CN113150199B - Recyclable photocuring 3D printing linear polymer part and preparation method and application thereof - Google Patents
Recyclable photocuring 3D printing linear polymer part and preparation method and application thereof Download PDFInfo
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- CN113150199B CN113150199B CN202010066454.4A CN202010066454A CN113150199B CN 113150199 B CN113150199 B CN 113150199B CN 202010066454 A CN202010066454 A CN 202010066454A CN 113150199 B CN113150199 B CN 113150199B
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- photosensitive resin
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- acrylate
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- 238000010146 3D printing Methods 0.000 title claims abstract description 111
- 229920000642 polymer Polymers 0.000 title claims abstract description 91
- 238000000016 photochemical curing Methods 0.000 title claims abstract description 88
- 238000002360 preparation method Methods 0.000 title abstract description 18
- 239000011347 resin Substances 0.000 claims abstract description 140
- 229920005989 resin Polymers 0.000 claims abstract description 140
- 239000000178 monomer Substances 0.000 claims abstract description 110
- 238000007639 printing Methods 0.000 claims abstract description 48
- 238000000034 method Methods 0.000 claims abstract description 41
- 239000000945 filler Substances 0.000 claims abstract description 40
- 238000004064 recycling Methods 0.000 claims abstract description 28
- 238000003756 stirring Methods 0.000 claims abstract description 28
- 239000000203 mixture Substances 0.000 claims abstract description 24
- 229920001169 thermoplastic Polymers 0.000 claims abstract description 22
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 22
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 claims description 27
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 18
- 239000006185 dispersion Substances 0.000 claims description 18
- 125000000217 alkyl group Chemical group 0.000 claims description 17
- JRWNODXPDGNUPO-UHFFFAOYSA-N oxolane;prop-2-enoic acid Chemical class C1CCOC1.OC(=O)C=C JRWNODXPDGNUPO-UHFFFAOYSA-N 0.000 claims description 16
- 229930006711 bornane-2,3-dione Natural products 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 14
- 229910021389 graphene Inorganic materials 0.000 claims description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 10
- -1 acylphosphine oxide Substances 0.000 claims description 9
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 9
- 229910001338 liquidmetal Inorganic materials 0.000 claims description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 8
- WURBFLDFSFBTLW-UHFFFAOYSA-N benzil Chemical group C=1C=CC=CC=1C(=O)C(=O)C1=CC=CC=C1 WURBFLDFSFBTLW-UHFFFAOYSA-N 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 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
- 239000012965 benzophenone Substances 0.000 claims description 6
- HPAFOABSQZMTHE-UHFFFAOYSA-N phenyl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)C1=CC=CC=C1 HPAFOABSQZMTHE-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- WXPWZZHELZEVPO-UHFFFAOYSA-N (4-methylphenyl)-phenylmethanone Chemical compound C1=CC(C)=CC=C1C(=O)C1=CC=CC=C1 WXPWZZHELZEVPO-UHFFFAOYSA-N 0.000 claims description 5
- AKVUWTYSNLGBJY-UHFFFAOYSA-N 2-methyl-1-morpholin-4-ylprop-2-en-1-one Chemical compound CC(=C)C(=O)N1CCOCC1 AKVUWTYSNLGBJY-UHFFFAOYSA-N 0.000 claims description 5
- IEOVKCGOIXZDRK-UHFFFAOYSA-N 5-bicyclo[2.2.1]hept-2-enylmethyl prop-2-enoate Chemical compound C1C2C(COC(=O)C=C)CC1C=C2 IEOVKCGOIXZDRK-UHFFFAOYSA-N 0.000 claims description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 5
- 229910052582 BN Inorganic materials 0.000 claims description 5
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 5
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 claims description 5
- 239000002041 carbon nanotube Substances 0.000 claims description 5
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 5
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 5
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims description 5
- 239000004408 titanium dioxide Substances 0.000 claims description 5
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 4
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 4
- FWWXYLGCHHIKNY-UHFFFAOYSA-N 2-ethoxyethyl prop-2-enoate Chemical compound CCOCCOC(=O)C=C FWWXYLGCHHIKNY-UHFFFAOYSA-N 0.000 claims description 4
- QZPSOSOOLFHYRR-UHFFFAOYSA-N 3-hydroxypropyl prop-2-enoate Chemical compound OCCCOC(=O)C=C QZPSOSOOLFHYRR-UHFFFAOYSA-N 0.000 claims description 4
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 4
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 4
- UEEJHVSXFDXPFK-UHFFFAOYSA-O N-dimethylethanolamine Chemical compound C[NH+](C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-O 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 125000004122 cyclic group Chemical group 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- OIWOHHBRDFKZNC-UHFFFAOYSA-N cyclohexyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1CCCCC1 OIWOHHBRDFKZNC-UHFFFAOYSA-N 0.000 claims description 4
- KBLWLMPSVYBVDK-UHFFFAOYSA-N cyclohexyl prop-2-enoate Chemical compound C=CC(=O)OC1CCCCC1 KBLWLMPSVYBVDK-UHFFFAOYSA-N 0.000 claims description 4
- PESYEWKSBIWTAK-UHFFFAOYSA-N cyclopenta-1,3-diene;titanium(2+) Chemical class [Ti+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 PESYEWKSBIWTAK-UHFFFAOYSA-N 0.000 claims description 4
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- MHCLJIVVJQQNKQ-UHFFFAOYSA-N ethyl carbamate;2-methylprop-2-enoic acid Chemical compound CCOC(N)=O.CC(=C)C(O)=O MHCLJIVVJQQNKQ-UHFFFAOYSA-N 0.000 claims description 4
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims description 4
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 4
- 239000000835 fiber Substances 0.000 claims description 4
- 125000000623 heterocyclic group Chemical group 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 claims description 4
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims description 4
- 125000003518 norbornenyl group Chemical group C12(C=CC(CC1)C2)* 0.000 claims description 4
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 claims description 4
- 150000004053 quinones Chemical class 0.000 claims description 4
- 150000003918 triazines Chemical class 0.000 claims description 4
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims 3
- 125000002362 bornane-2,3-dione group Chemical group 0.000 claims 3
- 239000000463 material Substances 0.000 abstract description 6
- 238000003912 environmental pollution Methods 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 abstract description 3
- VNQXSTWCDUXYEZ-UHFFFAOYSA-N 1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-dione Chemical compound C1CC2(C)C(=O)C(=O)C1C2(C)C VNQXSTWCDUXYEZ-UHFFFAOYSA-N 0.000 description 12
- 238000001723 curing Methods 0.000 description 12
- 238000011084 recovery Methods 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000000805 composite resin Substances 0.000 description 5
- 238000005119 centrifugation Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920001187 thermosetting polymer Polymers 0.000 description 2
