CN113583165B - Bio-based 3D printing resin and preparation method thereof - Google Patents
Bio-based 3D printing resin and preparation method thereof Download PDFInfo
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- CN113583165B CN113583165B CN202010367652.4A CN202010367652A CN113583165B CN 113583165 B CN113583165 B CN 113583165B CN 202010367652 A CN202010367652 A CN 202010367652A CN 113583165 B CN113583165 B CN 113583165B
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- 238000010146 3D printing Methods 0.000 title claims abstract description 78
- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- 239000011347 resin Substances 0.000 title abstract description 52
- 229920005989 resin Polymers 0.000 title abstract description 52
- 239000000178 monomer Substances 0.000 claims abstract description 27
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims abstract description 24
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 21
- 239000002028 Biomass Substances 0.000 claims abstract description 20
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 3
- PIPAGMGAJNEGEM-UHFFFAOYSA-N bis[2-hydroxy-3-(2-methylprop-2-enoyloxy)propyl] 2-methylidenebutanedioate Chemical compound C(C(=C)CC(=O)OCC(COC(C(=C)C)=O)O)(=O)OCC(COC(C(=C)C)=O)O PIPAGMGAJNEGEM-UHFFFAOYSA-N 0.000 claims description 31
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical group COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 30
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical group C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 30
- IVDFXGRFYDADBY-UHFFFAOYSA-N bis[2-hydroxy-3-(2-methylprop-2-enoyloxy)propyl] butanedioate Chemical group CC(=C)C(=O)OCC(O)COC(=O)CCC(=O)OCC(O)COC(=O)C(C)=C IVDFXGRFYDADBY-UHFFFAOYSA-N 0.000 claims description 28
- KDYFGRWQOYBRFD-UHFFFAOYSA-N succinic acid Chemical compound OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 17
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 claims description 15
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims description 13
- 239000011342 resin composition Substances 0.000 claims description 10
- 239000003054 catalyst Substances 0.000 claims description 6
- 239000003112 inhibitor Substances 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- 239000001384 succinic acid Substances 0.000 claims description 5
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 3
- -1 4-methylthiophenyl Chemical group 0.000 claims description 3
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 claims description 3
- ZMDDERVSCYEKPQ-UHFFFAOYSA-N Ethyl (mesitylcarbonyl)phenylphosphinate Chemical compound C=1C=CC=CC=1P(=O)(OCC)C(=O)C1=C(C)C=C(C)C=C1C ZMDDERVSCYEKPQ-UHFFFAOYSA-N 0.000 claims description 2
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 claims description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 9
- 125000001931 aliphatic group Chemical group 0.000 abstract description 7
- 238000000016 photochemical curing Methods 0.000 abstract description 6
- 238000009776 industrial production Methods 0.000 abstract description 2
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- 238000001723 curing Methods 0.000 description 23
- 239000011541 reaction mixture Substances 0.000 description 13
- 238000003756 stirring Methods 0.000 description 11
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
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- 238000003786 synthesis reaction Methods 0.000 description 6
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000011417 postcuring Methods 0.000 description 4
- 239000004925 Acrylic resin Substances 0.000 description 3
- 229920000178 Acrylic resin Polymers 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 125000001570 methylene group Chemical group [H]C([H])([*:1])[*:2] 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- JJLDVMLIPANDEW-UHFFFAOYSA-N 2-ethyloctyl 4-(dimethylamino)benzoate Chemical compound CCCCCCC(CC)COC(=O)C1=CC=C(N(C)C)C=C1 JJLDVMLIPANDEW-UHFFFAOYSA-N 0.000 description 2
- NNAHKQUHXJHBIV-UHFFFAOYSA-N 2-methyl-1-(4-methylthiophen-2-yl)-2-morpholin-4-ylpropan-1-one Chemical compound CC1=CSC(C(=O)C(C)(C)N2CCOCC2)=C1 NNAHKQUHXJHBIV-UHFFFAOYSA-N 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- RRAFCDWBNXTKKO-UHFFFAOYSA-N eugenol Chemical class COC1=CC(CC=C)=CC=C1O RRAFCDWBNXTKKO-UHFFFAOYSA-N 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 2
- 229920005610 lignin Polymers 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000007142 ring opening reaction Methods 0.000 description 2
- XVZXOLOFWKSDSR-UHFFFAOYSA-N Cc1cc(C)c([C]=O)c(C)c1 Chemical group Cc1cc(C)c([C]=O)c(C)c1 XVZXOLOFWKSDSR-UHFFFAOYSA-N 0.000 description 1
- NPBVQXIMTZKSBA-UHFFFAOYSA-N Chavibetol Natural products COC1=CC=C(CC=C)C=C1O NPBVQXIMTZKSBA-UHFFFAOYSA-N 0.000 description 1
- 239000005770 Eugenol Substances 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- UVMRYBDEERADNV-UHFFFAOYSA-N Pseudoeugenol Natural products COC1=CC(C(C)=C)=CC=C1O UVMRYBDEERADNV-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000002723 alicyclic group Chemical group 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 150000005130 benzoxazines Chemical class 0.000 description 1
- 239000011173 biocomposite Substances 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229960002217 eugenol Drugs 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
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Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Epoxy Resins (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to a bio-based 3D printing resin and a preparation method thereof. The preparation method of the bio-based 3D printing resin comprises the following steps: (1) Synthesizing a bio-based acrylate monomer from biomass and a bio-based glycidyl methacrylate raw material; (2) And mixing the bio-based acrylate monomer and the photoinitiator, and carrying out photocuring 3D printing to obtain the bio-based 3D printing resin. The bio-based 3D printing resin prepared by the invention is green in preparation method, simple in preparation process and easy for industrial production, the obtained resin has excellent comprehensive performance, can be directly applied to 3D printing, and the method for preparing the high-performance 3D printing resin by using the aliphatic biomass is initiated.
