CN110684162B - 4D printing resin and preparation method and application thereof - Google Patents
4D printing resin and preparation method and application thereof Download PDFInfo
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- CN110684162B CN110684162B CN201910833466.2A CN201910833466A CN110684162B CN 110684162 B CN110684162 B CN 110684162B CN 201910833466 A CN201910833466 A CN 201910833466A CN 110684162 B CN110684162 B CN 110684162B
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- acrylate
- methacrylate
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- 239000011347 resin Substances 0.000 title claims abstract description 74
- 229920005989 resin Polymers 0.000 title claims abstract description 74
- 238000007639 printing Methods 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 125000003172 aldehyde group Chemical group 0.000 claims abstract description 43
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 38
- NIXOWILDQLNWCW-UHFFFAOYSA-M acrylate group Chemical group C(C=C)(=O)[O-] NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 35
- 125000003277 amino group Chemical group 0.000 claims abstract description 34
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 15
- 230000002441 reversible effect Effects 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 7
- -1 2- (acryloyloxy) ethyl Chemical group 0.000 claims description 58
- 238000010146 3D printing Methods 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 23
- 239000007788 liquid Substances 0.000 claims description 21
- GOUHYARYYWKXHS-UHFFFAOYSA-N 4-formylbenzoic acid Chemical compound OC(=O)C1=CC=C(C=O)C=C1 GOUHYARYYWKXHS-UHFFFAOYSA-N 0.000 claims description 20
- 238000001723 curing Methods 0.000 claims description 19
- JHPBZFOKBAGZBL-UHFFFAOYSA-N (3-hydroxy-2,2,4-trimethylpentyl) 2-methylprop-2-enoate Chemical compound CC(C)C(O)C(C)(C)COC(=O)C(C)=C JHPBZFOKBAGZBL-UHFFFAOYSA-N 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 11
- 230000001476 alcoholic effect Effects 0.000 claims description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- 238000001029 thermal curing Methods 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 8
- RZVINYQDSSQUKO-UHFFFAOYSA-N 2-phenoxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC1=CC=CC=C1 RZVINYQDSSQUKO-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000000016 photochemical curing Methods 0.000 claims description 7
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 6
- 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 6
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 6
- 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 6
- 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 6
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 5
- 238000009833 condensation Methods 0.000 claims description 5
- 230000005494 condensation Effects 0.000 claims description 5
- 238000006482 condensation reaction Methods 0.000 claims description 5
- 238000004132 cross linking Methods 0.000 claims description 5
- 230000003213 activating effect Effects 0.000 claims description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- 239000012956 1-hydroxycyclohexylphenyl-ketone Substances 0.000 claims description 3
- FZSHSWCZYDDOCK-UHFFFAOYSA-N 2-methylprop-2-enoic acid;oxolane Chemical compound C1CCOC1.CC(=C)C(O)=O FZSHSWCZYDDOCK-UHFFFAOYSA-N 0.000 claims description 3
- CEXQWAAGPPNOQF-UHFFFAOYSA-N 2-phenoxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOC1=CC=CC=C1 CEXQWAAGPPNOQF-UHFFFAOYSA-N 0.000 claims description 3
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 3
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 claims description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 3
- MQDJYUACMFCOFT-UHFFFAOYSA-N bis[2-(1-hydroxycyclohexyl)phenyl]methanone Chemical compound C=1C=CC=C(C(=O)C=2C(=CC=CC=2)C2(O)CCCCC2)C=1C1(O)CCCCC1 MQDJYUACMFCOFT-UHFFFAOYSA-N 0.000 claims description 3
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 claims description 3
- 229940119545 isobornyl methacrylate Drugs 0.000 claims description 3
- JRWNODXPDGNUPO-UHFFFAOYSA-N oxolane;prop-2-enoic acid Chemical compound C1CCOC1.OC(=O)C=C JRWNODXPDGNUPO-UHFFFAOYSA-N 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 claims description 2
- 238000013007 heat curing Methods 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 230000003301 hydrolyzing effect Effects 0.000 claims description 2
- BFYJDHRWCNNYJQ-UHFFFAOYSA-N oxo-(3-oxo-3-phenylpropoxy)-(2,4,6-trimethylphenyl)phosphanium Chemical compound CC1=CC(C)=CC(C)=C1[P+](=O)OCCC(=O)C1=CC=CC=C1 BFYJDHRWCNNYJQ-UHFFFAOYSA-N 0.000 claims description 2
- 229920000431 shape-memory polymer Polymers 0.000 abstract description 11
- 230000008859 change Effects 0.000 abstract description 8
- 239000011521 glass Substances 0.000 abstract description 2
- 230000006399 behavior Effects 0.000 abstract 1
- 230000007334 memory performance Effects 0.000 abstract 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 17
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 9
- 238000001914 filtration Methods 0.000 description 9
- 239000002244 precipitate Substances 0.000 description 9
- 238000012545 processing Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 8
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 238000004440 column chromatography Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 5
- 239000004033 plastic Substances 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 4
- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-Ethyl-3-(3-dimethylaminopropyl)carbodiimide Substances CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 description 4
- ASOKPJOREAFHNY-UHFFFAOYSA-N 1-Hydroxybenzotriazole Chemical compound C1=CC=C2N(O)N=NC2=C1 ASOKPJOREAFHNY-UHFFFAOYSA-N 0.000 description 4
- FPQQSJJWHUJYPU-UHFFFAOYSA-N 3-(dimethylamino)propyliminomethylidene-ethylazanium;chloride Chemical compound Cl.CCN=C=NCCCN(C)C FPQQSJJWHUJYPU-UHFFFAOYSA-N 0.000 description 4
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000001588 bifunctional effect Effects 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 238000001819 mass spectrum Methods 0.000 description 3
- 229920001610 polycaprolactone Polymers 0.000 description 3
- 239000004632 polycaprolactone Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 238000002390 rotary evaporation Methods 0.000 description 3
- 239000012781 shape memory material Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 2
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 description 2
