CN104293116B - A kind of photocuring 3 D-printing material and preparation method and application - Google Patents
A kind of photocuring 3 D-printing material and preparation method and application Download PDFInfo
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- CN104293116B CN104293116B CN201410487896.0A CN201410487896A CN104293116B CN 104293116 B CN104293116 B CN 104293116B CN 201410487896 A CN201410487896 A CN 201410487896A CN 104293116 B CN104293116 B CN 104293116B
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- 239000000463 material Substances 0.000 title claims abstract description 38
- 238000007639 printing Methods 0.000 title claims abstract description 32
- 238000000016 photochemical curing Methods 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 11
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 10
- -1 2, 4, 6 trimethylbenzoyl ethoxyl Chemical group 0.000 claims abstract description 8
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- 239000003112 inhibitor Substances 0.000 claims abstract description 7
- 239000003381 stabilizer Substances 0.000 claims abstract description 7
- 239000004844 aliphatic epoxy resin Substances 0.000 claims abstract description 6
- 239000002270 dispersing agent Substances 0.000 claims abstract description 6
- KCTAWXVAICEBSD-UHFFFAOYSA-N prop-2-enoyloxy prop-2-eneperoxoate Chemical class C=CC(=O)OOOC(=O)C=C KCTAWXVAICEBSD-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 6
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229920001427 mPEG Polymers 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 238000009736 wetting Methods 0.000 claims abstract description 5
- 125000002592 cumenyl group Chemical group C1(=C(C=CC=C1)*)C(C)C 0.000 claims abstract description 4
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 239000005543 nano-size silicon particle Substances 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- DMEGYFMYUHOHGS-UHFFFAOYSA-N cycloheptane Chemical compound C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 6
- 239000012046 mixed solvent Substances 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- ZGMNAIODRDOMEK-UHFFFAOYSA-N 1,1,1-trimethoxypropane Chemical compound CCC(OC)(OC)OC ZGMNAIODRDOMEK-UHFFFAOYSA-N 0.000 claims description 3
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 230000006837 decompression Effects 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 3
- 125000005456 glyceride group Chemical group 0.000 claims description 3
- 239000012528 membrane Substances 0.000 claims description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 3
- 229910052753 mercury Inorganic materials 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 229910000077 silane Inorganic materials 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 229940059574 pentaerithrityl Drugs 0.000 claims description 2
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical group OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims description 2
- DFBDMKHCEZTHOH-UHFFFAOYSA-N 1,4,5-oxadithiepane Chemical compound C1CSSCCO1 DFBDMKHCEZTHOH-UHFFFAOYSA-N 0.000 claims 1
- 239000000843 powder Substances 0.000 claims 1
- 239000000052 vinegar Substances 0.000 claims 1
- 235000021419 vinegar Nutrition 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000013461 design Methods 0.000 abstract description 4
- KUSGATRNQCYALG-UHFFFAOYSA-N dithiepane Chemical compound C1CCSSCC1 KUSGATRNQCYALG-UHFFFAOYSA-N 0.000 abstract 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 abstract 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000007711 solidification Methods 0.000 description 5
- 230000008023 solidification Effects 0.000 description 5
- 229960004756 ethanol Drugs 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000010146 3D printing Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000001723 curing Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 208000035126 Facies Diseases 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000005422 blasting Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010107 reaction injection moulding Methods 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
- C09D163/10—Epoxy resins modified by unsaturated compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
- Materials For Photolithography (AREA)
- Polymerisation Methods In General (AREA)
- Epoxy Resins (AREA)
Abstract
Open a kind of photocuring 3 D-printing material of the present invention and preparation method and application, including following raw material: polyalcohol modified epoxy acrylate 20 ~ 32 parts, aliphatic epoxy resin 20 ~ 30 parts, methoxy poly (ethylene glycol) (350) monomethacrylates 15 ~ 25 parts, 5 oxa-s 1, 2 dithia cycloheptane 15 ~ 25 parts, 2, 4, 6 trimethylbenzoyl ethoxyl phenenyl phosphine oxides 1.0 ~ 2.0 parts, cumenyl ferrocene hexafluorophosphate 1.0 ~ 2.0 parts, triethanolamine 0.2 ~ 1.0 part, modified manometer silicon dioxide 0.5 ~ 2.0 part, polymerization inhibitor 0.2 ~ 1.0 part, levelling agent 0.5 ~ 1.0 part, wetting dispersing agent 0.2 ~ 1.0 part, stabilizer 0.4 ~ 1.0 part；Photocuring 3 D-printing material cohesion of the present invention height, processability and good film-forming property, the prepared intensity of profiled member, toughness and forming accuracy are greatly improved, and can be widely used in multiple fields high intensity, the manufactures of high-precision part such as industry manufacture, Design of Dies.
