 polycaprolactone Substances 0.000 claims description 4
- 229920000570 polyether Polymers 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 239000008096 xylene Substances 0.000 claims description 4
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 claims description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 3
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 3
- 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 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
- 230000009477 glass transition Effects 0.000 abstract description 11
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- 125000005442 diisocyanate group Chemical group 0.000 abstract 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 abstract 2
- 239000003054 catalyst Substances 0.000 abstract 1
- 238000001816 cooling Methods 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 239000003112 inhibitor Substances 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 6
- 230000033228 biological regulation Effects 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000011347 resin Substances 0.000 description 5
- 229920005989 resin Polymers 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 3
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 3
- 230000020477 pH reduction Effects 0.000 description 3
- 238000003848 UV Light-Curing Methods 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000012948 isocyanate Substances 0.000 description 2
- 150000002513 isocyanates Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 239000012855 volatile organic compound 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
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 206010040880 Skin irritation Diseases 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 239000012975 dibutyltin dilaurate Substances 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
- 150000002148 esters Chemical class 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 230000036556 skin irritation Effects 0.000 description 1
- 231100000475 skin irritation Toxicity 0.000 description 1
- 150000003384 small molecules Chemical class 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
- C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
-
- 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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
- C08G18/6666—Compounds of group C08G18/48 or C08G18/52
- C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
-
- 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
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- 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
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- 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 an ultraviolet-curing polyurethane acrylate and a preparation method thereof. The preparation method comprises the following steps: mixing diisocyanate and bisphenol A, and reacting at 40-60 DEG C to obtain modified diisocyanate; adding dibasic alcohol into the modified diisocyanate, and reacting at 60-80 DEG C while stirring to obtain a first reaction solution; adding polyhydroxy-carboxylic acid and a catalyst into the first reaction solution, and reacting at 70-80 DEG C while stirring to obtain a second reaction solution; adding hydroxyacrylate and a polymerization inhibitor into the second reaction solution at 50-60 DEG C to perform termination, heating to 70-85 DEG C, adding acetone, and continuing reacting for 2 hours to obtain a third reaction solution; and adding triethylamine into the third reaction solution at 40-50 DEG C, reacting, and cooling to obtain the ultraviolet-curing polyurethane acrylate. The preparation method can be used for preparing the ultraviolet-curing polyurethane acrylate with higher glass transition temperature and higher hardness.
Description
Technical field
The present invention relates to paint field, particularly a kind of UV-cured polyurethane acrylate and preparation method thereof.
Background technology
Traditional solvent-borne type UV-cured polyurethane acrylate in the application, need to add esters of acrylic acid reactive thinner to regulate the viscosity of oligomer resin, and these reactive thinners have certain skin irritation and volatility usually, after ultraviolet light polymerization, the complete small molecules of unreacted evaporate in air all can cause serious harm to workmen, user and environment.Along with the raising of people's environmental consciousness and various countries to volatile organic compounds (VOC) containing quantitative limitation, the water-borne UV-curing urethane acrylate product of exploitation low stain environment-friendly type has become everybody common recognition.
Aquosity ultraviolet light (UV) curing system combines traditional photo-cured coating and the plurality of advantages of water-borne coatings, replaces viscosity and the rheological property of reactive thinner regulation system with water, has the advantages such as nonflammable, process operation is convenient.But the solid content of the water borne UV curing resin of report only has 30-50% at present, and when solid content is more than 50%, viscosity sharply increases, and the performance of resin and film sharply reduces.And research focuses mostly in water-dispersion or emulsion system, this type of water-borne coatings is due to washiness in system, moreover evaporation of water enthalpy is higher, volatilization process is very slow, too much water makes to exchange dry and solidification rate faster for sacrifice the energy for cost, this increases 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 the higher and method of the UV-cured polyurethane acrylate that hardness is larger of glass transition temp.
In addition, a kind of UV-cured polyurethane acrylate is also provided.
