CN103214675A - Poly(methylsilane-carbosilane) and preparation method thereof - Google Patents
Poly(methylsilane-carbosilane) and preparation method thereof Download PDFInfo
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Abstract
The invention discloses poly(methylsilane-carbosilane) and a preparation method thereof. The structural formula of the poly(methylsilane-carbosilane) copolymer is shown in formula I which is shown in the specification, wherein x=0-0.2, y=0.03-0.2, z=0-0.25, n=10-30, R1 represents Me, Ph or C2-C8 aromatic hydrocarbon or alkane, R2 represents Me or H, and Y represents a group containing C-C unsaturated bond. The preparation method of the poly(methylsilane-carbosilane) comprises the following steps of: in an organic solvent, carrying out a Wurtz type condensation polymerization reaction on a chlorosilane monomer mixture and insufficient alkali metal to synthesize Si-Cl bond-containing intermediate polymer; and then obtaining liquid methylsilane-carbosilane copolymer containing a C-C unsaturated bond through a grignard coupling reaction. The poly(methylsilane-carbosilane) disclosed by the invention can be served as a silicon carbide ceramic precursor, has the advantages of high ceramic yield, good storage stability and adjustability in structure composition, and can be applied to precursors of ceramic coatings and block body materials, and impregnants of composite materials.
Description
Technical field
The present invention relates to a kind of poly-(methyl-monosilane-carbon silane) and preparation method thereof.
Background technology
Silicon carbide polymer ceramic precursor body is the preparation silicon carbide fiber, is equipped with the matrix resin of carborundum based material as the PIP legal system, the crucial starting material in fields such as silicon carbide-based high temperature resistant bonding, connection and complex phase ceramic preparation.At home and abroad in Yan Jiuhekaifa numerous silicon carbide precursor bodies, at present technology the most ripe, obtain wide use be by Pintsch process (about 470 ℃) Polycarbosilane (PCS) that the Kumada rearrangement obtains to take place by polydimethyl silane (PDMS) by the Yajima invention.Wherein, PDMS is obtained by excessive molten metal sodium reduction coupling polycondensation in xylene solvent by dimethyldichlorosilane(DMCS); And the cracking of PDMS needs high temperature or High Temperature High Pressure, has the low problem of facility investment height or synthetic yield, so the production cost height of PCS.Simultaneously, this PCS is the higher solid resin of softening temperature when ceramic yield is higher, when as the soaker of carborundum based material, needs to add solvent, and dipping efficient is not high.In addition, the C/Si of PCS split product ratio departs from pure SiC metering than higher, also is disadvantageous to some application.
Deficiency at PCS, American I nterrante laboratory is invented and has been carried out improvement and commercialization production by StarFire System company, prepared a kind of liquid Polycarbosilane (HPCS by grignard reaction coupling and lithium aluminium hydride reduction, AHPCS), its relevant patent is seen US2004/0063984A1, US2004/0138046A1, US2004/0138046A1, US2007/0093587A1, WO2008/066657-A1, WO2008/066662A2 etc.AHPCS is with-SiH
2CH
2-be backbone structure, the Polycarbosilane of preparation is generally branched structure, the low-viscosity (mobile) liquid of high ceramic yield, the suitable soaker of doing matrix material, but this route exists cost height, shortcoming that required quantity of solvent is big, and a large amount of si-h bonds that exist in the polymkeric substance make its storability relatively poor and be difficult to bulk material with the no bubble structure of its preparation.Utilize bigger mainly the comprising of influence in the basic metal reductive coupling route synthetic presoma: polydimethyl silane (PDMS) and poly-methyl hydrogen silane (PMS).The former storage stability is good, spinning property is high, be the presoma that commercial silicon carbide fiber is produced unique a large amount of uses at present, but it need can the cracking rearrangement obtain Polycarbosilane under severe condition, and the rich carbon of its split product is more, and C/Si is than being difficult for regulation and control as required.
The SiC presoma that another kind has material impact is polymethyl silicane (PMS) and modified product thereof.Is liquid by dimethyl dichlorosilane (DMCS) by the PMS that the condensation of Wurtz reaction sodium obtains, and ceramic yield is not high, and stability is bad, but spontaneous combustion in the air; And obviously improve through its ceramic yield after the 280-350 ℃ of left and right sides reflow treatment and stability, but also becoming solvable or insoluble infusible solid, its hydrolysis products contains element silicon more than needed usually simultaneously.