Description
Technical field
The invention belongs to polymeric material field, particularly a kind of photocuring 3 D-printing material and preparation method thereof with should
With.
Background technology
The sophisticated technology in multiple fields such as information technology, precision optical machinery, Laser Processing and new material is relied on to grow up
3 D-printing, be the main way of realization of layered manufacturing technology, this technology is truly realized by conceptual design to modelling
Transformation, huge on manufacturing industry impact, be referred to as one of the new technique promoting " industrial revolution for the third time ", in household electrical appliances, automobile, boat
The fields such as empty space flight, boats and ships, industrial design, medical treatment have obtained relatively broad application, according to the difference of blasting materials, three-dimensional
Printing technique is broadly divided into three types: adhesives 3 D-printing, melted material 3 D-printing and photo-curing material three-dimensional are beaten
Print.
Respective to reaction-injection moulding and optical soliton interaction advantage is organically combined by photocuring 3 D-printing, thus significantly
Improve forming efficiency, become the three-dimensional printing technology that at present development is the most active, the most popular, photosensitive for 3 D-printing
Resin is made up of prepolymer, ultraviolet initiator, reactive diluent and other auxiliary agent, and wherein, prepolymer is the master of photosensitive resin
Want composition, be that the group that can react further containing C=C, C=O, aromatic group etc. under illumination condition or be polymerized is many mostly
Functional group's macromolecular compound, can rapid polymerization solidification under the effect of light trigger；But photocuring 3 D-printing material exists
Forming accuracy is generally there is relatively low, the problem that cured strength is poor, and and printer on domestic market during use
And printed material mostly is external imported product, expensive and technical know-how, therefore develop a kind of own, solidification precision is high,
The photocuring 3 D-printing material that mechanical property is good, cheap is always this area problem demanding prompt solution.
Summary of the invention
For the problems referred to above, it is provided that a kind of adhesive force is high, moulding property is good photocuring 3 D-printing material and preparation side thereof
Method, to improve the intensity of profiled member, toughness and forming accuracy, the present invention is achieved in that
A kind of photocuring 3 D-printing material, in parts by weight, including following raw material:
Wherein, described modified manometer silicon dioxide is obtained by:
A) in terms of mass parts, respectively the nano silicon of 1 part and the silane coupler KH570 of 0.2 part are dissolved in containing 0.1
In the ethanol solution of part acetic acid, respectively with ultrasonic disperse 1-2h, then two kinds of solution are added autoclaves, 4MPa,
Under the conditions of 70-85 DEG C, with the rotating speed mixing 8-10h of 70-80rpm, after liquid to be mixed cooling, with the filter membrane that aperture is φ 0.22 μm
Decompression sucking filtration, with ethanol by the washing of sucking filtration product to neutral；
B) in terms of mass parts, by trimethoxypropane gave triglycidyl ether and trimethacrylate acid glyceride 1-in mass ratio
2:1 is configured to mixed solvent, and the sucking filtration product and the 1 part of mixed solvent that step A are obtained add in high-speed mixer, at 90-120
At a temperature of DEG C, after the rotating speed mixing 6-10min of 1020rpm, then by mixture with the rotating speed centrifugation 5-of 4000rpm
10min, takes washing of precipitate 5 times, and washing methods is to add acetone in precipitation, then is centrifuged 5-10min with 4000rpm；Will washing
After be deposited in 800 DEG C of vacuum environments be dried 8-12h, i.e. obtain modified manometer silicon dioxide.
Preferably, in the present invention, described polymerization inhibitor is FIRSTCURE ST-1, and stabilizer is tetramethylolmethane.
Preferably, in the present invention, described levelling agent is Glide 435, and wetting dispersing agent is Texaphor P61.
