CN113651920B - Acrylic liquid crystal photosensitive resin-based composition and application thereof in 405nm3D printing - Google Patents
Acrylic liquid crystal photosensitive resin-based composition and application thereof in 405nm3D printing Download PDFInfo
- Publication number
- CN113651920B CN113651920B CN202111145723.7A CN202111145723A CN113651920B CN 113651920 B CN113651920 B CN 113651920B CN 202111145723 A CN202111145723 A CN 202111145723A CN 113651920 B CN113651920 B CN 113651920B
- Authority
- CN
- China
- Prior art keywords
- liquid crystal
- acrylic
- photosensitive resin
- parts
- resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000011347 resin Substances 0.000 title claims abstract description 77
- 229920005989 resin Polymers 0.000 title claims abstract description 77
- 239000004973 liquid crystal related substance Substances 0.000 title claims abstract description 70
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 239000000203 mixture Substances 0.000 title claims abstract description 32
- 238000007639 printing Methods 0.000 title abstract description 12
- 239000003085 diluting agent Substances 0.000 claims abstract description 23
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 15
- 239000002518 antifoaming agent Substances 0.000 claims abstract description 14
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 9
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 9
- 229920002635 polyurethane Polymers 0.000 claims abstract description 9
- 239000004814 polyurethane Substances 0.000 claims abstract description 9
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 8
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 8
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 5
- 239000000047 product Substances 0.000 claims description 25
- -1 acrylic ester Chemical class 0.000 claims description 18
- 238000010146 3D printing Methods 0.000 claims description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 238000001723 curing Methods 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 8
- 239000003822 epoxy resin Substances 0.000 claims description 8
- 229920000647 polyepoxide Polymers 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 239000003112 inhibitor Substances 0.000 claims description 5
- 238000000016 photochemical curing Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 4
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 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
- HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 claims description 4
- 235000010354 butylated hydroxytoluene Nutrition 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 239000013530 defoamer Substances 0.000 claims description 4
- GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 claims description 4
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 4
- SHFJWMWCIHQNCP-UHFFFAOYSA-M hydron;tetrabutylazanium;sulfate Chemical compound OS([O-])(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC SHFJWMWCIHQNCP-UHFFFAOYSA-M 0.000 claims description 4
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical compound OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 claims description 4
- 238000003756 stirring Methods 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
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 claims description 4
- 229960000834 vinyl ether Drugs 0.000 claims description 4
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 3
- PUGOMSLRUSTQGV-UHFFFAOYSA-N 2,3-di(prop-2-enoyloxy)propyl prop-2-enoate Chemical compound C=CC(=O)OCC(OC(=O)C=C)COC(=O)C=C PUGOMSLRUSTQGV-UHFFFAOYSA-N 0.000 claims description 3
- HRPUANCEDYZMFT-UHFFFAOYSA-N 2-(1-hydroxycyclohexyl)-1-phenylethanone Chemical compound C=1C=CC=CC=1C(=O)CC1(O)CCCCC1 HRPUANCEDYZMFT-UHFFFAOYSA-N 0.000 claims description 3
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 3
- 229920000178 Acrylic resin Polymers 0.000 claims description 3
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 3
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 3
- DYUMLJSJISTVPV-UHFFFAOYSA-N phenyl propanoate Chemical compound CCC(=O)OC1=CC=CC=C1 DYUMLJSJISTVPV-UHFFFAOYSA-N 0.000 claims description 3
- 229920000570 polyether Polymers 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- LWNGJAHMBMVCJR-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenoxy)boronic acid Chemical compound OB(O)OC1=C(F)C(F)=C(F)C(F)=C1F LWNGJAHMBMVCJR-UHFFFAOYSA-N 0.000 claims description 2
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 claims description 2
- DPAVORBDLHTGCY-UHFFFAOYSA-N 1,2-dichlorothioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=C(Cl)C(Cl)=CC=C3SC2=C1 DPAVORBDLHTGCY-UHFFFAOYSA-N 0.000 claims description 2
- GJZFGDYLJLCGHT-UHFFFAOYSA-N 1,2-diethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=C(CC)C(CC)=CC=C3SC2=C1 GJZFGDYLJLCGHT-UHFFFAOYSA-N 0.000 claims description 2
- UYEDESPZQLZMCL-UHFFFAOYSA-N 1,2-dimethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=C(C)C(C)=CC=C3SC2=C1 UYEDESPZQLZMCL-UHFFFAOYSA-N 0.000 claims description 2
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 2
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 claims description 2
- SAMJGBVVQUEMGC-UHFFFAOYSA-N 1-ethenoxy-2-(2-ethenoxyethoxy)ethane Chemical compound C=COCCOCCOC=C SAMJGBVVQUEMGC-UHFFFAOYSA-N 0.000 claims description 2
- FODCFYIWOJIZQL-UHFFFAOYSA-N 1-methylsulfanyl-3,5-bis(trifluoromethyl)benzene Chemical compound CSC1=CC(C(F)(F)F)=CC(C(F)(F)F)=C1 FODCFYIWOJIZQL-UHFFFAOYSA-N 0.000 claims description 2
- VOBUAPTXJKMNCT-UHFFFAOYSA-N 1-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound CCCCCC(OC(=O)C=C)OC(=O)C=C VOBUAPTXJKMNCT-UHFFFAOYSA-N 0.000 claims description 2
- YIKSHDNOAYSSPX-UHFFFAOYSA-N 1-propan-2-ylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C(C)C YIKSHDNOAYSSPX-UHFFFAOYSA-N 0.000 claims description 2
