CN104292400A - Carbon-nanotube-reinforced photocuring three-dimensional printing material and preparation method thereof - Google Patents
Carbon-nanotube-reinforced photocuring three-dimensional printing material and preparation method thereof Download PDFInfo
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- CN104292400A CN104292400A CN201410485508.5A CN201410485508A CN104292400A CN 104292400 A CN104292400 A CN 104292400A CN 201410485508 A CN201410485508 A CN 201410485508A CN 104292400 A CN104292400 A CN 104292400A
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- 239000000463 material Substances 0.000 title claims abstract description 44
- 238000000016 photochemical curing Methods 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 238000010146 3D printing Methods 0.000 title abstract description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical class [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 49
- 238000007639 printing Methods 0.000 claims abstract description 27
- -1 isopropyl thioxanthene ketone Chemical class 0.000 claims abstract description 26
- 150000003512 tertiary amines Chemical class 0.000 claims abstract description 12
- 229920006150 hyperbranched polyester Polymers 0.000 claims abstract description 10
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical compound C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 claims abstract description 10
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- 229910052740 iodine Inorganic materials 0.000 claims abstract description 7
- 239000011630 iodine Substances 0.000 claims abstract description 7
- FIHBHSQYSYVZQE-UHFFFAOYSA-N 6-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCOC(=O)C=C FIHBHSQYSYVZQE-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000002041 carbon nanotube Substances 0.000 claims description 33
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 33
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 230000002708 enhancing effect Effects 0.000 claims description 9
- 239000013530 defoamer Substances 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 230000000977 initiatory effect Effects 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
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- 238000003756 stirring Methods 0.000 claims description 7
- 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 claims description 6
- 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 6
- 239000002253 acid Substances 0.000 claims description 6
- 238000013019 agitation Methods 0.000 claims description 6
- 230000033444 hydroxylation Effects 0.000 claims description 6
- 238000005805 hydroxylation reaction Methods 0.000 claims description 6
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 239000000376 reactant Substances 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
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- 238000001291 vacuum drying Methods 0.000 claims description 4
- JUVLPJNXBKOSFH-UHFFFAOYSA-N 2-(dimethylamino)-1-(4-morpholin-4-ylphenyl)butan-1-one Chemical compound C1=CC(C(=O)C(N(C)C)CC)=CC=C1N1CCOCC1 JUVLPJNXBKOSFH-UHFFFAOYSA-N 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
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- 239000012153 distilled water Substances 0.000 claims description 3
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- ZONYXWQDUYMKFB-UHFFFAOYSA-N flavanone Chemical compound O1C2=CC=CC=C2C(=O)CC1C1=CC=CC=C1 ZONYXWQDUYMKFB-UHFFFAOYSA-N 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
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- 239000012528 membrane Substances 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 239000001509 sodium citrate Substances 0.000 claims description 3
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 claims description 3
- 229940038773 trisodium citrate Drugs 0.000 claims description 3
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims 1
- 238000001723 curing Methods 0.000 abstract description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 2
- 239000003999 initiator Substances 0.000 abstract description 2
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 abstract 1
- 239000002518 antifoaming agent Substances 0.000 abstract 1
- 238000010961 commercial manufacture process Methods 0.000 abstract 1
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 abstract 1
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- 239000004593 Epoxy Substances 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
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- 238000013461 design Methods 0.000 description 1
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- 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
- 125000005843 halogen group Chemical group 0.000 description 1
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- 238000002844 melting Methods 0.000 description 1
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- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
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- Printing Plates And Materials Therefor (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Manufacture Or Reproduction Of Printing Formes (AREA)
Abstract
The invention discloses a carbon-nanotube-reinforced photocuring three-dimensional printing material and a preparation method thereof. The printing material is composed of epoxy acrylate, hyperbranched polyester acrylate, 1,6-hexanediol diacrylate, trimethylolpropane trimethyl acrylate, 2-phenyl-2,2-dimethylamino-1-(4-morpholinylphenyl)-1-butanone, isopropyl thioxanthene ketone, iodine onium diaryl hexafluorophosphate, a defoaming agent, a leveling agent, a wetting and dispersing agent, gamma-(methylacryloyloxy)propyltrimethoxy silane, a tertiary amine co-initiator and modified carbon nanotubes. The printing material has the advantages of high curing speed, obviously higher mechanical properties and high processibility, and can be widely used in the fields of commercial manufacture, product prototypes and the like.
