CN111378074A - Three-arm acrylate polyurethane 3D printing photosensitive resin and preparation method thereof - Google Patents
Three-arm acrylate polyurethane 3D printing photosensitive resin and preparation method thereof Download PDFInfo
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- CN111378074A CN111378074A CN202010306351.0A CN202010306351A CN111378074A CN 111378074 A CN111378074 A CN 111378074A CN 202010306351 A CN202010306351 A CN 202010306351A CN 111378074 A CN111378074 A CN 111378074A
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- acrylate
- polyurethane
- photosensitive resin
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- 229920005989 resin Polymers 0.000 title claims abstract description 147
- 239000011347 resin Substances 0.000 title claims abstract description 147
- 239000004814 polyurethane Substances 0.000 title claims abstract description 88
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 85
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 title claims abstract description 73
- 238000010146 3D printing Methods 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000003085 diluting agent Substances 0.000 claims abstract description 45
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 14
- 230000003014 reinforcing effect Effects 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 52
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 39
- 239000000047 product Substances 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 17
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 15
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 13
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 13
- CQEYYJKEWSMYFG-UHFFFAOYSA-N butyl acrylate Chemical compound CCCCOC(=O)C=C CQEYYJKEWSMYFG-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 claims description 11
- 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
- 125000005442 diisocyanate group Chemical group 0.000 claims description 10
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 10
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 claims description 9
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 9
- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 9
- AZIQALWHRUQPHV-UHFFFAOYSA-N prop-2-eneperoxoic acid Chemical compound OOC(=O)C=C AZIQALWHRUQPHV-UHFFFAOYSA-N 0.000 claims description 9
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- -1 acrylic ester Chemical class 0.000 claims description 7
- 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 6
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 6
- PSGCQDPCAWOCSH-UHFFFAOYSA-N (4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl) prop-2-enoate Chemical compound C1CC2(C)C(OC(=O)C=C)CC1C2(C)C PSGCQDPCAWOCSH-UHFFFAOYSA-N 0.000 claims description 5
- MYWOJODOMFBVCB-UHFFFAOYSA-N 1,2,6-trimethylphenanthrene Chemical compound CC1=CC=C2C3=CC(C)=CC=C3C=CC2=C1C MYWOJODOMFBVCB-UHFFFAOYSA-N 0.000 claims description 5
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 5
- 239000012467 final product Substances 0.000 claims description 5
- 239000003999 initiator Substances 0.000 claims description 5
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 4
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 4
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 4
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-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 3
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 claims description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 3
- 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 3
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 claims description 3
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 claims description 3
- 229940119545 isobornyl methacrylate Drugs 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 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 claims description 3
- CCJAYIGMMRQRAO-UHFFFAOYSA-N 2-[4-[(2-hydroxyphenyl)methylideneamino]butyliminomethyl]phenol Chemical compound OC1=CC=CC=C1C=NCCCCN=CC1=CC=CC=C1O CCJAYIGMMRQRAO-UHFFFAOYSA-N 0.000 claims description 2
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 claims description 2
- GNSFRPWPOGYVLO-UHFFFAOYSA-N 3-hydroxypropyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCO GNSFRPWPOGYVLO-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- NDWUBGAGUCISDV-UHFFFAOYSA-N 4-hydroxybutyl prop-2-enoate Chemical compound OCCCCOC(=O)C=C NDWUBGAGUCISDV-UHFFFAOYSA-N 0.000 claims description 2
- QYFVEEMPFRRFNN-UHFFFAOYSA-N 5,5-dimethylhexan-1-ol Chemical compound CC(C)(C)CCCCO QYFVEEMPFRRFNN-UHFFFAOYSA-N 0.000 claims description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 2
- AYLRODJJLADBOB-QMMMGPOBSA-N methyl (2s)-2,6-diisocyanatohexanoate Chemical compound COC(=O)[C@@H](N=C=O)CCCCN=C=O AYLRODJJLADBOB-QMMMGPOBSA-N 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- 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 2
- 238000001723 curing Methods 0.000 abstract description 19
- 238000000016 photochemical curing Methods 0.000 abstract description 18
- 230000008569 process Effects 0.000 abstract description 5
- 238000012360 testing method Methods 0.000 description 26
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 24
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- 239000002904 solvent Substances 0.000 description 10
- 239000003755 preservative agent Substances 0.000 description 9
- 230000002335 preservative effect Effects 0.000 description 9
- 239000004593 Epoxy Substances 0.000 description 8
- 230000035484 reaction time Effects 0.000 description 7
- 238000001291 vacuum drying Methods 0.000 description 7
- 238000001035 drying Methods 0.000 description 6
- 230000001976 improved effect Effects 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- SYKRJDYATXQKGB-UHFFFAOYSA-N 1-[2-(hydroxymethyl)phenyl]propan-1-one Chemical group CCC(=O)C1=CC=CC=C1CO SYKRJDYATXQKGB-UHFFFAOYSA-N 0.000 description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- 238000009835 boiling Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 229920001971 elastomer Polymers 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- PIZHFBODNLEQBL-UHFFFAOYSA-N 2,2-diethoxy-1-phenylethanone Chemical compound CCOC(OCC)C(=O)C1=CC=CC=C1 PIZHFBODNLEQBL-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 229920001730 Moisture cure polyurethane Polymers 0.000 description 2
- BDAHDQGVJHDLHQ-UHFFFAOYSA-N [2-(1-hydroxycyclohexyl)phenyl]-phenylmethanone Chemical compound C=1C=CC=C(C(=O)C=2C=CC=CC=2)C=1C1(O)CCCCC1 BDAHDQGVJHDLHQ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 239000003822 epoxy resin Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000009863 impact test Methods 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- QCCDLTOVEPVEJK-UHFFFAOYSA-N phenylacetone Chemical compound CC(=O)CC1=CC=CC=C1 QCCDLTOVEPVEJK-UHFFFAOYSA-N 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920000647 polyepoxide Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 229920005749 polyurethane resin Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- YIKSHDNOAYSSPX-UHFFFAOYSA-N 1-propan-2-ylthioxanthen-9-one Chemical compound S1C2=CC=CC=C2C(=O)C2=C1C=CC=C2C(C)C YIKSHDNOAYSSPX-UHFFFAOYSA-N 0.000 description 1
- 238000012935 Averaging Methods 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 206010034960 Photophobia Diseases 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 208000013469 light sensitivity Diseases 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 238000004383 yellowing Methods 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
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y70/00—Materials specially adapted for additive manufacturing
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
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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)
- Macromonomer-Based Addition Polymer (AREA)
Abstract
The invention provides a three-arm acrylate polyurethane 3D printing photosensitive resin, which comprises the following raw material components: three-arm acrylate polyurethane, a reactive diluent, a crosslinking agent, a photoinitiator and a reinforcing resin. The three-arm acrylate polyurethane 3D printing photosensitive resin has the advantages of high photocuring rate, green and environment-friendly curing process, simplicity in preparation, high preparation efficiency and the like, and meanwhile, the three-arm acrylate polyurethane 3D printing photosensitive resin has the advantages of high tensile strength, good impact resistance, high yield strength, high hardness and the like.