A preparation method for UV-cured polyurethane acrylate, comprises the steps:
Under the environment of protective gas, mixed by vulcabond with dihydroxyphenyl propane, in 40 ~ 60 DEG C of reactions 1 ~ 3 hour, obtain the vulcabond of modification, wherein, the mol ratio of described dihydroxyphenyl propane and described vulcabond was 1:2;
In the vulcabond of described modification, add dibasic alcohol, in 60 ~ 80 DEG C of stirring reactions 2 ~ 4 hours, obtain the first reaction solution, wherein, the mol ratio of the vulcabond of described dibasic alcohol and described modification was 1:2 ~ 6;
In described first reaction solution, add multi-hydroxy carboxy acid and catalyzer, in 70 ~ 80 DEG C of stirring reactions 1 ~ 2 hour, obtain the second reaction solution, wherein, the mol ratio of the vulcabond of described multi-hydroxy carboxy acid and described modification was 0.2 ~ 0.5:1;
Under the condition of 50 ~ 60 DEG C, in described second reaction solution, add hydroxy acrylate and stopper carries out end-blocking, react after 1 hour, be warming up to 70 ~ 85 DEG C, then add acetone, continue reaction 2 hours, obtain the 3rd reaction solution; And
Under the condition of 40 ~ 50 DEG C, in described 3rd reaction solution, add triethylamine, react 0.5 ~ 1.0 hour, obtain UV-cured polyurethane acrylate, wherein, the mol ratio of described triethylamine and described multi-hydroxy carboxy acid is 1 ~ 1.5:1.
Wherein in an embodiment, described vulcabond is selected from least one in Xylene Diisocyanate, dicyclohexyl methane diisocyanate, '-diphenylmethane diisocyanate, terephthalylidene vulcabond, hexamethylene diisocyanate and isophorone diisocyanate.
Wherein in an embodiment, described dibasic alcohol is selected from least one in polyether Glycols, polycaprolactone diols and PCDL.
Wherein in an embodiment, described multi-hydroxy carboxy acid is selected from least one in dimethylol propionic acid and dimethylolpropionic acid.
Wherein in an embodiment, described catalyzer is dibutyl tin laurate, and wherein, the mass ratio of described catalyzer and described multi-hydroxy carboxy acid is 0.1 ~ 1:3 ~ 8.
Wherein in an embodiment, described hydroxy acrylate is selected from least one in hydroxyethyl methylacrylate, Hydroxyethyl acrylate, pentaerythritol triacrylate, Rocryl 410, Propylene glycol monoacrylate and trimethylolpropane diacrylate.Wherein in an embodiment, described stopper is p methoxy phenol, and the mass ratio of wherein said stopper and described hydroxy acrylate is 0.1 ~ 1:20 ~ 60.
Wherein in an embodiment, be set forth in the condition of 50 ~ 60 DEG C under, described hydroxy acrylate is added and described stopper carries out end-blocking in described second reaction solution, react after 1 hour, be warming up to 70 ~ 85 DEG C, then add in the step of described acetone, the addition of described acetone is 3 ~ 10% of described second reaction solution and described hydroxy acrylate total mass.
A kind of UV-cured polyurethane acrylate prepared by the preparation method of above-mentioned UV-cured polyurethane acrylate.
The preparation method of above-mentioned UV-cured polyurethane acrylate is simple to operate, is easy to suitability for industrialized production.Above-mentioned UV-cured polyurethane acrylate by dihydroxyphenyl propane to vulcabond modification, obtain new isocyanate molecule structure, continue and dibasic alcohol, multi-hydroxy carboxy acid, acrylate monomers reacts, synthesize a kind of novel urethane acrylate, more aromatic ring rigid structure is introduced in molecular chain, make molecular weight rigidity reinforced, hard segment molecule chain movement is obstructed, promote the formation of soft or hard section microphase-separated state in molecular chain, improve its second-order transition temperature, add the hardness of resin.
