CN105601830B - A kind of photo-curing material and its application - Google Patents
A kind of photo-curing material and its application Download PDFInfo
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Abstract
The present invention relates to a kind of photo-curing materials, including following component：60 98wt% of hyperbranched polycarbosilanes；0 35wt% of reactive diluent；0.1 8wt% of photoinitiator；0 10wt% of additive；Hyperbranched polycarbosilanes are the hyperbranched polycarbosilanes containing unsaturated double-bond, and the number-average molecular weight of hyperbranched polycarbosilanes is between 300 15000；Unsaturated double-bond is acryloxy, methacryloxy, vinyl or allyl, and the content of unsaturated double-bond is 1 30wt% in hyperbranched polycarbosilanes.The invention further relates to photo-curing materials for the application of photocuring 3D printing and prepares the application of SiC components.Photo-curing material viscosity of the present invention is relatively low, and convenient for being ejected from the nozzle of 3D printing equipment, and curing rate is fast, shrinking percentage very little when solidification.
Description
Technical field
The present invention relates to curing materials fields, and in particular to a kind of photo-curing material and its application.
Background technology
Component, without mold, generation few waste material, behaviour of the 3D printing due to can rapidly produce arbitrarily complicated shape
Work is simple, shaping speed is fast, forming process is pollution-free and has apparent cost and odds for effectiveness in non-mass production,
Become the research hotspot of current rapid shaping technique.The forming principle of photocuring 3D printing technique is to utilize liquid photocurable material
Material quickly polymerize under light irradiation, and photo-curing material is changed into rapidly solid-state by liquid.
The photo-curing material of photocuring 3D printing is generally by photosensitive resin, reactive diluent (activated monomer), light-initiated
Agent and additive composition.Chinese invention patent (104559196 A of CN) discloses a kind of photocuring 3D printing material of water white transparency
Material, belongs to curing materials technical field.The printed material include organopolysiloxane containing vinyl group, silicon-hydrogen bond containing it is organic
Polysiloxanes, photoinitiator, reinforcing filler, auxiliary agent.Chinese invention patent (102516866 A of CN) discloses a kind of UV light
Change material, including following weight percentage components：Light-cured resin 40~60%；Photocuring diluent 25~45%；Light draws
Send out agent 2~10%；Ultraviolet light stable storage agent 0~0.8%；Nano filling 0.5~30%；Levelling agent 0.2~1%.
Photosensitive resin is ingredient mostly important in photo-curing material, and decision is played to the physical and chemical performance of resulting devices
The effect of property.Currently, the substantially macromolecule photosensitive resin containing unsaturated double-bond that photocuring 3D printing uses, it is such as unsaturated
Polyester, epoxy acrylic resin, polyurethane acrylic resin, polyester acrylate resin, polyoxyalkylene acrylate resin etc..But no
Saturated polyester photo-curing rate is slow, easily shrinks and resistance to acid and alkali is poor；Epoxy acrylic resin flexibility is poor；Polyester acrylate resin
Yellowing resistance is poor；Although polyurethane acrylic resin has a preferable comprehensive performance, but its photo-curing rate is relatively slow and viscosity also compared with
It is high；The mechanical strength of polyoxyalkylene acrylate resin, hardness and chemical-resistant are poor.In addition, in some special dimensions, need high-precision
The parts of degree, high-fire resistance and high intensity, these polymer-based photosensitive resins cannot be met the requirements.
In general, the type for being suitable for the photosensitive resin of photocuring 3D printing technique now is less, applicatory photosensitive
Resin does not catch up with development and the demand in market, so being badly in need of the usable photocuring 3D printing technique molding of exploitation novel high-performance
Photosensitive resin.Liquid hyperbranched polycarbosilanes ambient temperature mobility is good, at normal temperatures can long term storage, viscosity be low, small toxicity, no
Shrinking percentage very little, solidification post-crosslinking density are big when volatilization, solidification, and excellent with high rigidity, high-wearing feature and chemical-resistant etc.
