CN112794943B - Ultraviolet-heat curing composition for 3D printing and application thereof - Google Patents
Ultraviolet-heat curing composition for 3D printing and application thereof Download PDFInfo
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- 239000000203 mixture Substances 0.000 title claims abstract description 40
- 238000010146 3D printing Methods 0.000 title claims abstract description 26
- 238000013007 heat curing Methods 0.000 title claims abstract description 16
- RRAFCDWBNXTKKO-UHFFFAOYSA-N eugenol Chemical compound COC1=CC(CC=C)=CC=C1O RRAFCDWBNXTKKO-UHFFFAOYSA-N 0.000 claims abstract description 198
- 239000005770 Eugenol Substances 0.000 claims abstract description 100
- 229960002217 eugenol Drugs 0.000 claims abstract description 100
- NPBVQXIMTZKSBA-UHFFFAOYSA-N Chavibetol Natural products COC1=CC=C(CC=C)C=C1O NPBVQXIMTZKSBA-UHFFFAOYSA-N 0.000 claims abstract description 99
- UVMRYBDEERADNV-UHFFFAOYSA-N Pseudoeugenol Natural products COC1=CC(C(C)=C)=CC=C1O UVMRYBDEERADNV-UHFFFAOYSA-N 0.000 claims abstract description 99
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000003054 catalyst Substances 0.000 claims abstract description 36
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 18
- 238000001029 thermal curing Methods 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 7
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 5
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 5
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 26
- 239000004593 Epoxy Substances 0.000 claims description 23
- 239000001257 hydrogen Substances 0.000 claims description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims description 18
- 239000000178 monomer Substances 0.000 claims description 17
- 238000006116 polymerization reaction Methods 0.000 claims description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 16
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 16
- 239000003112 inhibitor Substances 0.000 claims description 16
- 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 16
- -1 zinc acetate tetrabutylammonium bromide Chemical compound 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 238000001723 curing Methods 0.000 claims description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 12
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 11
- NHXVNEDMKGDNPR-UHFFFAOYSA-N zinc;pentane-2,4-dione Chemical compound [Zn+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O NHXVNEDMKGDNPR-UHFFFAOYSA-N 0.000 claims description 10
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 7
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 238000000016 photochemical curing Methods 0.000 claims description 6
- 238000006459 hydrosilylation reaction Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 5
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 229920001296 polysiloxane Polymers 0.000 claims description 4
- NHGXDBSUJJNIRV-UHFFFAOYSA-M tetrabutylammonium chloride Chemical compound [Cl-].CCCC[N+](CCCC)(CCCC)CCCC NHGXDBSUJJNIRV-UHFFFAOYSA-M 0.000 claims description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 3
- 150000002148 esters Chemical group 0.000 claims description 3
- 239000004925 Acrylic resin Substances 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- CCOSOBKLKCHGNO-UHFFFAOYSA-N ethoxy-(2,4,6-trimethylbenzoyl)phosphinic acid Chemical compound C(C)OP(O)(=O)C(C1=C(C=C(C=C1C)C)C)=O CCOSOBKLKCHGNO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 239000010948 rhodium Substances 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims 2
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 claims 1
- 125000004573 morpholin-4-yl group Chemical group N1(CCOCC1)* 0.000 claims 1
- 230000002209 hydrophobic effect Effects 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 4
- 125000004185 ester group Chemical group 0.000 abstract 1
- 239000000047 product Substances 0.000 description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 238000005481 NMR spectroscopy Methods 0.000 description 10
- 239000007788 liquid Substances 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 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 description 8
- 229920005989 resin Polymers 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 238000005160 1H NMR spectroscopy Methods 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 229920001187 thermosetting polymer Polymers 0.000 description 4
- 239000003377 acid catalyst Substances 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- KWEKXPWNFQBJAY-UHFFFAOYSA-N (dimethyl-$l^{3}-silanyl)oxy-dimethylsilicon Chemical compound C[Si](C)O[Si](C)C KWEKXPWNFQBJAY-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- BSXVSQHDSNEHCJ-UHFFFAOYSA-N [(dimethyl-$l^{3}-silanyl)oxy-diphenylsilyl]oxy-dimethylsilicon Chemical compound C=1C=CC=CC=1[Si](O[Si](C)C)(O[Si](C)C)C1=CC=CC=C1 BSXVSQHDSNEHCJ-UHFFFAOYSA-N 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 235000012424 soybean oil Nutrition 0.000 description 2
- 239000003549 soybean oil Substances 0.000 description 2
- IHURAMOGEYTMPA-UHFFFAOYSA-N trimethyl-(methyl-methylsilyloxy-phenylsilyl)oxysilane Chemical compound C[SiH2]O[Si](C)(O[Si](C)(C)C)c1ccccc1 IHURAMOGEYTMPA-UHFFFAOYSA-N 0.000 description 2
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 1
