CN104177621A - Novel liquid polycarbosilane as well as preparation method and application thereof - Google Patents
Novel liquid polycarbosilane as well as preparation method and application thereof Download PDFInfo
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- CN104177621A CN104177621A CN201410398757.0A CN201410398757A CN104177621A CN 104177621 A CN104177621 A CN 104177621A CN 201410398757 A CN201410398757 A CN 201410398757A CN 104177621 A CN104177621 A CN 104177621A
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Abstract
The invention discloses a kind of novel low viscosities, the crosslinkable liquid Polycarbosilane of high storage stability and the preparation method and application thereof. The Polycarbosilane, for raw material, is obtained with or mixtures thereof chloromethyl alkoxy silane by grignard coupling reaction and reduction reaction, shown in structure such as formula (1). Simultaneously containing unsaturated bonds such as Si -- H bond and C=C in the structure, self-crosslinkable solidifies under certain condition, ceramic yield with higher, can be used as the silicon carbide precursor of polymer precursor dipping pyrolysis (PIP) technique. The Polycarbosilane, structure composition is adjustable, and storage stability is good, and viscosity is low, and boiling point is lower, has the application potential that silicon carbide ceramics presoma is used as chemical vapor deposition/chemical vapor infiltration (CVD/CVI). In addition, the Polycarbosilane can also substitute crosslinking agent of the divinylbenzene generally used as solid-state Polycarbosilane (PCS).
Description
Technical field
The present invention relates to a kind of new liquid Polycarbosilane and preparation method thereof, belong to the Material Field such as silicon carbide ceramics presoma and carbon silane fire resistant resin.
Background technology
The excellent properties such as that silicon carbide (SiC) ceramic matric composite has is high temperature resistant, low density, high strength, high-modulus, anti-thermal shock and radiation hardness, be strategic thermal structure material of new generation, be widely used in the fields such as aerospace, space technology, the energy, chemical industry, traffic.Its main preparation methods has the pyrolysis of polymer precursor dipping (PIP), reactive melt infiltration (RMI), chemical vapor infiltration (CVI) and CVI+PIP, the methods such as CVI+RMI.In CVI technique, the presoma generally adopting is METHYL TRICHLORO SILANE.It can discharge HCl gaseous corrosion equipment in process of production, and uses a large amount of hydrogen as reducing gas and carrier gas, proposes very high requirement to the safe and stable operation of equipment and maintenance, and facility investment and maintenance cost are high.Afterwards, investigators have developed liquid partially hydrogenated carbon silane as CVI/CVD SiC ceramic forerunner, solve etching problem, improved sedimentation rate, but still had free carbon too high levels maybe to need to pass into a large amount of hydrogen to reduce the problem of carbon content.
Polymkeric substance silicon carbide precursor body is the crucial starting material of PIP legal system for SiC ceramic matric composite, and the technology polydimethyl silane Pintsch process that passes through the most ripe and the most popular Yajima of being invention is reset the solid-state Polycarbosilane (PCS) obtaining at present.At first, PCS is mainly used in melt-spinning and prepares continuous SiC fiber, and softening temperature is higher, while preparing SiC ceramic matric composite by it by PIP technique, must add more organic solvent to dissolve just can use, and causes like this flooding efficiency low, and the rich carbon of ceramic product is more; Can reduce solvent load although reduce softening temperature, also can make its ceramic yield reduce, still cannot improve dipping efficiency.Although PCS adds the crosslinking coagents such as Vinylstyrene (DVB) also can improve dipping efficiency while solidifying, the free carbon too high levels of ceramic product, is unfavorable for the lifting of substrate performance; And easily autohemagglutination and affect use of DVB itself.In addition, existing PCS needs the condition preparation of high temperature or High Temperature High Pressure, and synthetic yield or efficiency are not high, and preparation cost is higher, has also affected its more massive commercial applications.
In order to improve dipping efficiency, investigators have developed liquid Si C ceramic forerunner, as polymethyl silicane (PMS), modified polymethyl silicane (as CN103214675A) and hyperbranched Polycarbosilane etc.In the hyperbranched Polycarbosilane of liquid state of the patent reports such as US2007/0093587A1, US2007/0167599A1, CN102675649A, for realizing high ceramic yield, its reaction raw materials is the Chloromethyltrichlorosilane of part methanolizing, contains a large amount of SiH in actual molecules structure
3end group.Highly active SiH
3although be conducive to improve ceramic yield, in storage process, easily produce hydrogen from polycondensation or with airborne reaction of moisture, viscosity also can increase, and is unfavorable for the storage of safety and stability, easily produces bubble when forming and hardening simultaneously.In presoma backbone molecule structure, introduce vinyl, allyl group isoreactivity group and other group such as methyl, phenyl and can improve these deficiencies, but the carbon residue rate of ceramic product will improve.Although compare the classical standby PCS of Yajima legal system, the group modified perhydro Polycarbosilane of vinyl, allyl group isoreactivity is due to low viscosity and high ceramic yield, flooding efficiency in PIP legal system during for SiC based composites is significantly improved, but further improve its stability in storage how, suppress to solidify foaming, and for PIP later stage process-cycle due to the porosity of matrix material and diminishing of aperture, the dipping efficiency technological approaches that significantly descends degradation aspect still urgently to wish novelty solves.
Summary of the invention
The object of the invention is to overcome the deficiency in prior art, a kind of more low viscosity of novel structure and the more crosslinkable liquid Polycarbosilane and preparation method thereof and application of high storage stability are provided.
The invention provides following technical scheme:
A kind of crosslinkable liquid Polycarbosilane, its structural formula is suc as formula shown in (1):
The wherein R reactive group for containing C=C, C ≡ C or cyclopropyl etc. independently of one another; M is positive integer, and m >=3; 0.05≤n≤2;
Described Polycarbosilane is ring texture or line ring structure, and in described line ring structure, the ratio of ring body structurc accounts for more than 20%.
In the present invention, described Polycarbosilane is preferably six-membered cyclic structure.
