CN105601830A - Photocuring material and application thereof - Google Patents
Photocuring material and application thereof Download PDFInfo
- Publication number
- CN105601830A CN105601830A CN201610149725.6A CN201610149725A CN105601830A CN 105601830 A CN105601830 A CN 105601830A CN 201610149725 A CN201610149725 A CN 201610149725A CN 105601830 A CN105601830 A CN 105601830A
- Authority
- CN
- China
- Prior art keywords
- photo
- curing material
- curing
- material according
- hyperbranched
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
- C04B35/565—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/60—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which all the silicon atoms are connected by linkages other than oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/16—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers in which all the silicon atoms are connected by linkages other than oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
- C04B2235/602—Making the green bodies or pre-forms by moulding
- C04B2235/6026—Computer aided shaping, e.g. rapid prototyping
Abstract
The invention relates to a photocuring material which comprises the following components in percentage by weight: 60-98% of hyperbranched polycarbosilane, 0-35% of active diluent, 0.1-8% of photoinitiator and 0-10% of additive, wherein the hyperbranched polycarbosilane contains an unsaturated double bond, and the number-average molecular weight of the hyperbranched polycarbosilane is 300-15,000; the unsaturated double bond is acryloyloxy, methylacryloyloxy, vinyl or allyl; and the content of the unsaturated double bond in the hyperbranched polycarbosilane is 1-30% by weight. The invention also relates to an application of the photocuring material in photocuring 3D printing and an application in preparation of a SiC component. The photocuring material provided by the invention has relatively low viscosity and is convenient to spray out of a nozzle of 3D printing equipment while the curing speed is high and the shrinkage rate in curing is little.
Description
Technical field
The present invention relates to curing materials field, be specifically related to a kind of photo-curing material and application thereof.
Background technology
3D print due to can produce rapidly the member of any complicated shape, without mould, produce fewWaste material, simple to operate, shaping speed is fast, forming process is pollution-free and tool in non-mass productionThere are obvious cost and odds for effectiveness, become the study hotspot of current rapid shaping technique. Photocuring 3DThe forming principle of printing technique is to utilize liquid photo-curing material that polymerization occurs fast under light irradiation, and light is solidFormed material changes into rapidly solid-state by liquid state.
Photocuring 3D prints the photo-curing material of use generally by photosensitive resin, reactive diluent (active listBody), light trigger and additive composition. Chinese invention patent (CN104559196A) is open a kind ofWater white photocuring 3D printed material, belongs to curing materials technical field. This printed material comprises and containingThe organopolysiloxane of vinyl group, the organopolysiloxane of silicon-hydrogen bond containing, light trigger, reinforcer,Auxiliary agent. Chinese invention patent (CN102516866A) discloses a kind of ultraviolet photocureable material, comprise asThe component of lower percentage by weight: light-cured resin 40～60%; Photocuring diluent 25～45%; Light-initiatedAgent 2～10%; Ultraviolet light stable storage agent 0～0.8%; Nano filling 0.5～30%; Levelling agent 0.2～1%.
Photosensitive resin is of paramount importance composition in photo-curing material, to the physical and chemical performance of resulting devicesPlay conclusive effect. Current, what photocuring 3D printed use is the height containing unsaturated double-bond substantiallyMolecule photosensitive resin, as unsaturated polyester (UP), epoxy acrylic resin, polyurethane acrylic resin, polyesterAcrylic resin, polyoxyalkylene acrylate resin etc. But unsaturated polyester (UP) photo-curing rate is slow, easily shrinkAnd resistance to acids and bases is poor; Epoxy acrylic resin pliability is poor; Polyester acrylic resin yellowing resistance is poor; Poly-Although urethane acrylate resin has preferably combination property, its photo-curing rate is slow and viscosity is also higher;Mechanical strength, hardness and the chemical-resistant of polyoxyalkylene acrylate resin are poor. In addition, at some special dimensions,Need high accuracy, high-fire resistance and high-intensity parts, these polymer-based photosensitive resins just can not be expiredFoot requirement.
