CN108624061A - A kind of photo-curable silicone and its preparation method and application for 3D printing - Google Patents
A kind of photo-curable silicone and its preparation method and application for 3D printing Download PDFInfo
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- CN108624061A CN108624061A CN201810272877.4A CN201810272877A CN108624061A CN 108624061 A CN108624061 A CN 108624061A CN 201810272877 A CN201810272877 A CN 201810272877A CN 108624061 A CN108624061 A CN 108624061A
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
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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
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
- C08K7/26—Silicon- containing compounds
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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
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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Abstract
The photo-curable silicone and its preparation method and application that the invention discloses a kind of for 3D printing.It is prepared by the component including following mass fraction：Side chain contains 100 parts of the polysiloxanes of vinyl, 2~20 parts of the small molecule crosslinking agent containing two or more sulfydryls, 0.5~5 part of photoinitiator, 0.08~0.17 part of surface modified silicon dioxide microballoon, 45~68 parts of solvent.The fast reaction under ultraviolet light cures the polysiloxanes that the present invention contains vinyl using side chain with sulfydryl, its hardening time reaches within 3 s under room temperature, without bad smell after solidification, material property is good, print procedure does not need backing material, process for preparation is solvent-free or a small amount of solvent, cubical contraction are small；In addition, preparation method is simple, the product after photocuring has stronger tearing toughness and suitable hardness, can meet the 3D printing material of the requirement of Medical filling material, have a extensive future.
Description
Technical field
The invention belongs to 3D printing technique fields.More particularly, to a kind of photo-curable silicone for 3D printing and
Preparation method and application.
Background technology
3D printing technique, also known as increases material manufacturing technology are a kind of threedimensional models for establishing object with computer, and as
The technology for relying on straight forming, is bioengineering, material processing and forming, automation control, multiple subjects such as computer modeling
Intersect, compared with conventional molding techniques, it does not need conventional tool, fixture and multi-step process, can be in an equipment
It produces the part of arbitrarily complicated shape automatically and accurately by program control, and greatly reduces manufacturing procedure, significantly contract
The short R＆D cycle of new product, reduce R＆D costs.3D printing technique is quickly grown in recent years, in aviation, manufacture, mould
Tool, education, medical treatment, food etc. have developed more and more application directions.Add without high temperature in 3D printing implementation process
Heat reduces energy consumption, is not necessarily to special solvent, reduces environmental pollution, ultra-violet curing is rapid, and production efficiency greatly improved. 3D
The development of printed material is one of 3 big key technologies of 3D printing technique, and material bottleneck has become limitation 3D printing development
Matter of utmost importance.The backbone structure of silicon rubber is polysiloxane structure, and chemical property is stablized relatively, clinically as medical material
The using effect of material has been obtained for being widely recognized as medical field, and there are many major companies all the medicine of exploitation silicon rubber at present
Strategic objective of the use scope as oneself.It is with higher temperature tolerance, resistance to oxidation, hydrophobicity, flexibility, permeability, resistance to
It is aging transparency height, physiological inertia, good, nontoxic, tasteless, not carcinogenic etc. with tissue and blood adhesion, biocompatibility
A series of good characteristics.Due to these characteristics of silicon rubber itself, polymethyl siloxane just becomes medical macromolecular materials
It is middle than more typical organosilicon macromolecule material.
But the hardening time of silicon rubber is longer, mobility prevent its from keep printing accuracy, it is therefore desirable to one
A support material completes the 3D printing of labyrinth；In addition, the hydrophobicity of silicon rubber and lower surface free energy, limit
It is printed while effective with other materials；Moreover, existing silicon rubber can release niff in print procedure, therefore mesh
The preceding 3D printing for silicon rubber still has larger problem, and the 3D printing of silicon rubber is than relatively difficult to achieve.Currently, can successfully realize
The technology of silicon rubber 3D printing, is mainly the following：(1) Hinton et al. has invented a kind of carboxylic second using hydrophilic and hydrophobic
The method that alkene polymer gel support material prints silicon rubber, in this method after the silicon rubber mixing of two-component, through 3D printer
Printing, cures, is successfully realized the 3D printing of silicon rubber at ambient temperature.But it needs support material in print procedure
Material, and hardening time is longer, and after the completion of solidification, need progress proper treatment to remove support material, process is relatively complicated.