- LWRBVKNFOYUCNP-UHFFFAOYSA-N 2-methyl-1-(4-methylsulfanylphenyl)-2-morpholin-4-ylpropan-1-one Chemical compound C1=CC(SC)=CC=C1C(=O)C(C)(C)N1CCOCC1 LWRBVKNFOYUCNP-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- 229930185605 Bisphenol Natural products 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N deuterated chloroform Substances [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
- 239000011903 deuterated solvents Substances 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- MZRQZJOUYWKDNH-UHFFFAOYSA-N diphenylphosphoryl-(2,3,4-trimethylphenyl)methanone Chemical compound CC1=C(C)C(C)=CC=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 MZRQZJOUYWKDNH-UHFFFAOYSA-N 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 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 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003348 petrochemical agent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 description 1
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 description 1
- 235000012141 vanillin Nutrition 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
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- 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
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/40—Esters of unsaturated alcohols, e.g. allyl (meth)acrylate
-
- 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)
- Macromonomer-Based Addition Polymer (AREA)
- Silicon Polymers (AREA)
Abstract
The invention discloses an ultraviolet-heat curing composition for 3D printing and application thereof, wherein the ultraviolet-heat curing composition comprises the following raw materials in parts by weight: 70-90 parts of eugenol acrylate; 10-30 parts of eugenol-based organosilicon epoxy acrylate; 3-10 parts of an ester exchange catalyst; 0.5-5 parts of a photoinitiator; the structural formulas of the eugenol acrylate and the eugenol organosilicon epoxy acrylate are respectively shown in the following formulas (I) to (II); in formula (I), Y is selected from H or CH3(ii) a In the formula (II), x is an integer of 1-5, y is an integer of 0-5, R1～R6Independently selected from alkyl, phenyl or vinyl with 1-3 carbon atoms, and Z is selected from H or CH3. A finished product prepared by using the ultraviolet-thermal curing composition as a raw material through a 3D printing technology and thermal curing has excellent mechanical property, hydrophobic property, low volume shrinkage and self-repairing property.
Description
Technical Field
The invention relates to the technical field of 3D printing, in particular to an ultraviolet-heat curing composition for 3D printing and application thereof.
Background
The ultraviolet 3D printing technology irradiates ultraviolet light of a product cross-section pattern to liquid resin containing unsaturated bonds to be cured layer by layer to obtain a final product, and has the advantages of high printing speed, high printing precision and the like. Most of the currently used ultraviolet curing resins for 3D printing are bisphenol epoxy acrylate resins, which have the advantages of high hardness, high curing speed, high glossiness and the like, but have high viscosity, and a large amount of diluents are required to be added to reduce the viscosity during use, so that potential damage is caused to users, the strength of a model is reduced, and the volume shrinkage rate is improved; and because of containing a large amount of ester bonds, the hydrophobicity is poor, and the service life of the printing model can be reduced.
With the decrease of petrochemical resources, the use of renewable resources to replace petrochemicals has become a trend. The renewable resources are generally extracts from plants, including vegetable oils, rosins, eugenol, vanillin, and the like. For example, chinese patent publication No. CN 102660387a discloses an acrylate-modified epoxidized soybean oil and a preparation method thereof, in which the epoxidized soybean oil is derived from natural ingredients as a main raw material, but its main chain structure is too long, resulting in poor thermal stability and mechanical properties, and does not have properties such as hydrophobicity. Therefore, ester exchange bonds can be introduced into the crosslinking network based on double bond polymerization to increase crosslinking density so as to improve mechanical properties.
Eugenol is a bio-based renewable resource, has low toxicity to human bodies and has certain biocompatibility. Due to its special structure, it has many reactive active sites and contains benzene ring, a highly rigid structure, making it a candidate target for replacing petroleum-based resins. The epoxy resin is prepared by epoxidizing the phenolic hydroxyl and allyl of eugenol by researchers, and coupling the epoxy resin to obtain various eugenol-based epoxy resins. However, the related research on eugenol epoxy acrylate is less, so the research is favorable for expanding the application of eugenol epoxy acrylate.
Disclosure of Invention
Aiming at the problems in the prior art, the invention discloses an ultraviolet-heat curing composition for 3D printing, and a finished product prepared from the ultraviolet-heat curing composition serving as a raw material through a 3D printing technology and heat curing has excellent mechanical property, hydrophobic property and low volume shrinkage rate and has self-repairing property.