Description
Technical Field
The invention relates to the technical field of photocuring materials and 3D printing, in particular to a three-arm acrylate polyurethane 3D printing photosensitive resin prepared by reacting an acrylate monomer with a polyurethane prepolymer.
Background
The photocuring 3D printing technique is a rapid prototyping technique that irradiates a photosensitive resin with ultraviolet rays of a certain wavelength to cause a polymerization reaction, thereby curing and bonding materials layer by layer to construct a three-dimensional object. The 3D printing process is implemented by using a 3D printer. The technical basic principle is that an object is printed and accumulated to be formed in a layered mode, specifically, a digital three-dimensional model of the needed object is input into a computer, the three-dimensional model is processed by computer software and divided into a plurality of thin layers, then ultraviolet light with certain wavelength irradiates photosensitive resin through a 3D printer, the cured and formed resin is stacked layer by layer, and finally a three-dimensional object is formed. The photocuring 3D printing method is simple in operation, short in object printing time, capable of printing various complex three-dimensional object models, high in precision, good in mechanical property of the objects and small in environmental pollution.
The photosensitive resin (UV resin) is composed of prepolymer or active monomer, photoinitiator, active diluent and the like, and the photosensitive resin receives certain ultraviolet light energy, so that the photosensitive substance in the system generates an active intermediate, and further the prepolymer or the active monomer is initiated to react and polymerize in a short time. The 3D printing photosensitive resin has the advantages of low cost, good fluidity, high curing speed, reusability and the like.
Disclosure of Invention
Based on the above technical background, the present inventors have made a keen search and, as a result, have found that: the three-arm acrylate polyurethane 3D printing photosensitive resin prepared from the three-arm acrylate polyurethane, the reactive diluent, the crosslinking agent, the photoinitiator and the reinforced resin has the advantages of high photocuring rate, green and environment-friendly curing process, simplicity in preparation, high preparation efficiency and the like, and meanwhile, has the advantages of high tensile strength, good impact resistance, high yield strength, high hardness and the like, so that the invention is completed.
The invention provides a three-arm acrylate polyurethane 3D printing photosensitive resin, which is prepared from the following raw material components: three-arm acrylate polyurethane, a reactive diluent, a cross-linking agent and a photoinitiator.
The second aspect of the present invention provides a method for preparing a three-arm acrylate polyurethane 3D printing photosensitive resin according to the first aspect of the present invention, comprising the steps of:
step 1, preparing polyacrylate polyurethane;
and (3) optionally adding the reinforced resin into the first mixture, stirring, and uniformly stirring to obtain a final product.
The three-arm acrylate polyurethane 3D printing photosensitive resin and the preparation method thereof provided by the invention have the following advantages:
(1) the invention provides an unreported three-arm acrylate polyurethane photosensitive resin;
(2) the three-arm acrylate polyurethane photosensitive resin disclosed by the invention has high photocuring rate and can be formed at one time;
(3) the sample band of the three-arm acrylate polyurethane photosensitive resin after 3D printing and curing has higher tensile property, yield property, impact resistance and hardness;
(4) the three-arm acrylate polyurethane photosensitive resin provided by the invention has good heat resistance;
(5) the three-arm acrylic polyurethane photosensitive resin can be used at room temperature.
Drawings
FIG. 1-a is a thermogravimetric plot of a 3D printed photosensitive resin photocured product prepared in example 4;
FIG. 1-b is a thermogravimetric plot of a 3D printed photosensitive resin photocured product prepared in example 5;
FIG. 1-c is a thermogravimetric plot of a 3D printed photosensitive resin photocured product prepared in example 6;
FIG. 1-d is a thermogravimetric plot of a cured product made from the reinforced resin;
FIG. 2 is a temperature rising DSC measurement graph of a 3D printed photo-cured product of the photosensitive resin prepared in examples 4 to 6;
FIG. 3 is a photo-DSC plot of the 3D printed photosensitive resins prepared in examples 4-6;
FIG. 4 is a graph of the actual conversion of photocuring of the 3D printing photosensitive resins of examples 4-6;
FIG. 5 is a stress-strain graph of a tensile specimen after photocuring of the photosensitive resin obtained in examples 4 to 6.
Detailed Description
The present invention will be described in detail below, and features and advantages of the present invention will become more apparent and apparent with reference to the following description.
The invention provides a three-arm acrylate polyurethane 3D printing photosensitive resin, which is prepared from the following raw material components: three-arm acrylate polyurethane, a reactive diluent, a cross-linking agent and a photoinitiator.
The reactive diluent mainly refers to low molecular weight epoxy compounds containing epoxy groups, and the low molecular weight epoxy compounds can participate in the curing reaction of epoxy resin and become a part of a cross-linked network structure of an epoxy resin cured product. It can not only reduce the viscosity of the system, but also participate in the curing reaction and keep the performance of the cured product.