- UAUCPJKNJJZFOE-UKTHLTGXSA-N 2,3-Bis(p-hydroxyphenyl)acrylonitrile Chemical compound C1=CC(O)=CC=C1\C=C(/C#N)C1=CC=C(O)C=C1 UAUCPJKNJJZFOE-UKTHLTGXSA-N 0.000 claims 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 claims description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 2
- OQBPCYUKFSJTDU-UHFFFAOYSA-N 4-Hydroxyphenyl-4-hydroxybenzoate Chemical compound C1=CC(O)=CC=C1OC(=O)C1=CC=C(O)C=C1 OQBPCYUKFSJTDU-UHFFFAOYSA-N 0.000 claims description 2
- HMBNQNDUEFFFNZ-UHFFFAOYSA-N 4-ethenoxybutan-1-ol Chemical compound OCCCCOC=C HMBNQNDUEFFFNZ-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 2
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 claims description 2
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 2
- ZCZFEIZSYJAXKS-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] prop-2-enoate Chemical compound OCC(CO)(CO)COC(=O)C=C ZCZFEIZSYJAXKS-UHFFFAOYSA-N 0.000 claims description 2
- FHLPGTXWCFQMIU-UHFFFAOYSA-N [4-[2-(4-prop-2-enoyloxyphenyl)propan-2-yl]phenyl] prop-2-enoate Chemical compound C=1C=C(OC(=O)C=C)C=CC=1C(C)(C)C1=CC=C(OC(=O)C=C)C=C1 FHLPGTXWCFQMIU-UHFFFAOYSA-N 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 150000008366 benzophenones Chemical class 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims description 2
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 239000000706 filtrate Substances 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- XKBGEWXEAPTVCK-UHFFFAOYSA-M methyltrioctylammonium chloride Chemical compound [Cl-].CCCCCCCC[N+](C)(CCCCCCCC)CCCCCCCC XKBGEWXEAPTVCK-UHFFFAOYSA-M 0.000 claims description 2
- 239000002480 mineral oil Substances 0.000 claims description 2
- 235000010446 mineral oil Nutrition 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- JRWNODXPDGNUPO-UHFFFAOYSA-N oxolane;prop-2-enoic acid Chemical compound C1CCOC1.OC(=O)C=C JRWNODXPDGNUPO-UHFFFAOYSA-N 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- LYXOWKPVTCPORE-UHFFFAOYSA-N phenyl-(4-phenylphenyl)methanone Chemical compound C=1C=C(C=2C=CC=CC=2)C=CC=1C(=O)C1=CC=CC=C1 LYXOWKPVTCPORE-UHFFFAOYSA-N 0.000 claims description 2
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 2
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 claims description 2
- CEYYIKYYFSTQRU-UHFFFAOYSA-M trimethyl(tetradecyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCCCC[N+](C)(C)C CEYYIKYYFSTQRU-UHFFFAOYSA-M 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- DDPRYTUJYNYJKV-UHFFFAOYSA-N 1,4-diethylpiperazine Chemical compound CCN1CCN(CC)CC1 DDPRYTUJYNYJKV-UHFFFAOYSA-N 0.000 claims 1
- IAMPNKHALGYNNB-UHFFFAOYSA-N 1-octoxy-4-phenylbenzene Chemical group C1=CC(OCCCCCCCC)=CC=C1C1=CC=CC=C1 IAMPNKHALGYNNB-UHFFFAOYSA-N 0.000 claims 1
- JZODKRWQWUWGCD-UHFFFAOYSA-N 2,5-di-tert-butylbenzene-1,4-diol Chemical compound CC(C)(C)C1=CC(O)=C(C(C)(C)C)C=C1O JZODKRWQWUWGCD-UHFFFAOYSA-N 0.000 claims 1
- JISNDAMZBNGEAC-UHFFFAOYSA-N 4-[2-(4-hydroxyphenyl)propyl]phenol Chemical compound C=1C=C(O)C=CC=1C(C)CC1=CC=C(O)C=C1 JISNDAMZBNGEAC-UHFFFAOYSA-N 0.000 claims 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- 125000004386 diacrylate group Chemical group 0.000 claims 1
- 150000002191 fatty alcohols Chemical class 0.000 claims 1
- 238000005516 engineering process Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 6
- 238000011161 development Methods 0.000 description 6
- 239000011342 resin composition Substances 0.000 description 6
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 5
- 230000000977 initiatory effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000009864 tensile test Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000004997 Liquid crystal elastomers (LCEs) Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- RIWRBSMFKVOJMN-UHFFFAOYSA-N 2-methyl-1-phenylpropan-2-ol Chemical compound CC(C)(O)CC1=CC=CC=C1 RIWRBSMFKVOJMN-UHFFFAOYSA-N 0.000 description 1
- 240000000972 Agathis dammara Species 0.000 description 1
- NSFGOWGWLHAJPC-UHFFFAOYSA-N COCOC.C(C=C)(=O)O Chemical compound COCOC.C(C=C)(=O)O NSFGOWGWLHAJPC-UHFFFAOYSA-N 0.000 description 1
- 229920002871 Dammar gum Polymers 0.000 description 1
- 239000004988 Nematic liquid crystal Substances 0.000 description 1
- VROZYAVRCSKZBY-UHFFFAOYSA-N OC1=CC=C(C=C1)C1=CC=C(C=C1)O.C(C=C)(=O)O Chemical compound OC1=CC=C(C=C1)C1=CC=C(C=C1)O.C(C=C)(=O)O VROZYAVRCSKZBY-UHFFFAOYSA-N 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- KNSXNCFKSZZHEA-UHFFFAOYSA-N [3-prop-2-enoyloxy-2,2-bis(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical class C=CC(=O)OCC(COC(=O)C=C)(COC(=O)C=C)COC(=O)C=C KNSXNCFKSZZHEA-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 238000005299 abrasion Methods 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005094 computer simulation Methods 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229940049945 duomax Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- JZMPIUODFXBXSC-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.CCOC(N)=O JZMPIUODFXBXSC-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007777 multifunctional material Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 230000021715 photosynthesis, light harvesting Effects 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- YRHRIQCWCFGUEQ-UHFFFAOYSA-N thioxanthen-9-one Chemical class C1=CC=C2C(=O)C3=CC=CC=C3SC2=C1 YRHRIQCWCFGUEQ-UHFFFAOYSA-N 0.000 description 1
Images
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
- 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
-
- 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
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/103—Esters of polyhydric alcohols or polyhydric phenols of trialcohols, e.g. trimethylolpropane tri(meth)acrylate
-
- 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
