CN113717324B - Photo-curable 3D printing conductive ionic gel and special photosensitive resin thereof and preparation method - Google Patents
Photo-curable 3D printing conductive ionic gel and special photosensitive resin thereof and preparation method Download PDFInfo
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- CN113717324B CN113717324B CN202111073335.2A CN202111073335A CN113717324B CN 113717324 B CN113717324 B CN 113717324B CN 202111073335 A CN202111073335 A CN 202111073335A CN 113717324 B CN113717324 B CN 113717324B
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- 239000011347 resin Substances 0.000 title claims abstract description 57
- 229920005989 resin Polymers 0.000 title claims abstract description 57
- 238000010146 3D printing Methods 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000000016 photochemical curing Methods 0.000 claims abstract description 32
- 239000004814 polyurethane Substances 0.000 claims abstract description 32
- 229920002635 polyurethane Polymers 0.000 claims abstract description 32
- -1 acrylic ester Chemical class 0.000 claims abstract description 30
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 21
- 239000002608 ionic liquid Substances 0.000 claims abstract description 15
- 239000000178 monomer Substances 0.000 claims abstract description 10
- 238000012545 processing Methods 0.000 claims abstract description 9
- 238000007639 printing Methods 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 229920005862 polyol Polymers 0.000 claims description 18
- 150000003077 polyols Chemical class 0.000 claims description 18
- 239000002994 raw material Substances 0.000 claims description 18
- 150000002500 ions Chemical class 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 150000002009 diols Chemical class 0.000 claims description 13
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 10
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 8
- 239000006096 absorbing agent Substances 0.000 claims description 8
- 125000005442 diisocyanate group Chemical group 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 239000002202 Polyethylene glycol Substances 0.000 claims description 6
- 238000001723 curing Methods 0.000 claims description 6
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 6
- 239000003112 inhibitor Substances 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 6
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 5
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 5
- JBTHDAVBDKKSRW-UHFFFAOYSA-N chembl1552233 Chemical compound CC1=CC(C)=CC=C1N=NC1=C(O)C=CC2=CC=CC=C12 JBTHDAVBDKKSRW-UHFFFAOYSA-N 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 5
- 229920001610 polycaprolactone Polymers 0.000 claims description 5
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- 229940073450 sudan red Drugs 0.000 claims description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 5
- 239000004925 Acrylic resin Substances 0.000 claims description 4
- 229920000178 Acrylic resin Polymers 0.000 claims description 4
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 4
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 claims description 4
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- 229920005906 polyester polyol Polymers 0.000 claims description 4
- 229920000570 polyether Polymers 0.000 claims description 4
- 229920000098 polyolefin Polymers 0.000 claims description 4
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 4
- 229920005749 polyurethane resin Polymers 0.000 claims description 4
- 238000011417 postcuring Methods 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 claims description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 3
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 3
- 229940043267 rhodamine b Drugs 0.000 claims description 3
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 claims description 3
- 229940124543 ultraviolet light absorber Drugs 0.000 claims description 3
- 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 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
- LCHAFMWSFCONOO-UHFFFAOYSA-N 2,4-dimethylthioxanthen-9-one Chemical compound C1=CC=C2C(=O)C3=CC(C)=CC(C)=C3SC2=C1 LCHAFMWSFCONOO-UHFFFAOYSA-N 0.000 claims description 2
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 2
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- BBAGPRAUWBSYDH-UHFFFAOYSA-N C(C)OP(OC(C1=C(C=C(C=C1C)C)C)=O)=O Chemical compound C(C)OP(OC(C1=C(C=C(C=C1C)C)C)=O)=O BBAGPRAUWBSYDH-UHFFFAOYSA-N 0.000 claims description 2
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 239000005062 Polybutadiene Substances 0.000 claims description 2
- 238000012644 addition polymerization Methods 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- JXCHMDATRWUOAP-UHFFFAOYSA-N diisocyanatomethylbenzene Chemical compound O=C=NC(N=C=O)C1=CC=CC=C1 JXCHMDATRWUOAP-UHFFFAOYSA-N 0.000 claims description 2
- MCPKSFINULVDNX-UHFFFAOYSA-N drometrizole Chemical compound CC1=CC=C(O)C(N2N=C3C=CC=CC3=N2)=C1 MCPKSFINULVDNX-UHFFFAOYSA-N 0.000 claims description 2
- 239000012948 isocyanate Substances 0.000 claims description 2
- 150000002513 isocyanates Chemical group 0.000 claims description 2
- KCWDJXPPZHMEIK-UHFFFAOYSA-N isocyanic acid;toluene Chemical class N=C=O.N=C=O.CC1=CC=CC=C1 KCWDJXPPZHMEIK-UHFFFAOYSA-N 0.000 claims description 2
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 2
- 229920002857 polybutadiene Polymers 0.000 claims description 2
- 239000004626 polylactic acid Substances 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 150000003512 tertiary amines Chemical group 0.000 claims description 2
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 2
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- 229920001748 polybutylene Polymers 0.000 claims 1
- 230000002745 absorbent Effects 0.000 abstract 1
