CN116333235B - Photo-curing acrylic resin material for 3D printing and preparation method thereof - Google Patents
Photo-curing acrylic resin material for 3D printing and preparation method thereof Download PDFInfo
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- CN116333235B CN116333235B CN202310373774.8A CN202310373774A CN116333235B CN 116333235 B CN116333235 B CN 116333235B CN 202310373774 A CN202310373774 A CN 202310373774A CN 116333235 B CN116333235 B CN 116333235B
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- iron powder
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- acrylic resin
- carbonyl iron
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- 239000000463 material Substances 0.000 title claims abstract description 59
- 239000004925 Acrylic resin Substances 0.000 title claims abstract description 41
- 229920000178 Acrylic resin Polymers 0.000 title claims abstract description 41
- 238000000016 photochemical curing Methods 0.000 title claims abstract description 36
- 238000010146 3D printing Methods 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000004814 polyurethane Substances 0.000 claims abstract description 34
- 229920002635 polyurethane Polymers 0.000 claims abstract description 34
- 239000002131 composite material Substances 0.000 claims abstract description 31
- -1 acrylic ester Chemical class 0.000 claims abstract description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000003085 diluting agent Substances 0.000 claims abstract description 24
- 229920001296 polysiloxane Polymers 0.000 claims abstract description 24
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 20
- 125000003368 amide group Chemical group 0.000 claims abstract description 17
- 125000001951 carbamoylamino group Chemical group C(N)(=O)N* 0.000 claims abstract description 17
- 239000000178 monomer Substances 0.000 claims abstract description 17
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 claims abstract description 15
- 125000003396 thiol group Chemical group [H]S* 0.000 claims abstract description 11
- 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 abstract description 10
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 claims abstract description 10
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 claims abstract description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 33
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 32
- 238000002156 mixing Methods 0.000 claims description 26
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 22
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 18
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 17
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 17
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 239000011259 mixed solution Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 12
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 12
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 11
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 10
- 238000013329 compounding Methods 0.000 claims description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- WARCRYXKINZHGQ-UHFFFAOYSA-N benzohydrazide Chemical compound NNC(=O)C1=CC=CC=C1 WARCRYXKINZHGQ-UHFFFAOYSA-N 0.000 claims description 9
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- WJJMNDUMQPNECX-UHFFFAOYSA-N dipicolinic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=N1 WJJMNDUMQPNECX-UHFFFAOYSA-N 0.000 claims description 8
- HVVWZTWDBSEWIH-UHFFFAOYSA-N [2-(hydroxymethyl)-3-prop-2-enoyloxy-2-(prop-2-enoyloxymethyl)propyl] prop-2-enoate Chemical compound C=CC(=O)OCC(CO)(COC(=O)C=C)COC(=O)C=C HVVWZTWDBSEWIH-UHFFFAOYSA-N 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- IKYAJDOSWUATPI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propane-1-thiol Chemical compound CO[Si](C)(OC)CCCS IKYAJDOSWUATPI-UHFFFAOYSA-N 0.000 claims description 6
- FMGBDYLOANULLW-UHFFFAOYSA-N 3-isocyanatopropyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)CCCN=C=O FMGBDYLOANULLW-UHFFFAOYSA-N 0.000 claims description 6
- 239000005711 Benzoic acid Substances 0.000 claims description 6
- 235000010233 benzoic acid Nutrition 0.000 claims description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 6
- 229920002545 silicone oil Polymers 0.000 claims description 6
- 235000010290 biphenyl Nutrition 0.000 claims description 5
- 239000004305 biphenyl Substances 0.000 claims description 5
- 125000006267 biphenyl group Chemical group 0.000 claims description 5
- VZJJZMXEQNFTLL-UHFFFAOYSA-N chloro hypochlorite;zirconium;octahydrate Chemical compound O.O.O.O.O.O.O.O.[Zr].ClOCl VZJJZMXEQNFTLL-UHFFFAOYSA-N 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000013007 heat curing Methods 0.000 claims description 5
- 239000005457 ice water Substances 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 4
- 238000001029 thermal curing Methods 0.000 claims description 4
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims 5
- 239000011347 resin Substances 0.000 abstract description 31
- 229920005989 resin Polymers 0.000 abstract description 31
- 238000005286 illumination Methods 0.000 abstract description 5
- 239000004970 Chain extender Substances 0.000 abstract description 4
- 239000011203 carbon fibre reinforced carbon Substances 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 239000012621 metal-organic framework Substances 0.000 abstract 1
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 8
- 230000002441 reversible effect Effects 0.000 description 6
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 238000001723 curing Methods 0.000 description 4
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical group CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 3
- 239000006096 absorbing agent Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 125000004185 ester group Chemical group 0.000 description 3
- 230000006870 function Effects 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- 230000002035 prolonged effect Effects 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000002009 diols Chemical class 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
- C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
- C08F290/06—Polymers provided for in subclass C08G
- C08F290/067—Polyurethanes; Polyureas
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
- B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/44—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
- 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
- C08F283/122—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes on to saturated polysiloxanes containing hydrolysable groups, e.g. alkoxy-, thio-, hydroxy-
-
- 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
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Civil Engineering (AREA)
- Composite Materials (AREA)
- Structural Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
The invention relates to the technical field of acrylic resin, in particular to a photocuring acrylic resin material for 3D printing and a preparation method thereof, wherein dihydric alcohol containing ureido and amide groups is prepared as a chain extender, and then trifunctional acrylic ester containing siloxane structures is used for end capping to obtain self-repairing polyurethane; the preparation method comprises the steps of using acryloylmorpholine, tripropylene glycol diacrylate and isobornyl acrylate to compound as a diluent, polymerizing the diluent and self-repairing polyurethane through carbon-carbon double bonds, and inserting sulfhydryl polysiloxane into a cross-linked network to form an interpenetrating network structure; preparing composite carbonyl iron powder by carrying out composite treatment on the carbonyl iron powder by using a metal organic framework, and arranging the composite carbonyl iron powder in order under the action of an externally applied magnetic field; the sulfydryl polysiloxane introduced into the resin material can effectively improve the weather resistance of the resin material, and sulfydryl-alkene clicking photopolymerization can occur between the sulfydryl polysiloxane and the siloxane-containing polyfunctional acrylate monomer under illumination.
