CN110028639A - A kind of photosensitivity Zr-B-Si-C ceramic forerunner and its in-situ preparation method - Google Patents
A kind of photosensitivity Zr-B-Si-C ceramic forerunner and its in-situ preparation method Download PDFInfo
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Abstract
The present invention relates to a kind of photosensitivity Zr-B-Si-C ceramic forerunner and its in-situ preparation methods.The method are as follows: methylvinyldichlorosilane and borane dimethylsulf iotade are uniformly mixed, metallic sodium is then added and carries out dechlorination, obtains methyl ethylene borosilicate alkane；Chloromethyltrichlorosilane, methyl chloride dimethyl dichlorosilane (DMCS) and bis cyclopentadienyl zirconium dichloride are uniformly mixed, magnesium metal is then added and carries out the first insulation reaction, reducing agent is added and carries out the second insulation reaction, obtain poly- zirconium carbon silane；Methyl ethylene borosilicate alkane and poly- zirconium carbon silane mixture is uniform, obtain vinyl Zr-B-Si-C alkane；Vinyl Zr-B-Si-C alkane is uniformly mixed with mercaptopropionic acid ester, photoinitiator initiated polymerization is then added, the ceramic forerunner is made.The present invention solves the problems such as traditional photocuring system viscosity is big, thermal stress is big, the decaying of structural member mechanical property, provides good raw material for photocuring 3D printing superhigh temperature ceramics structural member.
Description
Technical field
The invention belongs to technical field of ceramic material more particularly to a kind of photosensitivity Zr-B-Si-C ceramic forerunner and
Its in-situ preparation method.
Background technique
Based on the designability of organic polymer precursor body chemical component, specificity can be customized according to practical application request
The Zr-B-Si-C ceramic material of energy is to develop ZrB2A kind of new method of based ultra-high temperature ceramic material.Meanwhile with 3D printing
The fast development of technology, this quickly net forming technique can effectively solve ceramic-like materials processing difficulties, long preparation period,
The problem of small complex structural member even can not be processed.Based on the particularity of ceramics printing, photocuring processes are superhigh temperature ceramics 3D
The prefered method of printing.It is worth noting that, it is suitable for the presoma of photocuring ceramics 3D printing, polymer conversion method preparation pottery
It has to grow up by macromolecular chain by this link of crosslinking curing and form reticular structure, enable under receiving when porcelain
The high temperature pyrolysis process of one step generates fine and close ceramic material.But traditional photocuring system is concentrated mainly on unsaturated gather
Ester and esters of acrylic acid, rate of polymerization and double bond conversion rate are low, meet oxygen inhibition, to environmental requirement harshness；And it is based on free radical
Chain type autohemagglutination mechanism is easy to appear premature gelation, increases system viscosity, discharge the thermal stress generated when polymerization can not, causes
Material property decline；In addition, the photoinitiator amount ratio of traditional system is more, since photoinitiator to the absorption of ultraviolet light and declines
Subtract, cause light that cannot penetrate heavy wall, thus is not suitable for the preparation of coarse scale structures.These features and its conduct of traditional system
There are contradictions for 3D printing ceramic raw material.
In view of the above-mentioned problems, being highly desirable to provide a kind of fabricated in situ photosensitivity Zr-B-Si-C ceramic forerunner
New method, thus overcome traditional photocuring system there are viscosity the defects of big, thermal stress is big, the decaying of structural member mechanical property, with
Meets the needs of superhigh temperature ceramics 3D printing.
Summary of the invention
In order to solve at least one technical problem existing in the prior art, the present invention provides a kind of photosensitivity Zr-
B-Si-C ceramic forerunner and its in-situ preparation method.The present invention solves that traditional photocuring presoma viscosity is big, rate of polymerization
Low, thermal stress is big and needs to add ceramic powders and dispersing agent leads to complex process, unstable, provides a kind of suitable
It should be in the photosensitivity Zr-B-Si-C ceramic forerunner and its in-situ synthetic method of superhigh temperature ceramics 3D printing.
To achieve the goals above, the present invention provides a kind of photosensitivity Zr-B-Si-C ceramics precursor in first aspect
The in-situ preparation method of body, described method includes following steps:
(1) methylvinyldichlorosilane and borane dimethylsulf iotade are uniformly mixed with toluene solution, obtain the first mixing
Then liquid metallic sodium is added into first mixed liquor and carries out dechlorination, obtains methyl ethylene borosilicate alkane；
(2) Chloromethyltrichlorosilane, methyl chloride dimethyl dichlorosilane (DMCS) and bis cyclopentadienyl zirconium dichloride are uniformly mixed with organic solvent,
The second mixed liquor is obtained, magnesium metal is then added into second mixed liquor and carries out the first insulation reaction, obtains reaction solution, so
Reducing agent is added into the reaction solution afterwards and carries out the second insulation reaction, obtains poly- zirconium carbon silane；
It is (3) the methyl ethylene borosilicate alkane that step (1) obtains and the poly- zirconium carbon silane mixture that step (2) obtains is uniform,
Obtain vinyl Zr-B-Si-C alkane；
(4) the vinyl Zr-B-Si-C alkane that step (3) obtains is uniformly mixed with mercaptopropionic acid ester, obtains mixture, so
Photoinitiator is added into the mixture afterwards and causes photopolymerization reaction, photosensitivity Zr-B-Si-C ceramic forerunner is made.