The specific technical scheme is as follows:
the ultraviolet-heat curing composition for 3D printing comprises the following raw materials in parts by weight:
the structural formula of the eugenol acrylate is shown as the following formula (I), and the structural formula of the eugenol organosilicon epoxy acrylate is shown as the following formula (II);
in formula (I), Y is selected from H or CH3；
In the formula (II), x is an integer of 1-5, y is an integer of 0-5, R1～R6Independently selected from alkyl, phenyl or vinyl with 1-3 carbon atoms, and Z is selected from H or CH3。
The invention discloses an ultraviolet-heat curing composition mainly comprising eugenol acrylate and eugenol organosilicon epoxy acrylate, wherein a finished product prepared by blending the eugenol acrylate and the eugenol organosilicon epoxy acrylate in a proper proportion and performing 3D printing technology and subsequent heat treatment has excellent mechanical property, hydrophobic property, low volume shrinkage and self-repairing property. The contrast test shows that when the eugenol acrylate is singly adopted, the water contact angle is greatly reduced, and the volume shrinkage rate is increased; and when the eugenol-based organosilicon epoxy acrylate is singly adopted, the mechanical property of the eugenol-based organosilicon epoxy acrylate is greatly reduced.
The preparation of the eugenol acrylate comprises the following steps:
under inert atmosphere, mixing eugenol epoxy, acrylic monomer A, catalyst A and polymerization inhibitor A, and obtaining eugenol acrylate after complete reaction;
the acrylic monomer A is selected from acrylic acid and/or methacrylic acid;
the catalyst A is selected from one or more of triphenylphosphine, tetrabutylammonium bromide, triethylamine, N-dimethylbenzylamine and N, N-dimethylaniline;
the polymerization inhibitor A is selected from hydroquinone and/or p-hydroxyanisole.
The eugenol epoxy is prepared by referring to Chinese patent document with publication number CN 107445921A.
Preferably:
the mol ratio of the eugenol epoxy, the acrylic monomer A, the catalyst A and the polymerization inhibitor A is 1: 1-1.5: 0.02-0.07: 0.01 to 0.05;
the reaction temperature is 80-110 ℃, and the reaction time is 2-8 h.
The inert atmosphere is an inert gas commonly used in the art, such as nitrogen, helium, argon, and the like.
Preferably, the preparation comprises:
heating eugenol epoxy to 90-100 ℃, blending an acrylic monomer A, a catalyst A and a polymerization inhibitor A, and then dripping the mixture into the eugenol epoxy.
It has been found that the color of the product can be further improved, more nearly colorless and reduced in viscosity by using this sequence of addition.
The preparation method of the eugenol-based organosilicon epoxy acrylate comprises the following steps:
the method comprises the following steps: carrying out hydrosilylation reaction on eugenol epoxy and hydrogen-containing siloxane under the action of a catalyst B to obtain reaction liquid;
the structural formula of the hydrosiloxane is shown as the following formula (III):
in the formula (III), x is an integer of 1-5, y is an integer of 0-5, R1～R6Independently selected from alkyl, phenyl or vinyl with 1-3 carbon atoms;
preferably, the hydrogen-containing siloxane has the following structural formulas (III-1) to (III-3):
the catalyst B is selected from one or more of a platinum catalyst, a palladium catalyst and a rhodium catalyst;
step two: under an inert atmosphere, mixing an acrylic monomer C, a catalyst C and a polymerization inhibitor C with the reaction solution, and obtaining the eugenol-based organosilicon epoxy acrylate resin after the reaction is completed;
the acrylic monomer C is selected from acrylic acid and/or methacrylic acid;
the catalyst C is one or more selected from triphenylphosphine, tetrabutylammonium bromide, triethylamine, N-dimethylbenzylamine and N, N-dimethylaniline;
the polymerization inhibitor C is selected from hydroquinone and/or p-hydroxyanisole.
Preferably:
in the first step, the molar ratio of the eugenol epoxy to the hydrogen-containing siloxane is 1: 1-3;
the dosage of the catalyst B is 20-100 ppm of a silicon-hydrogen bond in the hydrogen-containing siloxane;
the temperature of the hydrosilylation reaction is 50-90 ℃, and the time is 4-10 hours;
in the second step, the molar ratio of the eugenol epoxy to the acrylic monomer C, the catalyst C and the polymerization inhibitor C is 1: 1-1.5: 0.02-0.07: 0.01 to 0.05;
the reaction temperature is 80-110 ℃, and the reaction time is 4-12 h.
Further preferably:
in the second step, the reaction solution is heated to 90-100 ℃, and then the acrylic monomer C, the catalyst C and the polymerization inhibitor C are mixed and dropped into the reaction solution. Likewise, this sequence of addition can further improve the color of the product, more towards colorless and lower the viscosity.