Description
Technical Field
The invention relates to the technical field of acrylic resin, in particular to a photo-curing acrylic resin material for 3D printing and a preparation method thereof.
Background
Along with the progress of science and technology, 3D printing technology with refinement and light weight is widely applied to various industries, and photo-curing 3D printing is widely applied due to the advantages of high efficiency, high forming speed and the like. The photosensitive resin is an important raw material for photo-curing 3D printing, and directly influences the printing speed and the curing and forming of the product.
The photosensitive resin used for 3D printing in the existing market mainly comprises a polymer monomer, a prepolymer, a diluent, a photoinitiator, a photosensitizer and the like, but with the rapid development of society, the requirements on the precision, strength, toughness, weather resistance and the like of printed products in the fields of manufacturing industry, chemical industry and the like are continuously improved, and the existing photosensitive resin has affected the progress of the photocuring 3D printing technology.
Disclosure of Invention
The invention aims to provide a photo-curing acrylic resin material for 3D printing and a preparation method thereof, which are used for solving the problems in the prior art.
In order to solve the technical problems, the invention provides the following technical scheme:
a preparation method of a photo-curing acrylic resin material for 3D printing comprises the following steps:
s1: preparing self-repairing polyurethane by using dihydric alcohol containing amido and ureido and polyfunctional acrylate monomer containing siloxane;
s2: under the nitrogen atmosphere, the photoinitiator, the self-repairing polyurethane, the diluent, the composite carbonyl iron powder and the sulfhydryl polysiloxane are ultrasonically mixed, and are photo-cured and thermally cured under the condition of an externally applied magnetic field, so that the photo-cured acrylic resin material for 3D printing is obtained.
Aiming at the problems that the light-cured acrylic resin in the existing market has lower comprehensive mechanical property and is difficult to repair after being subjected to mechanical damage, the invention provides the light-cured acrylic resin material for 3D printing, and urea bonds and amide bonds are introduced into the resin material through component adjustment, so that the tensile strength of the light-cured acrylic resin is improved, and meanwhile, the light-cured acrylic resin material is endowed with good self-repairing property; the carbonyl iron powder is subjected to composite treatment by using the metal organic frame to prepare composite carbonyl iron powder, the composite carbonyl iron powder is orderly arranged under the action of an external magnetic field, and the orderly uniformity of the dispersion of the composite carbonyl iron powder in the resin is improved, so that the toughness of the resin material is greatly improved, the effect of a light absorber is also achieved by introducing the metal organic frame, and the light curing efficiency of the resin material is improved; the sulfydryl polysiloxane introduced into the resin material can effectively improve the weather resistance of the resin material, and sulfydryl-alkene click photopolymerization can be generated between the sulfydryl polysiloxane and the polyfunctional acrylate monomer containing siloxane under illumination, so that the complexity of a crosslinked network in the resin material is improved, and the service life of the acrylic resin is effectively prolonged.
Further, the photo-curing acrylic resin material comprises the following components in parts by weight: 55-60 parts of self-repairing polyurethane, 1-2 parts of photoinitiator, 15-18 parts of diluent, 1-2 parts of sulfhydryl polysiloxane and 1-3 parts of composite carbonyl iron powder.
Further, the conditions of the applied magnetic field intensity are as follows: the magnetic field strength is 50mT, and the time is 5-10min.
Further, the working conditions of the photo-curing are: the wavelength of the irradiation light is 400-480nm, and the irradiation time is 10-15min; the working conditions for heat curing are: preserving heat at 40-50deg.C for 15-20min.