Description
Technical Field
The invention relates to a bio-based 3D printing resin and a preparation method thereof, belonging to the technical field of chemical industry and high polymer materials.
Background
The biomass has the characteristics of being renewable, environment-friendly, rich in resources, wide in distribution and the like, and is a sustainable and renewable macromolecule preparation raw material. Different biomasses have a variety of different reactive groups and chemical structures, and therefore they have the potential to produce polymers of different properties and uses. With the development of biorefinery technology, more and more high-quality, low-cost biomasses have been widely used in the preparation of polymers, such as biocomposites, epoxy resins, benzoxazines, polyimines, and the like. In order to utilize biomass in a more sustainable manner, new processing methods need to be introduced.
3D printing, also known as additive manufacturing, is a rapid prototyping technique. It constructs a 3D structure by printing a digital model file layer by layer. Compared with the traditional material reduction manufacturing technology, the 3D printing can reduce the waste of raw materials in the production process, so that the technology is more energy-saving and environment-friendly. Furthermore, 3D printing shows advantages in handling personalized custom structures and complex assemblies. In recent years, 3D printing has been applied to flexible printingThe fields of linear robots, energy storage equipment, nano devices, optical engineering and biological materials. Common 3D printing techniques include fused deposition modeling, laser sintering, and photopolymerization (including Stereolithography (SLA) and Digital Light Processing (DLP)). Each 3D printing technology has own characteristics and can meet different printing requirements. DLP obtains an image using ultraviolet rays, and then cures a resin thin layer of a certain thickness and shape each time. Therefore, the DLP can rapidly print a high-precision 3D structure. The resins used for photocuring 3D printing are mostly photosensitive acrylates, which have excellent thermo-mechanical properties, chemical resistance and good compatibility with high resolution 3D printing technologies, occupying more than half of the entire 3D printed polymer material market. Conventional photosensitive acrylates are generally derived from non-renewable petrochemical feedstocks, which are not sustainable. In recent years, some biobased acrylates for photocuring 3D printing have been reported. Chmely et al reported lignin-modified commercial stereolithography resins that, when 15wt% of modified lignin was added, the ductility of the resin was increased by 4-fold but the Young's modulus decreased by 43% and the initial thermal decomposition temperature (T) of the cured resin, as compared to commercial stereolithography resins di ) Reduction (see literature: sutton, j.t.; rajan, k.; harper, d.p.; chmely, S.C.ACS appl.Mater.Interfaces 2018,10 (42), 36456-36463). Reineke et al reported three acrylate monomers consisting of bio-based eugenol and lignin derivatives for SLA 3D printing and adjusted the resin properties by varying the ratio of these monomers (see literature: ding, r.; du, y.; goncalves, r.b.; francis, l.f.; reineke, t.m. ym.2019, 10 (9), 1067-1077.). However, this technology inevitably uses toxic dichloromethane as a solvent in the synthetic route on the one hand, which increases energy consumption and threatens human health; on the other hand, biomass having an aromatic or alicyclic structure is generally selected as a raw material to obtain a high-performance resin. In fact, aliphatic biomass has the advantages of wide sources and low cost, and therefore, the preparation of acrylic esters with excellent performance from aliphatic biomass by designing the molecular structure is an interesting challenge.
