CN105085925B - A kind of synthetic method of the Polycarbosilane of thermal curable crosslinking - Google Patents
A kind of synthetic method of the Polycarbosilane of thermal curable crosslinking Download PDFInfo
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Abstract
A kind of synthetic method of the Polycarbosilane of thermal curable crosslinking, comprises the following steps：With composite Polycarbosilane as raw material; composite Polycarbosilane is placed in reaction vessel with the organic silane compound containing 2 ~ 3 C=C groups; add dimethylbenzene; it is uniform miscible; add Si H addition reaction catalysts; after vacuumizing displacement high pure nitrogen, heating carries out Si H addition reactions under normal pressure under high pure nitrogen is protected or condition of high voltage.Simple synthetic method of the present invention, it is easy to implement, product PVCS in an inert atmosphere 400 DEG C treatment can self-curing crosslinking, be avoided that during heat treatment PCS melting outflow, ceramic yield can be significantly improved, the preceramic polymer of ceramic matric composite such as Cf/SiC, SiCf/SiC is suitable for use as.
Description
Technical field
The present invention relates to a kind of synthetic method of the precursor-Polycarbosilane for preparing carborundum based material, especially
It is related to a kind of synthetic method of heat-setting Polycarbosilane.
Background technology
Continuous Fiber Reinforced Ceramic Matrix Composites, are to grow up in recent years and valued class high-tech structure again
Material, has the advantages that high temperature resistant, corrosion-resistant, high-strength and high-ductility.Wherein, most study is carborundum (SiC) base composite wood
Material such as carbon fibre reinforced silicon carbide (Cf/SiC) and silicon carbide fiber reinforced silicon carbide (SiCf/SiC) composite, are mainly used in
The fields such as Aero-Space nuclear industry.The main preparation method for using is precursor dipping pyrolysismethod (Precursor
Infiltration and Pyrolysis, PIP), the method has that cost is relatively low, composite property is excellent and technology difficulty
Moderate the advantages of.When using the method, the silicon carbide substrate raw material for mainly using both at home and abroad is by polydimethylsiloxane PDMS
(Polydimethylsilane) the Polycarbosilane PCS (Polycarbosilane) of synthesis is reset in cracking, by carbon fiber or carbonization
Silica fibre fabric by after PCS solution impregnations, high temperature pyrolysis, and by it is repeated multiple times dipping pyrolysis cyclical after, PCS is converted into cause
Close silicon carbide substrate, is thus obtained C/SiC, SiC/SiC composite.But, because the PCS softening points for using are generally below
250 DEG C, therefore after with PCS solution impregnation fabrics, PCS is easily melted from fabric in intensification heat treatment process
Outflow, both reduces pickling efficiency, and environment is polluted again.And due in PCS structures containing only Si-H active groups, at 500 DEG C
Intermolecular cross-linking reaction can not below occur, low molecular weight part volatilization loss in PCS before causing to be pyrolyzed, more than 1000 DEG C
When being converted into SiC matrix ceramic conversion rate reduction, it is necessary to it is repeated multiple times dipping pyrolysis could be densified, thereby dramatically reduce system
Standby efficiency.Therefore, PCS is modified, introduces the active group that can be reacted with Si-H, but assign the solidification of its itself heat cross-linking
Characteristic, for improve PIP methods prepare SiC based composites preparation efficiency it is significant.
Regarding to the issue above, in document one, (Chen Manhua, the old proportioning towards brightness .PCS/DVB is studied with crosslinking, aerospace material
Technique, 2003, No3,49-52) in, it is crosslinking agent using divinylbenzene (divinyl-benzene, DVB), by PCS and DVB
400 DEG C are heated to after mixing and realize that heat cure is crosslinked, 1000 DEG C of converting rear ceramic yields reach 70%.But due to DVB's
Activity is higher, and autohemagglutination occurs during long-term storage at room temperature, and stability is poor.Additionally, the purity of industry DVB is only 56%, contain
The more ethyl styrene that can not be crosslinked, not only have impact on pickling efficiency, and thus in ceramic product introduce excessive
Carbon, the performance to composite brings adverse effect.(the curable ceramic yield Polycarbosilanes high of Yuan Qin, Song Yong ability of document two
Synthesis and performance study organosilicon materials, 2011,25 (6), 380-383.) use PCS and the silicon of tetramethyl tetravinyl ring four
Oxygen alkane (Tetravinyltetramethylcyclo-tetrasiloxane, V4) has been synthesized the Polycarbosilane containing vinyl
(Polyvinlycarbosilane, PVCS), can realize that self-crosslinking solidifies at 350 DEG C by Si―H addition reaction, and cured product exists
1000 DEG C of ceramic yields reach 80.0%.But oxygen is introduced after due to being reacted with V4 in PVCS, is produced in ceramics after pyrolysis is inorganization
SiC is produced in thingxOyImpurities phase, reduces the resistance to elevated temperatures of ceramic product.As can be seen that passing through introducing crosslinked agent DVB pairs
PCS carries out thermal crosslinking treatment, or assigns PCS self-curing characteristics by introducing vinyl in PCS, can effectively improve heat
The ceramic yield of product is solved, and the PCS melts outflow in reduction dipping process is extremely beneficial to, but currently available technology is difficult to
To with heat cure cross-linking properties and the excellent Polycarbosilane of pyrolized ceramic product property.