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002520 smart material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- ZMDDERVSCYEKPQ-UHFFFAOYSA-N Ethyl (mesitylcarbonyl)phenylphosphinate Chemical compound C=1C=CC=CC=1P(=O)(OCC)C(=O)C1=C(C)C=C(C)C=C1C ZMDDERVSCYEKPQ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- RBQRWNWVPQDTJJ-UHFFFAOYSA-N methacryloyloxyethyl isocyanate Chemical compound CC(=C)C(=O)OCCN=C=O RBQRWNWVPQDTJJ-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
Images
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
-
- 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
-
- 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
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Silicon Polymers (AREA)
Abstract
The invention discloses a 4D printing resin and a preparation method and application thereof. The resin comprises a fixed phase and a reversible phase, wherein the fixed phase is a cross-linked network structure formed by aldehyde groups on acrylate chains and amino groups of hyperbranched siloxane, and the reversible phase is a reversible phase which is formed by the acrylate chains and the hyperbranched siloxane and can change between a glass state and a rubber state along with temperature change. The preparation raw materials comprise: acrylate or methacrylate with aldehyde group, hyperbranched siloxane with amino group, commercial monofunctional acrylate or monofunctional methacrylate, and photoinitiator. The 4D printing resin prepared by the invention has excellent shape memory performance. And due to the reversible covalent bond, the resin can realize two diametrically opposite behaviors of temporary deformation and permanent deformation of the same shape memory polymer under different temperature conditions, and the application range of the 4D printing material can be greatly widened.
Description
Technical Field
The invention relates to a 4D printing resin, a preparation method and application thereof, in particular to a 4D printing shape memory polymer with dynamic reversible crosslinking constructed by reversible imine bonds, a preparation method and application thereof, and belongs to the field of intelligent polymer materials.
Background
Three-dimensional (3D) printing is a commonly applied additive manufacturing technique. It has multiple advantages over conventional manufacturing processes, particularly in the production of 3D objects with complex structures and precise dimensions. 3D printing has been widely used in the fields of personalized consumer products, flexible robots, nano devices, biomedical materials, aerospace, and the like. Recently, a fourth dimension, time, was added to 3D printing to make it intelligent, and a new four-dimensional (4D) printing concept was formed.
4D printing can be achieved by incorporating smart materials, Shape Memory Polymers (SMPs), into the 3D printing process. SMPs can respond to external stimuli (e.g., thermal, electrical, optical, magnetic, etc.) to change their shape over time, adding a time dimension to 3D printed structures, enabling 4D printing. In 4D printing materials, SMPs have the advantages of fast response and high strength. Shlomo Magdassi et al reacted polycaprolactone with isocyanoethyl methacrylate to produce bifunctional polycaprolactone-type methacrylates, which were 4D printed for use in flexible electronic devices (see: Matt Zarek, Michael Layani, Ido Cooperstein, Ela Sachyani, Daniel Cohn, and Shlomo Magdasi. advanced Materials,2016,28, 4449. sup. 4454). Ge et al blending polycaprolactone into methacrylate cross-linked resin systems to prepare 4D prints that are self-healing due to the presence of polycaprolactone (see documents: Biao Zhang, Wang Zhang, Zhiqiian Zhang, Yuan-Fang Zhang, Hardik Hingorani, Zhuangjian Liu, Jun Liu, and Qi Ge. ACS Applied Materials & Interfaces,2019,11, 10328-. These efforts have largely driven the development of 4D printing.
However, the photo-curing 4D printing shape memory materials reported in the prior art are generally bifunctional acrylate monomers, which are obtained by homopolymerization or copolymerization with other commercial monofunctional acrylate monomers to obtain a cross-linked polyacrylate resin. SMPs are typically cross-linked by covalent bonds, topologically fixed, and once the cross-linked structure is formed, its permanent shape cannot be changed. In practical use, the permanent shape of an object plays a crucial role in its function, and thus the change of the permanent shape of the 4D printing resin is of great significance to the widening of its application range.
Seawa et al propose a new class of smart materials (see: Zhengning, Seawa, Theradata shape memory polymers, macromolecules, 11 th 2017) named Thermadape memorypolmers, TASMPs, whose permanent shape can be changed by topological rearrangement (solid state plasticity) due to the dynamic covalent bonds in the TASMPs. However, the conventional TASMPs can only be used in the conventional process, and still have the defects of complex process, high material consumption and the like.
Therefore, it is an urgent technical problem to develop a 4D printing resin with dynamic cross-linking to widen the application range of 4D printing materials.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a 4D printing resin and a preparation method and application thereof.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the resin comprises a fixed phase and a reversible phase, wherein the fixed phase is a cross-linked network structure formed by aldehyde groups on acrylate chains and amino groups of hyperbranched siloxane, and the reversible phase is a reversible phase which is formed by the acrylate chains and the hyperbranched siloxane and can change between a glass state and a rubber state along with the change of temperature. According to the technical scheme of the invention, the preparation raw materials of the resin comprise:
acrylate or methacrylate with aldehyde group, hyperbranched siloxane with amino group, monofunctional acrylate or monofunctional methacrylate, and photoinitiator. Further, the mass ratio of the acrylate with aldehyde group or the methacrylate with aldehyde group, the hyperbranched siloxane with amino group, the monofunctional acrylate or the monofunctional methacrylate is (1-99) to (1-30) to (1-99), for example, the mass ratio is (1-60) to (5-25) to (10-90), and further, is (3-30) to (10-20) to (30-70); illustratively, the mass ratio is 10:10:90, 10:15:90, 10:20:90, 10:1:90, 10:30:90, 10:3: 90.