- 239000002250 absorbent Substances 0.000 abstract 1
- 239000000499 gel Substances 0.000 description 53
- 239000000203 mixture Substances 0.000 description 14
- 238000003756 stirring Methods 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 8
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 8
- 239000000017 hydrogel Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical group [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- FKXJWELJXMKBDI-UHFFFAOYSA-K [butyl-di(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(OC(=O)CCCCCCCCCCC)OC(=O)CCCCCCCCCCC FKXJWELJXMKBDI-UHFFFAOYSA-K 0.000 description 4
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 4
- 238000010907 mechanical stirring Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 2
- 230000001121 heart beat frequency Effects 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 230000037427 ion transport Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
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- 150000003839 salts Chemical class 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- ILBBNQMSDGAAPF-UHFFFAOYSA-N 1-(6-hydroxy-6-methylcyclohexa-2,4-dien-1-yl)propan-1-one Chemical compound CCC(=O)C1C=CC=CC1(C)O ILBBNQMSDGAAPF-UHFFFAOYSA-N 0.000 description 1
- AFSJUFFXOPXIOH-UHFFFAOYSA-N 1-ethyl-3-methyl-1,2-dihydroimidazol-1-ium;trifluoromethanesulfonate Chemical compound CC[NH+]1CN(C)C=C1.[O-]S(=O)(=O)C(F)(F)F AFSJUFFXOPXIOH-UHFFFAOYSA-N 0.000 description 1
- GTEXIOINCJRBIO-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]-n,n-dimethylethanamine Chemical compound CN(C)CCOCCN(C)C GTEXIOINCJRBIO-UHFFFAOYSA-N 0.000 description 1
- XVZXOLOFWKSDSR-UHFFFAOYSA-N Cc1cc(C)c([C]=O)c(C)c1 Chemical group Cc1cc(C)c([C]=O)c(C)c1 XVZXOLOFWKSDSR-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000013473 artificial intelligence Methods 0.000 description 1
- 239000012965 benzophenone Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229920006158 high molecular weight polymer Polymers 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000011664 nicotinic acid Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 229920000921 polyethylene adipate Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 230000008054 signal transmission Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 230000032258 transport Effects 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
- C08F283/006—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
-
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
- C08K5/3445—Five-membered rings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/41—Compounds containing sulfur bound to oxygen
- C08K5/42—Sulfonic acids; Derivatives thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/43—Compounds containing sulfur bound to nitrogen
- C08K5/435—Sulfonamides
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)
- Polyurethanes Or Polyureas (AREA)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention discloses a photosensitive resin for photo-curing 3D printing conductive ionic gel and a preparation method thereof. The conductive ionic gel is prepared by photosensitive resin and comprises 10-60 parts of polyurethane (methyl) acrylic ester, 0-40 parts of photo-curing monomer, 40-80 parts of ionic liquid, 0.1-5 parts of photoinitiator and 0.001-1 part of light absorbent. The conductive ionic gel with different three-dimensional structures can be constructed through digital light processing 3D printing, and has good mechanical properties (the maximum tensile strength can reach 7.42MPa, the maximum elongation at break can reach 1011%) and conductivity (can reach 3.22 mS/cm), and the working temperature range is wide (-30-200 ℃). The conductive ionic gel prepared by the invention can be applied to flexible sensors to monitor various movements of a human body.
Description
Technical Field
The invention belongs to the field of intelligent high polymer materials, and particularly relates to a photo-curable 3D printing conductive ionic gel, a special photosensitive resin thereof and a preparation method thereof.
Background
Along with the development of the fields of man-machine interaction, intelligent robots, human tissue imitation and the like, flexible sensors capable of converting external stimulus and environmental changes such as pressure, strain, temperature and the like into electrical signals become more and more important. Conventional flexible sensors are made by incorporating conductive particles or conductive polymers into an insulating flexible rubber matrix. However, such flexible sensors are generally less stretchable and cannot detect large deformations. Furthermore, the conductive layer and the insulating layer may cause delamination due to differences in modulus and elongation, and cause signal interruption or hysteresis. In addition, such sensors are generally opaque due to the addition of conductive particles. Such sensors are based on the transport of electrons, whereas naturally living organisms always rely on ion transport to transmit signals. Common ion transport based conductive materials are primarily hydrogels and ionogels. The ion conductive material has the advantages of high transparency, high tensile property and the like, and has very low hysteresis effect in signal transmission due to the continuity of the conductive medium. Because the hydrogel has good biocompatibility and similar mechanical properties of human tissues, scientific researchers have made a great deal of related researches on the application of the conductive hydrogel in the fields of wearable electronic equipment, human health monitoring, artificial intelligence and the like. However, the problem of moisture susceptibility of hydrogels affects the long-term use of flexible sensors. Moreover, hydrogels can only be used in a narrow temperature range.
