CN106366615B - A kind of nano-cellulose/photocurable resin material and the preparation method and application thereof for 3 D-printing - Google Patents
A kind of nano-cellulose/photocurable resin material and the preparation method and application thereof for 3 D-printing Download PDFInfo
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- CN106366615B CN106366615B CN201610844000.9A CN201610844000A CN106366615B CN 106366615 B CN106366615 B CN 106366615B CN 201610844000 A CN201610844000 A CN 201610844000A CN 106366615 B CN106366615 B CN 106366615B
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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
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/02—Polyalkylene oxides
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- 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
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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
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
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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
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
Abstract
Nano-cellulose/photocurable resin material and the preparation method and application thereof that the invention discloses a kind of for 3 D-printing.The preparation method combines high-speed stirred and ultrasonication using freeze-drying, and nano-cellulose is blended with water borne UV curing resin, nano-cellulose/photocurable resin material for 3 D-printing is prepared.This method is easy to operate and the rapid shaping of the controllable adjustment of nanofiber cellulose content and nano-cellulose in material may be implemented.Nano-cellulose/photocurable resin material prepared by the present invention has quick setting capabilities, can meet the requirement of photocureable rapid shaping.Obtained nano-cellulose/photocurable resin material has different viscosity numbers with the difference of nanofiber cellulose content, is suitable for different 3 D-printing forms, has broad application prospects.
Description
Technical field
The present invention relates to the photo-curing material technical fields for 3 D-printing, and in particular to is used for the nanometer of 3 D-printing
Cellulose/photocurable resin material and the preparation method and application thereof.
Background technology
As a kind of important natural macromolecular material and novel nano material, nano-cellulose has become to be ground both at home and abroad
The hot subject studied carefully.Due to nano-cellulose have higher mechanical performance, lower density, good biocompatibility, can
The features such as degradability and nanostructure effect, it is widely used in composite reinforcing material, biological medicine, chemical industry, food etc.
Field.It is three-dimensional as a kind of rapid shaping technique（3D）Printing technique is with shaping speed is fast, precision is high, planform is controllable
The advantages that, and the mock-up printed can almost penetrate into the every field of life.Rapid shaping technique is mainly solid including light
Change forming technique（SLA）, fused glass pellet（FDM）, layer separated growth（LOM）, selective laser sintering（SLS）, it is three-dimensional
Printing（3DP）And mask lithography（SGC）Deng.Currently, the new material that exploitation is applicable to any of the above 3D printing form has become
For research hotspot both domestic and external.
The use of nano-cellulose and the combination of 3D printing technique are by development potentiality and application prospect with bigger.The U.S.
Oak Ridge National Laboratory and American Process companies cooperate to be intended to usually promote 3D printing plastics using nanofiber
The intensity of resin（U.S.'s tackling key problem nano-cellulose 3D printing material [J] plastics industries, 2015,08:86.）.Due to nanofiber
Element itself cannot be heated and be occurred photopolymerization reaction, and exploitation at present also has suitable for the nano-cellulose new material of 3D printing
There is certain challenge.Torres-Rendon J G et al. are filled it into using the shear shinning characteristic of nano-cellulose
It meets in the ordered 3 D structure that alkali can dissolve（Torres‐Rendon J G, Femmer T, De Laporte L, et al.
Bioactive gyroid scaffolds formed by sacrificial templating of nanocellulose
and nanochitin hydrogels as instructive platforms for biomimetic tissue
engineering[J]. Advanced materials, 2015, 27(19): 2989-2995.）, this method can obtain
To the three-dimensional structure containing only nano-cellulose but its insufficient strength height.Markstedt K et.al by sodium alginate ion
The shear shinning characteristic of crosslinking feature and nano-cellulose has prepared the biological ink of suitable 3D printing（Markstedt K,
Mantas A, Tournier I, et al. 3D bioprinting human chondrocytes with
nanocellulose–alginate bioink for cartilage tissue engineering applications
[J]. Biomacromolecules, 2015, 16(5): 1489-1496.）, but its printing precision is not high enough.
