CN117946418A - Photocuring 3D printing preparation method and application of elastomer reinforced hydrogel composite material with strong interface bonding - Google Patents
Photocuring 3D printing preparation method and application of elastomer reinforced hydrogel composite material with strong interface bonding Download PDFInfo
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- 229920001971 elastomer Polymers 0.000 title claims abstract description 93
- 239000000806 elastomer Substances 0.000 title claims abstract description 93
- 239000000017 hydrogel Substances 0.000 title claims abstract description 92
- 239000002131 composite material Substances 0.000 title claims abstract description 50
- 238000000016 photochemical curing Methods 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 238000010146 3D printing Methods 0.000 title claims abstract description 27
- 229920005989 resin Polymers 0.000 claims abstract description 77
- 239000011347 resin Substances 0.000 claims abstract description 77
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims abstract description 34
- 239000004814 polyurethane Substances 0.000 claims abstract description 28
- 229920002635 polyurethane Polymers 0.000 claims abstract description 28
- 238000001723 curing Methods 0.000 claims abstract description 26
- 239000002994 raw material Substances 0.000 claims abstract description 24
- -1 acrylic ester Chemical class 0.000 claims abstract description 23
- 239000000178 monomer Substances 0.000 claims abstract description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 10
- 125000003396 thiol group Chemical group [H]S* 0.000 claims abstract description 9
- 239000003085 diluting agent Substances 0.000 claims abstract description 8
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 5
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 19
- 229920005862 polyol Polymers 0.000 claims description 16
- 150000003077 polyols Chemical class 0.000 claims description 16
- 239000002202 Polyethylene glycol Substances 0.000 claims description 14
- 229920001223 polyethylene glycol Polymers 0.000 claims description 14
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 10
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 10
- 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 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000005303 weighing Methods 0.000 claims description 10
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 8
- 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 8
- 239000003054 catalyst Substances 0.000 claims description 8
- 125000005442 diisocyanate group Chemical group 0.000 claims description 8
- 150000002009 diols Chemical class 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 229920000728 polyester Polymers 0.000 claims description 8
- 229920000570 polyether Polymers 0.000 claims description 8
- 238000006116 polymerization reaction Methods 0.000 claims description 8
- 238000007639 printing Methods 0.000 claims description 7
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 6
- KLGDRWGOXDJNPH-UHFFFAOYSA-N P(=O)(O)(O)O.C1(=CC=CC=C1)C=1C(=C(C(=O)[Li])C(=CC1C)C)C Chemical compound P(=O)(O)(O)O.C1(=CC=CC=C1)C=1C(=C(C(=O)[Li])C(=CC1C)C)C KLGDRWGOXDJNPH-UHFFFAOYSA-N 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- 239000003112 inhibitor Substances 0.000 claims description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 6
- 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 5
- 125000004386 diacrylate group Chemical group 0.000 claims description 5
- 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 5
- 239000007788 liquid Substances 0.000 claims description 5
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 claims description 4
- 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 4
- 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 4
- UWNADWZGEHDQAB-UHFFFAOYSA-N 2,5-dimethylhexane Chemical group CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 claims description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 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
- YQPJOSJJQYTSDL-UHFFFAOYSA-N n-(2-hydroxybutyl)propanamide Chemical compound CCC(O)CNC(=O)CC YQPJOSJJQYTSDL-UHFFFAOYSA-N 0.000 claims description 4
- 229920001610 polycaprolactone Polymers 0.000 claims description 4
- 239000004632 polycaprolactone Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- HAQZWTGSNCDKTK-UHFFFAOYSA-N 2-(3-sulfanylpropanoyloxy)ethyl 3-sulfanylpropanoate Chemical compound SCCC(=O)OCCOC(=O)CCS HAQZWTGSNCDKTK-UHFFFAOYSA-N 0.000 claims description 3
- LZDXRPVSAKWYDH-UHFFFAOYSA-N 2-ethyl-2-(prop-2-enoxymethyl)propane-1,3-diol Chemical compound CCC(CO)(CO)COCC=C LZDXRPVSAKWYDH-UHFFFAOYSA-N 0.000 claims description 3
- 239000012965 benzophenone Substances 0.000 claims description 3
- JQRRFDWXQOQICD-UHFFFAOYSA-N biphenylen-1-ylboronic acid Chemical compound C12=CC=CC=C2C2=C1C=CC=C2B(O)O JQRRFDWXQOQICD-UHFFFAOYSA-N 0.000 claims description 3
- 150000004662 dithiols Chemical class 0.000 claims description 3
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 3
- 239000011780 sodium chloride Substances 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
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 2
- JJSYPAGPNHFLML-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;3-sulfanylpropanoic acid Chemical compound OC(=O)CCS.OC(=O)CCS.OC(=O)CCS.CCC(CO)(CO)CO JJSYPAGPNHFLML-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
