CN111592620B - 用于3d打印的光固化材料 - Google Patents
用于3d打印的光固化材料 Download PDFInfo
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- CN111592620B CN111592620B CN202010483089.7A CN202010483089A CN111592620B CN 111592620 B CN111592620 B CN 111592620B CN 202010483089 A CN202010483089 A CN 202010483089A CN 111592620 B CN111592620 B CN 111592620B
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- nano tube
- carbon nano
- acrylate
- modified carbon
- composite powder
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- 239000000463 material Substances 0.000 title claims abstract description 43
- 238000010146 3D printing Methods 0.000 title claims abstract description 35
- 238000000016 photochemical curing Methods 0.000 title claims abstract description 19
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 66
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000011575 calcium Substances 0.000 claims abstract description 36
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 36
- 239000000843 powder Substances 0.000 claims abstract description 36
- 239000002131 composite material Substances 0.000 claims abstract description 35
- 230000009974 thixotropic effect Effects 0.000 claims abstract description 8
- 239000003085 diluting agent Substances 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 28
- 238000001914 filtration Methods 0.000 claims description 27
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical group [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 18
- 239000002041 carbon nanotube Substances 0.000 claims description 17
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 238000001816 cooling Methods 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 15
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 14
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 238000000227 grinding Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000002202 Polyethylene glycol Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 229920001223 polyethylene glycol Polymers 0.000 claims description 9
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 7
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 7
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 7
- -1 polytetrafluoroethylene Polymers 0.000 claims description 7