- DTGKSKDOIYIVQL-WEDXCCLWSA-N (+)-borneol Chemical group C1C[C@@]2(C)[C@@H](O)C[C@@H]1C2(C)C DTGKSKDOIYIVQL-WEDXCCLWSA-N 0.000 description 1
- 125000006652 (C3-C12) cycloalkyl group Chemical group 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
- 125000001559 cyclopropyl group Chemical group [H]C1([H])C([H])([H])C1([H])* 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000012767 functional filler Substances 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000012815 thermoplastic material Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/52—Amides or imides
- C08F120/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
- C08F120/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-acryloyl morpholine
-
- 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
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/10—Esters
- C08F120/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F120/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
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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)
- Polymerisation Methods In General (AREA)
Abstract
The invention discloses a recyclable photocuring 3D printing linear polymer part and a preparation method and application thereof. A composition for preparing a photocured 3D printed linear polymeric article comprising: at least one monomer of a photosensitive resin with a photoinitiator, and optionally a filler; the monomer of the photosensitive resin is a monofunctional thermoplastic photosensitive resin monomer. It can be recovered: adding a 3D printing linear polymer workpiece into a monomer of photosensitive resin, and stirring at a certain temperature to dissolve the workpiece to form a solution containing the resin monomer; wherein the monomers of the photosensitive resin are the same as the monomers of the photosensitive resin used to prepare the article. The photocuring 3D printing linear polymer workpiece can meet the requirements of photocuring printing, the multiplexing method of the workpiece is simple, the original performance can be kept, and meanwhile, the photocuring 3D printing can be performed for multiple times, so that the recycling of materials is realized, and the resource waste and the environmental pollution are reduced.
Description
Technical Field
The invention belongs to the technical field of 3D printed products, and particularly relates to a recyclable photocuring 3D printed linear polymer product and a preparation method and application thereof.
Background
Photocuring 3D printing is used as a novel forming technology, has the characteristics of high forming precision, high printing efficiency and the like, and can realize printing of micron, submicron and even nanoscale structures. However, photocuring 3D prints and uses material mostly is thermosetting photosensitive resin material, prints the finished piece and receives the external world and destroys the back, and the finished piece complex structure is difficult to recover, and the performance also can descend to some extent, is difficult to satisfy the in-service use demand, and photocuring 3D prints the unable recovery of finished piece simultaneously, is difficult to machine once more shaping, can cause environmental pollution, wasting of resources scheduling problem. Therefore, the photocuring 3D printing thermoplastic material attracts people's attention, and the subsequent processing or the processing of the traditional material as a sacrificial template to obtain a complex structure is facilitated.
Currently, in the prior art, the monomers used for photocuring 3D printing usually include at least a polyfunctional thermosetting photosensitive resin monomer as a printing raw material, and a crosslinked product is formed by photocuring. However, the crosslinked 3D printed product cannot be recycled, and is difficult to be processed and formed again, which may cause problems of environmental pollution, resource waste, and the like.
Disclosure of Invention
The present invention provides a composition for preparing a photocurable 3D printed linear polymeric article comprising: at least one monomer of a photosensitive resin with a photoinitiator, and optionally a filler; the monomer of the photosensitive resin is a monofunctional thermoplastic photosensitive resin monomer.
The invention also provides an application of the composition in preparation of a photocuring 3D printing linear polymer workpiece.
The invention also provides a photocuring 3D printing linear polymer product which is prepared from the raw materials containing the composition.
The invention also provides a preparation method of the photocuring 3D printing linear polymer workpiece, which comprises the following steps:
1) blending at least one monomer of the photosensitive resin with a photoinitiator to obtain a resin solution;
2) optionally adding or not adding a filler to the resin solution to produce a mixed dispersion;
3) and (3) carrying out photocuring 3D printing on the resin solution obtained in the step 1) or the mixed dispersion liquid obtained in the step 2) to obtain the photocuring 3D printing linear polymer workpiece.
The invention also provides a recycling method of the photocuring 3D printing linear polymer workpiece, which comprises the following steps: adding the 3D printing linear polymer workpiece into a monomer of photosensitive resin, and stirring at a certain temperature to dissolve the 3D printing linear polymer workpiece to form a solution containing the photosensitive resin monomer;
wherein the monomers of the photosensitive resin are the same as those of the photosensitive resin used for preparing the photocuring 3D printing linear polymer workpiece.
The invention also provides a cyclic printing method for the photocuring 3D printing of the linear polymer workpiece, which comprises the following steps:
a) adding a 3D printing linear polymer workpiece into a monomer of photosensitive resin, and stirring at a certain temperature to dissolve the 3D printing linear polymer workpiece to form a solution containing the photosensitive resin monomer;
b) blending the solution containing the photosensitive resin monomer with a photoinitiator to obtain a resin solution;
c) optionally adding or not adding a filler to the resin solution to produce a mixed dispersion;
d) carrying out photocuring 3D printing on the solution obtained in the step b) or the mixed dispersion liquid obtained in the step c), and obtaining the photocuring 3D printing linear polymer workpiece again.
The invention also provides a recovery method of the filler in the photocuring 3D printing linear polymer workpiece, which comprises the following steps: and centrifuging the solution containing the photosensitive resin monomer, which is recovered by the method for recovering the photocuring 3D printing linear polymer workpiece, so that the filler is agglomerated at the bottom, taking out the filler, washing and drying.
The invention has the beneficial effects that:
1. the preparation process of the composition for preparing the recyclable photocuring 3D printing linear polymer workpiece is simple, and the composition can be prepared by only adding and stirring the components at normal temperature.