Description
Technical field
The invention belongs to three Dimensional Printing of Rapid Prototyping and manufacture field, be specifically related to photocuring 3 D-printing material of a kind of carbon nanotube enhancing and preparation method thereof.
Background technology
3 D-printing (Three-dimensional Printing) is the Rapid Prototyping technique of rising in recent years, be called as " manufacturing technology with Industrial Revolution meaning ", obtain in fields such as household electrical appliances, automobile, aerospace, boats and ships, industrial design, medical treatment and applied comparatively widely, but although this technology is still in conceptual phase at home, but become the emphasis of Rapid Prototyping technique research at home and abroad, it has, and cost is low, the cycle is short, amendment is simple, the feature of dimensional stabilizing.
According to the difference of blasting materials, three-dimensional printing technology is mainly divided into three types: adhesives three-dimensional printing-forming, melting material three-dimensional printing-forming and photo-curing material three-dimensional printing-forming:
Photocuring three-dimensional printing-forming is based on droplet ejection technology, using photosensitive resin as printed material, according to part section shape, control printhead have in cross section the region of entity to print photocuring solid material and print photocuring propping material in the region needing to support, printing limit, photo-curing material limit solidification under the irradiation of ultraviolet lamp, so successively print successively solidification until workpiece completes, finally remove propping material and obtain molded part, because reaction-injection moulding and optical soliton interaction advantage separately organically combine by it, thus substantially increase forming efficiency, become development at present the most active, three-dimensional printing technology the most popular, photocuring printed material and photosensitive resin (UV ink for ink-jet print), liquid photosensitive resin is generally absorbed the light of sensitive wave length by light trigger after, be stimulated and change free radical or positively charged ion into, cause the unsaturated double-bond polymerization reaction take place of prepolymer and reactive thinner in resin subsequently, form the crosslinked structure of solidification, thus complete photosensitive resin from liquid state to solid-state transformation.Photosensitive resin for 3 D-printing is made up of prepolymer, ultraviolet initiator, reactive thinner and other auxiliary agent, wherein, prepolymer is the main component of photosensitive resin, the polyfunctional group macromolecular cpd of the group that can react further under illumination condition or be polymerized containing C=C, C=O, aromatic group etc. mostly, can rapid polymerization solidification under the effect of light trigger.Prepolymer decides the important mechanical property such as intensity, hardness, snappiness of the rear resin of liquid resinous viscosity, laser curing velocity and solidification.At present, the prepolymer for photocuring product mainly contains the free radical type prepolymers such as unsaturated polyester, epoxy acrylate, urethane acrylate and polyester acrylate, except this, also has the cationic prepolymer such as epoxy compounds and vinyl ether; But it is slower in use to there is curing speed in photocuring 3 D-printing material, the problem that cured strength is lower, and and printer on domestic market and printed material mostly are external imported product, expensive and technical know-how, therefore develop a kind of own, curing speed faster photocuring 3 D-printing material be this area problem demanding prompt solution always.
Summary of the invention
For the problems referred to above, a kind of novel, quick-setting photocuring 3 D-printing material and preparation method thereof is provided, and for multiple fields such as industry manufacture, product prototypes, as the quick manufacture of electric component, engine components, snap component, hinges, durable shell, mould etc., the present invention is achieved in that
The photocuring 3 D-printing material that carbon nanotube strengthens, its constitutive material and weight part are:
Epoxy acrylate 30 ~ 40 parts,
Hyperbranched polyester acrylic ester 15 ~ 20 parts,
1,6 hexanediol diacrylate 15 ~ 20 parts,
Trimethylolpropane trimethacrylate 16 ~ 26 parts,
2-phenyl 2,2-dimethylamino-1-(4-morpholinyl phenyl)-1-butanone 1.3 ~ 2.0 parts,
Isopropyl thioxanthone 1.0 ~ 2.0 parts,
Diaryl phosphofluoric acid salt compounded of iodine 1.0 ~ 2.0 parts,
Defoamer 0.1 ~ 1.0 part,
Flow agent 0.1 ~ 1.0 part,
Wetting dispersing agent 0.1 ~ 1.0 part,
γ-(methacryloxypropyl) propyl trimethoxy silicane 0.2 ~ 0.3 part,
Tertiary amine aided initiating 1.5 ~ 3.0 parts,
Modified carbon nano-tube 0.1 ~ 1.0 part.