In the invention, the reactive diluent is selected from one or more of methyl methacrylate, butyl acrylate, methyl acrylate, hydroxyethyl methacrylate, hydroxyethyl acrylate, isobornyl methacrylate, isobornyl acrylate, ethyl acrylate and ethyl methacrylate.
Preferably, the reactive diluent is selected from one or more of methyl methacrylate, butyl acrylate, isobornyl acrylate and ethyl acrylate;
more preferably, the reactive diluent is methyl methacrylate or butyl acrylate.
It has been found that the addition of a reactive diluent to the resin system, in particular methyl methacrylate or butyl acrylate, increases the reactivity and the adhesion of the resulting bars, and thus the tensile strength and hardness of the resulting bars.
Crosslinking agents, also known as curing agents, convert linear or slightly branched macromolecules into three-dimensional networks, thereby improving strength, heat resistance, abrasion resistance, and solvent resistance.
The cross-linking agent is selected from one or more of trimethylolpropane trimethacrylate, ethylene glycol dimethacrylate, trimethylolpropane triacrylate and pentaerythritol tetraacrylate.
Preferably, the cross-linking agent is selected from one or more of trimethylolpropane trimethacrylate and pentaerythritol tetraacrylate.
More preferably, the crosslinker is trimethylolpropane trimethacrylate. In the invention, trimethylolpropane trimethacrylate is more preferably used as the cross-linking agent because the price is low, the cost can be effectively reduced, the cross-linking density is moderate, the activity is high, and the mechanical property of the product obtained by photocuring the product is better, particularly the impact resistance is enhanced.
The photoinitiator is also called photosensitizer or light curing agent, and is a compound which can absorb energy with certain wavelength in an ultraviolet light region or a visible light region to generate free radicals, cations and the like so as to initiate the polymerization, crosslinking and curing of monomers.
The photoinitiator is selected from ultraviolet initiators.
Preferably, the photoinitiator is selected from one or more of 2-hydroxymethyl phenyl propane-1-ketone, diethoxy acetophenone, 1-hydroxycyclohexyl benzophenone, 2-hydroxy-2-methyl-1-p-ethyl ether phenyl acetone and isopropyl thioxanthone.
More preferably, the photoinitiator is 2-hydroxymethylphenylpropan-1-one.
The formula of the photosensitive resin is suitable for photocuring 3D printing, so a photoinitiator needs to be added into the resin formula, and the most preferable photoinitiator in the invention is 2-hydroxymethyl phenyl propane-1-ketone, and the photoinitiator has high initiation efficiency, good solubility, low odor, low pollution, yellowing resistance and good compatibility with an acrylate reactive diluent used in the invention. Therefore, when the curing agent is added into the photosensitive resin, the curing time of the resin can be effectively reduced, and the photosensitive resin is more environment-friendly and energy-saving.
The three-arm acrylate polyurethane, the reactive diluent, the crosslinking agent and the photoinitiator are added according to the following proportion, based on 100 parts by weight of the three-arm acrylate polyurethane,
0.1-60 parts by weight of reactive diluent;
0.1-50 parts by weight of a crosslinking agent;
2-20 parts of a photoinitiator.
Preferably, the acrylic polyurethane is a polyurethane based on 100 parts by weight of a three-arm acrylic polyurethane,
10-50 parts by weight of an active diluent;
20-40 parts by weight of a crosslinking agent;
2.5-15 parts by weight of a photoinitiator.
The three-arm acrylate polyurethane 3D printing photosensitive resin also comprises reinforced resin, and the reinforced resin is selected from one or more of Xitong SLA photosensitive resin and DPL photosensitive resin.
Preferably, the reinforced resin is selected from Xitong SLA photosensitive resin T001 series or T002 series.
More preferably, the reinforced resin is Xitong SLA photosensitive resin T002 liquid epoxy photosensitive resin (purchased from Zhuhai Xitong electronics, Inc.). The photosensitive resin has low viscosity, good intermiscibility with other additives, quick photocuring, low shrinkage and low price. The inventors found that adding a certain amount of a reinforcing resin to the photosensitive resin contributes to the improvement of mechanical properties of the photosensitive resin, such as tensile strength, impact strength, rockwell hardness, and the like. Tests show that the mechanical property of the resin is improved most quickly when the addition amount of the reinforced resin is 50-250 parts by weight based on 100 parts by weight of the three-arm acrylate polyurethane. Preferably, the reinforcing resin is added in an amount of 90 to 226 parts by weight.
The photocuring time of the three-arm acrylate polyurethane 3D printing photosensitive resin is 3 seconds.
The tensile strength of the resin sample strip after 3D printing is 10-45 Mpa, the highest yield strength can reach 48.8Mpa, and the impact strength is 25-92 KJ.m-2The hardness is 77-130 HRR.
The second aspect of the present invention provides a method for preparing a three-arm acrylate polyurethane 3D printing photosensitive resin according to the first aspect of the present invention, comprising the steps of:
step 1, preparing three-arm acrylate polyurethane;
and (3) optionally adding the reinforced resin into the first mixture, stirring, and uniformly stirring to obtain a final product.
This step is specifically described and illustrated below.
Step 1, preparing three-arm acrylate polyurethane.
The three-arm acrylate polyurethane is prepared by the following specific steps:
step 1-1, drying trimethylolpropane;
1-2, reacting trimethylolpropane, diisocyanate and a catalyst at constant temperature to generate a first product;
1-3, reacting p-methoxyphenol, hydroxyl acrylate and a first product to prepare three-arm acrylate polyurethane;
optionally, step 1-4, adding a diluent to the reaction system of step 1-3.
This step is specifically described and illustrated below.
Step 1-1, drying trimethylolpropane.
The drying is vacuum-pumping drying, preferably is carried out in a vacuum drying oven, and the drying time is 48-84 h, preferably 60-78 h, and more preferably 72 h. The drying treatment of trimethylolpropane is used to remove water carried by trimethylolpropane.