According to the technical scheme of the invention, the acrylate with aldehyde group can be selected from 2- (acryloyloxy) ethyl 4-formyl benzoate and/or 3- (acryloyloxy) ethyl 4-formyl benzoate.
According to the technical scheme of the invention, the methacrylate with aldehyde group can be selected from 2- (methacryloyloxy) ethyl 4-formyl benzoate and/or 3- (methacryloyloxy) ethyl 4-formyl benzoate.
According to the technical scheme of the invention, the hyperbranched siloxane with amino can be obtained by hydrolyzing 3-aminopropyltrimethoxysilane or 3-aminopropyltriethoxysilane.
According to the technical scheme of the invention, the monofunctional acrylate is a commercial monofunctional acrylate, for example, at least one selected from the group consisting of tetrahydrofuran acrylate, 2-phenoxyethyl acrylate, isobornyl acrylate and trimethylolpropane formal acrylate, and can be obtained from a commercial source.
According to the invention, the monofunctional methacrylate is a commercially available monofunctional methacrylate, and may be at least one selected from the group consisting of tetrahydrofuran methacrylate, 2-phenoxyethyl methacrylate, isobornyl methacrylate, benzyl methacrylate, and cyclohexyl methacrylate, for example, and may be obtained from a commercially available source.
The above monofunctional acrylates and monofunctional methacrylates do not contain an aldehyde group.
According to the technical scheme of the invention, the photoinitiator is selected from at least one of 1-hydroxycyclohexyl phenyl ketone, 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide, 2,4, 6-trimethylbenzoyl-ethoxy-phenyl phosphine oxide, bis (2,4, 6-trimethylbenzoyl) -phenyl phosphine oxide, 2-dimethoxy-1, 2-diphenylethanone, 2-ethyloctyl-4-dimethylamino benzoate and 4-p-toluene 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-acetone.
Further, the mass ratio of the photoinitiator to the amino group-containing hyperbranched siloxane is (0.5-5): 1-30), for example, the mass ratio is (1-3): 5-20, and exemplarily, the mass ratio is 1:5, 2:15, 1:10, 5:1, 0.5:30, 2: 3.
According to the technical scheme of the invention, the resin is shape memory resin. Further, the resin contains a dynamic cross-linking structure-reversible imine bond, and temporary deformation and permanent deformation of the resin can be achieved under different temperature conditions. Further, the temperature is the glass transition temperature ± 10 ℃ or the glass transition temperature + (50-70 ℃).
According to an aspect of the invention, the tensile strength of the resin is 4-15MPa, such as 6-12MPa, and by way of example, the tensile strength is 4.24MPa, 7.83MPa, 11.27 MPa.
According to an embodiment of the invention, the resin has a toughness of 1 to 3.5MPa, such as 2 to 3MPa, and for example, a toughness of 1.04MPa, 2.09MPa, 2.85 MPa.
According to the technical scheme of the invention, the shape fixing rate of the resin is more than 97%, for example more than 97.5% and more than 97.8%.
According to an aspect of the present invention, the shape recovery rate of the resin is 90% or more, for example 91% or more, and exemplarily 91.2%, 92%, 93.8%.
Further, the present invention also provides a method for preparing the above resin, the method comprising: and mixing and uniformly mixing acrylic ester with aldehyde group or methacrylic ester with aldehyde group, monofunctional acrylic ester or monofunctional methacrylic ester, a photoinitiator and hyperbranched siloxane with amino group, performing photocuring 3D printing, and then performing thermocuring to obtain the 4D printing resin.
According to the technical scheme of the invention, the preparation process of the acrylate or methacrylate with aldehyde group comprises the following steps: acrylic ester with alcoholic hydroxyl or methacrylic ester with alcoholic hydroxyl and p-formylbenzoic acid are taken as raw materials, and are subjected to condensation reaction in the presence of a condensing agent and a condensation activating agent to prepare acrylic ester with aldehyde group or methacrylic ester with aldehyde group. Wherein the acrylate with alcoholic hydroxyl group is selected from hydroxyethyl acrylate or hydroxypropyl acrylate; the methacrylate with alcoholic hydroxyl group is selected from hydroxyethyl methacrylate or hydroxypropyl methacrylate. Wherein the condensing agent is a carbodiimide compound, such as at least one of 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride and N, N' -dicyclohexylcarbodiimide. Wherein the condensation activator may be at least one selected from 4-dimethylaminopyridine, 1-hydroxybenzotriazole and the like. Further, the mol ratio of the acrylic ester with alcoholic hydroxyl group or the methacrylic ester with alcoholic hydroxyl group, the p-formylbenzoic acid, the condensing agent and the condensation activating agent is 1 (0.9-1.1) to (1-2) to (0.1-2), such as 1 (0.9-1.1) to (1.2-1.5) to (0.15-1.5); illustratively, the molar ratio is 1:1:1:0.1, 1:0.9:1.5:0.2, 1:1:2:0.15, 1:1:2:2, 1:0.9:1:1, 1.1:1:1.5: 1.5. Further, the condensation reaction is carried out at room temperature for 12-72 h; for example, the temperature is 20-40 ℃, and the reaction time is 6-48 h; illustratively, the temperature is 20 ℃, 30 ℃ or 40 ℃ and the time can be 6h, 12h, 24h or 48 h. Further, the condensation reaction is carried out in a solvent, and the solvent may be at least one selected from tetrahydrofuran, dichloromethane, and the like.
