CN117003989A - Epoxidized soybean oil-based acrylic ester-polyurethane UV light-cured resin and plant oil-based nail polish gel prepared from same and containing no TPO light initiator - Google Patents
Epoxidized soybean oil-based acrylic ester-polyurethane UV light-cured resin and plant oil-based nail polish gel prepared from same and containing no TPO light initiator Download PDFInfo
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- CN117003989A CN117003989A CN202310988953.2A CN202310988953A CN117003989A CN 117003989 A CN117003989 A CN 117003989A CN 202310988953 A CN202310988953 A CN 202310988953A CN 117003989 A CN117003989 A CN 117003989A
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- Prior art keywords
- acrylate
- soybean oil
- resin
- epoxidized soybean
- polyurethane
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- 239000011347 resin Substances 0.000 title claims abstract description 97
- 229920005989 resin Polymers 0.000 title claims abstract description 97
- 235000012424 soybean oil Nutrition 0.000 title claims abstract description 76
- 239000003549 soybean oil Substances 0.000 title claims abstract description 76
- 239000004814 polyurethane Substances 0.000 title claims abstract description 40
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 40
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 239000010773 plant oil Substances 0.000 title claims abstract description 5
- 239000003999 initiator Substances 0.000 title claims description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 71
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 48
- 150000008064 anhydrides Chemical class 0.000 claims abstract description 22
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 17
- 238000005886 esterification reaction Methods 0.000 claims abstract description 17
- 235000015112 vegetable and seed oil Nutrition 0.000 claims abstract description 13
- 239000008158 vegetable oil Substances 0.000 claims abstract description 13
- 239000004359 castor oil Substances 0.000 claims abstract description 12
- 235000019438 castor oil Nutrition 0.000 claims abstract description 12
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 claims abstract description 12
- 125000005442 diisocyanate group Chemical group 0.000 claims abstract description 11
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical compound OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000178 monomer Substances 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 9
- -1 acrylic ester Chemical class 0.000 claims abstract description 8
- 150000001412 amines Chemical class 0.000 claims abstract description 8
- 238000004132 cross linking Methods 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 57
- 238000006116 polymerization reaction Methods 0.000 claims description 46
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 45
- 239000003112 inhibitor Substances 0.000 claims description 45
- 239000003054 catalyst Substances 0.000 claims description 27
- 238000001723 curing Methods 0.000 claims description 23
- 238000002360 preparation method Methods 0.000 claims description 19
- 239000004593 Epoxy Substances 0.000 claims description 18
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims description 18
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 claims description 16
- 239000013530 defoamer Substances 0.000 claims description 16
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 15
- 239000007795 chemical reaction product Substances 0.000 claims description 15
- 238000000016 photochemical curing Methods 0.000 claims description 15
- 239000002994 raw material Substances 0.000 claims description 15
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 12
- 238000003848 UV Light-Curing Methods 0.000 claims description 11
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 10
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 10
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 10
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 claims description 9
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 9
- 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 9
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 8
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 7
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 7
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 7
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims description 7
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 7
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 6
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 6
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 claims description 5
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 claims description 5
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 claims description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 5
- 229920005830 Polyurethane Foam Polymers 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000011496 polyurethane foam Substances 0.000 claims description 5
- 229940044119 2-tert-butylhydroquinone Drugs 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 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- DZHSVSBJDNJICY-UHFFFAOYSA-N bis(4-methylphenyl)phosphoryl-(2,4,6-trimethylphenyl)methanone Chemical group C1=CC(C)=CC=C1P(=O)(C=1C=CC(C)=CC=1)C(=O)C1=C(C)C=C(C)C=C1C DZHSVSBJDNJICY-UHFFFAOYSA-N 0.000 claims description 4
- 229910021485 fumed silica Inorganic materials 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 claims description 3
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 3
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 claims description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 3
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 3
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 3
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 3
- FSDNTQSJGHSJBG-UHFFFAOYSA-N piperidine-4-carbonitrile Chemical compound N#CC1CCNCC1 FSDNTQSJGHSJBG-UHFFFAOYSA-N 0.000 claims description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 3
- ALQLPWJFHRMHIU-UHFFFAOYSA-N 1,4-diisocyanatobenzene Chemical compound O=C=NC1=CC=C(N=C=O)C=C1 ALQLPWJFHRMHIU-UHFFFAOYSA-N 0.000 claims description 2
- LIBFVQBAZPYQCJ-UHFFFAOYSA-N 2-oxaspiro[3.4]octane-1,3-dione Chemical compound O=C1OC(=O)C11CCCC1 LIBFVQBAZPYQCJ-UHFFFAOYSA-N 0.000 claims description 2
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 2
- TWLCPLJMACDPFF-UHFFFAOYSA-N cyclohexane;1,2-diisocyanatoethane Chemical compound C1CCCCC1.O=C=NCCN=C=O TWLCPLJMACDPFF-UHFFFAOYSA-N 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 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
- AUHHYELHRWCWEZ-UHFFFAOYSA-N tetrachlorophthalic anhydride Chemical compound ClC1=C(Cl)C(Cl)=C2C(=O)OC(=O)C2=C1Cl AUHHYELHRWCWEZ-UHFFFAOYSA-N 0.000 claims description 2
- 229920002397 thermoplastic olefin Polymers 0.000 abstract description 19
- 239000000463 material Substances 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 abstract description 2
- 238000000576 coating method Methods 0.000 abstract description 2
- 239000000499 gel Substances 0.000 description 22
- 238000012360 testing method Methods 0.000 description 16
- 150000008065 acid anhydrides Chemical class 0.000 description 11
- 238000001514 detection method Methods 0.000 description 8
- 230000035484 reaction time Effects 0.000 description 8
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- SOOZEQGBHHIHEF-UHFFFAOYSA-N methyltetrahydrophthalic anhydride Chemical compound C1C=CCC2C(=O)OC(=O)C21C SOOZEQGBHHIHEF-UHFFFAOYSA-N 0.000 description 4
- 238000007142 ring opening reaction Methods 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 206010074268 Reproductive toxicity Diseases 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000008034 disappearance Effects 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 239000011846 petroleum-based material Substances 0.000 description 2
- 229920000570 polyether Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000007696 reproductive toxicity Effects 0.000 description 2
- 231100000372 reproductive toxicity Toxicity 0.000 description 2
- 239000011342 resin composition Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 235000005811 Viola adunca Nutrition 0.000 description 1
- 240000009038 Viola odorata Species 0.000 description 1
- 235000013487 Viola odorata Nutrition 0.000 description 1
- 235000002254 Viola papilionacea Nutrition 0.000 description 1
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- STZIXLPVKZUAMV-UHFFFAOYSA-N cyclopentane-1,1,2,2-tetracarboxylic acid Chemical compound OC(=O)C1(C(O)=O)CCCC1(C(O)=O)C(O)=O STZIXLPVKZUAMV-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- ZHNUHDYFZUAESO-UHFFFAOYSA-N formamide Substances NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- 239000004611 light stabiliser Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000012985 polymerization agent Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
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- 230000008023 solidification Effects 0.000 description 1
- 241000894007 species Species 0.000 description 1
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Landscapes
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention belongs to the technical field of UV (ultraviolet) curing materials, and particularly relates to an epoxidized soybean oil-based acrylic ester-polyurethane UV (ultraviolet) curing resin and a plant oil-based nail polish gel prepared from the same and containing no TPO (thermoplastic olefin) photoinitiator. Firstly, reacting epoxidized soybean oil and acrylic ester at 100-130 ℃, cooling to 50-80 ℃ after the acid value is unchanged, and adding diisocyanate to continue the reaction to obtain prepolymer; and then, respectively carrying out esterification reaction on the two anhydride curing agents and hydroxyl acrylate, and introducing the two anhydride curing agents into a prepolymer for crosslinking reaction to finally obtain the epoxidized soybean oil-based acrylic ester-polyurethane UV light-cured resin. And uniformly mixing the obtained resin with TMO photoinitiator, amine modified resin, castor oil resin, active monomer, auxiliary agent and color paste to obtain the vegetable oil-based nail polish gel without TPO photoinitiator. The resin and the nail polish gel have high biological base content, and the obtained coating has better mechanical property.
