CN109867793A - A kind of preparation method of the heat-resistant polymer containing carborane and silane structure and its application in antioxidant coating - Google Patents
A kind of preparation method of the heat-resistant polymer containing carborane and silane structure and its application in antioxidant coating Download PDFInfo
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Abstract
The preparation method that a kind of heat-resistant polymer containing carborane and silane structure is provided the invention belongs to polymer science technical field and its application in antioxidant coating.Heat-resistant polymer containing carborane and silane structure in the present invention is synthesized by one pot of two-step method.Resin base antioxidant coating of the present invention is and SiC, TiO to be added using MSCB as raw material2Or ZrO2Upper resin base organic coating is successfully coated on carbon matrix material surface using dipping thermal conversion process for filler, which can significantly improve the middle low temperature antioxygenic property of basis material.The polymer that the present invention obtains has excellent thermal stability and thermo-oxidative stability, and the preparation process of corresponding antioxidant coating is simple, cost is relatively low, and the coating binding force between matrix that is evenly distributed is strong, is suitble to apply on large-sized structural component.
Description
Technical field
The invention belongs to polymer science technical fields, are related to a kind of heat-resistant polymer containing carborane and silane structure
Preparation method and its application in antioxidant coating.
Background technique
Carborane is the product that the boron atom in polyhedral boranes molecule is replaced by carbon atom.Especially enclosed carborane is
The cage structure of a kind of super armaticity, shows many representative properties of aroma system, has special thermal stability and chemistry
Stability.Wherein, the carborane of most study is bis- carbon of enclosed -1,2-, ten diborane (C of generation2B10H12), by two carbon atoms and
The icosahedron cage structure that ten boron atoms are formed, it to be the polyhedral structure of high symmetry, its fusing point that there are three types of isomers
It is 320 DEG C, is not easy to act on water, alkali, acid and oxidant.C h bond and C-B key in carborane have reactivity, by right
C h bond and C-B key are modified, and can get the various reactive monomers containing carborane radical.In carborane molecule boron atom compared with
Low nucleophilicity and strong electrophilic characteristic makes the unit of its Yi Yuhan aromatic ring form hyperconjugation, and due to its huge sky
Between steric effect, greatly improve the thermal stability and thermo-oxidative stability of carborane.Just because of uniqueness possessed by carborane
Property makes synthesis and application study containing carborane polymer receive the attention of polymer science circle personage.
The U.S., Russia began to develop carborane and its derivative from the 1960s, and attempted to develop it not
The application of same domain.It is most initially that Olin company successfully synthesizes the polysiloxanes of structure containing carborane, and successfully realizes commercialization.
Although China started to study hydroboron in the 1960s, the report in relation to carborane and its application
Seldom.With the development of China's aerospace cause, the demand of heat-resistant polymer is also greatly increased, therefore is carried out carbon containing
The research of borane polymers has important theory significance and application value.In recent years, studies in China scholar is by carborane structure
Be introduced into high performance resin, it is desirable to by carborane structure introducing further promoted high performance resin thermo-oxidative stability and
Dissolubility etc., this kind of high performance resin include poly(aryl ether ketone), polyimides, polybenzimidazoles, polybenzoxazoles, polyarylate etc..
For example, neat Shicheng of Beijing University of Chemical Technology et al. is once raw material using 1,7- carborane, the silicon in main chain containing carborane has been synthesized
Oxygen alkane polymer.The result shows that carborane silanol monomer can be used successfully to prepare in carborane siloxane polymer, also,
The introducing of carborane group can effectively improve the hot property of polymer.The Zhang Zhijie et al. of Chinese Academy of Sciences's chemistry institute then passes through
Bis- (the dimethylhydroxysilyl)-m- carboranes of 1,7- and ring triazanes are in (NH4)2SO4In the presence of polycondensation reaction synthesis
Three kinds of carboranes-siloxanes alternate copolymer, this new polymers can selected by hanging being crosslinked of vinyl group
At a temperature of be converted into thermosetting plastics.The result shows that this polymer has good thermal stability, also, vinyl group
Crosslinking helps to improve the thermal stability of polymer.Xing Tao of Electronic Engineering Inst., China Engineering Physics Inst et al. is also closed
At the novel soluble carborane polyimides with superelevation thermal stability.It is synthesis first between the fragrance of different structure
Position carborane amine diamines, then, by this new diamine and 4,4'- diphenyl ether dianhydride is polymerize, and being formed has different structure
With the meta position carborane polyimides of thermal stability.Gained amorphous polymer has moderate molecular weight, in organic solvent
With good dissolubility.Also, these polyimides show the medium thermal stability to superelevation with the difference of structure.