According to the technical scheme of the invention, the hyperbranched siloxane with amino can be obtained by hydrolysis reaction of a silane coupling agent with amino. Wherein the silane coupling agent with amino groups is selected from at least one of 3-aminopropyltrimethoxysilane and 3-aminopropyltriethoxysilane. Further, the hydrolysis temperature of the silane coupling agent with amino is 50-80 ℃, and the reaction time is 2-8 h; for example, the temperature is 60-70 ℃, and the reaction time is 3-6 h; illustratively, the temperature is 50 ℃, 60 ℃, 70 ℃ or 80 ℃ and the time is 2h, 4h, 6h, 8 h.
According to the technical scheme of the invention, the acrylate with aldehyde group, the methacrylate with aldehyde group, the monofunctional acrylate, the monofunctional methacrylate, the photoinitiator and the hyperbranched siloxane with amino group have the meanings and the proportions as described above.
According to the technical scheme of the invention, the operation of mixing in the resin preparation method comprises the following steps: the acrylate with aldehyde group or the methacrylate with aldehyde group, the monofunctional acrylate or the monofunctional methacrylate and the photoinitiator can be heated, stirred and mixed uniformly, and then the mixture is cooled to room temperature, and then the hyperbranched siloxane with amino group is added and stirred to obtain clear liquid. Wherein the temperature of the heating and mixing is 60 to 90 deg.C, such as 65 to 85 deg.C, and as an example, 70 deg.C, 80 deg.C.
According to the technical solution of the present invention, the 3D printing may be performed in a 3D printer known in the art, such as a Digital Light Processing (DLP)3D printer, for example, a 405nm Digital Light Processing (DLP)3D printer is selected.
According to the technical scheme of the invention, the photocuring comprises the following steps: the UV light is cured for 3-10min, for example 4-8min, and illustratively 5 min.
According to an aspect of the present invention, the heat curing includes: curing temperatures of 50-90 deg.C, such as 60-80 deg.C, for example, at 60 deg.C, 70 deg.C, 80 deg.C, 90 deg.C; the curing time is 6-48h, for example 8-40h, as an example 8h, 24h, 36 h.
According to an embodiment of the present invention, the method of preparing the resin comprises:
(1) taking acrylic ester with alcoholic hydroxyl or methacrylic ester with alcoholic hydroxyl and p-formylbenzoic acid as raw materials, taking carbodiimide compounds as condensing agents, and carrying out condensation reaction under the condition of a condensation activating agent to prepare acrylic ester with aldehyde group or methacrylic ester with aldehyde group;
(2) obtaining hyperbranched siloxane with amino through hydrolysis reaction of a silane coupling agent with amino;
(3) mixing and uniformly mixing acrylic ester with aldehyde group or methacrylic ester with aldehyde group, commercial monofunctional acrylic ester, commercial monofunctional methacrylic ester, photoinitiator and hyperbranched siloxane with amino group, firstly carrying out photocuring 3D printing, and then carrying out thermocuring to obtain the resin.
Further, the present invention provides the use of the above resin as a 4D printing material.
The invention has the beneficial effects that:
1. the photo-curing 4D printing shape memory materials reported in the prior art are generally bifunctional acrylate monomers, and then homopolymerized or copolymerized with other commercialized monofunctional acrylate monomers to obtain the crosslinking polyacrylate resin. Once the permanent crosslinks are formed, their permanent shape cannot be changed. In contrast, the 4D printing resin prepared by the present invention has a dynamic cross-linked structure, and can realize 2 diametrically opposite states of temporary deformation (elasticity) and permanent deformation (plasticity) of the same shape memory polymer under different temperature conditions.
2. The prior reported thermoadaptive shape memory polymer can only be used in the traditional process, and still has the defects of complex process, large material consumption, incapability of constructing complex structures and the like. The thermoadaptive shape memory polymer prepared by the method can be formed by 3D printing additive manufacturing, can be printed into a complex shape, and is high in precision.
3. Different from the prior art, the 4D printing resin provided by the invention has a large number of flexible siloxane structures, and the obtained resin has excellent mechanical properties.
4. The preparation method of the 4D printing resin provided by the invention has the characteristics of environmental protection, green color, simple preparation process, good process controllability and easiness in industrial production.
Drawings
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of 2- (methacryloyloxy) ethyl 4-formylbenzoate prepared in example 1 of the present invention;
FIG. 2 is a carbon nuclear magnetic resonance spectrum of 2- (methacryloyloxy) ethyl 4-formylbenzoate prepared in example 1 of the present invention;
FIG. 3 is a high resolution mass spectrum of 2- (methacryloyloxy) ethyl 4-formylbenzoate prepared in example 1 of the present invention;
FIG. 4 is an IR spectrum of 4D printed resins prepared according to examples 1,2, 3 and comparative example 1 of the present invention;
FIG. 5 is a shape memory process of a 4D printed flower prepared according to example 1 of the present invention;
FIG. 6 is a DMA diagram of the shape memory and plastic deformation reconfiguration process of the 4D printing material prepared in example 3 of the present invention;
fig. 7 is an illustration of the plastic deformation reconstruction and shape memory process of the 3D printed box prepared in example 3 of the present invention.
Detailed Description
The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
The resin properties were tested according to: the tensile test was carried out according to ISO 527 standard at a tensile speed of 2mm min-1The span was 25mm and the toughness was calculated from the integrated area of the tensile stress-strain curve.