Preferably, in the present invention, described modified carbon nano-tube obtains like this:
(1) 1g carbon nanotube is got, add 20ml hydrogen peroxide, ultrasonic disperse 2 ~ 4h under 40kHZ frequency, with deionized water rinsing reactant to neutral, be the filter membrane decompress filter of φ 0.22 μm again with aperture, and continuation is extremely neutral with deionized water wash, finally by vacuum-drying 8 ~ 10h at reactant 50 DEG C, namely obtains the carbon nanotube of purifying;
(2) be that mixing solutions made by the hydrogen peroxide of 5:1 and Trisodium Citrate by mass ratio, with sodium hydroxide adjustment pH for 7 ~ 8, carbon nanotube step 1 being obtained purifying adds in mixing solutions, supersound process 4 ~ 6h under room temperature, decompress filter again, be washed with distilled water to neutrality, last 80 DEG C of dry 12h, obtain hydroxylation carbon nanotube;
(3) getting 0.1g γ-(methacryloxypropyl) propyl trimethoxy silicane is dissolved in 50ml ethanol, regulate PH for 4 ~ 5 with oxalic acid, under 40kHZ frequency after ultrasonic hydrolysis 2 ~ 4h, add the hydroxylation carbon nanotube that 1g step 2 obtains, stir, at 70 ~ 85 DEG C of stirring reaction 6 ~ 8h, last with the centrifugal 8 ~ 10min of 4000pm, remove supernatant liquid, the precipitation of the black of acquisition used dehydrated alcohol with the centrifugal 8 ~ 10min of 4000rpm again, remove supernatant liquid, the precipitation obtaining black is placed in 60 DEG C of loft drier inner drying 12 ~ 15h, the desciccate obtained is modified carbon nano-tube.
Preferably, in the present invention, described tertiary amine aided initiating is tertiary amine acrylate.
Preferably, in the present invention, described defoamer is BYK307, and flow agent is Glide432, and wetting dispersing agent is Efka 4800, and silane coupling agent is γ-(methacryloxypropyl) propyl trimethoxy silicane.
Preferably, in the present invention, described epoxy acrylate molecular weight is 5000 ~ 6000, and the viscosity of hyperbranched polyester acrylic ester is 375mPaS.
Preferably, in the present invention, described modified carbon nano-tube external diameter is less than 8nm, and internal diameter is 2 ~ 5nm, and length is 0.5 ~ 2um.
A preparation method for the photocuring 3 D-printing material that carbon nanotube strengthens, comprises the following steps:
A () takes each raw material by the weight part of constitutive material, after epoxy acrylate and hyperbranched polyester acrylic ester mixing, stir 3h, obtain prepolymer with 400rpm;
B () is by 1,6-hexanediyl ester and trimethylolpropane trimethacrylate mixing, with the magnetic agitation 1 ~ 2h of 750rpm, add 2-phenyl 2 again, 2-dimethylamino-1-(4-morpholinyl phenyl)-1-butanone, isopropyl thioxanthone, diaryl phosphofluoric acid salt compounded of iodine and tertiary amine aided initiating, 750rpm magnetic agitation is to forming pale yellow transparent mixed solution;
C () adds defoamer, flow agent, wetting dispersing agent, the prepolymer of γ-(methacryloxypropyl) propyl trimethoxy silicane, modified carbon nano-tube and step a acquisition and the mixed solution of step b acquisition in ball mill, with rotating speed 200rpm, ratio of grinding media to material 5:1, every 10min alternate run, after running 9h altogether, namely obtain the photocuring 3 D-printing material that carbon nanotube strengthens.