And 1-2, reacting trimethylolpropane, diisocyanate and a catalyst at constant temperature to generate a first product.
The diisocyanate is selected from one or more of isophorone diisocyanate, dicyclohexylmethane-4, 4' -diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate and methyl cyclohexyl diisocyanate;
preferably, the diisocyanate is selected from one or more of isophorone diisocyanate, dicyclohexylmethane-4, 4' -diisocyanate and hexamethylene diisocyanate
More preferably, the diisocyanate is isophorone diisocyanate or dicyclohexylmethane-4, 4' -diisocyanate.
The tensile strength, yield strength and hardness of the prepared polyurethane resin can be improved by adding isophorone diisocyanate. The addition of dicyclohexylmethane-4, 4' -diisocyanate can effectively improve the impact strength of the prepared polyurethane resin.
The weighed diisocyanate was added to a three-necked flask, and nitrogen gas was introduced into the three-necked flask, and the temperature was raised.
Dissolving trimethylolpropane, which comprises the following steps: trimethylolpropane is weighed and placed in a brown bottle, and a solvent is added to the brown bottle to dissolve trimethylolpropane.
The solvent is selected from one or more of N-methyl pyrrolidone, N-dimethylformamide, dimethyl sulfoxide, N-dimethylacetamide, acetone and butanone.
Preferably, the solvent is selected from N-methylpyrrolidone or N, N-dimethylformamide.
More preferably, the solvent is N-methylpyrrolidone. The N-methyl pyrrolidone has the advantages of low toxicity, high boiling point, strong dissolving power, nonflammability, biodegradability, low recyclable volatility, high thermal stability and chemical stability, volatilization with water vapor, light sensitivity and the like.
The addition amount of the trimethylolpropane and the diisocyanate is 1: (4-7), preferably 1: (4.5-6), more preferably 1: (4.9-5.3).
After heating to a certain temperature, completely dissolved trimethylolpropane is added into the three-neck flask. Preferably, the trimethylolpropane is dropped using a glass dropper, and more preferably, the trimethylolpropane is dropped into a three-necked flask in four times.
The temperature is 60-80 ℃, preferably 65-75 ℃, and more preferably 70 ℃.
The concentration of the trimethylolpropane in the three-neck flask approaches zero by dropwise adding in batches, so that the materials in the three-neck flask are always in a hungry state or a semi-hungry state. By adopting the feeding mode, a large amount of monomer accumulation can not be generated, so that the adverse phenomena of over-high reaction speed, difficulty in timely heat dissipation, false adhesion and the like can be effectively avoided; meanwhile, the method is more favorable for generating more uniform polymer.
In order to avoid the residual trimethylolpropane in the brown bottle, the trimethylolpropane in the brown bottle can be completely placed in a three-neck flask to participate in the reaction. The solvent was added again to the brown bottle, and the bottle was rinsed and poured into a three-necked flask.
In order to accelerate the reaction process, a catalyst is dropwise added into the three-neck flask, and the catalyst is one or more selected from dibutyltin dilaurate, stannous octoate, triethylene diamine, trimethyl hydroxyethyl propane diamine and N, N-dimethylethanolamine.
Preferably, the catalyst is selected from dibutyltin dilaurate or stannous octoate.
More preferably, the catalyst is dibutyltin dilaurate, dibutyltin dilaurate can play a good catalytic role under the condition of a small adding amount, can effectively promote the reaction of isocyanate groups and hydroxyl groups, and has good solubility in most solvents.
The isothermal reaction is preferably carried out in an oil bath. In consideration of the specific properties of the raw materials and the solvent used in the present invention, the reaction temperature is not suitable to be close to or exceed the boiling points of the raw materials and the solvent, and in order to increase the reaction rate and avoid the reaction time from being too long, the reaction temperature is 60 to 80 ℃, preferably 65 to 75 ℃, and more preferably 70 ℃.
In the present invention, if the reaction time is too short, the reaction is incomplete, the residual monomer content is large, and the product yield is lowered. If the reaction time is too long, the production time is prolonged, and the production efficiency is lowered. The reaction temperature is matched with the optimal reaction temperature, and the constant-temperature reaction time is 60-180 min, preferably 90-150 min, and more preferably 120 min.
And 1-3, reacting the p-methoxyphenol and the hydroxyl acrylate with the first product to obtain the three-arm acrylate polyurethane.
And adding hydroxyl acrylate into the first product when the reaction temperature is reduced to 45-60 ℃, preferably 50-55 ℃, and more preferably 50 ℃.
The addition amount of the p-methoxyphenol, the hydroxyl acrylate and the trimethylolpropane is (0.01-0.02): 1, preferably (0.013-0.018): (2.5-6.5): 1, more preferably 0.0153: (3-6.2) 1.
The p-methoxyphenol is added in the invention mainly to prevent the double bond in the acrylate from polymerizing in synthesizing the three-arm acrylate polyurethane and prolong the storage life of the three-arm acrylate polyurethane prepolymer.
The hydroxyl acrylic ester is selected from one or more of hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, hydroxypropyl acrylate, 4-hydroxybutyl acrylate, N-hydroxymethyl acrylamide and 2-hydroxypropyl acrylate.
Preferably, the hydroxy acrylate is selected from hydroxyethyl methacrylate, hydroxyethyl acrylate or hydroxypropyl acrylate.
More preferably, the hydroxy acrylate is selected from hydroxyethyl methacrylate or hydroxyethyl acrylate.
The reaction is preferably carried out in an oil bath. The reaction temperature is 45-60 ℃, preferably 50-55 ℃, and more preferably 50 ℃. The reaction temperature is not too high and cannot exceed the boiling point of the hydroxy acrylate, and if the reaction temperature is too low, the reaction is not facilitated, and the reaction rate is reduced and the reaction progress is delayed.
The reaction time is 90-150 min, preferably 120 min. The reaction time is matched with the reaction temperature, and if the reaction time is too short, the reaction is incomplete, and the yield is reduced.
