CN106245055B - A kind of electrochemical method for synthesizing of the liquid polysilane containing block structure - Google Patents

A kind of electrochemical method for synthesizing of the liquid polysilane containing block structure Download PDF

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CN106245055B
CN106245055B CN201610838754.3A CN201610838754A CN106245055B CN 106245055 B CN106245055 B CN 106245055B CN 201610838754 A CN201610838754 A CN 201610838754A CN 106245055 B CN106245055 B CN 106245055B
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block structure
containing block
synthesizing
electrochemical method
liquid polysilane
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CN106245055A (en
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吴芸紫
谢征芳
王浩
简科
邵长伟
王军
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National University of Defense Technology
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    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B3/00—Electrolytic production of organic compounds
    • C25B3/20—Processes
    • C25B3/25—Reduction
    • 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

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Abstract

The present invention relates to a kind of electrochemical method for synthesizing of liquid polysilane containing block structure; the following steps are included: (1) is under inert gas atmosphere protection; halogenated silanes monomer is dissolved in organic solvent in electrolytic cell, stirs and be added electrolyte, obtains component a；(2) it under inert gas atmosphere protection, is powered to component a, cell reaction occurs and obtains component b；(3) end-capping reagent is added dropwise and terminates reaction, filtering and concentrating, extraction centrifugation, further concentration purification is to get the liquid polysilane containing block structure.The method of the present invention is gradually polymerize using cell reaction, it joined high conductive electrolyte, size of current and reactant concentration are controlled, molecular weight of product is controllable and uniformity is good, can further prepare the liquid polysilane containing block structure of purity is high, narrow molecular weight distribution.Electrochemical process simple process can react under normal temperature and pressure without conditions such as high temperature, high pressures, and condition is easily controllable, be suitable for large-scale production.

Description

A kind of electrochemical method for synthesizing of the liquid polysilane containing block structure
Technical field
The present invention relates to a kind of electrochemical method for synthesizing of liquid polysilane containing block structure, and in particular to one kind is with nothing The method of machine electrolyte and halogenated silanes electrochemistry formated liquid polysilane.
Background technique
SiC fiber has excellent high temperature resistant, anti-oxidant, corrosion-resistant and mechanical property, has well with ceramic matrix Compatibility, be the important reinforcement for preparing high-performance ceramic based composites (CMC).It is widely used in aerospace and The fields such as nuclear industry are one of the critical materials for developing aerospace cause.
Precursor pyrolysis and hot pressing is the SiC fiber main method for preparing thin diameter, is generally divided into synthesis, the precursor of precursor Melt spinning, fibrinogen cure treatment and fusion-free fibre the four big processes such as high temperature firing.1970s, day Continuous SiC fiber of the research group of this Yajima professor using Polycarbosilane (PCS) as precursor detailed information diameter.At present Until, PCS is still most successful and most representative precursor in preparation SiC fiber precursor.
The synthetic method of PCS is to synthesize polydimethylsiloxane through Wurtz coupling process polycondensation with dichlorodimethylsilane (PDMS), it then by PDMS Pintsch process resets to obtain PCS.Since its molecular weight only has 1000-10000, the original that PCS spinning obtains Silk is very fragile and solvable fusible, therefore need to aoxidize or be crosslinked otherwise insoluble insoluble to obtain in air Fiber just keeps fiber shape in high temperature firing.Infusible fiber generally passes through in 1200-1400 DEG C of inert atmosphere (N2、 Ar firing turns to SiC fiber with inorganic in).
The synthetic method of polysilane is in addition to Wurtz coupling process, and there are also homogeneous dehydrogenation coupling process, ring-opening polymerisation method, yin Ionic polymerization method and electrochemical reducing etc..