The present invention take carbon nanotube as reinforcement, the photocuring 3 D-printing material of preparation, curing speed is fast, mechanical property is significantly improved, processibility is strong, material hardness and shock strength comparatively traditional product significantly improve, material has less volumetric shrinkage, cementability between different layers is strong, the product produced there will not be splitting and warpage, can be used for multiple fields such as industry manufacture, product prototype, as the quick manufacture of electric component, engine components, snap component, hinges, durable shell, mould etc.
Embodiment
Embodiment 1 prepares modified carbon nano-tube
(1) purifying gets 1g carbon nanotube, add in 20ml hydrogen peroxide, ultrasonic disperse 2 ~ 4h under 40kHZ frequency, with deionized water rinsing reactant to neutral, be the filter membrane decompress filter of φ 0.22 μm again with aperture, and continuation with deionized water wash to neutral, after by vacuum-drying 8 ~ 10h at reactant 50 DEG C, obtain the carbon nanotube of purifying;
(2) hydroxylation process solution that the carbon nanotube hydrogen peroxide of above-mentioned purifying and Trisodium Citrate (mass ratio 5:1) are formed the pH adjusted through sodium hydroxide be 7 ~ 8, supersound process 4 ~ 6h under room temperature, decompress filter, be washed with distilled water to neutrality, be placed in 80 DEG C of dry 12h of loft drier, obtain hydroxylation carbon nanotube;
(3) coupling agent treatment is got 0.1g γ-(methacryloxypropyl) propyl trimethoxy silicane and is dissolved in 50ml ethanol, regulate PH for 4 ~ 5 with oxalic acid, ultrasonic hydrolysis 2 ~ 4h under 40kHZ frequency, getting the carbon nanotube that 1g step 2 obtains joins in the alcoholic solution of γ-(methacryloxypropyl) propyl trimethoxy silicane, stir, and at 70 ~ 85 DEG C of low rate mixing reaction 6 ~ 8h, subsequently the mixed solution obtained is poured in separator tube, with 4000pm centrifugation 8 ~ 10min, remove supernatant liquid, obtain the precipitation of black; The precipitation of black used dehydrated alcohol with 4000rpm centrifugation 8 ~ 10min again, remove supernatant liquid, the precipitation of the black obtained is placed in vacuum drying oven, at 60 DEG C, dry 12 ~ 15h, namely obtains modified carbon nano-tube.
The modified carbon nano-tube external diameter < 8nm that the present embodiment obtains, internal diameter is 2 ~ 5nm, and length is 0.5 ~ 2um.
Embodiment 2-4 prepares the photocuring 3 D-printing material that carbon nanotube strengthens
1, proportioning raw materials is as shown in table 1
The each proportioning raw materials of table 1 embodiment 2-4
| Raw material | Embodiment 2(unit: kg) | Embodiment 3(unit: kg) | Embodiment 4(unit: kg) |
| Epoxy acrylate | 30 | 36 | 40 |
| 1,6 hexanediol diacrylate | 20 | 18 | 15 |
| Trimethylolpropane trimethacrylate | 26 | 18 | 16 |
| 2-phenyl 2,2-dimethylamino-1-(4-morpholinyl phenyl)-1-butanone | 1.6 | 2.0 | 1.3 |
| Isopropyl thioxanthone | 1.0 | 1.5 | 2.0 |
| Diaryl phosphofluoric acid salt compounded of iodine | 2.0 | 1.5 | 1.0 |
| Tertiary amine acrylate | 1.5 | 2.0 | 3.0 |
| Defoamer BYK307 | 1.0 | 0.6 | 0.1 |
| Flow agent Glide432 | 0.1 | 0.6 | 1.0 |
| Wetting dispersing agent Efka 4800 | 1.0 | 0.5 | 0.1 |
| γ-(methacryloxypropyl) propyl trimethoxy silicane | 0.2 | 0.3 | 0.2 |
| Hyperbranched polyester acrylic ester | 15 | 18 | 20 |
| The modified carbon nano-tube that embodiment 1 obtains | 0.6 | 1.0 | 0.3 |
In embodiment 2-4, the CN2302 that the hyperbranched polyester acrylic ester used provides for Sartomer of the U.S..