Stereolithography apparatus（Stereo Lithography Apparatus,SLA）It is to be carried out using photocuring technology
The method successively shaped, operation principle are that it is anti-that polymerization occurs rapidly under ultraviolet light for polymerizable liquid photosensitive resin
It answers, liquid material becomes solid-state, and realizes its successively curing molding by computer control.The forming method is efficient, can be real
The controllable preparation of existing 3 D complex structure, the advantage especially in terms of printing precision become current 3D printing mainstream and answer
With one of technology.Nano-cellulose itself can neither melt the performance for also not having photocuring, cannot directly apply fusion sediment
Technology and SLA technology.Therefore so that nano-cellulose is had light-cured performance is that nano-cellulose can be applied to photocuring
3D printing field needs one of the critical issue solved.However, the research in relation to this respect and patent report are few at present, and
All there is application many insufficient or without reference to 3D printing in these reports.Such as Cellulose nanocrystal palpus（CNC）With it is modified
CNC is added in waterborne UV coating, enhances the wearability of coating（Vardanyan V, Poaty B, Chauve G, et
al. Mechanical properties of UV-waterborne varnishes reinforced by cellulose
nanocrystals[J]. Journal of Coatings Technology and Research, 2014, 11(6):
841-852.）, but the application of 3D printing is not referred to.Also NFC is prepared for using wet template dipping method（Nano-cellulose）/
HBP (hyperbranched photopolymerization object) nano composite membrane（Galland S, Leterrier Y, Nardi T, et al. UV‐
cured cellulose nanofiber composites with moisture durable oxygen barrier
properties[J]. Journal of Applied Polymer Science, 2014, 131(16).）, also it is not directed to 3D
The content of printing.A kind of method that ultraviolet light solidification method prepares high-performance fiber element/resin compounded film of patent document（Liu Shilin,
The Asia Tao Dandan, Hu Nannan, Liu Jingcheng, Liu Ren, Zhang Shengwen, the Liu Xiao Jiangsu [P]：CN102796275A,2012-11-28.）
With a kind of preparation method of lignocellulosic nanofiber/acrylic resin laminated film（Li great Gang, Xue Yingying, Li Mingzhu, Pan
It is good, Chen Zhendong, Li Xueting, the Jiangsu Hu Yue [P]：CN103396572A,2013-11-20.）Also all it is first by nanofiber
Element filters film forming, is then impregnated into light-cured resin, and carrying out post-processing by ultraviolet lighting prepares high performance laminated film
Material is not related to the content of 3D printing yet.These reports are all the compound of nano-cellulose and light-cured resin, but nanofiber
The molding of element is all that suction method obtains, and is then post-processed through photocuring, using being coating and film application, is not related to 3D printing material
The preparation of material.A kind of graphene oxide of patent document/light-cured resin composite material and preparation method and application（Wei Yanyan,
Ma Fengguo, woods moisten the Shandong hero [P]：CN103819656A,2014-05-28.）Disclose a kind of graphene oxide/photocuring
The preparation of resin composite materials, is applied in Stereo Lithography Apparatus.A kind of Fanglun slurry cake of patent document enhances light-cured resin
Composite material and preparation method（Packet seapeak, Zhang Jing, Jin Liang, Huang Shaowei, Liu Shi, the Guangdong Ye Yu soft [P]：
CN105273345A,2016-01-27.）It is compound to disclose a kind of Fanglun slurry cake enhancing light-cured resin can be applied to 3D printing
The preparation of material.Nano-cellulose is added in Stereo Lithography resin by Kumar S et al. so that mechanical performance obtains
It improves（Kumar S, Hofmann M, Steinmann B, et al. Reinforcement of
stereolithographic resins for rapid prototyping with cellulose nanocrystals
[J]. ACS applied materials & interfaces, 2012, 4(10): 5399-5407.）.It is domestic at present
There is not been reported for the preparation research of photocuring 3D printing material for nano-cellulose.