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 239000004115 Sodium Silicate Substances 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- ISAOCJYIOMOJEB-UHFFFAOYSA-N benzoin Chemical compound C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 6
- 235000019441 ethanol Nutrition 0.000 claims description 6
- 239000012528 membrane Substances 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 6
- 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 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- JNELGWHKGNBSMD-UHFFFAOYSA-N xanthone Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3OC2=C1 JNELGWHKGNBSMD-UHFFFAOYSA-N 0.000 claims description 6
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical group CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 229910021485 fumed silica Inorganic materials 0.000 claims description 5
- 125000000524 functional group Chemical group 0.000 claims description 5
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims description 4
- FZSHSWCZYDDOCK-UHFFFAOYSA-N 2-methylprop-2-enoic acid;oxolane Chemical compound C1CCOC1.CC(=C)C(O)=O FZSHSWCZYDDOCK-UHFFFAOYSA-N 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 4
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 4
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 4
- 239000012965 benzophenone Substances 0.000 claims description 4
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- 229920000570 polyether Polymers 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- PCLLJCFJFOBGDE-UHFFFAOYSA-N (5-bromo-2-chlorophenyl)methanamine Chemical compound NCC1=CC(Br)=CC=C1Cl PCLLJCFJFOBGDE-UHFFFAOYSA-N 0.000 claims description 3
- ZANRHLGMHYOWQU-UHFFFAOYSA-N 1,5-bis[4-(2-hydroxyethoxy)phenyl]-2,4-dimethylpentan-3-one Chemical compound C=1C=C(OCCO)C=CC=1CC(C)C(=O)C(C)CC1=CC=C(OCCO)C=C1 ZANRHLGMHYOWQU-UHFFFAOYSA-N 0.000 claims description 3
- PWMWNFMRSKOCEY-UHFFFAOYSA-N 1-Phenyl-1,2-ethanediol Chemical compound OCC(O)C1=CC=CC=C1 PWMWNFMRSKOCEY-UHFFFAOYSA-N 0.000 claims description 3
- 239000004593 Epoxy Chemical group 0.000 claims description 3
- HLJYBXJFKDDIBI-UHFFFAOYSA-N O=[PH2]C(=O)C1=CC=CC=C1 Chemical compound O=[PH2]C(=O)C1=CC=CC=C1 HLJYBXJFKDDIBI-UHFFFAOYSA-N 0.000 claims description 3