In general, the kind of photosensitive resin that is applicable to now photocuring 3D printing technique is less, can fitWith photosensitive resin do not catch up with development and the demand in market, so be badly in need of that development of new is high performance to be usedThe photosensitive resin of photocuring 3D printing technique moulding. Liquid hyperbranched Polycarbosilane room temperature good fluidity,Can long term storage under normal temperature, viscosity is low, toxicity is little, non-volatile, while solidifying shrinkage factor very little, solidify afterCrosslink density is large, and has the advantages such as high rigidity, high-wearing feature and chemical-resistant. But, by orderBefore, only have the document of little ultraviolet light polymerization about hyperbranched Polycarbosilane, and just study its purpleOuter photo-cur ing kinetics, and the impact on its conversion ratio and solidification rate such as light intensity, temperature, and do not haveReport uses hyperbranched Polycarbosilane as the photosensitive resin of photocuring 3D printed material.
Summary of the invention
The object of the invention is to for the deficiencies in the prior art, provide a kind of novel photo-curing material andIts application in photocuring 3D printing and preparation SiC member.
The technical scheme that the present invention solves the problems of the technologies described above is as follows:
A kind of photo-curing material, comprises following component:
Described hyperbranched Polycarbosilane is the hyperbranched Polycarbosilane containing unsaturated double-bond, hyperbranched poly carbonThe number-average molecular weight of silane is between 300-15000; Described unsaturated double-bond is acryloxy, methyl-propAlkene acyloxy, vinyl or pi-allyl, in hyperbranched Polycarbosilane, the content of unsaturated double-bond is 1-30wt％。
Hyperbranched Polycarbosilane containing unsaturated double-bond is to have highly branched large molecule, due to the degree of branchingHeight, molecular entanglement is few, and therefore, compared with the linear Polycarbosilane of same molecular amount, its viscosity is much lower,Conveniently from the shower nozzle of 3D printing device, eject; Secondly, crosslinkable work in hyperbranched PolycarbosilaneThe density of property group is large, and curing rate is fast; Hyperbranched Polycarbosilane has the apparatus derivatorius of height simultaneously,While solidifying, shrinkage factor is very little.
As preferably, described photo-curing material comprises following component:
According to the above ratio hyperbranched Polycarbosilane, reactive diluent, light trigger and additive machinery are stirredAfter mixing and mixing, get final product to obtain photo-curing material, the preparation method of this photo-curing material is simple.
As preferably, preparation method's bibliography (ChineseChemical of described hyperbranched PolycarbosilaneLetters, 2007,18,754-757.) and (Polymer, 2006,47,1519-1525.).
As preferably, described light trigger is selected from ultraviolet initiator or visible light initiator; DescribedUltraviolet initiator is selected from the one in 1-hydroxy-cyclohexyl phenyl ketone, benzophenone, diphenylhydroxyethanoneOr two kinds; Described visible light initiator is selected from two luxuriant or two [fluoro-3-(1H-of 2,6-bis-of (pentafluorophenyl group) titaniumPyrrole radicals-1) phenyl] titanium is luxuriant. Light trigger is a kind of energy absorbed radiation energy, chemistry occurs after exciting and becomeChange and produce the material of the reactive intermediate (free radical or cation) with initiated polymerization ability. Therefore,Light trigger is necessity composition of photo-curing material, and it plays decision to the photo-curing rate of photo-curing materialProperty effect.
As preferably, described reactive diluent is acrylate-based for containing, methacrylate based, secondThe monomer of thiazolinyl or ethyleneoxy. Reactive diluent is commonly referred to monomer or functional monomer, and it is a kind ofThe organic molecule that contains polymerizable functional group, in the various components of photo-curing material, it not only plays moltenSeparate and dilute the effect of photosensitive resin or regulation system viscosity, and can participate in Light Curing and affect lightThe photo-curing rate of curing materials and various performance, therefore selecting suitable reactive diluent is also photocuringThe important step of material prescription design. As further preferred, described reactive diluent is selected from two contractings threePropylene glycol diacrylate or diethoxy bisphenol a diacrylate.