The preparation method of a kind of photocuring 3 D-printing material of the present invention, comprises the following steps: in proportion by 2,4,
6-trimethylbenzoyl-ethyoxyl-phenyl phosphine oxide, cumenyl ferrocene hexafluorophosphate, methoxy poly (ethylene glycol)
(350) monomethacrylates and 5-oxa--1, after the mixing of 2-dithia cycloheptane, with the rotating speed magnetic agitation of 600-700rpm
1-2h, adds modified manometer silicon dioxide, is placed in ball mill mixing, and hybrid parameter is: rotating speed 600-800rpm, ratio of grinding media to material
20:1, mixes 6-8h；Polyalcohol modified epoxy acrylate, aliphatic epoxy resin, polymerization inhibitor, levelling is added in ball mill
Agent, stabilizer, triethanolamine and wetting dispersing agent, in ball mill with ratio of grinding media to material as 8:1, rotating speed 200-300rpm stir 12h,
I.e. obtain described photocuring 3 D-printing material.
The application in 3 D-printing of a kind of photocuring 3 D-printing material of the present invention.
The application in 3 D-printing of a kind of photocuring 3 D-printing material of the present invention, concrete forming method is such as
Under: uv cure machine high voltage mercury lamp power 2000W, main transmitting wavelength 365nm, scanning speed 10～18m/min, irradiation distance
6～10mm, solidify thickness 0.1mm, solidification temperature is room temperature, successively piles up molding with glass plate or cured resin for substrate.
The beneficial effects of the present invention is:
(1) nano silicon of tridimensional network has high temperature resistant, high tenacity, the characteristic such as wear-resisting, few interpolation
Amount can improve the mechanical property of composite, and the present invention is by using chemical reaction to be grafted and surface thing nano silicon
Reason two kinds of methods of coating combine and are modified processing, and improve nano silicon degree of scatter in the polymer, strengthen two
Interface cohesion between person.
(2) present invention is by the feature of high for Organic substance adhesive force, processability and good film-forming property and inorganic matter high rigidity, high-strength
Degree, the Dominant Facies that heat-resist and chemical resistance is good combine, and when utilizing cationic performed polymer ring-opening polymerisation, volumetric expansion reaches
To reducing the purpose shunk, prepared photocuring 3 D-printing material can make the intensity of profiled member, toughness and forming accuracy
It is greatly improved, is more widely used in industry multiple fields high intensity such as manufacture, Design of Dies, high-precision part
Manufacture, and low cost, it is easy to popularization and application.
Detailed description of the invention
Embodiment 1 prepares modified manometer silicon dioxide
A) chemical reaction graft modification, in terms of mass parts, first dries 20h by nano silicon at 80 DEG C, more respectively by 1
Nano silicon and the silane coupler KH570 of 0.2 part after the drying of part are dissolved in 10 parts of ethanol solutions containing acetic acid
In (mass ratio of acetic acid and dehydrated alcohol is 1:20), respectively with ultrasonic disperse 1-2h, then two kinds of solution are added reaction under high pressures
Still mixes, and under the conditions of 4MPa, 70-85 DEG C, with the rotating speed mixing 8-10h of 70-80rpm, after liquid to be mixed cooling, with aperture is
The filter membrane decompression sucking filtration of φ 0.22 μm, washs sucking filtration product continuously to neutral with ethanol；
B) surface physics coating modification, in terms of mass parts, by trimethoxypropane gave triglycidyl ether and trimethacrylate
Acid glyceride 1-2:1 in mass ratio is configured to mixed solvent, and the sucking filtration product and the 1 part of mixed solvent that step A are obtained add height
Speed mixer in, at a temperature of 90-120 DEG C, after the rotating speed mixing 6-10min of 1020rpm, then by mixture with
The rotating speed centrifugation 5-10min of 4000rpm, removes supernatant liquid, takes washing of precipitate 5 times, and washing methods is for adding in precipitation
Enter acetone, then be centrifuged 5-10min with 4000rpm；Being deposited in 800 DEG C of vacuum environments after washing is dried 8-12h, i.e. obtains
The modified manometer silicon dioxide that introducing double bond, lipophile further enhance.
Embodiment 2-4 prepares photocuring 3 D-printing material
1, in terms of mass parts, shown in table 1, raw material is prepared respectively
The each proportioning raw materials of table 1 embodiment 2-4
In embodiment 2-4, the polyalcohol modified epoxy acrylate used is that Shaanxi Xi Laiwu Industrial Co., Ltd. is raw
The EA205 produced, when 50 DEG C, viscosity is 800-1300mPa S；Methoxy poly (ethylene glycol) (350) monomethacrylates is the U.S.
The CD550 that Sartomer provides；The UVACURE 1500 that aliphatic epoxy resin provides for Qing Te industrial group of the U.S..