Ionic gels, which have both ionic liquid conductivity, stability, low volatility and polymer tensile properties, have been widely used in sensors, supercapacitors, lithium ion batteries and nano-triboelectric generators. The key problem to be solved in ionic gels is the leakage problem of ionic liquids, so good compatibility of ionic liquids with polymers is the key to preparing ionic liquids.
The 3D printing technology can be used for preparing the ionic gel sample with a complex three-dimensional structure and a bionic structure, and researches show that the microstructure can greatly improve the sensitivity of the sensor. Currently, direct-write 3D printing (Direct Ink Writing, DIW) is the most used printing method in the ion gel field. The shear-thinning ionic gel ink may be prepared by adding nanoparticles, high molecular weight polymers, and the like. Digital light processing (Digital Light Processing, DLP) photo-curing 3D printing projects a product cross-sectional pattern onto the surface of a liquid photosensitive resin, causing the irradiated resin to photo-cure layer by layer. The digital light processing technology has the greatest advantages of high printing speed, high printing precision and high resolution.
Disclosure of Invention
The invention aims to provide a photocuring 3D printing conductive ionic gel and a preparation method thereof. The conductive ionic gel is prepared by photo-curing photosensitive resin. The photosensitive resin can be used for constructing conductive ionic gels with different three-dimensional structures through digital light processing 3D printing, and the conductive ionic gel has good mechanical properties (the maximum tensile strength can reach 7.42MPa, the maximum elongation at break can reach 1011%) and conductivity (can reach 3.22 mS/cm), and the working temperature range is wide (-30-200 ℃). The conductive ionic gel prepared by the invention can be applied to flexible sensors to monitor various movements of a human body.
The invention provides a photosensitive resin for photo-curing 3D printing conductive ionic gel, which comprises the following raw materials in parts by mass: 10 to 60 parts of polyurethane (methyl) acrylic ester, 0 to 40 parts of photo-curing monomer, 40 to 80 parts of ionic liquid, 0.1 to 5 parts of photoinitiator and 0.001 to 1 part of light absorber.
The polyurethane (meth) acrylate means a polyurethane acrylate or a polyurethane methacrylate.
Preferably, the photosensitive resin comprises the following raw materials in parts by weight: 10-25 parts of polyurethane (methyl) acrylate, 10-40 parts of photo-curing monomer, 40-80 parts of ionic liquid (further 60-80 parts), 0.5-2 parts of photoinitiator and 0.005-0.06 part of light absorber.
In the invention, the polyurethane (methyl) acrylic ester is prepared by reacting diisocyanate with hydroxyl-terminated polyol to obtain isocyanate-terminated prepolymer and then reacting the isocyanate-terminated prepolymer with hydroxyl-containing (methyl) acrylic ester.
Wherein the diisocyanate is at least one selected from toluene diisocyanate, hydrogenated phenyl methane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate and phenyl methane diisocyanate.
The hydroxyl-terminated polyol is at least one selected from polyether polyol, polyester polyol and polyolefin polyol.
According to an embodiment of the present invention, the polyether polyol is selected from at least one of polyethylene glycol, polypropylene glycol, polytetrahydrofuran glycol.
According to an embodiment of the present invention, the polyester polyol is selected from at least one of polycaprolactone diol, polylactic acid diol, polyethylene adipate diol, polybutylene adipate diol.
According to an embodiment of the invention, the polyolefin polyol is selected from polybutadiene diols.
According to an embodiment of the invention, the hydroxyl terminated polyol has a number average molecular weight of 1000 to 10000g/mol.
According to an embodiment of the present invention, the hydroxyl group-containing (meth) acrylate is at least one selected from the group consisting of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, and hydroxypropyl methacrylate.
The polyurethane (methyl) acrylic resin can be prepared by the following steps:
s1: in the presence of a catalyst, mixing diisocyanate with hydroxyl-terminated polyol and an organic solvent, and carrying out gradual addition polymerization reaction to obtain isocyanate-terminated polyurethane resin;
s2: the isocyanate group-terminated polyurethane resin prepared above is reacted with hydroxyl-containing (meth) acrylate, and a polymerization inhibitor is added during the reaction to obtain polyurethane (meth) acrylate.