Blending is the conventional means of functionalized modification.In view of field is printed in 3D at present, there are many photocuring trees
Fat is applied, therefore this patent proposes in some light-cured resins of existing application, finds a kind of suitable photocuring tree
It is blended fat with nano-cellulose, to assign nano-cellulose light-cured performance, exists to solve current nano-cellulose
The technical bottleneck problem of photocuring 3D applications.For 3D printing application, ideal nano-cellulose/photocurable resin material is answered
This is with good mobility, the suitable rheological equationm of state, high nano-cellulose solid content and quick setting capabilities.Therefore it adopts
Nano-cellulose/photocurable resin material is prepared with blend method, needs the uniformity for solving nano-cellulose and resin alloy
How problem improves nano-cellulose solid content problem, suitable rheology and flowability problem and quick setting capabilities' problem.
Existing 3D printing photosensitive resin is broadly divided into two big systems, first, radical UV curing system, solidification rate is fast, but receives
The big precision of shrinkage is not high；Second is that Cationic curing systems, shrinking percentage is smaller, but solidification rate is again relatively low.In radically curing
Nano-cellulose is added in system photosensitive resin, cure shrinkage can be reduced to a certain extent and improve solidification precision.Therefore
The photosensitive resin of this patent selection radical UV curing system is blended with nano-cellulose.
Nano-cellulose is can be uniformly dispersed in water phase, and the nano-cellulose product that current various technologies of preparing obtain leads to
All it is often to occur and apply in the form of aqueous dispersions.Since the high water retention value of photosensitive resin and nano-cellulose co-mixing system is special
Property limits the raising of nano-cellulose solid content in dispersion liquid, and the mass fraction of nano-cellulose is usually low in General Decentralized liquid
In 2%.When therefore preparing nano-cellulose/photocurable resin material using blending method, nano-cellulose how is improved as possible and is existed
Content in co-mixing system is a problem needed to be considered.By adding the nano-cellulose of solid form when blending, then have
The content of nano-cellulose in co-mixing system may be improved.Therefore the nano-cellulose for how obtaining solid form is very crucial.
In the various drying means such as oven drying, freeze-drying, spray drying and supercritical drying, the method for freeze-drying is simply easy
Operation, will not change the original nano-scale of nano-cellulose, be that one kind obtaining solid form nano-cellulose and and then improves
The effective ways of nano-cellulose solid content in co-mixing system.
This patent is solid using its hydrophily and the aqueous light of photopolymerization using the nano-cellulose after being freeze-dried as raw material
Change resin to be blended, prepares photo curable nano-cellulose/photocurable resin material, nanofiber cellulose content may be implemented
Controllable adjustment in photocuring solution, curing solution viscosity is adjustable and the rapid shaping of nano-cellulose, three-dimensional structure
Controllable preparation.
Invention content
To solve the disadvantage that the prior art and shortcoming, the purpose of the present invention is exploitations can be used for the Performances of Novel Nano-Porous of 3D printing
Rice cellulose/photocurable resin material, and realize that the controllable adjustment of nanofiber cellulose content and the three-dimensional of nano-cellulose can
Prepared by the rapid shaping for controlling structure, specific technical solution is as follows.
A kind of preparation method of nano-cellulose/photocurable resin material for 3 D-printing, includes the following steps：
（1）The preparation of nano-cellulose dry sample：By nano-cellulose aqueous dispersions be placed in refrigerator -20 ~ -80 DEG C freezing 18 ~
Hour forms frozen glue for 24 hours, then is freeze-dried, and obtains nano-cellulose dry sample；
（2）The preparation of nano-cellulose water redisperse liquid：Under high shear agitation, the addition of nano-cellulose dry sample is gone
In ionized water, continue stirring 5 ~ 10 minutes；Then ultrasonication is carried out to mixed dispersion liquid with ultrasonic cell disruptor, obtained
To the nano-cellulose water redisperse liquid of nano-scale；
（3）The preparation of nano-cellulose/light-cured resin dispersion liquid：Water borne UV curing resin and photoinitiator are added
Into nano-cellulose water redisperse liquid, by high-speed stirred combination ultrasonication obtain evenly dispersed nano-cellulose/
Light-cured resin dispersion liquid；Then after defoaming treatment, the nano-cellulose for 3 D-printing/light-cured resin material is obtained
Material is placed in the shady and cool dry environment being protected from light and preserves.
Preferably, step（1）Described in nano-cellulose aqueous dispersions be to be combined by acid-hydrolysis method or TEMPO oxidizing process
Prepared by mechanical treatment, carboxyl-content is 0.86 ~ 1.73mmol/g.