- JSOVZQSFWPMPKN-UHFFFAOYSA-N 4-(3-sulfanylpropanoyloxy)butyl 3-sulfanylpropanoate Chemical compound SCCC(=O)OCCCCOC(=O)CCS JSOVZQSFWPMPKN-UHFFFAOYSA-N 0.000 claims description 2
- 239000004925 Acrylic resin Substances 0.000 claims description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-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
- JOBBTVPTPXRUBP-UHFFFAOYSA-N [3-(3-sulfanylpropanoyloxy)-2,2-bis(3-sulfanylpropanoyloxymethyl)propyl] 3-sulfanylpropanoate Chemical compound SCCC(=O)OCC(COC(=O)CCS)(COC(=O)CCS)COC(=O)CCS JOBBTVPTPXRUBP-UHFFFAOYSA-N 0.000 claims description 2
- 238000012644 addition polymerization Methods 0.000 claims description 2
- 150000001409 amidines Chemical class 0.000 claims description 2
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 2
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 2
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-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
- QNILTEGFHQSKFF-UHFFFAOYSA-N n-propan-2-ylprop-2-enamide Chemical compound CC(C)NC(=O)C=C QNILTEGFHQSKFF-UHFFFAOYSA-N 0.000 claims description 2
- 125000002524 organometallic group Chemical group 0.000 claims description 2
- FEUIEHHLVZUGPB-UHFFFAOYSA-N oxolan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC1CCCO1 FEUIEHHLVZUGPB-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
- 229920000747 poly(lactic acid) Polymers 0.000 claims description 2
- 229920001748 polybutylene Polymers 0.000 claims description 2
- 239000004626 polylactic acid Substances 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 2
- 239000001103 potassium chloride Substances 0.000 claims description 2
- 235000011164 potassium chloride Nutrition 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 150000005846 sugar alcohols Polymers 0.000 claims description 2
- 239000012970 tertiary amine catalyst Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 4
- 239000007784 solid electrolyte Substances 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 6
- 230000035945 sensitivity Effects 0.000 abstract description 4
- 239000008367 deionised water Substances 0.000 abstract description 3
- 229910021641 deionized water Inorganic materials 0.000 abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 9
- 239000005058 Isophorone diisocyanate Substances 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 6
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 229910052797 bismuth Inorganic materials 0.000 description 4
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
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- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000009864 tensile test Methods 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- GTEXIOINCJRBIO-UHFFFAOYSA-N 2-[2-(dimethylamino)ethoxy]-n,n-dimethylethanamine Chemical compound CN(C)CCOCCN(C)C GTEXIOINCJRBIO-UHFFFAOYSA-N 0.000 description 1
- 229920001651 Cyanoacrylate Polymers 0.000 description 1
- MWCLLHOVUTZFKS-UHFFFAOYSA-N Methyl cyanoacrylate Chemical compound COC(=O)C(=C)C#N MWCLLHOVUTZFKS-UHFFFAOYSA-N 0.000 description 1
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 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 1
- 125000005396 acrylic acid ester group Chemical group 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
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- 238000005452 bending Methods 0.000 description 1
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- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical class OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000021715 photosynthesis, light harvesting Effects 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910001251 solid state electrolyte alloy Inorganic materials 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 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 1
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- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention discloses a photocuring 3D printing preparation method of an elastomer reinforced hydrogel composite material with strong interface bonding and application of the photocuring 3D printing preparation method in flexible sensing. Firstly, preparing an elastomer photosensitive resin, wherein the raw materials comprise the following components: 20-70 parts of allyl modified polyurethane (methyl) acrylic ester, 10-50 parts of photo-curing diluent and 0.1-5 parts of photoinitiator; applying the elastomer photosensitive resin to DLP 3D printing to obtain an elastomer skeleton; the hydrogel photosensitive resin is prepared from the following raw materials in parts by weight: 5 to 20 parts of water-soluble photo-curing monomer, 0.1 to 10 parts of photo-curing cross-linking agent, 1 to 5 parts of sulfhydryl monomer, 60 to 90 parts of deionized water, 1 to 10 parts of inorganic salt and 0.1 to 5 parts of photoinitiator; pouring hydrogel photosensitive resin into an elastomer framework, and curing by ultraviolet light. The composite material has good mechanical properties given by the elastomer skeleton, retains excellent conductivity of the hydrogel, and realizes strong interface bonding property. The composite material is used as a flexible sensor, and shows excellent stability and high sensitivity.
Description
Technical Field
The invention belongs to the field of composite materials, and particularly relates to a photocuring 3D printing preparation method of an elastomer reinforced hydrogel composite material with strong interface bonding and application of the photocuring 3D printing preparation method in flexible sensing.