Wurtz coupling process synthesizes homopolymer and copolymer, and molecular weight is high, but reaction condition is fierce, and rate is difficult to control, and takes It is restricted for base type, molecular weight distribution is uneven, and molecular weight distribution is in polydispersity；Homogeneous dehydrogenation coupling process yield is high, SiRH2Sealing end, generates almost without ring, and narrow molecular weight distribution can introduce new official's energy side base, and selectivity is good, but raw material at This height, molecular weight is low, is in multi-modal, and steric interference is big；Ring-opening polymerisation method reaction condition is mild, the microcosmic knot of polymer Structure is controllable, but the activity functional groups that can be introduced are extremely limited, while the inhibition of the biggish substituent group of volume is apparent；Yin Ionic polymerization method molecular weight is high, narrow molecular weight distribution, and yield is high, can finely control polysilane structure, but what can be introduced directly into takes Extremely limited for base, the steric effect of substituent group is obvious.
Electrochemical reducing is a kind of polysilane synthetic method of rising in recent years, the method be by cathode in electrolytic cell also Former silane monomer produces polysilane.Electrochemical reaction mild condition, can composite structure is regular and molecular weight distribution compared with Narrow polysilane, yield are high.Hydroxyl, amino isoreactivity group can be especially introduced, so that the functionalization of polysilane be made to be opened up Width, therefore electrochemical reducing has good development prospect, is expected to substitution Wurtz method synthesis polydimethylsiloxane.
1999, Osaka, Japan gas company developed an electrochemistry route, and a magnesium is contained in an electrolytic cell Anode, an iron negative electrode, lithium chloride and frerrous chloride electrolyte, tetrahydrofuran solvent, at room temperature and atmospheric pressure, dichloro alkyl The polysilane average molecular weight of silane reductive polymerization, generation is about 10,000, but required voltage is higher.Kunai etc. is sun with mercury Pole, platinum are cathode, and glycol dimethyl ether is that solvent has synthesized various disilane, and yield is 45~94%, but required electrode conditions It is harsh.Shono is electrode in the same electrolyzer with THF and LiClO using magnesium4For electrolyte, it is electrolysed dichloromethyl phenylsilane Synthetic mesh polysilane (PMPS), yield 22%, molecular weight 3200, molecular weight distributing index 3.8,500~ 1500nm wavelength has strong absorption.
To sum up, presently, there are method, some reaction conditions are violent, have certain risk and reaction is not easy to control；Have Electric conductivity poor due to electrolyte during the energization, required voltage is higher, conduction time is longer or yield is lower, causes Polysilane yield or molecular weight are lower.
Summary of the invention
The technical problem to be solved by the present invention is to, overcome the deficiencies of existing technologies, provide it is a kind of in normal temperature and pressure, it is lesser The electrochemical method for synthesizing of ceramic fiber precursor under voltage passes through electrochemistry also by electrolyte and a variety of halogenated silanes monomers Former method synthesizes SiC ceramic fiber precursor, a kind of electrochemical method for synthesizing of the liquid polysilane containing block structure.
It is as follows that the technical scheme adopted by the invention to solve the technical problem: a kind of electricity of the liquid polysilane containing block structure Chemical synthesis process electrochemical method for synthesizing, comprising the following steps:
(1) halogenated silanes monomer is placed in reactor, organic solvent dissolution is added, stirs and be added electrolyte, reacts It is vacuumized in system, then with gas in inert gas replacement reaction system to normal pressure, repeats >=3 times, react to obtain active component a；
(2) in an inert atmosphere, it is powered to active component a, stirring occurs polymerization reaction and obtains component b, and dropwise reaction is whole Only agent is filtered and is concentrated filtrate to reaction terminating, be added in n-hexane and be centrifuged, collect supernatant liquid；Continue to be concentrated, be centrifuged, receives Collect supernatant liquid, it is repeatedly rear up to the liquid polysilane containing block structure twice.
Further, in step (1), the molecular formula of the halogenated silanes monomer is R4-mSiXm, wherein R has to be oxygen-free Machine group, preferably one or more of the saturated hydrocarbyl, unsaturated alkyl, halohydrocarbyl, aromatic radical of atomicity≤10 C, X It is the inorganic group number being connected with Si for one or more of inorganic group Cl, Br, I, F, m.
The species number of halogenated silanes is two or more.
Further, in step (1), the electrolytic cell is the electrolytic cell for being equipped with the electrodes such as Mg-Mg, Fe-Fe, Al-Al.