The monofunctional thermoplastic photosensitive resin monomer is matched with the filler, so that at least one function of heat, electricity, magnetism and the like can be given to a workpiece, and the mechanical property of the material is enhanced.
2. The photocuring 3D printing linear polymer workpiece can meet the requirements of photocuring printing, the multiplexing method of the workpiece is simple, the original performance can be kept, multiple times of photocuring 3D printing can be carried out, the material can be recycled (the cycle times are not limited and can be recycled all the time according to needs; research results show that after 3 times and higher cycles, the structure, mechanical properties and mechanical properties of the workpiece can be basically kept unchanged, and the photocuring 3D printing linear polymer workpiece has a good practical application prospect), and the resource waste and the environmental pollution are reduced.
3. The photocuring 3D printing linear polymer part can realize the recovery of the filler, realizes the efficient utilization and is beneficial to reducing the cost.
Drawings
FIG. 1 is a photograph of the original resin monomer solution and the recovered solution in example 1.
Fig. 2 is a stress-strain curve of the original part obtained in example 1 and the photo-cured 3D printed part obtained by the third recycling.
Fig. 3 is a photograph of the original article prepared in example 1 and a third recycled photocurable 3D printed article.
FIG. 4 is a photograph showing the dispersion of the filler before and after the resin solution was centrifuged in example 2.
Detailed Description
[ composition for preparing photocured 3D-printed Linear Polymer articles ]
As previously mentioned, the present invention provides a composition for preparing a photocurable 3D printed linear polymeric article comprising: at least one monomer of a photosensitive resin with a photoinitiator, and optionally a filler; the monomer of the photosensitive resin is a monofunctional thermoplastic photosensitive resin monomer.
In one embodiment, the composition consists of monomers of at least one photosensitive resin with a photoinitiator, and optionally a filler; the monomer of the photosensitive resin is a monofunctional thermoplastic photosensitive resin monomer.
Preferably, the monofunctional thermoplastic photosensitive resin monomer is selected from at least one of compounds represented by formula (1) or formula (2);
in the formula (1), R 1 Selected from H, one of the following substituted or unsubstituted groups: alkyl (e.g. C) 1-20 Alkyl radicals, e.g. C 1-12 Alkyl further exemplified by methyl, ethyl, propyl, butyl, hexyl, dodecyl and the like), cycloalkyl (e.g., C 3-20 Cycloalkyl radicals, further e.g. C 3-12 Cycloalkyl, further exemplified by cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, etc.), a heterocycle (e.g., tetrahydrofuran, etc.), a bridged ring (e.g., isobornyl, etc.), a polyurethane group, said substituted group being selected from hydroxy, alkoxy or norbornenyl; or, R 1 An alkoxylated group which is the above group, for example, an ethoxylated tetrahydrofuran group;
R 2 and R 3 Identical or different, independently of one another, from H, alkyl, aryl;
r is selected from H, methyl or ethyl;
in the formula (2), R' is selected from H, methyl or ethyl;
R’ 2 and R' 3 Identical or different, independently of one another, from H, alkyl, aryl; for example, R' 2 And R' 3 Are the same and are all selected from H;
x is selected from O or NR ";
r' is selected from H and alkyl.
In one embodiment, the monofunctional thermoplastic photosensitive resin monomer may be selected from at least one of monofunctional thermoplastic acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, epoxy acrylate, hydroxyethyl methacrylate, urethane acrylate, urethane methacrylate, lauryl acrylate, lauryl methacrylate, acryloyl morpholine, methacryloyl morpholine, cyclohexyl acrylate, cyclohexyl methacrylate, cyclotrimethylolpropane formal acrylate, ethoxylated tetrahydrofuran acrylate, 5-norbornene-2-methanol acrylate, isobornyl acrylate, ethoxyethyl acrylate, and 1, 3-propylene glycol monoacrylate; for example, at least one of acryloyl morpholine, methacryloyl morpholine, cyclotrimethylolpropane formal acrylate, ethoxylated tetrahydrofuran acrylate, 5-norbornene-2-methanol acrylate, and isobornyl acrylate; exemplified is at least one of acryloylmorpholine, ethoxylated tetrahydrofuran acrylate, isobornyl acrylate.
According to the present invention, the photoinitiator is selected from at least one of bibenzoyl, diphenylethanedione, dialkoxyacetophenone, camphorquinone, α -hydroxyalkylbenzone, α -aminoalkylbenzophenone, acylphosphine oxide, benzophenone, 4-methylbenzophenone, 2,4, 6-trimethylbenzophenone, triethanolamine, N-methylethanolamine, N-dimethylethanolamine, N-diethylethanolamine, quinone compounds, titanocene compounds, iodonium salt compounds, sulfonium salt compounds, and triazine compounds; preferably, the photoinitiator is selected from at least one of camphorquinone, 2,4, 6-trimethylbenzophenone, 4-methylbenzophenone and N-methylethanolamine; exemplary are camphorquinone and/or 2,4, 6-trimethylbenzophenone.
According to the invention, the filler is selected from at least one of silicon dioxide, ferroferric oxide, titanium dioxide, montmorillonite, boron nitride, graphene, molybdenum disulfide, graphene oxide, carbon nanotubes, fibers, Mxene and liquid metal; for example, at least one selected from silica, carbon nanotubes, montmorillonite, graphene, titanium dioxide, boron nitride nanoparticles; illustratively, the functional filler is selected from silica nanoparticles, graphene, and/or liquid metals.
According to the invention, the mass ratio of the photoinitiator to the monomers of the photosensitive resin is (0.01-5):100, preferably (0.1-3):100, more preferably (0.5-2):100, for example 0.5:100, 1:100, 1.5: 100.
According to the invention, the mass ratio of the filler to the monomers of the photosensitive resin is (0.01-20):100, preferably (0.1-10):100, more preferably (0.5-5):100, for example 0.1:100, 1:100, 2:100, 5: 100.
[ use of the composition ]
The invention provides application of the composition in preparation of a photocuring 3D printing linear polymer workpiece.
[ photocuring 3D printing Linear Polymer parts ]
The invention provides a photocuring 3D printing linear polymer part, and the 3D printing linear polymer part is prepared from raw materials containing the composition.