Accompanying drawing explanation
Fig. 1 is the schema of the preparation method of the UV-cured polyurethane acrylate of an embodiment.
Embodiment
Mainly in conjunction with the drawings and the specific embodiments UV-cured polyurethane acrylate and preparation method thereof is described in further detail below.
As shown in Figure 1, the preparation method of the UV-cured polyurethane acrylate of an embodiment, comprises the steps:
Step S110: under the environment of protective gas, mixed by vulcabond with dihydroxyphenyl propane, in 40 ~ 60 DEG C of reactions 1 ~ 3 hour, obtains the vulcabond of modification.
Wherein, the mol ratio of dihydroxyphenyl propane and vulcabond is 1:2.
Wherein, protective gas can be nitrogen or rare gas element.
Wherein, vulcabond is selected from least one in Xylene Diisocyanate, dicyclohexyl methane diisocyanate, '-diphenylmethane diisocyanate, terephthalylidene vulcabond, hexamethylene diisocyanate and isophorone diisocyanate.
Step S120: add dibasic alcohol in the vulcabond of modification, in 60 ~ 80 DEG C of stirring reactions 2 ~ 4 hours, obtains the first reaction solution.
Wherein, dibasic alcohol is selected from least one in polyether Glycols, polycaprolactone diols and PCDL.
Wherein, the mol ratio of the vulcabond of dibasic alcohol and modification is 1:2 ~ 6.
Step S130: add multi-hydroxy carboxy acid and catalyzer in the first reaction solution, in 70 ~ 80 DEG C of stirring reactions 1 ~ 2 hour, obtains the second reaction solution.
Wherein, the mol ratio of the vulcabond of multi-hydroxy carboxy acid and modification is 0.2 ~ 0.5:1.
Wherein, multi-hydroxy carboxy acid is selected from least one in dimethylol propionic acid and dimethylolpropionic acid.
Wherein, catalyzer is dibutyl tin laurate.Wherein, the mass ratio of catalyzer and multi-hydroxy carboxy acid is 0.1 ~ 1:3 ~ 8.
Step S140: under the condition of 50 ~ 60 DEG C, adds hydroxy acrylate in the second reaction solution and stopper carries out end-blocking, reacts after 1 hour, is warming up to 70 ~ 85 DEG C, then adds acetone, continues reaction 2 hours, obtains the 3rd reaction solution.
Wherein, hydroxy acrylate is selected from least one in hydroxyethyl methylacrylate, Hydroxyethyl acrylate, pentaerythritol triacrylate, Rocryl 410, Propylene glycol monoacrylate and trimethylolpropane diacrylate.
Wherein, the mol ratio of the vulcabond of described hydroxy acrylate and described modification is 0.4 ~ 0.8:1.
Wherein, stopper is p methoxy phenol.The mass ratio of stopper and hydroxy acrylate is 0.1 ~ 1:20 ~ 60.
Wherein, in step S140, the interpolation quality of acetone is 3 ~ 10% of the total mass of the second reaction solution and hydroxy acrylate.
Step S150: under the condition of 40 ~ 50 DEG C, adds triethylamine in the 3rd reaction solution, reacts and obtains UV-cured polyurethane acrylate in 0.5 ~ 1.0 hour.
Wherein, the mol ratio of triethylamine and multi-hydroxy carboxy acid is 1 ~ 1.5:1.
The preparation method of above-mentioned UV-cured polyurethane acrylate is simple to operate, is easy to suitability for industrialized production.Above-mentioned UV-cured polyurethane acrylate by dihydroxyphenyl propane to vulcabond modification, obtain new isocyanate molecule structure, continue and dibasic alcohol, multi-hydroxy carboxy acid, acrylate monomers reacts, synthesize a kind of novel urethane acrylate, more aromatic ring rigid structure is introduced in molecular chain, make molecular weight rigidity reinforced, hard segment molecule chain movement is obstructed, promote the formation of soft or hard section microphase-separated state in molecular chain, improve its second-order transition temperature, add the hardness of resin.