Description
Technical Field
The invention belongs to the technical field of UV (ultraviolet) curing materials, and particularly relates to an epoxidized soybean oil-based acrylic ester-polyurethane UV (ultraviolet) curing resin and a plant oil-based nail polish gel prepared from the same and containing no TPO (thermoplastic olefin) photoinitiator.
Background
Nail polish is one of a plurality of cosmetics, is generally used for hand/foot nails, has rich and varied colors and styles, has attractive and decorative effects, is deeply touted and loved by a plurality of women, and however, common nail polish contains substances harmful to human bodies. With the rise of UV curing technology, UV nail polish is a popular nail polish product in recent years, which is in the public view. The UV nail polish generally adopts a traditional UV lamp or an LED lamp for curing, and compared with the common nail polish, the UV nail polish has the advantages of environmental protection, no toxicity, high curing rate, longer maintenance time and the like, so that the nail polish gradually replaces the common nail polish.
The main components of the UV nail polish comprise main resin, a photoinitiator, an auxiliary agent and color paste, wherein the main component is the main resin. At present, the petroleum-based material is taken as main resin of the nail polish with a relatively large occupation ratio, but the petroleum-based material is non-renewable and is easy to cause environmental pollution. Therefore, a need exists for a low cost, environmentally friendly, renewable biomass resource based resin for the preparation of nail polish.
Photoinitiators are an important component of UV nail polish, and are indispensable, although the proportion of the formulation is generally not high. Although the initiator is various at present, many photoinitiators have the problems of containing harmful substances, low initiation efficiency, poor compatibility and the like. For example, the photoinitiator TPO is a photoinitiator commonly used in nail polish, however the European photo-curable coating ink industry has classified the photoinitiator TPO as a reproductive toxicity 2 in CLP (Classification, labeling and packaging) regulations, and the photoinitiator TPO is likely to be reclassified by the European Union as a reproductive toxicity 1B species in CMR, if such a classified change becomes realistic, meaning that the photoinitiator TPO will be disabled or restricted in many applications. Therefore, another photoinitiator which is suitable for nail polish and has good safety, high efficiency and good compatibility is needed to be searched, and the nail polish with good adhesive force, good wear resistance and good toughness is prepared.
Disclosure of Invention
The first object of the invention is to provide a method for preparing the epoxy soybean oil-based acrylate-polyurethane UV light-cured resin, the second object of the invention is to provide the epoxy soybean oil-based acrylate-polyurethane UV light-cured resin prepared by the preparation method, and the third object of the invention is to provide the application of the epoxy soybean oil-based acrylate-polyurethane UV light-cured resin.
According to a first aspect of the present invention, there is provided a method for preparing an epoxidized soybean oil-based acrylate-urethane UV photo-curing resin, comprising the steps of:
(1) Taking a first catalyst, a first polymerization inhibitor, epoxidized soybean oil and acrylic ester to react at the temperature of 100-130 ℃ and the speed of 200-300r/min, cooling to 50-80 ℃ after the acid value is unchanged, adding diisocyanate to continue to react until the NCO infrared peak disappears or the NCO value is lower than 0.2%, and obtaining a prepolymer;
(2) Taking a second catalyst, a second polymerization inhibitor, hydroxyl acrylate and two anhydride curing agents, respectively carrying out esterification reaction on the two anhydride curing agents and the hydroxyl acrylate at the temperature of 100-120 ℃ and the rotating speed of 200-300r/min until the reaction reaches 1777cm -1 -1850cm -1 Stopping the reaction when the infrared peak of the anhydride at the position disappears, and respectively naming reaction products obtained by esterification reaction of the two anhydride curing agents as a mixture 1 and a mixture 2;
(3) Adding the mixture 1 and the mixture 2 obtained in the step (2) into the prepolymer obtained in the step (1), stirring for 20-60min at 20-40 ℃, and fully crosslinking to obtain the polyurethane foam.
In the step (1), the reaction can be stopped after the acid value is measured once in the reaction process of the acrylic ester and the epoxidized soybean oil, and the reaction time does not need to be strictly controlled; the reaction product of acrylic ester and epoxidized soybean oil has low viscosity (4000-8000 mPa.s), no gel phenomenon and better thermal stability. After the reaction is finished, the temperature is reduced to 50-80 ℃ to add diisocyanate for reaction, the temperature is not required to be reduced to room temperature, and the control of the temperature is not strict; the acrylate and the epoxidized soybean oil are subjected to ring-opening reaction to generate hydroxyl, and diisocyanate is directly added into the hydroxyl to prepare the prepolymer through a one-pot method, so that the preparation process is simple.
In the step (3), the anhydride derivative and the prepolymer are used for crosslinking and compounding to participate in photo-curing.