Example 1
1) Preparation of methacrylate containing functional aldehyde group
52.1g of hydroxyethyl methacrylate, 60.1g of p-formylbenzoic acid and 4.89g of 4-dimethylaminopyridine are dissolved in 700mL of tetrahydrofuran and stirred, a tetrahydrofuran (300mL) solution of N, N' -dicyclohexylcarbodiimide (82.6g) is added dropwise, after the dropwise addition, the reaction solution slowly rises to 20 ℃, the reaction is continued for 48 hours, the reaction solution is obtained by filtration, the tetrahydrofuran is removed by vacuum rotary evaporation, 200mL of diethyl ether is added, and the precipitate is removed by filtration. The solution was then placed in a refrigerator overnight and the precipitate was removed by filtration. This step was repeated until no precipitate was present. Then dried over anhydrous sodium sulfate. After removal of the solvent, the residue was purified by column chromatography to give 2- (methacryloyloxy) ethyl 4-formylbenzoate. The hydrogen nuclear magnetic resonance spectrum, the carbon nuclear magnetic resonance spectrum and the high-resolution mass spectrum of the 2- (methacryloyloxy) ethyl 4-formylbenzoate are respectively shown in the figures 1,2 and 3.
2) Preparation of hyperbranched siloxanes with amino groups
A solution of 3-aminopropyltriethoxysilane (110.7g) and deionized water (10.8g) in ethanol (100mL) was reacted at 60 ℃ for 4 hours. After cooling to room temperature, the obtained solution was dried over anhydrous sodium sulfate, and the filtrate was rotary evaporated to obtain a clear liquid which was hyperbranched siloxane with amino groups.
3) Preparation of 4D printing resin
Isobornyl acrylate (60g), 2-phenoxyethyl acrylate (30g), 2- (methacryloyloxy) ethyl 4-formylbenzoate (10g), 2,4, 6-trimethylbenzoyl-diphenyl phosphorus oxide (1g) and bis (2,4, 6-trimethylbenzoyl) -phenyl phosphorus oxide (1g) are stirred at 70 ℃ for 10min to be uniformly mixed, cooled to room temperature, 10g of the amino-containing hyperbranched siloxane prepared in the step (2) is added and stirred for 5min to obtain clear liquid, and the obtained liquid is put into a 405nm Digital Light Processing (DLP)3D printer for 3D printing and forming. And (3) placing the printed 3D printing structure into an ultraviolet curing box, curing for 5min, and then placing into an oven, and performing thermocuring for 24h at 70 ℃ to enable an aldehyde group and an amino group to react to obtain a dynamic imine bond (see an infrared spectrogram in figure 4), so as to obtain the 4D printing resin.
FIG. 1 is a NMR spectrum of 2- (methacryloyloxy) ethyl 4-formylbenzoate, and it is understood that about 5.61ppm and 6.15ppm represent H at the vinyl double bond, about 10.11ppm represents H at the aldehyde group, and other peaks coincide with the H proton shifts of 2- (methacryloyloxy) ethyl 4-formylbenzoate, confirming the synthesis of the expected substance.
FIG. 2 is a NMR carbon spectrum of 2- (methacryloyloxy) ethyl 4-formylbenzoate, and from the chart, characteristic peaks (126.28ppm and 135.85ppm) of carbon atoms of vinyl double bonds and characteristic peaks (191.66ppm) of carbon atoms of aldehyde groups appeared, and the other peaks coincided with the characteristic peaks of carbon atoms of 2- (methacryloyloxy) ethyl 4-formylbenzoate, confirming that the desired substance was synthesized.
FIG. 3 is a high resolution mass spectrum of 2- (methacryloyloxy) ethyl 4-formylbenzoate, theoretical value [ M + Na ]+]285.0733, experimental value 285.0732, which corresponds to the theoretical value.
As can be seen from the ir spectrum of the 4D printing resin prepared in example 1 of fig. 4, the prepared 4D printing resin exhibited a characteristic peak (1641 cm) having C ═ N bond-1) The success of the preparation is indicated. Referring to Table 1, the tensile strength of the obtained resin was 11.2MPa, the toughness was 2.9MPa, the shape fixation rate was 97.5%, and the shape recovery rate was 93.8%.
Referring to fig. 5, which is a shape memory process of a 4D printed flower, firstly, a flower (original shape) which blooms is printed by a DLP printer, the temperature is raised to 76 ℃ (glass transition temperature +10 ℃), the flower is closed and cooled and fixed (temporary shape) under the action of external force, and when the polymer with the temporary shape is reheated to 76 ℃, the flower spontaneously blooms and returns to the original state (shape recovery).
Example 2
1) Preparation of methacrylate containing functional aldehyde group
52.1g of hydroxyethyl methacrylate, 54.1g of p-formylbenzoic acid and 9.78g of 4-dimethylaminopyridine are dissolved in 600mL of tetrahydrofuran and stirred, a tetrahydrofuran (400mL) solution of N, N' -dicyclohexylcarbodiimide (123.8g) is added dropwise, after the dropwise addition, the reaction solution slowly rises to 40 ℃, the reaction is continued for 12 hours, the reaction solution is obtained by filtration, the tetrahydrofuran is removed by vacuum rotary evaporation, 300mL of diethyl ether is added, and the precipitate is removed by filtration. The solution was then placed in a refrigerator overnight and the precipitate was removed by filtration. This step was repeated until no precipitate was present. Then dried over anhydrous sodium sulfate. After removal of the solvent, the residue was purified by column chromatography to give 2- (methacryloyloxy) ethyl 4-formylbenzoate.
2) Preparation of hyperbranched siloxanes with amino groups
A solution of 3-aminopropyltriethoxysilane (110.7g) and deionized water (10.8g) in ethanol (100mL) was reacted at 60 ℃ for 4 hours. After cooling to room temperature, the obtained solution was dried over anhydrous sodium sulfate, and the filtrate was rotary evaporated to obtain a clear liquid which was hyperbranched siloxane with amino groups.