As preferably, described additive be aided initiating, defoamer, antioxidant, levelling agent, pointOne or more in powder, delustering agent, stabilizing agent, filler, pigment, sintering aid. Though additiveThe ratio so accounting in photo-curing material is very little, but they play important work to the various performances of improving productWith.
As further preferred, described additive is aided initiating CN373, defoamer poly dimethyl siliconOxygen alkane or silicon carbide powder filler.
The invention provides the application that a kind of photo-curing material is printed for photocuring 3D.
The present invention also provides the application of a kind of photo-curing material for the preparation of SiC member. As preferably, profitPhoto-curing material is ejected on backing material with 3D printer, under visible ray or action of ultraviolet light, solidifiesBe shaped, through successively pile up after form 3 D stereo member, and by 3 D stereo member under oxygen free condition,1000～2000 DEG C of insulation 20～360min, obtain SiC member. As preferably, described ultraviolet light is500～700W medium pressure mercury lamp.
Through the stereochemical structure of crosslinked hyperbranched Polycarbosilane energy formation rule, in high-temperature sintering processKeep its dimensionally stable, and after being unlikely to resolve into little molecule segment, volatilization is overflowed, in addition, hyperbranched polyCarbon silane has very high ceramic yield and ceramic product approaches SiC stoichiometric proportion, so very applicableAs the precursor of SiC material.
Compared with the existing technology, beneficial effect of the present invention is embodied in:
(1) be highly branched large molecule containing the hyperbranched Polycarbosilane of unsaturated double-bond, due to the degree of branchingHeight, molecular entanglement is few, and therefore, compared with the linear Polycarbosilane of same molecular amount, its viscosity is much lower,The photo-curing material preparing can conveniently eject from the shower nozzle of 3D printing device;
(2) photo-curing material preparing, the density with crosslinkable active group is large, solidifies speedDegree is fast, and shrinkage factor is very little when curing;
(3) photo-curing material preparing, solidify after crosslink density large, therefore have Heat stability is good,The advantages such as high rigidity, high abrasion and chemical-resistant are good;
(4) photo-curing material is printed the member forming through 3D, can adopt high-sintering process to make high propertyThe SiC member of energy.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described in further detail, it is important to point out enforcementExample, only for the present invention is further detailed, can not be interpreted as limiting the scope of the invention.
Embodiment 1:
Step 1: synthetic containing the hyperbranched Polycarbosilane of vinyl
Bibliography (ChineseChemicalLetters, 2007,18,754-757.) is synthetic containing vinylHyperbranched Polycarbosilane, concrete steps are: magnesium chips (1.04mol) is added containing CH2＝CHCH2Cl(0.12mol)、Cl3SiCH2Cl (0.46mol) and Cl2Si(CH3)CH2The oxolane (200 of Cl (0.23mol)ML), in solvent, in 60 DEG C of reactions 12 hours, in ice-water bath, add afterwards lithium aluminium hydride reduction (0.37mol),And continue at 60 DEG C reaction 12 hours. After reaction finishes, pouring reaction solution into concentration is 4mol/LAqueous hydrochloric acid solution in and stir, stir after 2 hours, Xiang Shuizhong adds n-hexane (500mL), staticLayering, isolates organic phase and adopts dried over sodium sulfate, finally in 60 DEG C of dry obtaining containing vinyl of vacuumHyperbranched Polycarbosilane. Synthetic route is as follows (be it should be noted that, because dissaving structure is manyBecome and complexity, the structure shown in following synthetic route is only example).
Through characterizing, the number-average molecular weight that contains the hyperbranched Polycarbosilane of vinyl is 854, and weight average molecular weight is3658, viscosity at ambient temperature is 0.0356Pas, and the content of vinyl is 8.0wt%.
Step 2: the preparation of photo-curing material
The formula of photo-curing material is: hyperbranched Polycarbosilane (92wt%), ultraviolet light containing vinyl drawSend out agent 1-hydroxy-cyclohexyl phenyl ketone (4wt%) and benzophenone (3.6wt%), aided initiating CN373(0.4wt%), above-mentioned raw materials shading is mixed and normal temperature mechanical agitation 2h.