2, preparation method:
In ratio described in table 1 by 2,4,6-trimethylbenzoyl-ethyoxyl-phenyl phosphine oxide, cumenyl ferrocene
Hexafluorophosphate, methoxy poly (ethylene glycol) (350) monomethacrylates and 5-oxa--1, after the mixing of 2-dithia cycloheptane,
With rotating speed magnetic agitation 1-2h of 600-700rpm, form light yellow transparent solution, then be added thereto to modified nano-silica
Silicon, is placed in ball mill mixing, and hybrid parameter is: rotating speed 600-800rpm, ratio of grinding media to material 20:1, mixes 6-8h；In ball mill
Add polyalcohol modified epoxy acrylate, aliphatic epoxy resin, polymerization inhibitor, levelling agent, stabilizer, triethanolamine and moistening
Dispersant, in ball mill with ratio of grinding media to material as 8:1, rotating speed 200-300rpm stir 12h, i.e. obtain photocuring 3 D-printing material
Material.
3, respectively by embodiment 2-4 obtain photocuring 3 D-printing materials application in 3 D-printing molding and to solidification after
Material carries out performance detection, and testing result is as shown in table 2,
Molding parameter is: uv cure machine high voltage mercury lamp power 2000W, main transmitting wavelength 365nm, scanning speed 10～
18m/min, irradiation distance 6～10mm, solidify thickness 0.1mm, solidification temperature is room temperature, with glass plate and cured resin as base
Molding successively piled up by plate.
Table 2 embodiment 2-4 material property testing result
| Detection project | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Viscosity (25 DEG C) | 323mPa·S | 314mPa·S | 319mPa·S |
| Density (25 DEG C) | 1.1230g/cm3 | 1.1207g/cm3 | 1.1203g/cm3 |
| Threshold exposure amount | 9.7mJ/cm2 | 9.5mJ/cm2 | 9.3mJ/cm2 |
| Transmission depth | 0.19mm | 0.17mm | 0.21mm |
| Curing rate | 16.61m/min | 15.72m/min | 15.09m/min |
| Curing degree | 98.09% | 98.18% | 98.31% |
| Cubical contraction | 1.48% | 2.02% | 2.75% |
| Linear shrinkage ratio | 0.04% | 0.06% | 0.08% |
| Surface tension | 31.5mN/m | 31.4mN/m | 30.2mN/m |
| Glass transition temperature | 82.2℃ | 81.7℃ | 80.4℃ |
| Hardness | 89HD | 75HD | 67HD |
| Hot strength | 49MPa | 42MPa | 38MPa |
| Elastic modelling quantity | 1511MPa | 1400MPa | 1304MPa |
| Elongation at break | 9.8% | 8.7% | 8.0% |
| Bending strength | 68MPa | 64MPa | 56MPa |
| Impact strength | 31KJ/m2 | 30KJ/m2 | 22KJ/m2 |
Above example is only in order to illustrate technical scheme and unrestricted, although with reference to preferred embodiment to this
Bright it is described in detail, it will be understood by those within the art that, technical scheme can be modified,
It all should be contained in the middle of scope of the presently claimed invention.
Claims (6)
1. a photocuring 3 D-printing material, in parts by weight, including following raw material:
Polyalcohol modified epoxy acrylate 20 ~ 32 parts；
Aliphatic epoxy resin 20 ~ 30 parts；
Methoxy poly (ethylene glycol) 350 monomethacrylates 15 ~ 25 parts；
5-oxa--1,2-dithia cycloheptane 15 ~ 25 parts；
2,4,6-trimethylbenzoyl-ethyoxyl-phenyl phosphine oxide 1.0 ~ 2.0 parts；
Cumenyl ferrocene hexafluorophosphate 1.0 ~ 2.0 parts；
Triethanolamine 0.2 ~ 1.0 part；
Modified manometer silicon dioxide 0.5 ~ 2.0 part；
Polymerization inhibitor 0.2 ~ 1.0 part；
Levelling agent 0.5 ~ 1.0 part；
Wetting dispersing agent 0.2 ~ 1.0 part；
Stabilizer 0.4 ~ 1.0 part；
Wherein, described modified manometer silicon dioxide is obtained by:
A) in terms of mass parts, respectively the nano silicon of 1 part and the silane coupler KH570 of 0.2 part are dissolved in containing 0.1 portion of vinegar
In the ethanol solution of acid, respectively with ultrasonic disperse 1-2h, then two kinds of solution are added autoclave, at 4MPa, 70-85
Under the conditions of DEG C, with the rotating speed mixing 8-10h of 70-80rpm, after liquid to be mixed cooling, with the filter membrane decompression that aperture is φ 0.22 μm
Sucking filtration, with ethanol by the washing of sucking filtration product to neutral；
B) in terms of mass parts, by trimethoxypropane gave triglycidyl ether and trimethacrylate acid glyceride 1-2:1 in mass ratio
Being configured to mixed solvent, the sucking filtration product and the 1 part of mixed solvent that step A are obtained add in high-speed mixer, at 90-120 DEG C
At a temperature of, after the rotating speed mixing 6-10min of 1020 rpm, then by mixture with the rotating speed centrifugation 5-of 4000rpm
10min, takes washing of precipitate 5 times, and washing methods is to add acetone in precipitation, then is centrifuged 5-10min with 4000rpm；Will washing
After be deposited in 800 DEG C of vacuum environments be dried 8-12h, i.e. obtain modified manometer silicon dioxide.