The second step of the preparation of the eugenol-based organosilicon epoxy acrylate is similar to the preparation of the eugenol-based acrylate, and the types of the adopted inert atmosphere, the acrylic monomer, the catalyst and the polymerization inhibitor are similar in selectable range and are independent from each other.
The preparation of the eugenol-based organic silicon epoxy acrylate disclosed by the invention is synthesized by adopting a one-pot method, and firstly, in an inert atmosphere, the eugenol epoxy and the hydrogen-containing siloxane are subjected to hydrosilylation under the action of a catalyst to obtain the organic silicon eugenol epoxy. And then raising the temperature, adding an acrylate monomer, a catalyst and a polymerization inhibitor into the system, and introducing an acrylate group through an epoxy ring-opening esterification reaction to finally obtain the eugenol-based organosilicon epoxy acrylate. The preparation method has the advantages of no need of purification, simple process, no need of adding solvent, high yield and suitability for industrial large-scale production. In the preparation process, the monomer structure can be adjusted by selecting different hydrogen-containing siloxane, so that the performance of the polymer is changed, and the purpose of artificially adjusting and controlling the material performance is realized.
In the ultraviolet-light-heat curing composition, the types of the transesterification catalyst and the photoinitiator are not particularly required, and can be selected from conventional types in the field.
The ester exchange catalyst is at least one of zinc acetylacetonate, zinc acetate tetrabutylammonium bromide, tetrabutylammonium chloride or tetramethylammonium hydroxide.
The photoinitiator is selected from 2,4,6 (trimethylbenzoyl) diphenylphosphine oxide, 2,4, 6-trimethylbenzoylphosphonic acid ethyl ester, 2-methyl-1- [4- (methylthio) phenyl ] -2- (4-morpholinyl) -1-propanone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, 2-phenylbenzyl-2-dimethylamine-1- (4-morpholinylbenzylphenyl) butanone and the like.
Further preferably:
the structural formula of the eugenol acrylate is shown as the following formula (I-1), and the structural formula of the eugenol organosilicon epoxy acrylate is shown as the following formula (II-1);
preferably, the feed comprises the following raw materials in parts by weight:
tests show that the volume shrinkage of a finished product prepared by blending the raw materials with the structural formula in an optimal ratio and then performing 3D printing and thermocuring processes is lower than 6%, the application requirement of photocuring can be met, and the mechanical property and the hydrophobic property are good.
Still further preferably, the composition comprises the following raw materials in parts by weight:
tests show that the finished product finally prepared by adopting the further optimized formula has the best comprehensive performance.
The invention also discloses an application of the ultraviolet-heat curing composition in 3D printing, which comprises the following steps:
blending the ultraviolet curing composition, putting the blended ultraviolet curing composition into a 3D printer, carrying out photocuring to obtain a pre-cured material, and carrying out thermocuring to obtain a final product;
and (3) photo-curing: the wavelength of the LED ultraviolet lamp is 365-405 nm, and the curing speed of each layer is 1-10 s;
the temperature of the thermocuring is 180-200 ℃, and the time is 2-8 h.
Tests show that if the preparation process in the prior art is adopted, namely only photocuring is carried out without subsequent thermocuring, the tensile strength and the water contact angle of the finally prepared finished product are greatly reduced.
Further preferably, the thermosetting time is 4-6 h; still more preferably 6 h. Tests show that with the continuous optimization of the thermosetting time, the tensile strength and the water contact angle of the finally prepared finished product are continuously improved.
Compared with the prior art, the invention has the following advantages:
the invention discloses an ultraviolet-heat curing composition for 3D printing, which mainly comprises eugenol acrylate and eugenol organosilicon epoxy acrylate, wherein both the eugenol acrylate and the eugenol organosilicon epoxy acrylate use natural bio-eugenol resin to replace the existing petroleum-based resin, so that the environmental pollution is reduced, and the composition is more environment-friendly; wherein, siloxane chain segments are also introduced into the structure of the eugenol-based organosilicon epoxy acrylate to improve the hydrophobicity of the material. The ultraviolet-heat curing composition is applied to 3D printing, the process steps of firstly ultraviolet curing and then heat curing are adopted, the tensile strength, the hydrophobicity and the volume shrinkage rate of a finished product are greatly improved, the finished product can also be self-repaired by heating, and the service life of the finished product is greatly prolonged.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum 1H-NMR of eugenol epoxy acrylate prepared in example 1;
FIG. 2 is a nuclear magnetic resonance hydrogen spectrum 1H-NMR of eugenol tetramethyldisiloxane acrylate prepared in example 2;
FIG. 3 is a nuclear magnetic resonance hydrogen spectrum 1H-NMR of eugenol tetramethyl diphenyl trisiloxane acrylate prepared in example 4;
FIG. 4 is a nuclear magnetic resonance hydrogen spectrum 1H-NMR of eugenol pentamethyl phenyl trisiloxane acrylate prepared in example 6;
FIG. 5 is a comparison of the self-healing function of the bars prepared in example 9.