3) Preparation of 4D printing resin
Isobornyl acrylate (60g), 2-phenoxyethyl acrylate (30g), 2- (methacryloyloxy) ethyl 4-formylbenzoate (10g), 2,4, 6-trimethylbenzoyl-diphenyl phosphorus oxide (1g) and bis (2,4, 6-trimethylbenzoyl) -phenyl phosphorus oxide (1g) are stirred and uniformly mixed at 70 ℃ for 10min, cooled to room temperature, added with 15g of the amino-containing hyperbranched siloxane obtained in the step (2) and continuously stirred for 5min to obtain clear liquid, and the obtained liquid is put into a 405nm Digital Light Processing (DLP)3D printer for 3D printing and forming. And (3) placing the printed 3D printing structure into an ultraviolet curing box, curing for 5min, and then placing into an oven, and performing thermal curing at 70 ℃ for 24h to obtain 4D printing resin.
As can be seen from the infrared spectrum of the 4D printing resin prepared in example 2 in fig. 4, the prepared 4D printing resin exhibited a characteristic peak (1641 cm) having C ═ N bond-1) The success of the preparation is indicated.
Referring to Table 1, the tensile strength of the obtained resin was 7.8MPa, the toughness was 2.1MPa, the shape fixation rate was 97.5%, and the shape recovery rate was 92%.
Example 3
1) Preparation of methacrylate containing functional aldehyde group
52.1g of hydroxyethyl methacrylate, 66.1g of p-formylbenzoic acid and 7.34g of 4-dimethylaminopyridine are dissolved in 600mL of tetrahydrofuran and stirred, a tetrahydrofuran (400mL) solution of N, N' -dicyclohexylcarbodiimide (165.0g) is added dropwise, after the dropwise addition, the reaction solution slowly rises to 20 ℃, the reaction is continued for 24 hours, the reaction solution is obtained by filtration, the tetrahydrofuran is removed by vacuum rotary evaporation, 300mL of diethyl ether is added, and the precipitate is removed by filtration. The solution was then placed in a refrigerator overnight and the precipitate was removed by filtration. This step was repeated until no precipitate was present. Then dried over anhydrous sodium sulfate. After removal of the solvent, the residue was purified by column chromatography to give 2- (methacryloyloxy) ethyl 4-formylbenzoate.
2) Preparation of hyperbranched siloxanes with amino groups
A solution of 3-aminopropyltriethoxysilane (110.7g) and deionized water (10.8g) in ethanol (100mL) was reacted at 60 ℃ for 4 hours. After cooling to room temperature, the obtained solution was dried over anhydrous sodium sulfate, and the filtrate was rotary evaporated to obtain a clear liquid which was hyperbranched siloxane with amino groups.
3) Preparation of 4D printing resin
Isobornyl acrylate (60g), 2-phenoxyethyl acrylate (30g), 2- (methacryloyloxy) ethyl 4-formylbenzoate (10g), 2,4, 6-trimethylbenzoyl-diphenyl phosphorus oxide (1g) and bis (2,4, 6-trimethylbenzoyl) -phenyl phosphorus oxide (1g) are stirred and uniformly mixed at 70 ℃ for 10min, cooled to room temperature, 20g of the amino-containing hyperbranched siloxane prepared in the step (2) is added and continuously stirred for 5min to obtain clear liquid, and the obtained liquid is put into a 405nm Digital Light Processing (DLP)3D printer for 3D printing and forming. And (3) placing the printed 3D printing structure into an ultraviolet curing box, curing for 5min, and then placing into an oven, and performing thermal curing at 70 ℃ for 24h to obtain 4D printing resin.
As can be seen from the infrared spectrum of the 4D printing resin prepared in example 3 in fig. 4, the prepared 4D printing resin exhibited a characteristic peak (1641 cm) having C ═ N bond-1) The success of the preparation is indicated.
Referring to Table 1, the tensile strength of the obtained resin was 4.2MPa, the toughness was 1.0MPa, the shape fixation rate was 97.8%, and the shape recovery rate was 91.2%.
Figure 6 is a DMA diagram of the shape memory and plastic deformation reconstitution process for the polymer prepared in example 3. As shown, the splines first undergo a shape memory process: heating to 67 ℃, applying external force to enable the sample strip to obtain 8% of strain, cooling to 0 ℃, removing the external force, and fixing the sample strip into a temporary shape; the bars with the temporary shape of 8% strain were then heated to 67 c and the bars were shape recovered to recover the original shape. And then, carrying out plastic deformation reconstruction on the sample strip: heating the sample strip to 120 ℃, and applying an external force to enable the sample strip to reach the strain capacity of 4%; keeping the temperature for 60min, and removing the external force; in the process, reversible imine bonds are activated, exchange reaction occurs, so that the internal stress of the sample strip is eliminated, and the sample strip obtains permanent deformation.
Fig. 7 is a diagram showing plastic deformation reconstruction and shape memory process of a box obtained by 3D printing of the polymer prepared in example 3. Heating to 67 ℃ (glass transition temperature +10 ℃), fixing the 3D printed unfolded box into a three-dimensional box under the action of external force, and wrapping and fixing the three-dimensional box shape by hard tinfoil paper after cooling; continuously heating to 120 ℃, and keeping the temperature and the external force to enable the imine bond of the 4D printing material to generate reversible dynamic exchange reaction and eliminate the internal stress; cooling to room temperature, and fixing the new shape of the three-dimensional box to form a new permanent shape of the 4D printing material; heating the polymer with the novel shape of the three-dimensional box to 67 ℃, applying external force, and unfolding the box into a plane temporary shape; cooling to room temperature and fixing the temporary shape; when the polymer with the temporary shape is reheated to 67 ℃, the polymer will automatically revert from the temporary shape of the unfolded box to the permanent shape of the three-dimensional box. The above results show that the 4D printing material prepared by the present invention can change permanent shape, and the change of permanent shape does not affect the shape memory property of the material.