Jia Xudong of Nanjing University et al. then also passes through the point of azido-methyl meta position carborane (DAMC) and tolans (DABB) first
Hit the novel polyphenyl and oxazines performed polymer for reacting and having synthesized containing m- carborane primitive in main chain.After the solidification of these performed polymers, it is in
Reveal higher storage modulus and glass transition temperature (Tg), and also there is excellent thermo oxidative stability.
Generally speaking, carborane structure is introduced into polymer: on the one hand, the three-dimensional cagelike structure of carborane can support
Polymer molecular chain is opened, the regular arrangement of molecular resin is reduced, improves the dissolubility of resin, promote the processing performance of resin；Separately
On the one hand, the introducing of carborane structure can be obviously improved the thermo-oxidative stability of resin, this introducing mainly with inorganic elements boron has
It closes；In addition, the high temperature carbon yield and ceramic yield of resin, therefore knot containing carborane can be substantially improved in the introducing of carborane structure
Paper mulberry rouge has important application value in neutron shielding material, electronic material, optical material, adsorbent material, adhesive field.
Composite material of the carbon/carbon compound material as the full carbonaceous that a kind of matrix phase and reinforced phase are identity element, due to
It is only made of single carbon, not only the ablation resistance excellent with carbon and graphite material, low-density, thermal expansion coefficient
Low advantage, and there are also excellent mechanical properties, such as high intensity, high-modulus, good fracture toughness and wear-resisting property, lazy
In property atmosphere or vacuum, these performances can still be kept at a high temperature of 2000 DEG C or more, more importantly at 1500 DEG C
The performance that its intensity goes up not down as the temperature increases under the above hot environment becomes a kind of especially high-new with development prospect
Technologic material has been widely used in space flight and aviation day field and automotive field.But under air conditions, carbon fiber is 500
DEG C will rapid oxidation decompose, therefore the antioxidant defense of composite material is that it obtains widely applied key.To keep carbon carbon
The mechanical performance of multiple material, needs to carry out protection processing to its surface.To prevent C/C composite material from aoxidizing at high temperature, both at home and abroad
Researcher has carried out a large amount of theoretical and experimental study, develops a variety of antioxidant coating systems.It is anti-about carbon material surface
The coating preparation work of hot oxygen protection system has been developed that the thermal protection for carbon material surface, example there are many method
Such as method, chemical vapour deposition technique (CVD), ion sputtering process and homogenate method is seeped by powder bag to coat carbon material surface
Protection, but these methods come with some shortcomings.For example, powder bag, which seeps method, generally requires higher operation temperature (> 1800 DEG C)
It with longer sintering time (> 2h), generally requires repeatedly to be sintered further for laminated coating, these operations will lead to material sheet
The damage of body makes material internal generate internal stress simultaneously.Ion sputtering and CVD method generally require expensive operation equipment, furthermore
CVD method, ion sputtering and homogenate method generally require vacuumizing, therefore are generally difficult to implement to operate to large-sized structural component.