The PMS synthetic yield is not high in order to overcome, the not good enough drawback of stability, and regulation and control C/Si ratio, improves workability, and people carry out common sodium and contract by introducing other monomer again.As Bruno Boury etc. with MeSiCl
3And ViSiHCl
2With MeHSiCl
2Carry out common sodium and contract, obviously improved ceramic yield, and the adding antioxidant BHT improves stability in storage.In a word, all these improvement have obtained certain success, but still have some shortcomings to overcome.As in PMS and modifying process thereof in the past, in order to make Si-Cl key complete reaction, often adopt excessive sodium Metal 99.5, residual metal sodium brings certain security risk and cost to aftertreatment on the one hand, and the introducing to carbon carbon unsaturated link(age)s such as vinyl simultaneously brings certain obstacle.
Summary of the invention
The objective of the invention is to overcome the defective of above-mentioned materials, a kind of novel modified polymethyl silicane (promptly poly-(methyl-monosilane-carbon silane) multipolymer) and preparation method thereof is provided.
The structural formula of poly-(methyl-monosilane-carbon silane) multipolymer provided by the present invention is suc as formula shown in the I:
(formula I)
Wherein, x=0-0.2, y=0.03-0.2, z=0-0.25; N=10-30 (mean value); R
1Be Me (methyl) Ph (phenyl), the aromatic hydrocarbons of C2-C8 or alkane; R
2, R
3Be Me or H, Y is carbon containing carbon unsaturated link(age) or alkoxyl group active groups such as methoxyl group, oxyethyl group such as vinyl, allyl group, ethynyl;
Be the branched structure unit.
In this polymer molecular structure, (the CH of carbon silane
2SiR
2)
y(R
2Being Me or H) being introduced in when improving stability in storage of branched structure can obviously improve ceramic yield, and introduce (CH
2SiMe
2)
zStructure mainly is in order further to improve stability in storage, and is used for C/Si ratio in the cracking potteryization product.(MeSiR
1)
xStructure is the molecular structure of introducing for application-specific, is also included within the sodium condensation reaction part Si-H and participates in condensation reaction and form (MeSi)
xBranched structure.The particularly introducing of carbon carbon unsaturated link(age) such as end-vinyl has good processibility when can realize high ceramic yield, can be cured than under the mild conditions by platinum catalyst or superoxide.
For realizing goal of the invention, the present invention adopts following preparation route: in organic solvent, the chlorosilane monomer mixture synthesizes the midbody polymer that contains remaining Si-Cl key of straight or branched structure with exposed basic metal generation Wurtz type linked reaction, react by Grignard reagent subsequently and introduce carbon carbon unsaturated link(age), thereby obtain containing the liquid copolymer of active group with vinyl, allyl group or alkynyl.
Described chlorosilane monomer mixture is by MeHSiCl
2And ClCH
2SiR
2Cl
2Form; Perhaps described chlorosilane monomer mixture is by MeHSiCl
2, ClCH
2SiR
2Cl
2And following at least a monomer is formed: MeR
1SiCl
2And ClCH
2SiMeR
3Cl;
Wherein, described MeR
1SiCl
2Middle R
1Be Me, Ph, the aromatic hydrocarbons of C2-C8 or alkane;
Described ClCH
2SiR
2Cl
2And ClCH
2SiMeR
3R among the Cl
2, R
3Definition is with described formula I.
Concrete preparation process is as follows:
(1) raw material monomer and solvent system: with MeHSiCl
2Be main monomer, ClCH
2SiR
2Cl
2And ClCH
2SiMeR
3Cl is a time monomer, wherein, and ClCH
2SiR
2Cl
2With MeHSiCl
2Mol ratio be (0.025-0.20): 1, be preferably (0.05-0.10): 1; ClCH
2SiMeR
3Cl and MeHSiCl
2Mol ratio be (0-0.25): 1, according to concrete application to C/Si than and the requirement of stability in storage select.Can be application-specific in addition and introduce monomer M eR
1SiCl
2, R is (but being not limited to) methyl, phenyl, and the alkane of C2-C8 or aromatic hydrocarbons etc.; The solvent that is adopted comprises single non-protonic solvent such as toluene, dimethylbenzene, boiling point is higher than sherwood oil (alkane), dibutyl ether, ethylene glycol diethyl ether of 100 ℃ etc., or the mixed solvent of varsol such as toluene, dimethylbenzene, sherwood oil and ether solvent (as tetrahydrofuran (THF), methyltetrahydrofuran, dioxane, glycol dimethyl ether, diethylene glycol dimethyl ether).The ratio of ether solvent is generally 5-20vol% in the mixed solvent, but as adopting the crown ether solvent, its ratio can be low to moderate 2%.