Wherein the 3D printed linear polymeric article can be recycled and printed in a recycling manner.
Further, the 3D printed linear polymeric article may have similar or the same properties, and/or the same or a different structure after recycling and recycling printing as before recycling.
[ preparation method of photocuring 3D printing Linear Polymer parts ]
The invention provides a preparation method of the photocuring 3D printing linear polymer workpiece, which comprises the following steps:
1) blending at least one monomer of photosensitive resin with a photoinitiator to obtain a resin solution;
2) optionally adding or not adding a filler to the solution to produce a mixed dispersion;
3) and (2) carrying out photocuring 3D printing on the resin solution obtained in the step 1) or the mixed dispersion liquid obtained in the step 2) to obtain the photocuring 3D printing linear polymer workpiece.
Wherein the monomers, the photoinitiator and the filler of the photosensitive resin all have the meaning and mass ratio as described above.
According to the preparation method of the present invention, the preparation of the resin solution of step (1) and/or the mixed dispersion of step (2) is carried out under stirring. Further, step (1) and/or step (2) are both performed at low temperature. By low temperature is meant a temperature in the range of 15-60 deg.C, such as 20-60 deg.C, and is illustratively ambient (e.g., 15-40 deg.C, preferably 20-35 deg.C) or 60 deg.C.
According to the preparation method of the invention, the photocuring 3D printing is performed by using equipment known in the art, for example, a 3D printer such as creative three-dimensional, medium-end SLA500, small-side ONE and the like can be used.
According to the preparation method, in the step (3), the laser used in the photocuring 3D printing process is visible light or ultraviolet light. The wavelength range of the visible light is 415-780nm, for example, the wavelength is 430-600nm, and is typically 445 nm. Wherein the wavelength range of the ultraviolet light is 265-420nm, such as 300-400 nm.
According to the manufacturing method of the present invention, in the step (3), in the photocuring 3D printing process, the curing time of each printed layer is 1 to 900 seconds, for example, the curing time is 10 to 400 seconds, further such as 20 to 100 seconds, and exemplarily, the curing time of each printed layer is 10 seconds, 20 seconds, 30 seconds, or 60 seconds.
According to the preparation method of the present invention, in step (3), the layer thickness of each printed layer during the photocuring 3D printing is 5 to 100 μm, for example 10 to 100 μm, illustratively 50 μm, 100 μm.
[ method for recovering photocuring 3D printing linear polymer product ]
The invention provides a recovery method of the photocuring 3D printing linear polymer workpiece, which comprises the following steps: adding a 3D printing linear polymer workpiece into a monomer of photosensitive resin, and stirring at a certain temperature to dissolve the 3D printing linear polymer workpiece to form a solution containing a resin monomer;
wherein the monomers of the photosensitive resin are the same as those of the photosensitive resin used for preparing the 3D printing linear polymer workpiece.
The solution containing the resin monomer simultaneously contains the resin monomer dissolved from the printed product and the resin monomer added when the printed product is dissolved.
According to the invention, the mass ratio of the 3D printed linear polymeric article to the monomers of the photosensitive resin is (0.1-50): (50-99.9), such as (1-30): (70-90), exemplary 3:97, 5:95 or 10: 90.
According to the invention, said certain temperature is 20-200 deg.C, such as 30-160 deg.C, such as 50-130 deg.C, and illustratively 80 deg.C, 120 deg.C. Wherein the stirring time is 20min to 5h, such as 0.5 to 3h, exemplary 1 h.
According to the invention, the whole 3D printing linear polymer workpiece can be directly added into the monomer of the photosensitive resin, or the 3D printing linear polymer workpiece is firstly crushed and then added into the monomer of the photosensitive resin.
According to the invention, the 3D printing linear polymer part is prepared by the preparation method of the photocuring 3D printing linear polymer part.
[ Cyclic printing method for photocuring 3D printing of linear polymer parts ]
The invention provides a cyclic printing method for photocuring 3D printing of linear polymer workpieces, which comprises the following steps:
a) adding a 3D printing linear polymer workpiece into a monomer of photosensitive resin, and stirring at a certain temperature to dissolve the 3D printing linear polymer workpiece to form a solution containing a resin monomer;
wherein the monomer of the photosensitive resin is the same as the monomer of the photosensitive resin used for preparing the 3D printing linear part;
b) blending the solution containing the resin monomer with a photoinitiator to obtain a resin solution;
c) optionally adding or not adding a filler to the resin solution to obtain a mixed dispersion;
d) and (c) carrying out photocuring 3D printing on the solution obtained in the step b) or the mixed dispersion liquid obtained in the step c), and obtaining the photocuring 3D printing linear polymer workpiece again.
According to the invention, the monomers, fillers, photoinitiators of the photosensitive resin have the meaning as described above.
According to the invention, the mass ratio of the monomers of the photosensitive resin and the 3D printed linear polymer article has the meaning as described above.
According to the invention, the whole 3D printing linear polymer part can be directly added into the monomer of the photosensitive resin, or the 3D printing linear polymer part is firstly crushed and then added into the monomer of the photosensitive resin.
According to the invention, the mass ratio of the photoinitiator to the solution containing the resin monomer is (0.01-5):100, preferably (0.1-3):100, more preferably (0.5-2):100, exemplarily 0.3:100, 0.5:100, 1: 100.
According to the invention, the temperature stirring in step a) and the photocuring 3D printing in step D) have the meaning as described in step 1) and step 4) of the method for preparing a linear polymeric object by photocuring 3D printing.
According to the invention, the 3D printed linear polymer part in step a) is prepared by the preparation method of the photocuring 3D printed linear polymer part.
[ method for recovering Filler in photocuring 3D printing linear polymer product ]
The invention provides a method for recovering a filler in the photocuring 3D printing linear polymer workpiece, which comprises the following steps:
A1) adding a 3D printing linear polymer workpiece into a monomer of photosensitive resin, and stirring at a certain temperature to dissolve the 3D printing linear polymer workpiece to form a solution containing a resin monomer;
wherein the monomers of the photosensitive resin are the same as those of the photosensitive resin used for preparing the 3D printing linear polymer workpiece;
A2) and C) centrifuging the solution containing the resin monomer obtained in the step A1) to enable the filler to be agglomerated at the bottom, taking out the filler, washing and drying.
