CN107641200B - Thiol-ene photocuring resin for 3D printing and preparation method thereof - Google Patents
Thiol-ene photocuring resin for 3D printing and preparation method thereof Download PDFInfo
- Publication number
- CN107641200B CN107641200B CN201710857929.XA CN201710857929A CN107641200B CN 107641200 B CN107641200 B CN 107641200B CN 201710857929 A CN201710857929 A CN 201710857929A CN 107641200 B CN107641200 B CN 107641200B
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- Prior art keywords
- printing
- resin
- thiol
- ene
- acrylic resin
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- 239000011347 resin Substances 0.000 title claims abstract description 61
- 229920005989 resin Polymers 0.000 title claims abstract description 61
- OXBLVCZKDOZZOJ-UHFFFAOYSA-N 2,3-Dihydrothiophene Chemical compound C1CC=CS1 OXBLVCZKDOZZOJ-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000010146 3D printing Methods 0.000 title claims abstract description 26
- 238000000016 photochemical curing Methods 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 20
- 229920000178 Acrylic resin Polymers 0.000 claims abstract description 19
- 229920006295 polythiol Polymers 0.000 claims abstract description 17
- 239000003085 diluting agent Substances 0.000 claims abstract description 7
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 6
- 239000003999 initiator Substances 0.000 claims abstract description 6
- 239000000945 filler Substances 0.000 claims abstract description 5
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims description 10
- 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 10
- 238000003756 stirring Methods 0.000 claims description 10
- 239000002518 antifoaming agent Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 6
- 125000003396 thiol group Chemical class [H]S* 0.000 claims description 6
- 238000009736 wetting Methods 0.000 claims description 6
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 5
- 244000028419 Styrax benzoin Species 0.000 claims description 5
- 235000000126 Styrax benzoin Nutrition 0.000 claims description 5
- 235000008411 Sumatra benzointree Nutrition 0.000 claims description 5
- 229960002130 benzoin Drugs 0.000 claims description 5
- 235000019382 gum benzoic Nutrition 0.000 claims description 5
- 229920000570 polyether Polymers 0.000 claims description 5
- 239000004814 polyurethane Substances 0.000 claims description 5
- 229920002635 polyurethane Polymers 0.000 claims description 5
- -1 tetra (3-mercaptobutanoic acid) pentaerythritol ester Chemical class 0.000 claims description 5
- DXGLGDHPHMLXJC-UHFFFAOYSA-N oxybenzone Chemical compound OC1=CC(OC)=CC=C1C(=O)C1=CC=CC=C1 DXGLGDHPHMLXJC-UHFFFAOYSA-N 0.000 claims description 4
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 claims description 3
- 239000011258 core-shell material Substances 0.000 claims description 3
- 229920001971 elastomer Polymers 0.000 claims description 3
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 229920002545 silicone oil Polymers 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 16
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 239000002250 absorbent Substances 0.000 abstract description 5
- 230000002745 absorbent Effects 0.000 abstract description 5
- 238000004132 cross linking Methods 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000001723 curing Methods 0.000 abstract description 4
- 239000000178 monomer Substances 0.000 abstract description 4
- 238000007639 printing Methods 0.000 abstract description 4
- 230000005764 inhibitory process Effects 0.000 abstract description 3
- 238000006116 polymerization reaction Methods 0.000 abstract description 3
- 230000036632 reaction speed Effects 0.000 abstract description 3
- 238000000465 moulding Methods 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract description 2
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 238000006276 transfer reaction Methods 0.000 abstract 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 abstract 1
- 229920002554 vinyl polymer Polymers 0.000 abstract 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 11
- 238000000034 method Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 229920000728 polyester Polymers 0.000 description 5