Preferably, the mercaptopropionic acid ester is that polyalcohol is obtained with 3- mercaptopropionic acid through esterification；The polyalcohol choosing
From ethylene glycol, 6- hexylene glycol, 1,3- propylene glycol, glycerine, trimethylolpropane, trimethylolethane, pentaerythrite, poly- the third two
One of pure and mild multifunctional norbornene is a variety of；Preferably, the polyalcohol is selected from 1,3-PD, trihydroxy methyl third
One of alkane and pentaerythrite are a variety of.
Preferably, the polyalcohol is trimethylolpropane, and the trimethylolpropane rubs with the 3- mercaptopropionic acid
You are than being 1:(2~4) it is preferably 1:3.
Preferably, the organic solvent is selected from one of tetrahydrofuran, ether and isopropyl ether or a variety of；And/or it is described
Reducing agent is selected from the group being made of lithium aluminium hydride reduction and sodium borohydride；And/or the photoinitiator is selected from benzoyl peroxide, isopropyl
Base thioxanthone, 2,4,6- trimethyl benzoyl diphenyl base phosphine oxide, phenyl bis- (2,4,6- trimethylbenzoyls) oxidation
One of phosphine, 2,4,6- trimethylbenzoyl-ethyoxyl-phenyl phosphine oxide, benzophenone and dimethoxybenzoin are more
Kind；Preferably, the photoinitiator is dimethoxybenzoin.
Preferably, the content of photoinitiator described in the photosensitivity Zr-B-Si-C ceramic forerunner is not more than
1wt%.
Preferably, the molar ratio of the methylvinyldichlorosilane, the borane dimethylsulf iotade and the metallic sodium is
(2~4): 1:(5~8) it is preferably 3:1:6.
Preferably, the Chloromethyltrichlorosilane, the methyl chloride dimethyl dichlorosilane (DMCS) and the bis cyclopentadienyl zirconium dichloride rub
You are than being (8~12): (8~12): 1 preferably 10:10:1, the magnesium metal, the reducing agent and the bis cyclopentadienyl zirconium dichloride
Molar ratio is (25~35): (15~25): 1 preferably 30:20:1.
Preferably, the sulfydryl that the vinyl and the mercaptopropionic acid ester that the vinyl Zr-B-Si-C alkane contains contain
Molar ratio is 1:1.
Preferably, the temperature of first insulation reaction and/or second insulation reaction is 50~100 DEG C, the time 5
~36h.
The present invention provides photosensitive made from the in-situ preparation method as the present invention described in first aspect in second aspect
Perceptual Zr-B-Si-C ceramic forerunner.
The present invention at least have compared with prior art it is following the utility model has the advantages that
(1) the photosensitivity Zr-B-Si-C preceramic materials synthesized by the present invention, are a kind of liquid of good fluidity
Photocuring preceramic materials；The method of the present invention is gradually total by sulfydryl/vinyl monomer photopolymerization reaction mechanism free radical
The problem of poly- solve rate of polymerization and double bond conversion rate is low, meets oxygen inhibition, can effectively prevent premature gelation, system viscosity increases
Greatly, and when polymerizeing the problem of thermal stress generated can not discharge, the present invention while in-situ preparation Zr-B-Si-C ceramics precursor
Body, without adding Zr base solid phase ceramic powders and dispersing agent, solid agglomerate and viscosity when solving the printing of traditional photocuring ceramics
The problem of.
(2) heretofore described photosensitivity Zr-B-Si-C ceramic forerunner is prepared in subsequent polymer conversion method and is made pottery
It when porcelain, is grown up during crosslinking curing by macromolecular chain and forms reticular structure, enable the high temperature for bearing next step
Pyrolytic process generates fine and close ceramic material, and the present invention provides excellent for photocuring 3D printing superhigh temperature ceramics complex structural member
The raw material of matter.
Detailed description of the invention
Fig. 1 is the preparation flow schematic diagram in a specific embodiment of the invention.
Fig. 2 is the infrared spectrogram of photosensitivity Zr-B-Si-C ceramic forerunner prepared by the embodiment of the present invention 1
(FTIR spectrogram).In figure, abscissa Wavenumber indicates wave number, unit cm-1, ordinate T expression transmitance, unit
For %.
Fig. 3 is obtained after photosensitivity Zr-B-Si-C ceramic forerunner photocuring prepared by the embodiment of the present invention 1
The x-ray photoelectron spectroscopy figure (XPS spectrum figure) of Zr-B-Si-C ceramics prepolymer.In figure, abscissa Binding Energy is indicated
In conjunction with energy, unit eV, ordinate Intensity (a.u.) indicate intensity.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, right below in conjunction with the embodiment in the present invention
Technical solution of the present invention is clearly and completely described, it is clear that described embodiment is that a part of the invention is implemented
Example, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not making creativeness
Every other embodiment obtained, shall fall within the protection scope of the present invention under the premise of labour.