2, preparation method
(1) by proportioning raw materials, epoxy acrylate and hyperbranched polyester acrylic ester are pressed mixing, with the rotating speed mechanical stirring 3h of 400rpm, until form homogeneous, still prepolymer respectively;
(2) by di-functional reactive's thinner 1,6-hexanediyl ester and the mixing of polyfunctional group reactive thinner trimethylolpropane trimethacrylate, with 750rpm rotating speed magnetic agitation 1 ~ 2h, add radical photoinitiator 2-phenyl 2 again, 2-dimethylamino-1-(4-morpholinyl phenyl)-1-butanone, isopropyl thioxanthone and cationic photoinitiator diaryl phosphofluoric acid salt compounded of iodine and tertiary amine aided initiating tertiary amine acrylate, 750rpm magnetic agitation is to forming pale yellow transparent mixed solution;
(3) modified carbon nano-tube that the mixed solution obtained by prepolymer step 1 obtained, step 2, defoamer BYK307, flow agent Glide432, wetting dispersing agent Efka 4800, γ-(methacryloxypropyl) propyl trimethoxy silicane and embodiment 1 obtain adds in planetary ball mill and mixes, mixing process processing parameter is as follows: rotating speed 200rpm, ratio of grinding media to material 5:1, operation scheme is every 10min alternate run, operation total time is 9h, i.e. the photocuring 3 D-printing material of carbon nanotube enhancing.
3, implementation result
Uv cure machine high voltage mercury lamp power 1000W, main emission wavelength 365nm, metal halid lamp power 1000W, main emission wavelength 385nm, sweep velocity 18m/min, irradiation distance 8mm, solidification thickness 0.1mm, solidification value is room temperature, and desired properties test product prepared by the photocuring 3 D-printing material that the carbon nanotube obtained by embodiment 1 strengthens on photocuring 3 D-printing equipment.
Photocuring 3 D-printing material and the condensate performance thereof of the enhancing of embodiment 2-4 gained carbon nanotube are as shown in table 2:
Table 2 embodiment 2-4 gained printed material performance test results
| Project | Embodiment 2 | Implement 3 | Embodiment 4 |
| Viscosity (25 DEG C) | 213mPa·S | 221mPa·S | 234mPa·S |
| Density (25 DEG C) | 1.1203g/cm 3 | 1.1246g/cm 3 | 1.1251g/cm 3 |
| Threshold exposure amount | 9.8mJ/cm 2 | 9.6mJ/cm 2 | 9.7mJ/cm 2 |
| Transmission depth | 0.18mm | 0.17mm | 0.17mm |
| Curing speed | 19.41m/min | 19.36m/min | 19.34m/min |
| Degree of cure | 98.39% | 98.42% | 98.40% |
| Volumetric shrinkage | 3.48% | 3.29% | 3.25% |
| Surface tension | 31.2mN/m | 30.8mN/m | 31.3mN/m |
| Second-order transition temperature | 81.7℃ | 80.3℃ | 80.2℃ |
| Hardness | 75HD | 82HD | 89HD |
| Tensile strength | 39MPa | 40MPa | 39MPa |
| Young's modulus | 1211MPa | 1279MPa | 1267MPa |
| Elongation at break | 7.8% | 8.2% | 8.7% |
| Flexural strength | 48MPa | 52MPa | 53MPa |
| Shock strength | 21KJ/m 2 | 27KJ/m 2 | 30KJ/m 2 |
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (7)
1. a photocuring 3 D-printing material for carbon nanotube enhancing, its constitutive material and weight part are:
Epoxy acrylate 30 ~ 40 parts,
Hyperbranched polyester acrylic ester 15 ~ 20 parts,
1,6 hexanediol diacrylate 15 ~ 20 parts,
Trimethylolpropane trimethacrylate 16 ~ 26 parts,
2-phenyl 2,2-dimethylamino-1-(4-morpholinyl phenyl)-1-butanone 1.3 ~ 2.0 parts,
Isopropyl thioxanthone 1.0 ~ 2.0 parts,
Diaryl phosphofluoric acid salt compounded of iodine 1.0 ~ 2.0 parts,
Defoamer 0.1 ~ 1.0 part,
Flow agent 0.1 ~ 1.0 part,
Wetting dispersing agent 0.1 ~ 1.0 part,
γ-(methacryloxypropyl) propyl trimethoxy silicane 0.2 ~ 0.3 part,
Tertiary amine aided initiating 1.5 ~ 3.0 parts,
Modified carbon nano-tube 0.1 ~ 1.0 part.