Photocuring 3 D-printing material the most according to claim 1, it is characterised in that described polymerization inhibitor is FIRSTCURE
ST-1, stabilizer is tetramethylolmethane.
Photocuring 3 D-printing material the most according to claim 2, it is characterised in that described levelling agent is Glide 435, profit
Hygroscopic water powder is Texaphor P61.
4. the preparation method of photocuring 3 D-printing material as described in one of claim 1-3, comprises the following steps: in proportion will
2,4,6-trimethylbenzoyl-ethyoxyl-phenyl phosphine oxide, cumenyl ferrocene hexafluorophosphate, the poly-second of methoxyl group two
Alcohol 350 monomethacrylates and 5-oxa--1, after the mixing of 2-dithia cycloheptane, with the rotating speed magnetic agitation of 600-700rpm
1-2h, adds modified manometer silicon dioxide, is placed in ball mill mixing, and hybrid parameter is: rotating speed 600-800rpm, ratio of grinding media to material
20:1, mixes 6-8h；Polyalcohol modified epoxy acrylate, aliphatic epoxy resin, polymerization inhibitor, levelling is added in ball mill
Agent, stabilizer, triethanolamine and wetting dispersing agent, in ball mill with ratio of grinding media to material as 8:1, rotating speed 200-300rpm stir 12h,
I.e. obtain described photocuring 3 D-printing material.
5. photocuring 3 D-printing material application in 3 D-printing as described in one of claim 1-3.
Apply the most as claimed in claim 5, it is characterised in that concrete forming method is as follows: uv cure machine high voltage mercury lamp
Power 2000W, main transmitting wavelength 365nm, scanning speed 10 ~ 18m/min, irradiation distance 6 ~ 10mm, solidify thickness 0.1mm, Gu
Change temperature is room temperature, successively piles up molding with glass plate or cured resin for substrate.
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| CN105399905B (en) * | 2015-10-27 | 2018-10-16 | 南京航空航天大学 | A kind of photocurable three-dimensional printing materials and preparation method thereof |
| CN105566860A (en) * | 2015-12-11 | 2016-05-11 | 上海联泰科技股份有限公司 | Ceramic material for 3D (three-dimensional) light curing forming printing and preparation method thereof |
| CN105713332A (en) * | 2016-04-14 | 2016-06-29 | 北京石油化工学院 | Ultraviolet-curable resin composite for laser 3D printing and preparation method of ultraviolet-curable resin composite |
| CN108264756B (en) * | 2018-01-25 | 2020-11-24 | 哈尔滨工业大学 | Three-dimensional laser deposition forming 3D printing material and equipment |
| CN109486162A (en) * | 2018-11-16 | 2019-03-19 | 福州万象三维电子科技有限公司 | Degradable 3D printing material and preparation method thereof |
| CN109535662B (en) * | 2018-11-16 | 2021-03-19 | 福州万象三维电子科技有限公司 | 3D printing material and preparation method thereof |
| CN110776604A (en) * | 2019-10-31 | 2020-02-11 | 东莞理工学院 | Light-cured wax resin for DLP (digital light processing) type 3D printing and preparation method thereof |
| CN113321912B (en) * | 2021-06-08 | 2022-07-12 | 广东工业大学 | High-temperature-resistant 3D printing photosensitive resin and preparation method and application thereof |
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