Step 3: photocuring 3D prints
Above-mentioned photo-curing material in nozzle operation chamber forms droplet fast, then with certain speed andFrequency is ejected on backing material, under ultraviolet light (light source is 600W medium pressure mercury lamp) effect, is solidified intoShape forms 3 D stereo member after successively piling up. Through characterizing, its shore hardness is 80HD, stretchesIntensity is 90MPa, and stretch modulus is 1.55GPa, and heat distortion temperature is 296 DEG C, and cure shrinkage is0.6% and profiled member without buckling deformation.
Embodiment 2:
Step 1: the synthetic hyperbranched Polycarbosilane containing acryloxy
Bibliography (ChineseChemicalLetters, 2007,18,754-757.), synthetic containing Si-Cl keyHyperbranched Polycarbosilane, reference literature (Polymer, 2006,47,1519 – 1525) afterwards, obtains containing thirdThe hyperbranched Polycarbosilane of alkene acyloxy, concrete steps are: magnesium chips (1.0mol) is added and containedCH3CH2CH2Cl(0.20mol)，Cl3SiCH2Cl(0.15mol)，Cl2Si(CH3)CH2Cl(0.45mol)Oxolane (200mL) solvent in, in 60 DEG C reaction 12 hours, in ice-water bath, add afterwards2-hydroxyethylmethacry,ate (0.6mol) and pyridine (0.6mol) also react 1.5 hours. Reaction finishesAfter, remove by filter insoluble matter, filtrate is poured in the aqueous hydrochloric acid solution that concentration is 4mol/L and stirred, stirMix after 2 hours, Xiang Shuizhong adds n-hexane (500mL), and static layering is isolated organic phase and adoptsDried over sodium sulfate, finally in 60 DEG C of dry hyperbranched Polycarbosilanes that obtain containing acryloxy of vacuum. CloseBecome route as follows (it should be noted that, because dissaving structure is changeable, synthetic road as followsStructure in line is only example).
Through characterizing, the number-average molecular weight that contains the hyperbranched Polycarbosilane of acryloxy is 732, weight average moleculeAmount is 3241, and viscosity at ambient temperature is 0.0272Pas, and the content of acryloxy is 21.1wt%.
Step 2: the preparation of photo-curing material
The formula of photo-curing material is: containing hyperbranched Polycarbosilane (95.6wt%), the purple of acryloxyOuter light trigger diphenylhydroxyethanone (4wt%), aided initiating CN373 (0.4wt%), by above-mentioned raw materialsShading mixes and normal temperature mechanical agitation 2h.
Step 3: photocuring 3D prints
Above-mentioned photo-curing material in nozzle operation chamber forms droplet fast, then with certain speed andFrequency is ejected on backing material, under ultraviolet light (light source is 600W medium pressure mercury lamp) effect, is solidified intoShape forms 3 D stereo member after successively piling up. Through characterizing, its shore hardness is 93HD, stretchesIntensity is 105MPa, and stretch modulus is 1.73GPa, and heat distortion temperature is greater than 300 DEG C, cure shrinkageRate be 0.8% and profiled member without buckling deformation.
Step 4: sintering process
The 3 D stereo member of above-mentioned moulding is risen to 1200 DEG C with 10 DEG C/min speed, and in 1200 DEG CInsulation 2h, rises to 1800 DEG C with 5 DEG C/min speed afterwards, and in 1800 DEG C of insulation 1h, finalTo the SiC member of high performance 3 D stereo.
Embodiment 3:
Step 1: with reference to the synthetic hyperbranched Polycarbosilane containing vinyl of embodiment 1
Step 2: the preparation of photo-curing material
The formula of photo-curing material is: containing the hyperbranched Polycarbosilane (82wt%) of vinyl, active dilutionAgent tri (propylene glycol) diacrylate (10wt%), ultraviolet initiator 1-hydroxy-cyclohexyl phenyl ketone(4wt%) and benzophenone (3.6wt%), aided initiating CN373 (0.4wt%). By above-mentioned raw materialsShading mixes and normal temperature mechanical agitation 2h.