According to the present invention, the mass ratio of the monomers of the photosensitive resin and the 3D printed linear polymeric article has the meaning as described above.
According to the invention, the time of the centrifugation treatment is 3min to 2h, such as 5min to 1h, exemplary 10min, 20 min. Further, the rotational speed of the centrifugation process is 50-12000rpm, such as 5000-.
According to the invention, the whole 3D printing linear polymer workpiece can be directly added into the monomer of the photosensitive resin, or the 3D printing linear polymer workpiece is firstly crushed and then added into the monomer of the photosensitive resin.
According to the invention, the 3D printed linear polymer object in step a1) is prepared by the preparation method of the photocuring 3D printed linear polymer object.
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.
In the following examples and comparative examples, mechanical properties of printed articles were tested according to the resin cast property test method: GB/T2567-2008.
Example 1
1) Blending 100g of acryloyl morpholine and 0.5g of camphorquinone, magnetically stirring for 30min at normal temperature at the rotating speed of 600rpm to obtain an acryloyl morpholine resin solution;
2) carrying out photocuring 3D printing on the resin solution obtained in the step 1), wherein the laser wavelength is 445nm, the layer thickness of each layer is controlled to be 100 microns, the curing time of each layer is controlled to be 10s, and a photocuring 3D printing linear polymer workpiece can be obtained after printing is finished;
3) crushing (5g) the printing part obtained in the step 2), adding the crushed printing part into acryloyl morpholine monomer (95g), stirring at 80 ℃ for 1h to obtain a recovered solution, wherein the recovered solution simultaneously contains acryloyl morpholine dissolved out from the crushed printing part and acryloyl morpholine added during dissolution of the printing part; 4) adding 0.4g of camphorquinone into the solution obtained in the step 3), and magnetically stirring at normal temperature for 30min at the rotating speed of 600rpm to obtain a resin solution;
5) and (3) carrying out photocuring 3D printing on the resin solution obtained in the step 4), wherein the laser wavelength is 445nm, the layer thickness of each layer is controlled to be 100 microns, the curing time of each layer is controlled to be 10s, and the photocuring 3D printing linear polymer product can be obtained after printing.
FIG. 1 is a photograph showing the monomer solution of acryloylmorpholine resin and the recovered solution obtained in step 3), and it can be seen that: the 3D printed linear polymer part was completely dissolved in the recovered solution.
Fig. 2 is a stress-strain curve of the original printed article and the printed article after the third recovery, which shows that: the mechanical properties of the 3D printing linear polymer workpiece obtained before and after recovery are similar, and the requirements of photocuring printing can be met.
Fig. 3 is a photograph of the original printed article and the printed article after the third recycling, showing that: the structure of the printed article obtained by recycling and cyclically printing is basically the same as that of the original printed article.
Example 2
1) Mixing 100g of acryloyl morpholine, 0.5g of camphorquinone and 5g of liquid metal, and magnetically stirring at 60 ℃ for 30min at the rotating speed of 600rpm to obtain an acryloyl morpholine resin composite solution;
2) carrying out photocuring 3D printing on the resin composite solution obtained in the step 1), wherein the laser wavelength is 445nm, the layer thickness of each layer is controlled to be 100 microns, the curing time of each layer is controlled to be 10s, and a photocuring 3D printing linear polymer workpiece can be obtained after printing is finished;
3) crushing (5g) the printing part obtained in the step 2), adding the crushed printing part into an acryloyl morpholine monomer (95g), stirring at 80 ℃ for 1h to obtain a solution, wherein the recovered solution simultaneously contains acryloyl morpholine dissolved out from the crushed printing part and acryloyl morpholine added when the printing part is dissolved;
4) and (4) placing the solution obtained in the step 3) in a centrifuge, centrifuging for 10min at the rotating speed of 8000rpm, depositing the liquid metal at the bottom of the solution, taking out the solution, circularly washing the solution with ethanol, and placing the solution in a 60 ℃ drying oven for 3h to obtain the recovered liquid metal.
FIG. 4 is a photograph of the recovery solution before and after centrifugation, and it can be seen that the liquid metal is almost completely recovered by centrifugation.
Example 3
1) Blending 100g of acryloyl morpholine and 0.5g of camphorquinone, magnetically stirring for 30min at normal temperature at the rotating speed of 600rpm to obtain an acryloyl morpholine resin solution;
2) carrying out photocuring 3D printing on the resin solution obtained in the step 1), wherein the laser wavelength is 445nm, the layer thickness of each layer is controlled to be 50 microns, the curing time of each layer is controlled to be 10s, and a photocuring 3D printing linear polymer workpiece can be obtained after printing is finished;
3) crushing (3g) the printed part obtained in the step 2), adding the crushed printed part into an acryloyl morpholine monomer (97g), stirring at 80 ℃ for 1h to obtain a recovered solution, wherein the recovered solution simultaneously contains acryloyl morpholine dissolved out from the crushed printed part and acryloyl morpholine added when the printed part is dissolved;
4) adding 0.4g of camphorquinone into the solution obtained in the step 3), and magnetically stirring at normal temperature for 30min at the rotating speed of 600rpm to obtain a resin solution;
5) and (3) carrying out photocuring 3D printing on the resin solution obtained in the step 4), wherein the laser wavelength is 445nm, the layer thickness of each layer is controlled to be 50 microns, the curing time of each layer is controlled to be 10s, and the photocuring 3D printing linear polymer product can be obtained after printing is finished.
The mechanical properties of the 3D printing linear polymer workpiece obtained before and after recovery are similar, and the requirements of photocuring printing can be met.