The present invention provides a kind of preparation method of photosensitivity Zr-B-Si-C ceramic forerunner in first aspect, described
Method includes the following steps:
(1) with toluene solution by methylvinyldichlorosilane (C3H6Cl2) and borane dimethylsulf iotade ((CH Si3)2S·
BH3) be uniformly mixed, the first mixed liquor is obtained, metallic sodium (Na) is then added into first mixed liquor and carries out dechlorination, obtains
Methyl ethylene borosilicate alkane；In the present invention, the toluene solution is, for example, toluene standard solution；
(2) with organic solvent by Chloromethyltrichlorosilane (CH2Cl4Si), methyl chloride dimethyl dichlorosilane (DMCS) (C2H5Cl3Si) and
Bis cyclopentadienyl zirconium dichloride (C10H10Cl2Zr it) is uniformly mixed, obtains the second mixed liquor, magnesium metal then is added into second mixed liquor
(Mg) the first insulation reaction is carried out, reaction solution is obtained, reducing agent is then added into the reaction solution and carries out the second insulation reaction,
Obtain poly- zirconium carbon silane；
It is (3) the methyl ethylene borosilicate alkane that step (1) obtains and the poly- zirconium carbon silane mixture that step (2) obtains is uniform,
Obtain vinyl Zr-B-Si-C alkane；In the present invention, for example, poly- zirconium carbon silane is dissolved in tetrahydrofuran organic solvent, according to
Equivalent 2:1 ratio is added methyl ethylene borosilicate alkane and is uniformly mixed, in nitrogen (N2) slowly heat up under inert gas shielding, it steams
Solvent out obtains the alkane of Zr-B-Si-C containing vinyl；It in the present invention, can be by adjusting methyl ethylene borosilicate alkane and poly- zirconium
The ratio of both carbon silane ingredient achievees the purpose that adjust material composition and institutional framework；
(4) the vinyl Zr-B-Si-C alkane that step (3) obtains is uniformly mixed with mercaptopropionic acid ester, obtains mixture, so
Photoinitiator is added into the mixture afterwards and causes photopolymerization reaction, photosensitivity Zr-B-Si-C ceramic forerunner is made.
It illustrates, term " first ", " second " are used for description purposes only, and are not understood to indicate or imply phase
To importance；For the ordinary skill in the art, visual concrete condition understands the tool of above-mentioned term in the present invention
Body meaning.
In the present invention, photosensitivity Zr-B-Si-C ceramic forerunner is also denoted as photosensitivity zirconium-boron-silico-carbo ceramics
Presoma, photosensitivity Zr-B-Si-C preceramic materials or sulfydryl/vinyl Zr-B-Si-C ceramic forerunner, also by second
Alkenyl Zr-B-Si-C alkane is denoted as the alkane of Zr-B-Si-C containing vinyl.
The method of the present invention obtains methyl ethylene borosilicate alkane and poly- zirconium carbon silane by Wurtz coupling process respectively, in Zr-B-
Unsaturated group (vinyl) is introduced in Si-C alkane, in sulfydryl/vinyl Photopolymer System of Zr-B-Si-C presoma, instead
Rate is answered to be largely dependent on the structure of vinyl monomer, the present invention into Zr-B-Si-C ceramics polymer presoma by drawing
Enter sulfydryl/alkenes comonomer, is gradually copolymerized using sulfydryl/vinyl monomer photopolymerization reaction mechanism free radical and solves polymerization
The problem of rate and double bond conversion rate are low, meet oxygen inhibition, can effectively prevent premature gelation, and system viscosity increases, and when polymerizeing
The thermal stress of generation can not discharge, the problem of structural member mechanical property decaying etc., and the present invention is simultaneously before in-situ preparation Zr-B-Si-C
Body is driven, without adding Zr base solid phase ceramic powders and dispersing agent, solving solid agglomerate when traditional photocuring ceramics print and gluing
The problem of property, the addition for avoiding ceramic powders and dispersing agent leads to complex process, unstable problem.Prepared by the present invention
Photosensitivity Zr-B-Si-C ceramic forerunner is a kind of liquid photocurable preceramic materials of good fluidity, subsequent
When polymer conversion method preparation ceramics, is grown up during crosslinking curing by macromolecular chain and form reticular structure, made it
Enough high temperature pyrolysis processes for bearing next step generate fine and close ceramic material, the photosensitivity Zr-B-Si-C in the present invention
Ceramics precursor physical efficiency is as the good raw material of photocuring 3D printing superhigh temperature ceramics complex structural member.
According to some preferred embodiments, the mercaptopropionic acid ester is that polyalcohol is obtained with 3- mercaptopropionic acid through esterification
It arrives；In the present invention, sulfhydryl compound has a major impact response feature as important reactant, its structure and characteristic；
In view of finally to realize it is rapid photocuring and can preparative, pass through esterification obtain have different degrees of functionality sulfydryl third
Acid esters investigates the structure and characteristic of sulfhydryl compound to photocuring as the reactant for realizing the quick photopolymerization of sulfydryl/vinyl
The influence of reaction: the monomer (polyalcohol) with different degrees of functionality can be for example selected, and appropriate acidic catalyst is added, with first
Benzene is heated to boiling as solvent, and 3- mercaptopropionic acid is then added in a manner of dropwise addition and carries out esterification, reaction equation is such as
Shown in formula (1)；It is washed to neutrality after reaction, is evaporated under reduced pressure to mercaptopropionic acid ester products.
