CN108641369A - A kind of 3D printing light cure silicone rubber and its preparation method and application - Google Patents
A kind of 3D printing light cure silicone rubber and its preparation method and application Download PDFInfo
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- CN108641369A CN108641369A CN201810272878.9A CN201810272878A CN108641369A CN 108641369 A CN108641369 A CN 108641369A CN 201810272878 A CN201810272878 A CN 201810272878A CN 108641369 A CN108641369 A CN 108641369A
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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
- C08K7/16—Solid spheres
- C08K7/18—Solid spheres inorganic
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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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- 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
Abstract
The invention discloses a kind of 3D printing light cure silicone rubbers and its preparation method and application.It is prepared by the component including following mass fraction：Contain 100 parts of the polysiloxanes of vinyl, 1.5~10 parts of the small molecule crosslinking agent containing two or more sulfydryls, 0.3~2 part of photoinitiator, 0.1~2 part of surface modified silicon dioxide microballoon, 50~70 parts of solvent in end.The fast reaction under ultraviolet light cures the polysiloxanes that the present invention contains vinyl using end 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 3D printing light cure silicone rubber and its system
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 3D printing photocuring
Silastic material, lower viscosity, curing rate be fast, without bad smell, 3D printing plastic emitting effect is good, volume after material molding
Shrinking percentage is small, and print procedure does not need backing material, and the product after photocuring is with stronger tearing toughness and properly
Hardness, the 3D printing material of the requirement of Medical filling material can be met.
The object of the present invention is to provide a kind of 3D printing light cure silicone rubber materials.
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 3D printing light cure silicone rubber, is prepared by the component including following mass fraction：Contain second in end
100 parts of the polysiloxanes of alkenyl, 1.5~10 parts of the small molecule crosslinking agent containing two or more sulfydryls, photoinitiator 0.3
~2 parts, 0.1~2 part of surface modified silicon dioxide microballoon, 50~70 parts of solvent.
Based on inventive formulation, science determines the polysiloxanes for containing vinyl in end, 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, 3D printing light cure silicone rubber, is prepared by the component including following mass fraction：End
100 parts of polysiloxanes containing vinyl, 2~5 parts of the small molecule crosslinking agent containing two or more sulfydryls, photoinitiator
0.5~1.2 part, 0.12~0.18 part of surface modified silicon dioxide microballoon, 55~65 parts of solvent.
It is highly preferred that 3D printing light cure silicone rubber, is prepared by the component including following mass fraction：End
100 parts of the polysiloxanes of vinyl is contained in portion, and 3.5 parts of the small molecule crosslinking agent containing two or more sulfydryls is light-initiated
0.95 part of agent, 0.13 part of surface modified silicon dioxide microballoon, 57.5 parts of solvent.
Preferably, the viscosity that the polysiloxanes of vinyl is contained in the end is 600~30000cst；Its contents of ethylene
For 0.08~0.5mmol/g.
It is highly preferred that the viscosity that the polysiloxanes of vinyl is contained in the end is 600~10000cst；Its vinyl contains
Amount is 0.08~0.3mmol/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, 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 3D printing preparation methods of light cure silicone rubber, include the following steps：
S1. silicon dioxide nanosphere and surface modifier are added in toluene, 4~10h is reacted in 60~110 DEG C, it is cold
But, it centrifuges, washing, vacuum drying obtains surface modified silicon dioxide microballoon；Wherein, silicon dioxide nanosphere and table
The mass volume ratio of face modifying agent is 1:3~10；
S2. contain to end 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 3D printing light cure silicone rubber.
The present invention is not specially limited solvent for use, preferably tetrahydrofuran, ethyl acetate etc..
In addition, the 3D printing uses light cure silicone rubber in terms of the raw material as 3D printing, especially as or system
Application in standby curable product, 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 end 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 3D printing light cure silicone rubber, 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 150mL 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 600cst, contents of ethylene 0.08mmol/g) 100 mass parts that vinyl is contained in end are taken,
Photoinitiator α, 0.95 mass parts of α-diethoxy acetophenone is added, stirring makes photoinitiator dissolve, and above-mentioned surface is added and is modified
0.13 mass parts of silicon dioxide nanosphere add small molecule crosslinking agent 2,2 '-(1,2- second diyl dioxygen generation) double ethyl mercaptans
57.5 mass parts of 3.5 mass parts and tetrahydrofuran are uniformly mixed, and vacuumize removing bubble, obtain 3D printing photocuring silicon
Rubber.
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 2
1, a kind of 3D printing light cure silicone rubber, 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 150mL 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
Silicone oil (viscosity 1500cst, contents of ethylene 0.3mmol/g) 100 mass parts that vinyl is contained in end are taken,
0.5 mass parts of photoinitiator benzoin dimethylether are added, stirring makes photoinitiator dissolve, above-mentioned surface modified silicon dioxide is added
0.12 mass parts of nanoparticle, add small molecule crosslinking agent 2,2 '-(1,2- second diyl dioxygen generation) double 2 mass parts of ethyl mercaptan and
55 mass parts of tetrahydrofuran are uniformly mixed, and vacuumize removing bubble, obtain 3D printing light cure silicone rubber.
2, the viscosity of photo-curable silicone made from the present embodiment is about 700cps.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 3
1, a kind of 3D printing light cure silicone rubber, 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 200mL 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
Silicone oil (viscosity 5000cst, contents of ethylene 0.3mmol/g) 100 mass parts that vinyl is contained in end are taken,
1.2 mass parts of photoinitiator benzoin dimethylether are added, stirring makes photoinitiator dissolve, above-mentioned surface modified silicon dioxide is added
0.18 mass parts of nanoparticle add small molecule crosslinking agent 1, two mercaptan of 11- hendecanes, 5 mass parts and 65 mass of tetrahydrofuran
Part, it is uniformly mixed, and vacuumize removing bubble, obtains 3D printing light cure silicone rubber.
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 3D printing light cure silicone rubber, 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 200mL 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
Silicone oil (viscosity 8000cst, contents of ethylene 0.4mmol/g) 100 mass parts that vinyl is contained in end are taken,
0.3 mass parts of photoinitiator benzoin dimethylether are added, stirring makes photoinitiator dissolve, above-mentioned surface modified silicon dioxide is added
0.1 mass parts of nanoparticle add small molecule crosslinking agent 1, two mercaptan of 11- hendecanes, 1.5 mass parts and 50 matter of tetrahydrofuran
Part is measured, is uniformly mixed, and vacuumize removing bubble, obtains 3D printing light cure silicone rubber.
2, the viscosity of photo-curable silicone made from the present embodiment is about 3000cps.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 3D printing light cure silicone rubber, 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 200mL 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；30mL 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 0.5mmol/g) 100 mass that vinyl is contained in end
Part, 2 mass parts of photoinitiator benzoin dimethylether are added, stirring makes photoinitiator dissolve, and above-mentioned surface is added and is modified titanium dioxide
2 mass parts of silicon nanoparticle add small molecule crosslinking agent 1, two mercaptan of 11- hendecanes, 10 mass parts and 70 mass of tetrahydrofuran
Part, it is uniformly mixed, and vacuumize removing bubble, obtains 3D printing light cure silicone rubber.
2, the viscosity of photo-curable silicone made from the present embodiment is about 4000cps.When for 3D printing, 2.5s under room temperature
It 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 (grain size 15nm) 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 3D printing light cure silicone rubber, and the 3D printing is with photocuring silicon rubber
Glue is prepared by the component including following mass fraction：Contain 100 mass parts of silicone oil of vinyl, small molecule crosslinking in end
Agent 2,2 '-(1,2- second diyl dioxygen generation) double 20 mass parts of ethyl mercaptan, 1 mass parts of photoinitiator, surface modified silicon dioxide are micro-
0.125 mass parts of ball, 74 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 3D printing light cure silicone rubber, and the 3D printing is with photocuring silicon rubber
Glue is prepared by the component including following mass fraction：Contain 100 mass parts of silicone oil of vinyl, small molecule crosslinking in end
Agent 2,2 '-(1,2- second diyl dioxygen generation) double 1.25 mass parts of ethyl mercaptan, 1 mass parts of photoinitiator, surface modified silicon dioxide
0.125 mass parts of microballoon, 59.75 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 that comparative example 4 obtains, it is too glutinous, the test of mechanical performance can not be carried out.
Claims (10)
1. a kind of 3D printing light cure silicone rubber, which is characterized in that be prepared by the component including following mass fraction：End
Contain 100 parts of the polysiloxanes of vinyl, 1.5~10 parts of the small molecule crosslinking agent containing two or more sulfydryls, light in portion
0.3~2 part of initiator, 0.1~2 part of surface modified silicon dioxide microballoon, 40~70 parts of solvent.
2. 3D printing according to claim 1 light cure silicone rubber, which is characterized in that by including following mass fraction
Component is prepared：100 parts of the polysiloxanes of vinyl is contained in end, the small molecule crosslinking containing two or more sulfydryls
2~5 parts of agent, 0.5~1.2 part of photoinitiator, 0.12~0.18 part of surface modified silicon dioxide microballoon, 55~65 parts of solvent.
3. 3D printing according to claim 1 light cure silicone rubber, which is characterized in that contain vinyl in the end
The viscosity of polysiloxanes is 600~30000 cst；Its contents of ethylene is 0.08~0.5 mmol/g.
4. 3D printing according to claim 1 light cure silicone rubber, which is characterized in that it is described containing there are two or two with
The small molecule crosslinking agent of upper sulfydryl is selected from trimethylolpropane tris（2- mercaptoacetates）, trimethylolpropane tris（3- sulfydryls third
Acid esters）, 1,4- butanediols it is double（Mercaptoacetate）, 1,6- ethanthiols, pungent two mercaptan of 1,8-, two mercaptan of 1,9- nonyls, the 1,10- last of the ten Heavenly stems
Two mercaptan, two mercaptan of 1,11- hendecanes, four（3- mercaptopropionic acids）Pentaerythritol ester, 2,2 '-（1,2- second diyl dioxygen generations）Double second
One or more of mercaptan or glycol dimercaptosuccinate mixture.
5. 3D printing according to claim 1 light cure silicone rubber, which is characterized in that the photoinitiator is free radical
Type photoinitiator.
6. 3D printing according to claim 5 light cure silicone rubber, which is characterized in that the surface modified silicon dioxide
Microballoon is prepared by the following method：Silicon dioxide nanosphere and surface modifier are added in toluene, in 60~110 DEG C
4~10 h are reacted, it is cooling, it centrifuges, washing, vacuum drying obtains surface modified silicon dioxide microballoon；Wherein, titanium dioxide
The mass volume ratio of silicon nanoparticle and surface modifier is 1:3~10.
7. 3D printing according to claim 5 light cure silicone rubber, which is characterized in that the grain of the silicon dioxide microsphere
Diameter is 15~100 nm；The surface modifier is（3- mercaptopropyis）Triethoxysilane and/or（3- mercaptopropyls）First
Base diethoxy silane.
8. any 3D printing light cure silicone rubber of claim 1~7, which is characterized in that by the side included the following steps
Method is prepared：
S1. surface modified silicon dioxide microballoon is prepared according to the method described in claim 6；
S2. contain to end 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 3D printing light cure silicone rubber.
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 3D printing of claim 1~7 use light cure silicone rubber as or application in preparing curable product.
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| CN109810516A (en) * | 2018-12-29 | 2019-05-28 | 山东大学 | A kind of ultraviolet light cure silicone rubber and preparation method thereof for DIW3D printing |
| CN109810514A (en) * | 2019-01-28 | 2019-05-28 | 中国科学院兰州化学物理研究所 | A kind of photocuring auxiliary is straight to write 3D printing silicon rubber ink and preparation method thereof and a kind of three-dimensional structure silicon rubber |
| 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 |
| CN114717686A (en) * | 2022-03-18 | 2022-07-08 | 湖北灵造三维科技有限公司 | Photocuring 3D printing silicone rubber conductive elastic fiber and preparation method thereof |
| CN115160928A (en) * | 2022-05-13 | 2022-10-11 | 广钢气体(广州)有限公司 | Antibacterial silicone rubber coating and preparation method and application thereof |
| CN115785731A (en) * | 2022-12-01 | 2023-03-14 | 中山大学 | 3D printing magnetic response ink and preparation method and application thereof |
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| CN109810516A (en) * | 2018-12-29 | 2019-05-28 | 山东大学 | A kind of ultraviolet light cure silicone rubber and preparation method thereof for DIW3D printing |
| CN109810514A (en) * | 2019-01-28 | 2019-05-28 | 中国科学院兰州化学物理研究所 | A kind of photocuring auxiliary is straight to write 3D printing silicon rubber ink and preparation method thereof and a kind of three-dimensional structure silicon rubber |
| CN109810514B (en) * | 2019-01-28 | 2020-04-17 | 中国科学院兰州化学物理研究所 | Photocuring-assisted direct-writing 3D printing silicone rubber ink, preparation method thereof and three-dimensional structure silicone rubber |
| 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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| CN114717686A (en) * | 2022-03-18 | 2022-07-08 | 湖北灵造三维科技有限公司 | Photocuring 3D printing silicone rubber conductive elastic fiber and preparation method thereof |
| CN115160928A (en) * | 2022-05-13 | 2022-10-11 | 广钢气体(广州)有限公司 | Antibacterial silicone rubber coating and preparation method and application thereof |
| CN115785731A (en) * | 2022-12-01 | 2023-03-14 | 中山大学 | 3D printing magnetic response ink and preparation method and application thereof |
| CN115785731B (en) * | 2022-12-01 | 2023-10-24 | 中山大学 | 3D printing magnetic response ink and preparation method and application thereof |
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