Preferably, step（1）Described in the temperature that is freeze-dried be -40 ~ -68 DEG C, the time is 30 ~ 48 h.
Preferably, step（2）Described in high shear agitation rotating speed be 400 ~ 1500rpm.
Preferably, step（2）Described in ultrasonication time be 5 ~ 20min.
Preferably, step（2）In, the Adding Way of cellulose dry sample is：First be shredded into fritter be slow added into go from
In sub- water；Mass fraction of the nano-cellulose of addition in nano-cellulose/light-cured resin dispersion liquid is 0.1% ~ 10%（w/
w）.
Preferably, step（3）In, the water borne UV curing resin includes waterborne epoxy acrylate class, aqueous polyurethane
Esters of acrylic acid, waterborne polyester esters of acrylic acid, aqueous polyethyleneglycol diacrylate, aqueous silane base are acrylic resin modified
One or more of with water polyacrylic acid class；The water borne UV curing resin of addition is in nano-cellulose/light-cured resin point
Mass fraction in dispersion liquid is 5% ~ 40%（w/w）.
Preferably, step（3）Described in photoinitiator be acetophenone derivs, fragrant ketone, methyl phenyl ketone class, alkyl
One or more of benzophenone, diaryl iodonium salt, triaryl salt compounded of iodine and triaryl sulfonium salts；The photoinitiator of addition is in nanometer
Mass fraction in cellulose/light-cured resin dispersion liquid is 0.01% ~ 3%（w/w）.
Preferably, step（3）Described in high-speed stirred rotating speed be 400 ~ 1500rpm.
Preferably, step（3）Described in ultrasonication time be 2 ~ 6min.
Preferably, step（3）Described in defoaming treatment be the container for filling nano-cellulose/light-cured resin dispersion liquid
It is put into progress bubble elimination in supersonic wave cleaning machine.
Nano-cellulose/light-cured resin material of 3 D-printing is used for made from the preparation method described in any of the above-described
Material.
Nano-cellulose/photocurable resin material of 3 D-printing is used for made from the preparation method described in any of the above-described
In Stereo Lithography printing and the application in the printing of ink-jet photocuring, nano-cellulose/photocurable resin material obtained, receive
When rice content of cellulose is 0.1% ~ 2%, viscosity is less than 5Pa.s, meets viscosity requirement of the Stereo Lithography printing to ink；Nanometer
When content of cellulose is 2% ~ 10%, viscosity is higher than 5Pa.s, meets viscosity requirement of the inkjet printing to ink.
Further, nano-cellulose/photocurable resin material obtained for 3 D-printing is beaten in Stereo Lithography
The application of India and China, includes the following steps：
（1）Nano-cellulose/the photocurable resin material for meeting viscosity requirement is filled into Stereo Lithography Apparatus liquid bath, profit
Use digital micromirror device（Digital Micromirror Device, abbreviation DMD）Or film mask, in ultraviolet light
The lower solidification of irradiation, obtains carrying different pattern or not patterned hydrogel；
（2）After having cured one layer, lifting platform declines the distance of a cured thickness, makes be cured one layer to cover again above
New nano-cellulose/the photocurable resin material of one layer of lid continues to cure and successively cure, to realize nano-cellulose
The printing of three dimensional hydrogel.
Further, the wavelength of the ultraviolet light is 200 ~ 400nm；The cured time is 5s ~ 100s.
Compared with prior art, the present invention has the following advantages and beneficial effects：
（1）The preparation method of the novel nano cellulosic material for 3D printing of the present invention is simple for process, easily operated,
The rapid shaping of nano-cellulose can be achieved；
（2）In nano-cellulose/photocurable resin material produced by the present invention, the raising of nanofiber cellulose content can pass through
Nano-cellulose dry sample is added to realize, and nano-cellulose dry sample can be prepared by the method for freeze-drying；
（3）Nano-cellulose/photocurable resin material produced by the present invention, viscosity can be by changing nano-cellulose
Additive amount it is adjusted, can also by change nano-cellulose carboxyl-content or charged group characteristic it is adjusted,
To adapt to include that Stereo Lithography printing and ink-jet photocuring are printed upon interior different 3 D-printing forms, there is good answer
Use foreground；
（4）Nano-cellulose/photocurable resin material prepared by the present invention has quick setting capabilities, hardening time 5s
~ 100s can meet the requirement of photocureable rapid shaping.