In the present invention, the polyalcohol is selected from ethylene glycol, 6- hexylene glycol, 1,3-PD, glycerine, trihydroxy methyl third
One of alkane, trimethylolethane, pentaerythrite, polypropylene glycol and multifunctional norbornene are a variety of；Preferably, described
It is a variety of that polyalcohol is selected from one of 1,3- propylene glycol, trimethylolpropane and pentaerythrite.
According to some preferred embodiments, the polyalcohol is trimethylolpropane, the trimethylolpropane and institute
The molar ratio for stating 3- mercaptopropionic acid is 1:(2~4) (such as 1:2,1:2.5,1:3,1:3.5 or 1:4) be preferably 1:3；In this hair
In bright, when the polyalcohol is trimethylolpropane monomer, in the preparation process of the mercaptopropionic acid ester, preferably with first
Benzene is solvent, and acidic catalyst is the concentrated sulfuric acid, and preferably in the system using toluene as solvent, the trimethylolpropane
Concentration be 1mol/L, the concentration of the concentrated sulfuric acid is 0.1mol/L；For example, when the dosage of solvent toluene is 100mL, the concentrated sulfuric acid
Dosage is 0.01mol, and the dosage of the trimethylolpropane is 0.1mol.
According to some preferred embodiments, the organic solvent is selected from one of tetrahydrofuran, ether and isopropyl ether
It is or a variety of, it is preferred that the organic solvent is tetrahydrofuran；And/or the reducing agent is selected from by lithium aluminium hydride reduction and hydroboration
The group of sodium composition, it is preferred that the reducing agent is sodium borohydride；In the present invention, the reducing agent is selected from by lithium aluminium hydride reduction
Indicate that the reducing agent can be lithium aluminium hydride reduction, sodium borohydride or lithium aluminium hydride reduction and boron hydrogen with the group of sodium borohydride composition
Change the mixture of sodium.
According to some preferred embodiments, the photoinitiator is selected from benzoyl peroxide, isopropyl thioxanthone
(ITX), 2,4,6- trimethyl benzoyl diphenyl base phosphine oxide (TPO), phenyl bis- (2,4,6- trimethylbenzoyls) aoxidize
In phosphine (819), 2,4,6- trimethylbenzoyl-ethyoxyl-phenyl phosphine oxide (TEPO), benzophenone and dimethoxybenzoin
It is one or more；Preferably, the photoinitiator is dimethoxybenzoin.
According to some preferred embodiments, photoinitiator described in the photosensitivity Zr-B-Si-C ceramic forerunner
Content (mass percentage) be not more than 1wt%, i.e., the dosage of the described photoinitiator is no more than 1wt%；In light of the invention
In curing reaction, the dosage of the photoinitiator has important influence to photocuring reaction, and the photoinitiator is for example rested in peace
The dosage of fragrant dimethyl ether is no more than 1wt%；With more (the traditional photocuring system of photoinitiator amount ratio of traditional photocuring system
The dosage of photoinitiator be generally 5wt% or more) compare, the photoinitiator dosage in the present invention is seldom, can be effective
The problem of avoiding absorption and decaying due to the excessively multipair ultraviolet light of photoinitiator levels, causing light that cannot penetrate heavy wall reduces light
Initiator generates adverse effect to the chemical and physical properties for solidifying post-consumer polymer material, thereby may be ensured that produced by the present invention
The photosensitivity Zr-B-Si-C ceramic forerunner is suitable for the preparation of coarse scale structures and is suitable as 3D printing ceramics
Raw material.
According to some preferred embodiments, the methylvinyldichlorosilane, the borane dimethylsulf iotade and described
The molar ratio of metallic sodium is (2~4): 1:(5~8) (such as 2:1:5,2:1:6,2:1:7,2:1:8,3:1:5,3:1:6,3:1:
7,3:1:8,4:1:5,4:1:6,4:1:7 or 4:1:8) it is preferably 3:1:6；And/or the first that first mixed liquor contains
The molar concentration of base hydridovinyldichlorosilane is 1~2mol/L (such as 1,1.2,1.5,1.8 or 2mol/L).
According to some preferred embodiments, the Chloromethyltrichlorosilane ((chloromethyl) trichlorosilane), the methyl
The molar ratio of chloromethyl dichlorosilane ((chloromethyl) methyl-dichlorosilane) and the bis cyclopentadienyl zirconium dichloride is (8~12): (8~
12): 1 (such as 8:8:1,8:9:1,8:10:1,8:11:1,8:12:1,9:8:1,9:9:1,9:10:1,9:11:1,9:12:1,
10:8:1、10:9:1、10:10:1、10:11:1、10:12:1、11:8:1、11:9:1、11:10:1、11:11:1、11:12:1、
12:8:1,12:9:1,12:10:1,12:11:1 or 12:12:1) be preferably 10:10:1, the magnesium metal, the reducing agent and
The molar ratio of the bis cyclopentadienyl zirconium dichloride is (25~35): (15~25): 1 (such as 25:15:1,25:20:1,25:25:1,30:
15:1,30:20:1,30:25:1,35:15:1,35:20:1 or 35:25:1) it is preferably 30:20:1；And/or second mixing
The molar concentration of the bis cyclopentadienyl zirconium dichloride contained in liquid be 0.08~0.12mol/L (such as 0.08,0.09,0.1,0.11 or
0.12mol/L)。
According to some preferred embodiments, the molar ratio of the metallic sodium and the magnesium metal is 1:1.