In the present invention, described R is R independently of one another
1-(CR
2 2)
x-, wherein R
1cR
3 2=CR
3-, R
3c ≡ C-or (CH
2)
2cH-, R
2and R
3be H or C1-C4 alkyl (as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl or isobutyl-etc.) independently of one another, x is 0,1,2 or 3.Preferably, described R is CH independently of one another
2=CH-, CH
2=CHCH
2-, CH
2=C (CH
3)-, CH
3cH=CH-, HC ≡ C-, HC ≡ C-CH
2-or (CH
2)
2cH-.Be preferably CH
2=CH-.
In the present invention, SiH
3/ SiH
2si-H integration than much smaller than 1.35, be preferably less than 0.9, be more preferably less than 0.7, be also more preferably less than 0.5.
This novel crosslinkable liquid Polycarbosilane is that mixture taking independent chloromethyl trialkoxy silane or chloromethyl trialkoxy silane and chloromethyl dimethoxy chlorosilane, chloromethyl one methoxyl group dichlorosilane is as raw material, obtain by Ge Shi coupling and reduction reaction, its molecule be ring texture or line ring structure (wherein, the ratio of ring body structurc accounts for more than 20%), be preferably six-membered cyclic structure.The Polycarbosilane of this ring-type, molecular structure is symmetrical and stable, has good processing characteristics, and especially the introducing of the unsaturated link(age) such as Si-H key and C=C, makes it under the existence of platinum catalyst or superoxide, can under relatively mild condition, be cured.
The present invention also provides following technical scheme:
The preparation method of above-mentioned crosslinkable liquid Polycarbosilane, it comprises the steps:
(1) magnesium chips or magnesium powder are added in dry ether solvent, drip wherein mixture and the ether solvent of a small amount of chloromethyl trialkoxy silane or chloromethyl trialkoxy silane and chloromethyl dimethoxy chlorosilane, chloromethyl one methoxyl group dichlorosilane, after reaction causes, stir lower drip chloromethyl trialkoxy silane or chloromethyl trialkoxy silane and chloromethyl dimethoxy chlorosilane, chloromethyl one mixture of methoxyl group dichlorosilane and the mixing solutions of ether solvent, 0～80 DEG C of reaction 1～12h;
(2) stir the lower Grignard reagent that contains reactive group or halohydrocarbon or the chloromethyl silane compound containing reactive group that can form with magnesium scene Grignard reagent, 0～80 DEG C of reaction 1～36h of dripping;
(3) under stirring, add reductive agent, 0～80 DEG C of reaction 1～36h;
(4) under fully stirring, add deionized water, concentrated hydrochloric acid and lower boiling alkane ,-20～30 DEG C of reaction 0.5～5h, leave standstill 0.5～5h, isolate upper organic phase dry after phase-splitting, and distillation obtains product.
In the preparation method of above-mentioned crosslinkable liquid Polycarbosilane, ether solvent is selected from a kind of in ether, tetrahydrofuran (THF), 2-methyltetrahydrofuran, glycol dimethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, dibutyl ethylene glycol ether, methyl tertiary butyl ether, tert amyl methyl ether(TAME), cyclopentyl methyl ether etc. or mixture that they are two or more, is preferably tetrahydrofuran (THF), 2-methyltetrahydrofuran, methyl tertiary butyl ether or tert amyl methyl ether(TAME).Lower boiling alkane is selected from a kind of in pentane, pentamethylene, hexane and sherwood oil (30-60 DEG C) etc. or mixture that they are two or more, is preferably hexane and pentamethylene.And in the time adopting methyl tertiary butyl ether and cyclopentyl methyl ether, due to they self can with water phase-splitting well, therefore can separately add lower boiling alkane solvent when acidifying aftertreatment, thereby be very beneficial for the recycling of solvent.
In the preparation method of above-mentioned crosslinkable liquid Polycarbosilane, the alkoxyl group in chloromethyl trialkoxy silane is C1-C4 alkoxyl group, as methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, isobutoxy, tert.-butoxy etc.Preferably, described chloromethyl trialkoxy silane is chloromethyl Trimethoxy silane, chloromethyl triethoxyl silane or chloromethyl three isopropoxy silane, more preferably chloromethyl triethoxyl silane.
In the preparation method of above-mentioned crosslinkable liquid Polycarbosilane, in described mixture, the molar content of chloromethyl trialkoxy silane is more than 30%.
In the preparation method of above-mentioned crosslinkable liquid Polycarbosilane, the volume ratio of chloromethyl trialkoxy silane monomer and ether solvent is 1:1～1:5.
In the preparation method of above-mentioned crosslinkable liquid Polycarbosilane, be the unsaturated alkyl magnesium halide that contains vinyl or alkynyl containing the Grignard reagent of reactive group, be selected from following any one: CH
2=CH-MgBr, CH
2=CH-MgCl, CH
2=CHCH
2-MgBr, CH
2=C (CH
3)-MgBr, CH
3cH=CH-MgBr, CH
2=CHCH
2-MgCl, CH
3cH=CH-MgCl, HC ≡ C-MgBr, HC ≡ C-CH
2mgBr, is preferably CH
2=CH-MgBr; Halohydrocarbon containing reactive group comprises: CH
2=CHCH
2cl, CH
2=CHBr, HC ≡ C-CH
2br, (CH
2)
2cHBr; Chloromethyl silane compound comprises: ClCH
2siMeH
2, ClCH
2siH
2(CH=CH
2).
In the preparation method of above-mentioned crosslinkable liquid Polycarbosilane, reductive agent is lithium aluminum hydride, lithium hydride, magnesium hydride, sodium hydride or hydrolith, is preferably lithium aluminum hydride.
In the preparation method of above-mentioned crosslinkable liquid Polycarbosilane, the volume ratio of deionized water, concentrated hydrochloric acid and lower boiling alkane is 2:1:0.5～11:1:5.
The present invention also provides following technical scheme:
A kind of method of being prepared SiC pottery by above-mentioned crosslinkable liquid Polycarbosilane, wherein, in above-mentioned crosslinkable liquid Polycarbosilane structure, there is the addition of silicon hydrogen or Raolical polymerizable and form crosslinking structure in the unsaturated alkane groups such as Si-H and C=C, C ≡ C, thereby obtain the SiC pottery of higher ceramic yield under platinum catalyst or superoxide exist.
In the present invention, described platinum catalyst is Platinic chloride or Karstedt ' s catalyzer, and consumption is the 10-50ppm of Polycarbosilane quality; Described superoxide is dicumyl peroxide (DCP), and consumption is the 0.1-0.5wt% of Polycarbosilane quality.