- C08F267/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated polycarboxylic acids or derivatives thereof as defined in group C08F22/00
- C08F267/06—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated polycarboxylic acids or derivatives thereof as defined in group C08F22/00 on to polymers of esters
-
- 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
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/062—Polyethers
Landscapes
- 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)
- Materials Engineering (AREA)
- Polymerisation Methods In General (AREA)
Abstract
The invention discloses a composition based on acrylic liquid crystal photosensitive resin and application thereof in 405nm3D printing. The anti-foaming agent comprises, by weight, 10-70 parts of an acrylic liquid crystal photosensitive resin, 10-70 parts of a polyurethane acrylate resin, 0-25 parts of a polyethylene glycol dimethacrylate resin, 0-25 parts of an alkoxylated acrylate, 0-25 parts of a diluent, 0.1-10 parts of a photoinitiator, 0-5 parts of an antifoaming agent, 0-5 parts of a leveling agent and 0-5 parts of an antioxidant. The composition based on the acrylic liquid crystal photosensitive resin can be used for 405nm3D printing, and has the capability of printing complex structures; meanwhile, the characteristics of the acrylic liquid crystal photosensitive resin are reserved, and the printed product is excellent in heat resistance and good in mechanical property, and can be widely applied to the fields of fine electronic devices, aerospace and the like.
Description
Technical Field
The invention relates to the field of photosensitive resin processing and application thereof, in particular to an acrylic liquid crystal photosensitive resin-based composition and application thereof in 405nm3D printing.
Background
In recent years, 3D printing technology is in a high-speed development stage, attracting more and more researchers. Compared with the traditional manufacturing method, the 3D printing does not need to use a die, and the production period and cost of industrial products can be effectively reduced. With the development of 3D printing technology, it has been applied to the fields of aerospace technology, medical engineering, construction industry, electronic manufacturing, etc. Among various types of 3D printing techniques, stereolithography (SLA) stands out for advantages such as short curing time, high printing accuracy, energy saving and environmental protection. In addition, the printed article has excellent properties in terms of hardness, chemical resistance and abrasion resistance.
With the rapid development of 3D printing technology, higher requirements are being placed on the quality of photo-cured 3D printed products. The photosensitive resin is used as a raw material of SLA technology and mainly comprises epoxy resin, acrylic resin and polyester resin; these materials can be printed out into articles of complex construction such as jewelry, surgical stents, hand models, etc., but most of these articles are not used in fields such as aviation, aerospace, automotive, etc. These fields have high demands on the thermal stability and mechanical properties of the articles, which greatly limits the further development of SLA technology. Therefore, the development of novel high-performance photosensitive materials for photo-curing 3D printing is of great importance to both academic and industrial fields.
Liquid crystal resins have attracted attention from scientists due to their ordering of alignment and the like. Through years of development, the application of the method in 3D printing also achieves a certain effect. The liquid crystal elastomer (Liquid crystal elastomers, LCEs for short) is a soft multifunctional material combining the anisotropic order of liquid crystal molecules with the entropy elasticity of a lightly crosslinked polymer network. LCEs have special mechanical properties such as high energy dissipation, soft elasticity, programmable anisotropy, and negative poisson's ratio. Researchers have now made LCEs devices using click chemistry and ink direct write technology. However, the use of the liquid crystal photosensitive resin for three-dimensional light curing molding technology (SLA) 3D printing has not been reported yet.
The liquid crystal material has excellent optical, electrical and mechanical properties due to its unique molecular shape and chemical structure. The acrylate liquid crystal resin can be thermally cured under the condition of initiator initiation or thermal initiation to obtain the cured resin. However, due to the limitations of the initiating system and temperature, the thermosetting acrylate liquid crystal resin is generally polymerized by light. The polymerization temperature can be arbitrarily selected within the liquid phase temperature range when photopolymerization is adopted, and the two processes of orientation and polymerization can be completely independent, namely, the liquid crystal resin can be fully oriented and then polymerized. However, this method is relatively suitable for preparing thin films and is not suitable for articles with a large thickness.
The stereoscopic light curing molding technology (SLA) can rapidly obtain three-dimensional structural parts with arbitrary shapes by curing liquid crystal resin layer by laser. This technique well overcomes the limitations of light curing on the thickness and shape of the part. If the liquid crystal properties of the liquid crystal resin can be retained for application to 3D printing, the mechanical properties of the article must be improved to some extent. Therefore, a novel liquid crystal photosensitive resin is developed, and the application of the novel liquid crystal photosensitive resin in 3D printing has great potential.