- INQDDHNZXOAFFD-UHFFFAOYSA-N 2-[2-(2-prop-2-enoyloxyethoxy)ethoxy]ethyl prop-2-enoate Chemical compound C=CC(=O)OCCOCCOCCOC(=O)C=C INQDDHNZXOAFFD-UHFFFAOYSA-N 0.000 description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- JOBBTVPTPXRUBP-UHFFFAOYSA-N [3-(3-sulfanylpropanoyloxy)-2,2-bis(3-sulfanylpropanoyloxymethyl)propyl] 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(COC(=O)CCS)(COC(=O)CCS)COC(=O)CCS JOBBTVPTPXRUBP-UHFFFAOYSA-N 0.000 description 4
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 4
- 239000012965 benzophenone Substances 0.000 description 4
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 description 4
- WZRRRFSJFQTGGB-UHFFFAOYSA-N 1,3,5-triazinane-2,4,6-trithione Chemical compound S=C1NC(=S)NC(=S)N1 WZRRRFSJFQTGGB-UHFFFAOYSA-N 0.000 description 3
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000007822 coupling agent Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- VYMPLPIFKRHAAC-UHFFFAOYSA-N 1,2-ethanedithiol Chemical compound SCCS VYMPLPIFKRHAAC-UHFFFAOYSA-N 0.000 description 2
- PGTWZHXOSWQKCY-UHFFFAOYSA-N 1,8-Octanedithiol Chemical compound SCCCCCCCCS PGTWZHXOSWQKCY-UHFFFAOYSA-N 0.000 description 2
- GJRCLMJHPWCJEI-UHFFFAOYSA-N 1,9-Nonanedithiol Chemical compound SCCCCCCCCCS GJRCLMJHPWCJEI-UHFFFAOYSA-N 0.000 description 2
- 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 description 2
- TWWSEEHCVDRRRI-UHFFFAOYSA-N 2,3-Butanedithiol Chemical compound CC(S)C(C)S TWWSEEHCVDRRRI-UHFFFAOYSA-N 0.000 description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- CEXQWAAGPPNOQF-UHFFFAOYSA-N 2-phenoxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOC1=CC=CC=C1 CEXQWAAGPPNOQF-UHFFFAOYSA-N 0.000 description 2
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- NIAAGQAEVGMHPM-UHFFFAOYSA-N 4-methylbenzene-1,2-dithiol Chemical compound CC1=CC=C(S)C(S)=C1 NIAAGQAEVGMHPM-UHFFFAOYSA-N 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- VTLHIRNKQSFSJS-UHFFFAOYSA-N [3-(3-sulfanylbutanoyloxy)-2,2-bis(3-sulfanylbutanoyloxymethyl)propyl] 3-sulfanylbutanoate Chemical compound CC(S)CC(=O)OCC(COC(=O)CC(C)S)(COC(=O)CC(C)S)COC(=O)CC(C)S VTLHIRNKQSFSJS-UHFFFAOYSA-N 0.000 description 2
- DBHQYYNDKZDVTN-UHFFFAOYSA-N [4-(4-methylphenyl)sulfanylphenyl]-phenylmethanone Chemical compound C1=CC(C)=CC=C1SC1=CC=C(C(=O)C=2C=CC=CC=2)C=C1 DBHQYYNDKZDVTN-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000001023 inorganic pigment Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000005543 nano-size silicon particle Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000012860 organic pigment Substances 0.000 description 2
- 239000000049 pigment Substances 0.000 description 2
- ZJLMKPKYJBQJNH-UHFFFAOYSA-N propane-1,3-dithiol Chemical compound SCCCS ZJLMKPKYJBQJNH-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 235000010215 titanium dioxide Nutrition 0.000 description 2
- 229920006305 unsaturated polyester Polymers 0.000 description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 1
- IYAZLDLPUNDVAG-UHFFFAOYSA-N 2-(benzotriazol-2-yl)-4-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 IYAZLDLPUNDVAG-UHFFFAOYSA-N 0.000 description 1
- 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
- 229960000549 4-dimethylaminophenol Drugs 0.000 description 1
- CNGYZEMWVAWWOB-VAWYXSNFSA-N 5-[[4-anilino-6-[bis(2-hydroxyethyl)amino]-1,3,5-triazin-2-yl]amino]-2-[(e)-2-[4-[[4-anilino-6-[bis(2-hydroxyethyl)amino]-1,3,5-triazin-2-yl]amino]-2-sulfophenyl]ethenyl]benzenesulfonic acid Chemical compound N=1C(NC=2C=C(C(\C=C\C=3C(=CC(NC=4N=C(N=C(NC=5C=CC=CC=5)N=4)N(CCO)CCO)=CC=3)S(O)(=O)=O)=CC=2)S(O)(=O)=O)=NC(N(CCO)CCO)=NC=1NC1=CC=CC=C1 CNGYZEMWVAWWOB-VAWYXSNFSA-N 0.000 description 1
- LVGFPWDANALGOY-UHFFFAOYSA-N 8-methylnonyl prop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C=C LVGFPWDANALGOY-UHFFFAOYSA-N 0.000 description 1
- DAXREOFYACZDJD-UHFFFAOYSA-N C(C)C1=CC=2C(C3=CC=CC=C3SC2C(=C1)CC)=O.C1(=CC=CC=C1)[PH2]=O Chemical compound C(C)C1=CC=2C(C3=CC=CC=C3SC2C(=C1)CC)=O.C1(=CC=CC=C1)[PH2]=O DAXREOFYACZDJD-UHFFFAOYSA-N 0.000 description 1
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 1
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 1
- 125000005118 N-alkylcarbamoyl group Chemical group 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- NRCMAYZCPIVABH-UHFFFAOYSA-N Quinacridone Chemical compound N1C2=CC=CC=C2C(=O)C2=C1C=C1C(=O)C3=CC=CC=C3NC1=C2 NRCMAYZCPIVABH-UHFFFAOYSA-N 0.000 description 1