Example 4
1) Preparation of acrylic ester containing functional aldehyde group
46.5g of hydroxyethyl acrylate and 60.1g of p-formylbenzoic acid were dissolved in methylene chloride (800mL), and 1-hydroxybenzotriazole (108.1g) and 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride (153.4g) were added to the above solution at 0 ℃ and slowly warmed to room temperature, followed by further reaction for 6 hours, washing with water after completion of the reaction and drying with anhydrous sodium sulfate. After removal of the solvent, the residue was purified by column chromatography to give 2- (acryloyloxy) ethyl 4-formylbenzoate.
2) Preparation of hyperbranched siloxanes with amino groups
A solution of 3-aminopropyltrimethoxysilane (89.7g) and deionized water (13.5g) in ethanol (150mL) was reacted at 80 ℃ for 2 hours. After cooling to room temperature, the obtained solution was dried over anhydrous sodium sulfate, and the filtrate was rotary evaporated to obtain a clear liquid which was hyperbranched siloxane with amino groups.
3) Preparation of 4D printing resin
Tetrahydrofuran acrylate (30g), isobornyl methacrylate (30g), trimethylolpropane formal acrylate (30g), 2- (acryloyloxy) ethyl 4-formylbenzoate (10g), 1-hydroxycyclohexyl phenyl ketone (2.5g) and 2,4, 6-trimethylbenzoyl-ethoxy-phenyl phosphorus oxide (2.5g) are stirred for 10min at 60 ℃ and uniformly mixed, the mixture is cooled to room temperature, 1g of the hyperbranched siloxane with amino groups prepared in the step (2) is added and stirred for 5min to obtain clear liquid, and the obtained liquid is put into a 405nm Digital Light Processing (DLP)3D printer for 3D printing and forming. And (3) placing the printed 3D printing structure into an ultraviolet curing box, curing for 5min, and then placing into an oven, and performing thermal curing for 8h at 90 ℃ to obtain 4D printing resin.
Example 5
1) Preparation of acrylic ester containing functional aldehyde group
52.1g of hydroxypropyl acrylate and 60.1g of p-formylbenzoic acid were dissolved in methylene chloride (500mL), and 1-hydroxybenzotriazole (59.5g) and 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride (84.3g) were added to the above solution at 0 ℃ and slowly warmed to room temperature, followed by further reaction for 10 hours, washing with water after completion of the reaction and drying with anhydrous sodium sulfate. After removal of the solvent, the residue was purified by column chromatography to give 3- (acryloyloxy) propyl 4-formylbenzoate.
2) Preparation of hyperbranched siloxanes with amino groups
A solution of 3-aminopropyltrimethoxysilane (89.7g) and deionized water (18g) in ethanol (200mL) was reacted at 50 ℃ for 8 hours. After cooling to room temperature, the obtained solution was dried over anhydrous sodium sulfate, and the filtrate was rotary evaporated to obtain a clear liquid which was hyperbranched siloxane with amino groups.
3) Preparation of 4D printing resin
Tetrahydrofuran methacrylate (40g), 2-phenoxyethyl acrylate (50g), 3- (acryloyloxy) propyl 4-formylbenzoate (10g), 2-dimethoxy-1, 2-diphenylethanone (0.25g) and 2-ethyloctyl-4-dimethylamino benzoate (0.25g) are stirred for 10min at 80 ℃ and uniformly mixed, cooled to room temperature, added with 30g of the amino-containing hyperbranched siloxane prepared in the step (2) and continuously stirred for 5min to obtain clear liquid, and the obtained liquid is put into a 405nm Digital Light Processing (DLP)3D printer for 3D printing and forming. And (3) placing the printed 3D printing structure into an ultraviolet curing box, curing for 5min, and then placing into an oven, and performing thermal curing for 36h at 60 ℃ to obtain 4D printing resin.
Example 6
1) Preparation of methacrylate containing functional aldehyde group
57.7g of hydroxypropyl methacrylate and 60.1g of p-formylbenzoic acid were dissolved in methylene chloride (600mL), and 1-hydroxybenzotriazole (81.1g) and 1-ethyl- (3-dimethylaminopropyl) carbodiimide hydrochloride (115.1g) were added to the above solution at 0 ℃ and slowly warmed to room temperature, followed by reaction for 8 hours, washing with water after completion of the reaction and drying with anhydrous sodium sulfate. After removal of the solvent, the residue was purified by column chromatography to give 3- (methacryloyloxy) propyl 4-formylbenzoate.
2) Preparation of hyperbranched siloxanes with amino groups
A solution of 3-aminopropyltrimethoxysilane (89.7g) and deionized water (10g) in ethanol (100mL) was reacted at 60 ℃ for 5 hours. After cooling to room temperature, the obtained solution was dried over anhydrous sodium sulfate, and the filtrate was rotary evaporated to obtain a clear liquid which was hyperbranched siloxane with amino groups.
3) Preparation of 4D printing resin
2-phenoxyethyl methacrylate (20g), cyclohexyl methacrylate (70g), 3- (methacryloyloxy) propyl 4-formylbenzoate (10g) and 4-p-toluene 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-acetone (2g) are stirred for 10min at 80 ℃ and uniformly mixed, cooled to room temperature, added with 3g of the hyperbranched siloxane with amino group prepared in the step (2) and continuously stirred for 5min to obtain clear liquid, and the obtained liquid is put into a Digital Light Processing (DLP)3D printer with the wavelength of 405nm for 3D printing and forming. And (3) placing the printed 3D printing structure into an ultraviolet curing box, curing for 5min, and then placing into an oven, and performing thermal curing for 36h at 60 ℃ to obtain 4D printing resin.