Further, the photoinitiator is (4, 6-trimethylbenzoyl) phosphine oxide and diphenyl iodohexafluorophosphate in a mass ratio of 1:1, and compounding to obtain the product.
Further, the photoinitiator is an initiator which can reach a larger absorption peak under the irradiation of light with the wavelength of 400-480 nm.
Further, the diluent is acryloylmorpholine, tripropylene glycol diacrylate and isobornyl acrylate in a mass ratio of 1:1:2, compounding.
The invention prepares a three-dimensional structure photo-curing acrylic resin with shape memory and self-repairing function, which uses the combination of acryloylmorpholine, tripropylene glycol diacrylate and isobornyl acrylate as a diluent, the diluent and the self-repairing polyurethane are polymerized through carbon-carbon double bonds to form a cross-linked network structure with large molecular weight, mercapto polysiloxane is inserted in the cross-linked network, hydroxyl groups in the molecular chain of the mercapto polysiloxane and isocyanate groups in the self-repairing polyurethane form dynamic reversible covalent urethane bonds, and ester groups and hydrogen atoms in the urethane bonds form dynamic reversible non-covalent hydrogen bonds, so that an interpenetrating network structure is formed, and the self-repairing property of the resin material is improved.
Further, the preparation of the self-repairing polyurethane comprises the following steps:
(1) Mixing isophorone diisocyanate and diethanolamine, adding a mixed solution of benzoyl hydrazine and acetone in an ice-water bath for 1-2h, and preserving heat in an ice-salt bath for 1-2h to obtain dihydric alcohol containing amido and ureido;
(2) Mixing 3-isocyanatopropyl trimethoxy silane, methyl ethyl ketone, 4-methoxyphenol and dibutyl tin dilaurate, heating to 55 ℃, adding pentaerythritol triacrylate, preserving heat for 11-12h, and washing with n-hexane for 3-5 times to obtain a multifunctional acrylate monomer containing siloxane;
(3) Heating isophorone diisocyanate to 40 ℃, adding dibutyl tin dilaurate, heating to 65 ℃, adding a mixed solution of 1, 4-butanediol and acetone, preserving heat for 2 hours, adding a mixed solution of dihydric alcohol containing amide groups and ureido groups and acetone, preserving heat for 3 hours, adding a polyfunctional acrylate monomer containing siloxane and 4-methoxyphenol, and preserving heat for 2 hours at 65 ℃ to obtain the self-repairing polyurethane.
In the invention, benzoyl hydrazine, isophorone diisocyanate and diethanolamine are used for preparing a dihydric alcohol containing ureido and amide groups as a chain extender, a prepolymer formed by isophorone diisocyanate and 1, 4-butanediol is subjected to chain extension, and then trifunctional acrylic ester containing siloxane structure is used for blocking, so that self-repairing polyurethane is obtained, and the waterproof and dirt-resistant properties of the resin material are greatly improved.
Further, the preparation of the mercaptopolysiloxane comprises the following steps: mixing 3-mercaptopropyl methyl dimethoxy silane, hydroxy silicone oil and deionized water, adding hydrochloric acid, preserving the temperature for 4-5 hours at 68-70 ℃, washing with ethanol solution for 3-5 times, and drying to obtain mercaptopolysiloxane.
Further, the preparation of the composite carbonyl iron powder comprises the following steps:
1) Mixing zirconium oxychloride octahydrate, dipicolinate, benzoic acid, polyvinylpyrrolidone and N, N-dimethylformamide, ultrasonically stirring for 10-15min, heating to 120 ℃ in an autoclave, preserving heat for 46-48h, cooling, centrifugally washing with methanol for 3-5 times, and obtaining a metal organic frame;
2) Mixing carbonyl iron powder and diethyl ether, stirring, adding a metal organic frame, performing ultrasonic treatment for 5-10min, stirring for 22-24h, performing centrifugal separation, and washing with anhydrous diethyl ether to obtain the modified carbonyl iron powder.
The invention has the beneficial effects that:
the invention provides a photo-curing acrylic resin material for 3D printing and a preparation method thereof, and the photo-curing acrylic resin material prepared by the method has high strength, good self-repairing property and high water resistance and stain resistance, and meets the requirements of the 3D printing industry.
In the invention, benzoyl hydrazine, isophorone diisocyanate and diethanolamine are used for preparing a dihydric alcohol containing ureido and amide groups as a chain extender, a prepolymer formed by isophorone diisocyanate and 1, 4-butanediol is subjected to chain extension, urea bonds and amide bonds are introduced into a resin material, and the tensile strength of the photo-cured acrylic resin is improved, and meanwhile, good self-repairing property is provided; the trifunctional acrylate containing siloxane structure is used for end capping in the self-repairing polyurethane, and the trifunctional acrylate and the mercapto polysiloxane can generate mercapto-alkene click photopolymerization under the illumination, so that the complexity of a crosslinked network in the resin material is improved, and the water resistance, acid resistance and weather resistance of the resin material are improved.