Point.But so far, the cured document of only seldom ultraviolet light about hyperbranched polycarbosilanes, and only study it
The influence to its conversion ratio and solidification rate such as ultraviolet light cure kinetics and light intensity, temperature, will be hyperbranched without reporting
Polycarbosilane is used as the photosensitive resin of photocuring 3D printing material.
Invention content
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to provide a kind of novel photo-curing material and its solid in light
Change 3D printing and prepares the application in SiC components.
The technical solution that the present invention solves above-mentioned technical problem is as follows：
A kind of photo-curing material, including following component：
The hyperbranched polycarbosilanes are the hyperbranched polycarbosilanes containing unsaturated double-bond, the number of hyperbranched polycarbosilanes
Average molecular weight is between 300-15000；The unsaturated double-bond is acryloxy, methacryloxy, vinyl or alkene
Propyl, the content of unsaturated double-bond is 1-30wt% in hyperbranched polycarbosilanes.
Hyperbranched polycarbosilanes containing unsaturated double-bond are that have highly branched macromolecular, due to degree of branching height, molecule
Chain entanglement is few, therefore compared with the linear Polycarbosilane of identical molecular weight, viscosity is much lower, the convenient spray from 3D printing equipment
It is ejected in head；Secondly, the density of crosslinkable active group is big in hyperbranched polycarbosilanes, and curing rate is fast；Surpass simultaneously
Branched Polycarbosilane has the apparatus derivatorius of height, shrinking percentage very little when solidification.
Preferably, the photo-curing material includes following component：
Hyperbranched polycarbosilanes, reactive diluent, photoinitiator and additive mechanical agitation are mixed according to the above ratio equal
After even, you can obtain photo-curing material, the preparation method of the photo-curing material is simple.
Preferably, preparation method bibliography (the Chinese Chemical of the hyperbranched polycarbosilanes
Letters, 2007,18,754-757.) and (Polymer, 2006,47,1519-1525.).
Preferably, the photoinitiator is selected from ultraviolet initiator or visible light initiator；The ultraviolet light draws
It sends out agent and is selected from one or both of 1- hydroxycyclohexyl phenyl ketones, benzophenone, diphenylhydroxyethanone；The visible light draws
It sends out agent and is selected from bis- (pentafluorophenyl group) titaniums cyclopentadienyl or bis- [2,6- bis- fluoro- 3- (1H- pyrrole radicals -1) phenyl] titaniums cyclopentadienyl.Photoinitiator is a kind of
Radiation energy can be absorbed, after excitation occur chemical change and generate have cause polymerizing power reactive intermediate (free radical or
Cation) substance.Therefore, photoinitiator is the necessary composition of photo-curing material, its photo-curing rate to photo-curing material
Play decisive role.
Preferably, the reactive diluent is to contain acrylate-based, methacrylate, vinyl or ethylene
The monomer of oxygroup.Reactive diluent is commonly referred to as monomer or functional monomer, it is a kind of containing the organic of polymerizable functional group
Small molecule, the work that it not only acts as dissolving and dilutes photosensitive resin or regulation system viscosity in the various components of photo-curing material
With, and Light Curing can be participated in and influence the photo-curing rate of photo-curing material and various performances, therefore select suitably
Reactive diluent is also the important link of photo-curing material formula design.It is selected as further preferred, described reactive diluent
From tri (propylene glycol) diacrylate or diethoxy bisphenol a diacrylate.
Preferably, the additive be aided initiating, antifoaming agent, antioxidant, levelling agent, dispersant, delustering agent,
It is one or more in stabilizer, filler, pigment, sintering aid.Although the ratio very little that additive accounts in photo-curing material,
But they play an important role to the various performances for improving product.
It is aided initiating CN373, antifoaming agent dimethyl silicone polymer or carbonization as further preferred, described additive
Si powder filler.