Compared to the above, resin based coatings involved in the present invention have lot of advantages.Firstly, resin based coatings exist
Often it is solution state in operation, therefore can guarantees the adherency between coating and matrix, while being conducive to labyrinth sample
Coating.Further, since polymer can guarantee homogeneous on molecular dimension, therefore resin based coatings will not be as inorganic coating one
Sample occurs dispersing non-uniform phenomenon.And unsaturated bond is introduced in polymer of the main chain containing carborane and silane structure, lead to
That crosses hydrosilylation realization polymer solidifies the heat resistance for being crosslinked and can further promoting resin.Using the resinoid as coating
When applied to surface of carbon/carbon composite processing, the carborane on the carborane radical main polymer chain in superficial layer can be mentioned
High thermal oxidation prevents the degradation of material, improves Residual carbon, reaches demand resistant to high temperature with this.And carborane itself can be with
The performance for absorbing oxygen atom buffering matrix oxidation then can significantly improve the antioxidative stabilizer of matrix.Contain boron element and silicon simultaneously
There are also similar thermal expansion coefficients for the polymer material and carbon base body of element, therefore, have good bond performance, surface to matrix
Coating is not likely to produce crack.
Summary of the invention
In order to improve the heat resistance of high molecular polymer, the present invention introduces carborane and silane knot into main polymer chain
Structure, and realize by the addition reaction between the alkynyl and si-h bond in polymer the middle low-temperature setting of polymer.Benefit simultaneously
With dipping thermal conversion process, answered in carbon carbon and introduce resin-based antioxidant coating on material surface, middle low-temperature range can be big
Amplitude reduction carbon carbon answers the oxidation rate of material.
Technical solution of the present invention:
A kind of preparation method of the heat-resistant polymer containing carborane and silane structure, the specific steps are as follows:
Using APCB, butyl lithium and methyl hydrogen dichlorosilane as reactant, using " one pot of two-step method " synthesis containing carborane and
The heat-resistant polymer MSCB of silane structure；
APCB is added into the reaction flask equipped with magnetic agitation, constant pressure funnel device, mends nitrogen by vacuumizing
Gas in reaction system is all replaced as nitrogen by multi-pass operation, increases nitrogen flow and tetrahydrofuran is added into reaction flask,
Controlling the atmosphere in reaction flask is nitrogen atmosphere, wherein the volume of tetrahydrofuran is 4-4.5 times of butyl lithium volume；In ice water
Under the conditions of bath, butyl lithium reagent is added dropwise；After completion of dropwise addition, reacts at room temperature 1-2 hours, be warming up to 60-70 DEG C of reaction 1-2 hours；
Then, reaction system is placed in ice-water bath again, the tetrahydrofuran solution of methyl hydrogen dichlorosilane is added dropwise, control methyl
The volume ratio of hydrogen dichlorosilane and tetrahydrofuran is 1:6-10,70-80 DEG C is warming up to after completion of dropwise addition, polymerization reaction time 12-
20 hours；After reaction, it pours into saturated brine solution, product, liquid separation is extracted with methylene chloride, and remove with anhydrous magnesium sulfate
Water filters, rotates to obtain MSCB polymer, is placed under 50-80 DEG C of vacuum condition 10-15 hours dry；Wherein APCB, butyl lithium
Molar ratio with methyl hydrogen dichlorosilane is 1:2.0-2.2:1.0-1.2.
A kind of preparation method of the resin base antioxidant coating containing carborane and silane structure, steps are as follows:
It disperses MSCB, inorganic filler in nmp solvent by a certain percentage, coating answers material sample surfaces to carbon carbon, passes through
Heat treatment is converted into the antioxidant coating of MSCB base；
MSCB resin is dissolved in NMP, coating is formed；It chooses inorganic oxytolerant compound to be added as filler into coating, nothing
Machine filler is SiC, TiO2And ZrO2One or more of mixing, the wherein mass ratio of MSCB, NMP and inorganic filler
For 100:80-120:5-20；Then heat the coating at 80-100 DEG C, and magnetic agitation is dispersed 1-2 hours, it is ensured that system
It is uniformly dispersed；Then C/C is answered material sample to immerse in above-mentioned coating, then sample is placed in 80-100 DEG C of baking oven and is dried；Such as
This is repeated as many times, until carbon carbon answers the MSCB resin based coatings cladding of material sample surfaces whole quilt；Finally, above-mentioned MSCB is coated
C/C answer material sample and be placed in baking oven, carry out the step-up temperature curing reaction of MSCB resin, condition of cure is: 160-180
DEG C/1-3h, 190-210 DEG C/1-3h, 220-240 DEG C/1-3h, 260-280 DEG C/1-2h, 290-310 DEG C/1-2h.Solidification is completed
Corresponding resin base antioxidant coating is obtained afterwards.
Beneficial effects of the present invention: (1) synthesize " one pot of two step " of above-mentioned high temperature resistant MSCB resin may achieve, experiment
Easy to operate, yield is high.(2) for common thermosetting resin, the MSCB resin after solidification is in nitrogen and air item
Under part, high thermal stability and thermo-oxidative stability have been shown, has there is apparent heatproof advantage.(3) it is prepared by MSCB
Resin based coatings preparation process it is simple, it is at low cost, dispersion homogeneity it is good, can in 500-1000 DEG C of section effective protection carbon
Carbon, which answers material, reduces its oxidation rate.MSCB resin base antioxidant coating prepared by the present invention can be used for large-scale structure member.
Detailed description of the invention
Fig. 1 is nucleus magnetic hydrogen spectrum figure of the MSCB resin in deuterated chloroform solvent.
Fig. 2 is nuclear-magnetism carbon spectrogram of the MSCB resin in deuterated chloroform solvent.
Fig. 3 is the DSC curve of MSCB resin.
The FT-IR comparison diagram of MSCB resin after Fig. 4 is MSCB resin and solidifies.
Fig. 5 is the thermogravimetric curve of MSCB resin after solidifying.
Fig. 6 is the protection of different MSCB base coatings and exposed carbon carbon answer material sample thermogravimetric curve (30-1000 DEG C, 5 DEG C/
Min, 1000 DEG C of heat preservation 40min).
Fig. 7 is the thermogravimetric curve that the different MSCB base coating protections of 800 DEG C of heat treatments and exposed carbon carbon answer material sample.
Fig. 8 is the thermogravimetric curve that the different MSCB base coating protections of 600 DEG C of heat treatments and exposed carbon carbon answer material sample.
Specific embodiment
Only the present invention is further illustrated for the case study on implementation being provided below, but does not limit the scope of the invention.
Embodiment 1-3 is the preparation case of the heat-resistant polymer MSCB containing carborane and silane structure.
Embodiment 1:
8.9558g (26.0 is added into Shi Lanke bottles of 500ml equipped with magnetic agitation, constant pressure funnel device
Gas in reaction system is all replaced as nitrogen, increases nitrogen by mmol) APCB, the multi-pass operation by vacuumizing benefit nitrogen
155ml tetrahydrofuran is added into reaction flask for flow.Under the conditions of ice-water bath, the examination of 35.0 mL (56.0mmol) butyl lithium is added dropwise
Agent.It after completion of dropwise addition, reacts at room temperature 2 hours, is warming up to 70 DEG C and reacts 2 hours.Then, reaction system is placed in ice water again
In bath, be added dropwise methyl hydrogen dichlorosilane tetrahydrofuran solution (wherein methyl hydrogen dichlorosilane be 2.9ml
(26.5mmol), tetrahydrofuran 25ml), 80 DEG C, polymerization reaction time 20 hours are warming up to after completion of dropwise addition.Reaction terminates
Afterwards, it pours into saturated brine solution, product, liquid separation is extracted with methylene chloride, and remove water with anhydrous magnesium sulfate, filter, rotate
MSCB polymer is placed in drying 12 hours in 80 DEG C of vacuum ovens, obtains the product of 9.194g.Test product yield are as follows:
91.5%.
Embodiment 2:
4.4090g is added into Shi Lanke bottles of 250ml equipped with magnetic agitation, constant pressure funnel device
Gas in reaction system is all replaced as nitrogen, added by (12.8mmol) APCB, the multi-pass operation by vacuumizing benefit nitrogen
75ml tetrahydrofuran is added into reaction flask for big nitrogen flow.Under the conditions of ice-water bath, 16.5mL (26.4mmol) butyl is added dropwise
Lithium reagent.It after completion of dropwise addition, reacts at room temperature 1.5 hours, is warming up to 65 DEG C and reacts 1.5 hours.Then, reaction system is set again
In ice-water bath, be added dropwise methyl hydrogen dichlorosilane tetrahydrofuran solution (wherein methyl hydrogen dichlorosilane be 1.4ml
(12.8mmol), tetrahydrofuran 10ml), 75 DEG C, polymerization reaction time 18 hours are warming up to after completion of dropwise addition.Reaction terminates
Afterwards, it pours into saturated brine solution, product, liquid separation is extracted with methylene chloride, and remove water with anhydrous magnesium sulfate, filter, rotate
MSCB polymer is placed in drying 16 hours in 70 DEG C of vacuum ovens, obtains the product of 4.610g.Test product yield are as follows:
93.2%.
Embodiment 3:
2.2045g (6.4 mmol) is added into Shi Lanke bottles of 100ml equipped with magnetic agitation, constant pressure funnel device
Gas in reaction system is all replaced as nitrogen, increases nitrogen flow by APCB, the multi-pass operation by vacuumizing benefit nitrogen
35ml tetrahydrofuran is added into reaction flask.Under the conditions of ice-water bath, 8mL (12.8mmol) butyl lithium reagent is added dropwise.Knot is added dropwise
Shu Hou is reacted at room temperature 1 hour, is warming up to 60 DEG C and is reacted 1 hour.Then, reaction system is placed in ice-water bath again, dropwise plus
Entering the tetrahydrofuran solution of methyl hydrogen dichlorosilane, (wherein methyl hydrogen dichlorosilane is 0.7ml (6.4mmol), and tetrahydrofuran is
5ml), 70 DEG C, polymerization reaction time 12 hours are warming up to after completion of dropwise addition.After reaction, it pours into saturated brine solution, with
Methylene chloride extracts product, liquid separation, and is removed water with anhydrous magnesium sulfate, filters, rotates to obtain MSCB polymer, and it is dry to be placed in 60 DEG C of vacuum
It is 10 hours dry in dry case, obtain the product of 2.372g.Test product yield are as follows: 95.9%.
The nucleus magnetic hydrogen spectrum and carbon spectrogram for the MSCB resin being prepared are shown in that Fig. 1 and Fig. 2, DSC curve are shown in Fig. 3, it is known that
The curing exothermic peak of MSCB resin is between 247-293 DEG C.MSCB resin is placed in convection oven, heat cure is carried out and obtains
To the solidification MSCB resin of excellent heat resistance, the curing process condition of case study on implementation 3 is: 180 DEG C/2h, 200 DEG C/2h, and 230
DEG C/2h, 270 DEG C/1h, 300 DEG C/1h.The infared spectrum of uncured MSCB resin and the MSCB resin after solidifying is shown in Fig. 4, can
After knowing solidification, the acetenyl in MSCB resin has been completely disappeared, and shows that resin solidification is complete.The heat of MSCB resin is lost after solidification
Multigraph is shown in Fig. 5.Under a nitrogen atmosphere, 5% thermal weight loss temperature is up to 709 DEG C, and 10% thermal weight loss temperature has been over
The carbon yield of resin is up to 93.2% at 1000 DEG C, 1000 DEG C；Under air conditions, the MSCB resin after solidification occurs bright
Aobvious heat weight gain phenomenon still has 10.3% hot weight gain value at 1000 DEG C.This shows that the MSCB resin being prepared has pole
High thermal stability and thermo-oxidative stability.
Embodiment 4-7 is the method for preparing MSCB resin base antioxidant coating
A kind of embodiment 4: pure resin-based antioxidant coating preparation of MSCB
The MSCB resin of 0.8g is dissolved in the NMP of 1ml first, then heats the coating at 80 DEG C, and magnetic force stirs
Mix dispersion 1 hour, it is ensured that system is uniformly dispersed.Then C/C is answered material sample to immerse in above-mentioned coating, then sample is placed in
It is dried in 100 DEG C of baking ovens；It is so repeated as many times, until carbon carbon answers the MSCB resin based coatings cladding of material sample surfaces whole quilt.
It is placed in baking oven finally, the carbon carbon that above-mentioned MSCB is coated is answered material sample, carries out the step-up temperature curing reaction of MSCB resin, Gu
Change condition is: 180 DEG C/2 h, 200 DEG C/2h, 230 DEG C/2h, 270 DEG C/1h, 300 DEG C/1h.
A kind of embodiment 5: antioxidant coating preparation of MSCB resin base SiC filler
The MSCB resin of 0.6g is dissolved in the NMP of 0.8ml first, then the SiC of 0.06g is added into system.Then exist
100 DEG C are heated the coating, and magnetic agitation is dispersed 2 hours, it is ensured that system is uniformly dispersed.Then C/C is answered into the leaching of material sample
Enter in above-mentioned coating, then sample is placed in 90 DEG C of baking ovens and is dried；It is so repeated as many times, until to answer material sample surfaces complete for carbon carbon
The MSCB resin based coatings of portion's quilt coat.It is placed in baking oven finally, the carbon carbon that above-mentioned MSCB is coated is answered material sample, carries out MSCB
The step-up temperature curing reaction of resin, condition of cure is: 170 DEG C/2h, 190 DEG C/2h, and 220 DEG C/2h, 260 DEG C/1h, 290 DEG C/
1h。
A kind of embodiment 6: MSCB resin base TiO2It is prepared by the antioxidant coating of filler
The MSCB resin of 0.4g is dissolved in the NMP of 0.5ml first, then the TiO of 0.04g is added into system2.Then
Heat the coating at 90 DEG C, and magnetic agitation is dispersed 1.5 hours, it is ensured that system is uniformly dispersed.Then C/C is answered into material sample
It immerses in above-mentioned coating, then sample is placed in 95 DEG C of baking ovens and is dried；It is so repeated as many times, until carbon carbon answers material sample surfaces
The MSCB resin based coatings of whole quilts coat.It is placed in baking oven, carries out finally, the carbon carbon that above-mentioned MSCB is coated is answered material sample
The step-up temperature curing reaction of MSCB resin, condition of cure is: 180 DEG C/2.5h, 200 DEG C/2.5h, and 230 DEG C/2.5h, 270 DEG C/
1.5h, 300 DEG C/1.5h.
Embodiment 5:
The MSCB resin of 0.8g is dissolved in the NMP of 1.2ml first, then the ZrO of 0.08g is added into system2.Then
Heat the coating at 100 DEG C, and magnetic agitation is dispersed 1 hour, it is ensured that system is uniformly dispersed.Then C/C is answered into material sample
It immerses in above-mentioned coating, then sample is placed in 85 DEG C of baking ovens and is dried；It is so repeated as many times, until carbon carbon answers material sample surfaces
The MSCB resin based coatings of whole quilts coat.It is placed in baking oven, carries out finally, the carbon carbon that above-mentioned MSCB is coated is answered material sample
The step-up temperature curing reaction of MSCB resin, condition of cure is: 190 DEG C/2h, 210 DEG C/2h, and 240 DEG C/2h, 280 DEG C/1h, 310
℃/1 h。
The carbon carbon of above-mentioned difference MSCB resin based coatings protection answers material and unshielded exposed carbon carbon answers material in different disposal
At a temperature of thermogravimetic analysis (TGA), see Fig. 6, Fig. 7, Fig. 8.It can be seen that the resin-based coating of MSCB, which can obviously reduce carbon carbon, answers material
Oxidation weight loss rate, the inoxidizability that carbon carbon answers material sample is greatly improved.And inorganic filler SiC, TiO2And ZrO2
Introducing, can only improve the inoxidizability of MSCB resin based coatings in certain temperature range, wherein the effective temperature of SiC
Section is 600-800 DEG C；TiO2Effective temperature section be 600-1000 DEG C；ZrO2Effective temperature section be less than equal to 600
℃。
Claims (3)
1. a kind of preparation method of the heat-resistant polymer containing carborane and silane structure, which is characterized in that steps are as follows:
Using APCB, butyl lithium and methyl hydrogen dichlorosilane as reactant, carborane and silane are contained using " one pot of two-step method " synthesis
The heat-resistant polymer MSCB of structure；
APCB is added into the reaction flask equipped with magnetic agitation, constant pressure funnel device, mends the multiple of nitrogen by vacuumizing
Gas in reaction system is all replaced as nitrogen by operation, increases nitrogen flow and tetrahydrofuran is added into reaction flask, control
Atmosphere in reaction flask is nitrogen atmosphere, wherein the volume of tetrahydrofuran is 4-4.5 times of butyl lithium volume；In ice-water bath item
Under part, butyl lithium reagent is added dropwise；After completion of dropwise addition, reacts at room temperature 1-2 hours, be warming up to 60-70 DEG C of reaction 1-2 hours；Then,
Reaction system is placed in ice-water bath again, the tetrahydrofuran solution of methyl hydrogen dichlorosilane is added dropwise, controls methyl hydrogen two
The volume ratio of chlorosilane and tetrahydrofuran is 1:6-10,70-80 DEG C is warming up to after completion of dropwise addition, polymerization reaction time 12-20 is small
When；After reaction, it pours into saturated brine solution, product, liquid separation is extracted with methylene chloride, and remove water with anhydrous magnesium sulfate,
It filters, rotates to obtain MSCB polymer, be placed under 50-80 DEG C of vacuum condition 10-15 hours dry；Wherein APCB, butyl lithium and first
The molar ratio of base hydrogen dichlorosilane is 1:2.0-2.2:1.0-1.2.
2. a kind of preparation method of the resin base antioxidant coating containing carborane and silane structure, which is characterized in that steps are as follows:
It disperses MSCB, inorganic filler in nmp solvent by a certain percentage, material sample surfaces are answered in coating to carbon carbon, at heat
Reason is converted into the antioxidant coating of MSCB base；
MSCB resin is dissolved in NMP, coating is formed；Inorganic oxytolerant compound is chosen to be added as filler into coating, it is inorganic to fill out
Material is SiC, TiO2And ZrO2One or more of mixing, wherein MSCB, NMP and the mass ratio of inorganic filler are 100:
80-120:5-20；Then heat the coating at 80-100 DEG C, and magnetic agitation is dispersed 1-2 hours, it is ensured that system dispersion is equal
It is even；Then C/C is answered material sample to immerse in above-mentioned coating, then sample is placed in 80-100 DEG C of baking oven and is dried；So repeat
Repeatedly, until carbon carbon answers the MSCB resin based coatings cladding of material sample surfaces whole quilt；Finally, the C/C that above-mentioned MSCB is coated
Multiple material sample is placed in baking oven, carries out the step-up temperature curing reaction of MSCB resin, corresponding resin is obtained after the completion of solidification
Base antioxidant coating.
3. preparation method according to claim 2, which is characterized in that the condition of cure is: 160-180 DEG C/1-3h,
190-210 DEG C/1-3h, 220-240 DEG C/1-3h, 260-280 DEG C/1-2h, 290-310 DEG C/1-2h.
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| CN110423352A (en) * | 2019-07-26 | 2019-11-08 | 大连理工大学 | A kind of preparation method of the high-temperature resistant silicone of structure containing carborane material |
| CN112646190A (en) * | 2021-01-19 | 2021-04-13 | 苏州天大通利高分子材料有限公司 | High-temperature-resistant modified polyphenyl ether and preparation method thereof |
| CN117447909A (en) * | 2023-12-26 | 2024-01-26 | 成都虹润制漆有限公司 | Moisture curing type anti-corrosion coating for wind and rain roof and preparation method thereof |
| CN117447741A (en) * | 2023-12-21 | 2024-01-26 | 北京玻钢院复合材料有限公司 | High-temperature-resistant antioxidant hot-melt polyimide prepreg, composite material and preparation method thereof |
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