CN112250804A - Secondary curing 3D printing resin - Google Patents
Secondary curing 3D printing resin Download PDFInfo
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- CN112250804A CN112250804A CN202011149041.9A CN202011149041A CN112250804A CN 112250804 A CN112250804 A CN 112250804A CN 202011149041 A CN202011149041 A CN 202011149041A CN 112250804 A CN112250804 A CN 112250804A
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- secondary curing
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- 229920005989 resin Polymers 0.000 title claims abstract description 51
- 239000011347 resin Substances 0.000 title claims abstract description 51
- 238000010146 3D printing Methods 0.000 title claims abstract description 35
- 239000012948 isocyanate Substances 0.000 claims abstract description 12
- 150000002513 isocyanates Chemical group 0.000 claims abstract description 12
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 claims abstract description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims abstract description 9
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims abstract description 9
- 239000003085 diluting agent Substances 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims description 17
- 229920005862 polyol Polymers 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 150000003077 polyols Chemical class 0.000 claims description 13
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 8
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 6
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical group O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 6
- 239000000049 pigment Substances 0.000 claims description 6
- LVGFPWDANALGOY-UHFFFAOYSA-N 8-methylnonyl prop-2-enoate Chemical compound CC(C)CCCCCCCOC(=O)C=C LVGFPWDANALGOY-UHFFFAOYSA-N 0.000 claims description 5
- 229920002396 Polyurea Polymers 0.000 claims description 5
- 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 5
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 5
- VFHVQBAGLAREND-UHFFFAOYSA-N diphenylphosphoryl-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 VFHVQBAGLAREND-UHFFFAOYSA-N 0.000 claims description 5
- 229920000909 polytetrahydrofuran Polymers 0.000 claims description 5
- FKTHNVSLHLHISI-UHFFFAOYSA-N 1,2-bis(isocyanatomethyl)benzene Chemical compound O=C=NCC1=CC=CC=C1CN=C=O FKTHNVSLHLHISI-UHFFFAOYSA-N 0.000 claims description 4
- DXPPIEDUBFUSEZ-UHFFFAOYSA-N 6-methylheptyl prop-2-enoate Chemical group CC(C)CCCCCOC(=O)C=C DXPPIEDUBFUSEZ-UHFFFAOYSA-N 0.000 claims description 4
- 229920000768 polyamine Polymers 0.000 claims description 4
- 239000005056 polyisocyanate Substances 0.000 claims description 4
- 229920001228 polyisocyanate Polymers 0.000 claims description 4
- ISAOCJYIOMOJEB-UHFFFAOYSA-N desyl alcohol Natural products C=1C=CC=CC=1C(O)C(=O)C1=CC=CC=C1 ISAOCJYIOMOJEB-UHFFFAOYSA-N 0.000 claims description 3
- 239000003999 initiator Substances 0.000 claims description 3
- 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 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 3
- YXRKNIZYMIXSAD-UHFFFAOYSA-N 1,6-diisocyanatohexane Chemical compound O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O YXRKNIZYMIXSAD-UHFFFAOYSA-N 0.000 claims description 2
- GTELLNMUWNJXMQ-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical class OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(CO)(CO)CO GTELLNMUWNJXMQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 244000028419 Styrax benzoin Species 0.000 claims description 2
- 235000000126 Styrax benzoin Nutrition 0.000 claims description 2
- 235000008411 Sumatra benzointree Nutrition 0.000 claims description 2
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 2
- VEBCLRKUSAGCDF-UHFFFAOYSA-N ac1mi23b Chemical compound C1C2C3C(COC(=O)C=C)CCC3C1C(COC(=O)C=C)C2 VEBCLRKUSAGCDF-UHFFFAOYSA-N 0.000 claims description 2
- 229920000180 alkyd Polymers 0.000 claims description 2
- 229960002130 benzoin Drugs 0.000 claims description 2
- OHJMTUPIZMNBFR-UHFFFAOYSA-N biuret Chemical compound NC(=O)NC(N)=O OHJMTUPIZMNBFR-UHFFFAOYSA-N 0.000 claims description 2
- 125000004386 diacrylate group Chemical group 0.000 claims description 2
- KORSJDCBLAPZEQ-UHFFFAOYSA-N dicyclohexylmethane-4,4'-diisocyanate Chemical compound C1CC(N=C=O)CCC1CC1CCC(N=C=O)CC1 KORSJDCBLAPZEQ-UHFFFAOYSA-N 0.000 claims description 2
- 235000019382 gum benzoic Nutrition 0.000 claims description 2