Background
Hydrogels have been widely used in a variety of fields such as medical dressings, tissue engineering scaffolds, flexible sensors, etc. due to their high water content, good biocompatibility, continuous conductive phase, excellent extensibility and transparency, etc. However, hydrogels often have poor mechanical properties due to large water content, non-uniformity of the polymer network, and lack of efficient energy dissipation mechanisms, which affects their wider application. Recently, researchers have proposed various hydrogel-enhancing strategies such as dual network structures, nanoparticle or nanofiber enhancement, ionic coordination interactions, hydrophobic interactions, and the like. However, all these enhancement methods can make the hydrogel network compact, resulting in reduced conductivity of the hydrogel, losing the advantage of the hydrogel material, and affecting its application in flexible sensors. Therefore, how to prepare hydrogels with high mechanical and electrical properties at the same time remains a great challenge.
One possible strategy to improve both the mechanical properties of hydrogels and to maintain their high electrical conductivity is to compound them with elastomeric materials. The elastomer reinforced hydrogel composite material not only has high mechanical property endowed by the elastomer, but also has excellent conductivity of the hydrogel, and has great potential in the field of flexible sensing. However, the elastomer and the hydrogel are liable to form weak interface bonding due to great difference in surface characteristics, and researchers have improved interface bonding properties of the elastomer and the hydrogel material by various methods such as plasma treatment of the elastomer surface, gluing of cyanoacrylate monomer, addition of a silane coupling agent to the elastomer or hydrogel resin, and the like. Although these methods can improve the interfacial bonding properties of the material to some extent, even producing small amounts of chemical bond linkages, the strength of these chemical bonds is closely related to the nature of the material surface and the enhanced interfacial bonding is unstable. Therefore, how to improve the interfacial adhesion performance is the key for preparing elastomer-hydrogel composites, and it would be a great advance if stable chemical bond linkages could be obtained by well-defined chemical reactions.
Disclosure of Invention
The invention aims to provide a photocuring 3D printing preparation method of an elastomer reinforced hydrogel composite material with strong interface bonding and application of the photocuring 3D printing preparation method in flexible sensing.
The elastomer reinforced hydrogel composite material provided by the invention has good mechanical properties given by an elastomer skeleton, and meanwhile, excellent conductivity of the hydrogel is maintained. Moreover, by forming covalent bonds at the elastomer and hydrogel interface, strong interfacial bonding properties are achieved. The method is used for preparing the elastomer reinforced hydrogel composite material and is applied to a flexible sensor, and the method shows good stability and high sensitivity.
The invention provides a photocuring 3D printing preparation method of an elastomer reinforced hydrogel composite material with strong interface bonding, which comprises the following steps:
(1) The method comprises the steps of preparing elastomer photosensitive resin, wherein the elastomer photosensitive resin comprises the following raw material components in parts by mass: 20 to 70 parts of allyl modified polyurethane (methyl) acrylic ester
10-50 Parts of photo-curing diluent
0.1 To 5 parts of photoinitiator
(2) Applying the elastomer photosensitive resin to photo-curing 3D printing, and obtaining an elastomer skeleton through photo-curing; allyl groups are not cured during photocuring;
(3) The preparation method comprises the steps of preparing hydrogel photosensitive resin, wherein the hydrogel photosensitive resin comprises the following raw material components in parts by weight:
(4) Pouring the prepared hydrogel photosensitive resin into the elastomer skeleton prepared in the step (2), and curing the hydrogel resin through ultraviolet irradiation, wherein sulfhydryl groups in the hydrogel photosensitive resin react with allyl groups in the elastomer, so that covalent bonds are formed at the interface of the elastomer and the hydrogel, and the strong interface combination of the elastomer and the hydrogel is realized, so that the elastomer reinforced hydrogel composite material with the strong interface combination is obtained.
In the step (1) of the method, the allyl modified polyurethane (methyl) acrylate is prepared by reacting diisocyanate with hydroxyl-terminated polyester or polyether polyol and allyl-containing polyol to obtain isocyanate-terminated prepolymer, and then reacting with hydroxyl-containing (methyl) acrylate to obtain the allyl modified polyurethane (methyl) acrylate resin.
Wherein the diisocyanate is at least one selected from hydrogenated phenyl methane diisocyanate, isophorone diisocyanate (IPDI) and hexamethylene diisocyanate.
According to an embodiment of the present invention, the hydroxyl terminated polyester or polyether polyol is selected from at least one of polycaprolactone diol, polylactic acid diol, polyethylene glycol adipate diol, polybutylene glycol adipate diol, polyethylene glycol, polypropylene glycol, polytetrahydrofuran diol.
According to an embodiment of the invention, the hydroxyl terminated polyol has a number average molecular weight of 1000 to 10000g/mol.