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- ZWOASCVFHSYHOB-UHFFFAOYSA-N benzene-1,3-dithiol Chemical compound SC1=CC=CC(S)=C1 ZWOASCVFHSYHOB-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- UXWSUTBOOHDZIL-UHFFFAOYSA-N bis(1-hydroxycyclohexyl)methanone Chemical compound C1CCCCC1(O)C(=O)C1(O)CCCCC1 UXWSUTBOOHDZIL-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000010759 carbon-sulfur bond forming reactions Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- XCJYREBRNVKWGJ-UHFFFAOYSA-N copper(II) phthalocyanine Chemical compound [Cu+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 XCJYREBRNVKWGJ-UHFFFAOYSA-N 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000006081 fluorescent whitening agent Substances 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- MOUPNEIJQCETIW-UHFFFAOYSA-N lead chromate Chemical compound [Pb+2].[O-][Cr]([O-])(=O)=O MOUPNEIJQCETIW-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- YDKNBNOOCSNPNS-UHFFFAOYSA-N methyl 1,3-benzoxazole-2-carboxylate Chemical compound C1=CC=C2OC(C(=O)OC)=NC2=C1 YDKNBNOOCSNPNS-UHFFFAOYSA-N 0.000 description 1
- RZFODFPMOHAYIR-UHFFFAOYSA-N oxepan-2-one;prop-2-enoic acid Chemical compound OC(=O)C=C.O=C1CCCCCO1 RZFODFPMOHAYIR-UHFFFAOYSA-N 0.000 description 1
- FSDNTQSJGHSJBG-UHFFFAOYSA-N piperidine-4-carbonitrile Chemical compound N#CC1CCNCC1 FSDNTQSJGHSJBG-UHFFFAOYSA-N 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 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
- 238000000746 purification Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 229940116351 sebacate Drugs 0.000 description 1
- CXMXRPHRNRROMY-UHFFFAOYSA-L sebacate(2-) Chemical compound [O-]C(=O)CCCCCCCCC([O-])=O CXMXRPHRNRROMY-UHFFFAOYSA-L 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C08F283/10—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule
- C08F283/105—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers containing more than one epoxy radical per molecule on to unsaturated polymers containing more than one epoxy radical per molecule
-
- 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
-
- 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
-
- 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
-
- 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
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
- C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
-
- 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
- C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
-
- 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
-
- 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/34—Introducing sulfur atoms or sulfur-containing groups
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
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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)
- Ceramic Engineering (AREA)
- Civil Engineering (AREA)
- Composite Materials (AREA)
- Structural Engineering (AREA)
- Manufacturing & Machinery (AREA)
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Abstract
The invention relates to the technical field of 3D printing, in particular to mercaptan-alkene photocuring resin for 3D printing and a preparation method thereof. The thiol-ene photocuring resin for 3D printing is prepared from polythiol, an acrylic resin prepolymer, a reactive diluent, an initiator, an ultraviolet absorbent, a filler and an auxiliary agent. The 3D printing light-cured resin has the advantages that in the presence of a photoinitiator, when printing, polymerizing and molding are carried out, the volume shrinkage of a polymer is reduced due to the chain transfer reaction between double bonds and sulfydryl, oxygen-free polymerization inhibition is realized, the crosslinking degree and the reaction speed can be controlled according to different vinyl monomers, a small amount of photoinitiator is used, and the like. According to the invention, through introducing thiol-ene click chemical reaction into the 3D printing resin, the curing time can be shortened, the toughness and hardness of the 3D printing material can be improved, the production efficiency is improved, and the energy utilization rate is greatly improved.