- 239000000434 metal complex dye Substances 0.000 claims description 2
- 239000012860 organic pigment Substances 0.000 claims description 2
- JRWNODXPDGNUPO-UHFFFAOYSA-N oxolane;prop-2-enoic acid Chemical compound C1CCOC1.OC(=O)C=C JRWNODXPDGNUPO-UHFFFAOYSA-N 0.000 claims description 2
- 229920001610 polycaprolactone Polymers 0.000 claims description 2
- 239000004632 polycaprolactone Substances 0.000 claims description 2
- 239000004417 polycarbonate Substances 0.000 claims description 2
- 229920000515 polycarbonate Polymers 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 229920005906 polyester polyol Polymers 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920001451 polypropylene glycol Polymers 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 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 2
- 239000005058 Isophorone diisocyanate Substances 0.000 claims 2
- -1 polyoxypropylene Polymers 0.000 claims 2
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical class C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 claims 1
- 235000010290 biphenyl Nutrition 0.000 claims 1
- 239000004305 biphenyl Substances 0.000 claims 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims 1
- OUGJKAQEYOUGKG-UHFFFAOYSA-N ethyl 2-methylidenebutanoate Chemical compound CCOC(=O)C(=C)CC OUGJKAQEYOUGKG-UHFFFAOYSA-N 0.000 claims 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 claims 1
- 150000005217 methyl ethers Chemical class 0.000 claims 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims 1
- 239000000565 sealant Substances 0.000 claims 1
- 239000000126 substance Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 7
- 238000010438 heat treatment Methods 0.000 abstract description 6
- 238000007639 printing Methods 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 3
- 239000013013 elastic material Substances 0.000 abstract description 2
- 238000000465 moulding Methods 0.000 abstract description 2
- 229920000642 polymer Polymers 0.000 abstract 1
- 238000002156 mixing Methods 0.000 description 13
- 238000001723 curing Methods 0.000 description 11
- 238000005516 engineering process Methods 0.000 description 6
- 238000000016 photochemical curing Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 150000002009 diols Chemical class 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 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 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000004721 Polyphenylene oxide Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 229920000570 polyether Polymers 0.000 description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- XUMBMVFBXHLACL-UHFFFAOYSA-N Melanin Chemical compound O=C1C(=O)C(C2=CNC3=C(C(C(=O)C4=C32)=O)C)=C2C4=CNC2=C1C XUMBMVFBXHLACL-UHFFFAOYSA-N 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- FWWXYLGCHHIKNY-UHFFFAOYSA-N 2-ethoxyethyl prop-2-enoate Chemical compound CCOCCOC(=O)C=C FWWXYLGCHHIKNY-UHFFFAOYSA-N 0.000 description 1
- 239000004970 Chain extender Substances 0.000 description 1
- FHNINJWBTRXEBC-UHFFFAOYSA-N Sudan III Chemical compound OC1=CC=C2C=CC=CC2=C1N=NC(C=C1)=CC=C1N=NC1=CC=CC=C1 FHNINJWBTRXEBC-UHFFFAOYSA-N 0.000 description 1
- XQBCVRSTVUHIGH-UHFFFAOYSA-L [dodecanoyloxy(dioctyl)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCCCCCC)(CCCCCCCC)OC(=O)CCCCCCCCCCC XQBCVRSTVUHIGH-UHFFFAOYSA-L 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000000110 selective laser sintering Methods 0.000 description 1
- 229940099373 sudan iii Drugs 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- KSBAEPSJVUENNK-UHFFFAOYSA-L tin(ii) 2-ethylhexanoate Chemical compound [Sn+2].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O KSBAEPSJVUENNK-UHFFFAOYSA-L 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
-
- 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
- B33Y40/00—Auxiliary operations or equipment, e.g. for material handling
- B33Y40/20—Post-treatment, e.g. curing, coating or polishing
-
- 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/006—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00
- C08F283/008—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polymers provided for in C08G18/00 on to unsaturated polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Civil Engineering (AREA)
- Composite Materials (AREA)
- Structural Engineering (AREA)
- Ceramic Engineering (AREA)
- Polyurethanes Or Polyureas (AREA)