According to some preferred embodiments, vinyl and the sulfydryl third that the vinyl Zr-B-Si-C alkane contains
The molar ratio for the sulfydryl that acid esters contains is 1:1.In the present invention, sulfydryl and vinyl photopolymerization reaction be a free radical gradually
Copolyreaction, it is a chain growth and the polymerization reaction that chain tra nsfer back and forth carries out, and the proportion of sulfydryl and vinyl will affect double
Key conversion ratio；In the present invention, it is preferred to for vinyl Zr-B-Si-C alkane and mercaptopropionic acid ester will be contained by sulfydryl and vinyl functional
Group's 1:1 ratio mixing, is added suitable photoinitiator, by sulfydryl/vinyl Zr-B-Si-C photopolymerization reaction, synthesis has
The Zr-B-Si-C persursor material of photosensitivity.
In step (1) of the invention into step (4), the dosage and proportion, photoinitiator of related each raw material
Concentration in mixed liquor of dosage and each raw material to the Zr-B-Si-C ceramic forerunner of the obtained photosensitivity of the present invention
With important influence, suitable concentration of the proportion and each raw material of suitably each raw material of the present invention in mixed liquor
Advantageously ensure that obtained viscosity is low, cure shrinkage is low, the photosensitivity Zr-B-Si-C ceramics precursor of intensity and good toughness
Body；In the present invention, the more preferably described methylvinyldichlorosilane, the borane dimethylsulf iotade and the metallic sodium rub
You are than being 3:1:6, the molar ratio of the Chloromethyltrichlorosilane, the methyl chloride dimethyl dichlorosilane (DMCS) and the bis cyclopentadienyl zirconium dichloride
For 10:10:1, the molar ratio of the magnesium metal, the reducing agent and the bis cyclopentadienyl zirconium dichloride is 30:20:1, the poly- zirconium carbon silicon
Alkane and the methyl ethylene borosilicate alkane are uniformly mixed according to equivalent 2:1 ratio, what the vinyl Zr-B-Si-C alkane contained
The molar ratio for the sulfydryl that vinyl and the mercaptopropionic acid ester contain is 1:1, and the content of the photoinitiator is not more than
1wt% can so be further ensured that obtained viscosity is low, cure shrinkage is low, the photosensitivity Zr-B- of intensity and good toughness
Si-C ceramic forerunner.
According to some preferred embodiments, the temperature of first insulation reaction and/or second insulation reaction is
50~100 DEG C (such as 50 DEG C, 60 DEG C, 70 DEG C, 80 DEG C, 90 DEG C or 100 DEG C), the time be 5~36h (such as 5,10,15,20,
25,30 or 36h).In the present invention, first insulation reaction can be identical with the temperature and time of second insulation reaction
Or it is not identical.In the present invention, it is preferred to the temperature for first insulation reaction and second insulation reaction is 80 DEG C,
Time is 20h (heat preservation 20h).
According to some specific embodiments, process is prepared in situ in the photosensitivity Zr-B-Si-C ceramic forerunner
Include the following steps:
The synthesis of S1, mercaptopropionic acid ester: selecting trimethylolpropane is the monomer of different degrees of functionality, and is added appropriate acid
Catalyst is heated to boiling using toluene as solvent, and 3- mercaptopropionic acid is then added in a manner of dropwise addition and carries out esterification,
It is washed to neutrality after reaction, is evaporated under reduced pressure to mercaptopropionic acid ester products；Wherein, the dosage of solvent toluene is 100mL；It is acid
Catalyst is the concentrated sulfuric acid, dosage 0.01mol；The molar ratio of trimethylolpropane and 3- mercaptopropionic acid is 1:3.
The synthesis of S2, methyl ethylene borosilicate alkane: in N2Under inert gas shielding, 0.15mol methyl ethylene dichloro silicon
Alkane dissolves in 100mL toluene solution, and the borane dimethylsulf iotade of 0.05mol is then added, the first mixed liquor is obtained, then to described
The Na dechlorination of 0.3mol metal is added in first mixed liquor, stands at room temperature, extract, obtain liquid methyl ethylene boron after filtering
Silane.