The content of the invention
The technical problem to be solved in the present invention is to overcome the deficiencies in the prior art, there is provided it is poly- that a kind of thermal curable is crosslinked
The synthetic method of carbon silane, gained Polycarbosilane (being designated as PVCS below) contains active Si-H and vinyl, thermal curable crosslinking.
The present invention solves the technical scheme that its technical problem uses, a kind of synthesis of the Polycarbosilane of thermal curable crosslinking
Method, with composite Polycarbosilane as raw material, controllable silicon hydrogen is passed through with containing 2~3 organosilans of-C=C- groups
Addition reaction synthesizes the PVCS.
In this specification unless otherwise indicated, the purity of the high pure nitrogen is 99.999%.
The present invention specifically includes following steps：With composite Polycarbosilane as raw material, by composite with poly- carbon silicon
Alkane is placed in reaction vessel by a certain percentage with the organic silane compound containing 2~3-C=C- groups, by every gram of composite wood
Material Polycarbosilane adds the ratio of 5~20ml dimethylbenzene to add solvent xylene, uniform miscible, adds Si-H addition reactions
Catalyst, after vacuumizing displacement high pure nitrogen, heating carries out Si-H additions under normal pressure under high pure nitrogen is protected or condition of high voltage
Reaction；When reacting at ambient pressure, 90~100 DEG C are heated to while stirring under high pure nitrogen protection, and insulation reaction 8~20 is small
Shi Hou, stops reaction, and reaction mixture is placed in distilling apparatus after being cooled to room temperature, under high pure nitrogen protection, it is warming up to 160~
180 DEG C of distilling off solvent and unreacted silicon hydride compounds, obtain Polycarbosilane (PVCS) of the product containing vinyl；In condition of high voltage
During lower reaction, after vacuumizing displacement high pure nitrogen, pre- inflated with nitrogen is heated to 100~120 DEG C, and insulation reaction to 10~15MPa
After 8~20 hours, stop reaction, reaction mixture is placed in distilling apparatus after being cooled to room temperature, under high pure nitrogen protection, heat up
To 160~180 DEG C of distilling off solvent and unreacted silane compound, Polycarbosilane (PVCS) of the product containing vinyl is obtained.
The composite Polycarbosilane, is to reset the Polycarbosilane for synthesizing by polydimethylsiloxane cracking, its softening
Point is 180~220 DEG C, and number-average molecular weight is 1400~1800 (commercially available prod).
It is described containing in 2~3 organic silane compounds of-C=C- groups be free of O, Cl element, on silicon atom connect
In addition to vinyl, other groups are the saturation organic groups such as methyl, ethyl or propyl group to organic group, preferably such as dimethyl divinyl
Base silane (DVS), methyl trivinyl silane (TVS), structural formula is as follows：
The Si-H addition reaction catalysts are preferably chloroplatinic acid H2PtCl6·H2O, usage amount is for 100~150ppm
Preferably, its usage amount is with the quality of raw materials used composite Polycarbosilane as calculating benchmark.
The composite Polycarbosilane with containing 2~3 proportionings of the organic silane compound of-C=C- groups, with
Quality is than composite Polycarbosilane: contains 2~3 organic silane compound=1 of-C=C- groups: 0.1~0.8 is
Preferably.In composite with Polycarbosilane (PCS) and DVS reaction conditions, it is advisable with mass ratio PCS: DVS=1: 0.3~0.5；
Under composite Polycarbosilane and TVS reaction conditions, it is advisable with mass ratio PCS: TVS=1: 0.2~0.4.
The composite Polycarbosilane with contain 2~3 reaction bars of the organic silane compound of-C=C- groups
Part, when it is used containing 2~3 boiling points of the organic silane compound of-C=C- groups be less than 100 DEG C when, using under condition of high voltage
Reaction；It is such as under composite Polycarbosilane and DVS reaction conditions, composite Polycarbosilane and DVS is miscible in two
It is placed in autoclave after toluene, with pre- inflated with nitrogen to 10~15MPa of pressure, is heated to 100~120 DEG C, and insulation reaction 8~20
Hour is advisable.When the boiling point of organosilan used is equal to or higher than 100 DEG C, reacted using under condition of normal pressure；Such as in composite wood
It is under material Polycarbosilane and TVS reaction conditions, PCS and TVS is miscible in being placed in after dimethylbenzene in normal pressure reactor with 90~100
Insulation reaction is advisable for 8~20 hours at DEG C.
The Si-H addition reactions, i.e., by the control to reaction ratio and reaction condition, control hydrosilylation journey
Degree, obtains the Polycarbosilane PVCS being crosslinked with vinyl, thermal curable containing active Si-H.More specifically, by the reaction
The control of condition, with the number-average molecular weight that the silicon hydrogen extent of reaction for determining product PVCS relative raw materials PCS is 10~30%, PVCS
Within 1900~2300, the new peak for not producing HMW on the GPC curves of its molecular weight distribution, overall molecule amount point are determined
Cloth is uniformly advisable.If the silicon hydrogen extent of reaction is relatively low less than the vinyl groups content introduced in 10%, PVCS after reaction, adding
During heat treatment, heat cure crosslinking degree is relatively low, and solidification retention rate is low, it is difficult to realize complete heat cure；If silicon hydrogen is anti-after reaction
Answer degree higher than 30%, then in the presence of excessive hydrosilylation, in the intermolecular formation cross-linked structures of PCS, make the molecular weight of PVCS
Excessively increase, occur HMW new peak in graph of molecular weight distribution, this PVCS is molten in same dimethylbenzene when for impregnating
Insoluble matter is will appear under liquid concentration and causes viscosity to increase, it is difficult to realize homogeneous impregnation.
The calculating of the hydrosilylation degree：The infrared spectrum of raw material PCS and product PVCS is determined, is obtained respectively each
2100cm on comfortable infrared spectrum-1(Si-H) place, 1250cm-1(Si-CH3) place the ratio between characteristic absorption peak absorbance ASi-H/
ASi-CH3, i.e. (ASi-H/ASi-CH3)PCSWith (ASi-H/ASi-CH3)PVCS, the Si-H extents of reaction are obtained as the following formula：
The Si-H extents of reaction (%)=[(ASi-H/ASi-CH3)PCS—(ASi-H/ASi-CH3)PVCS]/(ASi-H/ASi-CH3)PCS×
100%.
The present invention is logical with containing 2~3 organic silane compounds of-C=C- groups using composite Polycarbosilane
The PVCS that hydrosilylation synthesis Si-H containing activity is crosslinked with vinyl, thermal curable is crossed, with simple synthetic method, it is easy to
The advantage of implementation, by the organosilan that is used without the foreign atoms such as O, Cl, and the control extent of reaction and the ratio of introducing,
Product PVCS compares raw material PCS, and the value added of carbon content is relatively low in composition, the composition and PCS of its converting ceramic product
Thermal decomposition product is identical, and simply carbon content is increased slightly.But when in use, due to heat treatment when can self-curing crosslinking, be avoided that PCS
Melting outflow, significantly improve ceramic yield, be more suitable for be used as ceramic matric composite such as Cf/SiC, SiCf/SiC precursor
Polymer.
Brief description of the drawings
Fig. 1 be raw material PCS-1 and reference examples 1, embodiment 2, reference examples it is 2-in-1 into product PVCS-7, PVCS-2, PVCS-8
Infrared spectrogram；
Fig. 2 is PCS-1 and embodiment 1, embodiment 2 and product PVCS-1, PVCS-2, the PVCS-8 synthesized by reference examples 2
Gel permeation chromatography (GPC) comparison diagram.
Specific embodiment
The present invention is described in further detail below in conjunction with specific embodiment.
It is below non-limiting examples of the invention.