Description of the drawings
Fig. 1 is the TEM figures of the front and back nano-cellulose of freeze-drying；
Fig. 2 is viscosity-rate curve of the photocuring dispersion liquid of different nanofiber cellulose contents；
Fig. 3 is viscosity-rate curve of the photocuring dispersion liquid of different nano-cellulose carboxyl-contents.
Specific implementation mode
With reference to embodiment and attached drawing, the present invention is described in further detail, but embodiments of the present invention and guarantor
It is without being limited thereto to protect range.
Embodiment 1
（1）Prepared by TEMPO oxidation bonding ultrasonic waves, carboxyl-content 1.22mmol/g, a concentration of 1wt% nanometer
After cellulose aqueous dispersions are placed in -20 DEG C of freezing hours for 24 hours of refrigerator, it is placed in freeze drier at -40 DEG C and freezes 30 hours, obtain
To nano-cellulose dry sample；
（2）Under the action of high speed machine stirs 900rpm, by nano-cellulose dry sample（0.5%, mass fraction）It tears up and adds
Enter to deionized water（74.4%, mass fraction）Beaker in, continue after adding stirring 10 minutes；Then ultrasonic wave wave cell is used
Pulverizer carries out ultrasonic wave 5 minutes to mixed dispersion liquid, and nano-cellulose water redisperse liquid is prepared；Fig. 1 is freeze-drying
The transmission electron microscope of front and back nano-cellulose（TEM）Figure, wherein a are the TEM figures before freeze-drying, and b is the TEM after freeze-drying
Figure；Fig. 1 is shown, the nano-cellulose of nanoscale still can be obtained after freeze-drying through the dispersion of mechanical agitation combination ultrasonic wave；
（3）Aqueous polyethyleneglycol diacrylate and fragrant ketone-type photoinitiators Irgacure 2959 are added to
It states in nano-cellulose water redisperse liquid, wherein the mass fraction of aqueous polyethyleneglycol diacrylate is 25%, fragrant ketone light
The mass fraction of initiator Irgacure 2959 is 0.1%；It is obtained by high-speed stirred 900rpm combination ultrasonications 4min
Evenly dispersed nano-cellulose/light-cured resin dispersion liquid；Then it is placed on the shady and cool dry environment being protected from light through defoaming treatment
Middle preservation.
Obtained nano-cellulose/light-cured resin mixed dispersion liquid is transparent, it is stable, without layering coacervation, static state is viscous
Spend it is relatively low, as shown in the rheological curve a in Fig. 2.
Embodiment 2
With embodiment 1, the difference is that nano-cellulose is in nano-cellulose/photocurable resin material dispersion liquid
Mass fraction is changed to 2.4%, and deionized water quality score is changed to 72.5%.Using same high-speed stirred 900rpm combination ultrasonic waves
Processing ultrasonication 4min obtains evenly dispersed nano-cellulose/light-cured resin dispersion liquid, is placed on through defoaming treatment
It is preserved in the dry environment being protected from light in cool place.
Nano-cellulose obtained/light-cured resin dispersion liquid mixed dispersion liquid is transparent, it is stable, without layering coacervation,
And quiescent solution viscosity is higher, as shown in the rheological curve b in Fig. 2.
By Fig. 2 analyses it is found that the carboxyl-content of nano-cellulose dispersion liquid is constant, the additive amount of nano-cellulose increases,
The viscosity of solidification dispersion liquid will increase, in low shear rate（Less than 10 s-1）Under, viscosity with the increase of shear rate it is rapid under
It is reduced to 5Pa.s.
Embodiment 3
With embodiment 2, the difference is that the carboxyl-content of nano-cellulose is respectively 1.61 mmol/g, 1.73
Mmol/g, other preparation conditions are all identical.