Example 4
1) Mixing 100g of acryloyl morpholine, 0.5g of camphorquinone and 1g of graphene, and magnetically stirring at 60 ℃ for 30min at the rotating speed of 600rpm to obtain an acryloyl morpholine resin composite solution;
2) carrying out photocuring 3D printing on the resin composite solution obtained in the step 1), wherein the laser wavelength is 445nm, the layer thickness of each layer is controlled to be 100 microns, the curing time of each layer is controlled to be 10s, and a photocuring 3D printing linear polymer workpiece can be obtained after printing is finished;
3) crushing (5g) the printing part obtained in the step 2), adding the crushed (5g) into an acryloyl morpholine monomer (95g), stirring at 80 ℃ for 1h to obtain a recovered solution, wherein the recovered solution simultaneously contains acryloyl morpholine dissolved out from the crushed printing part and acryloyl morpholine added when the printing part is dissolved;
4) placing the solution obtained in the step 3) in a centrifuge, centrifuging for 10min at the rotation speed of 8000rpm, depositing graphene at the bottom of the solution, taking out, repeatedly washing with ethanol, and placing in a 60 ℃ oven for 3h to obtain the recovered graphene.
Example 5
1) Blending 100g of ethoxylated tetrahydrofuran acrylate and 0.5g of camphorquinone, and magnetically stirring at normal temperature for 30min at the rotating speed of 600rpm to obtain an ethoxylated tetrahydrofuran acrylate resin solution;
2) carrying out photocuring 3D printing on the resin solution obtained in the step 1), wherein the wavelength of laser is 445nm, the thickness of each layer is controlled to be 50 microns, the curing time of each layer is controlled to be 30s, and a photocuring 3D printing linear polymer workpiece can be obtained after printing is finished;
3) crushing (10g) the printing part obtained in the step 2), adding the crushed printing part into an ethoxylated tetrahydrofuran acrylate monomer (90g), stirring at 80 ℃ for 1h to obtain a recovered solution, wherein the recovered solution simultaneously contains the ethoxylated tetrahydrofuran acrylate dissolved out from the crushed printing part and the ethoxylated tetrahydrofuran acrylate added when the printing part is dissolved;
4) adding 0.3g of camphorquinone into the solution obtained in the step 3), and magnetically stirring at normal temperature for 30min at the rotating speed of 600rpm to obtain a resin solution;
5) carrying out photocuring 3D printing on the resin solution obtained in the step 4), wherein the laser wavelength is 445nm, the layer thickness of each layer is controlled to be 50 microns, the curing time of each layer is controlled to be 30s, and the photocuring 3D printing linear polymer product can be obtained after printing.
The mechanical properties of the 3D printing linear polymer workpiece obtained before and after recovery are similar, and the requirements of photocuring printing can be met.
Example 6
1) Mixing 100g of ethoxylated tetrahydrofuran acrylate, 0.5g of camphorquinone and 1g of silicon dioxide, and magnetically stirring at 60 ℃ for 30min at the rotating speed of 600rpm to obtain an ethoxylated tetrahydrofuran acrylate resin composite solution;
2) carrying out photocuring 3D printing on the resin composite solution obtained in the step 1), wherein the laser wavelength is 445nm, the layer thickness of each layer is controlled to be 100 microns, the curing time of each layer is controlled to be 30s, and a photocuring 3D printing linear polymer workpiece can be obtained after printing is finished;
3) crushing (5g) the printing part obtained in the step 2), adding the crushed (5g) into an ethoxylated tetrahydrofuran acrylate monomer (95g), stirring at 80 ℃ for 1h to obtain a recovered solution, wherein the recovered solution simultaneously contains the ethoxylated tetrahydrofuran acrylate dissolved out from the crushed printing part and the ethoxylated tetrahydrofuran acrylate added when the printing part is dissolved;
4) placing the solution obtained in the step 3) in a centrifuge, centrifuging for 10min at the rotating speed of 8000rpm, depositing silicon dioxide at the bottom of the solution, taking out, repeatedly washing with ethanol, and placing in a 60 ℃ oven for 3h to obtain the recycled silicon dioxide.
When the photosensitive resin monomer in the examples is replaced by other substances listed in the specification, and the photoinitiator is replaced by other substances listed in the specification, 3D linear polymer parts capable of being recycled and printed in a recycling way can be prepared. The mechanical properties of the 3D printing linear polymer workpiece obtained before and after recovery are similar, and the requirements of photocuring printing can be met.
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 (24)
1. A recycling method for a photocuring 3D printing linear polymer workpiece is characterized by comprising the following steps:
1') preparing a composition for preparing a photocured 3D printed linear polymeric article;
2 ') preparing said 3D printed linear polymeric article from a feedstock comprising said composition of step 1');
3 ') adding the 3D printing linear polymer workpiece prepared in the step 2') into a monomer of photosensitive resin, and stirring at a certain temperature to dissolve the 3D printing linear polymer workpiece to form a solution containing the monomer of photosensitive resin;
wherein the monomers of the photosensitive resin are the same as those of the photosensitive resin used for preparing the 3D printing linear polymer workpiece;
the article is prepared from a feedstock selected from the group consisting of compositions used to prepare photocurable 3D printed linear polymeric articles;
the composition consists of at least one photosensitive resin monomer, a photoinitiator and a filler; the monomer of the photosensitive resin is a monofunctional thermoplastic photosensitive resin monomer;
the mass ratio of the photoinitiator to the monomers of the photosensitive resin is (0.01-5) to 100; the mass ratio of the filler to the monomer of the photosensitive resin is (0.01-20): 100;
the photoinitiator is selected from at least one of bibenzoyl, diphenylethanedione, dialkoxyacetophenone, alpha-hydroxyalkyl benzophenone, alpha-aminoalkyl benzophenone, acylphosphine oxide, benzophenone, 4-methylbenzophenone, 2,4, 6-trimethylbenzophenone, triethanolamine, N-methylethanolamine, N-dimethylethanolamine, N-diethylethanolamine, quinone compounds, titanocene compounds, iodonium salt compounds, sulfonium salt compounds and triazine compounds;
the filler is selected from at least one of silicon dioxide, ferroferric oxide, titanium dioxide, montmorillonite, boron nitride, graphene, molybdenum disulfide, graphene oxide, carbon nanotubes, fibers, Mxene and liquid metal;
the monofunctional thermoplastic photosensitive resin monomer is selected from at least one of compounds shown in a formula (1) or a formula (2);
formula (1) formula (2)
In the formula (1), R 1 Selected from H, one of the following substituted or unsubstituted groups: alkyl, cycloalkyl, heterocycle, bridged ring, urethane, said substituted group being selected from hydroxy, alkoxy or norbornenyl;
R 2 and R 3 Identical or different, independently of one another, from H, alkyl, aryl;
r is selected from H, methyl or ethyl;
in the formula (2), R' is selected from H, methyl or ethyl;
R’ 2 and R' 3 Identical or different, independently of one another, from H, alkyl, aryl;
x is selected from O or NR';
r' is selected from H and alkyl.
2. The recycling method according to claim 1, wherein the monofunctional thermoplastic photosensitive resin monomer is at least one selected from the group consisting of monofunctional thermoplastic acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, epoxy acrylate, hydroxyethyl methacrylate, urethane acrylate, urethane methacrylate, lauryl acrylate, lauryl methacrylate, acryloyl morpholine, methacryloyl morpholine, cyclohexyl acrylate, cyclohexyl methacrylate, cyclotrimethylolpropane formal acrylate, ethoxylated tetrahydrofuran acrylate, 5-norbornene-2-methanol acrylate, isobornyl acrylate, ethoxyethyl acrylate and 1, 3-propylene glycol monoacrylate.
3. The recycling method according to claim 1, wherein the method for preparing the photocured 3D printed linear polymer article comprises the steps of:
1) blending at least one monomer of photosensitive resin with a photoinitiator to obtain a resin solution;
2) adding a filler to the solution to produce a mixed dispersion;
3) and (3) carrying out photocuring 3D printing on the resin solution obtained in the step 1) or the mixed dispersion liquid obtained in the step 2) to obtain the photocuring 3D printing linear polymer workpiece.
4. The recycling process of claim 1, wherein the photoinitiator is selected from camphorquinone.
5. A cyclic printing method for photocuring 3D printing of linear polymer workpieces is characterized by comprising the following steps:
1') preparing a composition for preparing a photocured 3D printed linear polymeric article, said composition consisting of monomers of at least one photosensitive resin and a photoinitiator, and a filler; the monomer of the photosensitive resin is a monofunctional thermoplastic photosensitive resin monomer;
2 ') preparing said 3D printed linear polymeric article from a feedstock comprising said composition of step 1');
3 ') adding the 3D printing linear polymer part obtained in the step 2') into a monomer of photosensitive resin, and stirring at a certain temperature to dissolve the 3D printing linear polymer part to form a solution containing the monomer of photosensitive resin;
wherein the monomer of the photosensitive resin is the same as the monomer of the photosensitive resin used for preparing the 3D printing linear part;
4') blending the solution containing the photosensitive resin monomer with a photoinitiator to obtain a resin solution;
5') adding a filler to the resin solution to obtain a mixed dispersion;
6') carrying out photocuring 3D printing on the solution obtained in the step b) or the mixed dispersion liquid obtained in the step c), and obtaining the photocuring 3D printing linear polymer part again.
6. The method of claim 5, wherein the composition consists of monomers and photoinitiators of at least one photosensitive resin, and a filler; the monomer of the photosensitive resin is a monofunctional thermoplastic photosensitive resin monomer.
7. The method for cyclically printing according to claim 5, wherein the monofunctional thermoplastic photosensitive resin monomer is selected from at least one compound represented by formula (1) or formula (2);
formula (1) formula (2)
In the formula (1), R 1 Selected from H, one of the following substituted or unsubstituted groups: alkyl, cycloalkyl, heterocycle, bridged ring, urethane, said substituted group being selected from hydroxy, alkoxy or norbornenyl;
R 2 and R 3 Identical or different, independently of one another, from H, alkyl, aryl;
r is selected from H, methyl or ethyl;
in the formula (2), R' is selected from H, methyl or ethyl;
R’ 2 and R' 3 Identical or different, independently of one another, from H, alkyl, aryl;
x is selected from O or NR';
r' is selected from H and alkyl.
8. The method for recycling printing according to claim 5, wherein the monofunctional thermoplastic photosensitive resin monomer is selected from at least one of monofunctional thermoplastic acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, epoxy acrylate, hydroxyethyl methacrylate, urethane acrylate, urethane methacrylate, lauryl acrylate, lauryl methacrylate, acryloyl morpholine, methacryloyl morpholine, cyclohexyl acrylate, cyclohexyl methacrylate, cyclotrimethylolpropane formal acrylate, ethoxylated tetrahydrofuran acrylate, 5-norbornene-2-methanol acrylate, isobornyl acrylate, ethoxyethyl acrylate and 1, 3-propylene glycol monoacrylate.
9. The recycling printing method of claim 5, wherein said photoinitiator is selected from at least one of bibenzoyl, diphenylethanedione, dialkoxyacetophenone, α -hydroxyalkylbenzone, α -aminoalkylbenzophenone, acylphosphine oxide, benzophenone, 4-methylbenzophenone, 2,4, 6-trimethylbenzophenone, triethanolamine, N-methylethanolamine, N-dimethylethanolamine, N-diethylethanolamine, quinone compounds, titanocene compounds, iodonium salt compounds, sulfonium salt compounds, and triazine compounds.
10. The method of claim 5, wherein the photoinitiator is camphorquinone.
11. The recycling printing method of claim 5, wherein the filler is selected from at least one of silica, ferroferric oxide, titanium dioxide, montmorillonite, boron nitride, graphene, molybdenum disulfide, graphene oxide, carbon nanotubes, fibers, Mxene, and liquid metals.
12. The method of claim 5, wherein the mass ratio of the photoinitiator to the monomers of the photosensitive resin is (0.01-5): 100.
13. The recycling printing method of claim 5, wherein the mass ratio of the filler to the monomer of the photosensitive resin is (0.01-20): 100.
14. The cyclical printing method according to claim 5, wherein the steps 1 ') and 2') are in particular:
1) blending at least one monomer of photosensitive resin with a photoinitiator to obtain a resin solution;
2) adding a filler to the solution to prepare a mixed dispersion;
3) and (3) carrying out photocuring 3D printing on the resin solution obtained in the step 1) or the mixed dispersion liquid obtained in the step 2) to obtain the photocuring 3D printing linear polymer workpiece.