The invention prepares a three-dimensional structure photo-curing acrylic resin with shape memory and self-repairing functions, and utilizes the combination of acryloylmorpholine, tripropylene glycol diacrylate and isobornyl acrylate as a diluent, the diluent and the self-repairing polyurethane are polymerized through carbon-carbon double bonds to form a cross-linked network structure with large molecular weight, mercapto polysiloxane is inserted in the cross-linked network, hydroxyl groups in the molecular chain of the mercapto polysiloxane and isocyanate groups in the self-repairing polyurethane form dynamic reversible covalent urethane bonds, and ester groups and hydrogen atoms in the urethane bonds form dynamic reversible non-covalent hydrogen bonds, so that an interpenetrating network structure is formed, and the self-repairing property and comprehensive mechanical property of the resin material are improved.
According to the invention, the carbonyl iron powder is subjected to composite treatment by the metal organic frame to prepare the composite carbonyl iron powder, the composite carbonyl iron powder is orderly arranged under the action of an external magnetic field, and the orderly uniformity of the dispersion of the composite carbonyl iron powder in the resin is improved, so that the toughness of the resin material is greatly improved, the effect of a light absorber is also achieved by introducing the metal organic frame, the light curing efficiency of the resin material is improved, and the service life of the acrylic resin is effectively prolonged.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely in connection with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In addition, the technical solutions of the embodiments may be combined with each other, but it is necessary to base that the technical solutions can be realized by those skilled in the art, and when the technical solutions are contradictory or cannot be realized, the combination of the technical solutions should be considered to be absent and not within the scope of protection claimed in the present invention.
The following description of the embodiments of the present invention will be presented in further detail with reference to the examples, which should be understood as being merely illustrative of the present invention and not limiting.
Example 1: a preparation method of a photo-curing acrylic resin material for 3D printing comprises the following steps:
s1: the preparation of the self-repairing polyurethane comprises the following steps:
(1) Mixing 2.22g of isophorone diisocyanate and 1.05g of diethanolamine, adding a mixed solution of 1.36g of benzoyl hydrazine and 100mL of acetone in an ice-water bath for 1h, and preserving heat in an ice-salt bath for 1h to obtain dihydric alcohol containing amido and ureido;
(2) 5.14g of 3-isocyanatopropyl trimethoxysilane, 0.5g of methyl ethyl ketone, 500ppm of 4-methoxyphenol and 500ppm of dibutyltin dilaurate are mixed, the temperature is raised to 55 ℃, 7.45g of pentaerythritol triacrylate is added for heat preservation for 11 hours, and the mixture is washed 3 times with n-hexane to obtain a polyfunctional acrylate monomer containing siloxane;
(3) Heating 2.22g isophorone diisocyanate to 40 ℃, adding 2 drops of dibutyltin dilaurate, heating to 65 ℃, adding a mixed solution of 0.36g1, 4-butanediol and 5mL acetone, preserving heat for 2 hours, adding a mixed solution of 0.5g dihydric alcohol containing amido and ureido and 10mL acetone, preserving heat for 3 hours, adding 2g polyfunctional acrylate monomer containing siloxane and 800ppm 4-methoxyphenol, and preserving heat for 2 hours at 65 ℃ to obtain self-repairing polyurethane;
s2: under the nitrogen atmosphere, mixing a photoinitiator, self-repairing polyurethane, a diluent, composite carbonyl iron powder and sulfhydryl polysiloxane in an ultrasonic manner, and carrying out photo-curing and thermal curing under the condition of an externally applied magnetic field to obtain a photo-curing acrylic resin material for 3D printing;
the photo-curing acrylic resin material comprises the following components in parts by weight: 55 parts of self-repairing polyurethane, 1 part of photoinitiator, 15 parts of diluent, 1 part of sulfhydryl polysiloxane and 1 part of composite carbonyl iron powder;
the conditions of the external magnetic field intensity are as follows: the magnetic field strength is 50mT, and the time is 5min; the working conditions of the photo-curing are as follows: light with the wavelength of 400nm irradiates for 15min; the working conditions for heat curing are: preserving heat at 40 ℃ for 20min;
the photoinitiator is (2, 4, 6-trimethylbenzoyl) diphenyl phosphine oxide and diphenyl iodohexafluorophosphate in a mass ratio of 1:1, compounding to obtain the compound;
the diluent is acryloylmorpholine, tripropylene glycol diacrylate and isobornyl acrylate in a mass ratio of 1:1:2, compounding;
the preparation of the mercaptopolysiloxane comprises the following steps: mixing 4g of 3-mercaptopropyl methyl dimethoxy silane, 1.2g of hydroxy silicone oil and 26g of deionized water, adding 1.0wt% of hydrochloric acid, preserving the temperature at 68 ℃ for 5 hours, washing with ethanol solution for 3 times, and drying to obtain mercaptopolysiloxane;
the preparation of the composite carbonyl iron powder comprises the following steps:
1) Mixing 32.2mg of zirconium oxychloride octahydrate, 22.4mg of dipicolinic acid, 244mg of benzoic acid, 150mg of polyvinylpyrrolidone and 5mLN (methyl pyrrolidone), and N-dimethylformamide, ultrasonically stirring for 10min, heating to 120 ℃ in an autoclave, preserving heat for 46h, cooling, and centrifugally washing with methanol for 3 times to obtain a metal organic frame;
2) Mixing and stirring 2.79mg of carbonyl iron powder and 6mL of diethyl ether, adding 18mg of metal organic frame, carrying out ultrasonic treatment for 5min, stirring for 22h, carrying out centrifugal separation, and washing with anhydrous diethyl ether to obtain the modified carbonyl iron powder.