Optionally, step 1-4, adding a diluent to the reaction system of step 1-3.
If the reaction system is viscous during the reaction and the reaction is not facilitated, a diluent can be added into the reaction system for dilution. The preparation of the product is facilitated, and tests show that the addition of a proper amount of diluent is also beneficial to the improvement of the mechanical property of the finally prepared three-arm acrylate polyurethane.
The diluent is selected from the group consisting of methyl methacrylate, butyl acrylate, methyl acrylate, hydroxyethyl methacrylate, hydroxyethyl acrylate, ethyl methacrylate, acetone, methyl ethyl ketone and N-methyl pyrrolidone
Preferably, the diluent is selected from one or more of butyl acrylate, methyl methacrylate and acetone.
More preferably, the diluent is methyl methacrylate or acetone. The viscosity of the system can be reduced after the diluent is added, and the reaction is more favorably carried out.
The diluent is used in an amount of 2 to 5 parts by weight, preferably 3 to 4 parts by weight, and more preferably 3.7 parts by weight, based on 1 part by weight of trimethylolpropane.
If the amount of the diluent is too small or not added, the viscosity of the system is too high, the reaction cannot be carried out, the amount of the diluent can be carried out by stirring the reaction energy, the amount of the diluent is too large, and trace water in the diluent can influence the reaction of isocyanate groups and hydroxyl groups, which is also not favorable for the reaction and can cause the mechanical property of the finally prepared resin to be reduced.
And 2, placing the weighed three-arm acrylate polyurethane, the reactive diluent, the crosslinking agent and the photoinitiator into a container, stirring, and uniformly stirring to obtain a first mixture.
The reactive diluent is selected from one or more of methyl methacrylate, butyl acrylate, methyl acrylate, hydroxyethyl methacrylate, hydroxyethyl acrylate, isobornyl methacrylate, isobornyl acrylate, butyl acrylate and ethyl methacrylate. The reactive diluent is preferably one or more selected from methyl methacrylate, butyl acrylate, isobornyl acrylate and ethyl acrylate. More preferably methyl methacrylate or butyl acrylate.
The cross-linking agent is selected from one or more of trimethylolpropane trimethacrylate, ethylene glycol dimethacrylate, trimethylolpropane triacrylate and pentaerythritol tetraacrylate; preferably one or more selected from trimethylolpropane trimethacrylate and pentaerythritol tetraacrylate; more preferably trimethylolpropane trimethacrylate.
The photoinitiator is selected from ultraviolet initiators; preferably one or more selected from 2-hydroxymethyl phenyl propane-1-ketone, diethoxy acetophenone, 1-hydroxycyclohexyl benzophenone, 2-hydroxy-2-methyl-1-p-ethyl ether phenyl acetone and isopropyl thiaketone; more preferably from 2-hydroxymethylphenylpropan-1-one.
The three-arm acrylate polyurethane, the reactive diluent, the crosslinking agent and the photoinitiator are added according to the following proportion, based on 100 parts by weight of the three-arm acrylate polyurethane,
0.1-60 parts by weight of reactive diluent;
0.1-50 parts by weight of a crosslinking agent;
2-20 parts of a photoinitiator.
Preferably, the acrylic polyurethane is a polyurethane based on 100 parts by weight of a three-arm acrylic polyurethane,
10-50 parts by weight of an active diluent;
20-40 parts by weight of a crosslinking agent;
2.5-15 parts by weight of a photoinitiator.
More preferably, the acrylic polyurethane is a polyurethane based on 100 parts by weight of a three-arm acrylic polyurethane,
30-40 parts of reactive diluent;
30-35 parts by weight of a crosslinking agent;
6-13 parts of a photoinitiator.
Tests show that the mechanical properties of the cured product, such as tensile strength, hardness, impact resistance and the like, can be effectively improved by adding a proper amount of reactive diluent into the 3D printing photosensitive resin system.
The dosage of the cross-linking agent can directly influence the cross-linking density and the mechanical properties of the prepared final product, if too little cross-linking agent is added, the cross-linking density is low, and the mechanical properties such as tensile strength, hardness and the like are reduced; if too much crosslinking agent is added, too high a crosslinking density will result, and mechanical properties such as tensile strength will also be reduced.
The curing rate can be influenced by the using amount of the initiator, and if the initiator is too much, the curing speed is too high, so that the temperature of the system is too high in a short time; if the amount is too small, curing will be too slow.
And (3) optionally adding the reinforced resin into the first mixture, stirring, and uniformly stirring to obtain a final product.
In the experimental process, the inventor finds that the mechanical property of a sample after the resin is cured is greatly improved after the reinforced resin is added into the first mixture in the step 1, and particularly, after a proper amount of reinforced resin is added, the properties of the cured resin, such as impact resistance, tensile strength, hardness and the like, are improved.
The reinforced resin is selected from one or more of Xitong SLA photosensitive resin and DPL photosensitive resin; preferably, the reinforced resin is selected from Xitong SLA photosensitive resin T001 series or T002 series; more preferably, the reinforced resin is Xitong SLA photosensitive resin T002 liquid epoxy photosensitive resin (purchased from Zhuhai Xitong electronics, Inc.). The photosensitive resin has low viscosity, good intermiscibility with other additives, quick photocuring, low shrinkage and low price.
In the invention, based on 100 parts by weight of the three-arm acrylate polyurethane, when the addition amount of the reinforced resin is 50-250 parts by weight, the mechanical property of the resin is improved most rapidly. Preferably, the addition amount of the reinforcing resin is 90 to 226 parts by weight. More preferably, the reinforcing resin is added in an amount of 95 to 100 parts by weight.