Step 3: photocuring 3D prints
Above-mentioned photo-curing material in nozzle operation chamber forms droplet fast, then with certain speed andFrequency is ejected on backing material, under ultraviolet light (light source is 600W medium pressure mercury lamp) effect, is solidified intoShape forms 3 D stereo member after successively piling up. Through characterizing, its shore hardness is 86HD, stretchesIntensity is 89MPa, and stretch modulus is 1.56GPa, and heat distortion temperature is greater than 300 DEG C, cure shrinkageBe 0.7% and profiled member without buckling deformation.
Embodiment 4:
Step 1: with reference to the synthetic hyperbranched Polycarbosilane containing vinyl of embodiment 1
Step 2: the preparation of photo-curing material
The formula of photo-curing material is: containing the hyperbranched Polycarbosilane (80wt%) of vinyl, active dilutionTwo (pentafluorophenyl group) titaniums of agent diethoxy bisphenol a diacrylate (16wt%), visible light initiator are luxuriant(3.5wt%), defoamer dimethyl silicone polymer (0.5wt%), by above-mentioned raw materials shading mix and normal temperatureMechanical agitation 2h.
Step 3: photocuring 3D prints
Above-mentioned photo-curing material in nozzle operation chamber forms droplet fast, then with certain speed andFrequency is ejected on backing material, and solidified forming under radiation of visible light forms three-dimensional after successively piling upThree-dimensional member. Through characterizing, its shore hardness is 83HD, and hot strength is 87MPa, and stretch modulus is1.63GPa, 284 DEG C of heat distortion temperatures, cure shrinkage be 0.7% and profiled member without buckling deformation.
Embodiment 5:
Step 1: with reference to the synthetic hyperbranched Polycarbosilane containing acryloxy of embodiment 2
Step 2: the preparation of photo-curing material
The formula of photo-curing material is: containing the hyperbranched Polycarbosilane (90wt%) of acryloxy, visibleTwo [the fluoro-3-of 2,6-bis-(1H-pyrrole radicals-1) phenyl] titaniums luxuriant (3.5wt%) of light trigger, the poly-diformazan of defoamerRadical siloxane (0.5wt%), particle diameter are the silicon carbide powder (6wt%) of 1 micron, and above-mentioned raw materials is hiddenLight mixes and normal temperature mechanical agitation 2h.
Step 3: photocuring 3D prints
Above-mentioned photo-curing material in nozzle operation chamber forms droplet fast, then with certain speed andFrequency is ejected on backing material, and solidified forming under radiation of visible light forms three-dimensional after successively piling upThree-dimensional member. Through characterizing, its shore hardness is 96HD, and hot strength is 98MPa, and stretch modulus is1.84GPa, heat distortion temperature is greater than 300 DEG C, cure shrinkage be 0.5% and profiled member without buckling deformation.
Step 4: sintering process
The 3 D stereo member of above-mentioned moulding is risen to 1200 DEG C with 10 DEG C/min speed, and in 1200 DEG CInsulation 2h, rises to 1600 DEG C with 5 DEG C/min speed afterwards, and in 1600 DEG C of insulation 4h, finalTo the SiC member of high performance 3 D stereo.
From above-described embodiment, can find out, adopt photo-curing material of the present invention can obtain after 3D printsTo good heat resistance, hardness is high, mechanical performance is excellent and cure shrinkage is little member, and again through high temperatureSintering process can further be made high performance SiC member.
Claims (10)
1. a photo-curing material, is characterized in that, comprises following component:
Described hyperbranched Polycarbosilane is the hyperbranched Polycarbosilane containing unsaturated double-bond, hyperbranched poly carbonThe number-average molecular weight of silane is between 300-15000; Described unsaturated double-bond is acryloxy, methyl-propAlkene acyloxy, vinyl or pi-allyl, in hyperbranched Polycarbosilane, the content of unsaturated double-bond is 1-30wt％。
2. photo-curing material according to claim 1, is characterized in that, described photo-curing materialComprise following component:
3. photo-curing material according to claim 1 and 2, is characterized in that, described is light-initiatedAgent is selected from ultraviolet initiator or visible light initiator; Described ultraviolet initiator is selected from 1-hydroxyl hexamethyleneOne or both in base phenyl ketone, benzophenone, diphenylhydroxyethanone; Described visible light initiatorBe selected from two (pentafluorophenyl group) titanium luxuriant or two [the fluoro-3-of 2,6-bis-(1H-pyrrole radicals-1) phenyl] titaniums luxuriant.