2. the photocuring 3 D-printing material of carbon nanotube enhancing according to claim 1, is characterized in that, described modified carbon nano-tube obtains like this:
(1) get 1g carbon nanotube, add 20ml hydrogen peroxide, ultrasonic disperse 2 ~ 4h, with deionized water rinsing reactant to neutral, then be the filter membrane decompress filter of φ 0.22 μm with aperture, and continue washing to neutrality, finally by vacuum-drying 8 ~ 10h at reactant 50 DEG C, obtain the carbon nanotube of purifying;
(2) be that mixing solutions made by the hydrogen peroxide of 5:1 and Trisodium Citrate by mass ratio, with sodium hydroxide adjustment pH for 7 ~ 8, carbon nanotube step 1 being obtained purifying adds in mixing solutions, supersound process 4 ~ 6h, decompress filter again, be washed with distilled water to neutrality, last 80 DEG C of dry 12h, obtain hydroxylation carbon nanotube;
(3) getting 0.1g γ-(methacryloxypropyl) propyl trimethoxy silicane is dissolved in 50ml ethanol, regulate PH for 4 ~ 5 with oxalic acid, after ultrasonic hydrolysis 2 ~ 4h, add the hydroxylation carbon nanotube that 1g step 2 obtains, stir, at 70 ~ 85 DEG C of stirring reaction 6 ~ 8h, last with the centrifugal 8 ~ 10min of 4000pm, remove supernatant liquid, the precipitation of acquisition used dehydrated alcohol with the centrifugal 8 ~ 10min of 4000rpm again, be deposited in 60 DEG C of drying 12 ~ 15h by what obtain black, desciccate is modified carbon nano-tube.
3. the photocuring 3 D-printing material of carbon nanotube enhancing according to claim 2, it is characterized in that, described tertiary amine aided initiating is tertiary amine acrylate.
4. the photocuring 3 D-printing material of carbon nanotube enhancing according to claim 2, it is characterized in that, described defoamer is BYK307, and flow agent is Glide432, wetting dispersing agent is Efka 4800, and silane coupling agent is γ-(methacryloxypropyl) propyl trimethoxy silicane.
5. the photocuring 3 D-printing material of carbon nanotube enhancing according to claim 2, it is characterized in that, described epoxy acrylate molecular weight is 5000 ~ 6000, and the viscosity of hyperbranched polyester acrylic ester is 375mPaS.
6. the photocuring 3 D-printing material of carbon nanotube enhancing according to claim 2, it is characterized in that, described modified carbon nano-tube external diameter is less than 8nm, and internal diameter is 2 ~ 5nm, and length is 0.5 ~ 2um.
7. the preparation method of photocuring 3 D-printing material that carbon nanotube strengthens as described in one of claim 1-6, comprises the following steps:
A () takes each raw material by the weight part of constitutive material, after epoxy acrylate and hyperbranched polyester acrylic ester mixing, stir 3h, obtain prepolymer with 400rpm;
B () is by 1,6-hexanediyl ester and trimethylolpropane trimethacrylate mixing, magnetic agitation 1 ~ 2h, add 2-phenyl 2 again, 2-dimethylamino-1-(4-morpholinyl phenyl)-1-butanone, isopropyl thioxanthone, diaryl phosphofluoric acid salt compounded of iodine and tertiary amine aided initiating, magnetic agitation is to forming pale yellow transparent mixed solution;
C () adds defoamer, flow agent, wetting dispersing agent, the prepolymer of γ-(methacryloxypropyl) propyl trimethoxy silicane, modified carbon nano-tube and step a acquisition and the mixed solution of step b acquisition in ball mill, with rotating speed 200rpm, ratio of grinding media to material 5:1, every 10min alternate run, after running 9h altogether, namely obtain the photocuring 3 D-printing material that carbon nanotube strengthens.
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