The present invention provides the application that a kind of photo-curing material is used for photocuring 3D printing.
The present invention also provides the applications that a kind of photo-curing material is used to prepare SiC components.Preferably, utilizing 3D printer
Photo-curing material is ejected on backing material, the solidified forming under visible light or action of ultraviolet light is formed after successively accumulating
3 D stereo component, and under anaerobic by 3 D stereo component, 1000~2000 DEG C of 20~360min of heat preservation obtain SiC
Component.Preferably, the ultraviolet light is 500~700W medium pressure mercury lamps.
By the stereochemical structure of crosslinked hyperbranched polycarbosilanes energy formation rule, its shape is kept in high-temperature sintering process
Shape is stablized, and is unlikely to volatilization after resolving into small molecule segment and escapes, in addition, hyperbranched polycarbosilanes have very high ceramics production
Rate and ceramic product is close to SiC stoichiometric ratios, so being highly suitable as the precursor of SiC material.
Compared with the existing technology, beneficial effects of the present invention are embodied in：
(1) hyperbranched polycarbosilanes containing unsaturated double-bond are highly branched macromoleculars, due to degree of branching height, strand
It tangles few, therefore compared with the linear Polycarbosilane of identical molecular weight, viscosity is much lower, the photo-curing material energy being prepared
It is enough conveniently to be ejected from the nozzle of 3D printing equipment；
(2) photo-curing material being prepared, the density with crosslinkable active group is big, and curing rate is fast, and solid
Shrinking percentage very little when change；
(3) photo-curing material being prepared, solidification post-crosslinking density is big, therefore good, high rigidity, height with thermal stability
The advantages that wear-resisting and chemical-resistant is good；
(4) component that photo-curing material is formed through 3D printing can be used high-sintering process and high performance SiC structures be made
Part.
Specific implementation mode
Below in conjunction with specific embodiment, present invention is further described in detail, it is necessary to be pointed out that embodiment is served only for
The present invention is further detailed, limiting the scope of the invention is should not be understood as.
Embodiment 1：
Step 1：The synthesis of hyperbranched polycarbosilanes containing vinyl
Bibliography (Chinese Chemical Letters, 2007,18,754-757.) synthesizes the over-expense containing vinyl
Change Polycarbosilane, the specific steps are：Magnesium chips (1.04mol) is added and contains CH2=CHCH2Cl(0.12mol)、Cl3SiCH2Cl
(0.46mol) and Cl2Si(CH3)CH2In tetrahydrofuran (200mL) solvent of Cl (0.23mol), reacted 12 hours in 60 DEG C, it
Lithium aluminium hydride reduction (0.37mol) is added in ice-water bath afterwards, and continues at 60 DEG C and reacts 12 hours.After reaction, it will react molten
Liquid is poured into the aqueous hydrochloric acid solution of a concentration of 4mol/L and is stirred, and after stirring 2 hours, n-hexane (500mL) is added into water, quiet
Only be layered, isolate organic phase and using sodium sulphate dry, finally in vacuum 60 DEG C be dried to obtain the hyperbranched poly containing vinyl
Carbon silane.Synthetic route is as follows (it should be noted that due to changeable and complicated, the following synthetic route of dissaving structure
Shown in structure it is merely illustrative).
Through characterization, the number-average molecular weight of the hyperbranched polycarbosilanes containing vinyl is 854, weight average molecular weight 3658, room
Warm viscosity 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 polycarbosilanes (92wt%), ultraviolet initiator 1- hydroxyls containing vinyl
Butylcyclohexyl phenyl ketone (4wt%) and benzophenone (3.6wt%), aided initiating CN373 (0.4wt%), by above-mentioned raw materials
Shading mixing and room temperature mechanical agitation 2h.