The double propylene acid esters of nano-cellulose, deionized water, aqueous polyethylene glycol and photoinitiator are in entire dispersion liquid
Mass fraction is respectively 2.4%, 72.5%, 25%, 0.1%；The rheology of the nano-cellulose being prepared/light-cured resin dispersion liquid
Curve difference is as shown in Figure 3.
It is analyzed in conjunction with Fig. 2, Fig. 3 as it can be seen that working as quality of the nano-cellulose in nano-cellulose/light-cured resin dispersion liquid
When score immobilizes（2.4%）, carboxyl-content is improved, the viscosity of solidification dispersion liquid can be reduced.This is because using TEMPO
When oxidizing process prepares nano-cellulose, degree of oxidation is higher, and carboxyl-content is higher, the Nanowire obtained after mechanical treatment
The size for tieing up element is shorter, therefore obtained nano-cellulose/light-cured resin dispersion liquid mobility is better.
Embodiment 4
Using the photocuring dispersion liquid prepared in embodiment 1, the film with honeycomb and zero Poisson's ratio structure
Mask is covered in the upper surface of solidification dispersion liquid, in ultraviolet light（Wavelength 365nm）Irradiation under cure 20s, can respectively obtain has
The hydrogel of honeycomb pattern and zero Poisson's ratio pattern, the hydrogel water white transparency not only have different pore structures, but also bendable
Song has flexibility.
The photocuring dispersion liquid prepared in embodiment 1 and embodiment 2 is used respectively, the film mask with dumbbell shaped
It is covered in the upper surface of solidification dispersion liquid, then in ultraviolet light（Wavelength 365nm）Irradiation under cure 20s, use universal material testing
It is respectively 0.95MPa and 3.73MPa that machine, which measures its elasticity modulus,.
Embodiment 5
It is being received with embodiment 1 the difference is that water borne UV curing resin is that aqueous silane base is acrylic resin modified
Mass fraction in rice cellulose/light-cured resin dispersion liquid is constant, other preparation conditions are all identical.
The nano-cellulose being prepared/light-cured resin dispersion liquid it is transparent it is uniform, stable, without layering coacervation.Profit
Carry out the preparation of auxetic structure hydrogel, a length of 254nm of ultraviolet light wave, system as described in Example 4 with the photocuring dispersion liquid
It is standby obtain auxetic structure hydrogel water white transparency, it is flexible, there is flexibility.
Embodiment 6
（1）Prepared by TEMPO oxidation bonding ultrasonic waves, carboxyl-content 0.86mmol/g, a concentration of 1wt% nanometer
After cellulose aqueous dispersions are placed in freezing 18h hours of -50 DEG C of refrigerator, it is placed in freeze drier at -54 DEG C and freezes 39 hours, obtain
To nano-cellulose dry sample；
（2）Under the action of high speed machine stirs 400rpm, by nano-cellulose dry sample（0.1%, mass fraction）It tears up and adds
Enter to deionized water（59.89%, mass fraction）Beaker in, continue after adding stirring 5 minutes；Then ultrasonic wave wave cell is used
Pulverizer carries out ultrasonic wave 12 minutes to mixed dispersion liquid, and nano-cellulose water redisperse liquid is prepared；
（3）Aqueous polyethyleneglycol diacrylate and fragrant ketone-type photoinitiators Irgacure 2959 are added to
It states in nano-cellulose water redisperse liquid, wherein the mass fraction of aqueous polyethyleneglycol diacrylate is 40%, fragrant ketone light
The mass fraction of initiator Irgacure 2959 is 0.01%；It is obtained by high-speed stirred 400rpm combination ultrasonications 2min
Evenly dispersed nano-cellulose/light-cured resin dispersion liquid；Then it is placed on the shady and cool dry environment being protected from light through defoaming treatment
Middle preservation.
Obtained nano-cellulose/light-cured resin mixed dispersion liquid is transparent, it is stable, without layering coacervation, static state is viscous
Degree is less than nano-cellulose/light-cured resin mixed dispersion liquid that embodiment 1 obtains.
Carry out the preparation of auxetic structure hydrogel, ultraviolet wavelength as described in Example 4 using the photocuring dispersion liquid
For 365nm, be prepared auxetic structure hydrogel water white transparency, it is flexible, there is flexibility.