According to an embodiment of the present invention, in the step S1, the catalyst is a tertiary amine (such as triethylenediamine, bis (dimethylaminoethyl) ether) or an organometallic catalyst (such as stannous octoate, n-butyltin laurate);
according to an embodiment of the present invention, in the step S1, the organic solvent is selected from at least one of acetone and tetrahydrofuran;
according to an embodiment of the present invention, in the step S1, the catalyst is used in an amount of 200 to 600ppm; the reaction temperature of the polymerization reaction is 50-100 ℃ and the reaction time is 1-12 h;
according to an embodiment of the present invention, in the step S2, the polymerization inhibitor is at least one selected from hydroquinone and p-methoxyphenol;
according to an embodiment of the present invention, in the step S2, the polymerization inhibitor is used in an amount of 50 to 1000ppm; the reaction temperature of the reaction is 50-100 ℃ and the reaction time is 1-12 h;
the molar ratio of diisocyanate, hydroxyl terminated polyol, hydroxyl-containing (meth) acrylate is in turn 1: (0.65-0.85): (0.3-0.7).
In the invention, the photo-curing monomer is at least one selected from acrylic acid, hydroxyethyl methacrylate, hydroxyethyl acrylate, isobornyl acrylate, N-acryloylmorpholine and tert-butyl acrylate;
in the invention, the cation in the ionic liquid is selected from 1-alkyl-3-methylimidazole ions, and the alkyl in the 1-alkyl-3-methylimidazole ions can be C1-C16 alkyl;
the anions in the ionic liquid are at least one selected from trifluoromethane sulfonic acid ions, bis (trifluoromethane sulfonyl) imide ions, phosphorus hexafluoride ions and boron tetrafluoride ions;
in the invention, the photoinitiator is at least one selected from (2, 4, 6-trimethylbenzoyl) diphenyl phosphine oxide, phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide, ethyl (2, 4, 6-trimethylbenzoyl) phosphonate, benzophenone, isopropyl thioxanthone and 2, 4-dimethyl thioxanthone;
according to an embodiment of the invention, the light absorber is selected from at least one of the ultraviolet light absorbers UV-327, sudan red I, UV-P, rhodamine B.
According to one embodiment of the invention, the photosensitive resin comprises the following raw materials in parts by weight: polyurethane (methyl) acrylic ester-1 weight portion, acrylic acid hydroxyethyl ester 40 weight portions, 1, 3-dimethyl imidazole phosphorus hexafluoride salt 40 weight portions, phenyl bis (2, 4, 6-trimethyl benzoyl) phosphine oxide 1 weight portion, sudan red I0.03 weight portion.
According to one embodiment of the invention, the photosensitive resin comprises the following raw materials in parts by weight: 25 parts of polyurethane (methyl) acrylic ester, 25 parts of tert-butyl acrylate, 50 parts of 1-ethyl-3-methylimidazole trifluoromethane sulfonate, 1.5 parts of (2, 4, 6-trimethylbenzoyl) diphenyl phosphine oxide and 0.06 part of rhodamine B.
According to one embodiment of the invention, the photosensitive resin comprises the following raw materials in parts by weight: polyurethane (methyl) acrylic ester-3 parts, N-acryloylmorpholine 15 parts, 1, 3-dimethyl imidazole bis (trifluoromethyl) imide salt 60 parts, phenyl bis (2, 4, 6-trimethyl benzoyl) phosphine oxide 1 part and sudan red I0.005 part.
According to one embodiment of the invention, the photosensitive resin comprises the following raw materials in parts by weight: polyurethane (methyl) acrylic ester-4 parts, acrylic acid 10 parts, 1-ethyl-3-methylimidazole boron tetrafluoride salt 80 parts, (2, 4, 6-trimethylbenzoyl) 2 parts and sudan red I0.04 parts.
The invention also provides a preparation method of the photosensitive resin.
The preparation method of the photosensitive resin provided by the invention comprises the following steps: the preparation method comprises the steps of weighing polyurethane (methyl) acrylic ester, a photo-curing monomer, ionic liquid, a photoinitiator and a light absorber according to a proportion, pouring the mixture into a stirrer, and stirring and uniformly mixing the mixture at a low speed under the condition of avoiding light.
Wherein the rotating speed of low-speed stirring can be 400r/min, and the stirring time is 2-4 h.
The invention also provides application of the photosensitive resin.
The application of the photosensitive resin provided by the invention is the application of the photosensitive resin in light-cured 3D printing, in particular to the application in light-cured Stereolithography (SLA), digital light processing light-cured 3D printing (DLP) and Continuous Liquid Interface (CLIP) printing.
The invention also provides a photo-curing 3D printing conductive ionic gel sample.
The photo-curing 3D printing conductive ionic gel sample provided by the invention is obtained by photo-curing 3D printing the photosensitive resin provided by the invention.
Further, after the photo-curing 3D printing is finished, the method includes the steps of cleaning and post-curing the obtained sample.