Example 2: a preparation method of a photo-curing acrylic resin material for 3D printing comprises the following steps:
s1: the preparation of the self-repairing polyurethane comprises the following steps:
(1) Mixing 2.22g of isophorone diisocyanate and 1.05g of diethanolamine, adding a mixed solution of 1.36g of benzoyl hydrazine and 30mL of acetone in an ice-water bath for 1.5h, and preserving heat in an ice-salt bath for 1.5h to obtain dihydric alcohol containing amido and ureido;
(2) 5.14g of 3-isocyanatopropyl trimethoxysilane, 0.5g of methyl ethyl ketone, 500ppm of 4-methoxyphenol and 500ppm of dibutyltin dilaurate are mixed, the temperature is raised to 55 ℃, 7.45g of pentaerythritol triacrylate is added for heat preservation for 11.5 hours, and the mixture is washed with n-hexane for 4 times to obtain a polyfunctional acrylate monomer containing siloxane;
(3) Heating 2.22g isophorone diisocyanate to 40 ℃, adding 2 drops of dibutyltin dilaurate, heating to 65 ℃, adding a mixed solution of 0.36g1, 4-butanediol and 5mL acetone, preserving heat for 2 hours, adding a mixed solution of 0.5g dihydric alcohol containing amido and ureido and 10mL acetone, preserving heat for 3 hours, adding 2g polyfunctional acrylate monomer containing siloxane and 800ppm 4-methoxyphenol, and preserving heat for 2 hours at 65 ℃ to obtain self-repairing polyurethane;
s2: under the nitrogen atmosphere, mixing a photoinitiator, self-repairing polyurethane, a diluent, composite carbonyl iron powder and sulfhydryl polysiloxane in an ultrasonic manner, and carrying out photo-curing and thermal curing under the condition of an externally applied magnetic field to obtain a photo-curing acrylic resin material for 3D printing;
the photo-curing acrylic resin material comprises the following components in parts by weight: 58 parts of self-repairing polyurethane, 1.5 parts of photoinitiator, 17 parts of diluent, 1.5 parts of sulfhydryl polysiloxane and 2 parts of composite carbonyl iron powder;
the conditions of the external magnetic field intensity are as follows: the magnetic field strength is 50mT, and the time is 8s; the working conditions of the photo-curing are as follows: light with the wavelength of 460nm irradiates for 12min; the working conditions for heat curing are: preserving heat at 45 ℃ for 18min;
the photoinitiator is (2, 4, 6-trimethylbenzoyl) diphenyl phosphine oxide and diphenyl iodohexafluorophosphate in a mass ratio of 1:1, compounding to obtain the compound;
the diluent is acryloylmorpholine, tripropylene glycol diacrylate and isobornyl acrylate in a mass ratio of 1:1:2, compounding;
the preparation of the mercaptopolysiloxane comprises the following steps: mixing 4g of 3-mercaptopropyl methyl dimethoxy silane, 1.2g of hydroxy silicone oil and 26g of deionized water, adding 1.0wt% of hydrochloric acid, preserving the temperature for 4.5 hours at 69 ℃, washing with ethanol solution for 4 times, and drying to obtain mercaptopolysiloxane;
the preparation of the composite carbonyl iron powder comprises the following steps:
1) Mixing 32.2mg of zirconium oxychloride octahydrate, 22.4mg of dipicolinic acid, 244mg of benzoic acid, 150mg of polyvinylpyrrolidone and 5mLN (methyl pyrrolidone), and N-dimethylformamide, ultrasonically stirring for 13min, heating to 120 ℃ in an autoclave, preserving heat for 47h, cooling, and centrifugally washing for 4 times with methanol to obtain a metal organic frame;
2) Mixing and stirring 2.79mg of carbonyl iron powder and 6mL of diethyl ether, adding 18mg of metal organic frame, carrying out ultrasonic treatment for 5-10min, stirring for 23h, carrying out centrifugal separation, and washing with anhydrous diethyl ether to obtain the modified carbonyl iron powder.