The polyalcohol containing allyl is at least one of trimethylolpropane monoallyl ether and trimethylolpropane diallyl ether;
The hydroxyl-containing (methyl) acrylic ester is at least one selected from hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate;
the allyl modified polyurethane (methyl) acrylic ester is prepared by the following steps:
S1: in the presence of a catalyst, mixing diisocyanate with hydroxyl-terminated polyester or polyether polyol and allyl-containing polyol, and carrying out gradual addition polymerization reaction to obtain isocyanate-terminated prepolymer;
S2: reacting the isocyanate group-terminated prepolymer prepared above with hydroxyl-containing (meth) acrylate, and adding a polymerization inhibitor during the reaction to obtain allyl-modified polyurethane (meth) acrylate;
According to an embodiment of the present invention, in the step S1, the catalyst is a tertiary amine catalyst (such as triethylenediamine, bis (dimethylaminoethyl) ether) or an organometallic catalyst (such as stannous octoate, n-butyltin laurate, bismuth carboxylate);
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 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 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;
in the preparation process of the allyl modified polyurethane (methyl) acrylate, the feeding mole ratio of the diisocyanate, the hydroxyl terminated polyester or polyether polyol, the polyol containing allyl and the (methyl) acrylate containing hydroxyl is 1: (0.2-0.5): (0.2-0.5): (0.2-0.8);
In the step (1), the photo-curing diluent is at least one selected from hydroxyethyl acrylate, isobornyl acrylate, acryloylmorpholine, polyethylene glycol diacrylate, tetrahydrofuranyl acrylate and trimethylolpropane triacrylate;
In the step (1) of the method, 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, 2, 4-dimethylthioxanthone, azo dimethyl N-2-hydroxybutyl propionamide, azo diisobutyl amidine hydrochloride and phenyl (2, 4, 6-trimethylbenzoyl) lithium phosphate;
In the method step (1), the preparation of the elastomer photosensitive resin comprises the following steps: weighing the allyl modified polyurethane (methyl) acrylic ester and the photo-curing diluent according to the proportion, pouring the mixture into a stirrer, and mechanically stirring and uniformly mixing the mixture under the condition of avoiding light.
In the above method step (1), preferably, the raw material components of the elastomer photosensitive resin are as follows in parts by mass:
40-70 parts of allyl modified polyurethane (methyl) acrylic ester
30-50 Parts of photo-curing diluent
1 To 3 parts of photoinitiator
In the step (2) of the method, when the 3D printing is performed by photo-curing, the printing parameters of the 3D printer are set according to the photo-curing speed and the curing depth of the resin, and a model with smooth surface and high fineness is obtained.
The photo-cured 3D printing may be selected from at least one of: light curing Stereolithography (SLA), digital light processing light curing 3D printing (DLP), continuous Liquid Interface (CLIP) printing.
In the step (3), the water-based photo-curing monomer is at least one selected from acrylamide, N-isopropyl acrylamide, hydroxyethyl acrylate, acrylic acid, methacrylic acid and N-vinyl pyrrolidone;
The water-soluble photocuring cross-linking agent is at least one selected from polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, N-methylene diacrylamide, aqueous polyurethane acrylate and aqueous polyurethane methacrylate;
The sulfhydryl monomer is at least one selected from ethylene glycol di (3-mercaptopropionate), 1, 4-butanediol di (3-mercaptopropionate), trimethylolpropane tri (3-mercaptopropionate), pentaerythritol tetra (3-mercaptopropionate) and polyethylene glycol dithiol;
the inorganic salt is at least one of sodium chloride, potassium chloride, lithium chloride and calcium chloride;
The photoinitiator is at least one selected from (2, 4, 6-trimethylbenzoyl) diphenyl phosphine oxide, azodimethyl N-2-hydroxybutyl propionamide, phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide, ethyl (2, 4, 6-trimethylbenzoyl) phosphonate, diphenyl ketone, isopropyl thioxanthone, 2, 4-dimethylthioxanthone and phenyl (2, 4, 6-trimethylbenzoyl) lithium phosphate.
In the above method step (3), the preparation of the hydrogel photosensitive resin includes the following steps: weighing the water-soluble photocuring monomer, the photocuring crosslinking agent, the sulfhydryl monomer and the photoinitiator according to the proportion, pouring the mixture into a stirrer, and mechanically stirring and uniformly mixing the mixture under the light-shielding condition.
In the above method step (3), preferably, the hydrogel photosensitive resin comprises the following raw material components in parts by weight:
According to one embodiment of the invention, the raw materials of the elastomer photosensitive resin comprise the following components in parts by weight: 49 parts of allyl modified polyurethane acrylate, 49 parts of hydroxyethyl acrylate and 2 parts of phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide; the hydrogel photosensitive resin comprises the following raw materials in parts by mass: 11 parts of acrylamide, 3 parts of polyethylene glycol diacrylate, 1 part of polyethylene glycol dithiol, 80 parts of deionized water, 4 parts of lithium chloride and 1 part of phenyl (2, 4, 6-trimethylbenzoyl) lithium phosphate.
According to one embodiment of the invention, the raw materials of the elastomer photosensitive resin comprise the following components in parts by weight: 60 parts of allyl modified polyurethane acrylate, 38 parts of acryloylmorpholine and 2 parts of phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide; the hydrogel photosensitive resin comprises the following raw materials in parts by mass: 14 parts of acrylamide, 2 parts of N, N-methylene bisacrylamide, 1 part of ethylene glycol di (3-mercaptopropionate), 77 parts of deionized water, 5 parts of sodium chloride and 1 part of (2, 4, 6-trimethylbenzoyl) diphenyl phosphine oxide.