Preparation method's energy-conserving and environment-protective of above-mentioned UV-cured polyurethane acrylate, obtain UV-cured polyurethane acrylate and there is the advantages such as wear-resisting, sticking power is good, automatic assembly line application can be realized, easy construction, can be used for the products such as automobile, electronic product, furniture packaging printing, have broad application prospects.
A kind of UV-cured polyurethane acrylate prepared by the preparation method of above-mentioned UV-cured polyurethane acrylate.Because this UV-cured polyurethane acrylate adopts above-mentioned preparation method to prepare, above-mentioned UV-cured polyurethane acrylate is made to have higher glass transition temperature and larger hardness.
Be below specific embodiment part:
Embodiment 1
The preparation process of the UV-cured polyurethane acrylate of the present embodiment is as follows:
1, under logical nitrogen protection condition; to in the four mouthfuls of reaction flasks being placed with thermometer, prolong, stirring rod; after adding vulcabond; be placed in the water bath with thermostatic control of 45 DEG C; constant pressure funnel is utilized to be added drop-wise to by dihydroxyphenyl propane in four mouthfuls of reaction flasks; then in 40 DEG C of reactions 3 hours, the vulcabond of modification is obtained.Wherein, the mol ratio of dihydroxyphenyl propane and vulcabond is 1:2.Vulcabond is selected from Xylene Diisocyanate.
2, in the vulcabond of modification, add dibasic alcohol, in 60 DEG C of stirring reactions 4 hours, obtain the first reaction solution.Wherein, dibasic alcohol is selected from polyether Glycols.The mol ratio of the vulcabond of dibasic alcohol and modification is 1:2.
3, in the first reaction solution, add multi-hydroxy carboxy acid, and drip catalyzer, then in 70 DEG C of stirring reactions 2 hours, obtain the second reaction solution.Wherein, the mol ratio of the vulcabond of multi-hydroxy carboxy acid and modification is 0.2:1.Multi-hydroxy carboxy acid is selected from dimethylol propionic acid.Catalyzer is dibutyl tin laurate.Wherein, the mass ratio of catalyzer and multi-hydroxy carboxy acid is 0.1:3.
4, under the condition of 50 DEG C, in the second reaction solution, add hydroxy acrylate and stopper carries out end-blocking, react after 1 hour, be warming up to 70 DEG C, then add acetone regulation system viscosity, continue reaction 2 hours, obtain the 3rd reaction solution.Wherein, hydroxy acrylate is selected from hydroxyethyl methylacrylate.Wherein, the mol ratio of the vulcabond of hydroxyethyl methylacrylate and modification is 0.8:1, and stopper is p methoxy phenol.The mass ratio of stopper and hydroxy acrylate is 0.1:20.The interpolation quality of acetone is 3% of the second reaction solution and hydroxy acrylate total mass.
5, under the condition of 40 DEG C, in the 3rd reaction solution, add triethylamine, react 0.5 hour, obtain UV-cured polyurethane acrylate.Wherein, the mol ratio of triethylamine and multi-hydroxy carboxy acid is 1:1.
Thermogravimetric analyzer is adopted to test the glass transition temp of the UV-cured polyurethane acrylate of the present embodiment, adopt the pencil hardness of UV-cured polyurethane acrylate of GB6739-1996 test test the present embodiment, obtain the glass transition temp of the UV-cured polyurethane acrylate of the present embodiment and hardness in table 1.
Embodiment 2
The preparation process of the UV-cured polyurethane acrylate of the present embodiment is as follows:
1, under logical nitrogen protection condition; to in the four mouthfuls of reaction flasks being placed with thermometer, prolong, stirring rod; after adding vulcabond; be placed in the water bath with thermostatic control of 45 DEG C; constant pressure funnel is utilized to be added drop-wise to by dihydroxyphenyl propane in four mouthfuls of reaction flasks; then in 60 DEG C of reactions 1 hour, the vulcabond of modification is obtained.Wherein, the mol ratio of dihydroxyphenyl propane and vulcabond is 1:2.Vulcabond is selected from dicyclohexyl methane diisocyanate.