In following examples and reference examples, from two kinds of Polycarbosilanes for being typically used as composite raw material：Composite
Use Polycarbosilane PCS-1：Softening point is 200~218 DEG C, and number-average molecular weight is 1780；Composite Polycarbosilane PCS-2：
Softening point is 186~203 DEG C, and number-average molecular weight is 1650.
Embodiment 1
With PCS-1, dimethyl divinyl silane (DVS) for Material synthesis PVCS-1
PCS-1 and DVS is pressed 1:During 0.3 weight is than addition autoclave, in dimethylbenzene/PCS-1 for 10ml/g ratios add
Enter that dimethylbenzene is uniformly miscible, then chloroplatinic acid catalyst is added with the ratio (with weight of PCS-1 as calculating benchmark) of 100ppm, take out
After vacuum displacement high pure nitrogen, preliminary filling nitrogen pressure is heated to 120 DEG C to 10MPa, and insulation reaction stops reaction after 20 hours,
Reaction mixture is placed in distilling apparatus after being cooled to room temperature, under high pure nitrogen protection, is heated to 160 DEG C of distilling off solvent and not
After the DVS of reaction, product as light yellow solid PVCS-1 is obtained.
The present embodiment gained product as light yellow solid PVCS-1, measures its number-average molecular weightIt is 1951, its molecular weight
Breadth coefficientGel permeation chromatography (GPC) figure of raw material PCS-1 and product PVCS-1 is contrasted,
Such as Fig. 2, it can be seen that the molecular weight distribution of product PVCS-1 is still bimodal after reaction, but peak position slightly has shifting to HMW side
It is dynamic.The infrared spectrum of PVCS-1 is determined, it is identical with PCS-1, it can be seen that 2950cm in infrared spectrogram-1、2900cm-1Place
Si-CH3C-H stretching vibration peaks, 2100cm-1Place's Si-H stretching vibration peaks, 1400cm-1Place Si-CH3C-H deformation vibrations peak,
1360cm-1Place Si-CH2The C-H out-of-plane vibrations peak of-Si, 1250cm-1Place Si-CH3Deformation peak, 1020cm-1Place Si-CH2- Si's
Si-C-Si stretching vibration peaks, 820cm-1Place Si-CH3Swing and Si-C stretching vibration peaks.Compared with raw material PCS-1, can see
The Si-H absorption peak strengths for producing matter PVC S-1 weaken.Determine 2100cm on infrared spectrum-1(Si-H) place, 1250cm-1(Si-
CH3) the ratio between place's characteristic absorption peak absorbance ASi-H/ASi-CH3And compared with raw material PCS-1, can calculate the Si-H extents of reaction is
15.5%.Further, it is also possible to find out newly 3055cm is occurred in that in the infrared spectrogram of PVCS-1-1、3016cm-1And 1597cm-1
Place belongs to CH=CH2Stretching vibration peak.The decrease and CH=CH at Si-H peaks2The appearance at peak, shows that DVS molecules have passed through
The mode of Si―H addition reaction is incorporated into product molecule structure, and active Si-H is both contained in product PVCS, also contains CH=CH2.Produce
Matter PVC S-1 is soluble in dimethylbenzene, is completely dissolved in 50% xylene solution.PVCS-1 has Thermocurable, is determined in heating
When be difficult to measure softening point.PVCS-1 is placed in tube furnace, under nitrogen atmosphere protection, is risen to from room temperature by 100 DEG C/h
400 DEG C, 2 hours are incubated, the gel content for determining cured product is 99.4%, solidification retention rate is 96.7%.
Embodiment 2
It is Material synthesis PVCS-2 with PCS-2, DVS
LPCS-2 and DVS is pressed 1 respectively using method substantially the same manner as Example 1:0.4 is codissolved in mixing in dimethylbenzene
Add in autoclave afterwards, the reaction conditions different from embodiment 1 are shown in Table 1 with table 2 with the characteristic of product PVCS-2.
Embodiment 3
It is Material synthesis PVCS-3 with PCS-2, DVS
LPCS-2 and DVS is pressed 1 respectively using method substantially the same manner as Example 1:0.5 is codissolved in mixing in dimethylbenzene
Add in autoclave afterwards, the reaction conditions different from embodiment 1 are shown in Table 1 with table 2 with the characteristic of product PVCS-3.