Carbon-carbon double bonds and ester groups can be formed in the process of ring-opening reaction of the epoxidized soybean oil and acrylic ester, and the active groups can promote the quick solidification of the UV nail polish; and then hydroxyl and diisocyanate generated after the ring-opening reaction of the epoxidized soybean oil and the acrylic ester form amide bonds again, so that the hardness and toughness of the resin are improved, and the general performance requirements of the nail polish gel are met; in addition, the addition of the anhydride curing agent can promote the resin to be fully crosslinked, so that the raw materials are uniform and compatible, and better compatibility with TMO photoinitiator and components of the nail polish gel is realized.
In the process of preparing the resin, the special groups such as hydroxyl, double bond, ester group and the like are reacted, and the anhydride derivative and the prepolymer are subjected to crosslinking and compounding to participate in photo-curing, so that the viscosity of the resin can be greatly reduced, and the toughness, hardness and stability of a resin cured film are improved. The epoxy soybean oil-based acrylic ester-polyurethane UV light-cured resin has the viscosity of 6000-15000 mPa.s, the toughness of a resin cured film can reach 324%, the hardness can reach 4H, and the epoxy soybean oil-based acrylic ester-polyurethane UV light-cured resin has good thermal stability and can be stored in an oven at 90 ℃ for 15-30 days.
The epoxidized soybean oil-based acrylic ester-polyurethane UV light-cured resin provided by the invention has excellent basic performance, and can be applied to preparation of nail polish gel.
In some embodiments, in step (1), the epoxidized soybean oil is used in an amount of 20 to 70 parts by mass, the acrylic ester is used in an amount of 10 to 30 parts by mass, and the diisocyanate is used in an amount of 1 to 10 parts by mass; the amount of the first catalyst is 1 to 5wt% of the total reaction mass in the step (1), and the amount of the first polymerization inhibitor is 0.1 to 1.5wt% of the total reaction mass in the step (1). The total reaction mass referred to herein is epoxidized soybean oil and acrylate.
In some embodiments, in step (1), the molar ratio of epoxidized soybean oil to acrylate is 1: (3.5-4.5).
In some embodiments, in step (2), when preparing mixture 1 or mixture 2, the hydroxyl acrylate is used in an amount of 10 to 40 parts by mass, the acid anhydride curing agent is used in an amount of 10 to 60 parts by mass, the second catalyst is used in an amount of 1 to 3wt% based on the total reaction mass, and the second polymerization inhibitor is used in an amount of 0.05 to 1wt% based on the total reaction mass. The total reaction mass referred to herein is the hydroxy acrylate and anhydride curing agent.
In some embodiments, in step (2), the molar ratio of anhydride curative to hydroxy acrylate is 1: (0.5-1.5).
In some embodiments, in step (3), the prepolymer is used in an amount of 50 to 70 parts by mass and the mass ratio of mixture 1 to mixture 2 is 1 to 5:1.
In some embodiments, the acrylate is selected from at least one of methyl acrylate, butyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate, acrylic acid.
In some embodiments, the first catalyst is selected from at least one of triethylamine, tetrabutylammonium chloride, benzyltriethylammonium chloride, triphenylphosphine.
In some embodiments, the first polymerization inhibitor is selected from at least one of 2, 6-di-tert-butyl-p-cresol, p-hydroxyanisole, hydroquinone, 2-tert-butyl hydroquinone, basf 1076.
In some embodiments, the diisocyanate is selected from at least one of cyclohexane dimethylene diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, and terephthal-diisocyanate.
In some embodiments, the second catalyst is selected from at least one of triethylamine, tetrabutylammonium chloride, benzyltriethylammonium chloride, triphenylphosphine.
In some embodiments, the second polymerization inhibitor is selected from at least one of 2, 6-di-tert-butyl-p-cresol, p-hydroxyanisole, hydroquinone, 2-tert-butyl hydroquinone.
In some embodiments, the anhydride curing agent is selected from at least one of phthalic anhydride, cyclopentanedioic anhydride, tetrachlorophthalic anhydride, methyltetrahydrophthalic anhydride, maleic anhydride.
In some embodiments, the hydroxy acrylate is selected from at least one of hydroxy propyl acrylate, hydroxy ethyl methacrylate, hydroxy propyl methacrylate, hydroxy ethyl acrylate.
According to a second aspect of the present invention, there is provided an epoxidized soybean oil-based acrylate-urethane UV photo-curing resin prepared by the above-mentioned preparation method.
According to a third aspect of the invention, there is provided the use of the above-described epoxidized soybean oil based acrylate-polyurethane UV photo-curing resin in the preparation of nail polish.
According to a fourth aspect of the present invention, there is provided a vegetable oil-based nail polish gel free of TPO photoinitiator, comprising the following raw materials in parts by mass: 20-70 parts of the epoxy soybean oil-based acrylic ester-polyurethane UV light curing resin, 5-12 parts of TMO photoinitiator, 5-15 parts of amine modified resin, 5-20 parts of castor oil resin, 20-45 parts of active monomer, 2-10 parts of auxiliary agent and 2-10 parts of color paste.
The stability and viscosity of the resin affect the compatibility of the resin with the photoinitiator. Because the epoxy soybean oil-based acrylic ester-polyurethane UV light curing resin has good stability, the compatibility of the resin and the photoinitiator is better, and the resin is not easy to gel or polymerize in the reaction process of preparing the nail polish gel, so that the photoinitiator can absorb enough energy to initiate polymerization so as to perform deep curing. Meanwhile, the viscosity of the resin is small and is only 6000-15000 mPa.s, so that the photoinitiator can be more favorably dissolved in the resin. Therefore, the epoxidized soybean oil-based acrylate-polyurethane UV photo-curing resin of the present invention can be well adapted to TMO photo-initiators.
In some embodiments, the TMO photoinitiator is 2,4, 6-trimethylbenzoyl-bis (p-tolyl) phosphine oxide. 2,4, 6-trimethylbenzoyl-di (p-tolyl) phosphine oxide is an acylphosphine oxide, which can be prepared according to the method disclosed in publication number WO2020113585A 1.
The main characteristics of the TMO photoinitiator include: (1) high efficiency: the TMO photoinitiator has high response to ultraviolet light and blue-violet visible light, and has high initiation reaction efficiency; (2) safety: the TMO photoinitiator does not contain cancerogenic substances, and is not easy to cause potential safety hazards such as explosion, fire and the like; (3) compatibility: the TMO photoinitiator has good compatibility with other photoinitiators, light stabilizers and other chemicals, and can be matched with each other for use.
In some embodiments, the amine-modified resin is an amine-modified polyether acrylate.
In some embodiments, the castor oil resin is a castor oil-based urethane acrylic resin.