In the step (4), the amount of the hydrogel photosensitive resin is selected based on filling the voids of the elastomer skeleton.
In the step (4) of the method, the curing process is as follows: and (5) curing for 10-30min by adopting ultraviolet light in an ultraviolet box.
The elastomer reinforced hydrogel composite material with strong interface bonding prepared by the method also belongs to the protection scope of the invention.
The invention also provides application of the elastomer reinforced hydrogel composite material with strong interface bonding.
The application is the application of the elastomer reinforced hydrogel composite material in the preparation of the following products: flexible sensors, solid state electrolytes, tissue engineering scaffolds, and the like.
Compared with the prior art, the invention has the following advantages:
(1) The elastomer reinforced hydrogel composite material provided by the invention has good mechanical properties given by an elastomer skeleton and maintains excellent conductivity of the hydrogel;
(2) The elastomer reinforced hydrogel composite material prepared by the method has a large number of covalent bond connections at the interface, and has strong interface bonding performance;
(3) The preparation method of the elastomer reinforced hydrogel composite material adopts a DLP 3D printing mode, has high printing precision and can accurately control the three-dimensional structure of the elastomer reinforced hydrogel composite material;
(4) The elastomer reinforced hydrogel composite material prepared by the method has good mechanical property and excellent conductivity, and is applied to a flexible sensor, and excellent stability and high sensitivity are shown.
Drawings
FIG. 1 shows the tensile properties of the elastomeric photosensitive resin of example 1 after curing.
FIG. 2 shows the tensile properties of the hydrogel photosensitive resin of example 1 after curing.
Fig. 3 shows an elastomer reinforced hydrogel composite model made by DLP 3D printing in accordance with the present invention.
FIG. 4 shows the interfacial bonding properties of the composite prepared using the elastomer and hydrogel photosensitive resin of example 1 in comparison to the interfacial bonding properties of the composite prepared in comparative example 1.
FIG. 5 shows a plot of the resistivity of the material over time in a cyclic tensile test for a flexible sensor using the composite material prepared from the resin of example 1.
Fig. 6 shows the application of the composite material prepared by using the resin of example 1 to a flexible sensor for detecting the movement of a human body.
Detailed Description
The following detailed description of the invention is provided in connection with the accompanying drawings that are presented to illustrate the invention and not to limit the scope thereof. The examples provided below are intended as guidelines for further modifications by one of ordinary skill in the art and are not to be construed as limiting the invention in any way.
The experimental methods in the following examples, unless otherwise specified, are conventional methods, and are carried out according to techniques or conditions described in the literature in the field or according to the product specifications. Materials, reagents and the like used in the examples described below are commercially available unless otherwise specified.
Example 1 preparation of elastomer reinforced hydrogel composite with strong interfacial bonding
(1) Preparing an elastomer photosensitive resin:
The preparation of the allyl modified polyurethane acrylate comprises the following specific steps:
Into a flask were charged isophorone diisocyanate IPDI (22.2 g,100 mmol), polycaprolactone diol PCL-2000 (90 g,45 mmol), trimethylolpropane monoallyl ether TMPAE (5.22 g,30 mmol), and bismuth carboxylate (0.17 g, 0.4wt% of IPDI), and the reaction was carried out under nitrogen at 75 ℃. The reaction was monitored using fourier transform infrared spectroscopy, and when the absorption peak of the isocyanate group was no longer changed, nitrogen was removed and the temperature was reduced to 70 ℃. HEA (5.8 g,50 mmol) and HQ (0.03 g) were then added to the flask, and the reaction was carried out in air until the absorption peak of the isocyanate group in the Fourier transform infrared spectrum disappeared, to give a transparent viscous liquid (allyl-modified urethane acrylate).
Preparation of an elastomer photosensitive resin:
Firstly, weighing raw materials according to the formula proportion: the photosensitive resin comprises the following raw material components in parts by weight:
Allyl modified polyurethane acrylic ester 49 parts
Hydroxyethyl acrylate 49 parts
2 Parts of phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide
Then, the components are poured into a stirrer in turn, and the photosensitive resin is obtained by mechanically stirring and uniformly mixing under the condition of avoiding light.
(2) The prepared elastomer photosensitive resin is applied to DLP 3D printing equipment to prepare an elastomer skeleton, and the printing parameters of a 3D printer are set according to the photo-curing speed and the curing depth of the resin to obtain a model with smooth surface and high fineness.
(3) Preparation of hydrogel photosensitive resin:
Firstly, weighing raw materials according to the formula proportion: the photosensitive resin comprises the following raw material components in parts by weight:
phenyl (2, 4, 6-trimethylbenzoyl) lithium phosphate 1 part
Then, the components are poured into a stirrer in turn, and the photosensitive resin is obtained by mechanically stirring and uniformly mixing under the condition of avoiding light.