The synthesis of S3, poly- zirconium carbon silane: in N2Under inert gas shielding, by (chloromethyl) trichlorosilane and (chloromethyl) first
10:10:1 ratio is mixed in simultaneously in 100mL tetrahydrofuran in molar ratio for base-dichlorosilane and bis cyclopentadienyl zirconium dichloride, obtains second
Mixed liquor；Then the metal Mg of 0.3mol is added into second mixed liquor in 50~100 DEG C of 5~36h of the lower reaction of heat preservation (the
One insulation reaction), obtain reaction solution；Then be added into the reaction solution sodium borohydride reduction agent 0.2mol continue at 50~
5~36h of reaction (the second insulation reaction) is carried out under 100 DEG C of heat preservations, organic solvent is added in the mixed solution of acquisition, extraction has
Machine phase removes organic solvent, obtains the poly- zirconium carbon silane of liquid by standing, separation, filtering.
The synthesis of S4, vinyl Zr-B-Si-C alkane: poly- zirconium carbon silane is dissolved in tetrahydrofuran organic solvent, according to etc.
Equivalent 2:1 ratio is added methyl ethylene borosilicate alkane and is uniformly mixed, in N2It slowly heats up under inert gas shielding, steams solvent,
Obtain the alkane of Zr-B-Si-C containing vinyl.
The conjunction of S5, sulfydryl/vinyl Zr-B-Si-C photopolymerization presoma (photosensitivity Zr-B-Si-C ceramic forerunner)
At: the mercaptopropionic acid ester that the alkane of Zr-B-Si-C containing vinyl prepared in darkroom according to S4 is synthesized with S1 is by sulfydryl and vinyl
The mixing of functional group 1:1 (molar ratio) ratio, is added suitable dimethoxybenzoin photoinitiator, reacts duration 1200 at room temperature
Second, by sulfydryl/vinyl Zr-B-Si-C photopolymerization reaction, synthesis has the Zr-B-Si-C persursor material of photosensitivity；
The photoinitiator dimethoxybenzoin dosage is no more than 1wt%.
The present invention provides photosensitive made from the in-situ preparation method as the present invention described in first aspect in second aspect
Perceptual Zr-B-Si-C ceramic forerunner.Photosensitivity Zr-B-Si-C ceramic forerunner prepared by the present invention have viscosity it is low,
Cure shrinkage is low, intensity and the advantages that good toughness, is highly suitable as superhigh temperature ceramics 3D printing raw material.
Hereafter the present invention will be further detailed by way of example, but protection scope of the present invention is unlimited
In these embodiments.
Embodiment 1
A kind of preparation method of photosensitivity Zr-B-Si-C ceramic forerunner fabricated in situ is present embodiments provided, it is described
Preparation method includes the following steps:
S1,13.4g trimethylolpropane is incorporated to 100mL toluene solvant, addition acidic catalyst is the concentrated sulfuric acid, 1g；Add
Heat is added 31.8g3- mercaptopropionic acid, is sufficiently washed to neutrality after reaction, then vacuum distillation obtains mercaptopropionic acid to after boiling
Ester.
S2, in N2Under inert gas shielding, 21.2g methylvinyldichlorosilane is dissolved in 100mL toluene solution, with
The borane dimethylsulf iotade of 3.8g is added afterwards, obtains the first mixed liquor, 6.9g metal Na is then added into first mixed liquor
Dechlorination stands at room temperature, extracts, obtains liquid methyl ethylene borosilicate alkane after filtering.
S3, in N2Under inert gas shielding, by 18.4g (chloromethyl) trichlorosilane (CH2Cl4Si), 16.4g (chloromethyl)
Methyl-dichlorosilane (C2H5Cl3Si) with 2.9g bis cyclopentadienyl zirconium dichloride (C10H10Cl2Zr) it is mixed in 100mL organic solvent tetrahydrofuran
In, obtain the second mixed liquor；Then the metal Mg of 7.3g is added toward second mixed liquor in the lower reaction 20h of 80 DEG C of heat preservations (the
One insulation reaction), obtain reaction solution；Sodium borohydride reduction agent then is added toward the reaction solution and continues at the lower progress of 80 DEG C of heat preservations
It reacts 20h (the second insulation reaction)；Organic solvent is added in the mixed solution of acquisition, extracts organic phase, by standing, divides
From, filtering, remove organic solvent, obtain the poly- zirconium carbon silane of liquid.
S4, poly- zirconium carbon silane is dissolved in 100mL tetrahydrofuran organic solvent, methyl ethylene borosilicate alkane is added, will gather
Zirconium carbon silane and methyl ethylene borosilicate alkane are uniformly mixed in equivalent 2:1 ratio, in N2It slowly heats up under inert gas shielding,
Solvent is steamed, the alkane of Zr-B-Si-C containing vinyl is obtained.
S5, the alkane of Zr-B-Si-C containing vinyl for obtaining the obtained mercaptopropionic acid ester of S1 and S4 mix, and 3.5mL peace is added
The dosage for ceasing fragrant dimethyl ether photoinitiator, that is, dimethoxybenzoin is 0.9wt%, is generated after abundant photopolymerization reaction photosensitive
Perceptual Zr-B-Si-C ceramic forerunner；Wherein, the vinyl and the sulfydryl third that the alkane of Zr-B-Si-C containing vinyl contains
The molar ratio for the sulfydryl that acid esters contains is 1:1.