Abstract
本发明公开了一种二次固化3D打印树脂，所述二次固化3D打印树脂包括A组分、B组分和光引发剂，以质量份数计，所述A组分包括异氰酸酯基封端预聚物50‑80份，活性稀释剂20‑50份，所述B组分包括丙烯酸酯预聚物50‑80份，活性稀释剂20‑50份，紫外光引发剂占树脂总质量的1～5％。使用本发明提供的树脂3D打印成型后制品中异氰酸酯基团加热条件下进一步反应，形成一种双网络结构，可以有效提高制品的力学性能，而且通过设计调节树脂配方，可以获得满足不同的性能需求，从弹性材料到韧性材料均可简单制备得到，同时具有混合后的树脂在3D打印过程中非常稳定，打印窗口长。The invention discloses a secondary curing 3D printing resin. The secondary curing 3D printing resin includes a component A, a component B and a photoinitiator. In parts by mass, the component A includes an isocyanate group-terminated pre-polymer. 50-80 parts of polymer, 20-50 parts of reactive diluent, the B component includes 50-80 parts of acrylate prepolymer, 20-50 parts of reactive diluent, and ultraviolet photoinitiator accounts for 1-50 parts of the total resin mass 5%. The isocyanate group in the product after the resin 3D printing and molding provided by the present invention is further reacted under heating conditions to form a double network structure, which can effectively improve the mechanical properties of the product, and can meet different performance requirements by designing and adjusting the resin formula. , from elastic materials to tough materials can be easily prepared, and the mixed resin is very stable during the 3D printing process, and the printing window is long.
Description
Technical Field
The invention relates to the technical field of 3D printing materials, in particular to a secondary curing 3D printing resin.
Background
For different printing processes, 3D printing technologies can be generally classified into fused deposition modeling, selective laser sintering, and photocuring rapid prototyping. Among them, the photocuring rapid prototyping technology is a 3D printing technology which is the most widely and mature at present. In recent years, with the development of 3D printing technology, DLP/SLA is more and more widely applied, and has advantages that cannot be achieved by traditional processing technology in the processing of customized devices or complex components. But the defects of the required light-cured resin performance limit the further development and industrialization promotion of the technology. At present, the problem of insufficient mechanical properties of the glazing curing resin on the market generally exists.
Therefore, the method has important significance in improving the performance of the light-cured resin while considering the printing performance. CN111592621A discloses a two-component photocuring resin for 3D printing, which is prepared by mixing A, B components and carrying out photocuring, wherein isocyanate groups contained in the components respectively further react with active hydrogen, so that the mechanical property of the photocuring resin is improved. However, after the A, B components in the formula related by the invention patent are mixed, isocyanate contained in the system directly contacts with active hydrogen groups, the 3D printing window time of the resin is short, and the isocyanate and the active hydrogen react in the printing process to cause the whole curing condition, thereby causing printing failure and resin waste. CN111349197B discloses a dual-curing 3D printing photosensitive resin composition, which, like the above patent, also contains several key components of acrylate, isocyanate group-terminated prepolymer, chain extender (active hydrogen), so it also has the problem of short 3D printing window time.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a secondary curing resin, after curing and forming, isocyanate groups contained in a printed product further react under the heating condition, a double-network structure is constructed in the product, the performance of the product is improved, the product with different performance requirements can be obtained by designing and adjusting the formula of the resin, and the problem of short time of a 3D printing window of the resin is solved.
In order to achieve the purpose, the invention adopts the technical scheme that:
the secondary curing 3D printing resin comprises a component A, a component B and a photoinitiator, wherein the component A comprises 50-80 parts of isocyanate-terminated prepolymer and 20-50 parts of reactive diluent, the component B comprises 50-80 parts of acrylate prepolymer and 20-50 parts of reactive diluent, and the ultraviolet initiator accounts for 1-5% of the total mass of the resin.