15. A method for recycling filler in a photocuring 3D printing linear polymer workpiece is characterized by comprising the following steps:
1') preparing a composition for preparing a photocured 3D printed linear polymeric article, said composition consisting of monomers of at least one photosensitive resin and a photoinitiator, and a filler; the monomer of the photosensitive resin is a monofunctional thermoplastic photosensitive resin monomer;
2 ') preparing said 3D printed linear polymeric article from a feedstock comprising said composition of step 1');
3 ') adding the 3D printing linear polymer part obtained in the step 2') into a monomer of photosensitive resin, and stirring at a certain temperature to dissolve the 3D printing linear polymer part to form a solution containing the monomer of photosensitive resin;
the monomer of the photosensitive resin is the same as that of the photosensitive resin used for preparing the 3D printing linear polymer workpiece;
4') centrifuging the solution containing the photosensitive resin monomer to enable the filler to be agglomerated at the bottom, taking out the filler, washing and drying.
16. A recycling method according to claim 15, characterized in that said composition consists of at least one monomer of a photosensitive resin and a photoinitiator, and a filler; the monomer of the photosensitive resin is a monofunctional thermoplastic photosensitive resin monomer.
17. The recycling method according to claim 15, wherein the monofunctional thermoplastic photosensitive resin monomer is selected from at least one compound represented by formula (1) or formula (2);
formula (1) formula (2)
In the formula (1), R 1 Selected from H, one of the following substituted or unsubstituted groups: alkyl, cycloalkyl, heterocycle, bridged ring, urethane, said substituted group being selected from hydroxyl, alkoxy or norbornenyl;
R 2 and R 3 Identical or different, independently of one another, from H, alkyl, aryl;
r is selected from H, methyl or ethyl;
in the formula (2), R' is selected from H, methyl or ethyl;
R’ 2 and R' 3 Identical or different, independently of one another, from H, alkyl, aryl;
x is selected from O or NR';
r' is selected from H and alkyl.
18. The recycling method according to claim 15, wherein the monofunctional thermoplastic photosensitive resin monomer is at least one selected from the group consisting of monofunctional thermoplastic acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, epoxy acrylate, hydroxyethyl methacrylate, urethane acrylate, urethane methacrylate, lauryl acrylate, lauryl methacrylate, acryloyl morpholine, methacryloyl morpholine, cyclohexyl acrylate, cyclohexyl methacrylate, cyclotrimethylolpropane formal acrylate, ethoxylated tetrahydrofuran acrylate, 5-norbornene-2-methanol acrylate, isobornyl acrylate, ethoxyethyl acrylate and 1, 3-propylene glycol monoacrylate.
19. The recycling method according to claim 15, wherein the photoinitiator is at least one selected from the group consisting of dibenzoyl, diphenylethanedione, dialkoxyacetophenone, α -hydroxyalkylbenzone, α -aminoalkylbenzophenone, acylphosphine oxide, benzophenone, 4-methylbenzophenone, 2,4, 6-trimethylbenzophenone, triethanolamine, N-methylethanolamine, N-dimethylethanolamine, N-diethylethanolamine, quinone compounds, titanocene compounds, iodonium salt compounds, sulfonium salt compounds, and triazine compounds.
20. The recycling process according to claim 15, characterized in that the photoinitiator is selected from camphorquinone.
21. The recycling method according to claim 15, wherein the filler is selected from at least one of silica, ferroferric oxide, titanium dioxide, montmorillonite, boron nitride, graphene, molybdenum disulfide, graphene oxide, carbon nanotubes, fibers, Mxene, and liquid metals.
22. The recycling method according to claim 15, wherein the mass ratio of the photoinitiator to the monomer of the photosensitive resin is (0.01-5): 100.
23. The recycling method according to claim 15, wherein the mass ratio of the filler to the monomer of the photosensitive resin is (0.01-20): 100.
24. A recycling method according to claim 15, characterized in that said steps 1 ') and 2') are in particular:
1) blending at least one monomer of photosensitive resin with a photoinitiator to obtain a resin solution;
2) adding a filler to the solution to prepare a mixed dispersion;
3) and (3) carrying out photocuring 3D printing on the resin solution obtained in the step 1) or the mixed dispersion liquid obtained in the step 2) to obtain the photocuring 3D printing linear polymer workpiece.
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| US17/597,145 US12037424B2 (en) | 2019-09-12 | 2020-09-11 | Enhanced, self-healable or recoverable and recyclable 3D printed article and preparation method and use thereof |
| PCT/CN2020/114834 WO2021047649A1 (en) | 2019-09-12 | 2020-09-11 | Enhanced, self-repairable or recoverable, and recyclable 3d printed article, preparation method therefor and use thereof |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106554469A (en) * | 2016-11-23 | 2017-04-05 | 江苏宏泰高分子材料有限公司 | A kind of 3D printing photosensitive resin regulated and controled based on graphite phase carbon nitride light |
| CN107312133A (en) * | 2016-04-26 | 2017-11-03 | 中国科学院化学研究所 | A kind of visible light solidifying material and 3D printing device and product for 3D printing |
| CN110341097A (en) * | 2019-08-05 | 2019-10-18 | 浙江大学 | A kind of thermoplastic polymer and application based on DLP photocuring 3D printing |
-
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- 2020-01-20 CN CN202010066454.4A patent/CN113150199B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107312133A (en) * | 2016-04-26 | 2017-11-03 | 中国科学院化学研究所 | A kind of visible light solidifying material and 3D printing device and product for 3D printing |
| CN106554469A (en) * | 2016-11-23 | 2017-04-05 | 江苏宏泰高分子材料有限公司 | A kind of 3D printing photosensitive resin regulated and controled based on graphite phase carbon nitride light |
| CN110341097A (en) * | 2019-08-05 | 2019-10-18 | 浙江大学 | A kind of thermoplastic polymer and application based on DLP photocuring 3D printing |
Non-Patent Citations (1)
| Title |
|---|
| Reprocessable thermosets for sustainable threedimensional printing;Biao Zhang;《NATURE COMMUNICATIONS》;20181231;第9卷;全文 * |
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