There is the spy that viscosity is small, rate of polymerization is high by the photosensitivity Zr-B-Si-C ceramic forerunner that the present embodiment synthesizes
Point；In the present embodiment, it takes the photosensitivity Zr-B-Si-C ceramic forerunner liquid of synthesis to shake to be uniformly mixed, vacuum defoamation,
Glass mold is poured into, mold is placed horizontally at 20mW/cm as 20 DEG C of waters bath with thermostatic control2Under ultraviolet lamp, after irradiation solidification, obtain
To the ceramic prepolymer with certain elasticity, the presoma for illustrating that the present invention synthesizes can be used for photocuring 3D printing superhigh temperature ceramics
The raw material of complex structural member.
Embodiment 2
Embodiment 2 is substantially the same manner as Example 1, the difference is that:
In step s 5, the dosage of dimethoxybenzoin photoinitiator is that the dosage of the i.e. described dimethoxybenzoin of 1mL is
0.25wt%.
Embodiment 3
Embodiment 3 is substantially the same manner as Example 1, the difference is that:
In step s 5, the dosage of dimethoxybenzoin photoinitiator is that the dosage of the i.e. described dimethoxybenzoin of 2mL is
0.5wt%.
Embodiment 4
Embodiment 4 is substantially the same manner as Example 1, the difference is that:
In step s 5, the dosage of dimethoxybenzoin photoinitiator is that the dosage of the i.e. described dimethoxybenzoin of 3mL is
0.75wt%.
Embodiment 5
Embodiment 5 is substantially the same manner as Example 1, the difference is that:
In step s 5, the dosage of dimethoxybenzoin photoinitiator is that the dosage of the i.e. described dimethoxybenzoin of 6mL is
1.5wt%.
Embodiment 6
Embodiment 6 is substantially the same manner as Example 1, the difference is that:
The dosage of trimethylolpropane is 26.8g, the trimethylolpropane and the 3- mercaptopropionic acid in step sl
Molar ratio be 2:3.
The dosage of borane dimethylsulf iotade is 7.6g, the methylvinyldichlorosilane, borane dimethylsulfide in step s 2
The molar ratio of ether and metallic sodium is 3:2:6.
Bis cyclopentadienyl zirconium dichloride (C in step s310H10Cl2Zr dosage) is 5.8g, the Chloromethyltrichlorosilane, the first
The molar ratio of base chloromethyl dichlorosilane and the bis cyclopentadienyl zirconium dichloride is 5:5:1；The dosage of metal Mg is 14.6g, the metal
The molar ratio of magnesium, the reducing agent and the bis cyclopentadienyl zirconium dichloride is 15:10:1.
Comparative example 1
S1, in N2Under inert gas shielding, by 18.4g (chloromethyl) trichlorosilane, 16.4g (chloromethyl) methyl-dichloro
Silane and 2.9g bis cyclopentadienyl zirconium dichloride are mixed in 100mL organic solvent tetrahydrofuran, obtain mixed liquor；Then toward the mixed liquor
The metal Mg of 7.3g is added in the lower reaction 20h of 80 DEG C of heat preservations, obtains reaction solution；Sodium borohydride then is added also toward the reaction solution
Former agent continues under 80 DEG C of heat preservations and carries out reaction 20h；Organic solvent is added in the mixed solution of acquisition, extracts organic phase, leads to
Standing, separation, filtering are crossed, organic solvent is removed, obtains the poly- zirconium carbon silane of liquid.
S2, poly- zirconium carbon silane is dissolved in 100mL tetrahydrofuran organic solvent, methyl ethylene borosilicate alkane is added, will gather
Zirconium carbon silane and methyl ethylene borosilicate alkane are uniformly mixed in equivalent 2:1 ratio, in N2It slowly heats up under inert gas shielding,
Solvent is steamed, the alkane of Zr-B-Si-C containing vinyl is obtained.
S3, the alkane of Zr-B-Si-C containing vinyl for obtaining S2 mixing, are added 20mL dimethoxybenzoin photoinitiator and pacify
The dosage for ceasing fragrant dimethyl ether photoinitiator is 5wt%, generates Zr-B-Si-C presoma after abundant photopolymerization reaction.
In the present invention, the photosensitivity Zr-B-Si-C ceramic forerunner and comparative example 1 of Examples 1 to 6 preparation are made
Standby Zr-B-Si-C presoma is tested for the property, and the performance test results are as shown in table 1, and test method is as follows:
Viscosity: it at 25 DEG C, is tested using NDJ-8s digital display rotational viscometer according to GB/T1024-1988.
Curing time: the composition for being coated with 250 μ m-thicks by four sword wet film makers is sent on pretreated sheet glass
Enter and solidified in the laser beam of 405nm wavelength, with manual time-keeping, record curing time, is touched with finger with certain pressure
It touches by the ceramic forerunner of laser beam photo, thinks when tack-free cured.
Cure shrinkage: testing shrinking percentage with densimetry, is first surveyed using bottle method according to standard GB/T 15223-2008
The density of front and back must be solidified, calculated cure shrinkage (shrinking percentage), cure shrinkage be density after solidifying with it is before curing close
Degree difference with solidify after density percentage.