Therefore, based on the thought, the photosensitive resin composition for 405nm photo-curing 3D printing based on the acrylic liquid crystal resin is developed, so that the application of the acrylic liquid crystal resin is widened, and the defect of poor formability of the acrylic liquid crystal resin is overcome; and a novel photosensitive resin composition with high performance is obtained, which is favorable for popularization and promotion of the 405nm photocuring 3D printing technology.
Disclosure of Invention
Aiming at the situation and the deficiency of the prior art, the invention aims to provide a composition based on acrylic liquid crystal photosensitive resin with excellent thermal stability and mechanical property and application thereof in 405nm3D printing.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
a composition based on acrylic liquid crystal photosensitive resin comprises the following raw materials in parts by weight:
preferably, the synthetic route of the acrylic liquid crystal photosensitive resin is shown in fig. 1, and the synthetic steps comprise:
(1) 10 parts of a compound containing mesogenic elements and having-OH at the end, 50 to 500 parts of Epichlorohydrin (EHC) and 0.1 to 1.0 part of catalyst 1 are mixed by mol as raw materials, and N is introduced 2 Protecting, and then reacting for 5-24 hours at 40-100 ℃ to obtain a solution A;
(2) Slowly dripping 20-50 parts of NaOH solution (with the concentration of 30% -60%) into the solution A according to the mole, removing water generated by the reaction under reduced pressure by using a vacuum pump, continuously reacting for 0.1-4 hours, pouring the product into a separating funnel, filtering to remove NaCl, and removing redundant EHC from the obtained filtrate by using a rotary evaporator to obtain solution B;
(3) Mixing the solution B with a methanol/acetone solution (the ratio is 1.0:0.1-1.0:10), putting the mixture into a refrigerator for cooling and crystallizing, washing the obtained crystal with methanol, carrying out suction filtration, and drying the product in an oven at 60-100 ℃ to obtain a milky solid, namely liquid crystal epoxy resin C;
(4) Taking 10 parts of liquid crystal epoxy resin C and 0.1-1.0 part of polymerization inhibitor according to mol, adding the liquid crystal epoxy resin C and the polymerization inhibitor into a flask, setting the reaction temperature to 90-150 ℃, slowly dripping 20-25 parts of acrylic acid after the epoxy resin C is completely melted, dripping 0.01-0.1 part of catalyst 2, reacting for 0.5-5.0 hours, and cooling to obtain light yellow viscous resin, namely the acrylic acid liquid crystal photosensitive resin, wherein the synthetic route is as follows:
wherein the compound containing mesogens and having-OH at the end is one or a combination of 4-hydroxyphenyl 4-hydroxybenzoate, 4 '-biphenol, 3',5 '-tetramethyl biphenol, 4- ((4-hydroxyphenoxy) carbonyl) phenyl 4-hydroxybenzoate, 2, 3-bis (4-hydroxyphenyl) acrylonitrile, 4' -propylenebisphenol and the like; the catalyst 1 in the step (1) is one or a combination of tetramethyl ammonium chloride, tetrabutyl ammonium bromide, tetrabutyl ammonium chloride, tetraethyl ammonium bromide, tetrabutyl ammonium bisulfate, benzyl triethyl ammonium chloride, trioctyl methyl ammonium chloride, dodecyl trimethyl ammonium chloride, tetradecyl trimethyl ammonium chloride and the like; the polymerization inhibitor in the step (4) is one or a combination of hydroquinone, benzoquinone, methyl hydroquinone, p-hydroxyanisole, 2-tertiary butyl hydroquinone and 2, 5-di-tertiary butyl p-phenylene diphenol; the catalyst 2 in the step (4) is one or a combination of N, N-diethylaniline, N-dimethyl-p-toluidine, N-dimethylbenzylamine, N-dimethylcyclohexylamine, N '-dimethylpyridine, N' -diethylpiperazine and the like.
Preferably, the urethane acrylate resin is at least one selected from aliphatic urethane acrylate oligomer, aromatic urethane acrylate oligomer, urethane diacrylate and dimethacrylate.
Preferably, the polymerization degree of the polyethylene glycol dimethacrylate resin is 1-200.
Preferably, the alkoxylated acrylate monomer is at least one selected from glycerol triacrylate and pentaerythritol tetraacrylate.
Preferably, the diluent is at least one selected from styrene, acrylic ester diluent, acrylic hydroxy ester diluent, vinyl ether diluent and cyclohexane diluent; the acrylic diluent is at least one selected from methyl methacrylate, 1, 6-hexanediol diacrylate, isobornyl acrylate, tetrahydrofuran acrylate, tripropylene glycol diacrylate, hexanediol diacrylate, bisphenol A diacrylate, trimethylolpropane triacrylate, pentaerythritol acrylate, isobornyl acrylate and cyclotrimethylolpropane methylacrylate; the hydroxy acrylate diluent is at least one selected from hydroxy ethyl methacrylate, hydroxy propyl methacrylate and hydroxy ethyl acrylate; the vinyl ether diluent is at least one selected from 4-hydroxybutyl vinyl ether and diethylene glycol divinyl ether; the cyclohexane diluent is at least one selected from 4-vinyl epoxy cyclohexane and 4-vinyl epoxy cyclohexane.