Embodiment 4
With PCS-1, methyl trivinyl silane (TVS) for Material synthesis PVCS-4
PCS-1 and TVS is pressed 1:It is the ratio of 15ml/g by dimethylbenzene/PCS-1 during 0.2 weight is than addition reaction vessel
Example adds dimethylbenzene uniformly miscible, then adds chloroplatinic acid-catalysis with the ratio (with weight of PCS-1 as calculating benchmark) of 150ppm
Agent, after vacuumizing displacement high pure nitrogen, under normal pressure, is heated to 90 DEG C and carries out Si-H additions while stirring under high pure nitrogen protection
Reaction, insulation reaction stops reaction after 20 hours, reaction mixture is placed in distilling apparatus after being cooled to room temperature, in high pure nitrogen
Under protection, after being heated to 160 DEG C of distilling off solvent and unreacted DVS, product as light yellow solid PVCS-3, reaction condition are obtained
1 is shown in Table with table 2 with the characteristic of product PVCS-4.
Embodiment 5
It is Material synthesis PVCS-5 with PCS-1, TVS
PCS-1 and TVS is pressed 1 respectively using method same as Example 4:After 0.3 is codissolved in mixing in dimethylbenzene plus
Enter in reactor, the reaction conditions different from embodiment 4 are shown in Table 1 with table 2 with the characteristic of product PVCS-5.
Embodiment 6
It is Material synthesis PVCS-6 with PCS-2, TVS
PCS-2 and TVS is pressed 1 respectively using method same as Example 4:After 0.4 is codissolved in mixing in dimethylbenzene plus
Enter in reactor, the reaction conditions different from embodiment 4 are shown in Table 1 with table 2 with the characteristic of product PVCS-6.
Reference examples 1
It is Material synthesis PVCS-7 with PCS-1, DVS
PVCS-7 is synthesized using method same as Example 1, but PCS-1 and DVS is pressed 1:After 0.2 is codissolved in dimethylbenzene
Reaction, the reaction conditions different from embodiment 1 are shown in Table 1 with table 2 with the characteristic of product PVCS-7.
Reference examples 2
It is Material synthesis PVCS-8 with PCS-2, DVS
PVCS-8 is synthesized using method same as Example 2, but PCS-2 and DVS is pressed 1:After 0.6 is codissolved in dimethylbenzene
Reaction, the reaction conditions different from embodiment 1 are shown in Table 1 with table 2 with the characteristic of product PVCS-8.
The synthesis condition and product property of each embodiment PVCS of table 1
The dissolubility of PVCS, Thermocurable and ceramic yield obtained by each embodiment of table 2 and reference examples
* dissolubility is determined：Solvent xylene, concentration 50%；400 DEG C for the treatment of 1hr in * nitrogen atmospheres；
* * TG are determined, nitrogen atmosphere, 1000 DEG C.
The composition of the PCS of table 3 and PVCS and its thermal decomposition product
The characteristic of comparative example and the PVCS synthesized by reference examples is analyzed below, further illustrates spy of the invention
Point.
Accompanying drawing 1 is that the product PVCS as synthesized by PCS/DVS different proportions (corresponds to reference examples 1, embodiment 2, reference examples
It is 2-in-1 into product PVCS-7, PVCS-2, PVCS-8) with the infrared spectrogram of raw material PCS-1, compared with raw material PCS, can see
Go out in 2100cm-1The peak intensity for locating Si-H characteristic peaks weakens, and can obtain its corresponding extent of reaction PSi-H, while all going out in figure
3055cm is showed-1And 3016cm-1And 1597cm-1Place belongs to CH=CH2Stretching vibration peak.The decrease and CH at Si-H peaks
=CH2The appearance at peak, shows that DVS molecules are incorporated into PCS molecular structures by way of Si―H addition reaction, illustrates to synthesize
Containing active Si-H and CH=CH2The product PVCS of group.