(2) Chinese invention patent《A kind of preparation method of 3D printing ultraviolet curing transparent silicone resin composite material and application》(patent
Number CN105331115A) disclose a kind of 3D printing ultraviolet curing transparent silicone resin composite material, the preparation of this kind of material
Cheng Shi, first, with organosilicon materials and alkoxy silane with acryloxy, under the action of catalyst, warp is solidifying in a solvent
Peptization glue method prepares the organic siliconresin prepolymer with acryloxy；Secondly, the organosilicon materials with acryloxy are dripped
It is added in White Carbon black, obtains the reinforced filling that acryloxy is modified；Finally, it is taken off after prepolymer, filler, photoinitiator being mixed
Bubble, obtaining can be with 3D printing ultraviolet curing transparent silicone resin composite material.The disadvantages of this method is that stock preparation process is multiple
It is miscellaneous, excessive high hardness, it is easy to chipping.(3) in addition, Chinese invention patent《3D printing is with silicon-containing nano gel photocuring tree
The preparation method and applications of fat》(patent No. CN106146754A) describes a kind of 3D printing silicon-containing nano gel photocuring
The preparation process of the preparation method and applications of resin, this kind of material is by modification organic silicon oil and acrylic ester monomer, chain
Transfer agent, radical initiator and organic solvent are added in reaction kettle, by purification of products after reaction, obtain silicon-containing nano gel light
Solidified resin.But need to use a large amount of organic solvent in the stock preparation process of this method, do not meet Medical filling material
It is required that and product need to purify.
In order to promote the development of 3D printing technique, needing to develop at normal temperatures has certain mobility and lower viscous
Degree, curing rate be fast, without bad smell, 3D printing plastic emitting effect is good, cubical contraction is small after material molding, print procedure is not required to
Backing material is wanted, and the product after photocuring has stronger tearing toughness, has suitable hardness, can meet medical fill out
Fill the 3D printing material of the requirement of material.
Invention content
The technical problem to be solved by the present invention is to overcome above-mentioned the deficiencies in the prior art, provide a kind of light for 3D printing
Cured silicone material, lower viscosity, curing rate be fast, without bad smell, 3D printing plastic emitting effect is good, after material molding
Cubical contraction is small, and print procedure does not need backing material, and the product after photocuring have stronger tearing toughness with
Suitable hardness can meet the 3D printing material of the requirement of Medical filling material.
The object of the present invention is to provide a kind of Photocurable Silicone Materials for 3D printing.
Another object of the present invention is to provide the preparation method of above-mentioned Photocurable Silicone Material.
Another object of the present invention be to provide above-mentioned Photocurable Silicone Material as or prepare answering in curable product
With.
Above-mentioned purpose of the present invention is achieved through the following technical solutions：
A kind of photo-curable silicone for 3D printing is prepared by the component including following mass fraction：Side chain contains
There are 100 parts of the polysiloxanes of vinyl, 2~20 parts of the small molecule crosslinking agent containing two or more sulfydryls, photoinitiator
0.5~5 part, 0.08~0.17 part of surface modified silicon dioxide microballoon, 45~68 parts of solvent.
Based on inventive formulation, science determines the polysiloxanes that side chain contains vinyl, contains two or more mercaptos
The small molecule crosslinking agent of base, the proportion compatibility of photoinitiator, surface modified silicon dioxide microballoon and solvent materials, significantly improve
The curing rate of silastic material, under room temperature its hardening time reach within 3s, greatly improve the processing of 3D printing equipment
Efficiency, and cure after without bad smell, small toxicity, pollution is small, mobility is high, toughness is high, shrinking percentage is low, realization printed material
Dimensional accuracy controllability.
Preferably, the photo-curable silicone for 3D printing, is prepared by the component including following mass fraction：
Side chain contains 100 parts of the polysiloxanes of vinyl, 3~10 parts of the small molecule crosslinking agent containing two or more sulfydryls, light
0.8~1.3 part of initiator, 0.1~0.15 part of surface modified silicon dioxide microballoon, 50~62.5 parts of solvent.
It is highly preferred that the photo-curable silicone for 3D printing, by the component preparation including following mass fraction
At：Side chain contains 100 parts of the polysiloxanes of vinyl, and 3 parts of the small molecule crosslinking agent containing two or more sulfydryls, light draws
Send out 1 part of agent, 0.125 part of surface modified silicon dioxide microballoon, 62.5 parts of solvent.
Preferably, the viscosity that the side chain contains the polysiloxanes of vinyl is 500~50000cst；Its contents of ethylene
For 0.6~1.5mmol/g.
It is highly preferred that the viscosity that the side chain contains the polysiloxanes of vinyl is 500~10000cst；Its vinyl contains
Amount is 0.8~1.2mmol/g.
Preferably, the small molecule crosslinking agent containing two or more sulfydryls is selected from trimethylolpropane tris (2-
Mercaptoacetate), trimethylolpropane tris (3-thiopropionate), 1,4- butanediols bis- (mercaptoacetates), 1,6- oneself two sulphur
Pungent two mercaptan of alcohol, 1,8-, two mercaptan of 1,9- nonyls, two mercaptan of the 1,10- last of the ten Heavenly stems, two mercaptan of 1,11- hendecanes, four (3- mercaptopropionic acids) seasons
One or both of Doutrate, 2,2 '-(1,2- second diyl dioxygen generations) double ethyl mercaptans or glycol dimercaptosuccinate with
Upper mixture；When being used in mixed way, mixed proportion does not do considered critical.
Preferably, the photoinitiator is radical photoinitiator.
It is highly preferred that the photoinitiator is selected from benzoin dimethylether, benzoin ethyl ether, styrax, isopropyl ether, rests in peace
Fragrant butyl ether, diphenylethan, α, one or both of α-diethoxy acetophenone, alpha-hydroxyalkyl benzophenone or α-amine alkyl phenones
The above mixture；When being used in mixed way, mixed proportion does not do considered critical.
In order to further increase curing rate soon and remove offensive gases, it is further preferred that the photoinitiator
For benzoin dimethylether or diphenylethan.
Preferably, the surface modified silicon dioxide microballoon, is prepared by the following method：By silicon dioxide nanosphere
It is added in toluene with surface modifier, 4~10h is reacted in 60~110 DEG C, it is cooling, it centrifuges, washing, vacuum drying obtains
Surface modified silicon dioxide microballoon；Wherein, the mass volume ratio of silicon dioxide nanosphere and surface modifier is 1:3~10.
Preferably, the grain size of the silicon dioxide microsphere is 15~100nm.
Preferably, the surface modifier is (3- mercaptopropyis) triethoxysilane and/or (3- mercaptopropyls) first
Base diethoxy silane.
Preferably, silicon dioxide nanosphere is first placed in ultrasonic disperse 30min in toluene.
Preferably, reaction condition is：8h is reacted in 80 DEG C.
Preferably, the condition of the washing is：With ethyl alcohol and water washing 3~5 times.
The present invention also provides the preparation methods of the photo-curable silicone for 3D printing, include the following steps：
S1. surface modified silicon dioxide microballoon is prepared according to above-mentioned method；
S2. contain to side chain in the polysiloxanes of vinyl and photoinitiator is added, stir to dissolve, then in proportion successively
The surface modified silicon dioxide microballoon of addition step S1, small molecule crosslinking agent and solvent containing two or more sulfydryls,
It is uniformly mixed, vacuumizes removing bubble, obtain the photo-curable silicone for being used for 3D printing.
The present invention is not specially limited solvent for use, preferably tetrahydrofuran, ethyl acetate etc..
In addition, the photo-curable silicone for 3D printing is in terms of the raw material as 3D printing, especially in conduct
Or application in curable product is prepared, also within protection domain.
The curable product refers to Medical filling material, including but unlimited cardiac stent, artificial blood vessel etc..