Detailed Description
To further clarify the objects, technical solutions and advantages of the present invention, the following detailed description of the present invention is provided with reference to specific examples, which should not be construed as limiting the scope of the present invention.
In the following examples, hydrogen NMR 1H-NMR A Bruker Avance400 NMR spectrometer was used, as CDCl3Is a deuterated solvent.
The yield is the mass of eugenol-based silicone epoxy acrylate/(moles of eugenol × molar mass of eugenol-based silicone epoxy acrylate) × 100%.
The viscosity was measured using a rotational rheometer (HAAKE RS6000), 25 ℃.
Tensile strength was measured using a universal materials tester (Zwick/Roell Z020).
The water contact angle was measured using an optical contact angle gauge (OCA 20).
The volume shrinkage is tested according to the density before and after curing, and the test formula is as follows:
shrinkage factor ═ p (p)Rear end-ρFront side)/ρRear end×100％。
Example 1
Under the protection of nitrogen, 100g (0.45mol) of eugenol epoxy is heated to 90 ℃, mixed liquid (34.4 g (0.48mol) of acrylic acid, 5g (0.02mol) of triphenylphosphine and 1.8g (0.016mol) of hydroquinone) is dripped, and the temperature is heated to 105 ℃ after the dripping is finished to react for 6 hours, so that the eugenol organosilicon epoxy acrylate is obtained, wherein the structural formula is shown as the following formula. The yield is 98%, the viscosity at 25 ℃ is 500cps, and the nuclear magnetic resonance hydrogen spectrum data are shown in figure 1, wherein each peak corresponds to the hydrogen atom on the structure of the eugenol-based organosilicon epoxy acrylate prepared in the embodiment.
Example 2
Under the protection of nitrogen, adding a Kanster catalyst (30ppm) into 100g (0.45mol) of eugenol epoxy, heating to 60 ℃, and dropwise adding 31g (0.225mol) of 1,1,3, 3-tetramethyldisiloxane for 6 hours; then, the temperature was raised to 90 ℃ and the mixture (34.4 g (0.48mol) of acrylic acid, 5g (0.015mol) of tetrabutylammonium bromide and 1.8g of hydroquinone) was added dropwise
(0.016mol)), and after the dropwise addition is finished, heating to 105 ℃ for reaction for 6 hours to obtain the eugenol-based organosilicon epoxy acrylate, wherein the structural formula is shown as the following formula. The yield is 98%, the viscosity at 25 ℃ is 4000cps, and the nuclear magnetic resonance hydrogen spectrum data are shown in FIG. 2, wherein each peak corresponds to a hydrogen atom on the structure of the eugenol-based organosilicon epoxy acrylate prepared in the embodiment.
Example 3
Under the protection of nitrogen, adding chloroplatinic acid catalyst (50ppm) into 100g (0.45mol) of eugenol epoxy, heating to 60 ℃, and dropwise adding 31g (0.225mol) of 1,1,3, 3-tetramethyldisiloxane for 6 hours; then raising the temperature to 100 ℃, dropwise adding the mixed solution (48 g (0.675mol) of acrylic acid, 5g (0.02mol) of triphenylphosphine and 1.8g (0.015mol) of p-hydroxyanisole), and after the dropwise adding is finished, raising the temperature to 110 ℃ for reacting for 6 hours to obtain the eugenol-based organosilicon epoxy acrylate. Yield 95%, viscosity 3600cps at 25 ℃.
Example 4
Under the protection of nitrogen, adding a Kanst catalyst (50ppm) into 100g (0.45mol) of eugenol epoxy, heating to 70 ℃, and dropwise adding 75g (0.225mol) of 1,1,5, 5-tetramethyl-3, 3-diphenyl trisiloxane for 6 hours; then raising the temperature to 100 ℃, dropwise adding the mixed solution (37 g (0.51mol) of acrylic acid, 2.5g (0.01mol) of triphenylphosphine and 0.5g (0.005mol) of hydroquinone) and reacting for 12 hours to obtain the eugenol organosilicon epoxy acrylate. The structural formula is shown as the following formula. The yield was 95%, the viscosity at 25 ℃ was 29000cps, and the NMR data are shown in FIG. 3, in which the peaks correspond one-to-one to the hydrogen atoms on the eugenol-based silicone epoxy acrylate structure prepared in this example.