The cleaning can be performed on the sample by ethanol or isopropanol, and specifically can be: and (5) placing the sample blank into ethanol or isopropanol, and ultrasonically cleaning for 10min.
The post-curing process is as follows: and (5) curing for 5-20min in an ultraviolet box after ultraviolet light is adopted.
Compared with the prior art, the invention has the following advantages:
(1) The photosensitive resin for the photocuring 3D printing conductive ionic gel provided by the invention has low viscosity, is fast to cure under 405nm illumination, is suitable for common photocuring 3D printing equipment in the market, and has high printing product precision;
(2) The printed conductive ionic gel has good mechanical properties (the maximum tensile strength can reach 7.42MPa, the maximum elongation at break can reach 1011%) and conductivity (can reach 3.22 mS/cm), and the working temperature range is wide (-30-200 ℃). The flexible sensor has high sensitivity and can monitor various movements of a human body;
(3) In the range limited by the invention, the mechanical property and the conductivity of the conductive ionic gel can be adjusted by adjusting the molecular structure of polyurethane acrylic ester, the type of photo-curing monomer and the content of ionic liquid so as to adapt to different application scenes or application requirements;
(4) The polyurethane (methyl) acrylic resin in the photo-curing 3D printing resin provided by the invention has the characteristics of abundant raw materials, simple and controllable synthesis process, low cost and the like, and is beneficial to the industrial application of the resin.
Drawings
FIG. 1 shows the nuclear magnetic spectrum of the urethane acrylate prepared in example 1 of the present invention (the solvent is deuterated chloroform);
fig. 2 shows the tensile curves of the conductive ionic gel materials prepared by photo-curing 3D printing in examples 1 to 4 of the present invention.
Fig. 3 shows an ionogel model made by Digital Light Processing (DLP) 3D printing in example 3 of the present invention.
Fig. 4 shows a photograph of the conductive ionic gel material prepared in example 3 of the present invention as a conductor-lighted LED lamp.
FIG. 5 shows the DMA curve of the ionic gel prepared in example 3 of the present invention.
Fig. 6 shows that the conductive gel material prepared in example 3 of the present invention is used as a flexible sensor to monitor the heartbeat frequency.
Detailed Description
The invention will be further illustrated with reference to the following specific examples, but the invention is not limited to the following examples. The methods are conventional methods unless otherwise specified. The starting materials are available from published commercial sources unless otherwise specified.
Example 1
The preparation of the polyurethane acrylic ester comprises the following specific steps:
in a 250mL round-bottom flask equipped with mechanical stirring, nitrogen inlet, thermometer and dropping funnel, 22.2g (0.10 mol) of isophorone diisocyanate (IPDI) was added, and then a mixture of 100.0g (0.05 mol) of polyethylene glycol molecular weight 2000), 50.0g (0.025 mol) of polycaprolactone diol and 0.06g of stannous octoate catalyst was gradually introduced into the three-necked flask, while maintaining the temperature of the reaction system in the flask at 80 ℃. After the completion of the dropwise addition, the mixture was allowed to continue to react, a small amount of acetone was added to the system to reduce the viscosity, the degree of reaction was monitored by Fourier infrared, and when the infrared characteristic absorption peak of isocyanate groups was no longer reduced, a mixture of 0.05g of hydroquinone and 5.8g (0.05 mol) of hydroxyethyl acrylate was added dropwise to the system while maintaining the temperature of the system at 50 ℃. And after the dripping is finished, continuing to react until the characteristic absorption peak of the isocyanate group in the infrared spectrogram completely disappears, thus obtaining the polyurethane acrylate PUA-1.
Preparation of photosensitive resin for photo-curing 3D printing conductive ionic gel:
firstly, weighing raw materials according to the formula proportion: the photosensitive resin comprises the following raw material components in parts by weight:
then, the components are sequentially poured into a stirrer, stirred and uniformly mixed at a low speed under the light-shielding condition to obtain the photosensitive resin, wherein the stirring speed is 400r/min, and the stirring time is 4h.
Printing an ion gel product:
and the prepared photosensitive resin is guided into a resin tank of DLP 3D printing equipment for model printing, the printing parameters of a 3D printer are set according to the needs, and the model surface is smooth and has high fineness. And after printing, removing the support from the sample blank, putting the sample blank into ethanol, performing ultrasonic treatment for 10min, putting the sample blank into an ultraviolet box, and curing for 10min to finally obtain the 3D printing ionic gel product. The ionic gel had a conductivity of 0.10mS/cm at room temperature as measured by electrochemical impedance spectroscopy.
Example 2
The preparation of the polyurethane methacrylate comprises the following specific steps:
in a 500mL round-bottom flask equipped with mechanical stirring, a nitrogen inlet, a thermometer and a dropping funnel, 16.8g (0.1 mol) of Hexamethylene Diisocyanate (HDI) was added, and then a mixture of 80.0g (0.04 mol) of polycaprolactone diol (molecular weight 2000), 90.0g (0.03 mol) of polytetrahydrofuran diol (molecular weight 3000) and 0.04g of n-butyltin laurate was gradually added to the three-necked flask while maintaining the temperature of the reaction system in the flask at 90 ℃. After the completion of the dropwise addition, the mixture was allowed to continue to react, tetrahydrofuran was added to the system to reduce the viscosity, the extent of the reaction was monitored by Fourier infrared, and when the infrared characteristic absorption peak of isocyanate groups was no longer reduced, a mixture of 0.1g of hydroquinone and 7.8g (0.06 mol) of hydroxyethyl methacrylate was added dropwise to the system while maintaining the temperature of the system at 55 ℃. And after the dripping is finished, continuing to react until the characteristic absorption peak of the isocyanate group in the infrared spectrogram completely disappears, thus obtaining the polyurethane methacrylate PUA-2.
Preparation of photosensitive resin for photocuring 3D printing ion gel:
firstly, weighing raw materials according to the formula proportion: the photosensitive resin comprises the following raw material components in parts by weight:
then, the components are sequentially poured into a stirrer, stirred and uniformly mixed at a low speed under the light-shielding condition to obtain the photosensitive resin, wherein the stirring speed is 400r/min, and the stirring time is 3h.
Printing an ion gel product:
and the prepared photosensitive resin is guided into a resin tank of DLP 3D printing equipment for model printing, the printing parameters of a 3D printer are set according to the needs, and the model surface is smooth and has high fineness. And after printing, removing the support from the sample blank, putting the sample blank into ethanol, performing ultrasonic treatment for 10min, putting the sample blank into an ultraviolet box, and curing for 5min to finally obtain the 3D printing ionic gel product. The ionic gel had a conductivity of 0.21mS/cm at room temperature as measured by electrochemical impedance spectroscopy.
Example 3
The preparation of the polyurethane acrylic ester comprises the following specific steps:
in a 500mL round-bottom flask equipped with mechanical stirring, a nitrogen inlet, a thermometer and a dropping funnel, 22.2g (0.1 mol) of isophorone diisocyanate (IPDI) was added, and then a mixture of 80.0g (0.04 mol) of polytetrahydrofuran diol (molecular weight 2000), 30.0g (0.03 mol) of polyethylene glycol (molecular weight 1000) and 0.04g of catalyst of n-butyltin laurate was dropwise added to the three-necked flask, while maintaining the temperature of the reaction system in the flask at 90 ℃. After the completion of the dropwise addition, the mixture was allowed to continue to react, tetrahydrofuran was added to the system to reduce the viscosity, the degree of reaction was monitored by Fourier infrared, and when the infrared characteristic absorption peak of isocyanate groups was no longer reduced, a mixture of 0.05g of hydroquinone and 6.96g (0.06 mol) of hydroxyethyl acrylate was further added dropwise to the system while maintaining the system temperature at 60 ℃. And after the dripping is finished, continuing to react until the characteristic absorption peak of the isocyanate group in the infrared spectrogram completely disappears, thus obtaining the polyurethane acrylate PUA-3.
Preparation of photosensitive resin for photocuring 3D printing ion gel:
firstly, weighing raw materials according to the formula proportion: the photosensitive resin comprises the following raw material components in parts by weight:
then, the components are sequentially poured into a stirrer, stirred and uniformly mixed at a low speed under the condition of avoiding light to obtain the photosensitive resin, wherein the stirring speed is 400r/min, and the stirring time is 2h.
Printing an ion gel product:
and the prepared photosensitive resin is guided into a resin tank of DLP 3D printing equipment for model printing, the printing parameters of a 3D printer are set according to the needs, and the model surface is smooth and has high fineness. And after printing, removing the support from the sample blank, putting the sample blank into ethanol, performing ultrasonic treatment for 10min, putting the sample blank into an ultraviolet box, and curing for 15min to finally obtain the 3D printing ionic gel product. The ionic gel had a conductivity of 0.65mS/cm at room temperature as measured by electrochemical impedance spectroscopy.