Example 3: a preparation method of a photo-curing acrylic resin material for 3D printing comprises the following steps:
s1: the preparation of the self-repairing polyurethane comprises the following steps:
(1) Mixing 2.22g of isophorone diisocyanate and 1.05g of diethanolamine, adding a mixed solution of 1.36g of benzoyl hydrazine and 30mL of acetone in an ice-water bath for 2 hours, and preserving heat in an ice-salt bath for 2 hours to obtain dihydric alcohol containing amido and ureido;
(2) 5.14g of 3-isocyanatopropyl trimethoxysilane, 0.5g of methyl ethyl ketone, 500ppm of 4-methoxyphenol and 500ppm of dibutyltin dilaurate are mixed, the temperature is raised to 55 ℃, 7.45g of pentaerythritol triacrylate is added for heat preservation for 12 hours, and the mixture is washed 5 times with n-hexane to obtain a polyfunctional acrylate monomer containing siloxane;
(3) Heating 2.22g isophorone diisocyanate to 40 ℃, adding 3 drops of dibutyltin dilaurate, heating to 65 ℃, adding a mixed solution of 0.36g1, 4-butanediol and 5mL acetone, preserving heat for 2 hours, adding a mixed solution of 0.5g dihydric alcohol containing amido and ureido and 10mL acetone, preserving heat for 3 hours, adding 2g polyfunctional acrylate monomer containing siloxane and 800ppm 4-methoxyphenol, and preserving heat for 2 hours at 65 ℃ to obtain self-repairing polyurethane;
s2: under the nitrogen atmosphere, mixing a photoinitiator, self-repairing polyurethane, a diluent, composite carbonyl iron powder and sulfhydryl polysiloxane in an ultrasonic manner, and carrying out photo-curing and thermal curing under the condition of an externally applied magnetic field to obtain a photo-curing acrylic resin material for 3D printing;
the photo-curing acrylic resin material comprises the following components in parts by weight: 60 parts of self-repairing polyurethane, 2 parts of photoinitiator, 18 parts of diluent, 2 parts of sulfhydryl polysiloxane and 3 parts of composite carbonyl iron powder;
the conditions of the external magnetic field intensity are as follows: the magnetic field strength is 50mT, and the time is 10s; the working conditions of the photo-curing are as follows: light with the wavelength of 480nm irradiates for 10min; the working conditions for heat curing are: preserving heat at 50 ℃ for 15min;
the photoinitiator is (2, 4, 6-trimethylbenzoyl) diphenyl phosphine oxide and diphenyl iodohexafluorophosphate in a mass ratio of 1:1, compounding to obtain the compound;
the diluent is acryloylmorpholine, tripropylene glycol diacrylate and isobornyl acrylate in a mass ratio of 1:1:2, compounding;
the preparation of the mercaptopolysiloxane comprises the following steps: mixing 4g of 3-mercaptopropyl methyl dimethoxy silane, 1.2g of hydroxy silicone oil and 26g of deionized water, adding 1.0wt% of hydrochloric acid, preserving the temperature at 70 ℃ for 4 hours, washing with ethanol solution for 5 times, and drying to obtain mercaptopolysiloxane;
the preparation of the composite carbonyl iron powder comprises the following steps:
1) Mixing 32.2mg of zirconium oxychloride octahydrate, 22.4mg of dipicolinic acid, 244mg of benzoic acid, 150mg of polyvinylpyrrolidone and 5mLN (methyl pyrrolidone), and N-dimethylformamide, ultrasonically stirring for 15min, heating to 120 ℃ in an autoclave, preserving heat for 48h, cooling, and centrifugally washing with methanol for 5 times to obtain a metal organic frame;
2) Mixing and stirring 2.79mg of carbonyl iron powder and 6mL of diethyl ether, adding 18mg of metal organic frame, carrying out ultrasonic treatment for 10min, stirring for 24h, carrying out centrifugal separation, and washing with anhydrous diethyl ether to obtain the modified carbonyl iron powder.
Comparative example 1: in the preparation of the self-repairing polyurethane, no diol containing an amide group and an ureido group was prepared by using example 3 as a control group, and other procedures were normal.
Comparative example 2: in the preparation of the self-healing polyurethane, using example 3 as a control group, pentaerythritol triacrylate was used to replace the silicone-containing polyfunctional acrylate monomer, with other procedures being normal.
Comparative example 3: using example 3 as a control, no mercaptopolysiloxane was added and the other procedure was normal.
Comparative example 4: in example 3 as a control group, the composite carbonyl iron powder was replaced with carbonyl iron powder, and the other steps were normal.