Preferably, the photoinitiator is at least one of diphenyl- (4-phenylthio) phenylsulfonium hexafluoroantimonate, diphenyl- (4-phenylthio) phenylsulfonium hexafluorophosphate, 4-octoxydiphenyliodohexafluoroantimonate, bis (4-tert-butylphenyl) iodonium hexafluorophosphate, diphenyliodonium hexafluorophosphate, 4-isopropyl-4' -methyldiphenyliodonium tetrakis (pentafluorophenyl) borate, triphenylsulfonium tetrafluoroborate, tri-p-tolylsulfonium hexafluorophosphate, 1-hydroxy-cyclohexyl-acetophenone, α -dimethyl- α -hydroxyacetophenone, p-isopropylphenyl-2-hydroxydimethyl-acetone-1, benzophenone, chlorinated benzophenone, acrylated benzophenone, 4-phenylbenzophenone, 2-chlorinated thioxanthone, isopropylthioxanthone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, dimethylthioxanthone, diethylthioxanthone, dichloro thioxanthone, 2-phenylbenzyl-2-dimethylamine-1- (4-morpholinophenyl).
Preferably, the defoaming agent is at least one selected from silicone-based defoaming agents, mineral oil-based defoaming agents, polyether-based defoaming agents, and aliphatic alcohol-based defoaming agents.
Preferably, the leveling agent is at least one selected from acrylic leveling agents, organic silicon leveling agents and fluorocarbon leveling agents.
Preferably, the antioxidant is at least one selected from pentaerythritol tetra (3, 5-di-tert-butyl-4-hydroxy) phenylpropionate, phenyl tri (2, 4-di-tert-butyl) phosphite, N' -bis- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine and 2, 6-di-tert-butyl-4-methylphenol.
Preferably, the acrylic-based liquid crystal photosensitive resin composition is applied to 405nm photo-curing 3D printing to obtain a molded part. Carrying out ultraviolet light post-treatment on the obtained molded part, wherein the light intensity of ultraviolet light is 100W/cm 2 The ultraviolet curing time is 0-10 minutes.
By adopting the technical scheme, compared with the prior art, the invention has the beneficial effects that: according to the invention, the acrylic liquid crystal photosensitive resin is introduced into the photosensitive resin composition, so that the characteristics of the acrylic liquid crystal photosensitive resin can be maintained, and the printed product has excellent mechanical properties and thermal stability, so that the acrylic liquid crystal photosensitive resin can be widely applied to the fields of electronic devices, aerospace and the like. Meanwhile, the acrylic liquid crystal photosensitive resin composition for 3D printing provided by the invention has good printability, has the capability of printing complex structures, is low in preparation cost, effectively reduces the price of 405nm3D printing resin, and lays a foundation for large-scale application of 405nm3D printing technology.
Drawings
FIG. 1 is a synthetic route of an acrylic liquid crystal photosensitive resin according to the present invention.
FIG. 2 is a POM chart of the acrylic liquid crystal photosensitive resin-based composition prepared in example 1 of the present invention.
FIG. 3 is a model of a composition based on an acrylic liquid crystal photosensitive resin prepared in example 1 of the present invention printed on a 405nm3D printer.
FIG. 4 is a stress-strain curve of a spline tensile test of the acrylic liquid crystal photosensitive resin-based composition prepared in example 1 of the present invention and a spline tensile test of comparative example printed on a 405nm3D printer.
FIG. 5 is a stress-strain curve of a spline bending test of the acrylic liquid crystal photosensitive resin-based composition prepared in example 1 of the present invention and a spline printed in a 405nm3D printer of comparative example.
FIG. 6 is a graph showing the dynamic mechanical properties of a sample bar printed on a 405nm3D printer for a composition based on an acrylic liquid crystal photosensitive resin prepared in example 1 of the present invention.
Detailed Description
The following describes the present invention in further detail with reference to specific embodiments:
acrylic liquid crystal photosensitive resin:
4-hydroxyphenyl 4-hydroxybenzoate acrylic liquid crystal photosensitive resin, abbreviated as A-1;
4,4' -biphenol acrylic acid liquid crystal photosensitive resin, which is abbreviated as A-2;
polyurethane acrylate resin:
aliphatic urethane acrylate 1: purchased from sartomer company, product number CN9010, abbreviated as B-1;
aliphatic urethane acrylate 2: purchased from sand-dama company, product number CN991, abbreviated as B-2;
polyethylene glycol dimethacrylate resin:
polyethylene glycol dimethacrylate resin 1: purchased from sartomer company under the product number SR210, abbreviated as C-1;
polyethylene glycol dimethacrylate resin 2: purchased from sartomer company under the product number SR211, abbreviated as C-2;
alkoxylated acrylates:
ethoxylated pentaerythritol tetraacrylate, available from the company sand Duomax, product number SR494, abbreviated as D-1;
glycerol triacrylate, available from sand dammar company under the product number SR9020, abbreviated as D-2;
a diluent:
cyclotrimethylolpropane methylal acrylate: purchased from sand-dama company, product number SR351, abbreviated as E-1;
hydroxypropyl methacrylate: purchased from alaa Ding Shiji (Shanghai) limited, abbreviated as E-2;
hydroxyethyl methacrylate: purchased from alaa Ding Shiji (Shanghai) limited, abbreviated as E-3;
and (3) a photoinitiator:
2,4,6- (trimethylbenzoyl) diphenyl phosphine oxide, available from Ala Ding Shiji (Shanghai) Inc., product number photoinitiator TPO, abbreviated as F-1;
phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide: a product number photoinitiator, XBPO, abbreviated as F-2, available from ala Ding Shiji (shanghai) limited;
1-hydroxy-cyclohexyl-acetophenone: a product number photoinitiator 184, abbreviated as F-3, available from ala Ding Shiji (shanghai) limited;
defoaming agent:
organosilicon defoamer: purchased from Pick chemical company, germany, product number BYK-088, abbreviated as G-1;
polyether defoamer: purchased from Guangdong Union Fine chemical Co., ltd, product number B-299, abbreviated as G-2;
leveling agent:
organosilicon leveling agent: purchased from Anhui Jia Xinnuo chemical Co., ltd, product number WE-D5510, abbreviated as H-1;
polyacrylic leveling agent: purchased from Anhui Jia Xinnuo chemical Co., ltd, product number WE-D819, abbreviated as H-2;
antioxidant:
2, 6-di-tert-butyl-4-methylphenol: available from Aba Ding Shiji (Shanghai) Inc., product number antioxidant BHT, abbreviated as I-1;
pentaerythritol tetrakis (3, 5-di-tert-butyl-4-hydroxy) phenylpropionate: antioxidant 1010, abbreviated as I-2, available from Kayin chemical Co., guangzhou.