- 244000028419 Styrax benzoin Species 0.000 claims description 3
- 235000000126 Styrax benzoin Nutrition 0.000 claims description 3
- 235000008411 Sumatra benzointree Nutrition 0.000 claims description 3
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 claims description 3
- ULQMPOIOSDXIGC-UHFFFAOYSA-N [2,2-dimethyl-3-(2-methylprop-2-enoyloxy)propyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(C)(C)COC(=O)C(C)=C ULQMPOIOSDXIGC-UHFFFAOYSA-N 0.000 claims description 3
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims description 3
- VEBCLRKUSAGCDF-UHFFFAOYSA-N ac1mi23b Chemical compound C1C2C3C(COC(=O)C=C)CCC3C1C(COC(=O)C=C)C2 VEBCLRKUSAGCDF-UHFFFAOYSA-N 0.000 claims description 3
- 150000001251 acridines Chemical class 0.000 claims description 3
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 claims description 3
- 150000004056 anthraquinones Chemical class 0.000 claims description 3
- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical compound C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 claims description 3
- 229960002130 benzoin Drugs 0.000 claims description 3
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims description 3
- 235000019382 gum benzoic Nutrition 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 229940119545 isobornyl methacrylate Drugs 0.000 claims description 3
- RZFODFPMOHAYIR-UHFFFAOYSA-N oxepan-2-one;prop-2-enoic acid Chemical compound OC(=O)C=C.O=C1CCCCCO1 RZFODFPMOHAYIR-UHFFFAOYSA-N 0.000 claims description 3
- 150000002988 phenazines Chemical class 0.000 claims description 3
- 229920000728 polyester Polymers 0.000 claims description 3
- 229920001451 polypropylene glycol Polymers 0.000 claims description 3
- 229920001296 polysiloxane Polymers 0.000 claims description 3
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 claims description 3
- 150000003252 quinoxalines Chemical class 0.000 claims description 3
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 claims description 3
- RZLXRFDFCORTQM-UHFFFAOYSA-N OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCCn1c(=O)n(CCO)c(=O)n(CCO)c1=O Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OCCn1c(=O)n(CCO)c(=O)n(CCO)c1=O RZLXRFDFCORTQM-UHFFFAOYSA-N 0.000 claims description 2