In some embodiments, the reactive monomer is selected from at least one of hydroxyethyl methacrylate (HEMA), 1, 6-hexanediol diacrylate (HDDA), hydroxyethyl acrylate (HEA), 4-Acryloylmorpholine (ACMO), isobornyl acrylate (IBOA), tripropylene glycol diacrylate (TPGDA), trimethylolpropane triacrylate (TMPTA), dipropylene glycol diacrylate (DPGDA).
In some embodiments, the auxiliary agent comprises polymerization inhibitor, defoamer, anti-settling agent and leveling agent, wherein the mass ratio of the polymerization inhibitor, the defoamer, the anti-settling agent and the leveling agent is 0.01-0.5:0.05-0.5:1-5:0.1-2.5.
In some embodiments, the polymerization inhibitor is at least one of polymerization inhibitor 510, basf 264, basf 1010, basf 168, basf 1076.
In some embodiments, the defoamer is at least one of digao 910, digao 920, digao 825, digao 963.
In some embodiments, the anti-settling agent is at least one of fumed silica, BYK RHEYK-405, RHEYK-410, BYK RHEYK-420, basf EFKA RM 1463, basf EFKA FA 4600.
In some embodiments, the leveling agent is at least one of digao 270, digao 450, digao 440.
According to a fifth aspect of the present invention, there is provided a method for preparing the above-mentioned vegetable oil-based nail polish gel without TPO photoinitiator, comprising the steps of: uniformly mixing the components according to the proportion, heating to 45-75 ℃, stirring for 30-60min at the rotating speed of 300-400r/min, and then filtering to obtain the finished product.
The beneficial effects of the invention include:
(1) The epoxy soybean oil-based acrylic ester-polyurethane UV light-cured resin has the viscosity of 6000-15000 mPa.s, the toughness of a resin cured film can reach 324%, the hardness can reach 4H, the thermal stability is good, the epoxy soybean oil-based acrylic ester-polyurethane UV light-cured resin can be stored in a baking oven at 90 ℃ for 15-30 days, the basic performance is excellent, and the epoxy soybean oil-based acrylic ester-polyurethane UV light-cured resin can be applied to the preparation of nail polish gel.
(2) The epoxidized soybean oil-based acrylic ester-polyurethane UV light-cured resin and the nail polish prepared by the same have high bio-based content, do not contain pungent odor, and have higher mechanical properties such as hardness, adhesive force, toughness and the like.
(3) The invention provides a TMO photoinitiator which can be highly matched with a nail polish gel product, and is an optimal substitute for TPO photoinitiator.
(4) The nail polish gel product of the invention has the advantages of fast curing rate, convenient use, easy disassembly, long storage time, simple manufacturing process and lower cost, and is suitable for industrialized production.
Drawings
FIG. 1 is a synthetic route diagram of an epoxidized soybean oil based acrylate-urethane UV curable resin of example 1 of the present invention.
FIG. 2 shows the Fourier transform infrared spectra of the epoxidized soybean oil (designated ESO), acrylic acid (designated AA), isophorone diisocyanate (designated IPDI), prepolymer (designated IPAE) and the anhydride curing agents maleic anhydride (designated MA), methyltetrahydrophthalic anhydride (designated MTHPA) and the esterification reaction product (designated MA/MTHPA-HEA) in step (2) (3) and the final product (designated IPAE-2M) in example 1 of the present invention, respectively.
FIG. 3 shows the tensile strength test results of the epoxidized soybean oil-based acrylate-urethane UV curable resins prepared in examples 1 to 3 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but embodiments of the present invention are not limited thereto. The materials referred to in the following examples are all available from commercial sources.
Example 1
The preparation method of the epoxidized soybean oil-based acrylate-polyurethane UV light-cured resin comprises the following steps:
(1) In a 200ml three-neck flask, triphenylphosphine accounting for 2wt% of the total reaction mass in the step (1) is used as a catalyst, hydroquinone accounting for 0.2wt% of the total reaction mass is used as a polymerization inhibitor, 48g of epoxidized soybean oil and 14.2g of acrylic acid are used as raw materials, and the reaction is carried out at a high temperature of 110 ℃ at 280r/min until the acid value is unchanged; then, the temperature was lowered to 55℃and 3.2g of isophorone diisocyanate was added to the three-necked flask and reacted until the NCO infrared peak disappeared or the NCO value was less than 0.2%, to obtain a prepolymer.
(2) Using triethylamine accounting for 3wt% of the total reaction mass in the step (2) as a catalyst and 2-tertiary butyl hydroquinone accounting for 0.1wt% of the total reaction mass as a polymerization inhibitor, carrying out esterification reaction on 25g of hydroxyethyl acrylate and 35.8g of methyl tetrahydrophthalic anhydride at 110 ℃ and 250r/min until the reaction time reaches 1777cm -1 -1850cm -1 The reaction was stopped when the infrared peak of the acid anhydride disappeared, and the reaction product was designated as mixture 1.
(3) Using triethylamine accounting for 3wt% of the total reaction mass in the step (3) as a catalyst and 2-tertiary butyl hydroquinone accounting for 0.1wt% of the total reaction mass as a polymerization inhibitor, carrying out esterification reaction on 25g of hydroxyethyl acrylate and 21.11g of maleic anhydride at 110 ℃ and 250r/min until the reaction time reaches 1777cm -1 -1850cm -1 The reaction was stopped when the infrared peak of the acid anhydride disappeared, and the reaction product was designated as mixture 2.
(4) 22.7g of mixture 1 and 11.3g of mixture 2 (the ratio of mixture 1 to mixture 2 is 2:1) are added into the prepolymer obtained in the step (1), and the mixture is stirred for about 40 minutes at 30 ℃ to be fully crosslinked, so that the polyurethane foam is obtained.
FIG. 1 is a synthetic route diagram for the epoxidized soybean oil based acrylate-urethane UV curable resin of example 1.
FIG. 2 shows the Fourier transform infrared spectra of epoxidized soybean oil (designated ESO), acrylic acid (designated AA), isophorone diisocyanate (designated IPDI), prepolymer (designated IPAE) and the anhydride curing agents maleic anhydride (designated MA), methyltetrahydrophthalic anhydride (designated MTHPA) in steps (2) and (3) and the reaction products after the esterification reaction (i.e., mixture 1 and mixture 2. Since the peaks of mixture 1 and mixture 2 are substantially the same, mixture 1 and mixture 2 are collectively designated MA/MTHPA-HEA, and the Fourier transform infrared spectrum of the final product (designated IPAE-2M) in step (4)).