Examples 1-8 (i.e., preparation of samples 1# through 8 #)
The preparation method comprises the following steps: and (3) mixing and heating a proper amount of acrylic liquid crystal photosensitive resin, polyurethane acrylic ester resin, polyethylene glycol dimethacrylate resin, alkoxylated acrylic ester, diluent, defoamer, flatting agent and antioxidant to 30-80 ℃, stirring and mixing uniformly, cooling, adding a photoinitiator, and stirring uniformly to obtain yellow viscous liquid, namely the composition sample based on the acrylic liquid crystal photosensitive resin.
The relationship between the sample numbers and the kinds and proportions of the respective components is shown in Table 1.
TABLE 1
The prepared composition based on the acrylic liquid crystal photosensitive resin was poured into a Form2 3D printer manufactured by Formlabs, inc. of Fumlibs, U.S.A., and was molded after computer modeling, patterning and printing. Carrying out ultraviolet light curing and heat curing treatment on the obtained product; wherein the intensity of the ultraviolet light is 100W/cm 2 The ultraviolet curing time is 2min.
The photosensitive resin compositions were evaluated by observing the appearance of the cured products with respect to the products obtained in the above examples, and the results are shown in Table 2.
TABLE 2
Referring to FIG. 2, there is a POM chart of the acrylic liquid crystal photosensitive resin-based composition prepared in example 1 of the present invention. From the figure, it can be seen that as the temperature increases, a polarized light microscopic image of the acrylic crystalline photosensitive resin observed at room temperature can be seen, and that a distinct band texture and texture, which is a typical nematic liquid crystal texture, can be observed. It was further demonstrated that the acrylic liquid crystal photosensitive resin can exhibit liquid crystal properties at room temperature.
Referring to FIG. 3, a model was printed on a 405nm3D printer of the acrylic liquid crystal photosensitive resin-based composition prepared in example 1 of the present invention.
Referring to FIGS. 4 and 5, stress-strain curves of a spline tensile test and a bending test were printed on a 405nm3D printer for the acrylic liquid crystal photosensitive resin-based composition prepared in example 1 according to the present invention and comparative example, respectively. From these, the composition based on the acrylic liquid crystal photosensitive resin prepared in example 1 was found to have a tensile strength of 61.7MPa, an elongation at break of 17.5% and a flexural strength of 91.3MPa, which are superior to those of the comparative example, and it was found that it has excellent mechanical properties.
Referring to FIG. 6, a dynamic mechanical property test curve of a spline was printed on a 405nm3D printer for the composition based on the acrylic liquid crystal photosensitive resin prepared in example 1 of the present invention and comparative example. From these, the composition based on the acrylic liquid crystal photosensitive resin prepared in example 1 had a storage modulus of 2230MPa and a glass transition temperature of 89.8 ℃ which are superior to those of the comparative example, and it was found that it has excellent thermal stability.
The foregoing description is only a few examples of the present application and is not intended to limit the present application in any way, and although the present application is disclosed in the preferred examples, it is not intended to limit the present application, and any person skilled in the art may make some changes or modifications to the disclosed technology without departing from the scope of the technical solution of the present application, and the technical solution is equivalent to the equivalent embodiments.
Claims (9)
1. A composition based on an acrylic liquid crystal photosensitive resin, characterized in that: the raw materials are as follows by weight:
10-70 parts of acrylic liquid crystal photosensitive resin
10-70 parts of polyurethane acrylic resin
0-25 parts of polyethylene glycol dimethacrylate resin
0-25 parts of alkoxylated acrylic ester
0-25 parts of diluent
0.1-10 parts of photoinitiator
0-5 parts of defoaming agent
0-5 parts of leveling agent
0-5 parts of an antioxidant;
the preparation method of the acrylic liquid crystal photosensitive resin comprises the following steps:
(1) Mixing a compound containing mesogenic elements and having-OH at the end, epichlorohydrin and a catalyst 1 as raw materials, and introducing N 2 Protecting, and then reacting for 5-24 hours at the temperature of 40-100 ℃ to obtain a solution A;
(2) Slowly dripping NaOH solution into the solution A, decompressing and removing water generated by the reaction by using a vacuum pump, continuously reacting for 0.1-4 hours, pouring the product into a separating funnel, filtering to remove NaCl, and removing redundant epichlorohydrin from the obtained filtrate by using a rotary evaporator to obtain solution B;
(3) Mixing the solution B with a methanol/acetone solution, cooling and crystallizing, washing the obtained crystal with methanol, carrying out suction filtration, and drying the product to obtain liquid crystal epoxy resin C;
(4) Adding liquid crystal epoxy resin C and a polymerization inhibitor into a flask, setting the reaction temperature to be 90-150 ℃, slowly dropwise adding acrylic acid after the epoxy resin C is completely melted, dropwise adding a catalyst 2, reacting for 0.5-5.0 hours, and cooling to obtain acrylic acid liquid crystal photosensitive resin;
wherein the compound containing mesogens and having-OH at the end is one or a combination of 4-hydroxyphenyl 4-hydroxybenzoate, 4 '-biphenol, 3',5 '-tetramethyl biphenol, 4- ((4-hydroxyphenoxy) carbonyl) phenyl 4-hydroxybenzoate, 2, 3-bis (4-hydroxyphenyl) acrylonitrile and 4,4' -propylenebisphenol; the catalyst 1 in the step (1) is one or a combination of tetramethyl ammonium chloride, tetrabutyl ammonium bromide, tetrabutyl ammonium chloride, tetraethyl ammonium bromide, tetrabutyl ammonium bisulfate, benzyl triethyl ammonium chloride, trioctyl methyl ammonium chloride, dodecyl trimethyl ammonium chloride and tetradecyl trimethyl ammonium chloride; the polymerization inhibitor in the step (4) is one or a combination of hydroquinone, benzoquinone, methyl hydroquinone, p-hydroxyanisole, 2-tertiary butyl hydroquinone and 2, 5-di-tertiary butyl hydroquinone; the catalyst 2 in the step (4) is one or a combination of N, N-diethyl aniline, N-dimethyl-p-toluidine, N-dimethylbenzylamine, N-dimethylcyclohexylamine, N '-dimethylpyridine and N, N' -diethyl piperazine.