Intensity: standard GB/T1040 is pressed simultaneously to photosensitivity Zr-B-Si-C ceramic forerunner of the invention and contrast sample
It takes the condition of cure for solidifying 3min in the irradiation of 405nm wavelength laser beam that sample to be tested is made, tests and draw by standard GB/T9341
Stretch intensity, bending strength.
Table 1: the performance indicator of Examples 1 to 6 and comparative example 1.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although
Present invention has been described in detail with reference to the aforementioned embodiments, those skilled in the art should understand that: it still may be used
To modify the technical solutions described in the foregoing embodiments or equivalent replacement of some of the technical features；
And these are modified or replaceed, technical solution of various embodiments of the present invention that it does not separate the essence of the corresponding technical solution spirit and
Range.
Claims (10)
1. a kind of in-situ preparation method of photosensitivity Zr-B-Si-C ceramic forerunner, which is characterized in that the method includes such as
Lower step:
(1) methylvinyldichlorosilane and borane dimethylsulf iotade are uniformly mixed with toluene solution, obtain the first mixed liquor, so
Metallic sodium is added into first mixed liquor afterwards and carries out dechlorination, obtains methyl ethylene borosilicate alkane；
(2) Chloromethyltrichlorosilane, methyl chloride dimethyl dichlorosilane (DMCS) and bis cyclopentadienyl zirconium dichloride are uniformly mixed with organic solvent, are obtained
Then second mixed liquor magnesium metal is added into second mixed liquor and carries out the first insulation reaction, obtains reaction solution, then past
Reducing agent is added in the reaction solution and carries out the second insulation reaction, obtains poly- zirconium carbon silane；
(3) the methyl ethylene borosilicate alkane that step (1) obtains and the poly- zirconium carbon silane mixture that step (2) obtains is uniform, it obtains
Vinyl Zr-B-Si-C alkane；
(4) the vinyl Zr-B-Si-C alkane that step (3) obtains is uniformly mixed with mercaptopropionic acid ester, obtains mixture, it is then past
Photoinitiator is added in the mixture and causes photopolymerization reaction, photosensitivity Zr-B-Si-C ceramic forerunner is made.
2. in-situ preparation method according to claim 1, it is characterised in that:
The mercaptopropionic acid ester is that polyalcohol is obtained with 3- mercaptopropionic acid through esterification；
The polyalcohol is selected from ethylene glycol, 6- hexylene glycol, 1,3- propylene glycol, glycerine, trimethylolpropane, trihydroxy methyl second
One of alkane, pentaerythrite, polypropylene glycol and multifunctional norbornene are a variety of；
Preferably, it is a variety of to be selected from one of 1,3-PD, trimethylolpropane and pentaerythrite for the polyalcohol.
3. in-situ preparation method according to claim 2, it is characterised in that:
The polyalcohol is trimethylolpropane, the molar ratio of the trimethylolpropane and the 3- mercaptopropionic acid be 1:(2~
It 4) is preferably 1:3.
4. in-situ preparation method according to claim 1, it is characterised in that:
The organic solvent is selected from one of tetrahydrofuran, ether and isopropyl ether or a variety of；And/or
The reducing agent is selected from the group being made of lithium aluminium hydride reduction and sodium borohydride；And/or
The photoinitiator is selected from benzoyl peroxide, isopropyl thioxanthone, 2,4,6- trimethyl benzoyl diphenyl base oxygen
Change phosphine, bis- (2,4,6- trimethylbenzoyl) phosphine oxides of phenyl, the oxidation of 2,4,6- trimethylbenzoyl-ethyoxyl-phenyl
One of phosphine, benzophenone and dimethoxybenzoin are a variety of；
Preferably, the photoinitiator is dimethoxybenzoin.
5. in-situ preparation method according to claim 1, it is characterised in that:
The content of photoinitiator described in the photosensitivity Zr-B-Si-C ceramic forerunner is not more than 1wt%.
6. in-situ preparation method according to any one of claims 1 to 5, it is characterised in that:
The molar ratio of the methylvinyldichlorosilane, the borane dimethylsulf iotade and the metallic sodium is (2~4): 1:(5
It~8) is preferably 3:1:6.
7. in-situ preparation method according to any one of claims 1 to 5, it is characterised in that:
The molar ratio of the Chloromethyltrichlorosilane, the methyl chloride dimethyl dichlorosilane (DMCS) and the bis cyclopentadienyl zirconium dichloride be (8~
12): (8~12): 1 preferably 10:10:1, the molar ratio of the magnesium metal, the reducing agent and the bis cyclopentadienyl zirconium dichloride are (25
~35): (15~25): 1 preferably 30:20:1.
8. in-situ preparation method according to any one of claims 1 to 5, it is characterised in that:
The molar ratio for the sulfydryl that the vinyl and the mercaptopropionic acid ester that the vinyl Zr-B-Si-C alkane contains contain is 1:1.
9. in-situ preparation method according to any one of claims 1 to 5, it is characterised in that:
The temperature of first insulation reaction and/or second insulation reaction is 50~100 DEG C, and the time is 5~36h.
10. the photosensitivity Zr-B-Si-C ceramics precursor as made from claim 1 to 9 described in any item in-situ preparation methods
Body.
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