2, in the vulcabond of modification, add dibasic alcohol, in 80 DEG C of stirring reactions 2 hours, obtain the first reaction solution.Wherein, dibasic alcohol is selected from polycaprolactone diols.The mol ratio of the vulcabond of dibasic alcohol and modification is 1:6.
3, in the first reaction solution, add multi-hydroxy carboxy acid, and drip catalyzer, then in 80 DEG C of stirring reactions 1 hour, obtain the second reaction solution.Wherein, the mol ratio of multi-hydroxy carboxy acid and vulcabond is 0.5:1.Multi-hydroxy carboxy acid is selected from dimethylolpropionic acid.Catalyzer is dibutyl tin laurate.Wherein, the mass ratio of catalyzer and multi-hydroxy carboxy acid is 1:8.
4, under the condition of 60 DEG C, in the second reaction solution, add hydroxy acrylate and stopper carries out end-blocking, react after 1 hour, be warming up to 85 DEG C, then add acetone regulation system viscosity, continue reaction 2 hours, obtain the 3rd reaction solution.Wherein, hydroxy acrylate is selected from Hydroxyethyl acrylate.Wherein, the mol ratio of Hydroxyethyl acrylate and vulcabond is 0.7:1 stopper is p methoxy phenol.The mass ratio of stopper and hydroxy acrylate is 1:60.The interpolation quality of acetone is 10% of the total mass of the second reaction solution, hydroxy acrylate and stopper.
5, under the condition of 50 DEG C, in the 3rd reaction solution, add triethylamine, react 1.0 hours, obtain UV-cured polyurethane acrylate.Wherein, the mol ratio of triethylamine and multi-hydroxy carboxy acid is 1.5:1.
The identical testing method of embodiment 1 is adopted to obtain the UV-cured polyurethane acrylate glass transition temp of the present embodiment and hardness in table 1.
Embodiment 3
The preparation process of the UV-cured polyurethane acrylate of the present embodiment is as follows:
1, under logical nitrogen protection condition; to in the four mouthfuls of reaction flasks being placed with thermometer, prolong, stirring rod; after adding vulcabond; be placed in the water bath with thermostatic control of 45 DEG C; constant pressure funnel is utilized to be added drop-wise to by dihydroxyphenyl propane in four mouthfuls of reaction flasks; then in 50 DEG C of reactions 2 hours, the vulcabond of modification is obtained.Wherein, the mol ratio of dihydroxyphenyl propane and vulcabond is 1:2.Vulcabond is selected from '-diphenylmethane diisocyanate.
2, in the vulcabond of modification, add dibasic alcohol, in 70 DEG C of stirring reactions 3 hours, obtain the first reaction solution.Wherein, dibasic alcohol is selected from PCDL.The mol ratio of the vulcabond of dibasic alcohol and modification is 1:3.
3, in the first reaction solution, add multi-hydroxy carboxy acid, and drip catalyzer, then in 75 DEG C of stirring reactions 1.5 hours, obtain the second reaction solution.Wherein, the mol ratio of the vulcabond of multi-hydroxy carboxy acid and modification is 0.3:1.Multi-hydroxy carboxy acid be selected from dimethylol propionic acid and.Catalyzer is dibutyl tin laurate.Wherein, the mass ratio of catalyzer and multi-hydroxy carboxy acid is 0.5:3.