Preferably, the mixing ratio of the component A to the component B is 1:1, and the photoinitiator is added after the component A and the component B are mixed.
Preferably, the isocyanate group-ended prepolymer is one or a mixture of two of an isocyanate group-ended polyurethane prepolymer and a polyurea prepolymer.
Preferably, the acrylate prepolymer comprises one or more of a polyurethane acrylate prepolymer, an epoxy acrylate prepolymer and a polyester acrylate prepolymer.
Preferably, the reactive diluent in the A component and the B component is one or more of isooctyl acrylate, isodecyl acrylate, ethoxy ethyl acrylate, tetrahydrofuran acrylate, polyethylene glycol diacrylate, tricyclodecane dimethanol diacrylate, trimethylolpropane triacrylate and ethoxylated trimethylolpropane triacrylate.
Preferably, the ultraviolet light initiator is one or more of Irgacure 819, (2,4, 6-trimethylbenzoyl) diphenylphosphine oxide and benzoin dimethyl ether.
Preferably, the resin comprises a pigment, the pigment accounts for 0.01-0.5% of the total mass of the resin, and the pigment is one or more of an organic pigment, an ultraviolet curing color paste and a metal complex dye.
Preferably, the preparation method of the isocyanate group-ended prepolymer in the component A is as follows:
1) mixing the dehydrated oligomer polyol or polyamine and polyisocyanate according to the mass ratio of 1 (1.2-2), and stirring and uniformly mixing at 30-70 ℃;
2) adding a catalyst accounting for 0-1% of the total mass of the mixture, and continuously reacting for 1-8 h.
Preferably, the catalyst is one or more of stannous octoate, dibutyltin dilaurate and dioctyltin dilaurate.
Preferably, the polyisocyanate is one or more of Hexamethylene Diisocyanate (HDI), isophorone diisocyanate (IPDI), Xylylene Diisocyanate (XDI), Toluene Diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hydrogenated XDI, hydrogenated MDI, HDI trimer, and HDI biuret.
Preferably, the oligomer polyol or the polyamine is one or more of alkyd polyester polyol, polycaprolactone polyol, polycarbonate polyol, polypropylene oxide polyol, polytetrahydrofuran polyol, polyether polyol and polyether amine.
Preferably, the prepolymer end groups are isocyanate groups.
And (3) after the 3D printing resin is cured by ultraviolet light, carrying out heat treatment in an oven at the temperature of 60-120 ℃ for 3-24h to obtain a 3D printing product.
When the secondary curing 3D printing resin provided by the invention is applied, a printed product contains isocyanate groups, and the isocyanate groups react under the heating condition to form high molecular weight polyurethane, so that a double-network structure is formed with polyacrylate formed in the printing process. The reactions that occur under heating are as follows:
the invention has the advantages that: according to the secondary curing 3D printing resin provided by the invention, the isocyanate group in the product is further reacted under the heating condition after photocuring molding to construct a double-network structure, so that the mechanical property of the product can be effectively improved, different performance requirements can be met by designing and adjusting the resin formula, and the resin can be prepared from an elastic material to a tough material; when the resin system is used, the resin system does not have active hydrogen groups, so that the problems that the resin is integrally cured and fails to be printed due to the reaction between isocyanate groups and the active hydrogen in the resin in the 3D printing process are effectively avoided.
Detailed Description
The present invention will be described in detail with reference to specific examples.
Example 1
The isocyanate group-ended prepolymer is prepared as follows:
1) mixing the dehydrated polytetrahydrofuran diol (Mn-1000) and hexamethylene diisocyanate in a mass ratio of 1:1.5, and stirring at 50 ℃;
2) after the mixture is uniformly mixed, slowly dropwise adding dibutyltin dilaurate accounting for 0.2 percent of the total mass of the mixture, and continuously stirring for reaction for 3 hours to obtain the isocyanate-terminated polyurethane prepolymer.
The component A comprises: taking 75 parts of the polyurethane prepolymer, adding 25 parts of isooctyl acrylate, and uniformly stirring for later use;
and B component: 80 parts of commercially available DSM U-80 resin is taken, 10 parts of isooctyl acrylate is added, and the mixture is uniformly stirred for standby.
The A, B components are mixed according to the mass ratio of 1:1, and 3 percent of (2,4, 6-trimethylbenzoyl) diphenyl phosphine oxide and 0.1 percent of Clariant UV color paste-black N in the total mass of the mixing system are added and stirred uniformly.
Example 2
The isocyanate group-ended prepolymer is prepared as follows:
1) mixing dehydrated polytetrahydrofuran diol (Mn-2000) and hexamethylene diisocyanate in the mass ratio of 1:1.7, and stirring at 50 ℃;
2) after the mixture is uniformly mixed, slowly dropwise adding dibutyltin dilaurate accounting for 0.2 percent of the total mass of the mixture, and continuously stirring for reaction for 5 hours to obtain the isocyanate-terminated polyurethane prepolymer.
The component A comprises: taking 70 parts of the polyurethane prepolymer, adding 30 parts of isodecyl acrylate, and uniformly stirring for later use;
and B component: 80 parts of commercially available DSM U-80 resin is taken, 10 parts of isodecyl acrylate is added, and the mixture is uniformly stirred for standby.
The A, B components are mixed according to the mass ratio of 1:1, 3 percent of (2,4, 6-trimethylbenzoyl) diphenyl phosphine oxide and 0.1 percent of Clariant UV color paste-black N in the total mass of a mixing system are added, and the mixture is stirred and mixed evenly.
Example 3
The polyurea prepolymer is prepared by the following method:
uniformly mixing the dehydrated polyether amine (Mn-2000) and diphenylmethane diisocyanate in a mass ratio of 1:2, adding no catalyst, and stirring at 60 ℃ for reaction for 4 hours to obtain the isocyanate-terminated polyurea prepolymer.
The component A comprises: taking 70 parts of the polyurea prepolymer, adding 25 parts of isobornyl acrylate, and uniformly stirring for later use;
and B component: taking 70 parts of commercially available DSM U-61 resin, adding 20 parts of isodecyl acrylate, and uniformly stirring for later use.
The A, B components are mixed according to the mass ratio of 1:1, added with Irgacure 819 accounting for 3 percent of the total mass of the mixing system and Sudan III accounting for 0.03 percent of the total mass of the mixing system, and stirred and mixed evenly.
Example 4
The isocyanate group-ended prepolymer is prepared as follows:
1) mixing the dehydrated polytetrahydrofuran diol (Mn-650) and diphenylmethane diisocyanate in a mass ratio of 1:1.4, and stirring at 40 ℃;
2) after the mixture is uniformly mixed, slowly dropwise adding dibutyltin dilaurate accounting for 0.1 percent of the total mass of the mixture, and continuously stirring for reacting for 6 hours to obtain the isocyanate-terminated polyurethane prepolymer.
The component A comprises: taking 75 parts of the polyurethane prepolymer, adding 15 parts of isobornyl acrylate, and uniformly stirring for later use;
and B component: 70 parts of commercially available sartomer CN983 NS resin is taken, 40 parts of isobornyl acrylate is added, and the mixture is stirred uniformly for standby.
The A, B components are mixed according to the mass ratio of 1:1, 2 percent of (2,4, 6-trimethylbenzoyl) diphenyl phosphine oxide and 0.05 percent of melanin in the total mass of a mixing system are added, and the mixture is stirred and mixed evenly.
After all the samples of the above examples were completely photo-cured, they were further heat treated at 110 ℃ for 12 hours, wherein the samples of examples 1 and 2 were tested according to ASTM D412, and the samples of examples 3 and 4 were tested for properties according to ASTM D638, and the test results are shown in the following table:
the above embodiments are merely preferred embodiments of the present invention, and the protection scope of the present invention is not limited to the above embodiments, and any technical solutions belonging to the idea of the present invention should fall within the protection scope of the present invention. Several modifications and variations are possible in light of the above teaching and are to be considered within the scope of the present invention.
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