Step 3：Photocuring 3D printing
The above-mentioned photo-curing material of nozzle operation intracavitary quickly forms droplet, is then sprayed with certain speed and frequency
Onto backing material, the solidified forming under ultraviolet light (light source is 600W medium pressure mercury lamps) effect is formed three-dimensional after successively accumulating
Stereoscopic member.Through characterization, shore hardness 80HD, tensile strength 90MPa, stretch modulus 1.55GPa, heat distortion temperature
It it is 296 DEG C, cure shrinkage is 0.6% and molded part is without buckling deformation.
Embodiment 2：
Step 1：Synthesize the hyperbranched polycarbosilanes containing acryloxy
Bibliography (Chinese Chemical Letters, 2007,18,754-757.), synthesis key containing Si-Cl it is super
Branched Polycarbosilane, reference literature (Polymer, 2006,47,1519-1525), obtains containing the hyperbranched of acryloxy later
Polycarbosilane, the specific steps are：Magnesium chips (1.0mol) is added and contains CH3CH2CH2Cl (0.20mol), Cl3SiCH2Cl
(0.15mol), Cl2Si(CH3)CH2In tetrahydrofuran (200mL) solvent of Cl (0.45mol), reacted 12 hours in 60 DEG C, it
2- hydroxyethylmethacry,ates (0.6mol) and pyridine (0.6mol) is added in ice-water bath afterwards and reacts 1.5 hours.Reaction knot
Shu Hou is filtered to remove insoluble matter, filtrate is poured into the aqueous hydrochloric acid solution of a concentration of 4mol/L and is stirred, after stirring 2 hours, to
N-hexane (500mL) is added in water, static layering is isolated organic phase and dried using sodium sulphate, finally dry in 60 DEG C of vacuum
It is dry to obtain the hyperbranched polycarbosilanes containing acryloxy.Synthetic route is as follows (it should be noted that due to hyperbranched knot
Structure is changeable, and the structure in synthetic route as follows is merely illustrative).
Through characterization, the number-average molecular weight of the hyperbranched polycarbosilanes containing acryloxy is 732, and weight average molecular weight is
The content of 3241, viscosity at ambient temperature 0.0272Pas, acryloxy are 21.1wt%.
Step 2：The preparation of photo-curing material
The formula of photo-curing material is：It is hyperbranched polycarbosilanes (95.6wt%) containing acryloxy, ultraviolet light-initiated
Above-mentioned raw materials shading is mixed simultaneously room temperature mechanical agitation by agent diphenylhydroxyethanone (4wt%), aided initiating CN373 (0.4wt%)
2h。
Step 3：Photocuring 3D printing
The above-mentioned photo-curing material of nozzle operation intracavitary quickly forms droplet, is then sprayed with certain speed and frequency
Onto backing material, the solidified forming under ultraviolet light (light source is 600W medium pressure mercury lamps) effect is formed three-dimensional after successively accumulating
Stereoscopic member.Through characterization, shore hardness 93HD, tensile strength 105MPa, stretch modulus 1.73GPa, thermal deformation temperature
Degree is more than 300 DEG C, and cure shrinkage is 0.8% and molded part is without buckling deformation.
Step 4：Sintering process
Above-mentioned molding 3 D stereo component is risen to 1200 DEG C with 10 DEG C/min rates, and 2h is kept the temperature in 1200 DEG C, it
1800 DEG C are risen to 5 DEG C/min rates afterwards, and 1h is kept the temperature in 1800 DEG C, finally obtains the SiC components of high performance 3 D stereo.
Embodiment 3：
Step 1：The hyperbranched polycarbosilanes containing vinyl are synthesized with reference to embodiment 1
Step 2：The preparation of photo-curing material
The formula of photo-curing material is：Hyperbranched polycarbosilanes (82wt%), the contracting of reactive diluent two three containing vinyl
Propylene glycol diacrylate (10wt%), ultraviolet initiator 1- hydroxycyclohexyl phenyl ketones (4wt%) and benzophenone
(3.6wt%), aided initiating CN373 (0.4wt%).Above-mentioned raw materials shading is mixed into simultaneously room temperature mechanical agitation 2h.