Example 4
The preparation of the polyurethane acrylic ester comprises the following specific steps:
in a 1L round bottom flask equipped with mechanical stirring, nitrogen inlet, thermometer and dropping funnel, 16.8g (0.1 mol) of Hexamethylene Diisocyanate (HDI) was added, and then a mixture of 80.0g (0.04 mol) of polycaprolactone diol (molecular weight 2000), 35.0g (0.035) of polyethylene glycol (molecular weight 1000) and 0.06g of catalyst of n-butyltin laurate was dropwise added to the three-necked flask while maintaining the temperature of the reaction system in the flask at 70 ℃. After the completion of the dropwise addition, the mixture was allowed to continue to react, tetrahydrofuran was added to the system to reduce the viscosity, the degree of reaction was monitored by Fourier infrared, and when the infrared characteristic absorption peak of isocyanate groups was no longer reduced, a mixture of 0.02g of hydroquinone and 5.8g (0.05 mol) of hydroxyethyl acrylate was further added dropwise to the system while maintaining the system temperature at 60 ℃. And after the dripping is finished, continuing to react until the characteristic absorption peak of the isocyanate group in the infrared spectrogram completely disappears, thus obtaining the polyurethane acrylate PUA-4.
Preparation of photosensitive resin for photocuring 3D printing ion gel:
firstly, weighing raw materials according to the formula proportion: the photosensitive resin comprises the following raw material components in parts by weight:
then, the components are sequentially poured into a stirrer, stirred and uniformly mixed at a low speed under the light-shielding condition to obtain the photosensitive resin, wherein the stirring speed is 400r/min, and the stirring time is 3h.
Printing an ion gel product:
and the prepared photosensitive resin is guided into a resin tank of DLP 3D printing equipment for model printing, the printing parameters of a 3D printer are set according to the needs, and the model surface is smooth and has high fineness. And after printing, removing the support from the sample blank, putting the sample blank into ethanol, performing ultrasonic treatment for 10min, putting the sample blank into an ultraviolet box, and curing for 15min to finally obtain the 3D printing ionic gel product. The ionic gel had a conductivity of 3.22mS/cm at room temperature as measured by electrochemical impedance spectroscopy.
FIG. 1 shows the nuclear magnetic spectrum of the urethane acrylate prepared in example 1 of the present invention (the solvent is deuterated chloroform).
FIG. 2 shows the tensile curves of the ionic gels of examples 1-4 of the present invention. As can be seen from FIG. 2, the ionic gel in example 1 has a maximum elongation at break of 977% and a maximum tensile strength of 7.42MPa; the ionic gel in example 2 had a maximum elongation at break of 1011% and a maximum tensile strength of 2.08MPa; the ionic gel in example 3 had a maximum elongation at break of 530% and a maximum tensile strength of 0.28MPa; the ionic gel in example 4 had a maximum elongation at break of 127% and a maximum tensile strength of 0.04MPa.
Fig. 3 shows an ionogel model made by Digital Light Processing (DLP) 3D printing in example 3 of the present invention. As can be seen from fig. 3, the printed ion gel model has a smooth surface and high printing accuracy and resolution.
Fig. 4 shows a photograph of the conductive ionic gel material prepared in example 3 of the present invention as a conductor-lighted LED lamp. As can be seen from fig. 4, the ionic gel has good conductivity.
FIG. 5 shows the DMA and TGA curves of the ionic gels prepared in example 3 of the present invention. As can be seen from FIG. 5, the ionic gel has a glass transition temperature of-34.1 ℃ and an initial decomposition temperature of over 200 ℃, so that the operating temperature can reach-30 to 200 ℃.
Fig. 6 shows that the conductive gel material prepared in example 3 of the present invention is used as a flexible sensor to monitor the heartbeat frequency. As can be seen from fig. 6, the ion gel has high sensitivity when used as a flexible sensor.
The photosensitive resin for the photocuring 3D printing ionic gel prepared by the invention has low viscosity, is fast to cure under 405nm illumination, is suitable for common photocuring 3D printing equipment on the market, and has high printing product precision; the conductive ionic gel prepared by printing has good mechanical properties (the maximum tensile strength can reach 7.42MPa, the maximum elongation at break can reach 1011%) and conductivity (can reach 3.22 mS/cm), and the working temperature range is wide (-30-200 ℃). The conductive ionic gel prepared by the invention can be applied to flexible sensors to monitor various movements of a human body. The polyurethane (methyl) acrylic resin in the photo-curing 3D printing resin provided by the invention has the characteristics of abundant raw materials, simple and controllable synthesis process, low cost and the like, and is beneficial to the industrial application of the resin.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (11)
1. The photosensitive resin comprises the following raw materials in parts by weight: 10-60 parts of polyurethane (methyl) acrylic ester, 0-40 parts of photo-curing monomer, 40-80 parts of ionic liquid, 0.1-5 parts of photoinitiator and 0.001-1 part of light absorber;
the polyurethane (methyl) acrylic ester is prepared by reacting diisocyanate with hydroxyl-terminated polyol to obtain isocyanate-terminated prepolymer, and then reacting the isocyanate-terminated prepolymer with hydroxyl-containing (methyl) acrylic ester to obtain polyurethane (methyl) acrylic ester resin;
the light-cured monomer is at least one selected from acrylic acid, hydroxyethyl methacrylate, hydroxyethyl acrylate, isobornyl acrylate, N-acryloylmorpholine and tert-butyl acrylate;
the ionic liquid cation is selected from 1-alkyl-3-methylimidazole ion, and the anion is selected from at least one of bis (trifluoromethanesulfonyl) imide ion, trifluoromethanesulfonic acid ion, phosphorus hexafluoride ion and boron tetrafluoride ion;
the photoinitiator is at least one selected from (2, 4, 6-trimethylbenzoyl) diphenyl phosphine oxide, phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide, ethyl (2, 4, 6-trimethylbenzoyl) phosphonate, diphenyl ketone, isopropyl thioxanthone and 2, 4-dimethylthioxanthone;
the light absorber is at least one selected from ultraviolet light absorber UV-327, sudan red I, ultraviolet light absorber UV-P and rhodamine B.