2. The acrylic liquid crystal photosensitive resin-based composition according to claim 1, wherein: the polyurethane acrylic resin is at least one selected from aliphatic polyurethane acrylic oligomer, aromatic polyurethane acrylic oligomer, polyurethane diacrylate and dimethacrylate.
3. The acrylic liquid crystal photosensitive resin-based composition according to claim 1, wherein: the polymerization degree of the polyethylene glycol dimethacrylate resin is 1-200.
4. The acrylic liquid crystal photosensitive resin-based composition according to claim 1, wherein: the alkoxylated acrylate monomer is at least one selected from glycerol triacrylate and pentaerythritol tetraacrylate.
5. The acrylic liquid crystal photosensitive resin-based composition according to claim 1, wherein: the diluent is at least one selected from styrene, acrylic ester diluents, acrylic hydroxy ester diluents, vinyl ether diluents and cyclohexane diluents; the acrylic diluent is at least one selected from methyl methacrylate, 1, 6-hexanediol diacrylate, isobornyl acrylate, tetrahydrofuran acrylate, tripropylene glycol diacrylate, hexanediol diacrylate, bisphenol A diacrylate, trimethylolpropane triacrylate, pentaerythritol acrylate, isobornyl acrylate and cyclotrimethylolpropane methylacrylate; the hydroxy acrylate diluent is at least one selected from hydroxy ethyl methacrylate, hydroxy propyl methacrylate and hydroxy ethyl acrylate; the vinyl ether diluent is at least one selected from 4-hydroxybutyl vinyl ether and diethylene glycol divinyl ether; the cyclohexane diluent is 4-vinyl epoxy cyclohexane.
6. The acrylic liquid crystal photosensitive resin-based composition according to claim 1, wherein: the photoinitiator is at least one of diphenyl- (4-phenylthio) phenylsulfonium hexafluoroantimonate, diphenyl- (4-phenylthio) phenylsulfonium hexafluorophosphate, 4-octyloxybiphenyl iodohexafluoroantimonate, bis (4-tert-butylphenyl) iodonium hexafluorophosphate, diphenyliodonium hexafluorophosphate, 4-isopropyl-4' -methyldiphenyliodonium tetrakis (pentafluorophenyl) borate, triphenylsulfonium tetrafluoroborate, tri-p-tolylsulfonium hexafluorophosphate, 1-hydroxy-cyclohexyl-acetophenone, alpha-dimethyl-alpha-hydroxyacetophenone, p-isopropylphenyl-2-hydroxy-dimethyl acetone-1, benzophenone, chlorinated benzophenone, acrylated benzophenone, 4-phenylbenzophenone, 2-thioxanthone chloride, isopropyl thioxanthone, 2-hydroxy-2-methyl-1-phenyl-1-propanone, dimethylthioxanthone, diethyl thioxanthone, dichloro thioxanthone, 2-phenylbenzyl-2-dimethylamine-1- (4-morpholinophenyl).
7. The acrylic liquid crystal photosensitive resin-based composition according to claim 1, wherein: the defoaming agent is at least one selected from organosilicon defoaming agents, mineral oil defoaming agents, polyether defoaming agents and fatty alcohol defoaming agents;
the leveling agent is at least one of acrylic leveling agent, organic silicon leveling agent and fluorocarbon leveling agent;
the antioxidant is at least one selected from pentaerythritol tetra (3, 5-di-tert-butyl-4-hydroxy) phenylpropionate, phenyl tri (2, 4-di-tert-butyl) phosphite, N' -bis- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexamethylenediamine and 2, 6-di-tert-butyl-4-methylphenol.
8. The method for preparing the composition based on the acrylic liquid crystal photosensitive resin according to any one of claims 1 to 7, wherein the composition based on the acrylic liquid crystal photosensitive resin is prepared by mixing and heating the acrylic liquid crystal photosensitive resin, polyurethane acrylic ester resin, polyethylene glycol dimethacrylate resin, alkoxylated acrylic ester, diluent, defoamer, flatting agent and antioxidant to 30-80 ℃, stirring and mixing uniformly, cooling, adding a photoinitiator, and stirring uniformly.