Embodiment 7
（1）Prepared by TEMPO oxidation bonding ultrasonic waves, carboxyl-content 0.86mmol/g, a concentration of 1wt% nanometer
After cellulose aqueous dispersions are placed in freezing 21h hours of -80 DEG C of refrigerator, it is placed in freeze drier at -68 DEG C and freezes 48 hours, obtain
To nano-cellulose dry sample；
（2）Under the action of high speed machine stirs 1500rpm, by nano-cellulose dry sample（10%, mass fraction）It tears up and adds
Enter to deionized water（82%, mass fraction）Beaker in, continue after adding stirring 7 minutes；Then ultrasonic wave wave cell pulverization is used
Machine carries out ultrasonic wave 20 minutes to mixed dispersion liquid, and nano-cellulose water redisperse liquid is prepared；
（3）Aqueous polyethyleneglycol diacrylate and fragrant ketone-type photoinitiators Irgacure 2959 are added to
It states in nano-cellulose water redisperse liquid, wherein the mass fraction of aqueous polyethyleneglycol diacrylate is 5%, fragrant ketone light
The mass fraction of initiator Irgacure 2959 is 3%；It is obtained by high-speed stirred 1500rpm combination ultrasonications 6min
The nano-cellulose of even dispersion/light-cured resin dispersion liquid；Then it is placed in the shady and cool dry environment being protected from light through defoaming treatment
It preserves.
Obtained nano-cellulose/light-cured resin mixed dispersion liquid is transparent, it is stable, without layering coacervation, static state is viscous
Degree is apparently higher than nano-cellulose/light-cured resin mixed dispersion liquid that embodiment 1,2,3 and 6 obtains.Utilize the photocuring point
Dispersion liquid carries out the preparation of auxetic structure hydrogel as described in Example 4, and nothing can be still prepared in a length of 365nm of ultraviolet light wave
Color is transparent, it is flexible, there is flexible auxetic structure hydrogel.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, it is other it is any without departing from the spirit and principles of the present invention made by changes, modifications, substitutions, combinations, simplifications,
Equivalent substitute mode is should be, is included within the scope of the present invention.
Claims (8)
1. a kind of preparation method of nano-cellulose/photocurable resin material for 3 D-printing, which is characterized in that including with
Lower step：
（1）The preparation of nano-cellulose dry sample：By nano-cellulose aqueous dispersions be placed in refrigerator -20 ~ -80 DEG C freezing 18 ~ it is small for 24 hours
When form frozen glue, then be freeze-dried, obtain nano-cellulose dry sample；The nano-cellulose aqueous dispersions are by acid-hydrolysis method
Or the preparation of TEMPO oxidizing process combination mechanical treatments, carboxyl-content is 0.86 ~ 1.73mmol/g；The temperature of the freeze-drying
It it is -40 ~ -68 DEG C, the time is 30 ~ 48 h；
（2）The preparation of nano-cellulose water redisperse liquid：Under high shear agitation, deionization is added in nano-cellulose dry sample
In water, continue stirring 5 ~ 10 minutes；Then ultrasonication is carried out to mixed dispersion liquid with ultrasonic cell disruptor, is received
The nano-cellulose water redisperse liquid of meter ruler cun；The Adding Way of nano-cellulose dry sample is：Fritter is first shredded into again slowly to add
Enter into deionized water；Mass fraction of the nano-cellulose of addition in nano-cellulose/light-cured resin dispersion liquid be
0.1%~10%（w/w）；The rotating speed of the high shear agitation is 400 ~ 1500rpm；The time of the ultrasonication be 5 ~
20min；
（3）The preparation of nano-cellulose/light-cured resin dispersion liquid：Water borne UV curing resin and photoinitiator are added to and received
In rice cellulose water redisperse liquid, it is solid that evenly dispersed nano-cellulose/light is obtained by high-speed stirred combination ultrasonication
Change resin dispersion liquid；Then after defoaming treatment, nano-cellulose/photocurable resin material for 3 D-printing is obtained, is set
It is preserved in the shady and cool dry environment being protected from light.