The invention has the following beneficial effects:
(1) the invention provides a three-arm acrylate polyurethane 3D printing photosensitive resin which is high in photocuring rate and capable of being formed at one time, wherein the curing time of the photosensitive resin is 3 seconds;
(2) the three-arm acrylate polyurethane 3D printing photosensitive resin has high tensile strength up to 42.20Mpa, yield strength up to 48.80Mpa, excellent impact resistance up to 92 KJ.m-2The highest hardness can reach 126.9 HRR;
(3) the three-arm acrylate polyurethane 3D printing photosensitive resin has good heat resistance, and the thermal decomposition temperature is 300-500 ℃.
Examples
The invention is further illustrated by the following specific examples, which are intended to be illustrative only and not limiting to the scope of the invention.
Example 1 preparation of three-arm acrylate polyurethane
Putting Trimethylolpropane (TMP) (more than 0.06 mol) into a container, covering a container opening with a clean preservative film, tightly binding the preservative film on the container opening by using a rubber band, binding holes on the preservative film, and putting the container into a vacuum drying oven for vacuum drying for 72 hours. 0.189mol of isophorone diisocyanate (IPDI) was charged into a 250mL three-necked flask, and nitrogen gas was introduced thereinto. 0.06mol of Trimethylolpropane (TMP) dried under vacuum was weighed into a brown bottle and dissolved by heating with 5mL of N-methylpyrrolidone (NMP). After isophorone diisocyanate (IPDI) was heated to 70 ℃, Trimethylolpropane (TMP) dissolved in N-methylpyrrolidone (NMP) was added to the three-necked flask in four portions with a glass dropper, and then 2mL of N-methylpyrrolidone (NMP) was added to the three-necked flask after the flask was rinsed in a brown bottle and poured into the three-necked flask. 3 drops of dibutyltin dilaurate (DBTDL) were added to the flask, and the mixture was reacted for two hours at a constant temperature in an oil bath. When the reaction temperature was lowered to 50 ℃, 0.123g of p-methoxyphenol and 0.378mol of hydroxyethyl methacrylate (HEMA) were added to the three-necked flask and reacted for 2 hours, and during this time, if the reaction system was viscous, 30g of Methyl Methacrylate (MMA) was added to dilute the reaction system. Obtaining a product for later use.
Example 2 preparation of three-arm acrylate polyurethane
Putting Trimethylolpropane (TMP) (more than 0.06 mol) into a container, covering a container opening with a clean preservative film, tightly binding the preservative film on the container opening by using a rubber band, binding holes on the preservative film, and putting the container into a vacuum drying oven for vacuum drying for 72 hours. 0.189mol of isophorone diisocyanate (IPDI) was placed in a 250mL three-necked flask and nitrogen was passed through. 0.06mol of Trimethylolpropane (TMP) dried under vacuum was weighed into a brown bottle and dissolved by heating with 5mL of N-methylpyrrolidone (NMP). After isophorone diisocyanate (IPDI) was heated to 70 ℃, Trimethylolpropane (TMP) dissolved in N-methylpyrrolidone (NMP) was added to the three-necked flask in four portions with a glass dropper, and then 2mL of N-methylpyrrolidone (NMP) was added to the three-necked flask after the flask was rinsed in a brown bottle and poured into the three-necked flask. 3 drops of dibutyltin dilaurate (DBTDL) were added to the flask, and the mixture was reacted for two hours at a constant temperature in an oil bath. When the reaction temperature was lowered to 50 ℃, 0.123g of p-methoxyphenol and 0.378mol of hydroxyethyl acrylate (HEA) were added to the three-necked flask, and the reaction was carried out for 2 hours while the reaction solution was viscous, and 30g of Methyl Methacrylate (MMA) was added to dilute the reaction solution. Obtaining a product for later use.
Example 3 preparation of three-arm acrylate polyurethane
Putting Trimethylolpropane (TMP) (more than 0.06 mol) into a container, covering a container opening with a clean preservative film, tightly binding the preservative film on the container opening by using a rubber band, binding holes on the preservative film, and putting the container into a vacuum drying oven for vacuum drying for 72 hours. 0.152mol of dicyclohexylmethane-4, 4' -diisocyanate (HMDI) was charged into a 250mL three-necked flask, and nitrogen gas was introduced. 0.06mol of Trimethylolpropane (TMP) dried under vacuum was weighed into a brown bottle and dissolved by heating with 5mL of N-methylpyrrolidone (NMP). After isophorone diisocyanate (IPDI) was heated to 70 ℃, Trimethylolpropane (TMP) dissolved in N-methylpyrrolidone (NMP) was added to the three-necked flask in four portions with a glass dropper, and then 2mL of N-methylpyrrolidone (NMP) was added to the three-necked flask after the flask was rinsed in a brown bottle and poured into the three-necked flask. 3 drops of dibutyltin dilaurate (DBTDL) were added to the flask, and the mixture was reacted for two hours at a constant temperature in an oil bath. When the reaction temperature is reduced to 50 ℃, 0.123g of p-methoxyphenol is added into a three-neck flask, 0.189mol of hydroxyethyl methacrylate (HEMA) is added, the reaction is carried out for 2 hours, NMP is used as a solvent, the system is viscous in the reaction process, and 20mL of acetone is added for dilution. Obtaining a product for later use.
Example 4 preparation of three-arm acrylate polyurethane 3D printing photosensitive resin
104.55g of the sample prepared in example 1, 30g of methyl methacrylate, 6.47g of 2-hydroxymethylphenylpropan-1-one and 100g of Xitong SLA photosensitive resin T002 liquid epoxy photosensitive resin were put in a container and stirred uniformly for later use.
Example 5 preparation of three-arm acrylate polyurethane 3D printing photosensitive resin
99.20g of sample prepared in example 2, 30g of methyl methacrylate, 10g of butyl acrylate, 33.69g of trimethylolpropane trimethacrylate, 12.66g of 2-hydroxymethylphenylpropane-1-one and 100g of Xitong SLA photosensitive resin T002 liquid epoxy photosensitive resin are placed in a container and stirred uniformly for later use.