(4) Pouring the prepared hydrogel photosensitive resin into an elastomer skeleton prepared by DLP 3D printing, and curing for 20min in an ultraviolet curing box to obtain the elastomer reinforced hydrogel composite material with strong interface bonding.
Example 2 preparation of elastomer reinforced hydrogel composite with strong interfacial bonding
(1) Preparing an elastomer photosensitive resin:
The preparation of the allyl modified polyurethane acrylate comprises the following specific steps:
To the flask was added IPDI (22.2 g,100 mmol), PTMG-2000 (140 g,70 mmol) and bismuth carboxylate (0.089 g, 0.4wt% of IPDI), and the reaction was carried out under nitrogen at 80 ℃. The reaction was monitored using fourier transform infrared spectroscopy, and when the absorption peak of the isocyanate group was no longer changed, nitrogen was removed and the temperature was reduced to 70 ℃. HEA (3.48 g,30 mmol), trimethylolpropane diallyl ether TMPDE (6.42 g,30 mmol) and HQ (0.01 g) were then added to the flask and reacted in air until the absorption peak of the isocyanate groups disappeared in the Fourier transform infrared spectrum to give a transparent viscous liquid.
Preparation of an elastomer photosensitive resin:
Firstly, weighing raw materials according to the formula proportion: the photosensitive resin comprises the following raw material components in parts by weight:
60 parts of allyl modified polyurethane acrylic ester
38 Parts of acryloylmorpholine
2 Parts of ethyl (2, 4, 6-trimethylbenzoyl) phosphonate
Then, the components are poured into a stirrer in turn, and the photosensitive resin is obtained by mechanically stirring and uniformly mixing under the condition of avoiding light.
(2) The prepared elastomer photosensitive resin is applied to DLP 3D printing equipment to prepare an elastomer skeleton, and the printing parameters of a 3D printer are set according to the photo-curing rate and the curing depth of the resin to obtain a model with smooth surface and high fineness.
(3) Preparation of hydrogel photosensitive resin:
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 poured into a stirrer in turn, and the photosensitive resin is obtained by mechanically stirring and uniformly mixing under the condition of avoiding light.
(4) Pouring the prepared hydrogel photosensitive resin into an elastomer skeleton prepared by DLP 3D printing, and curing for 20min in an ultraviolet curing box to obtain the elastomer reinforced hydrogel composite material with strong interface bonding.
Comparative example, preparation of elastomer-reinforced hydrogel composite
The preparation of the polyurethane acrylic ester comprises the following specific steps:
Into a flask were charged isophorone diisocyanate IPDI (22.2 g,100 mmol), polycaprolactone diol PCL-2000 (140 g,70 mmol), and bismuth carboxylate (0.089 g,0.4 wt% of IPDI), and the reaction was carried out under nitrogen at 80 ℃. The reaction was monitored using fourier transform infrared spectroscopy, and when the absorption peak of the isocyanate group was no longer changed, nitrogen was removed and the temperature was reduced to 70 ℃. Then, hydroxyethyl acrylate HEA (6.96 g,60 mmol) and hydroquinone HQ (0.01 g) were added to the flask, and the reaction was carried out in air until the absorption peak of the isocyanate group in the Fourier transform infrared spectrum disappeared, to obtain a transparent viscous liquid.
Preparation of an elastomer photosensitive resin:
Firstly, weighing raw materials according to the formula proportion: the photosensitive resin comprises the following raw material components in parts by weight:
polyurethane acrylic acid ester 49 parts
Hydroxyethyl acrylate 49 parts
2 Parts of phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide
Then, the components are poured into a stirrer in turn, and the photosensitive resin is obtained by mechanically stirring and uniformly mixing under the condition of avoiding light.
The prepared elastomer photosensitive resin is applied to DLP 3D printing equipment to prepare an elastomer skeleton, and the printing parameters of a 3D printer are set according to the photo-curing rate and the curing depth of the resin to obtain a model with smooth surface and high fineness.
Preparation of hydrogel photosensitive resin:
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 poured into a stirrer in turn, and the photosensitive resin is obtained by mechanically stirring and uniformly mixing under the condition of avoiding light.
Pouring the prepared hydrogel photosensitive resin into an elastomer skeleton prepared by DLP 3D printing, and curing for 20min in an ultraviolet curing box to obtain the elastomer reinforced hydrogel composite material.
The electrical conductivity of the elastomer-reinforced hydrogel composites prepared in the above examples and comparative examples was measured, and the results are shown in table 1.
TABLE 1 conductivity of hydrogel matrix and elastomer-hydrogel composites
The results in table 1 show that after the hydrogel is compounded with the elastomer skeleton, the conductivity of the material remains unchanged, i.e. the composite material has excellent conductivity.