Succinic acid and itaconic acid are two important aliphatic bio-based raw materials, and the succinic acid and itaconic acid produced by glucose fermentation are listed as the 'first 12' most promising biomass materials by the U.S. department of energy. They have been used to prepare bio-based elastomers, polyesters, unsaturated polyesters, epoxy resins, and the like. Glycidyl Methacrylate (GMA) can provide both epoxy groups and acrylic double bonds, which are functional in the acrylic monomer synthesis and resin curing processes, respectively. The synthesis of GMA is generally based on methacrylic acid and epichlorohydrin. Methacrylic acid can be prepared from bio-based citric acid or itaconic acid, epichlorohydrin can be prepared from bio-based glycerol, and annual yield can reach 100kt. GMA can therefore also be considered a biobased material.
Starting from aliphatic biomass, the full-bio-based acrylate monomer is prepared by a green synthesis method and used for 3D printing, so that the acrylic resin with excellent comprehensive performance is obtained, and the acrylic resin has profound significance on the sustainable development of the photocuring acrylic resin.
Disclosure of Invention
In order to improve the technical problem, the invention provides a bio-based 3D printing resin composition, which comprises the following components in parts by mass:
100 parts of bio-based acrylate monomer and 0.1-10 parts of photoinitiator;
according to an embodiment of the present invention, the bio-based acrylate monomer may be bis (2-hydroxy-3- (methacryloyloxy) propyl) succinate or bis (2-hydroxy-3- (methacryloyloxy) propyl) 2-methylenesuccinate;
according to an embodiment of the present invention, the photoinitiator is selected from at least one of 1-hydroxycyclohexyl phenyl ketone, 2,4, 6-trimethylbenzoyl-diphenylphosphorous oxide, 2,4, 6-trimethylbenzoyl-ethoxy-phenylphosphorous oxide, bis (2, 4, 6-trimethylbenzoyl) -phenylphosphorous oxide, 2-dimethoxy-1, 2-diphenylethanone, 2-ethyloctyl-4-dimethylaminobenzoate, 4-p-toluene 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-propanone.
According to an embodiment of the invention, the composition comprises the following components in parts by mass: 100 parts of bio-based acrylate monomer and 0.5-5 parts of photoinitiator.
The invention also provides a preparation method of the bio-based 3D printing resin composition, which comprises the following steps:
(1) Biomass and bio-based Glycidyl Methacrylate (GMA) are taken as raw materials, and a catalyst and a polymerization inhibitor are added to synthesize a bio-based acrylate monomer;
(2) And mixing the bio-based acrylate monomer and the photoinitiator to obtain the bio-based 3D printing resin composition.
According to embodiments of the invention, the biomass may be succinic acid or itaconic acid;
according to an embodiment of the present invention, the catalyst is selected from at least one of triphenylphosphine, N-dimethylbenzylamine, and tetraethylammonium bromide;
according to the embodiment of the invention, the polymerization inhibitor is at least one selected from 4-methoxyphenol and hydroquinone;
according to an embodiment of the invention, the bio-based acrylate monomer has a viscosity of less than 1.3Pa · s, such as from 0.2 to 1.0Pa · s, further such as from 0.35 to 0.45Pa · s, from 0.65 to 0.75Pa · s;
according to an embodiment of the invention, the photoinitiator is selected from at least one of 1-hydroxycyclohexyl phenyl ketone, 2,4, 6-trimethylbenzoyl-diphenylphosphorus oxide, 2,4, 6-trimethylbenzoyl-ethoxy-phenylphosphorus oxide, bis (2, 4, 6-trimethylbenzoyl) -phenylphosphorus oxide, 2-dimethoxy-1, 2-diphenylethanone, 2-ethyloctyl-4-dimethylaminobenzoate, 4-p-toluene 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-propanone.
According to an embodiment of the invention, the molar ratio of biomass to glycidyl methacrylate in step (1) is from 0.5 to 1.5, such as from 0.8 to 1.2, further such as from 1 to 1.05;
according to an embodiment of the invention, the temperature of the reaction of step (1) is 60 to 150 ℃, e.g. 90 to 120 ℃, exemplary 90 ℃, 100 ℃, 120 ℃;
according to an embodiment of the invention, the reaction of step (1) is carried out for a period of time ranging from 1 to 8 hours, for example from 3 to 6 hours, exemplary 3 hours, 4 hours, 5 hours, 6 hours;
according to an embodiment of the present invention, the mass ratio of the catalyst, the polymerization inhibitor and the total amount of the biomass and the glycidyl methacrylate in step (1) is 0.1 to 5;
according to an embodiment of the present invention, the mass ratio of the bio-based acrylate monomer and the photoinitiator in step (2) is from 100 to 0.1, for example from 100 to 0.5, exemplary from 100 to 0.5, 100, 1, 100.