Description
Technical Field
The invention relates to the technical field of 3D printing, in particular to mercaptan-alkene photocuring resin for 3D printing and a preparation method thereof.
Background
Thiol-ene click chemistry describes the chemical reaction process visually as simple, efficient, practical as clicking a mouse, and is characterized by: (1) the reaction raw materials are easy to obtain, and the monomer has wide application range; (2) the method has high thermodynamic driving force and high reaction speed; (3) the reaction condition is simple and mild, and is hardly influenced by external environment (oxygen, water and the like); (4) no solvent is needed or the used solvent is easy to separate; (5) the yield is high, and the regularity of the product is good; (6) the product separation and purification method is simple. Click chemistry can utilize a series of efficient and reliable and selective C-S bond forming reactions to realize atomic connection, and carry out modular preparation of novel high-performance and functional polymers, so that the click chemistry has wide application as a connecting tool in the fields of organic synthesis, material science, molecular biology, biotechnology, high molecular synthesis and the like.
3D prints and is honored as the industrial revolution once more that overturns traditional manufacturing, and 3D printing technique utilizes the computer, turns into simple two-dimensional plane model with three-dimensional solid model, through computer control shaping procedure, finally obtains the manufacturing technology of the forming part of complicated shape. At present, dozens of rapid forming technologies exist, wherein the photocuring rapid forming technology is the earliest rapid forming technology, photosensitive resin is used as a material, and the characteristics of the resin directly influence the performance of a workpiece, the manufacturing time, the final precision of the part and the like. Currently, photosensitive resins are classified into 3 types: radical photosensitive resin, cationic photosensitive resin, and hybrid photosensitive resin. The traditional photosensitive resins can generate volume shrinkage in the photopolymerization process, directly affect the performance of a workpiece, cause the reduction of the properties such as adhesive force, hardness and the like, prolong the manufacturing time, affect the precision of the workpiece and cause serious oxygen inhibition.
Aiming at the technical problems in the prior art, providing a photosensitive resin material with new performance is a problem to be solved urgently.
Disclosure of Invention
In order to solve the problems in the prior art, the present invention provides a novel photosensitive resin for 3D printing technology: the thiol-ene photosensitive resin for 3D printing is prepared from polythiol, an acrylic resin prepolymer, a reactive diluent, an initiator, an ultraviolet absorbent, a filler and an auxiliary agent.
In a preferred embodiment, the thiol-ene photocurable resin is prepared according to the following mixture ratio:
the thiol-ene photocurable resin of the present invention includes at least one polythiol. The polythiol is an organic molecule containing at least two mercapto groups and having the general formula R- (S-H)n1Wherein R is an organic moiety having a valence n1, and n1 is at least 2.
The polythiol can be polymerized or crosslinked with the acrylate by irradiation with light in the presence of an initiator. The polythiol can include 2 or more thiol groups.
An illustrative example of a polythiol having 2 or more mercapto groups in the molecule is represented by the following formulae (1) (2) (3) (4):
compounds containing 2 or more thiol groups in the molecule are: 1, 2-ethanedithiol, 1, 3-propanedithiol, 1, 8-octanedithiol, 2, 3-butanedithiol, 1, 9-nonanedithiol, 2,2 '- (1, 2-ethanediylbenzoyloxy) bisethanethiol, pentaerythritol tetrakis (3-mercaptopropionate), mercaptosilicone oils, isophthalylthiol, 1, 4-benzenedimethylmercaptan, 4-methyl-1, 2-dimercaptobenzene, 4, 4' -thiobisthiophenol, 2,4, 6-trimercaptotriazine, pentaerythritol tetrakis (3-mercaptobutyrate). Such compounds may be used alone or in combination of two or more.
The functionality of the polythiol, the type and number of R groups, and the degree of crosslinking, hardness and flexibility of the material can be adjusted.
For example, when preparing high hardness, high stiffness materials, the preferred R groups are aryl, alkyl, N-alkylcarbamoyl. Preferred polythiols include m-benzenedithiol, 1, 4-benzenedimethylthiol, 4, 4' -thiobisthiophenol, 4-methyl-1, 2-dimercaptobenzene, 2,4, 6-trimercaptotriazine, and the like.