Accompanying drawing 2 is PCS-1 and embodiment 1, embodiment 2 and product PVCS-1, PVCS-2, the PVCS- synthesized by reference examples 2
8 GPC figure, it can be seen that the molecular weight distribution of raw material PCS-1 be in bimodal distribution, and product PVCS-1, PVCS-2 point
The distribution of son amount is also in bimodal distribution, is compared with PCS-1, and molecular weight distribution has been widened, and peak position has relatively low to bound macromolecule
The movement of degree, this explanation PVCS-1, PVCS-2 molecular weight improves to some extent compared to PCS, because molecular weight increases little,
With reference to ir data, illustrate that DVS has mainly only reacted a vinyl, and remain another vinyl with suspension type knot
In closing product molecule structure.And the molecular weight distribution curve of product PVCS-8 synthesized by reference examples 2 then show it is dramatically different
The characteristics of, it is not only bimodal to there occurs to a certain degree of skew of bound macromolecule, also it is about at 10 and 11min in the drip washing time
The peak of more macromolecule is occurred in that respectively, due to the superposition at the two peaks, is formd in that the drip washing time is 9.6~13min
Individual big bulge peak, correspondingly, as shown in table 1, its molecular weight significantly increases, and range of molecular weight distributions is substantially widened.With reference to infrared
Spectrometric Si-H extents of reaction, illustrate that two vinyl of some DVS there occurs reaction, in the intermolecular shapes of PCS
Into cross-linked structure.
From the analysis to accompanying drawing 1 and accompanying drawing 2, with reference to table 1 and the data of table 2, it can be seen that the features of the present invention：(1) lead to
Be introduced into vinyl in product PVCS by the hydrosilylation for crossing PCS and DVS or TVS, obtains the Si-H and CH=CH containing activity2Base
The product PVCS of group；(2) by controllable hydrosilylation, the structure of product is controlled.I.e. such as 1~embodiment of embodiment 6, control
The Si-H extents of reaction are 10~30% in reaction, and the number-average molecular weight of the product PVCS for so obtaining is 1900~2300, its point
The GPC curves of son amount distribution maintain the bimodal morphology of original PCS, and from structure, essence is to make the vinyl of introducing with suspension type
With reference on the molecular structure of former PCS；(3) with the PVCS of this structure, with combination property preferably.When Si-H reactions
Degree be less than 10% when such as reference examples 1, although can also obtain the Si-H and CH=CH containing activity2The product PVCS-7 of group, but by
It is not enough in vinyl is introduced, cross-linked structure is not formed in heat treatment, it is as shown in table 2 without heat curable properties；And work as Si-
The H extents of reaction are when being higher than 30% such as reference examples 2, although the PVCS-8 for obtaining has heat cure crosslinking feature, but due to synthesis instead
Middle cross-linked structure should be formed, cause the generation of high molecular weight molecules, occur insoluble matter, and solution when being dissolved in dimethylbenzene
Viscosity increase makes fabric be difficult to homogeneous impregnation.And only control the Si-H extents of reaction to be contained in the scope
Vinyl and vinyl in the case of suspended structure, product PVCS-1~PVCS- as synthesized by 1~embodiment of embodiment 6
6, just with good combination property：In inert atmosphere 400 DEG C treatment can self-curing crosslinking, solidification retention rate be higher than 95%, easily
It is dissolved in dimethylbenzene and solution viscosity is suitable, 1000 DEG C of pyrolized ceramic yields is 75%~83% (pyrolysis of the raw material PCS under the conditions of
Ceramic yield be 55%~60%).(4) additionally, just due to the reaction ratio and reaction condition by controlling DVS or TVS, control
The silicon hydrogen extent of reaction, also correspondingly controls the increase of carbon content for thus causing.As shown in table 3, using synthesized by the present invention
Product and its 1000 DEG C of carbon contents of thermal decomposition product and C/Si than incrementss in a less scope, will not be to being pyrolyzed
The performance of ceramic product brings influence.
In sum, the thermal curable that the present invention is set up is crosslinked the synthetic method of Polycarbosilane, and its feature is, with multiple
Condensation material Polycarbosilane is raw material, by anti-with the controllable Si―H addition reaction containing 2~3 organosilans of-C=C- groups
Should, synthesis obtains the level Polycarbosilane with-C=C- groups containing active Si-H, and this Polycarbosilane has heat cure self-crosslinking
Characteristic, it is possible to reduce material loss and environmental pollution, significantly improves pyrolized ceramic yield, and simple synthetic method, preparation cost
It is low, it is easy to accomplish batch production.Synthesized thermal curable Polycarbosilane can be used as the suitable pioneer of carborundum based material
Body, with important application value.
