CN109762010A - Sulfur-bearing silicon aryne resin and its composite material, preparation method - Google Patents
Sulfur-bearing silicon aryne resin and its composite material, preparation method Download PDFInfo
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Abstract
The invention discloses a kind of sulfur-bearing silicon aryne resin and its composite materials, preparation method.Its structural formula is as follows, any one of G in following radicals:OrR1And R2It independently is H, methyl, phenyl, vinyl or ethyl；N=1~5 and be integer.Stablize under the resin room temperature it is easy to maintain, can at 170~250 DEG C polymerization crosslinking solidify, have excellent mechanical property, thermal stability and thermo-oxidative stability；The high person of decomposition temperature of its solidfied material in nitrogen is up to 498 DEG C, and the aerial high person of decomposition temperature is up to 497 DEG C, heat resistance and mechanical property with higher.Sulfur-bearing silicon aryne resin composite material of the invention has preferably heat resistance and mechanical property, and bending strength is high, bending modulus is high, shear strength is high.
Description
Technical field
The present invention relates to a kind of sulfur-bearing silicon aryne resin and its composite materials, preparation method.
Background technique
Siliceous aryne (PSA) resin refers to the aryl polyyne resin that main chain contains element silicon, is a kind of organic inorganic hybridization
Resin can be used as thermosetting resin, have excellent heat resistance and mechanics with the resin composite materials that fiber and its fabric enhance
Performance, but be in brittleness after the solidification of siliceous aryne resin, mechanical strength slightly has deficiency, limits its answering in aerospace field
With.
Since two thousand two, East China University of Science Huang Farong seminar has carried out the basic theory of siliceous aryne resin and has answered
It is studied from structure and performance with research and has invented a series of siliceous aryne resins haveing excellent performance, such as Wang Canfeng
Boron element is introduced siliceous aryne resin knot by (Reactive and Functional Polymers, 2011,71:899~904)
In structure, the siliceous aryne resin of high heat resistance oxygen performance has been invented；It is old can it is high (High Performance Polymer, 2017,
Ehter bond: 595~601) being introduced into siliceous aryne resin backbone structure by 29 (5), and the siliceous virtue of excellent in mechanical performance is prepared
Alkynes resin.In currently available technology, there is not the correlative study that element sulphur is introduced into the siliceous aryne resin system of tradition also.
Summary of the invention
The present invention provides a kind of sulfur-bearing silicon aryne resin and its composite materials, preparation method.Sulfur-bearing silicon virtue of the invention
Alkynes resin is dark brown solid, stablizes under room temperature easy to maintain, polymerization crosslinking can solidify at 170~250 DEG C, have excellent power
Learn performance, thermal stability and thermo-oxidative stability；The high person of decomposition temperature of its solidfied material in nitrogen is aerial up to 498 DEG C
The high person of decomposition temperature is up to 497 DEG C, heat resistance and mechanical property with higher.Sulfur-bearing silicon aryne resin composite material of the invention
With preferably heat resistance and mechanical property, bending strength is high, bending modulus is high, shear strength is high.In a certain embodiment
In, carbon fibre reinforced composite bending strength can reach 404.3MPa, it is expected to be applied to the high-tech areas such as aerospace.
The present invention solves above-mentioned technical problem by the following technical programs.
The present invention provides a kind of sulfur-bearing silicon aryne resin, structural formula is as follows:
Wherein, any one of G in following radicals :-s-,Or
R1And R2It independently is H, methyl, phenyl, vinyl or ethyl；
N=1~5, and be integer.
In the present invention, the n is preferably 1~3, such as 1,2 or 3.
In the present invention, the number-average molecular weight of the sulfur-bearing silicon aryne resin is that Mn is preferably 2000~3000, more preferably
It is 2000~2500, such as 2367,2011,2297,2264,2498 or 2602.
In the present invention, the weight average molecular weight of the sulfur-bearing silicon aryne resin is that Mw is preferably 2500~4500, more preferably
It is 2500~4100, such as 3896,2956,3834,3808,3996 or 4059.
In the present invention, the polydispersity index Mw/Mn of the sulfur-bearing silicon aryne resin can be conventional for this field, and preferably 1
~1.7, it is more preferably 1.2~1.7, such as 1.65,1.47,1.67,1.68,1.60 or 1.56.
In the present invention, preferably, G is-s-, R1For methyl, R2For phenyl, more preferably, G is-S-, R1For methyl, R2For benzene
Base, Mn=2367, polydispersity index 1.65.
In the present invention, preferably, G is-S-, R1For methyl, R2For phenyl, more preferably, G is-S-, R1For methyl, R2For benzene
Base, Mn=2011, polydispersity index 1.47.
In the present invention, preferably, G is-S-, R1For methyl, R2For methyl, more preferably, G is-S-, R1For methyl, R2For first
Base, Mn=2297, polydispersity index 1.67.
In the present invention, preferably, G is-S-, R1For methyl, R2For H, more preferably, G is-S-, R1For methyl, R2For H, Mn
=2264, polydispersity index 1.68.
In the present invention, preferably, G isR1For methyl, R2For phenyl, more preferably, G isR1For first
Base, R2For phenyl, Mn=2498, polydispersity index 1.60.
In the present invention, preferably, G isR1For methyl, R2For phenyl, more preferably, G isR1For first
Base, R2For phenyl, Mn=2602, polydispersity index 1.56.
The present invention also provides a kind of sulfur-bearing ether structure (PSSA) or the preparation sides of the silicon aryne resin (PSFA) of sulfone structure
Method comprising following step:
1) halogenated hydrocarbons is added in the mixture of magnesium powder and organic solvent under an inert atmosphere, reaction generates the examination of alkyl format
Agent；
2) alkynes monomer is added in the alkyl grignard reagent and carries out reaction generation alkynes grignard reagent；Wherein, the alkynes list
Body is diacetylene diphenyl sulfide or diacetylene diphenyl sulphone (DPS)；
3) dichlorosilane is added in the alkynes grignard reagent and carries out polymerization reaction to obtain the final product.
Reaction process is as follows:
1.RBr+Mg→RMgBr
2.
Wherein, G be selected from-s- orR1And R2It independently is H, methyl, phenyl, vinyl or ethyl, n=1
~5, and be integer.Described G, R1、R2It is as previously described with n.
In step 1), the inert atmosphere can pass through the indifferent gas for being not involved in chemical reaction of conventional method in that art acquisition
Atmosphere, such as nitrogen atmosphere.
In step 1), the halogenated hydrocarbons can be conventional for this field, such as bromoethane.
In step 1), the halogenated hydrocarbons preferably adds as a solution.In halohydrocarbon solution, the concentration of halogenated hydrocarbons
Preferably 10~15mol/L, such as 12mol/L.In halohydrocarbon solution, the solvent used can be this field routine, generally
For tetrahydrofuran and/or toluene.
In step 1), according to common sense in the field it is found that the halogenated hydrocarbons is slowly added dropwise generally by constant pressure funnel into institute
It states in mixture, the time for adding of the halogenated hydrocarbons can be conventional for this field, preferably 10~60min.The halogenated hydrocarbons exists
Non-aqueous processing is carried out generally according to conventional method in that art using preceding.
In step 1), the molar ratio of the halogenated hydrocarbons and the magnesium powder can be conventional for this field, and preferably 1:(1.25~
, such as 1:1.25 1.5).
In step 1), the organic solvent can be the organic solvent that can be used for carrying out grignard reaction of this field routine, compared with
It goodly include one of tetrahydrofuran, methyltetrahydrofuran, glycol dimethyl ether, methylene chloride and toluene or a variety of.It is described
Organic solvent is carrying out Non-aqueous processing generally according to conventional method in that art using preceding.
In step 1), the reaction can be the condition of the grignard reaction of this field routine.The temperature of the reaction is preferably
It is 35~45 DEG C, such as 40 DEG C.The time of the reaction is preferably 1~3h.
In step 2), the molar ratio of the alkynes monomer and the alkyl halide can be conventional for this field, preferably 1:2.
In step 2), the alkynes monomer preferably adds as a solution.In alkynes monomer solution, the concentration of alkynes monomer
Preferably 0.25~0.85mol/L, such as 0.8mol/L.In alkynes monomer solution, the solvent used can be this field routine,
Generally one of tetrahydrofuran, methyltetrahydrofuran, glycol dimethyl ether, methylene chloride and toluene or a variety of.
In step 2), preferably, the alkyl lattice are added in the alkynes monomer by way of dropwise addition when ice-water bath is cooling
In formula reagent.The time for adding of the alkynes monomer is preferably 0.5~2h, such as 1.5h.
In step 2), the operation of the reaction and condition can be conventional for this field, preferably heating reflux reaction 1~
3h, such as it is heated to reflux 1.5h.
In step 3), the type of the dichlorosilane can be conventional for this field, is preferably comprised dimethyldichlorosilane, first
Base dichlorosilane, dichloromethyl phenylsilane, methylvinyldichlorosilane, diphenyl dichlorosilane and Methylethyl dichloro silicon
One of alkane is a variety of.
In step 3), the dichlorosilane preferably adds as a solution.In dichlorosilane solution, dichlorosilane
Concentration be preferably 3~15mol/L, such as 3mol/L, 4mol/L or 4.5mol/L.In dichlorosilane solution, use
Solvent can be conventional for this field, generally tetrahydrofuran, methyltetrahydrofuran, glycol dimethyl ether, methylene chloride and toluene
One of or it is a variety of.
In step 3), preferably, the alkynes lattice are added in the dichlorosilane by way of dropwise addition when ice-water bath is cooling
In formula reagent.The time for adding of the dichlorosilane can be conventional for this field, preferably 10~60min.
In step 3), the molar ratio of the alkynes monomer and the dichlorosilane can be conventional for this field, preferably (1~
2): 1, such as 1.33,1.5:1 or 2:1.
In step 3), the operation of the polymerization reaction and condition can be conventional for this field, preferably heating reflux reaction 1
~3h, such as heating reflux reaction 1.5h.
Preferably, the reaction solution that step 3) polymerization reaction generates is post-processed.The operation and condition of the post-processing
Can be conventional for this field, generally after removal solvent, be added solvent (such as toluene), with ice-water bath it is cooling after add terminator,
Adding concentration is that 40~60% (such as 50%) aqueous hydrochloric acid solutions react away remaining magnesium powder, is washed out to neutrality, dry,
Filtering, is dried removal solvent again.
Wherein, the washing is usually repeatedly to be washed with deionized water to neutrality.The operation of the removal solvent is generally adopted
With revolving method.The terminator can be terminator commonly used in the art, generally comprise one of water, acetic acid and hydrochloric acid
Or it is a variety of.
In the present invention, preferably, the silicon aryne resin (PSSA) of the sulfur-bearing ether structure is aoxidized, it can must contain sulfoxide
The silicon aryne resin (PSOA) of structure.Wherein, the operation of the oxidation and condition can be conventional for this field, generally in the steps below
It carries out: oxidant being added in the silicon aryne resin solution of sulfur-bearing ether structure and carries out oxidation reaction.Reaction process is as follows:
Wherein, R1And R2H, methyl, phenyl, vinyl or ethyl, n=1~5 independently are, and are integer.
Wherein, in the silicon aryne resin solution of sulfur-bearing ether structure, the organic solvent that uses can routinely can be molten for this field
Solve the silicon aryne resin of the sulfur-bearing ether structure, generally tetrahydrofuran, methyltetrahydrofuran, glycol dimethyl ether, two
One of chloromethanes and toluene are a variety of.In the silicon aryne resin solution of sulfur-bearing ether structure, the silicon aryne tree of sulfur-bearing ether structure
The concentration of rouge can be conventional for this field, preferably 0.2~0.5mol/L, such as 0.33mol/L.
Wherein, the oxidant species can be conventional for this field, preferably metachloroperbenzoic acid or hydrogen peroxide.
Wherein, preferably, the oxidant to be slowly added to the silicon aryne resin of sulfur-bearing ether structure when ice-water bath is cooling
In solution.
Wherein, the molar ratio of the silicon aryne resin of the sulfur-bearing ether structure and the oxidant can be conventional for this field, compared with
Goodly it is 1:(3~6), such as 1:3.
Wherein, the operation of the oxidation reaction and condition can be conventional for this field, generally reaction 12~for 24 hours at room temperature.
Wherein, preferably the reaction solution that oxidation reaction obtains is post-processed.The operation of the post-processing and condition can
It for this field routine, preferably carries out in the steps below: after filtering, washing 3~5 times with saturated sodium carbonate, then using deionized water
It washs to neutrality, anhydrous Na2SO4It dries, filters, removal solvent is dried again.
The present invention also provides a kind of sulfur-bearing silicon aryne resin composite material, raw material is using foregoing sulfur-bearing silicon virtue
Alkynes resin.
In the present invention, the sulfur-bearing silicon aryne resin composite material can pass through the method system of this field conventional composites materials
, such as die pressing.
The present invention also provides a kind of preparation methods of sulfur-bearing silicon aryne resin composite material comprising following step:
1) prepreg is made in the solution impregnating reinforcing fiber containing the sulfur-bearing silicon aryne resin；
2) after the prepreg being removed solvent, molded curing is formed up to the sulfur-bearing silicon aryne resin composite material.
In step 1), in the solution, the concentration of the sulfur-bearing silicon aryne resin can be conventional for this field, and preferably 35
~40wt%.The solvent used in the solution can be this field routine, may generally be tetrahydrofuran, methyltetrahydrofuran, second
One of glycol dimethyl ether, methylene chloride and toluene are a variety of.
In step 1), the reinforcing fiber can be reinforcing fiber of this field conventionally used for preparing composite material, generally
Carbon fiber or quartz fibre.The carbon fiber can be T300 carbon fiber, T700 carbon fiber or T800 carbon fiber.
In step 1), the operation of the dipping and condition can be conventional for this field.
In step 2), generally solvent can be removed after stacking the prepreg to desired height according to actual needs
Operation.
In step 2), the operation of the removal solvent and condition can be conventional for this field, carry out generally in vacuum drying oven.
In step 2), the molding operation of molded curing and condition can be conventional for this field, generally in vulcanizing press
Upper progress.The molding temperature of molded curing is preferably 170~300 DEG C.The molded curing molding time is preferably
For 8~12h.The molding pressure of molded curing is preferably 0.5~3MPa.The molding operation of molded curing is preferably
Include the following steps: under the pressure of 3MPa, 2h, 220 DEG C of heat preservation 2h, 260 DEG C of heat preservation 4h are successively kept the temperature at 180 DEG C can be at
Type.
On the basis of common knowledge of the art, above-mentioned each optimum condition, can any combination to get each preferable reality of the present invention
Example.
The reagents and materials used in the present invention are commercially available.
The positive effect of the present invention is that:
Sulfur-bearing silicon aryne resin of the invention is dark brown solid, stablize under room temperature it is easy to maintain, can be at 170~250 DEG C
Polymerization crosslinking solidification, has excellent mechanical property, thermal stability and thermo-oxidative stability；Decomposition temperature of its solidfied material in nitrogen
498 DEG C of Gao Zheda of degree, the aerial high person of decomposition temperature is up to 497 DEG C, heat resistance and mechanical property with higher.
Sulfur-bearing silicon aryne resin composite material of the invention has preferably heat resistance and mechanical property, bending strength
High, bending modulus height, shear strength are high.In a certain embodiment, carbon fibre reinforced composite bending strength be can reach
404.3MPa, it is expected to be applied to the high-tech areas such as aerospace.
Detailed description of the invention
Fig. 1 be embodiment 1 synthesize PSSA-1 resin hydrogen nuclear magnetic resonance spectrogram (1H-NMR)。
Fig. 2 is the infrared spectrogram (FTIR) for the PSSA-1 resin that embodiment 1 synthesizes.
Fig. 3 is TGA curve graph of the PSSA-1 resin cured matter of the synthesis of embodiment 1 in air and nitrogen.
Specific embodiment
The present invention is further illustrated below by the mode of embodiment, but does not therefore limit the present invention to the reality
It applies among a range.In the following examples, the experimental methods for specific conditions are not specified, according to conventional methods and conditions, or according to quotient
The selection of product specification.
The structure of sulfur-bearing silicon aryne resin synthesized by the present invention with hydrogen nuclear magnetic resonance spectrum (1) and infrared spectroscopy H-NMR
(FTIR) it characterizes；Hydrogen nuclear magnetic resonance spectrum analysis (1H-NMR 500 type high-resolution Fourier of U.S. Bruker company AVANCE) is used
Transform nuclear magnetic resonance spectrometer, working frequency 400MHz, solvent C DCl3, using TMS as internal standard；FTIR spectrum (FT-IR)
Analysis uses 6700 Fourier infrared spectrograph of Nicolet of U.S. NICOLET company, KBr pressed disc method, scanning range 4000-
400cm-1, resolution ratio 0.09cm-1, scanning times 32 times.
The heat resistance of resin cured matter is analyzed with thermogravimetic analysis (TGA) (TGA) method, and thermogravimetic analysis (TGA) (TGA) uses Switzerland
METTLER TOLEDO company's T GA/DSC 1LF type thermal gravimetric analyzer, heating rate are 10 DEG C/min, temperature range 50-
900 DEG C, the flow of nitrogen is 60mL/min.
The bending property of resin composite materials is tested with three-point bending method.Resin composite materials mechanical property uses Shenzhen
Newly think carefully 4204 type microcomputer controlled electronic universal tester of material tests Co., Ltd SANS CMT, every group of test bars 5~10
Root, results are averaged.By the GB/T 1499-2005 test bending strength of fiber cloth reinforced resin composite material flat plate and curved
Bent modulus, experiment loading velocity are 2mm/min, and when experiment is continuously loaded onto sample destruction.Fiber is tested by JC/T 773-1982
The interlaminar shear strength of cloth reinforced resin composite material flat plate, experiment loading velocity are 2mm/min, and when experiment is continuously loaded onto examination
Sample destroys.
Embodiment 1
The synthesis of the siliceous aryne resin PSSA-1 of Sulfide-containing Hindered
1) in a nitrogen atmosphere, in the 500mL four-hole boiling flask equipped with blender, constant pressure funnel, thermometer and condenser pipe
0.300mol magnesium powder and 60mL tetrahydrofuran is added, under ice-water bath through constant pressure funnel be slowly added dropwise 0.240mol bromoethane and
The mixed solution of 20mL tetrahydrofuran, about 10min are added dropwise, and react the 1h time after being added dropwise at 40 DEG C, and grey is made
Ethyl Grignard Reagent；
2) reaction solution is cooled to hereinafter, adding the 4 of 0.120mol, 4 '-diacetylene hexichol by room temperature using ice-water bath
The mixed liquor (in mixed solution, the concentration of alkynes monomer is 0.8mol/L) of thioether and 150mL tetrahydrofuran, 0.5h is added dropwise,
Reaction has gas releasing, back flow reaction 1.5h at 70 DEG C；
3) reaction solution is cooled to room temperature hereinafter, 0.080mol dichloromethyl phenylsilane and 20mL is added by constant pressure funnel
The mixed solution of tetrahydrofuran, time for adding about 10min, back flow reaction 1.5h at 70 DEG C after being added dropwise；Specific reaction process
It is as follows:
1.RBr+Mg→RMgBr
2.
Wherein, G is-S-, R1For methyl, R2For phenyl, n=2.
4) it will obtain 200mL toluene being added into reaction system, reaction solution is cooling after solution steams most of tetrahydrofuran
To room temperature hereinafter, the mixed liquor that 0.240mol glacial acetic acid and 20mL toluene are added dropwise again terminates reaction, then 50mL is added dropwise into flask
(25%) hydrochloric acid solution.Reaction solution is transferred to 1000mL separatory funnel, is washed to deionized water and is separated close to after neutrality
Anhydrous Na is added in upper organic phase out2SO4It dries, filters, vacuum distillation removes solvent, then in 60 DEG C of vacuum ovens
PSSA-1 resin, yield 95% can be obtained in 4h, and resin is dark brown solid, and melting range is 88~94 DEG C.
Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram for the PSSA-1 resin that embodiment 1 synthesizes1H-NMR(CDCl3).As shown in Figure 1,
It is solvent peak at 7.26ppm, the proton peak that the place 3.05ppm is ≡ C-H is Si-CH at 0.48ppm3Proton peak, 6.91~
Multiplet at 7.49ppm is the proton peak on phenyl ring, ≡ C-H and Si-CH3Proton peak relative integral area ratio be 1.0:
3.2, it is close with theoretical value 1.0:3.0.
Fig. 2 is the infrared spectrogram (FTIR) for the PSSA-1 resin that embodiment 1 synthesizes.As shown in Figure 2,3280cm-1Place is
The asymmetric stretching vibration peak of Terminal Acetylenes hydrogen；2962cm-1Place is-CH3Stretching vibration peak；2162cm-1Place is alkynyl-C ≡ C-
Stretching vibration peak；1179cm-1Place is the stretching vibration peak of C-S on aromatic ring.
PSSA-1 made from embodiment 1 is solid through " 170 DEG C/2h+210 DEG C of solidification/2h+250 DEG C of solidification/solidification 4h " condition
After change, the black solidfied material of fine and close light is obtained, powder is ground into and carries out thermogravimetric analysis.Fig. 3 is what embodiment 1 synthesized
TGA curve graph of the products obtained therefrom in air and nitrogen after PSSA-1 solidifies.From the figure 3, it may be seen that in a nitrogen atmosphere, weightlessness 5%
Temperature is 498 DEG C, and 800 DEG C of residual rates are 78.6%；In air atmosphere, weightless 5% temperature is 497 DEG C, and 800 DEG C of residual rates are
18.3%.
PSSA-1 made from embodiment 1 is prepared into casting resin solidfied material, casting resin solidfied material preparation method: first
First by casting matrix mold polish, in die surface even application release agent；Then mold is placed in 160-180 DEG C of vacuum drying oven
Preheat 2h.PSEA-P2-1 resin is poured into mold, after resin melting, about 0.5h is kept under vacuum, to remove air and molten
Agent is then transferred to solidification in high temperature oven until not occurring bubble in 3s.Curing process are as follows: Gu 170 DEG C/2h+210 DEG C of solidification/
Change 2h+250 DEG C/solidification 4h.It is demoulded after solidification, polishing batten to testing standard size.Bending property test sample size:
80×15×4mm3.The bending property of PSSA-1 casting resin solidfied material is tested with three point bending test method, as a result table
It is bright, bending strength 34.8MPa, bending modulus 2.3GPa.
Embodiment 2
The synthesis of the siliceous aryne resin PSSA-2 of Sulfide-containing Hindered
1) in a nitrogen atmosphere, in the 500mL four-hole boiling flask equipped with blender, constant pressure funnel, thermometer and condenser pipe
0.300mol magnesium powder and 60mL tetrahydrofuran is added, under ice-water bath through constant pressure funnel be slowly added dropwise 0.240mol bromoethane and
The mixed solution of 20mL tetrahydrofuran, about 10min are added dropwise, and react the 1h time after being added dropwise at 40 DEG C, and grey is made
Ethyl Grignard Reagent；
2) reaction solution is cooled to hereinafter, adding the 4 of 0.120mol, 4 '-diacetylene hexichol by room temperature using ice-water bath
The mixed liquor (in mixed solution, the concentration of alkynes monomer is 0.8mol/L) of thioether and 150mL tetrahydrofuran, 0.5h is added dropwise,
Reaction has gas releasing, back flow reaction 1.5h at 70 DEG C；
3) reaction solution is cooled to room temperature hereinafter, 0.060mol dichloromethyl phenylsilane and 20mL is added by constant pressure funnel
The mixed solution of tetrahydrofuran, time for adding about 10min, back flow reaction 1.5h at 70 DEG C after being added dropwise；The present embodiment it is anti-
Process such as embodiment is answered, product structure formula is same as Example 1, repetitive unit n=1.
4) it will obtain 200mL toluene being added into reaction system, reaction solution is cooling after solution steams most of tetrahydrofuran
To room temperature hereinafter, the mixed liquor that 0.240mol glacial acetic acid and 20mL toluene are added dropwise again terminates reaction, then 50mL is added dropwise into flask
(25%) hydrochloric acid solution.Reaction solution is transferred to 1000mL separatory funnel, is washed to deionized water and is separated close to after neutrality
Anhydrous Na is added in upper organic phase out2SO4It dries, filters, vacuum distillation removes solvent, then in 60 DEG C of vacuum ovens
PSSA-2 resin, yield 95% can be obtained in 4h, and resin is dark brown solid, and melting range is 72~85 DEG C.
PSSA-2 resin1H-NMR(CDCl3) analysis: it is solvent peak, the matter for being ≡ C-H at 3.02ppm at 7.26ppm
Sub- peak is Si-CH at 0.47ppm3Proton peak, the multiplet at 6.90~7.52ppm is the proton peak on phenyl ring, ≡ C-H
With Si-CH3Proton peak relative integral area ratio be 1.0:2.1, it is close with theoretical value 1.0:2.0.
The FTIR of PSSA-2 resin is analyzed: 3279cm-1Place is the asymmetric stretching vibration peak of Terminal Acetylenes hydrogen；3012cm-1Place
It is-CH3Stretching vibration peak；2202cm-1Place is the stretching vibration peak of alkynyl-C ≡ C-；1180cm-1Place is that C-S stretches on aromatic ring
Contracting vibration peak.
PSSA-2 made from embodiment 2 is solid through " 170 DEG C/2h+210 DEG C of solidification/2h+250 DEG C of solidification/solidification 4h " condition
After change, the black solidfied material of fine and close light is obtained, powder is ground into and carries out thermogravimetric analysis.Thermal weight loss point is carried out to solidfied material
Analysis, in a nitrogen atmosphere, weightless 5% temperature are 467 DEG C, and 800 DEG C of residual rates are 74.5%；In air atmosphere, 5% temperature of weightlessness
Degree is 460 DEG C, and 800 DEG C of residual rates are 16.7%.
2 products obtained therefrom of embodiment is prepared into casting resin solidfied material according to condition disclosed in embodiment 1.Casting resin
The bending property of solidfied material is tested with three point bending test method, the results showed that, bending strength 26.1MPa, bending die
Amount is 2.6GPa.
Embodiment 3
The synthesis of the siliceous aryne resin PSSA-3 of Sulfide-containing Hindered
1) in a nitrogen atmosphere, in the 500mL four-hole boiling flask equipped with blender, constant pressure funnel, thermometer and condenser pipe
0.300mol magnesium powder and 60mL tetrahydrofuran is added, under ice-water bath through constant pressure funnel be slowly added dropwise 0.240mol bromoethane and
The mixed solution of 20mL tetrahydrofuran, about 10min are added dropwise, and react the 1h time after being added dropwise at 40 DEG C, and grey is made
Ethyl Grignard Reagent；
2) reaction solution is cooled to hereinafter, adding the 4 of 0.120mol, 4 '-diacetylene hexichol by room temperature using ice-water bath
The mixed liquor (in mixed solution, the concentration of alkynes monomer is 0.8mol/L) of thioether and 150mL tetrahydrofuran, 0.5h is added dropwise,
Reaction has gas releasing, back flow reaction 1.5h at 70 DEG C；
3) reaction solution is cooled to room temperature hereinafter, 0.090mol dimethyldichlorosilane and 20mL tetra- is added by constant pressure funnel
The mixed solution of hydrogen furans, time for adding about 10min, back flow reaction 1.5h at 70 DEG C after being added dropwise；
4) it will obtain 200mL toluene being added into reaction system, reaction solution is cooling after solution steams most of tetrahydrofuran
To room temperature hereinafter, the mixed liquor that 0.240mol glacial acetic acid and 20mL toluene are added dropwise again terminates reaction, then 50mL is added dropwise into flask
(25%) hydrochloric acid solution.Reaction solution is transferred to 1000mL separatory funnel, is washed to deionized water and is separated close to after neutrality
Anhydrous Na is added in upper organic phase out2SO4It dries, filters, vacuum distillation removes solvent, then in 60 DEG C of vacuum ovens
4h, can be obtained PSSA-3 resin, yield 95%, and resin is orange/yellow solid.Product structure formula is as follows:
Wherein, G is-S-, R1For methyl, R2For first
Base, n=2.
PSSA-3 resin1H-NMR(CDCl3) analysis: it is solvent peak, the matter for being ≡ C-H at 3.12ppm at 7.26ppm
Sub- peak is Si-CH at 0.47ppm3Proton peak, the multiplet at 7.25~7.43ppm is the proton peak on phenyl ring, ≡ C-H
With Si-CH3Proton peak relative integral area ratio be 1.0:3.1, it is close with theoretical value 1.0:3.0.
The FTIR of PSSA-3 resin is analyzed: 3280cm-1Place is the asymmetric stretching vibration peak of Terminal Acetylenes hydrogen；3010cm-1Place
It is-CH3Stretching vibration peak；2201cm-1Place is the stretching vibration peak of alkynyl-C ≡ C-；1180cm-1Place is that C-S stretches on aromatic ring
Contracting vibration peak.
For PSSA-3 resin after the solidification of 170 DEG C/2h+210 DEG C/2h+250 DEG C/4h condition, the black for obtaining fine and close light is solid
Compound,
PSSA-3 made from embodiment 3 is solid through " 170 DEG C/2h+210 DEG C of solidification/2h+250 DEG C of solidification/solidification 4h " condition
After change, the black solidfied material of fine and close light is obtained, powder is ground into and carries out thermogravimetric analysis.Thermal weight loss point is carried out to solidfied material
Analysis, in a nitrogen atmosphere, weightless 5% temperature are 419 DEG C, and 800 DEG C of residual rates are 68.7%.
Embodiment 4
The synthesis of the siliceous aryne resin PSSA-4 of Sulfide-containing Hindered
1) in a nitrogen atmosphere, in the 500mL four-hole boiling flask equipped with blender, constant pressure funnel, thermometer and condenser pipe
0.300mol magnesium powder and 60mL methyltetrahydrofuran is added, 0.240mol bromoethane is slowly added dropwise through constant pressure funnel under ice-water bath
With the mixed solution of 20mL methyltetrahydrofuran, about 10min is added dropwise, and is reacted at 40 DEG C after being added dropwise the 1h time, system
Obtain the ethyl Grignard Reagent of grey；
2) reaction solution is cooled to hereinafter, adding the 4 of 0.120mol, 4 '-diacetylene hexichol by room temperature using ice-water bath
The mixed liquor (in mixed solution, the concentration of alkynes monomer is 0.8mol/L) of thioether and 150mL methyltetrahydrofuran, 0.5h is dripped
Finish, reaction has gas releasing, back flow reaction 1.5h at 70 DEG C；
3) reaction solution is cooled to room temperature hereinafter, 0.090mol methyl (hydrogen) dichlorosilane and 20mL is added by constant pressure funnel
The mixed solution of methyltetrahydrofuran, time for adding about 10min, back flow reaction 1.5h at 70 DEG C after being added dropwise；
4) it will obtain that 200mL toluene, reaction solution are added into reaction system after solution steams most of methyltetrahydrofuran
It is cooled to room temperature hereinafter, the mixed liquor that 0.240mol glacial acetic acid and 20mL toluene are added dropwise again terminates reaction, then is added dropwise into flask
The hydrochloric acid solution of 50mL (25%).Reaction solution is transferred to 1000mL separatory funnel, is washed to deionized water close to after neutrality
Upper organic phase is isolated, anhydrous Na is added2SO4It dries, filters, vacuum distillation removes solvent, then does in 60 DEG C of vacuum drying ovens
Dry 4h, can be obtained PSSA-4 resin, yield 95%, and resin is yellow solid.Product structure formula is as follows:
Wherein, G is-S-, R1For methyl, R2For H,
N=2.
PSSA-4 resin1H-NMR(CDCl3) analysis: it is solvent peak, the matter for being ≡ C-H at 3.12ppm at 7.26ppm
Sub- peak is Si-CH at 0.53ppm3Proton peak, be the proton peak of Si-H at 4.62ppm, it is multiple at 7.24~7.43ppm
Peak is the proton peak on phenyl ring, ≡ C-H and Si-CH3Proton peak relative integral area ratio be 1.0:3.3, and theoretical value 1.0:
3.0 close.
The FTIR of PSSA-4 resin is analyzed: 3282cm-1Place is the asymmetric stretching vibration peak of Terminal Acetylenes hydrogen；3020cm-1Place
It is-CH3Stretching vibration peak；2221cm-1Place is the stretching vibration peak of alkynyl-C ≡ C-；1180cm-1Place is C-S on aromatic ring
Stretching vibration peak.
For PSSA-4 resin after the solidification of 170 DEG C/2h+210 DEG C/2h+250 DEG C/4h condition, the black for obtaining fine and close light is solid
Compound,
PSSA-4 made from embodiment 4 is solid through " 170 DEG C/2h+210 DEG C of solidification/2h+250 DEG C of solidification/solidification 4h " condition
After change, the black solidfied material of fine and close light is obtained, powder is ground into and carries out thermogravimetric analysis.Thermal weight loss point is carried out to solidfied material
Analysis, in a nitrogen atmosphere, weightless 5% temperature are 528 DEG C, and 800 DEG C of residual rates are 82.3%.
Embodiment 5
The synthesis of siliceous aryne resin PSOA containing sulfoxide
Equipped with blender, thermometer and condenser pipe 500mL four-hole boiling flask in be added 0.10mol PSSA-1 resin and
300mL methylene chloride is slowly added to 0.30mol metachloroperbenzoic acid (m-CPBA) under ice-water bath, then anti-at room temperature
After answering 12h, obtained solution is transferred in 500mL separatory funnel, after unsaturated carbonate potassium solution repeatedly washs, then spend from
Anhydrous Na is added to neutrality in sub- water washing2SO4It dries, filters, vacuum distillation removes solvent, then in 60 DEG C of vacuum ovens
PSOA resin, yield 85% can be obtained in 4h, and resin is yellow solid, and melting range is 113 DEG C~116 DEG C.Product structure formula is as follows
It is shown:
Wherein, G isR1For methyl, R2
For phenyl, n=2.
PSOA resin1H-NMR(CDCl3) analysis: it is solvent peak, the proton for being ≡ C-H at 3.17ppm at 7.26ppm
Peak is Si-CH at 0.69ppm3Proton peak, the multiplet at 7.44~7.87ppm is the proton peak on phenyl ring, ≡ C-H with
Si-CH3Proton peak relative integral area ratio be 1.0:3.2, it is close with theoretical value 1.0:3.0.
The FTIR of PSOA resin is analyzed: 3283cm-1Place is the asymmetric stretching vibration peak of Terminal Acetylenes hydrogen；3051cm-1Place is-
CH3Stretching vibration peak；2159cm-1Place is the stretching vibration peak of alkynyl-C ≡ C-；1050cm-1Place is the stretching vibration of sulfoxide
Peak.
By PSOA made from embodiment 5 through " 170 DEG C/2h+210 DEG C of solidification/2h+250 DEG C of solidification/solidification 4h " condition solidification
Afterwards, the black solidfied material for obtaining fine and close light is ground into powder and carries out thermogravimetric analysis.Thermogravimetic analysis (TGA) is carried out to solidfied material,
In a nitrogen atmosphere, weightless 5% temperature is 449 DEG C, and 800 DEG C of residual rates are 75.6%；In air atmosphere, weightless 5% temperature
It is 431 DEG C, 800 DEG C of residual rates are 14.6%.
5 products obtained therefrom of embodiment is prepared into casting resin solidfied material according to condition disclosed in embodiment 1.Casting resin
Solidfied material is tested with three point bending test method, the results showed that, bending strength 36.2MPa, bending modulus 2.7GPa.
Embodiment 6
The synthesis of siliceous aryne resin PSFA containing sulfone
1) in a nitrogen atmosphere, in the 500mL four-hole boiling flask equipped with blender, constant pressure funnel, thermometer and condenser pipe
0.300mol magnesium powder and 60mL tetrahydrofuran is added, under ice-water bath through constant pressure funnel be slowly added dropwise 0.240mol bromoethane and
The mixed solution of 20mL tetrahydrofuran, about 10min are added dropwise, and react the 1h time after being added dropwise at 40 DEG C, and grey is made
Ethyl Grignard Reagent；
2) reaction solution is cooled to hereinafter, adding the 4 of 0.120mol, 4 '-diacetylene hexichol by room temperature using ice-water bath
The mixed liquor (in mixed solution, the concentration of alkynes monomer is 0.8mol/L) of sulfone and 150mL tetrahydrofuran, 0.5h is added dropwise, instead
Gas releasing, back flow reaction 1.5h at 70 DEG C should be had；
3) reaction solution is cooled to room temperature hereinafter, 0.080mol dichloromethyl phenylsilane and 20mL is added by constant pressure funnel
The mixed solution of tetrahydrofuran, time for adding about 10min, back flow reaction 1.5h at 70 DEG C after being added dropwise；
4) it will obtain 200mL toluene being added into reaction system, reaction solution is cooling after solution steams most of tetrahydrofuran
To room temperature hereinafter, the mixed liquor that 0.240mol glacial acetic acid and 20mL toluene are added dropwise again terminates reaction, then 50mL is added dropwise into flask
(25%) hydrochloric acid solution.Reaction solution is transferred to 1000mL separatory funnel, is washed to deionized water and is separated close to after neutrality
Anhydrous Na is added in upper organic phase out2SO4It dries, filters, vacuum distillation removes solvent, then in 60 DEG C of vacuum ovens
PSFA resin, yield 95% can be obtained in 4h, and resin is dark brown solid, and melting range is 120 DEG C~130 DEG C.Product structure formula is such as
Shown in lower:
Wherein, G isR1For methyl, R2
For phenyl, n=2.
PSFA resin1H-NMR(CDCl3) analysis: it is solvent peak, the proton for being ≡ C-H at 3.25ppm at 7.26ppm
Peak is Si-CH at 0.71ppm3Proton peak, the multiplet at 7.43~8.06ppm is the proton peak on phenyl ring, ≡ C-H with
Si-CH3Proton peak relative integral area ratio be 1.0:3.3, it is close with theoretical value 1.0:3.0.
The FTIR of PSFA resin is analyzed: 3278cm-1Place is the asymmetric stretching vibration peak of Terminal Acetylenes hydrogen；3066cm-1Place is-
CH3Stretching vibration peak；2161cm-1Place is the stretching vibration peak of alkynyl-C ≡ C-；1300cm-1Place is the stretching vibration peak of sulfone.
By 6 products obtained therefrom of embodiment through " 170 DEG C/2h+210 DEG C of solidification/2h+250 DEG C of solidification/solidification 4h " condition solidification
Afterwards, the black solidfied material for obtaining fine and close light is ground into powder and carries out thermogravimetric analysis.Thermogravimetic analysis (TGA) is carried out to solidfied material,
In a nitrogen atmosphere, weightless 5% temperature is 376 DEG C, and 800 DEG C of residual rates are 65.0%；In air atmosphere, weightless 5% temperature
It is 380 DEG C, 800 DEG C of residual rates are 12.6%.
6 products obtained therefrom of embodiment is prepared into casting resin solidfied material according to condition disclosed in embodiment 1.Casting resin
The bending property of solidfied material is tested with three point bending test method, the results showed that, bending strength 40.5MPa, bending die
Amount is 2.8GPa.
Embodiment 7
The preparation of sulfur-bearing silicon aryne resin composite material
Respectively by three kinds of sulfur-bearing silicon aryne resins (the product PSSA-1 of embodiment 1, the product PSOA of embodiment 5 and implementation
The product PSFA of example 6) it is dissolved in the solution for being made into that concentration is 35wt% in tetrahydrofuran solvent, it is cut out with resin solution to impregnate
Size be 15 × 10cm2T300 carbon fiber, take 12 layers of impregnated carbon cloth fitly to stack, and vacuum dry
Organic solvent is removed in case；Prepreg is placed on vulcanizing press, under the pressure of 3MPa, successively through 170 DEG C/solidification 2h
+ 210 DEG C of/solidifying 2h+250 DEG C/temperature programs for solidifying 4h, are prepared sulfur-bearing silicon aryne resin composite panel, having a size of
15cm×10cm×2cm。
The mechanical property that 1,5,6 gained resin of embodiment is prepared into resin composite materials is tested with three-point bending method, tool
Body test result is shown in Table 1.The result shows that sulfur-bearing silicon aryne resin composite material has preferable mechanical property, it may be desirable to be used for
The high-technology fields such as aerospace.
The mechanical property of table 1T300/ sulfur-bearing silicon aryne resin composite material
Remarks: the reinforcing fiber that T300 refers to is T300 carbon fiber.Bending strength and complete modulus test require batten ruler
Very little is 45 × 15 × 2mm3, interlayer shear test request batten is having a size of 20 × 6 × 2mm3.The preparation of 2~4 gained resin of embodiment
The mechanical property for obtaining resin composite materials is suitable with the mechanical property of T300/PSSA-1 in table 1.
Table 2 for Examples 1 to 6 product Mn, Mw and polydispersity index.In GPC test, made using polystyrene
For internal standard.Relative molecular weight (GPC) test equipment: 1515 type gel permeation chromatograph of Waters, US Waters；Test
Condition and method: make extracting solution, flow velocity 1mL/min with tetrahydrofuran.
Table 2
Claims (10)
1. a kind of sulfur-bearing silicon aryne resin, which is characterized in that its structural formula is as follows:
Wherein, any one of G in following radicals :-S-,Or
R1And R2It independently is H, methyl, phenyl, vinyl or ethyl；
N=1~5, and be integer.
2. sulfur-bearing silicon aryne resin as described in claim 1, which is characterized in that the n is 1~3, such as 1,2 or 3；
Or, it is 2000~3000 that the number-average molecular weight of the sulfur-bearing silicon aryne resin, which is Mn, preferably 2000~2500, such as
2367,2011,2297,2264,2498 or 2602；
Or, it is 2500~4500 that the weight average molecular weight of the sulfur-bearing silicon aryne resin, which is Mw, preferably 2500~4100, such as
3896,2956,3834,3808,3996 or 4059；
Or, the polydispersity index of the sulfur-bearing silicon aryne resin be 1~1.7, preferably 1.2~1.7, for example, 1.65,1.47,
1.67,1.68,1.60 or 1.56.
3. sulfur-bearing silicon aryne resin as described in claim 1, which is characterized in that G is-S-, R1For methyl, R2For phenyl, preferably
Ground G is-S-, R1For methyl, R2For phenyl, Mn=2367, polydispersity index 1.65；
Or, G is-S-, R1For methyl, R2For phenyl, preferably G is-S-, R1For methyl, R2For phenyl, Mn=2011, polydispersion
Index is 1.47；
Or, G is-S-, R1For methyl, R2For methyl, preferably G is-S-, R1For methyl, R2For methyl, Mn=2297, polydispersion
Index is 1.67；
Or, G is-S-, R1For methyl, R2For H, preferably G is-S-, R1For methyl, R2For H, Mn=2264, polydispersity index is
1.68；
Or, G isR1For methyl, R2For phenyl, preferably G isR1For methyl, R2For phenyl, Mn=
2498, polydispersity index 1.60；
Or, G isR1For methyl, R2For phenyl, preferably G isR1For methyl, R2For phenyl, Mn=
2602, polydispersity index 1.56.
4. a kind of preparation method of sulfur-bearing silicon aryne resin, which is characterized in that it includes the following steps:
1) halogenated hydrocarbons is added in the mixture of magnesium powder and organic solvent under an inert atmosphere, reaction generates alkyl grignard reagent；
2) alkynes monomer is added in the alkyl grignard reagent and carries out reaction generation alkynes grignard reagent；Wherein, the alkynes monomer is
Diacetylene diphenyl sulfide or diacetylene diphenyl sulphone (DPS)；
3) dichlorosilane is added in the alkynes grignard reagent and carries out polymerization reaction up to sulfur-bearing silicon aryne resin, structural formula is such as
Shown in lower:
Wherein, G be selected from-S- orR1And R2It independently is H, methyl, phenyl, vinyl or ethyl, n=1~5,
It and is integer.
5. the preparation method of sulfur-bearing silicon aryne resin as claimed in claim 4, which is characterized in that the R1、R2Independently with n
As described in Claims 2 or 3；
And/or in step 1), the inert atmosphere is nitrogen atmosphere；
And/or in step 1), the halogenated hydrocarbons is bromoethane；
And/or in step 1), the halogenated hydrocarbons adds as a solution；In halohydrocarbon solution, the concentration of halogenated hydrocarbons is preferable
Ground is 10~15mol/L, such as 12mol/L；In halohydrocarbon solution, the preferred solvents that use for tetrahydrofuran and/or first
Benzene；
And/or in step 1), the time for adding of the halogenated hydrocarbons is 10~60min；
And/or in step 1), the molar ratio of the halogenated hydrocarbons and the magnesium powder is 1:(1.25~1.5)；
And/or in step 1), the organic solvent includes tetrahydrofuran, methyltetrahydrofuran, glycol dimethyl ether, dichloromethane
One of alkane and toluene are a variety of；
And/or in step 1), the temperature of the reaction is 35~45 DEG C, such as 40 DEG C；
And/or in step 1), the time of the reaction is 1~3h.
6. the preparation method of sulfur-bearing silicon aryne resin as claimed in claim 4, which is characterized in that in step 2), the alkynes list
The molar ratio of body and alkyl halide is 1:2；
And/or in step 2), the alkynes monomer adds as a solution；In alkynes monomer solution, the concentration of alkynes monomer is preferable
Ground is 0.25~0.85mol/L, such as 0.8mol/L；In alkynes monomer solution, the preferred solvents that use for tetrahydrofuran, first
One of base tetrahydrofuran, glycol dimethyl ether, methylene chloride and toluene are a variety of；
And/or in step 2), when ice-water bath is cooling, the alkyl format examination is added in the alkynes monomer by way of dropwise addition
In agent；The time for adding of the alkynes monomer is preferably 0.5~2h；
And/or in step 2), the reaction is 1~3h of heating reflux reaction, such as is heated to reflux 1.5h；
And/or in step 3), the dichlorosilane includes dimethyldichlorosilane, dimethyl dichlorosilane (DMCS), aminomethyl phenyl dichloro
One of silane, methylvinyldichlorosilane, diphenyl dichlorosilane and Methylethyl dichlorosilane are a variety of；
And/or in step 3), the dichlorosilane adds as a solution；In dichlorosilane solution, dichlorosilane it is dense
Degree is preferably 3~15mol/L, such as 3mol/L, 4mol/L or 4.5mol/L；In dichlorosilane solution, use it is molten
Agent is preferably one of tetrahydrofuran, methyltetrahydrofuran, glycol dimethyl ether, methylene chloride and toluene or a variety of；
And/or in step 3), when ice-water bath is cooling, the alkynes format examination is added in the dichlorosilane by way of dropwise addition
In agent；The time for adding of the dichlorosilane is preferably 10~60min；
And/or in step 3), the molar ratio of alkynes monomer and the dichlorosilane is (1~2): 1, such as 1.33,1.5:1 or
2:1；
And/or in step 3), the polymerization reaction is 1~3h of heating reflux reaction, such as heating reflux reaction 1.5h.
7. the preparation method of sulfur-bearing silicon aryne resin as claimed in claim 4, which is characterized in that, will be described when G is-S-
Sulfur-bearing silicon aryne resin is aoxidized, and the silicon aryne resin of sulfoxide structure can must be contained；The operation of the oxidation is preferably comprised down
It states step: oxidant being added in sulfur-bearing silicon aryne resin solution and carries out oxidation reaction；
It include the preferred solvents of use tetrahydrofuran, methyltetrahydrofuran, ethylene glycol in the sulfur-bearing silicon aryne resin solution
One of dimethyl ether, methylene chloride and toluene are a variety of；
In the sulfur-bearing silicon aryne resin solution, the concentration of sulfur-bearing silicon aryne resin is preferably 0.2~0.5mol/L, such as
0.33mol/L；
The oxidant is preferably comprised metachloroperbenzoic acid or hydrogen peroxide；
Preferably, the oxidant is slowly added in sulfur-bearing silicon aryne resin solution when ice-water bath is cooling；
The molar ratio of sulfur-bearing silicon aryne resin and the oxidant is preferably 1:(3~6)；
The operation of the oxidation reaction preferably at room temperature reaction 12~for 24 hours.
8. a kind of sulfur-bearing silicon aryne resin composite material, raw material is using sulfur-bearing silicon virtue as claimed in any one of claims 1 to 3
Alkynes resin.
9. a kind of preparation method of the sulfur-bearing silicon aryne resin composite material as described in any one of claims 1 to 3, feature exist
In comprising following step:
1) prepreg is made in the solution impregnating reinforcing fiber containing the sulfur-bearing silicon aryne resin；
2) after the prepreg being removed solvent, molded curing is formed up to the sulfur-bearing silicon aryne resin composite material.
10. the preparation method of sulfur-bearing silicon aryne resin composite material as claimed in claim 9, which is characterized in that in step 1),
In the solution, the concentration of sulfur-bearing silicon aryne resin is 35~40wt%；
And/or in step 1), the solvent used in the solution includes tetrahydrofuran, methyltetrahydrofuran, glycol dinitrate
One of ether, methylene chloride and toluene are a variety of；
And/or in step 1), the reinforcing fiber is carbon fiber or quartz fibre；The carbon fiber is preferably comprised T300
Carbon fiber, T700 carbon fiber or T800 carbon fiber；
And/or in step 2), the molding temperature of molded curing is 170~300 DEG C；
And/or in step 2), the molded curing molding time is 8~12h；
And/or in step 2), the molding pressure of molded curing is 0.5~3MPa；
Preferably, the molding operation of molded curing includes the following steps: under the pressure of 3MPa, successively protected at 180 DEG C
Warm 2h, 220 DEG C of heat preservation 2h, 260 DEG C of heat preservation 4h, that is, plastic.
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| CN110922599A (en) * | 2019-12-12 | 2020-03-27 | 哈尔滨工业大学 | Bisphenol S hybrid silicon resin and synthetic method thereof |
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