2. The photosensitive resin according to claim 1, wherein:
the diisocyanate is at least one selected from toluene diisocyanate, hydrogenated phenyl methane diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate and phenyl methane diisocyanate;
the hydroxyl-terminated polyol is at least one selected from polyether polyol, polyester polyol and polyolefin polyol;
the hydroxyl-containing (methyl) acrylic ester is at least one selected from hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate.
3. The photosensitive resin according to claim 2, wherein:
the polyether polyol is at least one selected from polyethylene glycol, polypropylene glycol and polytetrahydrofuran glycol;
the polyester polyol is at least one selected from polycaprolactone diol, polylactic acid diol, polyethylene glycol adipate diol and polybutylene glycol adipate diol;
the polyolefin polyol is selected from polybutadiene diols;
the hydroxyl-terminated polyol has a number average molecular weight of 1000 to 10000g/mol.
4. A photosensitive resin according to any one of claims 1-3, wherein: the polyurethane (methyl) acrylic resin is prepared by the following steps:
s1: in the presence of a catalyst, mixing diisocyanate with hydroxyl-terminated polyol and an organic solvent, and carrying out gradual addition polymerization reaction to obtain isocyanate-terminated polyurethane resin;
s2: reacting the isocyanate group-terminated polyurethane resin with hydroxyl-containing (methyl) acrylic ester, and adding a polymerization inhibitor during the reaction to obtain polyurethane (methyl) acrylic ester;
wherein,
in the step S1, the catalyst is tertiary amine or organic metal catalyst;
in the step S1, the organic solvent is at least one selected from acetone and tetrahydrofuran;
in the step S1, the polymerization inhibitor is at least one selected from hydroquinone and p-methoxyphenol;
in the step S1, the dosage of the catalyst is 200-600 ppm; the reaction temperature of the polymerization reaction is 50-100 ℃ and the reaction time is 1-12 h;
in the step S2, the dosage of the polymerization inhibitor is 50-1000 ppm; the reaction temperature of the reaction is 50-100 ℃ and the reaction time is 1-12 h;
the molar ratio of diisocyanate, hydroxyl-terminated polyol and hydroxyl-containing (meth) acrylate is in turn 1: (0.65-0.85): (0.3-0.7).
5. A photosensitive resin according to any one of claims 1-3, wherein: the photosensitive resin comprises the following raw materials in parts by mass: 10-25 parts of polyurethane (methyl) acrylate, 10-40 parts of photo-curing monomer, 40-80 parts of ionic liquid, 0.5-2 parts of photoinitiator and 0.005-0.06 part of light absorber.
6. The method for producing a photosensitive resin according to any one of claims 1 to 5, comprising the steps of: the polyurethane (methyl) acrylic ester, the photo-curing monomer, the ionic liquid, the photoinitiator and the light absorber are weighed according to the proportion, poured into a stirrer, and stirred and uniformly mixed at a low speed under the condition of avoiding light.
7. Use of the photosensitive resin according to any one of claims 1 to 5 in photo-curing 3D printing.
8. Use according to claim 7, characterized in that: the application is in light-cured stereolithography, digital light processing light-cured 3D printing or continuous liquid interface printing.
9. A photo-cured 3D printed conductive ionic gel sample obtained by photo-curing 3D printing the photosensitive resin of any one of claims 1-5.
10. The photo-cured 3D printed conductive ionic gel sample of claim 9, wherein: after the photo-curing 3D printing is finished, the method further comprises the step of cleaning and post-curing the obtained sample;
the cleaning is carried out on the sample by ethanol or isopropanol;
the post-curing process is as follows: and (5) curing for 5-20min in an ultraviolet box after ultraviolet light is adopted.
11. Use of a photo-cured 3D printed conductive ionic gel sample according to claim 9 or 10 for the preparation of a flexible sensor.
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