The sources of the raw materials are as follows:
isophorone diisocyanate I109582, diethanolamine D112360, benzoyl hydrazine B104697, 3-isocyanatopropyl trimethoxysilane I191118, 4-methoxyphenol M170858, dibutyltin dilaurate D100274, pentaerythritol triacrylate P492035, 1, 4-butanediol B110391, (2, 4, 6-trimethylbenzoyl) diphenyl phosphine oxide T107643, diphenyliodohexafluorophosphate D131525, acryloylmorpholine A151729, tripropylene glycol diacrylate T162230, isobornyl acrylate I157699, 3-mercaptopropyl methyl dimethoxysilane M100619, zirconium octo-water zirconium oxychloride Z164495, bipyridine dicarboxylic acid B152120, polyvinylpyrrolidone P110611, N-dimethylformamide D111999): ala Ding Shiji; carbonyl iron powder 7439-89-6: western security Ji Yue biotechnology limited; hydroxyl silicone oil 58130-04-4: hubei huge science and technology limited company; acetone, methyl ethyl ketone, hydrochloric acid, ethanol, benzoic acid, diethyl ether, analytically pure: national drug group reagent.
Performance test: examples 1 to 3 and comparative examples 1 to 4 were tested, and the test results are shown in Table 1;
mechanical property test: cutting a sample into dumbbell-shaped sample bars with the length of 25mm, the width of 4mm and the thickness of 1mm, testing the mechanical properties of the sample by using a universal testing machine, wherein the interval between test clamps is 15mm, and the stretching rate is 50mm/min;
self-repairing performance test: cutting a sample with the length of 30mm, the width of 30mm and the thickness of 2mm, marking scratches with the length of 15mm and the depth of 1mm on the sample, then preserving heat for 1h at 70 ℃, and observing the repair condition of the material by using a microscope;
contact angle test: using a static drop contact angle measuring instrument, and testing with 4 mu L deionized water;
water resistance: cutting a sample with the length of 30mm, the width of 30mm and the thickness of 2mm, weighing and marking as m0, soaking the sample in deionized water at 100 ℃ for 10 hours, wiping the surface with absorbent paper, weighing and marking as m1, and the water absorption is m1/m0 multiplied by 100%;
acid resistance: the test pieces having a length of 100mm, a width of 20mm and a thickness of 2mm were immersed in a 30% dilute sulfuric acid solution for one week, and the test pieces were evaluated for acid resistance, and the test pieces were judged to be acceptable in that the test pieces were free from wrinkles, blisters, blushing and the like on the surfaces.
TABLE 1
The invention provides a photocuring acrylic resin material for 3D printing and a preparation method thereof, and the photocuring acrylic resin material prepared in the embodiments 1-3 of the application has good self-repairing property after being mechanically damaged, has water absorption lower than 2.8 percent and water contact angle higher than 130 degrees, is qualified in an acid resistance test, and meets the requirements of the 3D printing industry.
In the invention, a diol containing ureido and amide groups is prepared from benzoyl hydrazine, isophorone diisocyanate and diethanolamine to be used as a chain extender, a prepolymer formed by isophorone diisocyanate and 1, 4-butanediol is chain-extended, and urea bonds and amide bonds are introduced into a resin material, so that the tensile strength of the photo-cured acrylic resin is improved, and meanwhile, the self-repairing property of the photo-cured acrylic resin is endowed.
Comparing example 3 with comparative example 2, in the invention, the trifunctional acrylate containing siloxane structure is used for end capping, and the trifunctional acrylate and the mercapto polysiloxane can generate mercapto-alkene click photopolymerization under the illumination, thereby improving the complexity of a crosslinked network in the resin material, and further improving the water resistance and acid resistance of the resin material.
By comparing example 3 with comparative example 3, the invention prepares a three-dimensional structure photo-curing acrylic resin with shape memory and self-repairing function, and uses the combination of acryloylmorpholine, tripropylene glycol diacrylate and isobornyl acrylate as a diluent, the diluent and the self-repairing polyurethane are polymerized through carbon-carbon double bonds to form a cross-linked network structure with large molecular weight, mercaptopolysiloxane is inserted in the cross-linked network, hydroxyl groups in the molecular chain of the mercaptopolysiloxane and isocyanate groups in the self-repairing polyurethane form dynamic reversible covalent urethane bonds, and ester groups and hydrogen atoms in the urethane bonds form dynamic reversible non-covalent hydrogen bonds, so that an interpenetrating network structure is formed, and the self-repairing property of the resin material is improved. The sulfydryl polysiloxane introduced into the resin material can effectively improve the weather resistance of the resin material, and sulfydryl-alkene click photopolymerization can be generated between the sulfydryl polysiloxane and the polyfunctional acrylate monomer containing siloxane under illumination, so that the complexity of a crosslinked network in the resin material is improved, and the service life of the acrylic resin is effectively prolonged.