(2) Wurtz polycondensation: a, elder generation are to being with reactor vacuum nitrogen filling (or argon) displaced air of stirring, constant pressure funnel and reflux, add dry solvent and exposed sodium metal or Na-K alloy, then with the reactor heat temperature raising to alkali metal fusion, regulate to stir preparation basic metal sand; B, monomer solution is added drop-wise in the above-mentioned reactor, the control drop rate is steady with the temperature that keeps reaction system, typically is 100-110 ℃; C, be added dropwise to complete after, be warming up to 120-150 ℃ gradually, be incubated 4-10 hour, make the intermediate oligopolymer that contains remaining Si-Cl key; The mol ratio of the relative raw material monomer Si-Cl of wherein alkali-metal ratio key is 0.80-0.98, is typically 0.90-0.96, is foundation with next step content of introducing active group specifically.
(3) introduce the unsaturated active group of carbon carbon: this step can take single stage method also can take two-step approach.So-called single stage method is meant that the intermediate oligomer solution that contains the Si-Cl key is unprocessed, directly drips Grignard reagent or adds activatory magnesium, drips that the raw material that can generate Grignard reagent is on-the-spot to be formed Grignard reagent and carry out linked reaction to it; Two step method is carried out linked reaction with Grignard reagent after being meant and earlier the intermediate polymer filtration being removed solid salt again; Two step method is removed solid salt, and steams varsol, adds ether solvent, and processing step is many, technology is more numerous and diverse, but can make reaction more smooth and avoid the side reaction of active group.The simple cost of one-step technology is low, for fear of side reaction, carries out in room temperature and below 60 ℃ usually, adds CuCl catalyzer such as (but being not limited to CuCl) usually.Described linked reaction is by the midbody polymer solution and the CH=CH-MgBr that contain the Si-Cl key, CH=CH-MgCl, CH ≡ C-MgBr, CH ≡ C-MgCl, CH ≡ C-Li, CH=CHCH
2-MgBr or CH=CHCH
2Grignard reagents such as-MgCl react the silane-carbon silane copolymer that obtains containing corresponding active group down at 0-60 ℃.
(4) aftertreatment: a) acidizing extraction technology: by acidifying, hexane or petroleum ether extraction, the dilute hydrochloric acid washing separates purification processes to the polymkeric substance of introducing active group, and drying and underpressure distillation remove and desolvate, and are gathered (silane-carbon silane) finished product; B) anhydrous process: reaction product solution is filtered removal of solvent under reduced pressure; Add sherwood oil or the hexane dissolving of product 100-200% again, leave standstill more than 3 hours, filtration desolventizes, and is gathered (silane-carbon silane) finished product.
With respect to the prior art route, method of the present invention is by having following advantage: owing to use exposed basic metal, alkali metal-free was residual after reaction was finished, and therefore the security of aftertreatment technology was improved; Do not use LiAlH in the reaction process
4Deng expensive reagent, so cost is lower.In this polymkeric substance, contain the controlled unsaturated active group of carbon carbon, not only obviously improved ceramic yield (as shown in Figure 2), and significantly improved its cure process: adopted platinum catalyst or peroxide catalyst, can be cured at 120-180 ℃ of following 1-6h.
With respect to the prepared silicon carbide ceramics presoma of prior art route, the prepared liquid state poly-(silane-carbon silane) of present method has following advantage: ceramic yield height (60w%-70w%); Structure is formed (carbon silicon ratio, chain structure, molecular weight) and the adjustable advantage of rheological property; Can satisfy multiple use field (soaker of matrix material, dead size contoured body material etc.).AHPCS has ceramic yield height, advantage that viscosity is low, but easily foaming and cracking when solidifying; Though and its ceramic yield of polymkeric substance of the present invention is lower slightly, do not foam when it solidifies, the no bubble that is easy to get after the curing, flawless block, thus as coating, can the potteryization high temperature adhesive etc. Application Areas have more advantage.With AHPCS and poly-(silane-carbon silane) [PSCS of the present invention, embodiment 1] with 140 ℃ of the Karstedt catalyzer of 20ppm * 1h+180 ℃ * 3 * 20 * 40mm block after 2h solidifies, put into retort furnace with 10 ℃/min pyrolysis to 1000 ℃ and be incubated 1h, the AHPCS cured product becomes white powder, and the PSCS cured product still is the black block.Solid state nmr as shown in Figure 3 shows that the former complete oxidation is a silicon-dioxide, and the latter still is mainly the Si-C key.
Description of drawings
Fig. 1 is embodiment 1 a synthetic route synoptic diagram;
Fig. 2 is the thermogravimetric curve figure of embodiment 1 product; Wherein, the test carrier gas is a nitrogen, 10 ℃/min of temperature rise rate; PMS is the pure methyl polysilicon alkane of Comparative Examples, and mPMS is embodiment 1 product;
Fig. 3 is the solid of 1000 ℃ of pyrolysis after 1 hour in AHPCS and the embodiment 1 cured product PSCS air
29Si-NMR;
Fig. 4 is embodiment 1 product
29Si-NMR (on) and
1H-NMR (descending) spectrogram;
Fig. 5 is the thermogravimetric curve of embodiment 2 products;
Fig. 6 is the thermogravimetric curve of embodiment 3 products;
Fig. 7 is the thermogravimetric curve of embodiment 4 products.