4, under the condition of 55 DEG C, in the second reaction solution, add hydroxy acrylate and stopper carries out end-blocking, react after 1 hour, be warming up to 80 DEG C, then add acetone regulation system viscosity, continue reaction 2 hours, obtain the 3rd reaction solution.Wherein, hydroxy acrylate is selected from Rocryl 410.Wherein, the mol ratio of hydroxyethyl methylacrylate and vulcabond is 0.4:1 stopper is p methoxy phenol.The mass ratio of stopper and hydroxy acrylate is 0.5:20.The interpolation quality of acetone is 8% of the total mass of the second reaction solution, hydroxy acrylate and stopper.
5, under the condition of 45 DEG C, in the 3rd reaction solution, add triethylamine, react and obtain UV-cured polyurethane acrylate in 0.7 hour.Wherein, the mol ratio of triethylamine and multi-hydroxy carboxy acid is 1.2:1.
The identical testing method of embodiment 1 is adopted to obtain the glass transition temp of the UV-cured polyurethane acrylate of the present embodiment and hardness in table 1.
Embodiment 4
The preparation process of the UV-cured polyurethane acrylate of the present embodiment is as follows:
1, under logical nitrogen protection condition; to in the four mouthfuls of reaction flasks being placed with thermometer, prolong, stirring rod; after adding vulcabond; be placed in the water bath with thermostatic control of 45 DEG C; constant pressure funnel is utilized to be added drop-wise to by dihydroxyphenyl propane in four mouthfuls of reaction flasks; then in 55 DEG C of reactions 2 hours, the vulcabond of modification is obtained.Wherein, the mol ratio of dihydroxyphenyl propane and vulcabond is 1:2.Vulcabond is selected from terephthalylidene vulcabond.
2, in the vulcabond of modification, add dibasic alcohol, in 70 DEG C of stirring reactions 3 hours, obtain the first reaction solution.Wherein, dibasic alcohol is selected from PCDL.The mol ratio of dibasic alcohol and vulcabond is 1:4.
3, in the first reaction solution, add multi-hydroxy carboxy acid, and drip catalyzer, then in 75 DEG C of stirring reactions 2 hours, obtain the second reaction solution.Wherein, the mol ratio of multi-hydroxy carboxy acid and vulcabond is 0.5:1.Multi-hydroxy carboxy acid is selected from dimethylolpropionic acid.Catalyzer is dibutyl tin dilaurate.Wherein, the mass ratio of catalyzer and multi-hydroxy carboxy acid is 1:7.
4, under the condition of 55 DEG C, in the second reaction solution, add hydroxy acrylate and stopper carries out end-blocking, react after 1 hour, be warming up to 80 DEG C, then add acetone regulation system viscosity, continue reaction 2 hours, obtain the 3rd reaction solution.Wherein, hydroxy acrylate is selected from trimethylolpropane diacrylate.Wherein, the mol ratio of trimethylolpropane diacrylate and vulcabond is 0.4:1.Stopper is p methoxy phenol.The mass ratio of stopper and hydroxy acrylate is 1:50.The interpolation quality of acetone is 8% of the total mass of the second reaction solution, hydroxy acrylate and stopper.
5, under the condition of 45 DEG C, in the 3rd reaction solution, add triethylamine, react 0.5 hour, be then cooled to 40 DEG C, obtain UV-cured polyurethane acrylate.Wherein, the mol ratio of triethylamine and multi-hydroxy carboxy acid is 1.5:1.
The identical testing method of embodiment 1 is adopted to obtain the glass transition temp of the present embodiment and hardness in table 1.
What table 1 represented is glass transition temp and the hardness of the UV-cured polyurethane acrylate of embodiment 1 ~ 4.
Table 1
As can be seen from Table 1, the glass transition temp of above-mentioned UV-cured polyurethane acrylate is at least 40 DEG C, and hardness is at least 2H, and obviously, above-mentioned UV-cured polyurethane acrylate has higher glass transition temp and hardness.