- CQAIBOSCGCTHPV-UHFFFAOYSA-N bis(1-hydroxycyclohexa-2,4-dien-1-yl)methanone Chemical compound C1C=CC=CC1(O)C(=O)C1(O)CC=CC=C1 CQAIBOSCGCTHPV-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 10
- 238000012360 testing method Methods 0.000 abstract description 4
- 238000005452 bending Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 229910002090 carbon oxide Inorganic materials 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000002071 nanotube Substances 0.000 description 4
- 230000000844 anti-bacterial effect Effects 0.000 description 3
- 230000001580 bacterial effect Effects 0.000 description 3
- 238000000498 ball milling Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 235000011837 pasties Nutrition 0.000 description 3
- 229920000058 polyacrylate Polymers 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 2
- VMRIVYANZGSGRV-UHFFFAOYSA-N 4-phenyl-2h-triazin-5-one Chemical compound OC1=CN=NN=C1C1=CC=CC=C1 VMRIVYANZGSGRV-UHFFFAOYSA-N 0.000 description 2
- 241000588724 Escherichia coli Species 0.000 description 2
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000001963 growth medium Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- PDGQDNBBPDKZRE-UHFFFAOYSA-N (1-aminocyclohexa-2,4-dien-1-yl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(N)CC=CC=C1 PDGQDNBBPDKZRE-UHFFFAOYSA-N 0.000 description 1
- VVKZEEWRYIIUOF-UHFFFAOYSA-N (1-hydroxycyclohexa-2,4-dien-1-yl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CC=CC=C1 VVKZEEWRYIIUOF-UHFFFAOYSA-N 0.000 description 1
- HJIAMFHSAAEUKR-UHFFFAOYSA-N (2-hydroxyphenyl)-phenylmethanone Chemical compound OC1=CC=CC=C1C(=O)C1=CC=CC=C1 HJIAMFHSAAEUKR-UHFFFAOYSA-N 0.000 description 1
- YIJYFLXQHDOQGW-UHFFFAOYSA-N 2-[2,4,6-trioxo-3,5-bis(2-prop-2-enoyloxyethyl)-1,3,5-triazinan-1-yl]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCN1C(=O)N(CCOC(=O)C=C)C(=O)N(CCOC(=O)C=C)C1=O YIJYFLXQHDOQGW-UHFFFAOYSA-N 0.000 description 1
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- ZCILGMFPJBRCNO-UHFFFAOYSA-N 4-phenyl-2H-benzotriazol-5-ol Chemical compound OC1=CC=C2NN=NC2=C1C1=CC=CC=C1 ZCILGMFPJBRCNO-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 238000011960 computer-aided design Methods 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- FTWUXYZHDFCGSV-UHFFFAOYSA-N n,n'-diphenyloxamide Chemical compound C=1C=CC=CC=1NC(=O)C(=O)NC1=CC=CC=C1 FTWUXYZHDFCGSV-UHFFFAOYSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- SOGFHWHHBILCSX-UHFFFAOYSA-J prop-2-enoate silicon(4+) Chemical compound [Si+4].[O-]C(=O)C=C.[O-]C(=O)C=C.[O-]C(=O)C=C.[O-]C(=O)C=C SOGFHWHHBILCSX-UHFFFAOYSA-J 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