2. a kind of preparation side of nano-cellulose/photocurable resin material for 3 D-printing according to claim 1
Method, which is characterized in that step（3）In, the water borne UV curing resin includes waterborne epoxy acrylate class, aqueous polyurethane third
Olefin(e) acid esters, waterborne polyester esters of acrylic acid, aqueous polyethyleneglycol diacrylate, aqueous silane base it is acrylic resin modified and
One or more of water polyacrylic acid class；The water borne UV curing resin of addition is in nano-cellulose/light-cured resin dispersion
Mass fraction in liquid is 5% ~ 40%（w/w）.
3. a kind of preparation side of nano-cellulose/photocurable resin material for 3 D-printing according to claim 1
Method, which is characterized in that step（3）In, the photoinitiator is acetophenone derivs, fragrant ketone, methyl phenyl ketone class, alkyl
One or more of benzophenone, diaryl iodonium salt, triaryl salt compounded of iodine and triaryl sulfonium salts；The photoinitiator of addition is in nanometer
Mass fraction in cellulose/light-cured resin dispersion liquid is 0.01% ~ 3%（w/w）.
4. a kind of preparation side of nano-cellulose/photocurable resin material for 3 D-printing according to claim 1
Method, which is characterized in that step（3）In, the rotating speed of the high-speed stirred is 400 ~ 1500rpm；The time of the ultrasonication
For 2 ~ 6min；The defoaming treatment is to be put into progress bubble elimination in supersonic wave cleaning machine.
5. by any one of the claim 1 ~ 4 preparation method nano-cellulose/photocuring tree obtained for being used for 3 D-printing
Fat material.
6. by any one of the claim 1 ~ 4 preparation method nano-cellulose/photocuring tree obtained for being used for 3 D-printing
Application of the fat material in Stereo Lithography printing and the printing of ink-jet photocuring, which is characterized in that nano-cellulose/light obtained
In curing resin material, when nanofiber cellulose content is 0.1% ~ 2%, viscosity is less than 5Pa.s, meets Stereo Lithography printing to oil
The viscosity requirement of ink；When nanofiber cellulose content is 2% ~ 10%, viscosity is higher than 5Pa.s, meets viscosity of the inkjet printing to ink
It is required that.
7. application according to claim 6, which is characterized in that nano-cellulose/light obtained for 3 D-printing is solid
Change application of the resin material in Stereo Lithography printing, includes the following steps：
（1）Nano-cellulose/the photocurable resin material for meeting viscosity requirement is filled into Stereo Lithography Apparatus liquid bath, utilizes number
Word micro mirror device or film mask, cure under the irradiation of ultraviolet light, obtain carrying different pattern or not patterned
Hydrogel；
（2）After having cured one layer, lifting platform declines the distance of a cured thickness, makes be cured one layer to cover one again above
New nano-cellulose/the photocurable resin material of layer continues to cure and successively print, to realize nano-cellulose three-dimensional
The printing of hydrogel.
8. application according to claim 7, which is characterized in that the wavelength of the ultraviolet light is 200 ~ 400nm；It is described solid
The time of change is 5s ~ 100s.
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| JP7162589B2 (en) * | 2017-07-11 | 2022-10-28 | 住友化学株式会社 | Aqueous resin composition and molded article |
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| CN108031841B (en) * | 2017-10-31 | 2020-06-09 | 西安铂力特增材技术股份有限公司 | Forming method of metal-based nano composite material part |
| CN108003294B (en) * | 2017-12-07 | 2019-11-01 | 石狮市川大先进高分子材料研究中心 | The cellulose base light-cured resin of quick 3D printing is lifted for Continuous Liquid Phase |
| CN111732760B (en) * | 2020-01-05 | 2023-11-21 | 天津科技大学 | Preparation of nanocellulose-based photocuring 3D printing conductive material |
| CN111320890B (en) * | 2020-03-11 | 2021-04-30 | 华南农业大学 | Hemp stem core powder modified water-based UV (ultraviolet) curing coating and preparation method and application thereof |
| CN113388220B (en) * | 2020-03-13 | 2022-08-16 | 中国石油化工股份有限公司 | Low-viscosity photosensitive resin and preparation method thereof, and 3D printing product and preparation method thereof |
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