Further, in step (1), the electrolyte is LiAlH4、NaAlH4、KAlH4One or more of.
Further, in step (1) and (2), the organic solvent be tetrahydrofuran, benzene,toluene,xylene, monochloro methane, Methylene chloride, chloroform, carbon tetrachloride, glycol dimethyl ether, acetone, N, one or more of N- dimethyl sulfoxide.Institute It states organic solvent and is intended only as solvent, be not involved in synthetic reaction.
Further, in step (2), the reaction terminating agent is methyl-magnesium-bromide, bromoethane, a chlorobutane, chlorobenzene, allyl The one or more of base chlorine.
Further, in step (1) and (2), the reaction time determines according to the size of electrical current.
Further, in step (1) and (2), the inert gas is nitrogen or argon gas.
A kind of SiC ceramic precursor, the SiC ceramic precursor include according to the above-mentioned poly- silicon of the liquid containing block structure Liquid polysilane prepared by the electrochemical method for synthesizing of alkane.
Compared with the existing technology, using hydrogenation aluminium salt as electrolyte, the advantages of polysilane is prepared by electrochemical reaction Be: electrochemical reducing, which prepares polysilane, to be polymerize at normal temperatures and pressures, and reaction condition is mild, and risk is low, without height The harsh conditions such as warm high pressure；Aluminium salt is hydrogenated as electrolyte, electric conductivity is higher than common lithium salts, such as LiCl, LiClO4、LiBH4With And the other salt for being usually used in electrolyte such as NaCl, AlCl3、Et4NBF4Deng；Electroreduction reaction can be under lesser voltage Occur, and keeps a certain size current strength；Furthermore it is possible to reach solvent using the activity that hydrogenation aluminium salt is reacted with water The purpose further removed water.The method of the present invention has the advantages that
(1) polysilane is prepared by electrochemical method, it, can be to halogen under normal temperature and pressure without conditions such as high temperature, high pressures Plain silane is polymerize, and condition is easily controllable and energy saving；
(2) electrolyte and halogen silane monomer be not oxygen-containing, and polymerization will not introduce additional oxygen, therefore it is poly- to reduce product The oxygen content of silane；
(3) excellent conductivity of electrolyte can realize the Faradaic current of larger intensity under lesser voltage
(4) by the level of monomer, gradually it polymerize, product chain length is controllable and uniformity is good, can prepare with high purity, uniform The good polysilane of property.
Detailed description of the invention
Hereinafter, carrying out the embodiment that the present invention will be described in detail in conjunction with attached drawing, in which:
Fig. 1 is the reaction equation of monomer polymerization in the embodiment of the present invention 1；
Fig. 2 is the infrared spectrum (FTIR) of the liquid polysilane containing block structure of the embodiment of the present invention 1；
Fig. 3 is hydrogen nuclear magnetic resonance spectrogram of the liquid polysilane containing block structure of the embodiment of the present invention 1 in deuterium chlorine (1H-NMR)
Fig. 4 is the gel permeation chromatography (GPC) of the liquid polysilane containing block structure of the embodiment of the present invention 1；
Fig. 5 is the infrared spectrum (FTIR) of the crosslinking polysilane containing block structure of the embodiment of the present invention 1；
Fig. 6 is the thermogravimetric curve (TG) of the crosslinking polysilane containing block structure of the embodiment of the present invention 1；
Fig. 7 is the X-ray diffraction curve after the crosslinking polysilane pyrolysis containing block structure of the embodiment of the present invention 1 (XRD)。
Specific embodiment
Below with reference to embodiment and attached drawing, the invention will be further described.