Embodiment
The present invention will be described below by specific embodiment, but the present invention is not limited thereto.
Experimental technique described in the following embodiment if no special instructions, is ordinary method; Described reagent and material if no special instructions, all can obtain from commercial channels.
Embodiment 1,
Installation tool agitator on three mouthfuls of round-bottomed flasks of an exsiccant 3L, constant pressure funnel, reflux condensing tube, and gas operated device, the vacuum nitrogen filling displacement is three times then.Under the nitrogen protection; in there-necked flask, add the new distillatory dimethylbenzene of 750ml, the dioxane of 50ml and the Na that 3.53mol (normal 0.9 times of Si-Cl) is cut into small pieces, in constant pressure funnel, add dimethyl dichlorosilane (DMCS) (1.825mol)-chloromethylmethyldichlorsilane (0.09175mol) monomer mixture.Device be warming up to Na molten after, regulate and stir the preparation sodium sand, drip monomer mixture (3-4 hour), after being added dropwise to complete, continue to stop to stir 115 ℃ of reactions 4 hours, naturally cooling, shift to filter then, obtain containing the polymers soln of Si-Cl, steam to desolventize and add the 500ml tetrahydrofuran (THF) again and be used for next step Ge Shi linked reaction.
During grignard reaction, ViMgBr tetrahydrofuran solution (0.44L with 1.0mol/L, the effective Grignard reagent that contains 1.1 times of remaining Si-Cl amounts) is added drop-wise in the THF solution of above-mentioned enriched material, reacted 4 hours down in little backflow (55-60 ℃), stop to stir, be cooled to-5 ℃, the hydrochloric acid that drips excessive 250ml, 3mol/L then mixes with the normal hexane of 250ml with the hydrochloric acid ice water mixture of 300g ice, is added drop-wise in the solution that is generated after this Ge Shi linked reaction of quick stirring; After being added dropwise to complete, continue to stir half an hour, standing demix then.The salt acid elution of separation upper solution and usefulness 1mol/L three times is through anhydrous Na
2SO
4Dry, filtration, underpressure distillation desolventizes, and obtains final liquid light yellow product 62.6g (productive rate 65%), and viscosity is 1000mPa.s, and 1000 ℃ ceramic yield was 69% (its synthetic route and thermogravimetric curve is as shown in Figure 1 and Figure 2).Confirm the existence of vinyl group and the introducing of carbon silane from Fig. 4; As seen compare with unmodified polymethyl silicane from Fig. 2, embodiment 1 has significantly improved ceramic yield.This product is corresponding to the R among the formula I
2, R
3=CH
3, y=0.05, x=z=0, n=10 (mean value), Y=Vi (vinyl).Stored 6 months in 3 months or 5 ℃ 30 ℃ of sealed storage, the viscosity variation of this product is no more than 20%, and the contact paper does not burn.
Be warmed up to 1000 ℃ quality residual rate (being ceramic yield) under nitrogen or the argon atmospher, can visually see from the thermogravimetric curve of Fig. 2.
Embodiment 2,
Installation tool agitator on three mouthfuls of round-bottomed flasks of an exsiccant 3L, constant pressure funnel, reflux condensing tube, and gas operated device vacuumize displacement nitrogen three times then.Under nitrogen protection; in there-necked flask, add the Na that the new distillatory dimethylbenzene of 750ml, 50ml tetrahydrofuran (THF) and 4.0mol are cut into small pieces, in constant pressure funnel, add dimethyl dichlorosilane (DMCS) (1.825mol)-chloromethylmethyldichlorsilane (0.1825mol) mixed solution and the new dimethylbenzene that steams.Device be warming up to Na molten after, open and stir the preparation sodium sand, drip monomer solution, then 110-120 ℃ of reaction 5 hours, obtain containing the midbody polymer of Si-Cl key.After adding the dry tetrahydrofuran of 200ml, the 1.0mol/LViMgBr tetrahydrofuran solution of 440mL is added drop-wise in the above-mentioned reaction system,, reacted 6 hours, stop to stir naturally cooling in 60 ℃.Hydrochloric acid with excessive 100ml, 3mol/L mixes with the normal hexane of 250ml with the hydrochloric acid-mixture of ice and water of the hydrochloric acid ice water mixture of 200g ice then, be added drop-wise in the solution that is generated behind the grignard reaction of quick stirring, after being added dropwise to complete, continue to stir half an hour, static layering then, separate upper solution and use the hydrochloric acid of 1mol/L and the mixed solution of normal hexane to wash three times, use anhydrous Na then
2SO
4Dry filter, underpressure distillation filtrate obtains final light yellow liquid thickness product 75g (productive rate 60%).Viscosity is 5Pa.s, and the ceramic yield under 1000 ℃ of argon gas is 68% (as Fig. 5).This product is corresponding to the R among the formula I
2, R
3=CH
3, y=0.1, x=z=0, n=20 (mean value), Y=Vi (vinyl).Stored 6 months in 3 months or 5 ℃ 30 ℃ of sealed storage, the viscosity variation of this product is no more than 20%.