4. photo-curing material according to claim 1 and 2, is characterized in that, described active leanRelease agent and be selected from the monomer that contains acrylate-based, methacrylate based, vinyl or ethyleneoxy.
5. photo-curing material according to claim 4, is characterized in that, described reactive diluentBe selected from tri (propylene glycol) diacrylate or diethoxy bisphenol a diacrylate.
6. photo-curing material according to claim 1 and 2, is characterized in that, described additiveFor aided initiating, defoamer, antioxidant, levelling agent, dispersant, delustering agent, stabilizing agent, filler,One or more in pigment, sintering aid.
7. photo-curing material according to claim 6, is characterized in that, described additive is for helpingInitator CN373, defoamer dimethyl silicone polymer or silicon carbide powder filler.
8. what the photo-curing material as described in as arbitrary in claim 1～7 was printed for photocuring 3D shouldWith.
9. the photo-curing material as described in as arbitrary in claim 1～7 is for the preparation of the application of SiC member.
10. photo-curing material according to claim 9 is for the preparation of the application of SiC member, its spyLevy and be, utilize 3D printer that photo-curing material is ejected on backing material, at visible ray or ultraviolet lightThe lower solidified forming of effect forms 3 D stereo member after successively piling up, and by 3 D stereo member in nothingUnder oxygen condition, 1000～2000 DEG C of insulation 20～360min, obtain SiC member.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610149725.6A CN105601830B (en) | 2016-01-07 | 2016-03-16 | A kind of photo-curing material and its application |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2016100111855 | 2016-01-07 | ||
| CN201610011185 | 2016-01-07 | ||
| CN201610149725.6A CN105601830B (en) | 2016-01-07 | 2016-03-16 | A kind of photo-curing material and its application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105601830A true CN105601830A (en) | 2016-05-25 |
| CN105601830B CN105601830B (en) | 2018-10-02 |
Family
ID=55982230
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610149725.6A Active CN105601830B (en) | 2016-01-07 | 2016-03-16 | A kind of photo-curing material and its application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105601830B (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106047094A (en) * | 2016-07-21 | 2016-10-26 | 苏州泰仑电子材料有限公司 | UV (Ultraviolet) cured protective film capable of reducing final viscosity and preparation method thereof |
| CN106398574A (en) * | 2016-09-06 | 2017-02-15 | 哈尔滨工业大学无锡新材料研究院 | Polyacrylate pressure-sensitive adhesive and preparation method thereof |
| CN108147830A (en) * | 2018-01-17 | 2018-06-12 | 龙泉市金宏瓷业有限公司 | A kind of 3D printing ceramic setter composite material and preparation method thereof |
| CN109280395A (en) * | 2017-07-19 | 2019-01-29 | 北京恒创增材制造技术研究院有限公司 | A kind of product and preparation method thereof of photocurable quick shaping process preparation |
| CN109970450A (en) * | 2019-03-28 | 2019-07-05 | 天津大学 | A kind of light sensitive ceramics liquid and its ceramic member for 3D printing |
| CN110092873A (en) * | 2019-05-16 | 2019-08-06 | 广东工业大学 | A kind of photosensitive resin ceramics and its Stereo Lithography preparation method |
| CN110204730A (en) * | 2019-05-22 | 2019-09-06 | 中国科学院宁波材料技术与工程研究所 | A kind of Polycarbosilane of the crosslinkable groups containing high activity and preparation method thereof |
| CN111100298A (en) * | 2019-04-25 | 2020-05-05 | 杭州师范大学 | Optical transparent organic silicon material and preparation method thereof |
| KR20200078394A (en) * | 2018-12-21 | 2020-07-01 | 한국세라믹기술원 | Manufacturing method for Photocurable Polycarbosilane |