Embodiment 1
The present embodiment the following steps are included:
(1) by 5.676g (CH3)2SiCl2(44mmol) and 5.06g (CH3)HSiCl2(44mmol) is placed in flask, is added 0.6g LiAlH4, the dissolution of 100mL anhydrous tetrahydro furan is added, is vacuumized in reaction system, then with nitrogen displacement reaction system Interior gas is repeated 3 times to normal pressure, stirs (component a)；
(2) it under nitrogen atmosphere protection, being powered to reaction system in step (1), electrical current is set as 200mA, Reaction shown in 25.6 hours generation Fig. 1, is added 1mlCH3MgBr terminate reaction, filter and be concentrated filtrate, add 50ml just oneself Alkane, centrifuging and taking supernatant liquid continue to be concentrated, and supernatant liquid is collected in centrifugation, repeatedly rear twice poly- up to the liquid containing block structure Silane.The liquid polysilane can be used as the precursor of SiC ceramic.
Fig. 2 is the infrared spectrum of the liquid polysilane containing block structure of the embodiment of the present invention 1, as seen from the figure, wavelength 1000~1050cm-1The peak at place is the out-of-plane vibration peak of Si-O-Si key, 2130cm-1Place is the stretching vibration peak of Si -- H bond, 950-800cm-1The peak at place is the deformation vibration peak of Si -- H bond.And 3000cm-1The peak at place is that stretching for c h bond is saturated on methyl Vibration peak, 1270cm-1The peak at place is Si-CH3Middle CH3The deformation vibration peak of key, 770cm-1The peak at place is the flexible vibration of Si-C key Dynamic peak.
Fig. 3 is nucleus magnetic hydrogen spectrum figure of the liquid polysilane containing block structure of the embodiment of the present invention 1 in deuterium chlorine, can be obtained Know, the spike at chemical shift δ=7.26ppm is the intrinsic proton magnetic hill of deuterium chlorine, and spike is deuterium at chemical shift δ=0.24ppm The peak chlorine internal standard TMS, the spike at chemical shift δ=0.35ppm correspond to Si-CH3On hydrogen, broad peak at δ=3.8~4.0ppm Belong to the hydrogen on Si-H.The figure is the result shows that silane monomer and LiAlH4Reaction generates Si -- H bond.
Fig. 4 is the GPC spectrogram of the liquid polysilane containing block structure prepared by the present embodiment 1, the result shows that, liquid is poly- The number-average molecular weight M of silanenIt is 660, weight average molecular weight MwIt is 803, molecular weight distribution index PDi (Mw/Mn) it is 1.22, explanation Liquid polysilane molecular weight has obtained good control, and molecular weight distribution is relatively narrow.
Fig. 5 is the infrared spectrum of the liquid polysilane cross-linking products containing block structure of the embodiment of the present invention 1, can by figure Know, 1000~1050cm of wavelength-1The peak at place is the out-of-plane vibration peak of Si-O-Si key, 2130cm-1Place is the flexible vibration of Si -- H bond Dynamic peak, 950-800cm-1The peak at place is the deformation vibration peak of Si -- H bond.And 3000cm-1The peak at place is that c h bond is saturated on methyl Stretching vibration peak, 1270cm-1The peak at place is Si-CH3Middle CH3The deformation vibration peak of key, 770cm-1The peak at place is stretching for Si-C key Contracting vibration peak.With the comparison of the infrared spectrogram of liquid polysilane it is found that the intensity at Si -- H bond peak weakens, illustrate in cross-linking process Coupling reaction has occurred in Si -- H bond.
Fig. 6 is the TG curve of crosslinking polysilane prepared by the present embodiment 1, it can be seen that polysilane is in nitrogen atmosphere Ceramic yield is 67.35% at 1000 DEG C.
Fig. 7 is that crosslinking polysilane prepared by the present embodiment 1 is ceramic in argon gas under 1000 DEG C, 1200 DEG C, 1400 DEG C of high temperature Change the X-ray diffractogram of product, as seen from the figure, in nitrogen atmosphere at a high temperature of 1400 DEG C, ceramic product is in the angle of diffraction The diffraction maximum of 38.5 °, 60.5 °, 72.5 ° positions is (1 1 1) crystallographic plane diffraction peak (JCPDS PDF#65-0360) of SiC, explanation Product is SiC crystal under this superhigh temperature, it was demonstrated that the polysilane of the implementation case can prepare SiC ceramic.