In the preparation of highly flexible, high toughness materials, the preferred R groups are polyether groups, alkoxy groups, straight chain alkyl groups, siloxane groups. Preferred polythiols include, 1, 2-ethanedithiol, 1, 3-propanedithiol, 1, 8-octanedithiol, 2, 3-butanedithiol, 1, 9-nonanedithiol, 2,2' - (1, 2-ethanediylberoxy) bisethanethiol, pentaerythritol tetrakis (3-mercaptopropionate), mercaptosilicone oils, pentaerythritol tetrakis (3-mercaptobutyrate), and the like.
The thiol-ene photosensitive resin preferably includes at least one polythiol, and about 5 to 30 parts by weight, more preferably about 10 to 20 parts by weight, of the polythiol, relative to the total weight of the composition.
The thiol-ene photocurable resin of the present invention includes at least one acrylic oligomer. The acrylic resin prepolymer in the thiol-ene light-cured resin forms the main component of the light-cured resin system, and the performance of the acrylic resin prepolymer greatly determines the main performance of the cured material. Generally, a prepolymer has a large molecular weight, and when cured, the volume shrinkage is small, and the curing speed is high, but the prepolymer has a large molecular weight, and the viscosity is high, so that more monomer dilution is required, and the high viscosity of the system affects the forming accuracy and forming efficiency of the 3D printing technology. Therefore, the choice of the prepolymer and its content is particularly important. The acrylic resin oligomer in the thiol-ene photosensitive resin comprises one or more of epoxy acrylic resin, polyester acrylic resin, polyurethane acrylic resin, unsaturated polyester, organic silicon acrylate prepolymer and polyether acrylic resin.
In the present invention, when a high-hardness, high-rigidity material is produced, epoxy acrylic resin, polyester acrylic resin and unsaturated polyester are preferable. In the preparation of a high-flexibility and high-toughness material, polyurethane acrylic resin, silicone acrylic resin and polyether acrylic resin are preferred.
The thiol-ene photosensitive resin preferably includes at least one acrylic oligomer in an amount of about 10 to about 60 parts by weight, more preferably about 20 to about 50 parts by weight, relative to the total weight of the composition.
The thiol-ene photocurable resin of the present invention includes at least one reactive diluent. Preferably, the reactive diluent is one or more of hydroxyethyl acrylate, hydroxyethyl methacrylate, caprolactone acrylate, isodecyl acrylate, polyethylene glycol monoacrylate, 2-phenoxyethyl methacrylate, 1, 6-hexanediol diacrylate, dipropylene glycol diacrylate, dicyclopentadiene (meth) acrylate, triethylene glycol diacrylate, propoxylated neopentyl glycol diacrylate, pentachlorophenyl (meth) acrylate, trimethylolpropane triacrylate and pentaerythritol triacrylate, dipentaerythritol tetraacrylate, EO-modified bisphenol A di (meth) acrylate, PO-modified bisphenol A di (meth) acrylate, in an amount of about 5 to 40 parts by weight, more preferably about 10 to 35 parts by weight, relative to the total weight of the composition.
The thiol-ene photocurable resin of the present invention contains an initiator including one or more of benzoin dimethyl ether (DMAP), 2-hydroxy-2-methyl-1-phenyl-1-propanone, 1-hydroxycyclohexyl ketone, 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide, bis (2,4,6, -trimethylbenzoyl) phenylphosphine oxide 2, 4-diethylthioxanthone, benzophenone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropanone-1, and 4-benzoyl-4' -methyldiphenylsulfide. About 0.1 to 10 parts by weight, more preferably about 0.5 to 6 parts by weight, based on the total weight of the composition.
The thiol-ene photosensitive resin of the present invention includes at least one ultraviolet absorber. The curing depth of the 3D photosensitive resin can be adjusted through the using amount of the ultraviolet absorber, so that the precision of the resin curing material is adjusted. The ultraviolet absorbent comprises one or more of 2-hydroxy-4-n-neoxy benzophenone, 2-hydroxy-4-methoxy-5-sulfonic acid benzophenone, 2- (2 '-hydroxy-5' -tert-octylphenyl) benzotriazole and bis (2,2,6, 6-pentamethyl-4-piperidyl) sebacate. About 0.01 to about 1 part by weight, more preferably about 0.1 to about 0.5 part by weight, relative to the total weight of the composition.
The mercaptan-alkene light-cured resin comprises a filler, preferably comprises one or more of superfine calcium carbonate, superfine silicon dioxide, talcum powder and nano core-shell rubber. About 0.5 to 8 parts by weight, more preferably about 1 to 5 parts by weight, based on the total weight of the composition.