| KR20210084331A (en) * | 2019-12-27 | 2021-07-07 | 한국세라믹기술원 | Carbosilane Photocurable Composition and Manufacturing method of the Same |
| JP2021176623A (en) * | 2020-05-08 | 2021-11-11 | 武漢工程大学Wuhan Institute of Technology | Production method of separation membrane based on high solid silicon carbide slurry |
| CN114395259A (en) * | 2021-12-10 | 2022-04-26 | 中国科学院宁波材料技术与工程研究所 | Organic silicon composition and application thereof |
| CN115504804A (en) * | 2022-10-18 | 2022-12-23 | 中国科学院金属研究所 | Method for manufacturing SiOC porous heat insulation structure through continuous additive manufacturing |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20220089887A1 (en) * | 2020-09-24 | 2022-03-24 | Raytheon Technologies Corporation | Photo-curable liquid composition for additive manufacturing of ceramic |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101024683A (en) * | 2006-02-20 | 2007-08-29 | 四川大学 | Reactable resin and optical-imaging composition |
| CN101122742A (en) * | 2007-09-14 | 2008-02-13 | 西北工业大学 | Superbranched poly-siloxane base photoresist |
-
2016
- 2016-03-16 CN CN201610149725.6A patent/CN105601830B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101024683A (en) * | 2006-02-20 | 2007-08-29 | 四川大学 | Reactable resin and optical-imaging composition |
| CN101122742A (en) * | 2007-09-14 | 2008-02-13 | 西北工业大学 | Superbranched poly-siloxane base photoresist |
Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106047094B (en) * | 2016-07-21 | 2018-04-20 | 苏州泰仑电子材料有限公司 | Protective film for reducing final viscosity of UV curing types and preparation method thereof |
| CN106047094A (en) * | 2016-07-21 | 2016-10-26 | 苏州泰仑电子材料有限公司 | UV (Ultraviolet) cured protective film capable of reducing final viscosity and preparation method thereof |
| CN106398574A (en) * | 2016-09-06 | 2017-02-15 | 哈尔滨工业大学无锡新材料研究院 | Polyacrylate pressure-sensitive adhesive and preparation method thereof |
| CN109280395A (en) * | 2017-07-19 | 2019-01-29 | 北京恒创增材制造技术研究院有限公司 | A kind of product and preparation method thereof of photocurable quick shaping process preparation |
| CN109280395B (en) * | 2017-07-19 | 2021-09-07 | 北京恒创增材制造技术研究院有限公司 | Product prepared by photocuring rapid molding process and preparation method thereof |
| CN108147830A (en) * | 2018-01-17 | 2018-06-12 | 龙泉市金宏瓷业有限公司 | A kind of 3D printing ceramic setter composite material and preparation method thereof |
| KR20200078394A (en) * | 2018-12-21 | 2020-07-01 | 한국세라믹기술원 | Manufacturing method for Photocurable Polycarbosilane |
| KR102349496B1 (en) | 2018-12-21 | 2022-01-11 | 한국세라믹기술원 | Manufacturing method for Photocurable Polycarbosilane |
| CN109970450A (en) * | 2019-03-28 | 2019-07-05 | 天津大学 | A kind of light sensitive ceramics liquid and its ceramic member for 3D printing |
| CN109970450B (en) * | 2019-03-28 | 2021-06-08 | 天津大学 | Photosensitive ceramic liquid for 3D printing and ceramic part thereof |
| CN111100298A (en) * | 2019-04-25 | 2020-05-05 | 杭州师范大学 | Optical transparent organic silicon material and preparation method thereof |
| CN111100298B (en) * | 2019-04-25 | 2022-05-27 | 杭州师范大学 | Optical transparent organic silicon material and preparation method thereof |
| WO2020228054A1 (en) * | 2019-05-16 | 2020-11-19 | 广东工业大学 | Photosensitive resin ceramic and stereolithography preparation method therefor |
| CN110092873A (en) * | 2019-05-16 | 2019-08-06 | 广东工业大学 | A kind of photosensitive resin ceramics and its Stereo Lithography preparation method |
| CN110204730B (en) * | 2019-05-22 | 2022-03-08 | 中国科学院宁波材料技术与工程研究所 | Polycarbosilane containing high-activity crosslinkable group and preparation method thereof |