Embodiment 3,
Installation tool agitator on three mouthfuls of round-bottomed flasks of an exsiccant 2L, constant pressure funnel, reflux condensing tube, and gas operated device, after vacuumizing displacement nitrogen three times then, in there-necked flask, add the Na that the new distillatory dimethylbenzene of 300ml-dioxane mixing solutions and 35.32g (1.53mol) are cut into small pieces, in constant pressure funnel, add the mixed solution and the new dimethylbenzene that steams of dimethyl dichlorosilane (DMCS) (0.73mol)-chloromethylmethyldichlorsilane (0.0365mol)-CMDMCS chloromethyl dimethyl chlorosilane (0.073mol).Device heats up, and after melting to Na, regulates and stirs, and the preparation sodium sand drips monomer mixed solution, after being added dropwise to complete, maintain the temperature at 100-120 ℃, reacted 8 hours, stop to stir, naturally cooling shifts then and filters, inert atmosphere distillation down, and the concentrated midbody polymer that obtains is used for grignard reaction.
During grignard reaction, the THF solution (excessive 5%-15%) of 1.0mol/L ViMgBr is added drop-wise in the THF solution of above-mentioned enriched material, 30 ℃ of reactions 6 hours stop to stir naturally cooling.Hydrochloric acid-mixture of ice and water with excessive 3mol/L mixes with the normal hexane of 150ml then, be added drop-wise in the solution that is generated behind the grignard reaction of quick stirring, after being added dropwise to complete, continue to stir half an hour, static layering then, separate upper solution and use the hydrochloric acid of 1mol/L and the mixed solution of normal hexane to wash three times, use anhydrous Na then
2SO
4Dry filter, underpressure distillation desolventizes, and obtaining productive rate is that 70%, 1000 ℃ of ceramic yield is 63.5% liquid resin (see figure 6).This product is corresponding to the R among the formula I
2, R
3=CH
3, x=0, y=0.05, z=0.1, n=9, Y=Vi (vinyl).Stored 10 months in 5 months or 5 ℃ 30 ℃ of sealed storage, the viscosity variation of this product is no more than 20%.
Embodiment 4,
Installation tool agitator on three mouthfuls of round-bottomed flasks of an exsiccant 2L, constant pressure funnel, reflux condensing tube reaches gas operated device, vacuumizes the air and the steam of the system of removing then, displacement nitrogen.Under nitrogen protection; in there-necked flask, add the new distillatory dimethylbenzene of 300ml, the methyltetrahydrofuran of 30ml and the Na that 35.32g is cut into small pieces, in constant pressure funnel, add the mixed solution of dimethyl dichlorosilane (DMCS) (0.73mol)-chloromethylmethyldichlorsilane (0.0365mol)-CMDMCS chloromethyl dimethyl chlorosilane (0.073mol).Device be warming up to Na molten after, regulate and stir the preparation sodium sand, drip monomer solution, after being added dropwise to complete, maintain the temperature at 106 ℃, reacted 5 hours, after reducing to room temperature, successively drip 0.7ml methyl alcohol, contain the 10ml methyltetrahydrofuran of 0.4g cuprous chloride, add the ViMgBr methyltetrahydrofuran solution 108mL of 1.9mol/L then, react 3h under the room temperature.The same then hcl acidifying that carries out, hexane extraction, washing, drying desolventize, and obtain 38.4g (productive rate 87%), and ceramic yield is 63.5% product liquid (see figure 7).This product is corresponding to the R among the formula I
2, R
3=CH
3, y=0.05, z=0.1, n=9, Y=Vi (vinyl).Stored 12 months in 6 months or 5 ℃ 30 ℃ of nitrogen-sealed storages, the viscosity variation of this product is no more than 20%.
Installation tool agitator on three mouthfuls of round-bottomed flasks of an exsiccant 2L, constant pressure funnel, reflux condensing tube reaches gas operated device, vacuumizes the air and the steam of the system of removing then, displacement nitrogen.Under nitrogen protection, in there-necked flask, add the new distillatory dimethylbenzene of 300ml, the tetrahydrofuran (THF) of 30ml and the Na that 42.9g is cut into small pieces, in constant pressure funnel, add MeHSiCl
2(0.73mol), ClCH
2HSiCl
2(0.03mol), ClCH
2The mixed solution of HMeSiCl (0.1825mol).Device be warming up to Na molten after, regulate and stir the preparation sodium sand, drip monomer solution, after being added dropwise to complete, maintain the temperature at 106 ℃, reacted 4 hours, after reducing to room temperature, successively drip 0.7ml methyl alcohol, contain the 10ml tetrahydrofuran (THF) of 0.33g cuprous chloride and 0.11g lithium chloride, add the ethynyl bromination magnesium tetrahydrofuran solution 120mL of 0.5mol/L then, react 2h under the room temperature.Argon shield is filtered down, steams solvent, adds exsiccant sherwood oil (60-90) 50ml, stirs pyrolysis, leaves standstill one day, filters, and steams solvent and gets 38.4g (productive rate 75%), and ceramic yield is 77% light yellow liquid product.This product is corresponding to the R among the formula I
2, R
3=H, y=0.04, z=0.25, n=30, Y=-C ≡ CH (ethynyl).Stored 6 months in 3 months or 5 ℃ 30 ℃ of nitrogen-sealed storages, the viscosity variation of this product is no more than 30%.
Embodiment 6,
Installation tool agitator on three mouthfuls of round-bottomed flasks of an exsiccant 2L, constant pressure funnel, reflux condensing tube reaches gas operated device, vacuumizes the air and the steam of the system of removing then, displacement nitrogen.Under nitrogen protection, in there-necked flask, add the new distillatory dimethylbenzene of 300ml, the tetrahydrofuran (THF) of 60ml and the Na that 38.4g is cut into small pieces, in constant pressure funnel, add MeHSiCl
2(0.73mol), ClCH
2MeSiCl
2(0.05mol), ClCH
2The mixed solution of HMeSiCl (0.073mol).Device be warming up to Na molten after, regulate and stir the preparation sodium sand, drip monomer solution, after being added dropwise to complete, maintain the temperature at 106 ℃, react 4 hours, reduce to room temperature, filtration, filtrate for later use.In the there-necked flask of another 2L, add dry activatory magnesium chips of 5g and 10ml tetrahydrofuran (THF), with the tetrahydrofuran solution dropwise reaction of 16.1g chlorallylene and 90ml 2 hours, prepare the allyl grignard reagent of 0.20mol, add and contain 0.33g cuprous chloride and 0.11g lithium chloride, then midbody polymer filtrate is dripped 45 ℃ of reaction 2h down.Argon shield is filtered down, steams solvent, adds exsiccant sherwood oil (60-90) 50ml, stirs pyrolysis, leaves standstill one day, filters, and steams solvent and gets 32.3g (productive rate 70%), and ceramic yield is 67% light yellow liquid product.This product is corresponding to the R among the formula I
2=CH
3, R
3=H, y=0.07, z=0.1, n=20, Y=-CH
2-CH=CH
2(allyl group).Stored 6 months in 3 months or 5 ℃ 30 ℃ of nitrogen-sealed storages, the viscosity variation of this product is no more than 25%.
Embodiment 7,
Installation tool agitator on three mouthfuls of round-bottomed flasks of an exsiccant 2L, constant pressure funnel, reflux condensing tube reaches gas operated device, vacuumizes the air and the steam of the system of removing then, displacement nitrogen.Under nitrogen protection, in there-necked flask, add the new distillatory dimethylbenzene of 350ml, the glycol dimethyl ether of 60ml and the Na that 44.9g is cut into small pieces, in constant pressure funnel, add MeHSiCl
2(0.73mol), MePhSiCl
2(0.15mol), ClCH
2MeSiCl
2(0.05mol), ClCH
2The mixed solution of HMeSiCl (0.073mol).Device be warming up to Na molten after, regulate and stir the preparation sodium sand, drip monomer solution, after being added dropwise to complete, maintain the temperature at 106 ℃, react 4 hours, reduce to room temperature, filtration, filtrate for later use.In the there-necked flask of another 2L, add dry activatory magnesium chips of 5g and 10ml tetrahydrofuran (THF), with the tetrahydrofuran solution dropwise reaction of 16.1g chlorallylene and 90ml 2 hours, prepare the allyl grignard reagent of 0.20mol, add and contain 0.33g cuprous chloride and 0.11g lithium chloride, then midbody polymer filtrate is dripped 45 ℃ of reaction 2h down.Argon shield is filtered down, steams solvent, adds exsiccant sherwood oil (60-90) 50ml, and stirring and dissolving left standstill one day, filters, and steams solvent and gets 32.3g (productive rate 75%), and ceramic yield is 62% light yellow liquid product.This product is corresponding to the R among the formula I
1=Ph, x=0.2; R
2=CH
3, R
3=H, y=0.07, z=0.1, n=20, Y=-CH
2-CH=CH
2(allyl group).Stored 6 months in 3 months or 5 ℃ 30 ℃ of nitrogen-sealed storages, the viscosity variation of this product is no more than 25%.
Embodiment 8,
Installation tool agitator on three mouthfuls of round-bottomed flasks of an exsiccant 2L, constant pressure funnel, reflux condensing tube reaches gas operated device, vacuumizes the air and the steam of the system of removing then, displacement nitrogen.Under nitrogen protection, in there-necked flask, add the new distillatory dimethylbenzene of 350ml, the glycol dimethyl ether of 60ml and the Na that 44.9g is cut into small pieces, in constant pressure funnel, add MeHSiCl
2(0.73mol), MePhSiCl
2(0.15mol), ClCH
2MeSiCl
2(0.05mol), ClCH
2The mixed solution of HMeSiCl (0.073mol).Device be warming up to Na molten after, regulate and stir the preparation sodium sand, drip monomer solution, after being added dropwise to complete, maintain the temperature at 106 ℃, reacted 4 hours, and reduced to room temperature, stir and slowly to add down through 3A molecular sieve drying anhydrous methanol 10ml two days later, fully react 2h, filter, steam solvent and get 34.5g (productive rate 83%), ceramic yield is 55% light yellow liquid product.This product is corresponding to the R among the formula I
1=Ph, x=0.2; R
2=CH
3, R
3=H, y=0.07, z=0.1, n=20, Y=-OCH
3(methoxyl group).Stored 6 months in 3 months or 5 ℃ 30 ℃ of nitrogen-sealed storages, the viscosity variation of this product is no more than 25%.Under the condition of this product moisture in adding tin catalyst and ingress of air, can room temperature be cured.
Comparative Examples
Installation tool agitator on three mouthfuls of round-bottomed flasks of an exsiccant 3L, constant pressure funnel, reflux condensing tube, and gas operated device, the vacuum nitrogen filling displacement is three times then.Under the nitrogen protection, in there-necked flask, add the new distillatory dimethylbenzene of 750ml, the dioxane of 50ml and the Na that 4.4mol (normal 1.1 times of Si-Cl) is cut into small pieces, in constant pressure funnel, add dimethyl dichlorosilane (DMCS) (2.0mol).Device be warming up to Na molten after, regulate and stir the preparation sodium sand, drip dimethyl dichlorosilane (DMCS) monomer solution (3-4 hour), after being added dropwise to complete, continue 115 ℃ of reactions 4 hours, stop to stir, naturally cooling slowly drips methanol consumption metal remained sodium then, filters then to revolve and steams the light yellow liquid oily matter that obtains 51g, productive rate is 58%, its ceramic yield of thermal weight loss test shows be 30% (as among Fig. 2 a).This product can cause paper burning in the several seconds to air-sensitive behind the contact paper.
Claims (9)
1. poly-(methyl-monosilane-carbon silane) shown in the formula I:
(formula I)
Wherein, x=0-0.2, y=0.03-0.2, z=0-0.25; N=10-30;
R
1Be selected from aromatic hydrocarbons or the alkane of any one methyl in the following radicals, phenyl, C2-C8; R
2, R
3Be Me or H, Y is for containing carbon carbon unsaturated link(age) or alkoxyl group;
Be the branched structure unit.
2. the method for preparing poly-(methyl-monosilane-carbon silane) shown in the claim 1 Chinese style I, comprise the steps: in organic solvent, make chlorosilane monomer mixture and exposed basic metal generation Wurtz type polycondensation, the midbody polymer that contains the Si-Cl key of synthetic straight or branched structure; Obtain the liquid methyl-monosilane carbon silane copolymer of carbon containing carbon unsaturated link(age) subsequently by the Ge Shi linked reaction, be poly-(methyl-monosilane-carbon silane) shown in the described formula I.
3. method according to claim 2 is characterized in that: described chlorosilane monomer mixture is by MeHSiCl
2And ClCH
2SiR
2Cl
2Form; Perhaps described chlorosilane monomer mixture is by MeHSiCl
2, ClCH
2SiR
2Cl
2And following at least a monomer is formed: MeR
1SiCl
2And ClCH
2SiMeR
2Cl;
Wherein, described MeR
1SiCl
2Middle R
1Definition with described formula I;
Described ClCH
2SiR
2Cl
2And ClCH
2SiMeR
2R among the Cl
2Definition is with described formula I.