Example 6 preparation of three-arm acrylate polyurethane 3D printing photosensitive resin
44.37g of the sample prepared in example 3, 1.21g of 2-hydroxymethylphenylpropan-1-one and 100g of Xitong SLA photosensitive resin T002 liquid epoxy photosensitive resin were put in a container and stirred uniformly for further use.
Examples of the experiments
Experimental example 13D printing of sample strips
Since the HMDI reaction product of example 6 contains acetone, the product was poured into a large beaker and dried in a vacuum oven for 48 hours prior to formulating the 3D printed photosensitive resin.
And pouring the prepared 3D printing photosensitive resin into a resin disc of the photocuring 3D printer, putting the resin disc back into the photocuring 3D printer, installing a sucker, turning on a power supply of the 3D printer, enabling the machine to enter a preparation state, starting a computer, turning on special software of the 3D printer, displaying the success of online, and respectively printing a tensile sample strip and an impact sample strip.
Before the performance test of the test sample strip is carried out, the surface of the test sample strip is cleaned by absolute ethyl alcohol, and after the test sample strip is naturally dried, the test sample strip is irradiated by a UVLED ultraviolet surface light source for 10 seconds, so that the test sample strip is cured more completely.
The actual conversion curve of the light-curing for the 3D printing photosensitive resins of examples 4 to 6 is shown in fig. 4, and it can be seen from fig. 4 that the light-curing conversion of the 3D printing photosensitive resin obtained in example 4 is higher than that of the 3D printing photosensitive resins obtained in examples 5 and 6, and the conversion of the photosensitive resin obtained in example 4 after 3 seconds reaches 80% or more.
Experimental example 2 thermogravimetric testing
5-15 mg of the photocured samples prepared in examples 4-6 were placed in a clean alumina crucible of a thermogravimetric analyzer SDT Q600, and the temperature of the thermogravimetric analyzer was raised from room temperature to 600 ℃ at a temperature rise rate of 10 ℃/min under a nitrogen atmosphere. The test results are shown in FIGS. 1-a, 1-b and 1-c, respectively. Wherein, fig. 1-d is a thermal weight loss curve chart of Xitong SLA photosensitive resin T002 liquid epoxy photosensitive resin.
As can be seen from FIGS. 1-a, 1-b, 1-c and 1-D, the decomposition temperatures of the resin samples were between 300 ℃ and 500 ℃ and the thermogravimetric curves of the resin samples were approximately the same, indicating that the thermal stabilities of the photocured 3D-printed specimens were approximately the same.
Experimental example 3DSC test
5-15 mg of the photo-cured samples prepared in examples 4-6 were put into a clean aluminum crucible of a differential scanning calorimeter DSC Q2000 for sample pressing, then put into the differential scanning calorimeter DSC Q2000, a blank reference was put into the crucible, and the temperature of the differential scanning calorimeter was increased from-70 ℃ to 200 ℃ at a heating rate of 10 ℃/min in a nitrogen atmosphere, and the results are shown in FIG. 2. FIG. 3 shows the photo-DSC measurement profile 2.
As can be seen from FIG. 2, the glass transition temperature of the reinforced resin after photocuring was 54 ℃ and the glass transition temperature of the three-arm acrylate polyurethane modified reinforced resin was between 30 ℃ and 40 ℃ according to DSC data analysis.
As can be seen from fig. 3, the heat generation of the photocuring reaction was maximized within about 3 seconds, and the curve was gradually gentle after 20 seconds of the reaction, and the reaction was almost complete. The heat release peaks are integrated to obtain the actual curing heat release of the HEMA/PU photosensitive resin, the HEA/PU photosensitive resin, the HMDI/PU photosensitive resin and the reinforced resin which are respectively 215.5J/g, 189.2J/g, 194.9J/g and 306.0J/g.
Experimental example 4 tensile Strength and yield Strength testing
And (3) testing tensile property: starting a computer, starting a microcomputer-controlled electronic universal testing machine, starting special software, selecting plastic tensile property measurement (GB/T1040-2006) from a data board, inputting relevant experimental data of a sample strip according to the gauge length, the width and the thickness of the tensile sample strip measured by a vernier caliper and the room temperature measured by a thermometer, clamping the tensile sample strip by using the microcomputer-controlled electronic universal testing machine, starting the universal testing machine, testing the tensile sample strip at the speed of 10 mm/min, and measuring the tensile strength and the yield strength. The results are shown in tables 1 and 2, respectively. The stress strain curve is shown in fig. 5.
TABLE 1 test results of tensile Strength of specimens
As can be seen from Table 1, the photosensitive resins obtained in examples 1 and 3 respectively had the highest tensile strength, and the average tensile strength was 42.20 MPa. The photosensitive resins obtained in examples 2 and 3 had tensile strengths inferior to those of the reinforcing resin.
TABLE 2 spline yield Strength test
As can be seen from table 2, the average yield strength of the 3D printing photosensitive resin prepared from the three-arm acrylate urethane prepared in example 1 was the highest, which was 48.80Mpa, whereas the average yield strength of the 3D printing photosensitive resin prepared in examples 2 and 3 was far less than that of the reinforcing resin.
Example 5 impact testing
The impact performance test comprises the following specific operation processes: and opening the simply supported beam impact testing machine, and checking whether the testing machine runs normally. The impact bar thickness and residual width were measured. And placing the impact sample strip on the sample support, enabling the notch of the test piece to face the hammer body of the impact hammer and be vertical to the swinging surface of the impact hammer, and hanging the impact hammer on the hanging and swinging mechanism. And loosening the impact hammer, breaking the sample strip, recording impact energy, and calculating impact strength according to the recorded energy. The results are shown in Table 3.
TABLE 3 test results of impact strength of sample bars
As can be seen from Table 3, the average yield strengths of the 3D printing photosensitive resins prepared from the three-arm acrylate polyurethane prepared in examples 1-3 are all high, and the average yield strength of the photosensitive resin prepared in example 3 is the highest and can reach 92 KJ.m-2. Are much higher than the yield strength of the reinforced resin.