Step 3：Photocuring 3D printing
The above-mentioned photo-curing material of nozzle operation intracavitary quickly forms droplet, is then sprayed with certain speed and frequency
Onto backing material, the solidified forming under ultraviolet light (light source is 600W medium pressure mercury lamps) effect is formed three-dimensional after successively accumulating
Stereoscopic member.Through characterization, shore hardness 86HD, tensile strength 89MPa, stretch modulus 1.56GPa, heat distortion temperature
More than 300 DEG C, cure shrinkage is 0.7% and molded part is without buckling deformation.
Embodiment 4：
Step 1：The hyperbranched polycarbosilanes containing vinyl are synthesized with reference to embodiment 1
Step 2：The preparation of photo-curing material
The formula of photo-curing material is：Hyperbranched polycarbosilanes (80wt%), reactive diluent diethoxy containing vinyl
Bis- (pentafluorophenyl group) titaniums of base bisphenol a diacrylate (16wt%), visible light initiator luxuriant (3.5wt%), the poly- diformazan of antifoaming agent
Above-mentioned raw materials shading is mixed simultaneously room temperature mechanical agitation 2h by radical siloxane (0.5wt%).
Step 3：Photocuring 3D printing
The above-mentioned photo-curing material of nozzle operation intracavitary quickly forms droplet, is then sprayed with certain speed and frequency
Onto backing material, solidified forming, forms 3 D stereo component after successively accumulating under visible light illumination.Through characterization, Shao
Family name's hardness is 83HD, tensile strength 87MPa, stretch modulus 1.63GPa, and 284 DEG C of heat distortion temperature, cure shrinkage is
0.7% and molded part without buckling deformation.
Embodiment 5：
Step 1：The hyperbranched polycarbosilanes containing acryloxy are synthesized with reference to embodiment 2
Step 2：The preparation of photo-curing material
The formula of photo-curing material is：Hyperbranched polycarbosilanes (90wt%) containing acryloxy, visible light initiator
Bis- [2,6- bis- fluoro- 3- (1H- pyrrole radicals -1) phenyl] titaniums luxuriant (3.5wt%), antifoaming agent dimethyl silicone polymer (0.5wt%),
Above-mentioned raw materials shading is mixed simultaneously room temperature mechanical agitation 2h by the silicon carbide powder (6wt%) that grain size is 1 micron.
Step 3：Photocuring 3D printing
The above-mentioned photo-curing material of nozzle operation intracavitary quickly forms droplet, is then sprayed with certain speed and frequency
Onto backing material, solidified forming, forms 3 D stereo component after successively accumulating under visible light illumination.Through characterization, Shao
Family name's hardness is 96HD, tensile strength 98MPa, stretch modulus 1.84GPa, and heat distortion temperature is more than 300 DEG C, cure shrinkage
For 0.5% and molded part without buckling deformation.
Step 4：Sintering process
Above-mentioned molding 3 D stereo component is risen to 1200 DEG C with 10 DEG C/min rates, and 2h is kept the temperature in 1200 DEG C, it
1600 DEG C are risen to 5 DEG C/min rates afterwards, and 4h is kept the temperature in 1600 DEG C, finally obtains the SiC components of high performance 3 D stereo.
Heat resistance can be obtained after 3D printing from can be seen that photo-curing material using the present invention in above-described embodiment
Component good, hardness is high, mechanical performance is excellent and cure shrinkage is small, and height can further be made through high-sintering process again
The SiC components of performance.