The auxiliary agent contained in the thiol-ene photocurable resin of the present invention preferably includes one or more of a coupling agent, a polymerization inhibitor, a leveling agent, a defoaming agent, a fluorescent brightener, a wetting dispersant or a pigment, and the coupling agent is preferably KH-560 or KH-570. The pigment comprises an inorganic pigment and an organic pigment, wherein the inorganic pigment is one of titanium white, lithopone, lead chrome yellow and iron blue; the organic pigment is one of red powder, azo yellow, phthalocyanine blue and quinacridone. The auxiliary agent is preferably 0.1 to 3 parts by weight, and more preferably 0.2 to 4 parts by weight.
The invention introduces a new polymerization mechanism in the 3D printing photosensitive resin: thiol-ene click chemistry has the advantages of high reaction speed, no oxygen inhibition and no solvent, and the crosslinking degree, hardness and flexibility of the material can be adjusted through different functionalities and substituent groups R.
Correspondingly, the invention also provides a preparation method of the thiol-ene photocuring resin for 3D printing, which comprises the following steps: and mixing the polythiol, the acrylate prepolymer, the reactive diluent, the initiator, the ultraviolet absorbent, the filler and the auxiliary agent, and stirring at 20-60 ℃ for 30-120 minutes to obtain the thiol-ene photocuring 3D printing material. Wherein the stirring temperature is preferably 30-50 ℃, and more preferably 30-40 ℃; the stirring time is preferably 40 to 100 minutes, and more preferably 50 to 90 minutes.
The thiol-ene photocuring resin for 3D printing introduces thiol-ene click chemistry into 3D photocuring printing, has simple, convenient and efficient thiol-ene click chemistry, produces no or harmless by-products in the reaction process, is easy to apply, can be rapidly carried out at room temperature, can accurately control the reaction by selecting an exposure area and time, is applied to the field of 3D photocuring printing, provides a novel 3D photocuring reaction mode, and can control the hardness, strength and toughness of materials by selecting and proportioning the types of polythiol and acrylate.
For further understanding of the present invention, the following embodiments are provided to illustrate the technical solutions of the present invention in detail, and the scope of the present invention is not limited by the following embodiments.
Detailed Description
The raw materials adopted in the embodiment of the invention are all commercially available.
Example 1
The thiol-ene photocuring resin can be applied to 3D printing, and comprises the following components in percentage by mass: 13 percent of 1, 4-benzenedimethylmercaptan, 12 percent of pentaerythritol tetrakis (3-mercaptopropionate), 15 percent of epoxy acrylate, 21 percent of polyester acrylate, 20 percent of dicyclopentadiene (methyl) acrylate, 10 percent of hydroxyethyl acrylate, 3 percent of benzoin dimethyl ether, 5 percent of nano silicon dioxide, 0.1 percent of 2-hydroxy-4-methoxybenzophenone, 0.2 percent of defoaming agent, 0.3 percent of wetting dispersant, 0.2 percent of flatting agent and 0.2 percent of KH-560 coupling agent. Stirring temperature is 25 ℃, and stirring time is 90 min.
Example 2
The thiol-ene photocuring resin can be applied to 3D printing, and comprises the following components in percentage by mass: 20% of mercapto silicone oil, 6% of tetra (3-mercaptobutanoic acid) pentaerythritol ester, 15% of polyether acrylic resin, 15% of polyurethane acrylic resin, 30% of 1, 6-hexanediol diacrylate, 5% of benzoin dimethyl ether, 8% of nano core-shell rubber, 0.1% of 2-hydroxy-4-methoxybenzophenone, 0.3% of defoaming agent, 0.3% of wetting dispersant and 0.3% of flatting agent. Stirring at 30 deg.C for 60 min.
Example 3
The thiol-ene photocuring resin can be applied to 3D printing, and comprises the following components in percentage by mass: 10% of 4, 4' -thiobisthiophenol, 12.85% of 2,4, 6-trimercapto triazine, 20% of polyester acrylate, 15% of epoxy acrylate, 15% of dipentaerythritol tetraacrylate, 20% of 2-phenoxyethyl methacrylate, 4% of 2-hydroxy-2-methyl-1-phenyl-1-acetone, 2% of superfine calcium carbonate, 0.2% of 2-hydroxy-4-methoxy-5-sulfonic acid benzophenone, 0.3% of defoaming agent, 0.3% of wetting dispersant, 0.3% of flatting agent and 0.05% of fluorescent whitening agent. Stirring temperature is 40 ℃, and stirring time is 90 min.