Comparative example 1 preparation of a hyperbranched Silicone Polymer
Isobornyl acrylate (60g), 2-phenoxyethyl acrylate (30g), 2- (methacryloyloxy) ethyl 4-formylbenzoate (10g) prepared in example 3, 2,4, 6-trimethylbenzoyl-diphenylphosphorus oxide (1g), and bis (2,4, 6-trimethylbenzoyl) -phenylphosphorus oxide (1g) were uniformly mixed by stirring at 70 ℃ for 10min, and the resulting liquid was put into a 405nm Digital Light Processing (DLP)3D printer and subjected to 3D printing molding. And (3) placing the printed 3D printing structure into an ultraviolet curing box, curing for 5min, and then placing into an oven to be thermally cured for 24h at 70 ℃.
As can be seen from the ir spectrum of the 4D printed resin prepared in comparative example 1 of fig. 4, the resin without hyperbranched siloxane in comparative example 1 has no characteristic peak of C ═ N bond.
Referring to Table 1, the resulting resin had a tensile strength of 7.9MPa, a toughness of only 0.03MPa, and no shape memory properties. The above results show that the introduction of the hyperbranched siloxane can not only significantly improve the toughness of the resin, but also obtain the shape memory material.
TABLE 1
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (13)
1. The resin is characterized by comprising a fixed phase and a reversible phase, wherein the fixed phase is a cross-linked network structure formed by aldehyde groups on acrylate chains and amino groups of hyperbranched siloxane, and the reversible phase is a reversible phase formed by the acrylate chains and the hyperbranched siloxane and capable of changing between a glassy state and a rubber state along with temperature; the preparation raw materials of the resin comprise: acrylate or methacrylate with aldehyde group, hyperbranched siloxane with amino group, monofunctional acrylate or monofunctional methacrylate, and photoinitiator.
2. The resin according to claim 1, wherein the mass ratio of the acrylate or methacrylate with aldehyde group, the hyperbranched siloxane with amino group, the monofunctional acrylate or methacrylate is (1-199): (1-30): (1-99).
3. The resin of claim 1, wherein the mass ratio of the photoinitiator to the amino group-containing hyperbranched siloxane is (0.5-5) to (1-30).
4. The resin according to claim 1, wherein the acrylate with an aldehyde group is selected from 2- (acryloyloxy) ethyl 4-formylbenzoate and/or 3- (acryloyloxy) propyl 4-formylbenzoate;
the methacrylate with aldehyde group is selected from 2- (methacryloyloxy) ethyl 4-formyl benzoate and/or 3- (methacryloyloxy) propyl 4-formyl benzoate;
the hyperbranched siloxane with amino is obtained by hydrolyzing 3-aminopropyltrimethoxysilane or 3-aminopropyltriethoxysilane;
the monofunctional acrylate is at least one selected from tetrahydrofuran acrylate, 2-phenoxyethyl acrylate, isobornyl acrylate and trimethylolpropane formal acrylate;
the monofunctional methacrylate is at least one selected from tetrahydrofuran methacrylate, 2-phenoxyethyl methacrylate, isobornyl methacrylate, benzyl methacrylate and cyclohexyl methacrylate;
the photoinitiator is at least one selected from 1-hydroxycyclohexyl phenyl ketone, 2,4, 6-trimethylbenzoyl-diphenyl phosphine oxide, 2,4, 6-trimethylbenzoyl-ethoxy-phenyl phosphine oxide, bis (2,4, 6-trimethylbenzoyl) -phenyl phosphine oxide, 2-dimethoxy-1, 2-diphenyl ethanone, 2-ethyl octyl-4-dimethylamino benzoate and 4-p-toluene 2-methyl-1- (4-methylthiophenyl) -2-morpholinyl-1-acetone.
5. The resin according to any one of claims 1 to 4, wherein the resin is a shape memory resin, and the resin contains a dynamic cross-linking structure-reversible imine bond, and the temporary deformation and the permanent deformation of the resin can be achieved under different temperature conditions.
6. The resin of claim 5, wherein the resin has a tensile strength of 4 to 15MPa and a toughness of 1 to 3.5 MPa.
7. A process for the preparation of a resin according to any one of claims 1 to 6, characterized in that it comprises: and mixing and uniformly mixing acrylic ester with aldehyde group or methacrylic ester with aldehyde group, monofunctional acrylic ester or monofunctional methacrylic ester, a photoinitiator and hyperbranched siloxane with amino group, performing photocuring 3D printing, and performing thermocuring to obtain the resin.
8. The method according to claim 7, wherein the step of preparing the acrylate or methacrylate having an aldehyde group comprises: acrylic ester with alcoholic hydroxyl or methacrylic ester with alcoholic hydroxyl and p-formylbenzoic acid are taken as raw materials, and are subjected to condensation reaction in the presence of a condensing agent and a condensation activating agent to prepare acrylic ester with aldehyde group or methacrylic ester with aldehyde group.
9. The method according to claim 7, wherein the hyperbranched siloxane having an amino group is obtained by hydrolysis of an amino group-containing silane coupling agent.
10. The production method according to any one of claims 7 to 9, wherein the operation of mixing in the resin production method comprises: firstly, heating, stirring and uniformly mixing acrylic ester with aldehyde group or methacrylic ester with aldehyde group, monofunctional acrylic ester or monofunctional methacrylic ester and photoinitiator, cooling to room temperature, then adding the hyperbranched siloxane with amino group, and stirring to obtain clear liquid.
11. The production method according to any one of claims 7 to 9, wherein the photocuring includes: ultraviolet curing for 3-10 min.
12. The production method according to any one of claims 7 to 9, wherein the heat curing comprises: the curing temperature is 50-90 ℃, and the curing time is 6-48 h.
13. Use of a resin according to any of claims 1 to 6 as a 4D printing material.
Priority Applications (1)
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