Classifications
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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
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
-
- 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
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
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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
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
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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
- 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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- 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
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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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
- C08F283/124—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes on to polysiloxanes having carbon-to-carbon double bonds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
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Abstract
本发明提供了一种用于3D打印的光固化材料,其按重量百分比包含:光固化低聚物20‑40wt%、活性稀释剂5‑30wt%、光引发剂0.1‑1wt%、触变促进剂1‑10wt%、改性碳纳米管/磷硅酸钙复合粉体20‑50wt%。本发明的光固化材料能顺利实现SLA/DLP原理的3D打印工艺,制作的产品具有0.1~0.2%的低体积收缩率,机械强度高,韧性好,拉伸强度100~120MPa,弯曲强度在120~130MPa,断裂伸长15~20%,户外耐候性测试六个月,机械性能指标保持在98~100%,可以作为终端产品材料使用。
Description
技术领域
本发明涉及3D打印材料,具体涉及一种用于3D打印的光固化材料。
背景技术
3D打印是借助于计算机辅助设计与控制,将液体(粉末)材料通过层层叠加的方式来制造固体三维物体的成型方法,该技术发展至今,以立体光刻(SLA)和数字光处理技术(DLP)成型精度最好。SLA/DLP 3D成型技术所用材料均为液体光固化树脂,在特定波长的光能量下辐射固化,液体光敏树脂变成固体交联结构,材料本质上属于热固性塑胶材料,且具有比传统热固性交联结构材料更高的交联密度,具有硬而脆的天然缺陷,耐疲劳性能差,抗老化性能差,无法应用于终端产品。
发明内容
鉴于背景技术中存在的问题,本发明的目的在于提供一种用于3D打印的光固化材料,该光固化材料具有特有的触变性,触变性赋予其具有适用于3D打印工艺的特性,经光固化成型后的产品,具有收缩率小、耐高温性、耐磨性、耐久性以及其他相应的性能,可用于军工、航天、汽车、生物医疗、电子电路等领域。
为了实现上述目的,本发明提供了一种用于3D打印的光固化材料,按重量百分比,包含:
进一步地,所述改性碳纳米管/磷硅酸钙复合粉体的制备方法包括以下步骤:1)将硝酸钙、摩尔浓度为0.1-1mol/L的硅酸钠溶液、摩尔浓度为0.1-1mol/L的磷酸氢二胺溶液和改性碳纳米管依次投入反应釜中,重量比为1:10:10:0.1;2)启动反应釜的搅拌装置,计量器以0.5L/min的速度滴加氨水,保持溶液的pH为8-9,并继续搅拌16-17小时,然后过滤去除滤液,并依次用去离子水和无水乙醇充分洗涤残余固体,滤干后再真空100℃烘干,得到胚料;3)将所述胚料放入真空炉中,真空度1Mpa,600-700℃锻烧2-2.5小时,自然冷却后研磨,得到改性碳纳米管/磷硅酸钙复合粉体。
进一步地,所述改性碳纳米管/磷硅酸钙复合粉体粒径为1-
5μm。
进一步地,所述改性碳纳米管的制备方法为:1)将碳纳米管浸入浓硝酸中加热10h,温度150℃,过滤,去离子水洗涤至pH为6-7,100℃真空干燥3h,自然冷却,研磨后得到氧化碳纳米管;2)将所述氧化碳纳米管加入到乙醇溶液中,再滴加3-胺丙基三乙氧基硅烷,80℃下搅拌2-5h,经Φ0.45μm聚四氟乙烯膜过滤,无水乙醇洗涤,120℃真空干燥,得到改性碳纳米管。
进一步地,所述光固化低聚物包括聚丙烯酸酯、有机硅丙烯酸酯、环氧丙烯酸酯、聚酯丙烯酸酯、聚醚丙烯酸酯和聚氨酯丙烯酸酯中的一种或者组合。
进一步地,所述活性稀释剂为二环戊二烯甲基丙烯酸酯、四氢呋喃甲基丙烯酸酯、二苯氧基乙基丙烯酸酯、甲基丙烯酸异冰片酯、丙烯酸己内酯、环三羟甲基丙烷缩甲醛丙烯酸酯、环己烷二甲醇二丙烯酸酯、聚乙二醇二甲基丙烯酸酯、(丙氧化)新戊二醇二甲基丙烯酸酯、三环癸烷二甲醇二丙烯酸酯、三(2-羟乙基)异氰尿酸三丙烯酸酯、季戊四醇三丙烯酸酯中的至少一种。
进一步地,所述光引发剂为安息香、苯乙酮、联苯酰缩酮、蒽醌、三苯基膦、苯甲酰基氧化膦、双酰基氧化膦、苯甲酮、噻吨酮、氧杂蒽酮、吖啶衍生物、吩嗪衍生物、喹喔啉衍生物、1-苯基-1,2-丙二酮-2-O-苯甲酰肟、4-(2-羟基乙氧基)苯基-(2-丙基)酮、1-氨基苯酮和1-羟基苯酮中的至少一种。
进一步地,所述触变促进剂为聚乙二醇、聚丙二醇、聚四氢呋喃以及气相二氧化硅中的一种或几种。
进一步地,还包括1-10wt%的强度促进剂,所述强度促进剂为羟基官能团丙烯酸酯、羧基官能团丙烯酸酯、环氧基官能团丙烯酸酯中的一种或几种。
进一步地,所述触变促进剂和强度促进剂附着于改性碳纳米管/磷硅酸钙复合粉体的表面。
本发明的有益技术效果如下:
(1)本发明创造性地将独特的改性碳纳米管/磷硅酸钙复合粉体加入3D打印用光敏树脂体系中,不仅赋予光敏树脂合适的触变性,而且光固化后制得的产品高尺寸稳定性、耐高温性、高模量、高硬度、高耐磨性、较好的阻尼性、生物相容性以及极好的抗老化等综合性能,尤其是利用了碳纳米管的杀菌性和磷硅酸钙的生物相容性,使3D打印产品更加适用于医疗领域。
(2)强度促进剂改善改性碳纳米管/磷硅酸钙复合粉体与光敏树脂中的相容性和分散性,提高机械强度,而且协同改性碳纳米管/磷硅酸钙复合粉体以改善光固化材料的触变性---剪切变稀,使得3D打印平台下落时对光固化材料施加的力促使其粘度变小,利于3D打印工艺顺利进行。
(3)本发明的光固化材料能顺利实现SLA/DLP原理的3D打印工艺,制作的产品具有0.1~0.2%的低体积收缩率,机械强度高,韧性好,拉伸强度100~120MPa,弯曲强度在120~130MPa,断裂伸长15~20%,户外耐候性测试六个月,机械性能指标保持在98~100%,可以作为终端产品材料使用。
具体实施方式
为使发明的上述目的、特征和优点能够更加明显易懂,下面对本发明的具体实施方式做详细的说明。
在下面的描述中阐述了很多具体细节以便于充分理解本发明,但是本发明还可以采用其它不同于在此描述的其它方式来实施,本领域技术人员可以在不违背本发明内涵的情况下做类似推广,因此本发明不受下面公开的具体实施例的限制。
根据本发明的用于3D打印的光固化材料按重量百分比包含:
在根据本发明的用于3D打印的光固化材料中,所述改性碳纳米管/磷硅酸钙复合粉体的制备方法可包括以下步骤:1)将硝酸钙、摩尔浓度为0.1-1mol/L的硅酸钠溶液、摩尔浓度为0.1-1mol/L的磷酸氢二胺溶液和改性碳纳米管依次投入反应釜中,重量比为1:10:10:0.1;2)启动反应釜的搅拌装置,计量器以0.5L/min的速度滴加氨水,保持溶液的pH为8-9,并继续搅拌16-17小时,然后过滤去除滤液,并依次用去离子水和无水乙醇充分洗涤残余固体,滤干后再真空100℃烘干,得到胚料;3)将所述胚料放入真空炉中,真空度1Mpa,600-700℃锻烧2-2.5小时,自然冷却后研磨,得到改性碳纳米管/磷硅酸钙复合粉体。
在根据本发明的用于3D打印的光固化材料中,所述改性碳纳米管/磷硅酸钙复合粉体粒径可为1-5μm。
在根据本发明的用于3D打印的光固化材料中,所述改性碳纳米管的制备方法可为:1)将碳纳米管浸入浓硝酸中加热10h,温度150℃,过滤,去离子水洗涤至pH为6-7,100℃真空干燥3h,自然冷却,研磨后得到氧化碳纳米管;2)将所述氧化碳纳米管加入到乙醇溶液中,再滴加3-胺丙基三乙氧基硅烷,80℃下搅拌2-5h,经Φ0.45μm聚四氟乙烯膜过滤,无水乙醇洗涤,120℃真空干燥,得到改性碳纳米管。
在根据本发明的用于3D打印的光固化材料中,所述光固化低聚物可包括聚丙烯酸酯、有机硅丙烯酸酯、环氧丙烯酸酯、聚酯丙烯酸酯、聚醚丙烯酸酯和聚氨酯丙烯酸酯中的一种或者组合。
在根据本发明的用于3D打印的光固化材料中,所述活性稀释剂可为二环戊二烯甲基丙烯酸酯、四氢呋喃甲基丙烯酸酯、二苯氧基乙基丙烯酸酯、甲基丙烯酸异冰片酯、丙烯酸己内酯、环三羟甲基丙烷缩甲醛丙烯酸酯、环己烷二甲醇二丙烯酸酯、聚乙二醇二甲基丙烯酸酯、(丙氧化)新戊二醇二甲基丙烯酸酯、三环癸烷二甲醇二丙烯酸酯、三(2-羟乙基)异氰尿酸三丙烯酸酯、季戊四醇三丙烯酸酯中的至少一种。