Example 4
The thiol-ene photocuring resin can be applied to 3D printing, and comprises the following components in percentage by mass: 20% of pentaerythritol tetra (3-mercaptopropionate), 8% of polyurethane acrylate, 10% of epoxy acrylate, 20% of polyester acrylate, 15.7% of triethylene glycol diacrylate, 18% of dipentaerythritol tetraacrylate, 1% of 4-benzoyl-4' -methyl diphenyl sulfide, 3% of benzoin dimethyl ether, 3% of nano silicon dioxide, 0.2% of 2-hydroxy-4-methoxy benzophenone, 0.3% of defoaming agent, 0.3% of wetting dispersant, 0.3% of flatting agent and 0.2% of titanium white. Stirring at 30 deg.C for 100 min.
The following table 1 shows thiol-ene photocurable resins obtained by changing the component ratios according to the method of example 1:
the properties of the photocurable resins prepared in examples 1-9 of the present invention were measured, respectively, and the results are shown in table 2.
Table 2 results of measuring properties of thiol-ene 3D printing photocurable resins prepared in examples 1 to 9
From the test results given in the table above it can be seen that:
the product prepared from the thiol-ene photocuring resin obtained in the example 1 has the characteristics of high strength and high hardness.
The thiol-ene photocurable resin obtained in example 2 is characterized by high toughness, low viscosity, high flexibility, soft touch and high impact strength.
The product prepared from the thiol-ene photocuring resin obtained in the embodiment 3 has the characteristics of high hardness, high strength, excellent toughness and impact strength, and good comprehensive performance.
The thiol-ene photocurable resin obtained in example 4 can be used to prepare articles with high toughness, high impact, and excellent hardness and impact strength.
The thiol-ene photocurable resin obtained in example 5 has a higher resin viscosity due to a higher epoxy acrylate resin content. The articles prepared from the resin are characterized by high strength and high stiffness, have acceptable impact strength, but are inferior to examples 1-4.
The thiol-ene photocurable resin obtained in example 6 contains a higher proportion of reactive diluent, the viscosity of the resin is lower, but the higher proportion of monomer results in a great reduction in the strength of the material. Meanwhile, because the content of the ultraviolet absorbent is higher, the hardness of the product prepared by the resin is reduced.
The thiol-ene photocuring resin obtained in example 7 has a higher proportion of polythiol, and beyond the preferable range, the resin can be used for preparing products with higher crosslinking degree, and polymers contain more ester bond groups, and have high hardness and high strength, but lower toughness and impact strength.
The thiol-ene photocuring resin obtained in example 8 has a low polythiol proportion, is lower than the preferred range, and can be used for preparing products with low crosslinking degree and low material strength and hardness.
The thiol-ene photocurable resin obtained in example 9 has a high ratio of acrylic oligomer, and if the ratio is outside the preferable range, the viscosity of the resin is high, which is not favorable for printing and molding, and has a large influence on the accuracy of the cured resin.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
Claims (2)
1. The thiol-ene photocuring resin can be applied to 3D printing, and comprises the following components in percentage by mass: 20% of mercapto silicone oil, 6% of tetra (3-mercaptobutanoic acid) pentaerythritol ester, 15% of polyether acrylic resin, 15% of polyurethane acrylic resin, 30% of 1, 6-hexanediol diacrylate, 5% of benzoin dimethyl ether, 8% of nano core-shell rubber, 0.1% of 2-hydroxy-4-methoxybenzophenone, 0.3% of defoaming agent, 0.3% of wetting dispersant and 0.3% of flatting agent.
2. A preparation method of thiol-ene photocuring resin for 3D printing is characterized by comprising the following steps:
mixing the polythiol, the acrylic resin prepolymer, the reactive diluent, the initiator, the ultraviolet absorber, the filler and the auxiliary agent in the mass ratio, and stirring at a high speed for 30-120 minutes at 20-50 ℃ to obtain the thiol-ene photocuring resin for 3D printing.
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| Publication number | Publication date |
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| CN107641200A (en) | 2018-01-30 |
| CN112358580A (en) | 2021-02-12 |
| CN112358580B (en) | 2023-05-16 |
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