Claims (6)
1. the synthetic method of the Polycarbosilane of a kind of thermal curable crosslinking, it is characterised in that comprise the following steps：With composite
It is raw material with Polycarbosilane, composite Polycarbosilane is pressed one with containing 2 ~ 3 organic silane compounds of-C=C- groups
Certainty ratio is placed in reaction vessel, adds the ratio of 5 ~ 20ml dimethylbenzene to add solvent two with Polycarbosilane in every gram of composite
Toluene, it is uniform miscible, Si-H addition reaction catalysts are added, after vacuumizing displacement high pure nitrogen, under high pure nitrogen protection
Heating carries out Si-H addition reactions under normal pressure or condition of high voltage；When reacting at ambient pressure, under high pure nitrogen protection while stirring
90 ~ 100 DEG C are heated to, and insulation reaction is after 8 ~ 20 hours, stops reaction, and reaction mixture is placed in into distilling apparatus after being cooled to room temperature
In, under high pure nitrogen protection, 160 ~ 180 DEG C of distilling off solvent and unreacted silicon hydride compounds are warming up to, product is obtained containing second
The Polycarbosilane of alkenyl；When reacting under elevated pressure conditions, vacuumize displacement high pure nitrogen after, pre- inflated with nitrogen to 10 ~ 15MPa, plus
Heat is to 100 ~ 120 DEG C, and insulation reaction is after 8 ~ 20 hours, stops reaction, and reaction mixture is placed in into distilling apparatus after being cooled to room temperature
In, under high pure nitrogen protection, 160 ~ 180 DEG C of distilling off solvent and unreacted silane compound are warming up to, obtain product and contain
The Polycarbosilane of vinyl；
The composite Polycarbosilane, is to reset the Polycarbosilane for synthesizing by polydimethylsiloxane cracking, and its softening point is
180 ~ 220 DEG C, number-average molecular weight is 1400 ~ 1800；
The proportionings of the composite Polycarbosilane and the organic silane compound containing 2 ~ 3-C=C- groups, composite
With Polycarbosilane: contain 2 ~ 3 organic silane compound mass ratio=1 of-C=C- groups: 0.1 ~ 0.8；
It is described containing in 2 ~ 3 organic silane compounds of-C=C- groups be free of O, Cl element, on silicon atom connect organic group
In addition to vinyl, other groups are saturation organic group methyl, ethyl or propyl group for group.
2. the synthetic method of the Polycarbosilane of thermal curable according to claim 1 crosslinking, it is characterised in that described to contain
2 ~ 3 organic silane compounds of-C=C- groups are dimethyl divinyl silane or methyl trivinyl silane.
3. the synthetic method of the Polycarbosilane of thermal curable according to claim 1 and 2 crosslinking, it is characterised in that described
Si-H addition reaction catalysts are chloroplatinic acid H2PtCl6·H2O。
4. the synthetic method of the Polycarbosilane of thermal curable according to claim 3 crosslinking, it is characterised in that the chlorine platinum
The usage amount of acid is 100 ~ 150ppm, and its usage amount is with the quality of raw materials used composite Polycarbosilane as calculating benchmark.
5. the synthetic method of the Polycarbosilane of thermal curable according to claim 1 and 2 crosslinking, it is characterised in that multiple
Under condensation material Polycarbosilane and DVS reaction conditions, composite Polycarbosilane: DVS mass ratio=1: 0.3 ~ 0.5；Multiple
Under condensation material Polycarbosilane and TVS reaction conditions, composite Polycarbosilane: TVS mass ratio=1: 0.2 ~ 0.4.
6. the synthetic method of the Polycarbosilane of thermal curable according to claim 1 and 2 crosslinking, it is characterised in that described
The reaction conditions of composite Polycarbosilane and the organic silane compound containing 2 ~ 3-C=C- groups, when it is used contain 2 ~
When 3 boiling points of the organic silane compound of-C=C- groups are less than 100 DEG C, reacted using under condition of high voltage；When organosilicon used
When the boiling point of alkane is equal to or higher than 100 DEG C, reacted using under condition of normal pressure.