9. Use of a composition based on an acrylic crystalline photosensitive resin according to any one of claims 1 to 7, characterized in that: the composition based on the acrylic liquid crystal photosensitive resin is used for 405nm photo-curing 3D printing to obtain a molded part, the obtained molded part is subjected to ultraviolet light post-treatment, and the light intensity of ultraviolet light is 100W/cm 2 The ultraviolet curing time is 0-10 minutes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111145723.7A CN113651920B (en) | 2021-09-28 | 2021-09-28 | Acrylic liquid crystal photosensitive resin-based composition and application thereof in 405nm3D printing |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111145723.7A CN113651920B (en) | 2021-09-28 | 2021-09-28 | Acrylic liquid crystal photosensitive resin-based composition and application thereof in 405nm3D printing |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113651920A CN113651920A (en) | 2021-11-16 |
| CN113651920B true CN113651920B (en) | 2023-06-06 |
Family
ID=78494481
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111145723.7A Active CN113651920B (en) | 2021-09-28 | 2021-09-28 | Acrylic liquid crystal photosensitive resin-based composition and application thereof in 405nm3D printing |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113651920B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110554567A (en) * | 2019-08-28 | 2019-12-10 | 浙江福斯特新材料研究院有限公司 | resin composition and use thereof |
| CN112646085A (en) * | 2020-12-24 | 2021-04-13 | 泉州师范学院 | Bismaleimide resin-based photosensitive resin composition and application thereof in 405nm 3D printing |
| CN113292685A (en) * | 2021-06-17 | 2021-08-24 | 江西金石三维智能制造科技有限公司 | Three-dimensional photo-molding resin with low shrinkage rate and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100988271B1 (en) * | 2007-09-19 | 2010-10-18 | 주식회사 엘지화학 | photosensitive resin, methode for producing thereof, photosenssitive resin composition and cured product using the same |
| KR102171222B1 (en) * | 2018-08-17 | 2020-10-28 | 한국과학기술연구원 | Composites with enhanced thermal conductivity and method preparing the same |
-
2021
- 2021-09-28 CN CN202111145723.7A patent/CN113651920B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110554567A (en) * | 2019-08-28 | 2019-12-10 | 浙江福斯特新材料研究院有限公司 | resin composition and use thereof |
| CN112646085A (en) * | 2020-12-24 | 2021-04-13 | 泉州师范学院 | Bismaleimide resin-based photosensitive resin composition and application thereof in 405nm 3D printing |
| CN113292685A (en) * | 2021-06-17 | 2021-08-24 | 江西金石三维智能制造科技有限公司 | Three-dimensional photo-molding resin with low shrinkage rate and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 3D打印用双酚A型环氧丙烯酸光敏树脂的制备;王鹤;合成树脂及塑料(第04期);第38-41页 * |
| 丙烯酸液晶树脂基质作为新型口腔修复材料的初步研究;贺晓萍;生物医学工程与临床;第21卷(第02期);第121-125页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113651920A (en) | 2021-11-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1754915B (en) | Silicone resin composition and molded product thereof | |
| TWI465466B (en) | Hardened composition and hardened product thereof | |
| CN102206293B (en) | Photoinitiator, UV curing coating and in mo1d decoration method | |
| US20070160937A1 (en) | Photocurable resin composition and a method for forming a pattern | |
| JP6579335B2 (en) | Polymerizable composition containing reactive silsesquioxane compound | |
| CN112646085B (en) | Bismaleimide resin-based photosensitive resin composition and application thereof in 405nm 3D printing | |
| JP5091407B2 (en) | Multifunctional (meth) acrylate and method for producing the same | |
| CN113736217B (en) | Composition based on liquid crystal epoxy photosensitive resin and application of composition in 355nm3D printing | |
| TW201834065A (en) | Substrate pretreatment compositions for nanoimprint lithography | |
| CN113831461B (en) | Bismaleimide/acrylic acid liquid crystal photosensitive resin-based composition and application thereof in 405nm3D printing | |
| EP2049594A1 (en) | Method of preparing resin composition for artificial marble chip having high specific gravity and high index of refraction | |
| KR101532334B1 (en) | Photocurable Resin Compositions Having High Refractive Index | |
| KR101532341B1 (en) | Photocurable Resin Compositions Having High Refractive Index | |
| CN113651920B (en) | Acrylic liquid crystal photosensitive resin-based composition and application thereof in 405nm3D printing | |
| CN106928896A (en) | A kind of acidproof edge sealing adhesive of ultraviolet light polymerization | |
| JPWO2016163561A1 (en) | Polymerizable resin composition containing reactive silsesquioxane compound | |
| CN109988540B (en) | LED light-cured adhesive composition, transfer-printed curing adhesive and preparation method | |
| KR20110006163A (en) | Photocurable fluoro resin composition and method for preparing of mold using the same | |
| JP5698566B2 (en) | Silicone resin composition and molded body thereof | |
| KR20090084340A (en) | Photocurable resin composition and method for preparing of mold using the same | |
| JP6848825B2 (en) | Photocurable composition and its cured product | |
| CN117586621A (en) | Silicon chain-containing acrylic liquid crystal photosensitive resin composition and application thereof in 3D printing | |
| US11603424B2 (en) | Crosslinkable compositions having a low viscosity for coatings and materials having a high refractive index and having a high heat deflection temperature | |
| CN117551238A (en) | Photo-curable 3D printing orientation acrylic-based liquid crystal photosensitive resin composition | |
| KR101514745B1 (en) | Photocurable resin composition for thermal decomposition master model mold of precision casting |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |