CN104559196A - Colorless and transparent light-cured 3D printing material - Google Patents
Colorless and transparent light-cured 3D printing material Download PDFInfo
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- CN104559196A CN104559196A CN201410836878.9A CN201410836878A CN104559196A CN 104559196 A CN104559196 A CN 104559196A CN 201410836878 A CN201410836878 A CN 201410836878A CN 104559196 A CN104559196 A CN 104559196A
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Abstract
The invention discloses a colorless and transparent light-cured 3D printing material and belongs to the technical field of cured materials. The printing material comprises organopolysiloxane containing a vinyl group, organopolysiloxane containing a silicon-hydrogen bond, a photoinitiator, reinforcing filler and an aid. A preparation method of the material comprises steps as follows: evenly mixing the organopolysiloxane containing the vinyl group, the organopolysiloxane containing the silicon-hydrogen bond, the reinforcing filler and the aid in percentage by mass; then adding the photoinitiator, and evenly mixing the mixture to obtain the colorless light-cured 3D printing material. The printing material has the benefits as follows: (1) the light-cured product is colorless, good in transparency and elastic; (2) the light-cured material is low in molding shrinkage, and the volume shrinkage is lower than 1.0%; (3) all components in a resin mixture participate in curing, no volatile solvent exists, and pollution is avoided; (4) the printing material is high in curing light source applicability, and the maximum curable light wavelength is 405 nm.
Description
Technical field
The invention belongs to solidify material field, particularly one water white photocuring 3D printed material and preparation method thereof.
Background technology
Organosilicon polymer take siloxane bond as main chain, by half inorganic half organic high molecular compound of silicon and organic group group side chain.The singularity of structure imparts the performance of its many excellence, as high-low temperature resistant, weather-proof, ageing-resistant, corrosion-resistant, low surface tension and physiological inertia etc.Photocuring technology has fast setting, less energy-consumption, high-level efficiency, the advantage such as pollution-free, meeting " 3E " principle: Energy (energy-conservation), Ecology (ecological, environmental protective), Economy (economy) completely, is a kind of eco-friendly green technology.Photocurable Silicone Material due to the excellent properties and photocuring technology having organosilicon material concurrently efficient, energy-conservation, and enjoy favor, and be progressively used widely.The combination of organosilicon material and photocuring technology, the new field that not only made the application extension of organosilicon material arrive, and add new excellent kind for photo-curing material.
In general, photo-curable silicone system forms primarily of 3 kinds of components: the polysiloxane (organosilicon preformed polymer) of photosensitivity, light trigger and reactive thinner.In addition according to concrete purposes, also other filler or auxiliary agent can be added.
Photo-curable silicone is mainly divided into 6 types by its reaction type: sulfydryl-vinyl addition reaction-type, radically curing response type, cationic curing response type, styryl polysiloxane, vinyl ether functional's polysiloxane and Si―H addition reaction type.
(1) sulfydryl-vinyl addition reaction-type organosilicon systems is containing the line-type polymethylvinylsiloxwith of vinyl, and the polymethyl siloxane with containing sulfydryl, under the existence of photosensitizers, solidifies through UV-irradiation.The speed of photoresponse of this system is fast, does not disturb, can form soft whippy cured film by oxygen inhibition.But this system stability in storage is undesirable, and the time is longer, the viscosity of system will increase gradually, and the tensile strength of cured film has a declining tendency; In addition, the mercaptan in this system has strong stink, and the more traditional hydrocarbon system polythiol price of organosilicon polythiol is high, and market is difficult to accept.
(2) radically curing response type organosilicon is mainly acroleic acid esterification polysiloxane, and the advantage of its high reaction activity and low cost has won market, becomes the focus of photosensitivity organosilicon preformed polymer research field.Acrylate-based radical reaction mechanism of can pressing under UV-irradiation reacts.The photocuring reaction of acrylate group is active general higher, and speed of reaction is very fast, and chemistry, the physical stability of cured layer are good, can obtain desirable viscosity, and have certain antioxygen polymerizing power by adjustment formula, cheap.Within 1979, French Rhone-Poulenc company have developed the organic silicon acrylic ester of uV curable.First the organic silicon acrylic ester of radical UV curing introduces to the market as from shape coating (also known as separant, release agent) by nineteen eighty-three Goldschmidt company.But this system in the curing process usually can with volumetric shrinkage, and oxygen inhibition effect is obvious, makes it need the protection of nitrogen when photocuring.
(3) cationic curing response type organosilicon systems contains the linear organopolysiloxane of epoxide group, solidifies under the existence of cationic photoinitiator through UV-irradiation.When there is cationic photopolymerization in epoxy group(ing), the epoxide group with ring strain is opened, and forms tension-free ehter bond, and volumetric shrinkage is very little, is even zero; Therefore, can not produce the such contraction of acroleic acid esterification polysiloxane during the photopolymerization of epoxy-functional polysiloxane, this is the large advantage of one.A lot of work has been done in the synthesis and property of epoxy-functional polysiloxane by GE company, and commercial epoxy-functional polysiloxane is mainly from the said firm.Be usually used in the unsaturated epoxy compound of modified organic silicon oxygen alkane mainly containing vinyl or allylic epoxy compounds, as glycidyl allyl ether, glycidyl acrylate, bicyclo hexene pentadiene and 4-vinyl-1,2-epoxy hexane etc.In addition reaction of silicon with hydrogen process, the existence of platinum catalyst easily causes the generation of heterocycle epoxy polysiloxane, also be easy to epoxy group(ing) ring-opening reaction occurs, this can cause the generation of gel, also make the storage time of epoxy polysiloxane obviously decline, so need to add tertiary amine stabilizers in reaction system simultaneously.
(4) vinyl ethers monomer is containing H
2the monomer of C=CH-O-base.The carbon-carbon double bond of vinyl ether is electron rich double bond, and its reactive behavior, higher than general vinyl monomer, can carry out radical polymerization, cationoid polymerisation and charge-transfer complex alternating copolymerization.Therefore, vinyl ether polysiloxanes can be applied in multiple photocuring system, as free radical system, cationic system and hybrid systems (radically curing and cationic curing exist) simultaneously.Vinyl ether resin is subject to people's attention gradually due to characteristics such as its high reaction activity, hypotoxicity, low smell, high viscosity, but synthesis material vinyl ether price is higher, make vinyl ethers photo-curing material at home photocuring industry still fail obtain generally apply.
(5) styryl also has photosensitivity, and the Styrene and its derivatives of cheapness and many resins have good copolymerized characteristic, can improve cured film hardness and physical strength.If introduced by styryl in polysiloxane molecule, not only can give polysiloxane photosensitivity, also can overcome the shortcoming that pure silicone resin intensity is low.The great advantage of styryl polysiloxane UV curing system is inexpensive.The shortcoming that this photocuring system exists is also more, as high in volatility, inflammableness is high, smell is large, speed of response is slower, and curing performance is also not so good as other photocuring system.
(6) addition reaction of silicon with hydrogen type organosilicon systems curing mechanism be Polymethyl methacrylate containing vinyl and linear poly-hydrogen methylsiloxane under the effect of platinum catalyst, solidify through UV-irradiation.This system, without the need to carrying out photosensitization modification to organo-siloxane, utilizes existing silicone resin to carry out photocuring reaction in the presence of photoinitiators, simplifies reaction process, reduce cost.But research at present mainly concentrates on UV curing system, the organosilicon curing system research for visible light-sensitive is less.
Summary of the invention
Main purpose of the present invention is to provide a kind of water white transparency 3D printed material adopting metal combination photoinitiator;
Another object of the present invention is to provide a kind of and prepares water white transparency and have the method for elastic 3D printed material.
For achieving the above object, the present invention adopts following technical scheme:
A kind of water white photocuring 3D printed material, its formula is as follows:
Further, at least containing two vinyl groups be connected with silane in described every a part of organopolysiloxane containing vinyl group, contents of ethylene is 0.1-10.0wt%, viscosity is 100-10000mPaS, vinyl in vinyl silicone oil is positioned at molecule chain end or is positioned in the middle of molecular chain, comprises the compound of following formula I, II and III:
Wherein R
1, R
2, R
3, R
4, R
5, R
6for identical or different alkyl, such as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, also can be vinyl, phenyl, 3,3,3-trifluoro propyls; Different R3 or R4 makes formula I can be multipolymer; N is integer.
Wherein R
1, R
2, R
3, R
4, R
5, R
6and R
7for identical or different alkyl, such as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, also can be vinyl, phenyl, 3,3,3-trifluoro propyls; Vi is vinyl; N is the integer of>=2, and m is also integer.
Wherein R
1, R
2, R
3, R
4, R
5, R
6and R
7for identical or different alkyl, such as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, also can be vinyl, phenyl; Vi is vinyl; N is the integer of>=2, and m is also integer.
Further, the described organopolysiloxane containing vinyl group comprises the dimethyl polysiloxane of dimethyl ethenyl siloxy end-blocking, the dimethyl siloxane of dimethyl ethenyl siloxy end-blocking and methylphenyl siloxane multipolymer, the dimethyl siloxane of dimethyl ethenyl siloxy end-blocking and the multipolymer of methyl vinyl silicone, the dimethyl siloxane of dimethyl ethenyl siloxy end-blocking and the multipolymer of diphenyl siloxane, the dimethyl siloxane of dimethyl ethenyl siloxy end-blocking and the multipolymer of diphenyl siloxane and methyl vinyl silicone, the dimethyl siloxane of dimethyl ethenyl siloxy end-blocking and the multipolymer of methylphenyl siloxane and methyl vinyl silicone, the vinyl polysiloxane of dimethyl hydroxyl end-blocking, the dimethyl siloxane of dimethyl hydroxyl siloxy end-blocking and the multipolymer of methyl vinyl silicone, the multipolymer of the dimethyl polysiloxane of dimethyl hydroxyl end-blocking and methylphenyl siloxane and methyl vinyl silicone, the dimethyl siloxane of dimethyl hydroxyl siloxy end-blocking and the multipolymer of diphenyl siloxane and methyl vinyl silicone, the vinyl polysiloxane of trimethylsiloxy group end-blocking, the dimethyl siloxane of trimethylsiloxy group end-blocking and the multipolymer of methyl vinyl silicone, the multipolymer of the dimethyl siloxane of trimethylsiloxy group end-blocking and methylbenzene and siloxanes and methyl vinyl silicone, the multipolymer of the dimethyl siloxane of trimethylsiloxy group end-blocking and diphenyl siloxane and diphenyl siloxane and methyl vinyl silicone.
Further, at least containing three hydrogen atoms be connected with silicon in every a part of organopolysiloxane of described silicon-hydrogen bond containing, hydrogen content is 0.3-3.0wt%.Comprise the multipolymer of the multipolymer of the methylhydrogenpolysi,oxane of trimethylsiloxy group end-blocking, the dimethyl siloxane of trimethylsiloxy group end-blocking and methyl hydrogen siloxane, your methylhydrogenpolysi,oxane of dimethyl hydrogen siloxy end-blocking, the dimethyl siloxane of dimethyl hydrogen siloxy end-blocking and methyl hydrogen siloxane, by (CH3)
3siO
1/2segment, (CH3)
2hSiO
1/2segment and SiO
2the multipolymer of segment composition.
Further, described light trigger is the platinum group catalyst of the addition reaction of the polysiloxane rolled into a ball for polysiloxane and the hydrosilyl group-containing of siliceous hydrogen atom, and described platinum group catalyst comprises the title complex of the title complex of Platinic chloride, the title complex of the alcohol of Platinic chloride or ketone solution, Platinic chloride and alkene, Platinic chloride and vinylsiloxane, Platinic chloride and diethyl phthalate.
Further, described reinforcing filler comprises the mixture of one or more in fumed silica, precipitated silica, MQ resin containing vinyl, MT resin, MD resin, MTQ resin, MDQ resin, MDT resin, and reinforcing filler viscosity is 1000--30000mPas.
Further, described auxiliary agent comprises defoamer, flow agent, stablizer, inhibitor.
A preparation method for water white photocuring 3D printed material, its concrete steps are:
(1) by containing the organopolysiloxane of the organopolysiloxane of vinyl, silicon-hydrogen bond containing, reinforcing filler and auxiliary agent mixing and stirring by mass percentage;
(2) add light trigger again, be uniformly mixed, obtain non-colored light solidification 3D printed material.
Compared with the preparation technology of water white transparency photocuring 3D printed material in prior art, the feature of preparation technology of the present invention is: (1) water white transparency 3D printed material adopts metal combination photoinitiator to cause addition reaction of silicon with hydrogen, curing reaction speed is fast, and curable optical source wavelength scope is large; (2) molding shrinkage is low, cured product water white transparency, and has elasticity; (3) non-volatility solvent, photosensitive resin composition all participates in solidification, and VOC free discharges, pollution-free.
Compared with prior art, the beneficial effect of photocuring 3D printed material of the present invention is: photo-cured products is colourless, and the transparency is got well and had elasticity; After photocuring, forming materials shrinking percentage is low, and volumetric shrinkage is lower than 1.0%; In resin compound, all components all participates in solidification, and non-volatility solvent is pollution-free; Wide to curing light source suitability, the longest 405nm of curable optical wavelength.
The present invention is in order to improve the application performance of photo-curable silicone system, metal combination photoinitiator is adopted to cause addition reaction of silicon with hydrogen, and improved the formula of 3D printed material, improve the stability of photo-curable silicone system as far as possible, improve curing speed and the shaping efficiency of 3D printed material.
The curable optical source wavelength scope of the water white transparency photocuring 3D printed material in the present invention is large, curing reaction speed is fast, the stability of significant increase photo-curable silicone system and range of application.
In addition, " part " and " % " in the present invention, if no special instructions, refers to weight basis respectively.
Embodiment
Embodiment 1
Preparation technology:
(1) dimethyl polysiloxane of 70g dimethyl ethenyl siloxy end-blocking, the methylhydrogenpolysi,oxane of 12g trimethylsiloxy group end-blocking, 7g fumed silica, 8g inhibitor mixed are stirred.
(2) add the alcoholic solution of 3g Platinic chloride in the mixture obtained in (1), be uniformly mixed, water white photocuring 3D printed material can be obtained.
Be applied in container on photocuring 3D printer by this photocuring 3D printed material, print test at 25 DEG C, solidification rate is fast, and the molded article transparency is general, and intensity is high.
Embodiment 2
The dimethyl siloxane of dimethyl ethenyl siloxy end-blocking and methylphenyl siloxane multipolymer
Preparation technology:
(1) by the multipolymer of the dimethyl siloxane of the dimethyl siloxane of 65g dimethyl ethenyl siloxy end-blocking and methylphenyl siloxane multipolymer, 20g trimethylsiloxy group end-blocking and methyl hydrogen siloxane, 10g containing MQ resin, the 4g defoamer mixing and stirring of vinyl.
(2) add the title complex of 1g Platinic chloride and diethyl phthalate in the mixture obtained in (1), be uniformly mixed, water white photocuring 3D printed material can be obtained.
Be applied in container on photocuring 3D printer by this photocuring 3D printed material, print test at 25 DEG C, solidification rate is fast, and the molded article transparency is good, and intensity is high.
Embodiment 3
Preparation technology:
(1) dimethyl polysiloxane of 40g dimethyl ethenyl siloxy end-blocking, the methylhydrogenpolysi,oxane of 30g trimethylsiloxy group end-blocking, 20g fumed silica, 9.999g inhibitor mixed are stirred.
(2) add the alcoholic solution of 0.001g Platinic chloride in the mixture obtained in (1), be uniformly mixed, water white photocuring 3D printed material can be obtained.
Be applied in container on photocuring 3D printer by this photocuring 3D printed material, print test at 25 DEG C, solidification rate is slow, and the molded article transparency is general, and intensity is low.
Embodiment 4
Preparation technology:
(1) by the multipolymer of the dimethyl siloxane of the dimethyl siloxane of 74.9g dimethyl ethenyl siloxy end-blocking and methylphenyl siloxane multipolymer, 5g trimethylsiloxy group end-blocking and methyl hydrogen siloxane, 0.1g containing MQ resin, the 10g defoamer mixing and stirring of vinyl.
(2) add the title complex of 10g Platinic chloride and diethyl phthalate in the mixture obtained in (1), be uniformly mixed, water white photocuring 3D printed material can be obtained.
Be applied in container on photocuring 3D printer by this photocuring 3D printed material, print test at 25 DEG C, solidification rate is fast, and the molded article transparency is good, and intensity is general.
Embodiment 5
Preparation technology:
(1) dimethyl polysiloxane of 90g dimethyl ethenyl siloxy end-blocking, the methylhydrogenpolysi,oxane of 5g trimethylsiloxy group end-blocking, 1.5g fumed silica, 0.5g inhibitor mixed are stirred.
(2) add the alcoholic solution of 3g Platinic chloride in the mixture obtained in (1), be uniformly mixed, water white photocuring 3D printed material can be obtained.
Be applied in container on photocuring 3D printer by this photocuring 3D printed material, print test at 25 DEG C, solidification rate is fast, and the molded article transparency is general, and intensity is general.
Claims (8)
1. a water white photocuring 3D printed material, is characterized in that: the component comprising following mass percent:
2. a kind of water white photocuring 3D printed material as claimed in claim 1, it is characterized in that: at least containing two vinyl groups be connected with silane in described every a part of organopolysiloxane containing vinyl group, contents of ethylene is 0.1-10.0wt%, viscosity is 100-10000mPaS, vinyl in vinyl silicone oil is positioned at molecule chain end or is positioned in the middle of molecular chain, comprises the compound of following formula I, II and III:
Wherein R
1, R
2, R
3, R
4, R
5, R
6for identical or different alkyl, n is integer;
Wherein R
1, R
2, R
3, R
4, R
5, R
6and R
7for identical or different alkyl, Vi is vinyl, and n is the integer of>=2, and m is also integer;
Wherein R
1, R
2, R
3, R
4, R
5, R
6and R
7for identical or different alkyl, Vi is vinyl; N is the integer of>=2, and m is also integer.
3. the one water white photocuring 3D printed material as described in as arbitrary in claim 1 or 2, it is characterized in that: the described organopolysiloxane containing vinyl group comprises the dimethyl polysiloxane of dimethyl ethenyl siloxy end-blocking, the dimethyl siloxane of dimethyl ethenyl siloxy end-blocking and methylphenyl siloxane multipolymer, the dimethyl siloxane of dimethyl ethenyl siloxy end-blocking and the multipolymer of methyl vinyl silicone, the dimethyl siloxane of dimethyl ethenyl siloxy end-blocking and the multipolymer of diphenyl siloxane, the dimethyl siloxane of dimethyl ethenyl siloxy end-blocking and the multipolymer of diphenyl siloxane and methyl vinyl silicone, the dimethyl siloxane of dimethyl ethenyl siloxy end-blocking and the multipolymer of methylphenyl siloxane and methyl vinyl silicone, the vinyl polysiloxane of dimethyl hydroxyl end-blocking, the dimethyl siloxane of dimethyl hydroxyl siloxy end-blocking and the multipolymer of methyl vinyl silicone, the multipolymer of the dimethyl polysiloxane of dimethyl hydroxyl end-blocking and methylphenyl siloxane and methyl vinyl silicone, the dimethyl siloxane of dimethyl hydroxyl siloxy end-blocking and the multipolymer of diphenyl siloxane and methyl vinyl silicone, the vinyl polysiloxane of trimethylsiloxy group end-blocking, the dimethyl siloxane of trimethylsiloxy group end-blocking and the multipolymer of methyl vinyl silicone, the multipolymer of the dimethyl siloxane of trimethylsiloxy group end-blocking and methylbenzene and siloxanes and methyl vinyl silicone, the multipolymer of the dimethyl siloxane of trimethylsiloxy group end-blocking and diphenyl siloxane and diphenyl siloxane and methyl vinyl silicone.
4. a kind of water white photocuring 3D printed material as claimed in claim 1, it is characterized in that: at least containing three hydrogen atoms be connected with silicon in every a part of organopolysiloxane of described silicon-hydrogen bond containing, hydrogen content is 0.3-3.0wt%, comprise the methylhydrogenpolysi,oxane of trimethylsiloxy group end-blocking, the dimethyl siloxane of trimethylsiloxy group end-blocking and the multipolymer of methyl hydrogen siloxane, your methylhydrogenpolysi,oxane of dimethyl hydrogen siloxy end-blocking, the dimethyl siloxane of dimethyl hydrogen siloxy end-blocking and the multipolymer of methyl hydrogen siloxane, by (CH3) 3SiO1/2 segment, (CH3) multipolymer of 2HSiO1/2 segment and SiO2 segment composition.
5. a kind of water white photocuring 3D printed material as claimed in claim 1, it is characterized in that: described light trigger is platinum group catalyst, described platinum group catalyst comprises the title complex of the title complex of Platinic chloride, the title complex of the alcohol of Platinic chloride or ketone solution, Platinic chloride and alkene, Platinic chloride and vinylsiloxane, Platinic chloride and diethyl phthalate.
6. a kind of water white photocuring 3D printed material as claimed in claim 1, it is characterized in that: described reinforcing filler comprises the mixture of one or more in fumed silica, precipitated silica, MQ resin containing vinyl, MT resin, MD resin, MTQ resin, MDQ resin, MDT resin, and reinforcing filler viscosity is 1000--30000mPas.
7. a kind of water white photocuring 3D printed material as claimed in claim 1, is characterized in that: described auxiliary agent comprises defoamer, flow agent, stablizer, inhibitor.
8. the preparation method of a kind of water white photocuring 3D printed material as claimed in claim 1, is characterized in that: comprise the following steps:
(1) by containing the organopolysiloxane of the organopolysiloxane of vinyl, silicon-hydrogen bond containing, reinforcing filler and auxiliary agent mixing and stirring by mass percentage;
(2) add light trigger again, be uniformly mixed, obtain non-colored light solidification 3D printed material.
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