The present invention also provides following technical scheme:
The preparation method of the ceramic sample of above-mentioned crosslinkable liquid Polycarbosilane, it comprises the steps:
The product that in step (4) to above-mentioned preparation method, distillation obtains is cured processing, and cured product obtains ceramic sample through high temperature sintering again.
In the present invention, described solidification treatment is carried out in inert atmosphere (nitrogen or argon gas).Typical program curing is: 80～150 DEG C of insulation 2h, 150～280 DEG C of insulation 4h.
In the present invention, described high temperature sintering be cured product under nitrogen or argon gas atmosphere, 800～1600 DEG C insulation 0.5-10h obtain ceramic sample.
Above-mentioned crosslinkable liquid Polycarbosilane, can be used as the linking agent of the solid-state PCS of business Yajima method, and 5～50wt% that its consumption is PCS, is preferably 10～30wt%.In addition, this Polycarbosilane also can be used as the presoma matrix resin that PIP technique is prepared the SiC based composites of carbon fiber or silicon carbide fiber enhancing.Have, this Polycarbosilane (when molecular weight control is lower) also can be used as CVD/CVI silicon carbide ceramics presoma again.
The invention has the advantages that: the first, the key starting material that use in the present invention are chloromethyl trialkoxy silane, corrosion-free to equipment, good stability is convenient to store, cheap and easy to get; The second, Polycarbosilane prepared by the present invention, ceramic yield is high, can be used as PIP high-performance silicon carbide ceramic forerunner; The 3rd, by feed change kind and ratio, the present invention also can prepare low-molecular-weight polycarbosilane, and boiling point is lower, and split product environmentally safe can be used as CVD/CVI silicon carbide ceramics presoma; The 4th, Polycarbosilane prepared by the present invention, molecular weight is lower and containing ring texture, there is lower viscosity, especially in the dipping efficiency that improves PIP later stage process-cycle, the porosity and the aspect, aperture that reduce final matrix material have advantage, thereby improve mechanical property and the antioxidant property of matrix material.The 5th, the present invention is preferred to reaction raw materials and condition, has reduced SiH in molecular structure
3/ SiH
2relative proportion, improved stability in storage.And adopt unsaturated group Grignard reagent to carry out end-blocking to ring compound, can further reduce SiH on the one hand
3content, can improve ceramic yield simultaneously and suppress to solidify foamed phenomenon.In addition, the low viscosity of Polycarbosilane of the present invention and containing unsaturated active group, makes it be suitable as PCS linking agent and uses, can be at the cure process that obviously improves PCS, when improving its ceramic yield, substantially do not increase the free carbon content of its ceramic product.
Brief description of the drawings
Fig. 1 is thermal weight loss (TG) curve of embodiment 1 product;
Fig. 2 is embodiment 2 products and suction heat release (DSC) curve that adds platinum catalyst;
Fig. 3 is thermal weight loss (TG) curve of embodiment 2 cured products;
Fig. 4 is thermal weight loss (TG) curve of PCS and embodiment 5 cured products;
Fig. 5 is the pattern of 1000 DEG C of cracking ceramic samples of embodiment 5 solidified sample, wherein (a) is the exterior appearance of the ceramic sample after PCS self cure, is (b) exterior appearance of ceramic sample after PCS and embodiment 5 product crosslinking curings;
Fig. 6 is with ClCH
2si (OMe)
1.75cl
1.25the high branching perhydro Polycarbosilane (HPCS) of preparing for raw material and vinyl modified perhydro Polycarbosilane (VHPCS)
1h-NMR;
Fig. 7 is with ClCH
2si (OEt)
3the HPCS preparing for raw material and VHPCS's
1h-NMR.
Embodiment
Below in conjunction with embodiment, the present invention is described further.It should be noted that, following embodiment can not be served as limiting the scope of the invention, and any improvement of making on basis of the present invention is all without prejudice to spirit of the present invention.
Comparative example
Dry tri-mouthfuls of round-bottomed flasks of 1L, connect mechanical stirrer, reflux condensing tube, and constant pressure funnel and gas operated device, then vacuumize displacement nitrogen three times, and heat gun baking is simultaneously except the steam of attachment removal.Under nitrogen atmosphere, in reaction flask, add 5.0g magnesium chips, then add 4mL tetrahydrofuran (THF), be heated to 40 DEG C.To the ClCH that adds 2.44g in constant pressure funnel
2si (OMe)
1.75cl
1.25(be ClCH
2si (OMe)
2cl:ClCH
2si (OMe) Cl
2mol ratio is the mixture of 3:1) and the mixing solutions of 2mL tetrahydrofuran (THF), be slowly added drop-wise in reaction flask to cause grignard reaction.In constant pressure funnel, add 49.0g ClCH
2si (OMe)
1.75cl
1.25with the mixing solutions of 150mL tetrahydrofuran (THF), under stirring, be added drop-wise in above reaction system with suitable speed, then insulation reaction 9h at 60 DEG C.Then add the methyltetrahydrofuran solution of 60.32g vinyl bromination magnesium by constant pressure funnel, 50 DEG C of insulation reaction 3h.After reaction finishes, add 7.45g lithium aluminum hydride, continue at 50 DEG C of reaction 6h.
Add 368mL deionized water, 130mL concentrated hydrochloric acid and 150mL hexane, at 0～5 DEG C, react 0.5～2h, stratification, water 150mL hexane extraction, merge organic phase, and with the dilute hydrochloric acid washing of the 1.2mol/L of 260mL three times, separate organic phase, add 15g anhydrous magnesium sulfate drying, filtration is revolved to steam and is obtained final product, for the liquid Polycarbosilane of yellow, productive rate is 75%, and ceramic yield is 75%.This product corresponding to the R in formula (1) is-CH=CH
2, n=0.32, its molecular weight M
w=1683, M
n=720.At room temperature sealed storage 3 months of this product, viscosity is increased to 100cP from 40cP.Fig. 6 is with ClCH
2si (OMe)
1.75cl
1.25the high branching perhydro Polycarbosilane (HPCS) of preparing for raw material and vinyl modified perhydro Polycarbosilane (VHPCS)
1h-NMR, wherein 4.10ppm is the SiH in 6 rings
2, the SiH that 3.90ppm is linear structure
2, and 3.61ppm is SiH
3.Should
1h-NMR stave is bright, its SiH
2(ring)/SiH
2(line)/SiH
3si-H integration than for 0.38/1.0/1.86, taking linear structure as main, contain more SiH
3.