The invention also provides the resin obtained by the preparation method. The resin is bio-based 3D printing resin.
The invention further provides an application of the bio-based acrylate monomer in a 3D printing resin material.
The invention further provides the resin composition and application of the resin obtained by the preparation method in 3D printing.
Advantageous effects
The beneficial effects obtained by the invention are as follows:
1. the raw materials used in the invention, namely itaconic acid, succinic acid and glycidyl methacrylate, are all derived from biomass, so that the provided bio-based 3D printing resin monomer is a full bio-based monomer (the bio-based content of the monomer is 100%), and the use of petrochemical resources can be avoided, thereby being more beneficial to the sustainable development of high polymer materials.
2. The resin applied to 3D printing needs to meet a certain viscosity range, so that the resin suitable for 3D printing is obtained by adding a diluent into the 3D printing resin (the viscosity is less than 1.3Pa · s), but the addition of the diluent can reduce the crosslinking density of the resin and deteriorate the comprehensive performance of the material.
3. The bio-based acrylate provided by the invention is directly used as an excellent 3D printing resin material, is applied to a 3D printing process, and is beneficial to overcoming the defect that the traditional photocuring reaction material (especially a system needing a filler) cannot be suitable for large-piece molding due to low curing depth, and the like.
4. The bio-based 3D printing resin monomer provided by the invention is a full aliphatic biomass monomer, but still has excellent thermal and mechanical properties, and a method for preparing high-performance 3D printing resin from aliphatic biomass raw materials is initiated.
5. The preparation method of the bio-based 3D printing resin provided by the invention has the characteristics of environmental protection, green color, simple preparation process, good process controllability and easiness in industrial production.
Drawings
FIG. 1 is a schematic diagram (reaction scheme) of the synthesis scheme of bis (2-hydroxy-3- (methacryloyloxy) propyl) succinate provided in example 1 of the present invention and bis (2-hydroxy-3- (methacryloyloxy) propyl) 2-methylenesuccinate provided in example 2 of the present invention;
FIG. 2 is a NMR spectrum of bis (2-hydroxy-3- (methacryloyloxy) propyl) succinate provided in example 1 of the present invention;
FIG. 3 is a NMR spectrum of bis (2-hydroxy-3- (methacryloyloxy) propyl) 2-methylenesuccinate provided in example 2 of the present invention;
FIG. 4 is a high resolution mass spectrum of bis (2-hydroxy-3- (methacryloyloxy) propyl) succinate provided in example 1 of the present invention;
FIG. 5 is a high resolution mass spectrum of bis (2-hydroxy-3- (methacryloyloxy) propyl) 2-methylenesuccinate provided in example 1 of the present invention;
FIG. 6 is a 3D complex structure provided in embodiment 1 of the present invention;
fig. 7 is a 3D complex structure provided in embodiment 2 of the present invention;
fig. 8 shows the heat resistance of the 3D complex structure provided in example 2 of the present invention at high temperature.
FIG. 9 is a sample provided in comparative example 1 of the present invention.
Detailed Description
The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the techniques realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise specified, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
Example 1
1) Preparation of bis (2-hydroxy-3- (methacryloyloxy) propyl) succinate
47.2g of succinic acid, 113.7g of glycidyl methacrylate, 1.6g of triphenylphosphine and 0.32g of 4-methoxyphenol were added to the flask, and the reaction mixture was slowly heated and stirred at 100 ℃ for reaction for 5 hours. Finally, a pale yellow liquid was obtained, i.e., bis (2-hydroxy-3- (methacryloyloxy) propyl) succinate. The viscosity at 50 ℃ was 0.42 pas.
2) Preparation of 3D printing resin
Bis (2-hydroxy-3- (methacryloyloxy) propyl) succinate (100 g), phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide (1 g) and stirring at 70 ℃ for 20min are uniformly mixed to obtain clear liquid, and the obtained liquid is put into a 405nm Digital Light Processing (DLP) 3D printer for 3D printing and forming. And (4) placing the printed 3D printing structure into an ultraviolet curing box for curing for 5min.
In this example, the synthesis reaction formula, NMR spectrum and high resolution mass spectrum of bis (2-hydroxy-3- (methacryloyloxy) propyl) succinate are shown in FIGS. 1,2 and 4, respectively.
Referring to the attached FIG. 1, it is a schematic diagram (reaction formula) of the synthetic flow of bis (2-hydroxy-3- (methacryloyloxy) propyl) succinate provided by example 1 of the present invention, and the reaction is a ring-opening reaction of carboxylic acid and epoxy group.