The above embodiment only have expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (9)
1. a preparation method for UV-cured polyurethane acrylate, is characterized in that, comprises the steps:
Under the environment of protective gas, mixed by vulcabond with dihydroxyphenyl propane, in 40 ~ 60 DEG C of reactions 1 ~ 3 hour, obtain the vulcabond of modification, wherein, the mol ratio of described dihydroxyphenyl propane and described vulcabond was 1:2;
In the vulcabond of described modification, add dibasic alcohol, in 60 ~ 80 DEG C of stirring reactions 2 ~ 4 hours, obtain the first reaction solution, wherein, the mol ratio of the vulcabond of described dibasic alcohol and described modification was 1:2 ~ 6;
In described first reaction solution, add multi-hydroxy carboxy acid and catalyzer, in 70 ~ 80 DEG C of stirring reactions 1 ~ 2 hour, obtain the second reaction solution, wherein, the mol ratio of the vulcabond of described multi-hydroxy carboxy acid and described modification was 0.2 ~ 0.5:1;
Under the condition of 50 ~ 60 DEG C, in described second reaction solution, add hydroxy acrylate and stopper carries out end-blocking, react after 1 hour, be warming up to 70 ~ 85 DEG C, then add acetone, continue reaction 2 hours, obtain the 3rd reaction solution; Wherein, the mol ratio of the vulcabond of described hydroxy acrylate and described modification be 0.4 ~ 0.8:1 and
Under the condition of 40 ~ 50 DEG C, in described 3rd reaction solution, add triethylamine, react 0.5 ~ 1.0 hour, obtain UV-cured polyurethane acrylate, wherein, the mol ratio of described triethylamine and described multi-hydroxy carboxy acid is 1 ~ 1.5:1.
2. the preparation method of UV-cured polyurethane acrylate according to claim 1, it is characterized in that, described vulcabond is selected from least one in Xylene Diisocyanate, dicyclohexyl methane diisocyanate, '-diphenylmethane diisocyanate, terephthalylidene vulcabond, hexamethylene diisocyanate and isophorone diisocyanate.
3. the preparation method of UV-cured polyurethane acrylate according to claim 1, is characterized in that, described dibasic alcohol is selected from least one in polyether Glycols, polycaprolactone diols and PCDL.
4. the preparation method of UV-cured polyurethane acrylate according to claim 1, is characterized in that, described multi-hydroxy carboxy acid is selected from least one in dimethylol propionic acid and dimethylolpropionic acid.
5. the preparation method of UV-cured polyurethane acrylate according to claim 1, is characterized in that, described catalyzer is dibutyl tin laurate, and wherein, the mass ratio of described catalyzer and described multi-hydroxy carboxy acid is 0.1 ~ 1:3 ~ 8.
6. the preparation method of UV-cured polyurethane acrylate according to claim 1, it is characterized in that, described hydroxy acrylate is selected from least one in hydroxyethyl methylacrylate, Hydroxyethyl acrylate, pentaerythritol triacrylate, Rocryl 410, Propylene glycol monoacrylate and trimethylolpropane diacrylate.
7. the preparation method of UV-cured polyurethane acrylate according to claim 1, is characterized in that, described stopper is p methoxy phenol, and the mass ratio of described stopper and described hydroxy acrylate is 0.1 ~ 1:2 ~ 60.
8. the preparation method of UV-cured polyurethane acrylate according to claim 1, it is characterized in that, be set forth in the condition of 50 ~ 60 DEG C under, described hydroxy acrylate is added and described stopper carries out end-blocking in described second reaction solution, react after 1 hour, be warming up to 70 ~ 85 DEG C, then add in the step of described acetone, the interpolation quality of described acetone is 3 ~ 10% of described second reaction solution and described hydroxy acrylate total mass.
9. the UV-cured polyurethane acrylate for preparing of the preparation method of the UV-cured polyurethane acrylate as described in claim 1 ~ 8 any one.
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| CN113913148A (en) * | 2021-12-03 | 2022-01-11 | 深圳市浩力新材料技术有限公司 | UV curing adhesive and preparation method thereof |
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