4. method according to claim 3 is characterized in that: described ClCH
2SiR
2Cl
2With MeHSiCl
2Mol ratio be (0.025-0.20): 1, be preferably (0.05-0.10): 1; Described ClCH
2SiMeR
3Cl and MeHSiCl
2Mol ratio be (0-0.25): 1; Described MeR
1SiCl
2With MeHSiCl
2Mol ratio be (0-0.2): 1.
5. according to each described method among the claim 2-4, it is characterized in that: described organic solvent is the mixed solvent of single non-protonic solvent or described single aprotic solvent and ether solvent;
Described aprotic solvent is specially varsol;
Described ether solvent comprises alkyl oxide, cyclic ethers, aryl oxide and/or crown ether;
Described ether solvent is alkyl oxide, cyclic ethers and/or aryl oxide, and its volume fraction is the 5-20% of described mixed solvent; Described ether solvent is a crown ether, and its volume fraction is the 2-20% of described mixed solvent.
6. according to each described method among the claim 2-5, it is characterized in that: described basic metal is Li, Na, K or Na-K alloy, is preferably Na; The mol ratio of Si-Cl is 0.80-0.98 in described basic metal and the described chlorosilane monomer mixture: 1, be preferably 0.90-0.96: 1.
7. according to each described method among the claim 2-6, it is characterized in that: the temperature of reaction of described Wurtz type polycondensation is 100-150 ℃, and the reaction times is 4-10 hour.
8. according to each described method among the claim 2-7, it is characterized in that: described Ge Shi linked reaction is to carry out 1-6 hour reaction by the midbody polymer of the described Si-Cl of containing key and grignard reagent under 0-60 ℃.
9. method according to claim 8 is characterized in that: described grignard reagent be selected from following any one: CH=CH-MgBr, CH=CH-MgCl, CH ≡ C-MgBr, CH ≡ C-MgCl, CH ≡ C-Li, CH=CHCH
2-MgBr and CH=CHCH
2-MgCl.
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Cited By (8)
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| CN108864431A (en) * | 2018-04-26 | 2018-11-23 | 华东理工大学 | A kind of capped branched liquid polysilane impregnating agent of alkynyl and preparation method thereof |
| CN108948361A (en) * | 2018-07-24 | 2018-12-07 | 中国科学院化学研究所 | A kind of poly- (silane-carbon silane) and preparation method thereof |
| CN109384932A (en) * | 2018-10-29 | 2019-02-26 | 北京瑞思达化工设备有限公司 | A kind of technique of continuous production types of silicon carbide-based ceramics precursor polymethyl silicane |
| CN110204730A (en) * | 2019-05-22 | 2019-09-06 | 中国科学院宁波材料技术与工程研究所 | A kind of Polycarbosilane of the crosslinkable groups containing high activity and preparation method thereof |
| CN111592652A (en) * | 2020-06-23 | 2020-08-28 | 内蒙古三友化学有限公司 | Preparation method of modified polymethylsilane |
| CN113999397A (en) * | 2021-11-15 | 2022-02-01 | 航天特种材料及工艺技术研究所 | Preparation method and application of low-cost liquid polycarbosilane |
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| CN108864431A (en) * | 2018-04-26 | 2018-11-23 | 华东理工大学 | A kind of capped branched liquid polysilane impregnating agent of alkynyl and preparation method thereof |
| CN108948361A (en) * | 2018-07-24 | 2018-12-07 | 中国科学院化学研究所 | A kind of poly- (silane-carbon silane) and preparation method thereof |
| CN108948361B (en) * | 2018-07-24 | 2020-06-26 | 中国科学院化学研究所 | Poly (silane-carbosilane) and preparation method thereof |
| CN109384932A (en) * | 2018-10-29 | 2019-02-26 | 北京瑞思达化工设备有限公司 | A kind of technique of continuous production types of silicon carbide-based ceramics precursor polymethyl silicane |
| CN110204730A (en) * | 2019-05-22 | 2019-09-06 | 中国科学院宁波材料技术与工程研究所 | A kind of Polycarbosilane of the crosslinkable groups containing high activity and preparation method thereof |
| 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 |
| CN111592652A (en) * | 2020-06-23 | 2020-08-28 | 内蒙古三友化学有限公司 | Preparation method of modified polymethylsilane |
| CN113999397A (en) * | 2021-11-15 | 2022-02-01 | 航天特种材料及工艺技术研究所 | Preparation method and application of low-cost liquid polycarbosilane |
| CN115322217A (en) * | 2022-08-11 | 2022-11-11 | 中国科学院化学研究所 | High-refractive-index polymerizable monomer for liquid crystal display light path adjusting coating and preparation method thereof |
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