Comparing example 3 with comparative example 4, the carbonyl iron powder is subjected to composite treatment by using a metal organic frame to prepare composite carbonyl iron powder, the composite carbonyl iron powder is orderly arranged under the action of an external magnetic field, and the orderly uniformity of the dispersion of the composite carbonyl iron powder in the resin is improved, so that the toughness of the resin material is greatly improved, the effect of a light absorber is also achieved by introducing the metal organic frame, and the light curing efficiency of the resin material is improved.
The foregoing description is only exemplary embodiments of the present invention and is not intended to limit the scope of the invention, and all equivalent structural changes made by the present invention or direct/indirect application in other related technical fields are included in the scope of the present invention.
Claims (8)
1. A method for preparing a photo-curable acrylic resin material for 3D printing, comprising the steps of:
s1: preparing self-repairing polyurethane by using dihydric alcohol containing amido and ureido and polyfunctional acrylate monomer containing siloxane;
s2: under the nitrogen atmosphere, mixing a photoinitiator, self-repairing polyurethane, a diluent, composite carbonyl iron powder and sulfhydryl polysiloxane in an ultrasonic manner, and carrying out photo-curing and thermal curing under the condition of an externally applied magnetic field to obtain a photo-curing acrylic resin material for 3D printing;
the diluent is acryloylmorpholine, tripropylene glycol diacrylate and isobornyl acrylate in a mass ratio of 1:1:2, compounding;
the preparation of the composite carbonyl iron powder comprises the following steps:
1) Mixing zirconium oxychloride octahydrate, dipicolinate, benzoic acid, polyvinylpyrrolidone and N, N-dimethylformamide, ultrasonically stirring for 10-15min, heating to 120 ℃ in an autoclave, preserving heat for 46-48h, cooling, centrifugally washing with methanol for 3-5 times, and obtaining a metal organic frame;
2) Mixing carbonyl iron powder and diethyl ether, stirring, adding a metal organic frame, performing ultrasonic treatment for 5-10min, stirring for 22-24h, performing centrifugal separation, and washing with anhydrous diethyl ether to obtain the modified carbonyl iron powder.
2. The method for preparing a photo-curable acrylic resin material for 3D printing according to claim 1, wherein the composition of the photo-curable acrylic resin material is as follows in parts by mass: 55-60 parts of self-repairing polyurethane, 1-2 parts of photoinitiator, 15-18 parts of diluent, 1-2 parts of sulfhydryl polysiloxane and 1-3 parts of composite carbonyl iron powder.
3. The method for preparing a photocurable acrylic material for 3D printing according to claim 1, wherein the conditions of the externally applied magnetic field are: the magnetic field strength is 50mT, and the time is 5-10min.
4. The method for preparing a photocurable acrylic material for 3D printing according to claim 1, wherein the working conditions of the photocuring are: the wavelength of the irradiation light is 400-480nm, and the irradiation time is 10-15min; the working conditions for heat curing are: preserving heat at 40-50deg.C for 15-20min.
5. The method for preparing a photo-curable acrylic resin material for 3D printing according to claim 1, wherein the photoinitiator is (4, 6-trimethylbenzoyl) phosphine oxide and diphenyl iodohexafluorophosphate in a mass ratio of 1:1, and compounding to obtain the product.
6. The method for preparing a photocurable acrylic material for 3D printing according to claim 1, wherein the preparation of the self-repairing polyurethane comprises the steps of:
(1) Mixing isophorone diisocyanate and diethanolamine, adding a mixed solution of benzoyl hydrazine and acetone in an ice-water bath for 1-2h, and preserving heat in an ice-salt bath for 1-2h to obtain dihydric alcohol containing amido and ureido;
(2) Mixing 3-isocyanatopropyl trimethoxy silane, methyl ethyl ketone, 4-methoxyphenol and dibutyl tin dilaurate, heating to 55 ℃, adding pentaerythritol triacrylate, preserving heat for 11-12h, and washing with n-hexane for 3-5 times to obtain a multifunctional acrylate monomer containing siloxane;
(3) Heating isophorone diisocyanate to 40 ℃, adding dibutyl tin dilaurate, heating to 65 ℃, adding a mixed solution of 1, 4-butanediol and acetone, preserving heat for 2 hours, adding a mixed solution of dihydric alcohol containing amide groups and ureido groups and acetone, preserving heat for 3 hours, adding a polyfunctional acrylate monomer containing siloxane and 4-methoxyphenol, and preserving heat for 2 hours at 65 ℃ to obtain the self-repairing polyurethane.
7. The method for preparing a photocurable acrylic material for 3D printing according to claim 1, wherein the preparation of the mercaptopolysiloxane comprises the steps of: mixing 3-mercaptopropyl methyl dimethoxy silane, hydroxy silicone oil and deionized water, adding hydrochloric acid, preserving the temperature for 4-5 hours at 68-70 ℃, washing with ethanol solution for 3-5 times, and drying to obtain mercaptopolysiloxane.
8. A photocurable acrylic material for 3D printing, characterized by being prepared by the preparation method according to any one of claims 1 to 7.
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