Referring to FIG. 2, which is a NMR spectrum of bis (2-hydroxy-3- (methacryloyloxy) propyl) succinate provided in example 1 of the present invention, it can be seen that about 6.13ppm, 5.62ppm represent H at the C = C double bond, about 2.50ppm, 3.86-3.56ppm and 4.49-4.11ppm represent H at the hydroxy, methyl and methylene groups, respectively, about 2.74-2.62ppm represent H at the methylene group introduced by succinic acid, and about 1.95ppm represents H at the methyl group.
Referring to FIG. 4, which is a high resolution mass spectrum of bis (2-hydroxy-3- (methacryloyloxy) propyl) succinate provided in example 1 of the present invention, [ M + Na ] is shown + ]Has an experimental value of 425.1418, which corresponds to the theoretical value of 425.1418.
Referring to fig. 6, which is a 3D complex structure provided in example 1 of the present invention, it is shown that bis (2-hydroxy-3- (methacryloyloxy) propyl) succinate can be used for high precision 3D printing.
Referring to Table 1, the tensile strength, elongation at break, tensile modulus, glass transition temperature, and heat distortion temperature (0.455 MPa) of the obtained resin were 31.1MPa, 3.42. + -. 0.25%, 1616. + -. 15MPa, 144 ℃ and 115 ℃ respectively.
Example 2
1) Preparation of bis (2-hydroxy-3- (methacryloyloxy) propyl) 2-methylenesuccinate
52.0g of itaconic acid, 113.7g of glycidyl methacrylate, 1.66g of triphenylphosphine and 0.33g of 4-methoxyphenol were added to the flask, and then the reaction mixture was slowly heated and stirred at 100 ℃ for 5 hours. Finally, a pale yellow liquid, i.e. bis (2-hydroxy-3- (methacryloyloxy) propyl) 2-methylenesuccinate, was obtained. The viscosity at 50 ℃ was 0.69 pas.
2) Preparation of 3D printing resin
Bis (2-hydroxy-3- (methacryloyloxy) propyl) 2-methylenesuccinate (100 g), phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide (1 g) and stirring at 70 ℃ for 20min are mixed uniformly to obtain clear liquid, and the obtained liquid is put into a 405nm Digital Light Processing (DLP) 3D printer for 3D printing and forming. And (4) placing the printed 3D printing structure into an ultraviolet curing box and then curing for 5min.
In this example, the synthesis reaction formula, nuclear magnetic resonance hydrogen spectrum and high resolution mass spectrum of bis (2-hydroxy-3- (methacryloyloxy) propyl) 2-methylenesuccinate are shown in FIGS. 1, 3 and 5, respectively.
Referring to the attached FIG. 1, it is a schematic diagram (reaction formula) of the synthesis scheme of bis (2-hydroxy-3- (methacryloyloxy) propyl) 2-methylenesuccinate provided in example 2 of the present invention, and the reaction is a ring-opening reaction of carboxylic acid and epoxy group.
Referring to FIG. 3, which is a NMR spectrum of bis (2-hydroxy-3- (methacryloyloxy) propyl) 2-methylenesuccinate provided in practice 2 of the present invention, it can be seen that about 6.43 to 6.32ppm, 5.76ppm and 3.40ppm represent the C = C double bond on the itaconic acid unit and the H on the methylene, and about 6.13ppm and 5.62ppm represent the H on the C = C double bond at both ends of the compound.
Referring to FIG. 5, which is a high resolution mass spectrum of bis (2-hydroxy-3- (methacryloyloxy) propyl) 2-methylenesuccinate provided in example 2 of the present invention, it can be seen that [ M + Na ] + ]Has an experimental value of 437.1420, which corresponds to the theoretical value 437.1418.
Referring to fig. 7, which is a 3D complex structure provided in example 2 of the present invention, it shows that bis (2-hydroxy-3- (methacryloyloxy) propyl) 2-methylenesuccinate can be used for high precision 3D printing with a precision as high as 200 μm.
Referring to the attached figure 8, the 3D complex structure provided by the embodiment 2 of the invention is completely intact after 1 hour, and the weight is loaded by 100g at 250 ℃; the resin is still intact after 1h under the load of 1000g weight at 180 ℃, which shows that the resin has good heat resistance.
Referring to Table 1, the tensile strength, elongation at break, tensile modulus, glass transition temperature, heat distortion temperature (0.455 MPa) of the resulting resin were 45.2MPa, 0.84%, 4480MPa, 183 ℃ and over 250 ℃, respectively.