Embodiment 1
Dry tri-mouthfuls of round-bottomed flasks of 1L, connect mechanical stirrer, reflux condensing tube, and constant pressure funnel and gas operated device, then vacuumize displacement nitrogen three times, and heat gun baking is simultaneously except the steam of attachment removal.Under nitrogen atmosphere, in reaction flask, add 5.0g magnesium chips, then add 4mL tetrahydrofuran (THF), be heated to 30 DEG C.To the mixing solutions that adds 2.97g chloromethyl triethoxyl silane and 2mL tetrahydrofuran (THF) in constant pressure funnel, be slowly added drop-wise in reaction flask to cause grignard reaction.To the mixing solutions that adds 59.17g chloromethyl triethoxyl silane and 150mL tetrahydrofuran (THF) in constant pressure funnel, under stirring, be added drop-wise in above reaction system insulation reaction 4h at 30 DEG C with suitable speed.Then add the methyltetrahydrofuran solution of 69.0g vinyl bromination magnesium (1.6mol/L) by constant pressure funnel, 30 DEG C of insulation reaction 6h.After reaction finishes, add 7.45g lithium aluminum hydride, continue at 30 DEG C of reaction 10h.
Add 368mL deionized water, 130mL concentrated hydrochloric acid and 150mL hexane, at 0～5 DEG C, react 0.5～2h, stratification, water 150mL hexane extraction, merge organic phase, and with the dilute hydrochloric acid washing of 260mL, 1.7mol/L three times, separate organic phase, add 15.0g anhydrous magnesium sulfate drying, filtration is revolved to steam and is obtained final product, for light yellow liquid Polycarbosilane, productive rate is 73%, and this product corresponding to the R in formula (1) is-CH=CH
2, n=0.32, its molecular weight M
w=1162, M
n=584.At room temperature sealed storage 5 months of this product, viscosity does not almost change, and is approximately 41cP.Under nitrogen atmosphere, this Polycarbosilane is 30.7% at the TGA ceramic yield of 1000 DEG C; And through Karstedt catalyzer (40ppm) 120～220 DEG C of catalytic crosslinkings solidify after, the TGA ceramic yield (1000 DEG C) of its cured product is 87.0%.
Embodiment 2
Dry tri-mouthfuls of round-bottomed flasks of 1L, connect mechanical stirrer, reflux condensing tube, and constant pressure funnel and gas operated device, then vacuumize displacement nitrogen three times, and heat gun baking is simultaneously except the steam of attachment removal.Under nitrogen atmosphere, in reaction flask, add 19.2g magnesium chips, then add the 2-methyltetrahydrofuran of 30mL, be heated to 50 DEG C.To the mixing solutions that adds 1.20g chloromethyl Trimethoxy silane and 2-methyltetrahydrofuran (2mL) in constant pressure funnel, be slowly added drop-wise in reaction flask to cause grignard reaction.To the 2-methyltetrahydrofuran mixing solutions that adds 67.1g chloromethyl Trimethoxy silane (0.4mol) and 170mL in constant pressure funnel, under stirring, be added drop-wise in above reaction system insulation reaction 6h at 50 DEG C with suitable speed.Then slowly add 40g allyl bromide 98 (0.33mol) by constant pressure funnel, 50 DEG C of insulation reaction 5h.After reaction finishes, add 5.45g lithium aluminum hydride, continue at 50 DEG C of reaction 13h.
Add 240mL deionized water, 60mL concentrated hydrochloric acid and 60mL hexane, at 0～5 DEG C, react 0.5～2h, stratification, separates organic phase; Water 100mL hexane extraction, merge organic phase twice, and with the dilute hydrochloric acid 120mL washing of 1.2mol/L three times, separate organic phase, add 20.0g anhydrous magnesium sulfate drying, filtration is revolved to steam and is obtained final product, is the liquid Polycarbosilane of yellow, productive rate is 94%, and this product corresponding to the R in formula (1) is-CH
2-CH=CH
2, n=0.75, its molecular weight M
w=686, M
n=410.At room temperature sealed storage 5 months of this product, viscosity does not almost change, and is approximately 7cP.The solidified sample of this Polycarbosilane is safran solid, and under nitrogen atmosphere, the ceramic yield of 1200 DEG C is 77.6%.
Embodiment 3
Dry tri-mouthfuls of round-bottomed flasks of 500mL, connect mechanical stirrer, reflux condensing tube, and constant pressure funnel and gas operated device, then vacuumize displacement nitrogen three times, and heat gun baking is simultaneously except the steam of attachment removal.Under nitrogen atmosphere, in reaction flask, add fast 12.9g magnesium chips, then add 15mL glycol dimethyl ether and 1-2 grain iodine crystal, 70 DEG C are heated five minutes.To the mixing solutions that adds 100g chloromethyl triethoxyl silane (0.47mol) and 200mL glycol dimethyl ether in constant pressure funnel, first slowly drip 1-3% in reaction flask to cause grignard reaction.Determine after initiation, stir, and mixed solution is added drop-wise in above reaction system to insulation reaction 8h at 70 DEG C with suitable speed.Then add the tetrahydrofuran solution of the vinyl chlorination magnesium (2.0mol/L) of 250mL by constant pressure funnel, 70 DEG C of reaction 5h, then add 5.45g lithium aluminum hydride, under 50 DEG C of stirrings, react 8h.
Under stirring, above-mentioned reaction soln is slowly joined in the mixed solution being formed by 180mL deionized water, 80mL concentrated hydrochloric acid and 150mL hexane in (be chilled in advance-5 DEG C following) beaker, then continue to react 0.5～1h at 0～5 DEG C.Transfer to stratification in separating funnel, separate organic phase; Water 90mL hexane extraction, merge organic phase twice, and with dilute hydrochloric acid (1.2mol/L) washing of 80mL three times, separate organic phase, adding 16.0g anhydrous magnesium sulfate drying, filter, revolve steaming and obtain final product, is the liquid Polycarbosilane of brown color, productive rate is 86%, and this product corresponding to the R in formula (1) is-CH=CH
2, n=0.97, its molecular weight M
w=2393, M
n=806.At room temperature sealed storage 6 months of this product, viscosity does not almost change, and is approximately 191cP, and gel time exceedes 2 years.The solidified sample of this Polycarbosilane is brown solid, and under nitrogen atmosphere, the ceramic yield of 1300 DEG C is 75.7%.
Embodiment 4
Dry tri-mouthfuls of round-bottomed flasks of 1L, connect mechanical stirrer, reflux condensing tube, and constant pressure funnel and gas operated device, then vacuumize displacement nitrogen three times, and heat gun baking is simultaneously except the steam of attachment removal.Under nitrogen atmosphere, in reaction flask, add fast 19g magnesium chips, then add 25mL diethylene glycol dimethyl ether, be heated to 40 DEG C.In constant pressure funnel, add the mixing solutions of 127.4g chloromethyl three isopropoxy silane (0.5mol), 4.5g chlorallylene (0.06mol) and 200mL diethylene glycol dimethyl ether, the 1-3% that first slowly drips total amount in reaction flask to cause grignard reaction.Then under stirring, be added drop-wise in above reaction system insulation reaction 8h at 80 DEG C with suitable speed.Then cool at 50 DEG C, first add after 45g chloromethyl one methoxyl group dichlorosilane (0.125mol) reaction 5h by constant pressure funnel, add the corundum ceramic pearl of 10g lithium hydride and 1～3mm, under rapid stirring at 60 DEG C of reduction reaction 12h.
Add 300mL deionized water, 120mL concentrated hydrochloric acid and 120mL hexane, at 0～5 DEG C, react 0.5～2h, stratification, water 120mL hexane extraction, merge organic phase, and with dilute hydrochloric acid (1.5mol/L) washing of 100mL three times, separate organic phase, add 20.0g anhydrous magnesium sulfate drying, filtration is revolved to steam and is obtained final product, for the liquid Polycarbosilane of yellow, productive rate is 85%, and this product corresponding to the R in formula (1) is-CH
2-CH=CH
2, n=0.1, its molecular weight M
w=769, M
n=484.At room temperature sealed storage 6 months of this product, viscosity does not almost change, and is approximately 11cP.This Polycarbosilane and solid-state PCS are white solid after solidifying, and under nitrogen atmosphere, the ceramic yield of 1000 DEG C is 76.8%.
Embodiment 5
Dry tri-mouthfuls of round-bottomed flasks of 1L, connect mechanical stirrer, reflux condensing tube, and constant pressure funnel and gas operated device, then vacuumize displacement nitrogen three times, and heat gun baking is simultaneously except the steam of attachment removal.Under nitrogen atmosphere, in reaction flask, add fast 11.0g magnesium chips, then add 20mL methyltetrahydrofuran, be heated to 78 DEG C.To the mixing solutions that adds 85g chloromethyl triethoxyl silane (0.4mol) and 150mL methyltetrahydrofuran in constant pressure funnel, first slowly drip about 1-3% in reaction flask to cause grignard reaction.Under stirring, keep suitable speed to drip, insulation reaction 12h at 80 DEG C.Then add the methyltetrahydrofuran solution (1.6mol/L) of 180mL vinyl bromination magnesium by constant pressure funnel, 65 DEG C of insulation reaction 4h.After reaction finishes, add 5.85g lithium aluminum hydride, continue at 60 DEG C of reaction 12h.
Add 250mL deionized water, 100mL concentrated hydrochloric acid, at 0～5 DEG C, react 0.5～2h, stratification, separates organic phase; Water 120mL hexane extraction, merge organic phase, and with dilute hydrochloric acid (1.5mol/L) washing of 120mL three times, separate organic phase, add 36.0g anhydrous magnesium sulfate drying, filtration is revolved to steam and is obtained final product, is the liquid Polycarbosilane of brown color, productive rate is 79%, and this product corresponding to the R in formula (1) is-CH=CH
2, n=0.66, its molecular weight M
w=1385, M
n=541.At room temperature sealed storage 5 months of this product, viscosity does not almost change, and is approximately 87cP.The ceramic yield of solid-state PCS is 58%, and the self cure temperature in nitrogen, more than 450 DEG C, easily foams; And this Polycarbosilane that adds 20w% as linking agent after, this PCS can solidify at nitrogen 180-230 DEG C, its ceramic yield brings up to 80.7%, its exterior appearance is as shown in Figure 5.
Embodiment 6
Dry tri-mouthfuls of round-bottomed flasks of 1L, connect mechanical stirrer, reflux condensing tube, and constant pressure funnel and gas operated device, then vacuumize displacement nitrogen three times, and heat gun baking is simultaneously except the steam of attachment removal.Under nitrogen atmosphere, in reaction flask, add fast 15.0g magnesium chips, then add the 2-methyltetrahydrofuran of 20mL, be heated to 40 DEG C, and add 0.5ml ethylene dibromide activation magnesium chips.To the mixing solutions that adds 85g chloromethyl triethoxyl silane (0.4mol) and 170mL tetrahydrofuran (THF) in constant pressure funnel, the 1-3% that first drips total amount in reaction flask to cause grignard reaction.Then under stirring, be added drop-wise in above reaction system insulation reaction 6h at 40 DEG C with suitable speed.Then add 17.0g Cyclopropyl Bromide (0.14mol) by constant pressure funnel, 40 DEG C of insulation reaction 9h.After reaction finishes, add 7.63g lithium aluminum hydride, continue at 40 DEG C of reaction 11h.
Add 300mL deionized water, 100mL concentrated hydrochloric acid and 100mL hexane, at 0～5 DEG C, react 0.5～2h, stratification, water 100mL hexane extraction, merge organic phase, and with dilute hydrochloric acid (1.5mol/L) washing of 90mL three times, separate organic phase, add 15.0g anhydrous magnesium sulfate drying, filtration is revolved to steam and is obtained final product, for the liquid Polycarbosilane of brown color, productive rate is 75%, and this product corresponding to the R in formula (1) is-CH (CH
2)
2, n=0.31, its molecular weight M
w=1052, M
n=524.At room temperature sealed storage 5 months of this product, viscosity does not almost change, and is approximately 36cP.To this Polycarbosilane that adds 5w% in solid-state PCS as linking agent after, PCS can solidify at nitrogen 180-230 DEG C, its ceramic yield brings up to 66.7%.
Embodiment 7
Dry tri-mouthfuls of round-bottomed flasks of 1L, connect mechanical stirrer, reflux condensing tube, and constant pressure funnel and gas operated device, then vacuumize displacement nitrogen three times, and heat gun baking is simultaneously except the steam of attachment removal.Under nitrogen atmosphere, in reaction flask, add fast 28.0g magnesium chips, after vacuum stirring heat-activated 2h, be cooled to 50 DEG C, then add 40mL cyclopentyl methyl ether.To the mixing solutions that adds 85.3g chloromethyl Trimethoxy silane (0.5mol) and 220mL cyclopentyl methyl ether in constant pressure funnel, first the 1-3% of total amount is added drop-wise in reaction flask to cause grignard reaction, then under stirring, be added drop-wise in above reaction system insulation reaction 2h at 55 DEG C with suitable speed.Then add 42g chlorallylene (0.55mol) and 40ml cyclopentyl methyl ether mixing solutions by constant pressure funnel, 55 DEG C of insulation reaction 8h, then add 4.74g lithium aluminum hydride, at 55 DEG C of reduction reaction 12h.
Add 240mL deionized water, 80mL concentrated hydrochloric acid, at 0～5 DEG C, react 0.5～2h, stratification, 100mL cyclopentyl methyl ether extraction for water, merge organic phase, and with dilute hydrochloric acid (1.2mol/L) washing of 130mL three times, separate organic phase, add 25g anhydrous magnesium sulfate drying, filtration is revolved to steam and is obtained final product, for the liquid Polycarbosilane of brown color, productive rate is 86%, and this product corresponding to the R in formula (1) is-CH
2-CH=CH
2, n=0.94, its molecular weight M
w=824, M
n=421.At room temperature sealed storage 5 months of this product, viscosity does not almost change, and is approximately 6cP.To this Polycarbosilane that adds 15w% in solid-state PCS as linking agent after, PCS can solidify at nitrogen 180-230 DEG C, its ceramic yield brings up to 70.5%.
Embodiment 8
Dry tri-mouthfuls of round-bottomed flasks of 1L, connect mechanical stirrer, reflux condensing tube, and constant pressure funnel and gas operated device, then vacuumize displacement nitrogen three times, and heat gun baking is simultaneously except the steam of attachment removal.Under nitrogen atmosphere, in reaction flask, add 5.08g magnesium chips, then add 5mL tetrahydrofuran (THF), be heated to 30 DEG C.To the mixing solutions that adds 1.78g chloromethyl triethoxyl silane, 1.18g chloromethyl one methoxyl group dichlorosilane and 3mL tetrahydrofuran (THF) in constant pressure funnel, be slowly added drop-wise in reaction flask to cause grignard reaction.To the mixing solutions that adds 35.50g chloromethyl triethoxyl silane, 23.47g chloromethyl one methoxyl group dichlorosilane and 160mL tetrahydrofuran (THF) in constant pressure funnel, under stirring, be added drop-wise in above reaction system insulation reaction 3h at 30 DEG C with suitable speed.Then add the methyltetrahydrofuran solution of 10.47g vinyl bromination magnesium by constant pressure funnel, 30 DEG C of insulation reaction 3h.After reaction finishes, add 5.83g lithium aluminum hydride, continue at 30 DEG C of reaction 4h.
Add 218mL deionized water, 64mL concentrated hydrochloric acid and 90mL hexane, at 0～5 DEG C, react 0.5～2h, stratification, water 90mL hexane extraction, merge organic phase, and with the dilute hydrochloric acid washing of the 1.2mol/L of 170mL three times, separate organic phase, add 9.0g anhydrous magnesium sulfate drying, filtration is revolved to steam and is obtained final product, for light yellow liquid Polycarbosilane, productive rate is 80%, and this product corresponding to the R in formula (1) is-CH=CH
2, n=0.05, its molecular weight M
w=462, M
n=384.At room temperature sealed storage 5 months of this product, viscosity does not almost change.Under nitrogen atmosphere, this Polycarbosilane is 28% at the ceramic yield of 1000 DEG C.
Embodiment 9
Dry tri-mouthfuls of round-bottomed flasks of 1L, connect mechanical stirrer, reflux condensing tube, and constant pressure funnel and gas operated device, then vacuumize displacement nitrogen three times, and heat gun baking is simultaneously except the steam of attachment removal.Under nitrogen atmosphere, in reaction flask, add fast 16.77g magnesium chips, then add 20mL methyl tertiary butyl ether and 0.5ml ethylene dibromide, 5 points of kinds of micro-backflow.To the mixing solutions that adds 127.5g chloromethyl three isopropoxy silane (0.5mol) and 300mL methyl tertiary butyl ether in constant pressure funnel, first slowly drip total amount 1～3% in reaction flask to cause grignard reaction.Then under stirring, be added drop-wise in above reaction system with suitable speed, insulation reaction 5h at 55 DEG C, then add 18g chloromethyl vinyl dichlorosilane by constant pressure funnel, 55 DEG C are continued reaction 5h.After reaction finishes, add 0.2g Zinc Chloride Anhydrous, the 300g aluminum oxide mill pearl that 27g sodium hydride and diameter are 1-3mm, continues, at 55 DEG C of reaction 24h, to be cooled to room temperature.
By in the above-mentioned dilute hydrochloric acid that adds the 3mol/L that solution joins 350mL, at 0～5 DEG C, react 0.5～2h, stratification, 150mL methyl tertiary butyl ether extraction for water, merge organic phase, and with dilute hydrochloric acid (1.2mol/L) washing of 150mL three times, separate organic phase, add 25.0g anhydrous magnesium sulfate drying, filtration is revolved to steam and is obtained final product, for the liquid Polycarbosilane of brown color, productive rate is 83%, and this product corresponding to the R in formula (1) is-CH=CH
2, n=0.17, its molecular weight M
w=763, M
n=469.At room temperature sealed storage 5 months of this product, viscosity does not almost change, and is approximately 14cP.To this Polycarbosilane that adds 10w% in PCS as linking agent after, PCS can solidify at nitrogen 180-230 DEG C, its ceramic yield brings up to 66.2%.
Embodiment 10
Dry tri-mouthfuls of round-bottomed flasks of 1L, connect mechanical stirrer, reflux condensing tube, and constant pressure funnel and gas operated device, then vacuumize displacement nitrogen three times, and heat gun baking is simultaneously except the steam of attachment removal.Under nitrogen atmosphere, in reaction flask, add 16.0g magnesium chips, then add the 2-methyltetrahydrofuran of 20mL, be heated to 45 DEG C.To the mixing solutions that adds 63.8g chloromethyl triethoxyl silane (0.3mol), 35.0g chloromethyl dimethoxy chlorosilane (0.2mol), 18.0g chloromethyl one methoxyl group dichlorosilane (0.1mol) and 240mL methyltetrahydrofuran in constant pressure funnel, first drip total amount 1～4% in reaction flask to cause grignard reaction, then under stirring, be added drop-wise in above reaction system insulation reaction 8h at 45 DEG C with suitable speed.Then add the methyltetrahydrofuran solution of 70mL vinyl bromination magnesium (1.6mol/L) by constant pressure funnel, 45 DEG C of insulation reaction 6h.After reaction finishes, add 11.4g lithium aluminum hydride, continue at 45 DEG C of reaction 12h.
Add 300mL deionized water, 110mL concentrated hydrochloric acid and 60mL hexane, at 0～5 DEG C, react 0.5～2h, stratification, water is used 60mL hexane extraction again, merge organic phase twice, and with the dilute hydrochloric acid washing of the 1.2mol/L of 120mL three times, separate organic phase, add 20.0 g anhydrous magnesium sulfate dryings, filtration is revolved to steam and is obtained final product, for light yellow liquid Polycarbosilane, productive rate is 77%, and this product corresponding to the R in formula (1) is-CH=CH
2, n=0.15, its molecular weight M
w=5387, M
n=1412.At room temperature sealed storage 5 months of this product, viscosity does not almost change, and is approximately 120cP.Under nitrogen atmosphere, this Polycarbosilane is 78% at the ceramic yield of 1000 DEG C.
Embodiment 11
Dry tri-mouthfuls of round-bottomed flasks of 1L, connect mechanical stirrer, reflux condensing tube, and constant pressure funnel and gas operated device, then vacuumize displacement nitrogen three times, and heat gun baking is simultaneously except the steam of attachment removal.Under nitrogen atmosphere, in reaction flask, add 15.6g magnesium chips, then add tert amyl methyl ether(TAME) and the 1mL ethylene dibromide of 20mL.In constant pressure funnel, add the mixing solutions of 106.4g chloromethyl triethoxyl silane and 200mL tert amyl methyl ether(TAME), first drip total amount 1～4% in reaction flask to cause grignard reaction, then under stirring, be added drop-wise in above reaction system insulation reaction 6h at 65 DEG C with suitable speed.Add 5.4g chloromethyl vinyl silanes (ClCH by constant pressure funnel again
2siViH
2) and the mixed solution of 10mL tert amyl methyl ether(TAME), 65 DEG C of insulation reaction 4h.After reaction finishes, add 9.8g lithium aluminum hydride, continue at 55 DEG C of reaction 6h.
Add 300mL deionized water, 100mL concentrated hydrochloric acid, at 0～5 DEG C, react 0.5～2h, stratification, separates organic phase; Water is again with the extraction of 120mL tert amyl methyl ether(TAME), merge organic phase twice, and with the dilute hydrochloric acid washing of the 1.2mol/L of 120mL three times, separate organic phase, add 20.0g anhydrous magnesium sulfate drying, filtration is revolved to steam and is obtained final product, is light yellow liquid Polycarbosilane, productive rate is 77%, and this product corresponding to the R in formula (1) is-CH=CH
2, n=0.1, its molecular weight M
w=4860, M
n=1412.At room temperature sealed storage 5 months of this product, viscosity does not almost change, and is approximately 120cP.Under nitrogen atmosphere, this Polycarbosilane is 72% at the ceramic yield of 1000 DEG C.
In the liquid Polycarbosilane of embodiments of the invention 1-11, all taking ring texture as main, and SiH
3content is lower, its SiH
2(ring)/SiH
2(line)/SiH
3si-H integration than for (3.5～1.0)/1.0/ (1.2～1.84).Concrete embodiment's 3 as shown in Figure 7
1h-NMR spectrum, wherein upper figure is with embodiment 3 same reaction conditions but does not add the pure Polycarbosilane spectrogram of vinyl modified, its SiH/SiH
2(ring)/SiH
2(line)/SiH
3si-H integration than for 0.29/2.7/1.0/1.72, in its molecule taking ring structure as main; Figure below be described in embodiment 3 containing vinyl Polycarbosilane, its SiH/SiH
2(ring)/SiH
2(line)/SiH
3integration than for 1.62/3.43/1.0/1.19, because the introducing of vinyl has not only increased crosslinking activity group, and due to end-blocking effect, its SiH
3content further reduces, and is conducive to improve its stability in storage.
Claims (10)
1. a crosslinkable liquid Polycarbosilane, its structural formula is suc as formula shown in (1):
The wherein R reactive group for containing C=C, C ≡ C or cyclopropyl etc. independently of one another; M is positive integer, and m >=3; 0.05≤n≤2;
Described Polycarbosilane is ring texture or line ring structure, and in described line ring structure, the ratio of ring body structurc accounts for more than 20%.
2. crosslinkable liquid Polycarbosilane according to claim 1, is characterized in that, described Polycarbosilane is six-membered cyclic structure.
Preferably, described R is R independently of one another
1-(CR
2 2)
x-, wherein R
1cR
3 2=CR
3-, R
3c ≡ C-or (CH
2)
2cH-, R
2and R
3be H or C1-C4 alkyl (as methyl, ethyl, n-propyl, sec.-propyl, normal-butyl or isobutyl-etc.) independently of one another, x is 0,1,2 or 3.Preferably, described R is CH independently of one another
2=CH-, CH
2=CHCH
2-, CH
2=C (CH
3)-, CH
3cH=CH-, HC ≡ C-, HC ≡ C-CH
2-or (CH
2)
2cH-.Be preferably CH
2=CH-.
Preferably, SiH
3/ SiH
2si-H integration than much smaller than 1.35, be preferably less than 0.9, be more preferably less than 0.7, be also more preferably less than 0.5.
3. crosslinkable liquid Polycarbosilane according to claim 1 and 2, it is characterized in that, described crosslinkable liquid Polycarbosilane be mixture taking independent chloromethyl trialkoxy silane or chloromethyl trialkoxy silane and chloromethyl dimethoxy chlorosilane, chloromethyl one methoxyl group dichlorosilane as raw material, obtain by Ge Shi coupling and reduction reaction.
4. the preparation method of the crosslinkable liquid Polycarbosilane described in any one in claims 1 to 3, it comprises the steps:
(1) magnesium chips or magnesium powder are added in dry ether solvent, drip wherein mixture and the ether solvent of a small amount of chloromethyl trialkoxy silane or chloromethyl trialkoxy silane and chloromethyl dimethoxy chlorosilane, chloromethyl one methoxyl group dichlorosilane, after reaction causes, stir lower drip chloromethyl trialkoxy silane or chloromethyl trialkoxy silane and chloromethyl dimethoxy chlorosilane, chloromethyl one mixture of methoxyl group dichlorosilane and the mixing solutions of ether solvent, 0～80 DEG C of reaction 1～12h;
(2) stir the lower Grignard reagent that contains reactive group or halohydrocarbon or the chloromethyl silane compound containing reactive group that can form with magnesium scene Grignard reagent, 0～80 DEG C of reaction 1～36h of dripping;
(3) under stirring, add reductive agent, 0～80 DEG C of reaction 1～36h;
(4) under fully stirring, add deionized water, concentrated hydrochloric acid and lower boiling alkane ,-20～30 DEG C of reaction 0.5～5h, leave standstill 0.5～5h, isolate upper organic phase dry after phase-splitting, and distillation obtains product.
5. preparation method according to claim 4, it is characterized in that, ether solvent is selected from a kind of in ether, tetrahydrofuran (THF), 2-methyltetrahydrofuran, glycol dimethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, methyl tertiary butyl ether, tert amyl methyl ether(TAME), cyclopentyl methyl ether etc. or mixture that they are two or more, is preferably tetrahydrofuran (THF), 2-methyltetrahydrofuran, methyl tertiary butyl ether or tert amyl methyl ether(TAME).Lower boiling alkane is selected from a kind of in pentane, pentamethylene, hexane and sherwood oil (30-60 DEG C) etc. or mixture that they are two or more, is preferably hexane and pentamethylene.
Preferably, the alkoxyl group in chloromethyl trialkoxy silane is C1-C4 alkoxyl group, as methoxyl group, oxyethyl group, positive propoxy, isopropoxy, n-butoxy, isobutoxy, tert.-butoxy etc.Preferably, described chloromethyl trialkoxy silane is chloromethyl Trimethoxy silane, chloromethyl triethoxyl silane or chloromethyl three isopropoxy silane, more preferably chloromethyl triethoxyl silane.
Preferably, in described mixture, the molar content of chloromethyl trialkoxy silane is more than 30%.
Preferably, the volume ratio of chloromethyl trialkoxy silane monomer and ether solvent is 1:1～1:5.
Preferably, be the unsaturated alkyl magnesium halide that contains vinyl or alkynyl containing the Grignard reagent of reactive group, be selected from following any one: CH
2=CH-MgBr, CH
2=CH-MgCl, CH
2=CHCH
2-MgBr, CH
2=C (CH
3)-MgBr, CH
3cH=CH-MgBr, CH
2=CHCH
2-MgCl, CH
3cH=CH-MgCl, HC ≡ C-MgBr, HC ≡ C-CH
2mgBr, is preferably CH
2=CH-MgBr; Halohydrocarbon containing reactive group comprises: CH
2=CHCH
2cl, CH
2=CHBr, HC ≡ C-CH
2br, (CH
2)
2cHBr; Chloromethyl silane compound comprises: ClCH
2siMeH
2, ClCH
2siH
2(CH=CH
2).
Preferably, reductive agent is lithium aluminum hydride, lithium hydride, magnesium hydride, sodium hydride or hydrolith, is preferably lithium aluminum hydride.
Preferably, the volume ratio of deionized water, concentrated hydrochloric acid and lower boiling alkane is 2:1:0.5～11:1:5.
6. prepared the method for SiC pottery by the crosslinkable liquid Polycarbosilane described in any one in claims 1 to 3 for one kind, wherein, in above-mentioned crosslinkable liquid Polycarbosilane structure, there is the addition of silicon hydrogen or Raolical polymerizable and form crosslinking structure in the unsaturated alkane groups such as Si-H and C=C, C ≡ C, thereby obtain the SiC pottery of higher ceramic yield under platinum catalyst or superoxide exist.
7. method according to claim 6, is characterized in that, described platinum catalyst is Platinic chloride or Karstedt ' s catalyzer, and consumption is the 10-50ppm of Polycarbosilane quality; Described superoxide is dicumyl peroxide (DCP), and consumption is the 0.1-0.5wt% of Polycarbosilane quality.
8. the preparation method of the ceramic sample of the crosslinkable liquid Polycarbosilane described in any one in claims 1 to 3, it comprises the steps:
The product that in the step (4) of preparation method to claim 4 or 5, distillation obtains is cured processing, and cured product obtains ceramic sample through high temperature sintering again.
9. preparation method according to claim 8, is characterized in that, described solidification treatment is carried out in inert atmosphere (nitrogen or argon gas).Typical program curing is: 80～150 DEG C of insulation 2h, 150～280 DEG C of insulation 4h.
Preferably, described high temperature sintering be cured product under nitrogen or argon gas atmosphere, 800～1600 DEG C insulation 0.5-10h obtain ceramic sample.
10. the application of the crosslinkable liquid Polycarbosilane described in any one in claims 1 to 3, is characterized in that, can be used as the linking agent of the solid-state PCS of business Yajima method, 5～50wt% that its consumption is PCS, is preferably 10～30wt%.Or this Polycarbosilane also can be used as the presoma matrix resin that PIP technique is prepared the SiC based composites of carbon fiber or silicon carbide fiber enhancing.Or this Polycarbosilane also can be used as CVD/CVI silicon carbide ceramics presoma.
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