在根据本发明的用于3D打印的光固化材料中,所述光引发剂可为安息香、苯乙酮、联苯酰缩酮、蒽醌、三苯基膦、苯甲酰基氧化膦、双酰基氧化膦、苯甲酮、噻吨酮、氧杂蒽酮、吖啶衍生物、吩嗪衍生物、喹喔啉衍生物、1-苯基-1,2-丙二酮-2-O-苯甲酰肟、4-(2-羟基乙氧基)苯基-(2-丙基)酮、1-氨基苯酮和1-羟基苯酮中的至少一种。
在根据本发明的用于3D打印的光固化材料中,还可包括0.1-10wt%的光吸收剂,所述光吸收剂为羟基二苯甲酮、羟苯基苯并三唑、草酰替苯胺、二苯甲酮、羟苯基三嗪或苯并三唑中的至少一种。
在根据本发明的用于3D打印的光固化材料中,所述触变促进剂可为聚乙二醇、聚丙二醇、聚四氢呋喃以及气相二氧化硅中的一种或几种。
在根据本发明的用于3D打印的光固化材料中,还可包括1-
10wt%的强度促进剂,所述强度促进剂为羟基官能团丙烯酸酯、羧基官能团丙烯酸酯、环氧基官能团丙烯酸酯中的一种或几种。
在根据本发明的用于3D打印的光固化材料中,所述触变促进剂和强度促进剂可附着于改性碳纳米管/磷硅酸钙复合粉体的表面。
在根据本发明的用于3D打印的光固化材料中,还可包含0.1-5wt%的抗氧剂,所述抗氧剂为受阻胺、受阻酚中的一种或者组合。
以下,结合具体实施例对本发明的用于3D打印的光固化材料进行具体说明。
实施例一
1)将碳纳米管浸入浓硝酸中加热10h,温度150℃,过滤,
去离子水洗涤至pH为6,100℃真空干燥3h,自然冷却,研磨后得到氧化碳纳米管;2)将所述氧化碳纳米管加入到乙醇溶液中,再滴加3-胺丙基三乙氧基硅烷,80℃下搅拌2h,经Φ0.45μm聚四氟乙烯膜过滤,无水乙醇洗涤,120℃真空干燥,得到改性碳纳米管。
2)将硝酸钙、摩尔浓度为0.1mol/L的硅酸钠溶液、摩尔浓度为0.1mol/L的磷酸氢二胺溶液和改性碳纳米管依次投入反应釜中,重量比为1:10:10:0.1;启动反应釜的搅拌装置,计量器以0.5L/min的速度滴加氨水,保持溶液的pH为8,并继续搅拌16小时,然后过滤去除滤液,并依次用去离子水和无水乙醇充分洗涤残余固体,滤干后再真空100℃烘干,得到胚料;将所述胚料放入真空炉中,真空度1Mpa,600℃锻烧2小时,自然冷却后研磨,得到改性碳纳米管/磷硅酸钙复合粉体。
3)准备以下物料:聚丙烯酸酯20wt%,二环戊二烯甲基丙烯酸酯5wt%,安息香乙醚0.1wt%,聚乙二醇1wt%,丙烯酸羟丙酯1wt%,改性碳纳米管/磷硅酸钙复合粉体20wt%和羟苯基三嗪0.1wt%。
首先,聚乙二醇,丙烯酸羟丙酯和改性碳纳米管/磷硅酸钙复合粉体提前放置于球磨机中进行120℃的球磨,干燥后得到促进剂附着的改性的碳纳米管/磷硅酸钙复合粉体。
最后,按配比在反应釜中混合均匀促进剂改性的碳纳米管/磷硅酸钙复合粉体以及其他原料,逐渐升温至65℃,同时抽真空至负压0.2MPa,于1200转/分钟条件下,分散搅拌2小时,自然冷却和过滤,即得到膏状的到用于3D打印的光固化材料。
实施例二
1)将碳纳米管浸入浓硝酸中加热10h,温度150℃,过滤,去离子水洗涤至pH为7,100℃真空干燥3h,自然冷却,研磨后得到氧化碳纳米管;2)将所述氧化碳纳米管加入到乙醇溶液中,再滴加3-胺丙基三乙氧基硅烷,80℃下搅拌5h,经Φ0.45μm聚四氟乙烯膜过滤,无水乙醇洗涤,120℃真空干燥,得到改性碳纳米管。
2)将硝酸钙、摩尔浓度为1mol/L的硅酸钠溶液、摩尔浓度为1mol/L的磷酸氢二胺溶液和改性碳纳米管依次投入反应釜中,重量比为1:10:10:0.1;启动反应釜的搅拌装置,计量器以0.5L/min的速度滴加氨水,保持溶液的pH为9,并继续搅拌17小时,然后过滤去除滤液,并依次用去离子水和无水乙醇充分洗涤残余固体,滤干后再真空100℃烘干,得到胚料;将所述胚料放入真空炉中,真空度1Mpa,700℃锻烧2.5小时,自然冷却后研磨,得到改性碳纳米管/磷硅酸钙复合粉体。
3)准备以下物料:有机硅丙烯酸酯40wt%,四氢呋喃甲基丙烯酸酯30wt%,苯乙酮1wt%,聚四氢呋喃10wt%,甲基丙烯酸10wt%,改性碳纳米管/磷硅酸钙复合粉体50wt%和苯甲酸(2,
2,6,6-四甲基-4-羟基哌啶)酯5wt%。
首先,聚四氢呋喃,甲基丙烯酸和改性碳纳米管/磷硅酸钙复合粉体提前放置于球磨机中进行120℃的球磨,干燥后得到促进剂附着的改性的碳纳米管/磷硅酸钙复合粉体。
最后,按配比在反应釜中混合均匀促进剂改性的碳纳米管/磷硅酸钙复合粉体以及其他原料,逐渐升温至70℃,同时抽真空至负压0.2MPa,于2000转/分钟条件下,分散搅拌2小时,自然冷却和过滤,即得到膏状的到用于3D打印的光固化材料。
实施例三
1)将碳纳米管浸入浓硝酸中加热10h,温度150℃,过滤,去离子水洗涤至pH为6.5,100℃真空干燥3h,自然冷却,研磨后得到氧化碳纳米管;2)将所述氧化碳纳米管加入到乙醇溶液中,再滴加3-胺丙基三乙氧基硅烷,80℃下搅拌3h,经Φ0.45μm聚四氟乙烯膜过滤,无水乙醇洗涤,120℃真空干燥,得到改性碳纳米管。