Example 5
Under the protection of nitrogen, adding chloroplatinic acid catalyst (50ppm) into 100g (0.45mol) of eugenol epoxy, heating to 70 ℃, and dropwise adding 75g (0.225mol) of 1,1,5, 5-tetramethyl-3, 3-diphenyl trisiloxane for 6 hours; then raising the temperature to 100 ℃, dropwise adding the mixed solution (32.5 g (0.45mol) of acrylic acid, 2g (0.015mol) of N, N-dimethylbenzylamine and 1.8g (0.015mol) of p-hydroxyanisole), and reacting for 6 hours to obtain the eugenol-based organosilicon epoxy acrylate. Yield 98%, viscosity 31000cps at 25 ℃.
Example 6
Under the protection of nitrogen, adding a Kanst catalyst (50ppm) into 100g (0.45mol) of eugenol epoxy, heating to 70 ℃, and dropwise adding 60.8g (0.225mol) of 3-phenyl pentamethyl trisiloxane for 6 hours; then raising the temperature to 100 ℃, and dropwise adding the mixed solution (48 g (0.675mol) of acrylic acid, 7.5g (0.03mol) of triphenylphosphine and 2.5g (0.02mol) of p-hydroxyanisole) to react for 4 hours to obtain the eugenol-based organosilicon epoxy acrylate. The structural formula is shown as the following formula. Yield 25 ℃ viscosity 26000 cps. The NMR data are shown in FIG. 4, in which the peaks correspond to the hydrogen atoms on the structure of the eugenol-based organosilicon epoxy acrylate prepared in this example.
Example 7
Under the protection of nitrogen, adding chloroplatinic acid catalyst (70ppm) into 100g (0.45mol) of eugenol epoxy, and then dropwise adding 60.8g (0.025mol) of 3-phenyl pentamethyl trisiloxane at 70 ℃ under the protection of nitrogen for 5 hours; then raising the temperature to 100 ℃, dropwise adding the mixed solution (33 g (0.45mol) of acrylic acid, 2g (0.015mol) of N, N-dimethylbenzylamine and 1.5g (0.015mol) of hydroquinone) and reacting for 8 hours to obtain the eugenol-based organosilicon epoxy acrylate. Viscosity 28000cps at 25 ℃.
Example 8
70g of eugenol epoxy acrylate prepared in example 1, 30g of eugenol tetramethyl disiloxane acrylate prepared in example 2 and 5g of zinc acetylacetonate are mixed and heated to form liquid, 2g of photoinitiator phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide is added and uniformly mixed, the mixture is placed into a 395nm ultraviolet light 3D printer to print a dumbbell type sample strip model, and then the model is placed into an oven at 180 ℃ to be baked for 6 hours to prepare the cured model. The tensile strength, water contact angle, and volume shrinkage data of the resulting samples are shown in Table 1 below.
Example 9
80g of the eugenol epoxy acrylate prepared in example 1, 20g of the eugenol tetramethyl disiloxane acrylate prepared in example 2 and 5g of zinc acetylacetonate are mixed and heated to form a liquid, 2g of a photoinitiator phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide is added to be uniformly mixed, the mixture is placed into a 395nm ultraviolet 3D printer to print a dumbbell type sample strip model, and the model is placed into an oven at 180 ℃ to be baked for 6 hours to prepare a cured model. The tensile strength, water contact angle, and volume shrinkage data of the resulting samples are shown in Table 1 below.
After the surface of the sample strip prepared in the embodiment is marked by a blade, the sample strip is placed into an oven at 180 ℃ to be baked for 2 hours, and the scratch width is obviously reduced, which indicates that the material has a self-repairing function. The pictures before (left) and after (right) repair are shown in FIG. 5.
Example 10
90g of eugenol epoxy acrylate prepared in example 1, 10g of eugenol tetramethyl disiloxane acrylate prepared in example 2 and 5g of zinc acetylacetonate are mixed and heated to form liquid, 2g of photoinitiator phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide is added and uniformly mixed, the mixture is placed into a 395nm ultraviolet light 3D printer to print a dumbbell type sample strip model, and after the model is placed into an oven at 180 ℃ and baked for 6 hours, the cured model is prepared. The tensile strength, water contact angle, and volume shrinkage data of the resulting samples are shown in Table 1 below.