TABLE 1
Example 3
1) Preparation of bis (2-hydroxy-3- (methacryloyloxy) propyl) succinate
47.2g succinic acid, 113.7g glycidyl methacrylate, 0.8g triphenylphosphine and 0.16g 4-methoxyphenol were added to the flask, and then the reaction mixture was slowly heated and stirred at 120 ℃ for 6h. Finally, a pale yellow liquid, i.e. bis (2-hydroxy-3- (methacryloyloxy) propyl) succinate, was obtained. The viscosity at 50 ℃ was 0.43 pas.
2) Preparation of 3D printing resin
Bis (2-hydroxy-3- (methacryloyloxy) propyl) succinate (100 g), phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide (5 g) and stirring at 50 ℃ for 20min are uniformly mixed to obtain clear liquid, and the obtained liquid is put into a 405nm Digital Light Processing (DLP) 3D printer for 3D printing and forming. And (4) placing the printed 3D printing structure into an ultraviolet curing box and then curing for 5min.
Example 4
1) Preparation of bis (2-hydroxy-3- (methacryloyloxy) propyl) 2-methylenesuccinate
52.0g of itaconic acid, 113.7g of glycidyl methacrylate, 0.83g of triphenylphosphine and 0.17g of 4-methoxyphenol were added to the flask, and the reaction mixture was slowly heated and stirred at 120 ℃ for 6h. Finally, a pale yellow liquid was obtained, which was bis (2-hydroxy-3- (methacryloyloxy) propyl) 2-methylenesuccinate. The viscosity at 50 ℃ was 0.70 pas.
2) Preparation of 3D printing resin
Bis (2-hydroxy-3- (methacryloyloxy) propyl) 2-methylenesuccinate (100 g), phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide (5 g) and stirring at 50 ℃ for 20min are uniformly mixed to obtain a clear liquid, and the obtained liquid is put into a 405nm Digital Light Processing (DLP) 3D printer for 3D printing and forming. And (5) putting the printed 3D printing structure into an ultraviolet curing box for post curing for 5min.
Example 5
1) Preparation of bis (2-hydroxy-3- (methacryloyloxy) propyl) succinate
47.2g of succinic acid, 113.7g of glycidyl methacrylate, 2.4g of triphenylphosphine and 0.8g of 4-methoxyphenol were charged in the flask, and then the reaction mixture was slowly heated and stirred at 90 ℃ for reaction for 3 hours. Finally, a pale yellow liquid was obtained, i.e., bis (2-hydroxy-3- (methacryloyloxy) propyl) succinate. The viscosity at 50 ℃ was 0.41 pas.
2) Preparation of 3D printing resin
Bis (2-hydroxy-3- (methacryloyloxy) propyl) succinate (100 g), phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide (0.5 g) and stirring at 90 ℃ for 20min were uniformly mixed to obtain a clear liquid, and the obtained liquid was put into a 405nm Digital Light Processing (DLP) 3D printer for 3D printing and molding. And (4) placing the printed 3D printing structure into an ultraviolet curing box and then curing for 5min.
Example 6
1) Preparation of bis (2-hydroxy-3- (methacryloyloxy) propyl) 2-methylenesuccinate
52.0g of itaconic acid, 113.7g of glycidyl methacrylate, 2.49g of triphenylphosphine and 0.83g of 4-methoxyphenol were added to the flask, and the reaction mixture was slowly heated and stirred at 90 ℃ for 3h. Finally, a pale yellow liquid, i.e. bis (2-hydroxy-3- (methacryloyloxy) propyl) 2-methylenesuccinate, was obtained. The viscosity at 50 ℃ was 0.68 pas.
2) Preparation of 3D printing resin
Bis (2-hydroxy-3- (methacryloyloxy) propyl) 2-methylenesuccinate (100 g), phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide (0.5 g) and stirring at 90 ℃ for 20min were mixed uniformly to obtain a clear liquid, and the obtained liquid was put into a 405nm Digital Light Processing (DLP) 3D printer for 3D printing and molding. And (4) placing the printed 3D printing structure into an ultraviolet curing box and then curing for 5min.
Example 7
1) Preparation of bis (2-hydroxy-3- (methacryloyloxy) propyl) succinate
49.56g of succinic acid, 113.7g of glycidyl methacrylate, 1.64g of triphenylphosphine and 0.33g of 4-methoxyphenol were added to the flask, and then the reaction mixture was slowly heated and stirred at 100 ℃ for 5 hours. Finally, a pale yellow liquid was obtained, i.e., bis (2-hydroxy-3- (methacryloyloxy) propyl) succinate. The viscosity at 50 ℃ was 0.42 pas.
2) Preparation of 3D printing resin
Bis (2-hydroxy-3- (methacryloyloxy) propyl) succinate (100 g), phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide (1 g) were stirred at 70 ℃ for 20min and mixed uniformly to obtain a clear liquid, and the obtained liquid was put into a 405nm Digital Light Processing (DLP) 3D printer for 3D printing and molding. And (5) putting the printed 3D printing structure into an ultraviolet curing box for post curing for 5min.
Example 8
1) Preparation of bis (2-hydroxy-3- (methacryloyloxy) propyl) 2-methylenesuccinate
54.6g of itaconic acid, 113.7g of glycidyl methacrylate, 1.68g of triphenylphosphine and 0.34g of 4-methoxyphenol were added to the flask, and then the reaction mixture was slowly heated and stirred at 100 ℃ for reaction for 5 hours. Finally, a pale yellow liquid was obtained, which was bis (2-hydroxy-3- (methacryloyloxy) propyl) 2-methylenesuccinate. The viscosity at 50 ℃ was 0.69 pas.
2) Preparation of 3D printing resin
Bis (2-hydroxy-3- (methacryloyloxy) propyl) 2-methylenesuccinate (100 g), phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide (1 g) and stirring at 70 ℃ for 20min are uniformly mixed to obtain a clear liquid, and the obtained liquid is put into a 405nm Digital Light Processing (DLP) 3D printer for 3D printing and forming. And (5) putting the printed 3D printing structure into an ultraviolet curing box for post curing for 5min.
Example 9
1) Preparation of bis (2-hydroxy-3- (methacryloyloxy) propyl) succinate
49.56g of succinic acid, 113.7g of glycidyl methacrylate, 0.82g of triphenylphosphine and 0.16g of 4-methoxyphenol were added to the flask, and then the reaction mixture was slowly heated and stirred at 120 ℃ for reaction for 6 hours. Finally, a pale yellow liquid, i.e. bis (2-hydroxy-3- (methacryloyloxy) propyl) succinate, was obtained. The viscosity at 50 ℃ was 0.40 pas.
2) Preparation of 3D printing resin
Bis (2-hydroxy-3- (methacryloyloxy) propyl) succinate (100 g), phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide (5 g) and stirring at 50 ℃ for 20min are uniformly mixed to obtain clear liquid, and the obtained liquid is put into a 405nm Digital Light Processing (DLP) 3D printer for 3D printing and forming. And (4) placing the printed 3D printing structure into an ultraviolet curing box and then curing for 5min.
Example 10
1) Preparation of bis (2-hydroxy-3- (methacryloyloxy) propyl) 2-methylenesuccinate
54.6g of itaconic acid, 113.7g of glycidyl methacrylate, 0.84g of triphenylphosphine and 0.17g of 4-methoxyphenol were added to the flask, and the reaction mixture was slowly heated and stirred at 120 ℃ for 6h. Finally, a pale yellow liquid, i.e. bis (2-hydroxy-3- (methacryloyloxy) propyl) 2-methylenesuccinate, was obtained. The viscosity at 50 ℃ was 0.71 pas.
2) Preparation of 3D printing resin
Bis (2-hydroxy-3- (methacryloyloxy) propyl) 2-methylenesuccinate (100 g), phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide (5 g) and stirring at 50 ℃ for 20min are mixed uniformly to obtain clear liquid, and the obtained liquid is put into a 405nm Digital Light Processing (DLP) 3D printer for 3D printing and forming. And (5) putting the printed 3D printing structure into an ultraviolet curing box for post curing for 5min.
Example 11
1) Preparation of bis (2-hydroxy-3- (methacryloyloxy) propyl) succinate
49.56g of succinic acid, 113.7g of glycidyl methacrylate, 2.45g of triphenylphosphine and 0.82g of 4-methoxyphenol were added to the flask, and then the reaction mixture was slowly heated and stirred at 90 ℃ for reaction for 3 hours. Finally, a pale yellow liquid was obtained, i.e., bis (2-hydroxy-3- (methacryloyloxy) propyl) succinate. The viscosity at 50 ℃ was 0.43 pas.
2) Preparation of 3D printing resin
Bis (2-hydroxy-3- (methacryloyloxy) propyl) succinate (100 g), phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide (0.5 g) and stirring at 90 ℃ for 20min were uniformly mixed to obtain a clear liquid, and the obtained liquid was put into a 405nm Digital Light Processing (DLP) 3D printer for 3D printing and molding. And (4) placing the printed 3D printing structure into an ultraviolet curing box and then curing for 5min.
Example 12
1) Preparation of bis (2-hydroxy-3- (methacryloyloxy) propyl) 2-methylenesuccinate
54.6g of itaconic acid, 113.7g of glycidyl methacrylate, 2.52g of triphenylphosphine and 0.84g of 4-methoxyphenol were added to the flask, and the reaction mixture was slowly heated and stirred at 90 ℃ for 3h. Finally, a pale yellow liquid was obtained, which was bis (2-hydroxy-3- (methacryloyloxy) propyl) 2-methylenesuccinate. The viscosity at 50 ℃ was 0.68 pas.
2) Preparation of 3D printing resin
Bis (2-hydroxy-3- (methacryloyloxy) propyl) 2-methylenesuccinate (100 g), phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide (0.5 g) and stirring at 90 ℃ for 20min were mixed uniformly to obtain a clear liquid, and the obtained liquid was put into a 405nm Digital Light Processing (DLP) 3D printer for 3D printing and molding. And (4) placing the printed 3D printing structure into an ultraviolet curing box and then curing for 5min.
Comparative example 1
1) Preparation of bis (2-hydroxy-3- (methacryloyloxy) propyl) 2-methylenesuccinate
52.0g of itaconic acid, 113.7g of glycidyl methacrylate, 1.66g of triphenylphosphine and 0.33g of 4-methoxyphenol were added to the flask, and then the reaction mixture was slowly heated and stirred at 100 ℃ for 5 hours. Finally, a pale yellow liquid, i.e. bis (2-hydroxy-3- (methacryloyloxy) propyl) 2-methylenesuccinate, was obtained. The viscosity at 50 ℃ was 0.69 pas.
2) Preparation of photocurable resin
Bis (2-hydroxy-3- (methacryloyloxy) propyl) 2-methylenesuccinate (100 g), phenylbis (2, 4, 6-trimethylbenzoyl) phosphine oxide (1 g) were stirred at 70 ℃ for 20min and mixed uniformly to obtain a clear liquid, and the obtained liquid was poured into a mold and cured with ultraviolet light for 5min. The solidified product has irregular shape, rough edges and large bubbles (see fig. 9).
By comparing the products of the example, the characteristics (such as the transmission depth of 227 micrometers, the viscosity of less than 1.3 pas and the like) of the bis (2-hydroxy-3- (methacryloyloxy) propyl) 2-methylene succinate resin are further embodied, so that the resin is better matched with the photocuring 3D printing technology, and can be printed and cured layer by layer, so that a large-size defect-free high-precision complex 3D curing structure can be prepared, and the resin has wide application advantages.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made without departing from the spirit and principle of the present invention shall fall within the protection scope of the present invention.
Claims (4)
1. A bio-based 3D printing resin composition comprises the following components in parts by mass:
100 parts of bio-based acrylate monomer and 0.5-5 parts of photoinitiator;
the bio-based acrylate monomer is bis (2-hydroxy-3- (methacryloyloxy) propyl) succinate or bis (2-hydroxy-3- (methacryloyloxy) propyl) 2-methylenesuccinate;
the photoinitiator is selected from at least one of 1-hydroxycyclohexyl phenyl ketone, 2,4, 6-trimethylbenzoyl-diphenyl phosphorus oxide, 2,4, 6-trimethylbenzoyl-ethoxy-phenyl phosphorus oxide, bis (2, 4, 6-trimethylbenzoyl) -phenyl phosphorus oxide, 2-dimethoxy-1, 2-diphenylethanone, 2-ethyloctyl-4-dimethylamino benzoate and 4-p-toluene 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-acetone;
the viscosity of the bio-based acrylate monomer is 0.2-1.0 Pa.s;
the preparation method of the resin composition is characterized by comprising the following steps of:
(1) Taking biomass and bio-based glycidyl methacrylate as raw materials, and adding a catalyst and a polymerization inhibitor to obtain a bio-based acrylate monomer;
(2) Mixing a bio-based acrylate monomer and a photoinitiator to obtain a bio-based 3D printing resin composition;
the molar ratio of the biomass to the glycidyl methacrylate in the step (1) is 1-1.05;
the reaction temperature in the step (1) is 90-120 ℃;
the reaction time of the step (1) is 3-6 h;
the mass ratio of the catalyst and the polymerization inhibitor to the total amount of the biomass and the glycidyl methacrylate in the step (1) is 0.5-1.5;
the mass ratio of the bio-based acrylate monomer and the photoinitiator in the step (2) is (100);
the biomass is succinic acid or itaconic acid; the catalyst is triphenylphosphine; the polymerization inhibitor is 4-methoxyphenol.
2. The resin composition of claim 1, wherein the bio-based acrylate monomer has a viscosity of 0.35 to 0.45 Pa-s or 0.65 to 0.75 Pa-s.
3. The resin composition according to claim 1, wherein the mass ratio of the bio-based acrylate monomer and the photoinitiator in the step (2) is 100.
4. Use of the resin composition according to any one of claims 1 to 3 for 3D printing.
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