2)将硝酸钙、摩尔浓度为0.1-1mol/L的硅酸钠溶液、摩尔浓度为0.5mol/L的磷酸氢二胺溶液和改性碳纳米管依次投入反应釜中,重量比为1:10:10:0.1;启动反应釜的搅拌装置,计量器以0.5L/min的速度滴加氨水,保持溶液的pH为8.5,并继续搅拌16.5小时,然后过滤去除滤液,并依次用去离子水和无水乙醇充分洗涤残余固体,滤干后再真空100℃烘干,得到胚料;将所述胚料放入真空炉中,真空度1Mpa,650℃锻烧2.2小时,自然冷却后研磨,得到改性碳纳米管/磷硅酸钙复合粉体。
3)按配比在反应釜中先依次添加和搅拌混合均匀以下物料:聚醚丙烯酸酯30wt%,聚乙二醇二甲基丙烯酸酯20wt%,1-氨基苯酮0.5wt%,粒径10-20nm的气相二氧化硅5wt%,甲基丙烯酸8wt%和改性碳纳米管/磷硅酸钙复合粉体30wt%;
首先,气相二氧化硅,甲基丙烯酸和改性碳纳米管/磷硅酸钙复合粉体提前放置于球磨机中进行120℃的球磨,干燥后得到促进剂附着的改性的碳纳米管/磷硅酸钙复合粉体。
最后,按配比在反应釜中混合均匀促进剂附着的改性的碳纳米管/磷硅酸钙复合粉体以及其他原料,逐渐升温至70℃,同时抽真空至负压0.2MPa,于2000转/分钟条件下,分散搅拌2小时,自然冷却和过滤,即得到膏状的到用于3D打印的光固化材料。
对比例一
除不包含改性碳纳米管/磷硅酸钙复合粉体以外,其他与实施一相同。
对比例二
除在混合前不提前制备促进剂附着的改性的碳纳米管/磷硅酸钙复合粉体外,而是直接混合各原料,其他具体的工艺参数或步骤与实施例二相同。
对比例三
除不经过任何处理的碳纳米管替换改性碳纳米管/磷硅酸钙复合粉体以外,其他与实施一相同。
性能测试
1、机械性能
分别用上述实施例及对比例所配制的光固化材料,3D打印厚度2mm,长100mm,宽10mm的片状样条,进行按照树脂的标准测试方法测试各项机械性能。
2、杀菌率
将大肠杆菌溶解分散在质量分数为0.9%的氯化钠溶液中制成细菌悬浮液。将样条完全浸没于细菌悬浮液中,置于37℃的恒温培养箱中进行培养24h。再取20μL细菌悬浮液涂布在平板培养基上,将平板培养基37℃培养24h,对平板上的菌落进行计数,计算得出杀菌率。参照HG/T3950-2007进行抗菌率测试,供试菌种为大肠杆菌。
性能测试结果如下表所示:
从表中可以看出,实施例相比对比例具有更好的综合性能,如较好的机械性能,较小的收缩率、耐候性以及杀菌性。
上述实施例为本发明较佳的实施方式,但本发明的实施方式并不受上述实施例的限制,其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化,均应为等效的置换方式,都包含在本发明的保护范围之内。
Claims (4)
1.一种用于3D打印的光固化材料,其特征在于,按重量百分比,包含:
所述改性碳纳米管/磷硅酸钙复合粉体的制备方法包括以下步骤:
1)将硝酸钙、摩尔浓度为0.1-1mol/L的硅酸钠溶液、摩尔浓度为0.1-1mol/L的磷酸氢二胺溶液和改性碳纳米管依次投入反应釜中,重量比为1:10:10:0.1;
2)启动反应釜的搅拌装置,计量器以0.5L/min的速度滴加氨水,保持溶液的pH为8-9,并继续搅拌16-17小时,然后过滤去除滤液,并依次用去离子水和无水乙醇充分洗涤残余固体,滤干后再真空100℃烘干,得到胚料;
3)将所述胚料放入真空炉中,真空度1Mpa,600-700℃锻烧2-2.5小时,自然冷却后研磨,得到改性碳纳米管/磷硅酸钙复合粉体;
所述改性碳纳米管/磷硅酸钙复合粉体粒径为1-5μm;
所述改性碳纳米管的制备方法为:1)将碳纳米管浸入浓硝酸中加热10h,温度150℃,过滤,去离子水洗涤至pH为6-7,100℃真空干燥3h,自然冷却,研磨后得到氧化碳纳米管;2)将所述氧化碳纳米管加入到乙醇溶液中,再滴加3-胺丙基三乙氧基硅烷,80℃下搅拌2-5h,经Φ0.45μm聚四氟乙烯膜过滤,无水乙醇洗涤,120℃真空干燥,得到改性碳纳米管;
所述触变促进剂为聚乙二醇、聚丙二醇、聚四氢呋喃以及气相二氧化硅中的一种或几种;
所述强度促进剂为羟基官能团丙烯酸酯、甲基丙烯酸、环氧基官能团丙烯酸酯中的一种或几种;
原料在混合前将触变促进剂、强度促进剂和改性碳纳米管/磷硅酸钙复合粉体提前球磨得到所述触变促进剂和强度促进剂附着的改性碳纳米管/磷硅酸钙复合粉体。
2.根据权利要求1所述的用于3D打印的光固化材料,其特征在于,所述光固化低聚物包括有机硅丙烯酸酯、环氧丙烯酸酯、聚酯丙烯酸酯、聚醚丙烯酸酯和聚氨酯丙烯酸酯中的一种或者组合。
3.根据权利要求1所述的用于3D打印的光固化材料,其特征在于,所述活性稀释剂为二环戊二烯甲基丙烯酸酯、四氢呋喃甲基丙烯酸酯、二苯氧基乙基丙烯酸酯、甲基丙烯酸异冰片酯、丙烯酸己内酯、环三羟甲基丙烷缩甲醛丙烯酸酯、环己烷二甲醇二丙烯酸酯、聚乙二醇二甲基丙烯酸酯、(丙氧化)新戊二醇二甲基丙烯酸酯、三环癸烷二甲醇二丙烯酸酯、三(2-羟乙基)异氰尿酸三丙烯酸酯、季戊四醇三丙烯酸酯中的至少一种。
4.根据权利要求1所述的用于3D打印的光固化材料,其特征在于,所述光引发剂为安息香、苯乙酮、联苯酰缩酮、蒽醌、三苯基膦、苯甲酰基氧化膦、双酰基氧化膦、苯甲酮、噻吨酮、氧杂蒽酮、吖啶衍生物、吩嗪衍生物、喹喔啉衍生物、1-苯基-1,2-丙二酮-2-O-苯甲酰肟、4-(2-羟基乙氧基)苯基-(2-丙基)酮、1-氨基苯酮和1-羟基苯酮中的至少一种。
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