Example 6 hardness test
The method comprises the following specific operation steps: the plastic Rockwell hardness tester is opened, the HRR measurement scale is selected, 60Kg total test force is selected, the 12.7mm pressure head is replaced, and the load retention time is 2 seconds. The specimen is placed on the specimen mount with the indenter aligned with the specimen and then loaded with the test force. And measuring the hardness of the seven points, and averaging to obtain the average hardness of the sample strips. The results are shown in Table 4.
TABLE 4 sample hardness test results
As can be seen from table 4, the hardness of the 3D printing photosensitive resin made of the three-arm acrylate polyurethane prepared in example 1 and example 2 can reach 120HRR or more, which is higher than that of the reinforced resin.
The invention has been described in detail with reference to specific embodiments and illustrative examples, but the description is not intended to be construed in a limiting sense. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, which fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
Claims (10)
1. The three-arm acrylate polyurethane 3D printing photosensitive resin is characterized by comprising the following raw material components: three-arm acrylate polyurethane, a reactive diluent, a cross-linking agent and a photoinitiator.
2. The three-arm acrylate polyurethane 3D printing photosensitive resin of claim 1,
the active diluent is selected from one or more of methyl methacrylate, butyl acrylate, methyl acrylate, hydroxyethyl methacrylate, hydroxyethyl acrylate, isobornyl methacrylate, isobornyl acrylate, ethyl acrylate and ethyl methacrylate;
the cross-linking agent is selected from one or more of trimethylolpropane trimethacrylate, ethylene glycol dimethacrylate, trimethylolpropane triacrylate and pentaerythritol tetraacrylate;
the photoinitiator is selected from ultraviolet initiators.
3. The three-arm acrylate polyurethane 3D printing photosensitive resin of claim 1,
the three-arm acrylate polyurethane 3D printing photosensitive resin is prepared by adding the following raw material components in parts by weight: based on 100 parts by weight of the three-arm acrylate polyurethane,
0.1-60 parts by weight of reactive diluent;
0.1-50 parts by weight of a crosslinking agent;
2-20 parts by weight of a photoinitiator;
preferably, the acrylic polyurethane is a polyurethane based on 100 parts by weight of a three-arm acrylic polyurethane,
10-50 parts by weight of an active diluent;
20-40 parts by weight of a crosslinking agent;
2.5-15 parts by weight of a photoinitiator.
4. The three-arm acrylate polyurethane 3D printing photosensitive resin of claim 1,
the raw material components of the three-arm acrylate polyurethane 3D printing photosensitive resin also comprise reinforced resin;
the reinforced resin is selected from one or more of Xitong SLA photosensitive resin and DPL photosensitive resin, and preferably, the reinforced resin is selected from the T001 series or the T002 series of Xitong SLA photosensitive resin.
5. The three-arm acrylate polyurethane 3D printing photosensitive resin of claim 4,
the reinforcing resin is added in an amount of 50 to 250 parts by weight, preferably 90 to 226 parts by weight, based on 100 parts by weight of the three-arm acrylate polyurethane.
6. The three-arm acrylate polyurethane 3D printing photosensitive resin of claim 1,
the curing time of the three-arm acrylate polyurethane 3D printing photosensitive resin is 3 seconds;
the tensile strength of the three-arm acrylic ester polyurethane 3D printed photosensitive resin spline after 3D printing is 10-45 Mpa, the yield strength is 2-48.8 Mpa, and the impact strength is 25-92 KJ.m-2The hardness is 77 to 130 HRR.
7. A preparation method of three-arm acrylate polyurethane 3D printing photosensitive resin is characterized by comprising the following steps:
step 1, preparing polyacrylate polyurethane;
step 2, placing the weighed three-arm acrylate polyurethane, the reactive diluent, the crosslinking agent and the photoinitiator into a container for stirring, and uniformly stirring to obtain a first mixture;
and (3) optionally adding the reinforced resin into the first mixture, stirring, and uniformly stirring to obtain a final product.
8. The method according to claim 7, wherein, in step 1,
the three-arm acrylate polyurethane is prepared by the following specific steps:
1-2, reacting trimethylolpropane, diisocyanate and a catalyst at constant temperature to generate a first product;
1-3, reacting p-methoxyphenol, hydroxyl acrylate and a first product to prepare three-arm acrylate polyurethane;
optionally, step 1-4, adding a diluent to the reaction system of step 1-3.
9. The method according to claim 8, wherein, in step 1,
the diisocyanate is selected from one or more of isophorone diisocyanate, dicyclohexylmethane-4, 4' -diisocyanate, toluene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate and methyl cyclohexyl diisocyanate;
the catalyst is selected from one or more of dibutyltin dilaurate, stannous octoate, triethylenediamine, trimethyl hydroxyethyl propane diamine and N, N-dimethylethanolamine;
the addition ratio of the trimethylolpropane to the diisocyanate is 1: (4-7);
the constant temperature reaction temperature is 60-80 ℃;
the hydroxyl acrylic ester is selected from one or more of hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, hydroxypropyl acrylate, 4-hydroxybutyl acrylate, N-hydroxymethyl acrylamide and 2-hydroxypropyl acrylate;
the addition ratio of the p-methoxyphenol, the hydroxyl acrylate and the trimethylolpropane is (0.01-0.02): (2-7): 1.
10. the production method according to claim 7,
the three-arm acrylate polyurethane, the reactive diluent, the crosslinking agent and the photoinitiator are added according to the following weight ratio, based on 100 parts by weight of the three-arm acrylate polyurethane,
0.1-60 parts by weight of reactive diluent;
0.1-50 parts by weight of a crosslinking agent;
2-20 parts by weight of a photoinitiator;
in an optional step 3, the reinforced resin is selected from one or more of Xitong SLA photosensitive resin and DPL photosensitive resin, preferably from the T001 series or the T002 series of the Xitong SLA photosensitive resin;
the reinforcing resin is added in an amount of 50 to 250 parts by weight based on 100 parts by weight of the three-arm acrylate polyurethane.
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