By embodiment 1 it is found that electrolysis method reduction chlorosilane monomer prepares the polysilane containing block structure, nothing under normal temperature and pressure High voltage need to be applied, can cause and polymerize with containing halogen silane, it can be achieved that gradually polymerizeing, product chain length is controllable and uniform Property it is good, can further prepare purity is high, the good ceramics of uniformity, condition is easily controllable and energy saving.Simple process, and can connect It is continuous to carry out, it is suitable for large-scale production.
It is obvious to a person skilled in the art that invention is not limited to the details of the above exemplary embodiments, Er Qie In the case where without departing substantially from spirit or essential attributes of the invention, the present invention can be realized in other specific forms.Therefore, no matter From the point of view of which point, the present embodiments are to be considered as illustrative and not restrictive, and the scope of the present invention is by appended power Benefit requires rather than above description limits, it is intended that all by what is fallen within the meaning and scope of the equivalent elements of the claims Variation is included within the present invention.
In addition, it should be understood that although this specification is described in terms of embodiments, but not each embodiment is only wrapped Containing an independent technical solution, this description of the specification is merely for the sake of clarity, and those skilled in the art should It considers the specification as a whole, the technical solutions in the various embodiments may also be suitably combined, forms those skilled in the art The other embodiments being understood that.

Claims (8)

1. a kind of electrochemical method for synthesizing of the liquid polysilane containing block structure, it is characterised in that: the following steps are included:
(1) halogenated silanes monomer is placed in electrolytic cell, a certain amount of organic solvent is added and dissolves and a certain amount of electrolysis is added Matter vacuumizes in reaction system, then with gas in inert gas replacement reaction system to normal pressure, repeats >=3 times, obtain active component a；
(2) under inert gas atmosphere protection, size of current is controlled, is powered to component a, cell reaction occurs and obtains component b；Drop Reaction terminating agent is added to terminate reaction, filtering and concentrating, extraction centrifugation, further concentration purification is poly- to get the liquid containing block structure Silane；
In step (1), the electrolyte is LiAlH4、NaAlH4、KAlH4One or more of.
2. the electrochemical method for synthesizing of the liquid polysilane according to claim 1 containing block structure, it is characterised in that: step Suddenly in (1), the halogenated silanes monomer molecule formula is R4-mSiXm, wherein R is oxygen-free organic group, specially C atom ≤ 10 one or more of saturated hydrocarbyl, unsaturated alkyl, halohydrocarbyl are counted, X is in inorganic group Cl, Br, I or F One or more, m are the halogen atom number being connected with Si；The species number of halogenated silanes is two or more.
3. the electrochemical method for synthesizing of the liquid polysilane according to claim 1 containing block structure, it is characterised in that: step Suddenly in (1), the electrolytic cell is the electrolytic cell for being equipped with Mg-Mg, Fe-Fe, Al-Al electrode.
4. the electrochemical method for synthesizing of the liquid polysilane according to claim 1 containing block structure, it is characterised in that: step Suddenly in (1), the organic solvent is tetrahydrofuran, benzene,toluene,xylene, monochloro methane, methylene chloride, chloroform, tetrachloro Change carbon, glycol dimethyl ether, acetone, N, one or more of N- dimethyl sulfoxide.
5. the electrochemical method for synthesizing of the liquid polysilane according to claim 1 containing block structure, it is characterised in that: step Suddenly in (2), the reaction terminating agent is the one or more of methyl-magnesium-bromide, bromoethane, a chlorobutane, chlorobenzene, allyl chloride.
6. the electrochemical method for synthesizing of the liquid polysilane according to claim 1 containing block structure, it is characterised in that: step Suddenly in (2), the time of the reaction determines according to the size of electrical current.
7. the electrochemical method for synthesizing of the liquid polysilane according to claim 1 containing block structure, it is characterised in that: step Suddenly in (2), the inert gas is nitrogen or argon gas.
8. a kind of SiC ceramic precursor, it is characterised in that: the SiC ceramic precursor includes any one of according to claim 1-7 Liquid polysilane prepared by the electrochemical method for synthesizing of the liquid polysilane containing block structure.
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