Example 11
80g of the eugenol epoxy acrylate prepared in example 1, 20g of the eugenol tetramethyl disiloxane acrylate prepared in example 2 and 5g of zinc acetylacetonate are mixed and heated to form a liquid, 2g of a photoinitiator phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide is added to be uniformly mixed, the mixture is placed into a 395nm ultraviolet 3D printer to print a dumbbell type sample strip model, and the model is placed into an oven at 180 ℃ to be baked for 2 hours to prepare a cured model. The tensile strength, water contact angle, and volume shrinkage data of the resulting samples are shown in Table 1 below.
Example 12
80g of the eugenol epoxy acrylate prepared in example 1, 20g of the eugenol tetramethyl disiloxane acrylate prepared in example 2 and 5g of zinc acetylacetonate are mixed and heated to form a liquid, 2g of a photoinitiator phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide is added to be uniformly mixed, the mixture is placed into a 395nm ultraviolet 3D printer to print a dumbbell type sample strip model, and the model is placed into an oven at 180 ℃ to be baked for 4 hours to prepare a cured model. The tensile strength, water contact angle, and volume shrinkage data of the resulting samples are shown in Table 1 below.
Comparative example 1
100g of eugenol epoxy acrylate prepared in example 1 and 5g of zinc acetylacetonate are mixed and heated to form liquid, 2g of photoinitiator phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide is added and uniformly mixed, the mixture is placed into a 395nm ultraviolet light 3D printer to print a dumbbell type sample strip model, and then the model is placed into an oven at 180 ℃ to be baked for 6 hours to prepare the cured model. The tensile strength, water contact angle, and volume shrinkage data of the resulting samples are shown in Table 1 below.
Comparative example 2
100g of eugenol tetramethyldisiloxane acrylate prepared in example 2 and 5g of zinc acetylacetonate were mixed and heated to become liquid, 2g of photoinitiator phenylbis (2,4, 6-trimethylbenzoyl) phosphine oxide was added to be mixed uniformly, the mixture was placed into a 395nm ultraviolet 3D printer to print a dumbbell type sample strip model, and after the printing of the dumbbell type sample strip model was completed, the model was placed into an oven at 180 ℃ to be baked for 6 hours, so as to prepare a cured model. The tensile strength, water contact angle, and volume shrinkage data of the resulting samples are shown in Table 1 below.
Comparative example 3
80g of the eugenol epoxy acrylate prepared in example 1, 20g of the eugenol tetramethyl disiloxane acrylate prepared in example 2 and 5g of zinc acetylacetonate were mixed and heated to become liquid, 2g of the photoinitiator phenyl bis (2,4, 6-trimethylbenzoyl) phosphine oxide was added and mixed uniformly, and the mixture was placed in a 395nm ultraviolet 3D printer to print a dumbbell bar model, so that a cured model was prepared. The tensile strength, water contact angle, and volume shrinkage data of the resulting samples are shown in Table 1 below.
TABLE 1
Observing the data in table 1, in comparative examples 8-10, increasing the content of eugenol epoxy acrylate increases the tensile strength, but decreases the water contact angle and increases the volume shrinkage, and the volume 5 shrinkage requirement of general light-cured resin is less than 6%, so that the eugenol epoxy acrylate accounts for 20-30% of the total resin mass optimally. At this time, tensile strength, hydrophobicity and volume shrinkage are all in good levels.
Comparing examples 8-10 with comparative examples 1-2, when the eugenol epoxy acrylate is independently cured, the finished product has good tensile strength, poor hydrophobicity and large volume shrinkage; and the tensile strength of the finished product is extremely poor when the eugenol organic silicon epoxy acrylate is independently cured. When the two are blended, the finished product is firstly subjected to photocuring and then is subjected to thermocuring, and the obtained finished product has excellent hydrophobic property and low volume shrinkage rate, and the mechanical property of the finished product is superior to that of the finished product when the two are used independently. At the same time
Comparing examples 9, 11-12 with comparative example 3, if no thermosetting is performed, the prepared finished product has the worst performance, and the thermosetting process is essential. And the thermal curing reaction time can influence the performance of a finished product, the mechanical property and the hydrophobicity of the finished product are greatly improved along with the extension of the thermal curing time, and when the thermal curing time is 6 hours, the comprehensive performance is optimal. .