FIG. 1 shows the tensile properties of the elastomeric photosensitive resin of example 1 after curing. The results show that the elastomer has excellent mechanical properties, the tensile strength of the elastomer is 6.9MPa, and the elongation at break is 520.6%.
FIG. 2 shows the tensile properties of the hydrogel photosensitive resin of example 1 after curing. The results showed that the tensile strength of the hydrogel was 0.028MPa and the elongation at break was 681.2%.
FIG. 3 shows an elastomer reinforced hydrogel composite model made by DLP 3D printing in accordance with the present invention; wherein a and b are printed elastomer frameworks, and c and d are elastomer reinforced hydrogel composite materials.
FIG. 4 shows the interfacial bonding properties of the composite prepared using the elastomer and hydrogel photosensitive resin of example 1 in comparison to the interfacial bonding properties of the composite prepared in comparative example 1. The interface performance is evaluated by adopting a tensile test, and the preparation steps of the sample are as follows: and pouring the elastomer resin into a mould, and obtaining the elastomer film through photo-curing. Then, pouring hydrogel resin on the surface of the elastomer, and performing ultraviolet curing to obtain a test sample. The elastomeric resin in example 1 contains allyl groups in its molecular structure, the hydrogel resin contains mercapto monomers, and the resin in comparative example has no allyl and mercapto groups. The results show that when there is a covalent bond connection at the interface of the elastomer and the hydrogel, the hydrogel layer is stretch deformed with the elastomer until the elastomer breaks; whereas in a composite material without covalent bonds, the hydrogel layer is completely detached from the elastomer during the stretch deformation.
FIG. 5 shows the performance of a composite material prepared using the resin of example 1 applied to a flexible sensor; the results show that the rate of change of resistance (ΔR/R0) of the flexible sensor remains stable during 100% cycles of stretching, indicating that the material has excellent stability for use as a flexible sensor.
Fig. 6 shows the application of the composite material prepared by using the resin of example 1 to a flexible sensor for detecting the movement of a human body. The results show that the flexible sensor keeps the same resistance change rate in the repeated stretching-bending cyclic movement of the elbow of the human body, and the composite material can accurately detect the elbow movement of the human body and has excellent stability.
The elastomer reinforced hydrogel composite material with strong interface bonding has good mechanical properties given by an elastomer skeleton, and meanwhile, excellent conductivity of the hydrogel is maintained. Moreover, by introducing covalent bonds at the interface of the elastomer and the hydrogel, a strong interfacial bonding property is achieved. The elastomer reinforced hydrogel composite material prepared by the method is applied to a flexible sensor, and has excellent stability and high sensitivity.
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 (10)
1. A DLP 3D printing preparation method of an elastomer-reinforced hydrogel composite material with strong interface bonding, comprising the steps of:
(1) The method comprises the steps of preparing elastomer photosensitive resin, wherein the elastomer photosensitive resin comprises the following raw material components in parts by mass: 20 to 70 parts of allyl modified polyurethane (methyl) acrylic ester
10-50 Parts of photo-curing diluent
0.1 To 5 parts of photoinitiator
(2) Applying the elastomer photosensitive resin to photo-curing 3D printing, and obtaining an elastomer skeleton through photo-curing; allyl groups are not cured during photocuring;
(3) The preparation method comprises the steps of preparing hydrogel photosensitive resin, wherein the photosensitive resin comprises the following raw material components in parts by weight:
(4) Pouring the prepared hydrogel photosensitive resin into the elastomer skeleton prepared in the step (2), and curing the hydrogel resin through ultraviolet irradiation, wherein sulfhydryl groups in the hydrogel photosensitive resin react with allyl groups in the elastomer, so that covalent bonds are formed at the interface of the elastomer and the hydrogel, and the strong interface combination of the elastomer and the hydrogel is realized, so that the elastomer reinforced hydrogel composite material with the strong interface combination is obtained.
2. The method of manufacturing according to claim 1, characterized in that: in the step (1), the allyl modified polyurethane (methyl) acrylate is prepared by reacting diisocyanate with hydroxyl-terminated polyester or polyether polyol and allyl-containing polyol to obtain isocyanate-terminated prepolymer, and then reacting with hydroxyl-containing (methyl) acrylate to obtain allyl modified polyurethane (methyl) acrylate resin;
Or, in the step (1), the photo-curing diluent is at least one selected from hydroxyethyl acrylate, isobornyl acrylate, acryloylmorpholine, polyethylene glycol diacrylate, tetrahydrofuranyl acrylate and trimethylolpropane triacrylate;
Or, in the step (1), 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, 2, 4-dimethyl thioxanthone, azo dimethyl N-2-hydroxybutyl propionamide, azo diisobutyl amidine hydrochloride and phenyl (2, 4, 6-trimethylbenzoyl) lithium phosphate.