Compared with prior art, the present invention has the advantages that：
The polysiloxanes that the present invention contains vinyl using side chain is handed over the small molecule containing two or more sulfydryls
Join agent fast reaction under ultraviolet light to cure, under room temperature its hardening time reach within 3s, without bad smell, material after solidification
Expect that performance is good, 3D printing materials'use can be used as；And this photocuring silicone rubber applications are in 3D printing technique, print procedure
Backing material is not needed, material process for preparation is solvent-free or a small amount of solvent, and cubical contraction is small after material molding；In addition, it is made
Preparation Method is simple, and the product after photocuring has stronger tearing toughness and suitable hardness, can meet medical filling material
The 3D printing material of the requirement of material.The 3D printing material of this high comprehensive performance has broad application prospects.
Specific implementation mode
Further illustrated the present invention below in conjunction with specific embodiment, but embodiment the present invention is not done it is any type of
It limits.Unless stated otherwise, the present invention uses reagent, method and apparatus is the art conventional reagent, methods and apparatus.
Unless stated otherwise, following embodiment agents useful for same and material are purchased in market.
Embodiment 1
1, a kind of photo-curable silicone for 3D printing, is prepared by following methods：
(1) prepared by surface modified silicon dioxide nanoparticle
The silicon dioxide nanosphere 2g of the 15nm grain sizes of vapor phase method preparation is taken, ultrasonic disperse is in equipped with 150 mL toluene
In there-necked flask, ultrasonic disperse 30min；After the completion of dispersion, the there-necked flask equipped with condensing unit, agitating device is placed in oil bath,
It is heated to 80 DEG C；6mL surface modifiers (3- mercaptopropyis) triethoxysilane (MPES) is measured, is put into constant pressure funnel, is dripped
It is added in reaction system, time for adding is about 20min；After being added dropwise to complete, the reaction was continued 4h is cooling after the completion of reaction, centrifugation,
With ethyl alcohol and water washing 3~5 times, 50 DEG C of vacuum dryings obtain surface modified silicon dioxide nanoparticle.
(2) photocuring silicon rubber is prepared
Silicone oil (viscosity 500cst, contents of ethylene 0.8mmol/g) 100 mass parts that side chain contains vinyl are taken,
1 mass parts of photoinitiator diphenylethan are added, stirring makes photoinitiator dissolve, above-mentioned surface modified silicon dioxide nanometer is added
0.125 mass parts of microballoon add double 3 mass parts of ethyl mercaptan of small molecule crosslinking agent 2,2 '-(1,2- second diyl dioxygen generation) and four
62.5 mass parts of hydrogen furans are uniformly mixed, and vacuumize removing bubble, obtain the photo-curable silicone for 3D printing.
2, the viscosity of photo-curable silicone made from the present embodiment is about 150cps.When for 3D printing, 1.5s under room temperature
It can cure, and be generated in print procedure and without bad smell after solidification.
Embodiment 2
1, a kind of photo-curable silicone for 3D printing, is prepared by following methods：
(1) prepared by surface modified silicon dioxide nanoparticle
The silicon dioxide nanosphere 2g of the 15nm grain sizes of vapor phase method preparation is taken, ultrasonic disperse is in equipped with 150 mL toluene
In there-necked flask, ultrasonic disperse 30min；After the completion of dispersion, the there-necked flask equipped with condensing unit, agitating device is placed in oil bath,
It is heated to 80 DEG C；8mL surface modifiers (3- mercaptopropyis) triethoxysilane (MPES) is measured, is put into constant pressure funnel, is dripped
It is added in reaction system, time for adding is about 20min；After being added dropwise to complete, the reaction was continued 6h is cooling after the completion of reaction, centrifugation,
With ethyl alcohol and water washing 3~5 times, 50 DEG C of vacuum dryings obtain surface modified silicon dioxide nanoparticle.
(2) photocuring silicon rubber is prepared
Take silicone oil (viscosity 1000cst, contents of ethylene 1.2mmol/g) 100 mass that side chain contains vinyl
Part, 0.8 mass parts of photoinitiator benzoin dimethylether are added, stirring makes photoinitiator dissolve, and above-mentioned surface is added and is modified dioxy
0.1 mass parts of SiClx nanoparticle add small molecule crosslinking agent 2,2 '-(1,2- second diyl dioxygen generation) double 3 mass of ethyl mercaptan
Part and 50 mass parts of tetrahydrofuran are uniformly mixed, and vacuumize removing bubble, obtain the photo-curable silicone for 3D printing.
2, the viscosity of photo-curable silicone made from the present embodiment is about 300cps.When for 3D printing, 2s can under room temperature
With solidification, and generated in print procedure and without bad smell after solidification.
Embodiment 3
1, a kind of photo-curable silicone for 3D printing, is prepared by following methods：
(1) prepared by surface modified silicon dioxide nanoparticle
The silicon dioxide nanosphere 3g of the 30nm grain sizes of vapor phase method preparation is taken, ultrasonic disperse is in equipped with 200 mL toluene
In there-necked flask, ultrasonic disperse 30min；After the completion of dispersion, the there-necked flask equipped with condensing unit, agitating device is placed in oil bath,
It is heated to 80 DEG C；10mL surface modifiers (3- mercaptopropyis) methyldiethoxysilane (MPES) is measured, constant pressure funnel is put into
In, it is added dropwise in reaction system, time for adding is about 30min；After being added dropwise to complete, the reaction was continued 6h is cooling after the completion of reaction,
Centrifugation, with ethyl alcohol and water washing 3~5 times, 50 DEG C of vacuum dryings obtain surface modified silicon dioxide nanoparticle.
(2) photocuring silicon rubber is prepared
Take silicone oil (viscosity 5000cst, contents of ethylene 0.6mmol/g) 100 mass that side chain contains vinyl
Part, 1.3 mass parts of photoinitiator benzoin dimethylether are added, stirring makes photoinitiator dissolve, and above-mentioned surface is added and is modified dioxy
0.15 mass parts of SiClx nanoparticle add small molecule crosslinking agent 1, two mercaptan of 11- hendecanes, 10 mass parts and tetrahydrofuran
50 mass parts are uniformly mixed, and vacuumize removing bubble, obtain the photo-curable silicone for 3D printing.
2, the viscosity of photo-curable silicone made from the present embodiment is about 2000cps.When for 3D printing, 2s can under room temperature
With solidification, and generated in print procedure and without bad smell after solidification.
Embodiment 4
1, a kind of photo-curable silicone for 3D printing, is prepared by following methods：
(1) prepared by surface modified silicon dioxide nanoparticle
The silicon dioxide nanosphere 3g of the 70nm grain sizes of vapor phase method preparation is taken, ultrasonic disperse is in equipped with 200 mL toluene
In there-necked flask, ultrasonic disperse 30min；After the completion of dispersion, the there-necked flask equipped with condensing unit, agitating device is placed in oil bath,
It is heated to 80 DEG C；18mL surface modifiers (3- mercaptopropyis) methyldiethoxysilane (MPES) is measured, constant pressure funnel is put into
In, it is added dropwise in reaction system, time for adding is about 30min；After being added dropwise to complete, the reaction was continued 6h is cooling after the completion of reaction,
Centrifugation, with ethyl alcohol and water washing 3~5 times, 50 DEG C of vacuum dryings obtain surface modified silicon dioxide nanoparticle.
(2) photocuring silicon rubber is prepared
Take silicone oil (viscosity 10000cst, contents of ethylene 1.0mmol/g) 100 mass that side chain contains vinyl
Part, 0.5 mass parts of photoinitiator benzoin dimethylether are added, stirring makes photoinitiator dissolve, and above-mentioned surface is added and is modified dioxy
0.08 mass parts of SiClx nanoparticle add small molecule crosslinking agent 1, two mercaptan of 11- hendecanes, 2 mass parts and tetrahydrofuran 45
Mass parts are uniformly mixed, and vacuumize removing bubble, obtain the photo-curable silicone for 3D printing.
2, the viscosity of photo-curable silicone made from the present embodiment is about 4000cps.When for 3D printing, 2s can under room temperature
With solidification, and generated in print procedure and without bad smell after solidification.