Claims (10)
1. The ultraviolet-heat curing composition for 3D printing is characterized by comprising the following raw materials in parts by weight:
the structural formula of the eugenol acrylate is shown as the following formula (I), and the structural formula of the eugenol organosilicon epoxy acrylate is shown as the following formula (II);
in formula (I), Y is selected from H or CH3；
Formula (A), (B) andin II), x is an integer of 1 to 5, y is an integer of 0 to 5, R1～R6Independently selected from alkyl, phenyl or vinyl with 1-3 carbon atoms, and Z is selected from H or CH3。
2. The uv-thermally curing composition for 3D printing according to claim 1, wherein the preparation of the eugenol acrylate comprises:
under inert atmosphere, mixing eugenol epoxy, acrylic monomer A, catalyst A and polymerization inhibitor A, and obtaining eugenol acrylate after complete reaction;
the acrylic monomer A is selected from acrylic acid and/or methacrylic acid;
the catalyst A is selected from one or more of triphenylphosphine, tetrabutylammonium bromide, triethylamine, N-dimethylbenzylamine and N, N-dimethylaniline;
the polymerization inhibitor A is selected from hydroquinone and/or p-hydroxyanisole.
3. The UV-thermally curable composition for 3D printing according to claim 2, wherein the molar ratio of the eugenol epoxy, the acrylic monomer A, the catalyst A and the polymerization inhibitor A is 1: 1-1.5: 0.02-0.07: 0.01 to 0.05;
the reaction temperature is 80-110 ℃, and the reaction time is 4-12 h.
4. The uv-thermally curing composition for 3D printing according to claim 1, wherein the preparation of the eugenol-based silicone epoxy acrylate comprises the steps of:
the method comprises the following steps: carrying out hydrosilylation reaction on eugenol epoxy and hydrogen-containing siloxane under the action of a catalyst B to obtain reaction liquid;
the structural formula of the hydrosiloxane is shown as the following formula (III):
in the formula (III), x is an integer of 1-5, y is an integer of 0-5, R1～R6Independently selected from alkyl, phenyl or vinyl with 1-3 carbon atoms;
the catalyst B is selected from one or more of a platinum catalyst, a palladium catalyst and a rhodium catalyst;
step two: under an inert atmosphere, mixing an acrylic monomer C, a catalyst C and a polymerization inhibitor C with the reaction solution, and obtaining the eugenol-based organosilicon epoxy acrylate resin after the reaction is completed;
the acrylic monomer C is selected from acrylic acid and/or methacrylic acid;
the catalyst C is one or more selected from triphenylphosphine, tetrabutylammonium bromide, triethylamine, N-dimethylbenzylamine and N, N-dimethylaniline;
the polymerization inhibitor C is selected from hydroquinone and/or p-hydroxyanisole.
5. The uv-thermally curable composition for 3D printing according to claim 4, wherein:
in the first step, the molar ratio of the eugenol epoxy to the hydrogen-containing siloxane is 1: 1;
the dosage of the catalyst B is 20-100 ppm of a silicon-hydrogen bond in the hydrogen-containing siloxane;
the temperature of the hydrosilylation reaction is 50-90 ℃, and the time is 4-10 hours;
in the second step, the molar ratio of the eugenol epoxy to the acrylic monomer C, the catalyst C and the polymerization inhibitor C is 1: 1-1.5: 0.02-0.07: 0.01 to 0.05;
the reaction temperature is 80-110 ℃, and the reaction time is 4-12 h.
6. The uv-thermally curable composition for 3D printing according to claim 1, wherein:
the ester exchange catalyst is selected from one or more of zinc acetylacetonate, zinc acetate tetrabutylammonium bromide, tetrabutylammonium chloride and tetramethylammonium hydroxide;
the photoinitiator is selected from one or more of 2,4,6- (trimethylbenzoyl) diphenylphosphine oxide, 2,4, 6-trimethylbenzoyl phosphonic acid ethyl ester, 2-methyl-1- [4- (methylthio) phenyl ] -2- (4-morpholinyl) -1-acetone, 2-hydroxy-2-methyl-1-phenyl-1-acetone and 2-phenylbenzyl-2-dimethylamine-1- (4-morpholinylbenzyl phenyl) butanone.
7. The UV-thermally curable composition for 3D printing according to any one of claims 1 to 6, wherein:
the structural formula of the eugenol acrylate is shown as the following formula (I-1), and the structural formula of the eugenol organosilicon epoxy acrylate is shown as the following formula (II-1);
8. the UV-thermally curing composition for 3D printing according to claim 7, comprising the following raw materials in parts by weight:
9. use of a uv-thermally curable composition according to any of claims 1 to 8 for 3D printing, comprising the steps of:
blending the ultraviolet curing composition, putting the blended ultraviolet curing composition into a 3D printer, carrying out photocuring to obtain a pre-cured material, and carrying out thermocuring to obtain a finished product;
the wavelength of the LED ultraviolet lamp is 365-405 nm, and the curing speed of each layer is 1-10 s;
the temperature of the thermocuring is 180-200 ℃, and the time is 2-8 h.
10. Use of the uv-thermally curable composition according to claim 9 for 3D printing, wherein the thermal curing time is 4 to 6 hours.
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