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| CN105601317B (en) * | 2015-12-18 | 2018-07-27 | 厦门纳美特新材料科技有限公司 | A kind of SiCN aeroges and preparation method thereof |
| CN105601316B (en) * | 2015-12-18 | 2018-07-27 | 厦门纳美特新材料科技有限公司 | A kind of carbonization silica aerogel and preparation method thereof |
| CN105600785B (en) * | 2015-12-24 | 2017-11-07 | 中国科学院宁波材料技术与工程研究所 | A kind of preparation method for the silica aerogel that is carbonized |
| CN106467610B (en) * | 2016-09-14 | 2019-06-18 | 中国科学院宁波材料技术与工程研究所 | A kind of preparation method of the liquid hyperbranched polycarbosilanes containing acryloxy |
| CN108047970A (en) * | 2017-12-12 | 2018-05-18 | 苏州铂邦胶业有限公司 | A kind of good silicone sealant of weatherability and preparation method thereof |
| CN108558409A (en) * | 2018-07-09 | 2018-09-21 | 俞雪利 | A kind of foam silicon carbide ceramics and use the liquid metal filter that it is material |
| CN108752038A (en) * | 2018-07-09 | 2018-11-06 | 宁波设会物联网科技有限公司 | It is a kind of with can be thermally cured Polycarbosilane preparation foam silicon carbide ceramics |
| CN108794053A (en) * | 2018-07-09 | 2018-11-13 | 俞雪利 | A kind of material is the porous media combustor of foam silicon carbide ceramics |
| CN108727059A (en) * | 2018-07-09 | 2018-11-02 | 宁波设会物联网科技有限公司 | It is a kind of can be thermally cured the preparation method that Polycarbosilane prepares foam silicon carbide ceramics |
| CN108821790B (en) * | 2018-09-14 | 2019-06-21 | 宁波设会物联网科技有限公司 | Can be thermally cured the method that Polycarbosilane and tungstic acid prepare foamed ceramics |
| CN109160815B (en) * | 2018-09-14 | 2019-12-13 | 宁波设会物联网科技有限公司 | Preparation method of high-temperature-resistant silicon carbide-tantalum carbide foam ceramic |
| CN108947578A (en) * | 2018-09-14 | 2018-12-07 | 宁波设会物联网科技有限公司 | A kind of preparation method of high-temperature resistant silicon carbide-hafnium carbide foamed ceramics |
| CN109293366A (en) * | 2018-10-12 | 2019-02-01 | 宁波设会物联网科技有限公司 | Can be thermally cured the preparation method that Polycarbosilane 3D printing prepares silicon carbide ceramics |
| CN109251034A (en) * | 2018-10-12 | 2019-01-22 | 宁波设会物联网科技有限公司 | A kind of 3D printing prepares silicon carbide ceramics and the use of its is ceramic-lined pipeline |
| CN109516828B (en) * | 2018-10-15 | 2021-03-30 | 广东工业大学 | Novel connection method of silicon carbide ceramic for core, silicon carbide ceramic prepared by connection method and application of silicon carbide ceramic |
| CN110511034A (en) * | 2019-08-05 | 2019-11-29 | 广东工业大学 | A kind of high yield ceramics and its preparation method and application |
| CN112048069A (en) * | 2020-08-05 | 2020-12-08 | 福建立亚化学有限公司 | Curing treatment method for micromolecular liquid carbosilane by-product |
| CN112126066A (en) * | 2020-09-24 | 2020-12-25 | 宁波曙翔新材料股份有限公司 | Preparation method of polycarbosilane with high silicon-hydrogen content |
| CN112126065B (en) * | 2020-09-24 | 2023-05-02 | 宁波曙翔新材料股份有限公司 | Preparation method of solid silicon carbide ceramic precursor |
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| US4737552A (en) * | 1986-06-30 | 1988-04-12 | Dow Corning Corporation | Ceramic materials from polycarbosilanes |
| JP3413486B2 (en) * | 2000-03-14 | 2003-06-03 | 独立行政法人産業技術総合研究所 | Method for producing aromatic polycarbosilane |
| CN101240070B (en) * | 2007-02-09 | 2012-05-30 | 中国人民解放军国防科学技术大学 | Method for synthesizing supercritical fluid of ceramic precursor polycarbosilane |
| WO2014019188A1 (en) * | 2012-08-02 | 2014-02-06 | Henkel (China) Company Limited | Polycarbosilane and curable compositions for led encapsulants comprising same |
| CN103254440B (en) * | 2013-06-15 | 2014-12-10 | 厦门大学 | Method of preparing liquid anaerobic polyferrocarbosilane |
| CN103772710B (en) * | 2014-02-26 | 2016-02-17 | 中国人民解放军国防科学技术大学 | A kind of synthetic method of high softening-point spinning-grade Polycarbosilane |
| CN104177621B (en) * | 2014-08-14 | 2017-03-29 | 中国科学院化学研究所 | A kind of liquid Polycarbosilane and preparation method and application |
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