Embodiment 5
1, a kind of photo-curable silicone for 3D printing, is prepared by following methods：
(1) prepared by surface modified silicon dioxide nanoparticle
The silicon dioxide nanosphere 3g of the 100nm grain sizes of vapor phase method preparation is taken, ultrasonic disperse is in equipped with 200 mL toluene
There-necked flask in, ultrasonic disperse 30min；After the completion of dispersion, the there-necked flask equipped with condensing unit, agitating device is placed in oil bath
In, it is heated to 80 DEG C；30mL surface modifiers (3- mercaptopropyis) methyldiethoxysilane (MPES) is measured, constant pressure is put into
It in funnel, is added dropwise in reaction system, time for adding is about 30min；After being added dropwise to complete, the reaction was continued 6h is cold after the completion of reaction
But, it centrifuges, with ethyl alcohol and water washing 3~5 times, 50 DEG C of vacuum dryings obtain surface modified silicon dioxide nanoparticle.
(2) photocuring silicon rubber is prepared
Take silicone oil (viscosity 50000cst, contents of ethylene 1.0mmol/g) 100 mass that side chain contains vinyl
Part, 5 mass parts of photoinitiator benzoin dimethylether are added, stirring makes photoinitiator dissolve, and above-mentioned surface is added and is modified titanium dioxide
0.17 mass parts of silicon nanoparticle add small molecule crosslinking agent 1, two mercaptan of 11- hendecanes, 20 mass parts and tetrahydrofuran 68
Mass parts are uniformly mixed, and vacuumize removing bubble, obtain the photo-curable silicone for 3D printing.
2, the viscosity of photo-curable silicone made from the present embodiment is about 10000cps.When for 3D printing, under room temperature
1.5s can cure, and be generated in print procedure and without bad smell after solidification.
Comparative example 1 is added without surface modified silicon dioxide microballoon
This comparative example is identical as 1 method therefor of embodiment, differs only in the surface modification without preparation process (1)
Silicon dioxide microsphere, step are added without surface modified silicon dioxide microballoon in (2).
Compared with photo-curable silicone 3D printing material made from embodiment 1, the photocuring made from this comparative example is organic
The object that silicon 3D printing file printing obtains, tearing strength are substantially reduced, and cannot meet the needs used.
Unmodified silicon dioxide microsphere is added in comparative example 2
This comparative example is identical as 1 method therefor of embodiment, differs only in the surface modification without preparation process (1)
Silicon dioxide microsphere is directly added into unmodified silicon dioxide microsphere (15 nm of grain size) in step (2).
Compared with photo-curable silicone 3D printing material made from embodiment 1, the photocuring made from this comparative example is organic
The object that silicon 3D printing file printing obtains, although the object that surface modified silicon dioxide microballoon is not added for tearing strength has
It is improved, but raising degree is smaller, still cannot meet the needs used.
Comparative example 3 changes material proportion
This comparative example provides a kind of preparation method of the photo-curable silicone for 3D printing, and the light for being used for 3D printing is solid
Change organosilicon, is prepared by the component including following mass fraction：Side chain contains 100 mass parts of silicone oil of vinyl, small point
Sub- crosslinking agent 2,2 '-(1,2- second diyl dioxygen generation) double 40 mass parts of ethyl mercaptan, 1 mass parts of photoinitiator, surface are modified dioxy
0.125 mass parts of SiClx microballoon, 99.5 mass parts of solvent；Remaining step is consistent with embodiment 1 with operation.
Experimental result shows that there is a small amount of stickum on solidified sample surface, influences to use.
Comparative example 4 changes material proportion
This comparative example provides a kind of preparation method of the photo-curable silicone for 3D printing, and the light for being used for 3D printing is solid
Change organosilicon, is prepared by the component including following mass fraction：Side chain contains 100 mass parts of silicone oil of vinyl, small point
Sub- crosslinking agent 2,2 '-(1,2- second diyl dioxygen generation) double 1 mass parts of ethyl mercaptan, 1 mass parts of photoinitiator, surface are modified titanium dioxide
0.125 mass parts of silicon microballoon, 64.5 mass parts of solvent；Remaining step is consistent with embodiment 1 with operation.
Experimental result shows that sample solidification is incomplete, has and largely has neither part nor lot in reaction, sample size containing vinyl polysiloxane
Not up to require.
Experimental example 3D printing material product the performance test results
The performance data of the photo-curable silicone of 1 present invention of table
Note：The sample curing degree that comparative example 4 obtains is too small, can not carry out measuring mechanical property.