Claims (7)
1. a kind of photo-curing material is used for the application of photocuring 3D printing, the photo-curing material, including following component：
The hyperbranched polycarbosilanes are the hyperbranched polycarbosilanes containing unsaturated double-bond, and the number of hyperbranched polycarbosilanes is divided equally
Son amount is between 300-15000；The unsaturated double-bond be acryloxy, methacryloxy, vinyl or allyl,
The content of unsaturated double-bond is 1-30wt% in hyperbranched polycarbosilanes.
2. photo-curing material according to claim 1 is used for the application of photocuring 3D printing, which is characterized in that the light
Initiator is selected from ultraviolet initiator or visible light initiator；The ultraviolet initiator is selected from 1- hydroxycyclohexylphenyl first
One or both of ketone, benzophenone, diphenylhydroxyethanone；The visible light initiator be selected from bis- (pentafluorophenyl group) titaniums it is luxuriant or
Bis- [2,6- bis- fluoro- 3- (1H- pyrrole radicals -1) phenyl] titanium cyclopentadienyls.
3. photo-curing material according to claim 1 is used for the application of photocuring 3D printing, which is characterized in that the work
Property diluent be selected from containing acrylate-based, methacrylate, vinyl or ethyleneoxy monomer.
4. photo-curing material according to claim 3 is used for the application of photocuring 3D printing, which is characterized in that the work
Property diluent be selected from tri (propylene glycol) diacrylate or diethoxy bisphenol a diacrylate.
5. photo-curing material according to claim 1 is used for the application of photocuring 3D printing, which is characterized in that described adds
It is aided initiating, antifoaming agent, antioxidant, levelling agent, dispersant, delustering agent, stabilizer, filler, pigment, sintering aid to add agent
In it is one or more.
6. photo-curing material according to claim 5 is used for the application of photocuring 3D printing, which is characterized in that described adds
It is aided initiating CN373, antifoaming agent dimethyl silicone polymer or silicon carbide powder filler to add agent.
7. a kind of photo-curing material is used to prepare the application of SiC components, photo-curing material is ejected into support using 3D printer
On material, the solidified forming under visible light or action of ultraviolet light forms 3 D stereo component after successively accumulating, and three-dimensional is vertical
Under anaerobic, 1000~2000 DEG C of 20~360min of heat preservation obtain SiC components to body component；
The photo-curing material, including following component：
The hyperbranched polycarbosilanes are the hyperbranched polycarbosilanes containing unsaturated double-bond, and the number of hyperbranched polycarbosilanes is divided equally
Son amount is between 300-15000；The unsaturated double-bond be acryloxy, methacryloxy, vinyl or allyl,
The content of unsaturated double-bond is 1-30wt% in hyperbranched polycarbosilanes.
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 |
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| 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 |
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| Publication Number | Publication Date |
|---|---|
| CN105601830A CN105601830A (en) | 2016-05-25 |
| CN105601830B true CN105601830B (en) | 2018-10-02 |
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| 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 |
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| 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 |
| KR102349496B1 (en) * | 2018-12-21 | 2022-01-11 | 한국세라믹기술원 | Manufacturing method for Photocurable Polycarbosilane |
| CN109970450B (en) * | 2019-03-28 | 2021-06-08 | 天津大学 | Photosensitive ceramic liquid for 3D printing and ceramic part thereof |
| CN111100298B (en) * | 2019-04-25 | 2022-05-27 | 杭州师范大学 | Optical transparent organic silicon material and preparation method thereof |
| 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 |
| KR102481522B1 (en) * | 2019-12-27 | 2022-12-27 | 한국세라믹기술원 | Carbosilane Photocurable Composition and Manufacturing method of the Same |
| CN111470869B (en) * | 2020-05-08 | 2022-07-19 | 武汉工程大学 | Preparation method of separation membrane based on high-solid-content silicon carbide slurry |
| CN114395259B (en) * | 2021-12-10 | 2024-07-16 | 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 |
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| CN101024683A (en) * | 2006-02-20 | 2007-08-29 | 四川大学 | Reactable resin and optical-imaging composition |
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