As can be seen from FIG. 2, 1625cm of infrared spectrum of IPAE -1 There appears a stretching vibration peak of C=C double bond, 3480cm -1 A hydroxyl peak appears at the site, indicating that the epoxy group has opened with AA and a hydroxyl group has been formed; at the same time, at 812cm -1 There was observed a peak associated with an epoxy group, 2927cm -1 And 2853cm -1 There was a stretching vibration peak attributed to ESO-generated-CH 3 and-CH 2 Stretching vibration of (a); in the infrared spectrum of IPDI, 2260cm -1 The characteristic peak at this point is due to the stretching vibration of the-NCO group, accompanied by the appearance of an amide vibration peak of the-NHCOO-group in the IR spectrum of IPAE (1525 cm -1 ) 2260cm -1 The disappearance of the infrared peak indicates that isophorone diisocyanate has participated in the reaction; 1850cm in the IR spectrum of MA, MTHPA -1 -1777cm -1 The peak at which it belongs to the stretching vibration of the anhydride and the disappearance of the anhydride peak in MA/MTHPA-HEA indicates that MA, MTHPA has reacted completely with hydroxyethyl acrylate HEA.
Example 2
The preparation method of the epoxidized soybean oil-based acrylate-polyurethane UV light-cured resin comprises the following steps:
(1) In a 200ml three-neck flask, taking triethylamine accounting for 5wt% of the total reaction mass in the step (1) as a catalyst, taking basf 1076 accounting for 0.3wt% of the total reaction mass as a polymerization inhibitor, taking 55g of epoxidized soybean oil and 17g of ethyl acrylate as raw materials, and reacting at a high temperature of 125 ℃ at 280r/min until the acid value is unchanged; then, the temperature was lowered to 50℃and 2.88g of toluene diisocyanate was added to the three-necked flask and reacted until the NCO infrared peak disappeared or the NCO value was less than 0.2% to obtain a prepolymer.
(2) Using triethylamine accounting for 3wt% of the total reaction mass in the step (2) as a catalyst and 2-tertiary butyl hydroquinone accounting for 0.25wt% of the total reaction mass as a polymerization inhibitor, carrying out esterification reaction on 25g of hydroxypropyl methacrylate and 31.92g of methyltetrahydrophthalic anhydride at 120 ℃ and 250r/min until the reaction time reaches 1777cm -1 -1850cm -1 The reaction was stopped when the infrared peak of the acid anhydride disappeared, and the reaction product was designated as mixture 1.
(3) Using triethylamine accounting for 3wt% of the total reaction mass in the step (3) as a catalyst and 2-tertiary butyl hydroquinone accounting for 0.25wt% of the total reaction mass as a polymerization inhibitor, carrying out esterification reaction on 25g of hydroxypropyl methacrylate and 18.84g of maleic anhydride at 120 ℃ and 250r/min until the reaction time reaches 1777cm -1 -1850cm -1 The reaction was stopped when the infrared peak of the acid anhydride disappeared, and the reaction product was designated as mixture 2.
(4) Adding 12.5g of mixture 1 and 12.5g of mixture 2 (the ratio of mixture 1 to mixture 2 is 1:1) into the prepolymer obtained in the step (1), stirring at 35 ℃ for about 30min, and fully crosslinking.
The raw materials and products of example 2 were subjected to fourier transform infrared spectrum detection, and the detection results are similar to those of example 1, and are not described here again for the sake of economy.
Example 3
The preparation method of the epoxidized soybean oil-based acrylate-polyurethane UV light-cured resin comprises the following steps:
(1) In a 200ml three-neck flask, benzyl triethyl ammonium chloride accounting for 1.2 weight percent of the total reaction mass in the step (1) is taken as a catalyst, 2, 6-di-tert-butyl-p-cresol accounting for 0.15 weight percent of the total reaction mass is taken as a polymerization inhibitor, 52g of epoxidized soybean oil and 14g of methyl acrylate are taken as raw materials, and the reaction is carried out at a high temperature of 105 ℃ for 280r/min until the acid value is unchanged; then, the temperature was lowered to 75℃and 3.96g of diphenylmethane diisocyanate was added to the three-necked flask and reacted until the NCO infrared peak disappeared or the NCO value was less than 0.2%, to obtain a prepolymer.
(2) By walkingIn the step (2), triethylamine accounting for 3 weight percent of the total reaction mass is taken as a catalyst, 2-tertiary butyl hydroquinone accounting for 0.22 weight percent of the total reaction mass is taken as a polymerization inhibitor, 25g of hydroxyethyl acrylate and 37.52g of methyl tetrahydrophthalic anhydride are subjected to esterification reaction at 105 ℃ and 250r/min until the reaction reaches 1777cm -1 -1850cm -1 The reaction was stopped when the infrared peak of the acid anhydride disappeared, and the reaction product was designated as mixture 1.
(3) Using triethylamine accounting for 3wt% of the total reaction mass in the step (3) as a catalyst and 2-tertiary butyl hydroquinone accounting for 0.22wt% of the total reaction mass as a polymerization inhibitor, carrying out esterification reaction on 25g of hydroxyethyl acrylate and 20.69g of maleic anhydride at 105 ℃ and 250r/min until the reaction time reaches 1777cm -1 -1850cm -1 The reaction was stopped when the infrared peak of the acid anhydride disappeared, and the reaction product was designated as mixture 2.
(4) 22.5g of mixture 1 and 7.5g of mixture 2 (the ratio of mixture 1 to mixture 2 is 3:1) are added into the prepolymer obtained in the step (1), and the mixture is stirred for about 20min at 30 ℃ to be fully crosslinked, so that the polyurethane foam is obtained.
The raw materials and products of example 3 were subjected to fourier transform infrared spectrum detection, and the detection results are similar to those of example 1, and are not described here again for the sake of economy.
Example 4
The preparation method of the epoxidized soybean oil-based acrylate-polyurethane UV light-cured resin comprises the following steps:
(1) In a 200ml three-neck flask, tetrabutylammonium chloride accounting for 3.5 weight percent of the total reaction mass in the step (1) is taken as a catalyst, 2, 6-di-tert-butyl-p-cresol accounting for 0.5 weight percent of the total reaction mass is taken as a polymerization inhibitor, 35g of epoxidized soybean oil and 10.26g of 2-ethylhexyl acrylate are taken as raw materials, and the reaction is stopped at a high temperature of 110 ℃ at 280r/min until the acid value is unchanged; then, the temperature was lowered to 65℃and 1.81g of paraphenylene diisocyanate was added to the three-necked flask and reacted until the NCO infrared peak disappeared or the NCO value was less than 0.2%, to obtain a prepolymer.
(2) Using triethylamine accounting for 3wt% of the total reaction mass in the step (2) as a catalyst and p-hydroxyanisole accounting for 0.15wt% of the total reaction mass as a resistorA polymerization agent, which is prepared by carrying out esterification reaction on 25g of hydroxyethyl methacrylate and 32g of methyltetrahydrophthalic anhydride at 115 ℃ and 250r/min until 1777cm -1 -1850cm -1 The reaction was stopped when the infrared peak of the acid anhydride disappeared, and the reaction product was designated as mixture 1.
(3) Using triethylamine accounting for 3wt% of the total reaction mass in the step (3) as a catalyst and p-hydroxyanisole accounting for 0.15wt% of the total reaction mass as a polymerization inhibitor, carrying out esterification reaction on 25g of hydroxyethyl methacrylate and 54.92g of tetrachloro-dimethyl anhydride at 115 ℃ and 250r/min until the reaction time reaches 1777cm -1 -1850cm -1 The reaction was stopped when the infrared peak of the acid anhydride disappeared, and the reaction product was designated as mixture 2.
(4) 42g of mixture 1 and 10.5g of mixture 2 (the ratio of mixture 1 to mixture 2 is 4:1) were added to the prepolymer obtained in the step (1), and the mixture was stirred at 30℃for about 50 minutes, followed by sufficient crosslinking.
The raw materials and products of example 4 were subjected to fourier transform infrared spectrum detection, and the detection results are similar to those of example 1, and are not described here again for the sake of economy.
Example 5
The preparation method of the epoxidized soybean oil-based acrylate-polyurethane UV light-cured resin comprises the following steps:
(1) In a 200ml three-neck flask, triphenylphosphine accounting for 4.3 weight percent of the total reaction mass in the step (1) is used as a catalyst, 2, 6-di-tert-butyl-p-cresol accounting for 0.25 weight percent of the total reaction mass is used as a polymerization inhibitor, 42g of epoxidized soybean oil and 12.4g of butyl acrylate are used as raw materials, and the reaction is stopped at a high temperature of 130 ℃ at 280r/min until the acid value is unchanged; then, the temperature was lowered to 65℃and 3.26g of cyclohexanedimethylene diisocyanate was added to the three-necked flask and reacted until the NCO infrared peak disappeared or the NCO value was less than 0.2% to obtain a prepolymer.
(2) Using triethylamine accounting for 3wt% of the total reaction mass in the step (2) as a catalyst and 2-tertiary butyl hydroquinone accounting for 0.12wt% of the total reaction mass as a polymerization inhibitor, carrying out esterification reaction on 25g of hydroxyethyl acrylate and 34.85g of methyl tetrahydrophthalic anhydride at 105 ℃ and 250r/min,reaction to 1777cm -1 -1850cm -1 The reaction was stopped when the infrared peak of the acid anhydride disappeared, and the reaction product was designated as mixture 1.
(3) Using triethylamine accounting for 3wt% of the total reaction mass in the step (3) as a catalyst and 2-tertiary butyl hydroquinone accounting for 0.12wt% of the total reaction mass as a polymerization inhibitor, carrying out esterification reaction on 25g of hydroxyethyl acrylate and 45.24g of cyclopentanetetraic acid dianhydride at 105 ℃ and 250r/min until the reaction time reaches 1777cm -1 -1850cm -1 The reaction was stopped when the infrared peak of the acid anhydride disappeared, and the reaction product was designated as mixture 2.
(4) 48.3g of mixture 1 and 9.6g of mixture 2 (the ratio of mixture 1 to mixture 2 is 5:1) are added into the prepolymer obtained in the step (1), and the mixture is stirred for about 60 minutes at 30 ℃ to be fully crosslinked, so that the polyurethane foam is obtained.
The raw materials and products of example 5 were subjected to fourier transform infrared spectrum detection, and the detection results are similar to those of example 1, and are not described here again for the sake of economy.
To verify the performance of the epoxidized soybean oil-based acrylate-urethane UV light-cured resin of the present invention, viscosity test and pencil hardness test were performed on the epoxidized soybean oil-based acrylate-urethane UV light-cured resins prepared in examples 1 to 5, and tensile strength test was performed on the epoxidized soybean oil-based acrylate-urethane UV light-cured resins prepared in examples 1 to 3.
1. Test method
(1) Viscosity test: the viscosity of the resin is tested by using a modularized intelligent high-grade rheometer (MCR 502) at the temperature of 25 ℃, the number of collected data points is 25 by using a CP25-2 rotor (the diameter of a conical plate rotor is 25 mm), and the shearing rate is 0.01-100 S -1 The air pressure was 5bar.
(2) Pencil hardness test: the test was carried out according to the method of GB/T6739-1996.
(3) Tensile strength test: firstly, the epoxy soybean oil-based acrylic ester-polyurethane UV light curing resin is irradiated under the lamp source of an ultraviolet light curing machine for 30 S The irradiation distance is 10cm, and the photo-curing film can be obtained, and then the electronic universal tester is used for carrying out the photo-curing filmAnd (5) tensile test. The tensile rate was 10mm/min, a tensile load was applied along the longitudinal axis until the rectangular specimen ruptured, five measurements were made for each group, and the average value was calculated.
2. Test results
(1) The results of the viscosity test of the epoxidized soybean oil-based acrylate-urethane UV photo-curing resins prepared in examples 1 to 5 are shown in table 1.
TABLE 1 results of viscosity test
| Resin composition | Viscosity (mPa. S) |
| Example 1 | 8288 |
| Example 2 | 9850 |
| Example 3 | 11200 |
| Example 4 | 10588 |
| Example 5 | 12640 |
As can be seen from Table 1, the viscosities of the epoxidized soybean oil-based acrylate-urethane UV curable resins prepared in examples 1 to 5 were 8288 to 12640 mPa.s, indicating that the epoxidized soybean oil-based acrylate-urethane UV curable resins of the present invention have lower viscosities.
(2) The pencil hardness test results of the epoxidized soybean oil-based acrylate-urethane UV photo-curing resins prepared in examples 1 to 5 are shown in table 2.
TABLE 2 Pencil hardness test results
| Resin composition | Example 1 | Example 2 | Example 3 | Example 4 | Example 5 |
| Hardness of pencil | 4H | 2H | H | 2H | B |
As can be seen from Table 2, the pencil hardness of the photo-cured films prepared from the epoxidized soybean oil-based acrylate-polyurethane UV photo-cured resins of examples 1 to 5 was in the range of B to 4H, which indicates that the photo-cured films prepared from the epoxidized soybean oil-based acrylate-polyurethane UV photo-cured resins of the present invention had a good hardness.
(3) The tensile strength test results of the epoxidized soybean oil based acrylate-urethane UV light-cured resins prepared in examples 1 to 3 are shown in fig. 3, in which 1IPAE-2M, 2IPAE-2M, 3IPAE-2M refer to the light-cured films prepared from the epoxidized soybean oil based acrylate-urethane UV light-cured resins of examples 1, 2, and 3, respectively.
As can be seen from fig. 3, the toughness of the photo-cured films prepared from the epoxidized soybean oil-based acrylate-urethane UV photo-cured resins of examples 1 to 3 was 200% or more, wherein the toughness of the photo-cured film prepared from the epoxidized soybean oil-based acrylate-urethane UV photo-cured resin of example 1 was 324%. The photo-curing film prepared from the epoxidized soybean oil-based acrylic ester-polyurethane UV photo-curing resin has good toughness.
The epoxidized soybean oil-based acrylate-urethane UV photo-curing resins prepared in examples 1 to 5 were then used to prepare nail polish gel, respectively.
In the following examples, the amine-modified resin used was an amine-modified polyether acrylate (CAS: 188012-57-9), and the manufacturing company was Kaiping color chemical Co., ltd.
The castor oil resin is castor oil-based polyurethane acrylic resin, and the preparation method can be referred to Chinese patent application 202010850894.9.
The TMO photoinitiator was 2,4, 6-trimethylbenzoyl-di (p-tolyl) phosphine oxide, available from the company of biend chemical industry, inc.
Example 6
The vegetable oil-based nail polish gel without TPO photoinitiator comprises 35.47g of epoxy soybean oil-based acrylate-polyurethane UV light curing resin prepared in example 1, 8.42g of amine modified resin, 10.22g of castor oil resin, 5g of TMO photoinitiator, 31.69g of 1, 6-hexanediol diacrylate (HDDA) active monomer, 5.5g of auxiliary agent and 3.7g of black paste; wherein, the auxiliary agent is composed of polymerization inhibitor, defoamer, anti-settling agent and leveling agent according to the mass ratio of 0.2:0.5:3.5:1.3, wherein the polymerization inhibitor is basf 1010, the defoamer is digao 910, the anti-settling agent is basf EFKA RM 1463, and the flatting agent is digao 270.
When the nail polish gel is prepared, the components are uniformly mixed according to the proportion, then heated to 60 ℃, stirred for 30min at the rotating speed of about 350r/min, and then filtered to obtain the finished product.
Example 7
The vegetable oil-based nail polish gel without TPO photoinitiator comprises 38.66g of the epoxy soybean oil-based acrylate-polyurethane UV light curing resin prepared in the embodiment 2, 6.4g of amine modified resin, 12.8g of castor oil resin, 6g of TMO photoinitiator, 26.79g of isobornyl acrylate (IBOA) active monomer, 4.75g of auxiliary agent and 4.6g of white paste; wherein, the auxiliary agent is composed of polymerization inhibitor, defoamer, anti-settling agent and leveling agent according to the mass ratio of 0.01:0.05:3.19:1.5, wherein the polymerization inhibitor is basf 264, the defoamer is digao 910, the anti-settling agent is fumed silica, and the flatting agent is digao 440.
The preparation is similar to that of example 6.
Example 8
The vegetable oil-based nail polish gel without TPO photoinitiator comprises 37.21g of epoxy soybean oil-based acrylate-polyurethane UV light curing resin prepared in example 3, 12.78g of amine modified resin, 9.76g of castor oil resin, 7.5g of TMO photoinitiator, 23.82g of tripropylene glycol diacrylate (TPGDA) active monomer, 6.5g of auxiliary agent and 2.43g of yellow slurry, wherein the auxiliary agent comprises polymerization inhibitor, defoamer, anti-settling agent and leveling agent according to the mass ratio of 0.5:0.5:4:1.5, wherein the polymerization inhibitor is polymerization inhibitor 510, the defoamer is digao 825, the anti-settling agent is RHEYBYK-410, and the flatting agent is digao 450.
The preparation is similar to that of example 6.
Example 9
The vegetable oil-based nail polish gel without TPO photoinitiator comprises 36.75g of epoxy soybean oil-based acrylate-polyurethane UV light curing resin prepared in example 4, 6.55g of amine modified resin, 11.69g of castor oil resin, 7.25g of TMO photoinitiator, 28.66g of hydroxyethyl acrylate (HEA) active monomer, 5.32g of auxiliary agent and 3.78g of blue paste, wherein the auxiliary agent comprises polymerization inhibitor, defoamer, anti-settling agent and leveling agent according to the mass ratio of 0.02:0.12:3.98:1.2, wherein the polymerization inhibitor is basf 168, the defoamer is digao 963, the anti-settling agent is BYK RHEOBYK-405, and the flatting agent is digao 270.
The preparation is similar to that of example 6.
Example 10
The vegetable oil-based nail polish gel without TPO photoinitiator comprises 27.4g of epoxy soybean oil-based acrylate-polyurethane UV light curing resin prepared in example 5, 7.58g of amine modified resin, 10.02g of castor oil resin, 8.25g of TMO photoinitiator, 35.8g of 4-Acryloylmorpholine (ACMO) active monomer, 5.75g of auxiliary agent and 5.2g of green paste, wherein the auxiliary agent comprises polymerization inhibitor, defoamer, anti-settling agent and leveling agent according to the mass ratio of 0.13:0.25:3.51:1.86, wherein the polymerization inhibitor is basf 1076, the defoamer is digao 920, the anti-settling agent is fumed silica, and the flatting agent is digao 440.
The preparation is similar to that of example 6.
To verify the performance of the vegetable oil-based nail polish gel of the present invention without TPO photoinitiator, the nail polish gels prepared in examples 6-10 were subjected to comprehensive tests of curing, odor, hardness, adhesion, storage stability, viscosity, etc., and the test methods and test results are shown in Table 3.
TABLE 3 results of Performance test of nail polish
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As can be seen from table 3, the curing conditions of the nail polish prepared in all examples meet the requirements; the smell is 1 grade, and the smell is smaller; the hardness is H-3H, and the hardness is higher; the adhesive has no falling off phenomenon, and has better adhesive force; the storage stability is excellent; the viscosity is low, and the water can flow; standing in dark for 90 days without layering; the wear resistance is good; the flexibility is good.
What has been described above is merely some embodiments of the present invention. It will be apparent to those skilled in the art that various modifications and improvements can be made without departing from the spirit of the invention.
Claims (10)
1. The preparation method of the epoxidized soybean oil-based acrylic ester-polyurethane UV light-cured resin is characterized by comprising the following steps of:
taking a first catalyst, a first polymerization inhibitor, epoxidized soybean oil and acrylic ester to react at 100-130 ℃, cooling to 50-80 ℃ after the acid value is unchanged, adding diisocyanate to continue to react until the NCO infrared peak disappears or the NCO value is lower than 0.2%, and obtaining a prepolymer;
taking a second catalyst, a second polymerization inhibitor, hydroxyl acrylate and two anhydride curing agents, and respectively carrying out esterification reaction on the two anhydride curing agents and the hydroxyl acrylate at the reaction temperature of 100-120 ℃ until the reaction temperature reaches 1777cm -1 -1850cm -1 Stopping the reaction when the infrared peak of the anhydride at the position disappears, and respectively naming reaction products obtained by esterification reaction of the two anhydride curing agents as a mixture 1 and a mixture 2;
adding the mixture 1 and the mixture 2 into the prepolymer, and performing crosslinking reaction for 20-60min at 20-40 ℃ to obtain the polyurethane foam.
2. The method for preparing the epoxidized soybean oil-based acrylate-polyurethane UV light-cured resin according to claim 1, wherein the amount of epoxidized soybean oil is 20-70 parts by mass, the amount of acrylate is 10-30 parts by mass, and the amount of diisocyanate is 1-10 parts by mass; the dosage of the first catalyst is 1-5wt% of the total reaction mass, and the dosage of the first polymerization inhibitor is 0.1-1.5wt% of the total reaction mass;
when the mixture 1 or the mixture 2 is prepared, the dosage of the hydroxyl acrylate is 10-40 parts by mass, the dosage of the anhydride curing agent is 10-60 parts by mass, the dosage of the second catalyst is 1-3wt% of the total reaction mass, and the dosage of the second polymerization inhibitor is 0.05-1wt% of the total reaction mass;
the mass ratio of the mixture 1 to the mixture 2 is 1-5:1.
3. The method for preparing the epoxidized soybean oil-based acrylate-polyurethane UV photo-curing resin according to claim 1 or 2, wherein the acrylate is at least one selected from the group consisting of methyl acrylate, butyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate and acrylic acid;
the first catalyst is at least one selected from triethylamine, tetrabutylammonium chloride, benzyl triethylammonium chloride and triphenylphosphine;
the first polymerization inhibitor is at least one selected from 2, 6-di-tert-butyl p-cresol, p-hydroxyanisole, hydroquinone, 2-tert-butyl hydroquinone and basf 1076;
the diisocyanate is at least one selected from cyclohexane dimethylene diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate and p-phenylene diisocyanate;
the second catalyst is at least one selected from triethylamine, tetrabutylammonium chloride, benzyl triethylammonium chloride and triphenylphosphine;
the second polymerization inhibitor is at least one selected from 2, 6-di-tert-butyl p-cresol, p-hydroxyanisole, hydroquinone and 2-tert-butyl hydroquinone;
the anhydride curing agent is at least one selected from phthalic anhydride, cyclopentanedioic anhydride, tetrachlorophthalic anhydride, methyltetrahydrophthalic anhydride and maleic anhydride;
the hydroxyl acrylate is at least one selected from hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate and hydroxyethyl acrylate.
4. An epoxidized soybean oil-based acrylate-urethane UV photocurable resin produced by the production process of any one of claims 1 to 3.
5. The use of the epoxidized soybean oil based acrylate-polyurethane UV photo-curing resin of claim 4 in the preparation of nail polish.
6. The vegetable oil-based nail polish gel without the TPO photoinitiator is characterized by comprising the following raw materials in parts by weight: the epoxy soybean oil-based acrylate-polyurethane UV light curing resin according to claim 4, wherein the epoxy soybean oil-based acrylate-polyurethane UV light curing resin comprises, by weight, 20-70 parts of an TMO light initiator, 5-12 parts of an amine modified resin, 5-15 parts of a castor oil resin, 5-20 parts of an active monomer, 20-45 parts of an auxiliary agent, 2-10 parts of an auxiliary agent and 2-10 parts of color paste.
7. The TPO photoinitiator-free vegetable oil-based nail polish gum of claim 6, wherein the TMO photoinitiator is 2,4, 6-trimethylbenzoyl-di (p-tolyl) phosphine oxide.
8. The TPO photoinitiator-free vegetable oil-based nail polish gum of claim 6 or 7, wherein the reactive monomer is selected from at least one of hydroxyethyl methacrylate, 1, 6-hexanediol diacrylate, hydroxyethyl acrylate, 4-acryloylmorpholine, isobornyl acrylate, tripropylene glycol diacrylate, trimethylolpropane triacrylate, dipropylene glycol diacrylate.
9. The plant oil-based nail polish free of TPO photoinitiator according to claim 8, wherein the auxiliary agent comprises polymerization inhibitor, defoamer, anti-settling agent and leveling agent, and the mass ratio of the polymerization inhibitor, the defoamer, the anti-settling agent and the leveling agent is 0.01-0.5:0.05-0.5:1-5:0.1-2.5;
the polymerization inhibitor is at least one of polymerization inhibitor 510, pasteur 264, pasteur 1010, pasteur 168 and Pasteur 1076;
the defoamer is at least one of digao 910, digao 920, digao 825 and digao 963;
the anti-settling agent is at least one of fumed silica, BYK RHEYBYK-405, RHEYBYK-410, BYK RHEYBYK-420, basoff EFKA RM 1463 and Basoff EFKA FA 4600;
the leveling agent is at least one of digao 270, digao 450 and digao 440.
10. A process for preparing a TPO photoinitiator-free vegetable oil-based nail polish according to any one of claims 6 to 9, comprising the steps of: uniformly mixing the components according to the proportion, heating to 45-75 ℃, stirring for 30-60min at the rotating speed of 300-400r/min, and then filtering to obtain the finished product.
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| CN202310988953.2A CN117003989B (en) | 2023-08-07 | 2023-08-07 | Epoxy soybean oil-based acrylic ester polyurethane UV light-cured resin and prepared vegetable oil-based nail polish gel without TPO light initiator |
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| CN102660387A (en) * | 2012-04-12 | 2012-09-12 | 广州市博兴化工科技有限公司 | Acrylic acid ester modified epoxy soybean oil, its preparation method and application thereof |
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| US20220395449A1 (en) * | 2021-06-04 | 2022-12-15 | Lilaque, Inc. | Bio-gel composition and nail care system |
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| CN102660387A (en) * | 2012-04-12 | 2012-09-12 | 广州市博兴化工科技有限公司 | Acrylic acid ester modified epoxy soybean oil, its preparation method and application thereof |
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| US20220395449A1 (en) * | 2021-06-04 | 2022-12-15 | Lilaque, Inc. | Bio-gel composition and nail care system |
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