Claims (10)
1. a kind of photo-curable silicone for 3D printing, which is characterized in that by the component preparation including following mass fraction
At：Side chain contains 100 parts of the polysiloxanes of vinyl, 2~20 parts of the small molecule crosslinking agent containing two or more sulfydryls,
0.5~5 part of photoinitiator, 0.08~0.17 part of surface modified silicon dioxide microballoon, 45~68 parts of solvent.
2. the photo-curable silicone according to claim 1 for 3D printing, which is characterized in that by including following mass parts
Several components are prepared：Side chain contains 100 parts of the polysiloxanes of vinyl, the small molecule containing two or more sulfydryls
3~10 parts of crosslinking agent, 0.8~1.3 part of photoinitiator, 0.1~0.15 part of surface modified silicon dioxide microballoon, solvent 50~62.5
Part.
3. the photo-curable silicone according to claim 1 for 3D printing, which is characterized in that the side chain contains second
The viscosity of the polysiloxanes of alkenyl is 500~50000 cst；Its contents of ethylene is 0.6~1.5 mmol/g.
4. the photo-curable silicone according to claim 1 for 3D printing, which is characterized in that it is described containing there are two or two
The small molecule crosslinking agent of a above sulfydryl is selected from trimethylolpropane tris（2- mercaptoacetates）, trimethylolpropane tris（3- mercaptos
Base propionic ester）, 1,4- butanediols it is double（Mercaptoacetate）, 1,6- ethanthiols, pungent two mercaptan of 1,8-, two mercaptan of 1,9- nonyls, 1,
Two mercaptan of the 10- last of the ten Heavenly stems, two mercaptan of 1,11- hendecanes, four（3- mercaptopropionic acids）Pentaerythritol ester, 2,2 '-（1,2- second diyl dioxygens
Generation）One or more of double ethyl mercaptans or glycol dimercaptosuccinate mixture.
5. the photo-curable silicone according to claim 1 for 3D printing, which is characterized in that the photoinitiator is certainly
By fundamental mode photoinitiator.
6. the photo-curable silicone according to claim 1 for 3D printing, which is characterized in that the surface is modified two
Silicon oxide microsphere is prepared by the following method：Silicon dioxide nanosphere and surface modifier are added in toluene, in 60~
110 DEG C of 4~10 h of reaction, cooling, centrifugation, washing, vacuum drying obtain surface modified silicon dioxide microballoon；Wherein, two
The mass volume ratio of silica nanoparticle and surface modifier is 1:3~10.
7. the photo-curable silicone according to claim 6 for 3D printing, which is characterized in that the silica is micro-
The grain size of ball is 15~100 nm；The surface modifier is（3- mercaptopropyis）Triethoxysilane and/or（3- sulfenyls third
Base）Methyldiethoxysilane.
8. according to any photo-curable silicone for being used for 3D printing of claim 1~7, which is characterized in that by including following
The method of step is prepared：
S1. surface modified silicon dioxide microballoon is prepared according to the method described in claim 6；
S2. contain to side chain in the polysiloxanes of vinyl and photoinitiator is added, stir to dissolve, then add successively in proportion
Enter the surface modified silicon dioxide microballoon of step S1, small molecule crosslinking agent and solvent containing two or more sulfydryls, mixes
It closes uniformly, vacuumizes removing bubble, obtain the photo-curable silicone for being used for 3D printing.
9. any photo-curable silicone for 3D printing of claim 1~7 is in terms of the raw material as 3D printing
Using.
10. any photo-curable silicone for 3D printing of claim 1~7 as or in terms of preparing curable product
Using.
Priority Applications (1)
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| CN113817324A (en) * | 2021-10-28 | 2021-12-21 | 中国科学院兰州化学物理研究所 | Photocuring 3D printing silicone rubber ink and preparation method thereof |
| CN113891917A (en) * | 2019-03-20 | 2022-01-04 | 斯派克塑胶股份公司 | Siloxane additive manufacturing composition |
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| CN113817324A (en) * | 2021-10-28 | 2021-12-21 | 中国科学院兰州化学物理研究所 | Photocuring 3D printing silicone rubber ink and preparation method thereof |
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