3. The preparation method according to claim 2, characterized in that:
the diisocyanate is at least one selected from hydrogenated phenyl methane diisocyanate, isophorone diisocyanate (IPDI) and hexamethylene diisocyanate;
the hydroxyl-terminated polyester or polyether polyol is at least one selected from polycaprolactone diol, polylactic acid diol, polyethylene glycol adipate diol, polybutylene glycol adipate diol, polyethylene glycol, polypropylene glycol and polytetrahydrofuran diol;
the hydroxyl-terminated polyol has a number average molecular weight of 1000-10000 g/mol;
the polyalcohol containing allyl is at least one of trimethylolpropane monoallyl ether and trimethylolpropane diallyl ether;
The hydroxyl-containing (methyl) acrylic ester is at least one selected from hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate and hydroxypropyl methacrylate.
4. A method of preparation according to claim 2 or 3, characterized in that: the allyl modified polyurethane (methyl) acrylic ester is prepared by the following steps:
S1: in the presence of a catalyst, mixing diisocyanate with hydroxyl-terminated polyester or polyether polyol and allyl-containing polyol, and carrying out gradual addition polymerization reaction to obtain isocyanate-terminated prepolymer;
S2: reacting the isocyanate group-terminated prepolymer prepared above with hydroxyl-containing (meth) acrylate, and adding a polymerization inhibitor during the reaction to obtain allyl-modified polyurethane (meth) acrylate;
preferably, in the step S1, the catalyst is a tertiary amine catalyst or an organometallic catalyst;
preferably, in the step S2, the polymerization inhibitor is at least one selected from hydroquinone and p-methoxyphenol;
Preferably, 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;
Preferably, in the step S2, the amount of the polymerization inhibitor is 50 to 1000ppm; the reaction temperature of the reaction is 50-100 ℃ and the reaction time is 1-12 h;
Preferably, in the preparation process of the allyl modified polyurethane (methyl) acrylate, the feeding mole ratio of the diisocyanate, the hydroxyl terminated polyester or polyether polyol, the allyl-containing polyol and the hydroxyl-containing (methyl) acrylate is 1: (0.2-0.5): (0.2-0.5): (0.2-0.8).
5. The method according to any one of claims 1 to 4, wherein: in the step (1), the preparation of the elastomer photosensitive resin comprises the following steps: weighing the allyl modified polyurethane (methyl) acrylic ester and the photo-curing diluent according to the proportion, pouring the mixture into a stirrer, and mechanically stirring and uniformly mixing the mixture under the condition of avoiding light.
6. The production method according to any one of claims 1 to 5, characterized in that: in the step (3), the water-soluble photo-curing monomer is at least one selected from acrylamide, N-isopropyl acrylamide, hydroxyethyl acrylate, acrylic acid, methacrylic acid and N-vinyl pyrrolidone;
Or, in the step (3), the water-soluble photo-curing cross-linking agent is at least one selected from polyethylene glycol diacrylate, polyethylene glycol dimethacrylate, N-methylene bisacrylamide, aqueous polyurethane acrylate and aqueous polyurethane methacrylate;
Or, in the step (3), the mercapto monomer is at least one selected from ethylene glycol di (3-mercaptopropionate), 1, 4-butanediol di (3-mercaptopropionate), trimethylolpropane tri (3-mercaptopropionate), pentaerythritol tetra (3-mercaptopropionate) and polyethylene glycol dithiol;
Or, in the step (3), the inorganic salt is at least one selected from sodium chloride, potassium chloride, lithium chloride and calcium chloride;
Or, in the step (3), the photoinitiator is at least one selected from (2, 4, 6-trimethylbenzoyl) diphenyl phosphine oxide, azodimethyl N-2-hydroxybutyl propionamide, phenyl bis (2, 4, 6-trimethylbenzoyl) phosphine oxide, ethyl (2, 4, 6-trimethylbenzoyl) phosphonate, benzophenone, isopropyl thioxanthone, 2, 4-dimethylthioxanthone and phenyl (2, 4, 6-trimethylbenzoyl) lithium phosphate.
7. The production method according to any one of claims 1 to 6, characterized in that: in the step (3), the preparation of the hydrogel photosensitive resin comprises the following steps: weighing the water-soluble photocuring monomer, the photocuring crosslinking agent, the sulfhydryl monomer and the photoinitiator according to the proportion, pouring the mixture into a stirrer, and mechanically stirring and uniformly mixing the mixture under the light-shielding condition.
8. The production method according to any one of claims 1 to 7, characterized in that:
in the step (2), the photo-curing 3D printing is selected from at least one of the following: light curing Stereolithography (SLA), digital light processing light curing 3D printing (DLP), continuous Liquid Interface (CLIP) printing;
Or, in the step (4), the curing process is as follows: and (5) curing for 10-30min by adopting ultraviolet light in an ultraviolet box.
9. The elastomer-reinforced hydrogel composite with strong interface bonding of any one of claims 1-8.
10. Use of the elastomer-reinforced hydrogel composite with strong interfacial bonding of claim 9 for the preparation of at least one of the following products: flexible sensor, solid electrolyte, tissue engineering scaffold.
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