| CN110204730A (en) * | 2019-05-22 | 2019-09-06 | 中国科学院宁波材料技术与工程研究所 | A kind of Polycarbosilane of the crosslinkable groups containing high activity and preparation method thereof |
| KR20210084331A (en) * | 2019-12-27 | 2021-07-07 | 한국세라믹기술원 | Carbosilane Photocurable Composition and Manufacturing method of the Same |
| KR102481522B1 (en) * | 2019-12-27 | 2022-12-27 | 한국세라믹기술원 | Carbosilane Photocurable Composition and Manufacturing method of the Same |
| JP7008990B2 (en) | 2020-05-08 | 2022-01-25 | 武漢工程大学 | Method for Producing Separation Membrane Based on High Solid Silicon Carbide Slurry |
| JP2021176623A (en) * | 2020-05-08 | 2021-11-11 | 武漢工程大学Wuhan Institute of Technology | Production method of separation membrane based on high solid silicon carbide slurry |
| CN114395259A (en) * | 2021-12-10 | 2022-04-26 | 中国科学院宁波材料技术与工程研究所 | Organic silicon composition and application thereof |
| CN115504804A (en) * | 2022-10-18 | 2022-12-23 | 中国科学院金属研究所 | Method for manufacturing SiOC porous heat insulation structure through continuous additive manufacturing |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105601830B (en) | 2018-10-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105601830A (en) | Photocuring material and application thereof | |
| CN109280395B (en) | Product prepared by photocuring rapid molding process and preparation method thereof | |
| JP2008546888A (en) | Polymerizable composition containing solid filler, article formed thereby and method of forming | |
| ES2868630T3 (en) | Production and use of porous bead polymers in 3D printing according to the binder injection process | |
| CN104914675A (en) | Photosensitivity siloxane and hyperbranched polyether polyol-containing photosensitive resin composition used for used for three-dimensional rapid moulding | |
| EP3010978A1 (en) | Compositions for three-dimensional (3d) printing | |
| CN104761994A (en) | Preparation method of photocuring organic silicon modified epoxy resin paint film | |
| CN108147830A (en) | A kind of 3D printing ceramic setter composite material and preparation method thereof | |
| CN101775197B (en) | Viscosity reducible radiation curable resin composition | |
| CN105308123A (en) | Silica-containing resin composition and method for producing same, and molded article produced from silica-containing resin composition | |
| JP2010189600A (en) | Thermally conductive and insulative resin molding | |
| CN104672402A (en) | Conducting photosensitive resin for 3D printing and preparation method thereof | |
| CN108384406A (en) | A kind of graphene oxide UV is coating material solidified and preparation method thereof | |
| CN104932197B (en) | Expansion polymerization imprinting adhesive for nanoimprint | |
| CN101885901A (en) | Biphenyl-structure-contained epoxy resin/montmorillonite nano composite material | |
| EP3872051A1 (en) | Ceramic slurries with photoreactive-photostable hybrid binders | |
| CN101555308A (en) | Unsaturated polyester resin for alpine rock | |
| CN103172795B (en) | Silicon containing hybrid resin and preparation method thereof | |
| CN108840967B (en) | Additive manufacturing method based on ring-opening metathesis polymerization reaction | |
| KR20200078394A (en) | Manufacturing method for Photocurable Polycarbosilane | |
| CN113480893B (en) | Preparation method of UV conductive ink of inorganic dispersant modified nano silver wire | |
| CN104910681A (en) | Solder resist ink formula and production process thereof | |
| JP5278488B2 (en) | Thermally conductive insulating resin molding | |
| EP3872052A1 (en) | Ceramic slurries with photoreactive-photostable hybrid binders | |
| CN104710577B (en) | A kind of rostone manufacturing rostone hydroxy acrylate emulsion, preparation method and make |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |