CN108624058A - A method of improving methyl vinyl silicone rubber mechanical property - Google Patents
A method of improving methyl vinyl silicone rubber mechanical property Download PDFInfo
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- CN108624058A CN108624058A CN201710182653.XA CN201710182653A CN108624058A CN 108624058 A CN108624058 A CN 108624058A CN 201710182653 A CN201710182653 A CN 201710182653A CN 108624058 A CN108624058 A CN 108624058A
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Abstract
The invention discloses a kind of methods improving methyl vinyl silicone rubber mechanical property, the raw-silastic continuously of 100 mass parts are added in ethyl acetate first, heating water bath simultaneously continues stirring to obtain raw rubber solution；Then the silicon-carbon composite nano tube for weighing 1~3 mass parts is placed in ethyl acetate solution, obtains uniform dispersion liquid；Then mixed liquor is added in raw rubber solution obtained, stirs evenly and is evaporated while stirring, SNTs@CNTs/ raw-silastic continuouslies are obtained after vacuum drying；Then 100 mass parts SNTs@CNTs/ raw-silastic continuouslies are made into its uniform roll banding in the double roller of 40~44 DEG C of temperature；Then 2,5 dimethyl, 2,5 di-t-butyl hexane peroxide of 0.1~0.5 mass parts is added, continues to be kneaded uniformly acquisition rubber compound；Rubber compound is finally fitted into 9~10min of hot pressing sulfidization moldings in mold, sulfide film is obtained after cooling.SNTs coats the tensile strength and elongation at break that silicon rubber is greatly improved in CNTs in the present invention, improves the mechanical property of silicon rubber.
Description
Technical field
The invention belongs to field of rubber materials, more particularly, are related to a kind of raising methyl vinyl silicone rubber power
The method for learning performance.
Background technology
Silicon rubber (SR) raw rubber, i.e. linear polysiloxane are with Si-O alternately for main chain, and side group is the line style of organic group
Half inorganic polymer can become rubber-like elastic body by crosslinking.SR has many excellent performances, such as Inverter fed motor, resistance to height
Low temperature, ultra-violet radiation resisting etc. are a kind of novel insulating materials, wherein high-temperature silicon disulfide rubber, in chilling shrink type cable accessory
In existing application.But so that silicon rubber is used widely in insulation applications, material should also have excellent mechanical property.
With the fast development of nanosecond science and technology, silicon rubber is modified using nano material, has made the multinomial property of silicon rubber
Breakthrough can be obtained.Carbon nanotube (Carbon nanotubes, CNTs) has big specific surface area, and with high-strength
Degree and high-modulus.Improve Mechanical Properties of Silicone Rubber by supporting material of carbon nanotube, there is certain feasibility.
Invention content
The technical purpose of the present invention is to overcome the deficiencies of the prior art and provide a kind of raising methyl vinyl silicone rubber power
The method for learning performance.Mechanical property before and after thermo-oxidative ageing in order to improve SR, the present invention is first by nano-tube (silica
Nanotubes, abbreviation SNTs) surfaces CNTs are coated to, it is then that it is compound with SR progress, improve power before and after the thermo-oxidative ageing of SR
Learn performance.
The technical purpose of the present invention is achieved by following technical proposals：
A method of methyl vinyl silicone rubber mechanical property being improved, steps are as follows：
Step 1, the raw-silastic continuously of 100 mass parts is added in ethyl acetate, 60~64 DEG C of heating water baths simultaneously continue
Stirring to obtain raw rubber solution；
Step 2, the silicon-carbon composite nano tube (SNTs@CNTs) for weighing 1~3 mass parts is placed in ethyl acetate solution, is surpassed
Sonication obtains uniform dispersion liquid；Then mixed liquor is added in raw rubber solution made from step 1, is stirred evenly and 90
It is evaporated while stirring at~92 DEG C, SNTs CNTs/ raw-silastic continuouslies is obtained after vacuum drying；
Step 3, by SNTs@CNTs/ raw-silastic continuouslies made from 100 mass parts steps 3 40~44 DEG C of temperature double roller
On, it is kneaded 6~10min, makes its uniform roll banding；Then 2,5- dimethyl -2,5- di-t-butyls of 0.1~0.5 mass parts are added
Butylperoxyhexane continues 13~15min of mixing, is kneaded and uniformly obtains rubber compound；
Step 4, rubber compound prepared by step 3 is fitted into mold, in 180 ± 1 DEG C of temperature, the condition of 5~8MPa of pressure
Lower hot pressing 9~10min sulfidization moldings obtain sulfide film after cooling；
Silica is arranged on the outer wall of carbon nanotube using carbon nanotube as inner tube in the silicon-carbon composite nano tube
Layer, the silicon dioxide layer form Silica Nanotube on the outside of carbon nanotube；In the structure of silicon-carbon composite nano tube,
Carbon nanotube and Silica Nanotube form coaxial sleeve structure, and inner tube is carbon nanotube, and outer tube is silica nanometer
Pipe；
The preparation method of the silicon-carbon composite nano tube is, simultaneously by the evenly dispersed formation suspension of carboxylic carbon nano-tube
It is alkalinity to adjust pH value, then ethyl orthosilicate is added in the suspension of carboxylic carbon nano-tube, be sufficiently mixed and is uniformly divided
It dissipates；Solid matter is detached, 550~650 DEG C is heated to from room temperature in an inert atmosphere and is heat-treated, then naturally cool to room
Temperature.
In the step 1, the raw-silastic continuously is methyl vinyl silicone rubber.
In the step 2, carboxylic carbon nano-tube is dispersed in absolute ethyl alcohol and forms suspension, uses ammonium hydroxide
It is 8~10 to adjust pH value, specifically, weighs carboxylic carbon nano-tube (CNTs-COOH) and is put into beaker, anhydrous second is added
Alcohol, stirring keep CNTs dispersions abundant.Dispersion liquid is put into ultrasonic cell disrupte machine, ice-bath ultrasonic process 1h, power 500W, work
It is 3s, intermittent time 2s to make the time, weighs ammonium hydroxide, is added rapidly to adjust pH value in suspension obtained above to be alkalinity 8
~10, strong stirring 0.5h obtain the suspension of carboxylic carbon nano-tube.
In the step 2, ethyl orthosilicate (TEOS) is dispersed in absolute ethyl alcohol, is forming stable homogeneous just
Ethyl silicate solution, then teos solution is added in the suspension of carboxylic carbon nano-tube, specifically, weigh just
Silester (TEOS), is put into the absolute ethyl alcohol of 300ml, and stirring fully obtains the solution of stable homogeneous.Solution is quickly added
Enter in suspension, strong stirring 2h obtains mixed liquor, this mixed liquor is put into ultrasonic cell disrupte machine again, ice-bath ultrasonic process
30min (power 500W, working time 3s, intermittent time 2s) takes out after the completion of processing, and sealing and standing is for 24 hours.
In the step 2, inert atmosphere is nitrogen, helium or argon gas；From 20~25 DEG C of room temperature with 5~10 DEG C/min
Speed is warming up to 550~650 DEG C and is heat-treated at least 2 hours, and preferably 600~650 DEG C are heat-treated 2~5 hours, specific next
It says, is filtered after standing, filter product and be placed in vacuum drying oven, dried at 60~80 DEG C, after dry, with mortar by solid
Sample grinds to obtain powder, and powder is placed in Muffle furnace and is heat-treated.
It is as shown in Fig. 1, bonded using carboxyl and the ethyl orthosilicate realization of carbon nano tube surface in the step 2,
It heats up and is heat-treated again, so that ethyl orthosilicate is in carbon nano tube surface in-situ preparation silica.Pass through carbon nanotube table
The carboxyl-content in face, the dosage of ethyl orthosilicate adjust the appearance structure of silicon-carbon composite nano tube, i.e., to silicone tube thickness, silicone tube
Continuity degree etc. is regulated and controled；If carboxylic carbon nano-tube usage amount is 1 parts by weight (i.e. each parts by weight are 1g), positive silicic acid second
Ester usage amount is respectively 2.5 parts by weight, 5 parts by weight and 7.5 parts by weight, and silicone tube thickness is 5~15nm；And in carbon nanotube outer wall
Form the preferable silicone tube of continuity degree (sectional silicone tube, the content because of carbon nano tube surface carboxyl and distribution).
In the step 2, vacuum drying condition is that 46~48h is dried in vacuo at 58~60 DEG C.
In the step 3,0.2~0.3 parts by weight 2,5- dimethyl -2,5- di-t-butyl hexane peroxides are preferably taken.
In the step 4, die size is 140 × 140 × 2mm3, preferably in 180 ± 1 DEG C of temperature, pressure 7MPa
Under the conditions of hot pressing 9min sulfidization moldings.
Beneficial effects of the present invention：
For SR systems, CNTs is modified using common carbon chain molecules, after modification with the molecule knot of silicone rubber matrix
Structure still gap is larger, and the purpose for improving CNTs and matrix compatibility is not achieved.Further, since the caliber of CNTs is small, surface energy
Greatly, since the effect of Van der Waals force is also easy to produce reunion between Guan Yuguan, this will make the load transference of manufactured composite material
It reduces, is unfavorable for the performance of its excellent properties.And after SNTs claddings CNTs, the interaction force between CNTs pipes is isolated, substantially
Degree improves the dispersibility of CNTs.In order to improve the dispersibilities of CNTs in the polymer, cladding is carried out to CNTs using SNTs and is repaiied
Decorations.In addition, using solution blended process, to promote dispersibility of the nano-tube enveloped carbon nanometer tube nano-particle in silicon rubber.
The modified silicon rubber prepared using the present invention, compared to blank sample, the tensile strength and extension at break of CNTs/SR composite materials
Rate is promoted, and therefore, the tensile strength and elongation at break of silicon rubber is greatly improved in SNTs claddings CNTs, improves
The mechanical property of silicon rubber.
Description of the drawings
Fig. 1 is the structure of silicon-carbon composite nano tube of the present invention and prepares schematic diagram.
Fig. 2 is infrared spectrum (FTIR spectrums) figure of several substances in the present invention, wherein (a) is CNTs, CNTs-COOH；(b)
For CNTs, SNTs and SNTs@CNTs.
Fig. 3 is X-ray diffraction spectrum (XRD) figure of several substances in the present invention, wherein (a) is CNTs, it is (b) SNTs, (c)
For SNTs-1@CNTs, it is (d) SNTs-2@CNTs, is (e) SNTs-3@CNTs.
Fig. 4 is transmission electron microscope (TEM) figure (1) of silicon-carbon composite nano tube of the present invention.
Fig. 5 is the TEM figures (2) of silicon-carbon composite nano tube of the present invention, wherein (a) is CNTs, it is (b) SNTs-1@CNTs,
(c) it is SNTs-2@CNTs, is (d) SNTs-3@CNTs.
Fig. 6 is the EDS energy spectrum analysis figures of SNTs@CNTs in the present invention, wherein (a) is SNTs-1@CNTs, it is (b) SNTs-
2@CNTs (c) are SNTs-3@CNTs.
Fig. 7 is the transmission electron microscope photo of SNTs in the present invention, wherein (a) is SNTs-1, is (b) SNTs-2, is (c)
SNTs-3。
Fig. 8 is the thermogravimetric curve of several substances in the present invention, and (a) is that thermal weight loss is bent under CNTs, CNTs-COOH argon gas
Line (b) is thermogravimetric curve under CNTs, SNTs and SNTs@CNTs air.
Fig. 9 is the Fracture scan figure of the composite material of several substances and silicon rubber in the present invention, wherein (a) is CNTs/SR,
(b) it is SNTs-1@CNTs/SR, is (c) SNTs-2@CNTs/SR, be (d) SNTs-3@CNTs/SR, is (e) SNTs/SR.
Specific implementation mode
The present invention is further detailed with reference to embodiment and attached drawing.
The material essential information used is as shown in the table：
Key instrument and equipment are as shown in the table：
| Title | Model | Manufacturer |
| Electronic balance | AL104 | Plum Teller-support benefit Instrument Ltd. |
| Ultrasonic cell disruptor | JY92-IIN | Xin Zhi bio tech ltd, Ningbo |
| Multiplex vavuum pump of circulating water type | SHB-III | Zhengzhou Greatwall Scientific Industrial ＆ Trading Co., Ltd. |
| Electric vacunm drying case | DZG-401B | Tianjin sky laboratory apparatus Co., Ltd |
| Electric drying oven with forced convection | DGG-101-0B | Tianjin sky laboratory apparatus Co., Ltd |
| Double roll mill | SR-160B | Zhanjiang machinery plant |
| High temperature hydraulic forming machine | YJ450 | Yuyao Hua Cheng hydraulic pressure electromechanics Co., Ltd |
| Punching testing machine | CP-25 | Shanghai rubber machinery plant |
| Fourier Transform Infrared Spectrometer | NICOLET 560 | NICOLET companies of the U.S. |
| Universal tensile testing machine | M350-20KN | Testometric |
By the way of collosol and gel, make nano-tube (SNTs) with the CNTs (CNTs-COOH) after acidification for mould
Plate grows up on its surface.
First, acidification is carried out to original CNTs.2.0g graphitized carbon nano pipes are weighed to be placed in there-necked flask.It weighs
The 180ml concentrated sulfuric acids and 60ml concentrated nitric acids are placed in graduated cylinder, and the concentrated sulfuric acid is added in there-necked flask first, are opened and are stirred, heating water bath,
Heating temperature is set as 60 DEG C.After to be heated to 60 DEG C, concentrated nitric acid is added in there-necked flask, makes system in sealed condensating reflux condition
4h is reacted under part.After reaction, all drugs in there-necked flask are poured into the large beaker for having filled appropriate distilled water, it is heavy to stand
Drop.It waits for that upper layer spent acid is poured out recycling after particle precipitation, then the carbon after appropriate distilled water washing acidification is added into beaker
Nanotube continues standing sedimentation, then so cycle is filtered, is first washed with distilled water up to the close neutrality of supernatant liquor,
It is washed with ethanol in proper amount when pH is close to 7.Filtered product is placed in baking oven and is dried for 24 hours.Product after drying is placed in
It grinds in mortar, until being in powdered, product is preserved mounted in labeling in sample sack
Then, SNTs is coated to by the surfaces CNTs by sol-gal process.Specifically, first, weigh CNTs-COOH powder
End, ultrasonic disperse obtain the uniform suspension of CNTs-COOH in ethanol solution；Second, ammonium hydroxide is weighed, is added rapidly to above-mentioned
In suspension obtained, strong stirring 0.5h, it is 10 to obtain the mixed liquor of stable homogeneous and adjust pH；Third weighs 2.5 respectively
Again, the TEOS of 5 times, 7.5 times CNTs-COOH mass is put into ethanol solution and is uniformly mixed；4th, third is walked into acquired solution
It is added in mixing suspension obtained by second step, strong stirring 2h obtains the evenly dispersed suspension of SNTs claddings CNTs；5th, it will
SNTs@CNTs suspensions settle 2 days at room temperature, filter, ultrasonic disperse；6th, repeat filter and ultrasound 3-4 times, will most
Gained suspension filters eventually, and is dried at 60 DEG C；7th, the product after drying is heat-treated under 600 DEG C of nitrogen atmosphere
5h obtains three kinds of SNTs@CNTs powder.Three kinds of SNTs@CNTs powder of gained are respectively designated as the dosage of TEOS from less to more
SNTs-1@CNTs, SNTs-2@CNTs and SNTs-3@CNTs.
Simultaneously by SNTs-1@CNTs, SNTs-2@CNTs and SNTs-3@CNTs powder in air atmosphere at 600 DEG C at heat
Corresponding SNTs powder is made in reason 5h.
As shown in Fig. 2, (a) is the FTIR spectrograms of CNTs and CNTs-COOH.Hydroxyl, carboxyl and carbon nanotube absorb
Water O-H keys stretching vibration characteristic peak, correspond in CNTs and CNTs-COOH infrared lines, in 3407cm-1With
1643cm-1Locate the larger absorption peak of intensity；1565cm-1The absorption peak at place belongs to the vibration peak of the C=C keys of carbon material, and
This peak is considered as the property and concentration for being strongly depend on oxide on surface.It can be seen that original carbon pipe is in 1565cm-1Place
Peak is not occurred, and there is apparent new peak in the position in the carbon pipe after being acidified.In addition, acidification carbon pipe is in 1713cm-1Wavelength
Place shows that a weaker absorption peak, this peak correspond to the C=O vibration peaks of carboxyl functional group, and intensity is by the surfaces CNTs
The carboxyl functional group concentration connect influences very big.It is acidified carbon pipe C=C stretching vibration peaks (1565cm-1) and C=O stretching vibration peaks
(1713cm-1) enhancing, this can be attributed to the effect of oxygen-containing group (- COOH ,-OH etc.).This result confirms that acidification carbon is received
The surface of mitron produces oxygen-containing functional group, this is conducive to generations of the subsequent SNTs on the surfaces CNTs.(b) it is CNTs, SNTs
With the infrared spectrogram of SNTs@CNTs.In SNTs spectrograms, 1109cm-1, 798cm-1And 476cm-1The absorption peak at place is SNTs
Upper Si-O-Si keys stretching vibration peak；1627cm-1, 957cm-1And 3460cm-1Nearby width absorption peak represents silicone hydroxyl and silicon is received
The stretching vibration characteristic peak of the O-H keys for the water that mitron absorbs.On the infrared spectrum of SNTs@CNTs, it not only observed and come from
The distinctive absorption peaks of SNTs, also in 1380-1410cm-1Occurs a new characteristic peak in range, this peak is in original CNTs
With do not occur on SNTs, it is considered to be covalently bound on CNTs and be formed by as SNTs -- caused by Si-O-C- key chatterings.
In addition, the absorption peak and-OH structures of SNTs-1@CNTs, SNTs-2@CNTs and SNTs-3@CNTs at-Si-O-Si- structures
Stretching vibration peak intensity is incremented by successively.This may be due in SNTs-1@CNTs, SNTs-2@CNTs and SNTs-3@CNTs
SNTs contents gradually increase.According to infrared spectrum comparative analysis, it can further assert that SNTs is successfully coated to CNTs tables
Face, and the covering amount different from of three kinds of SNTs@CNTs.
Such as the XRD spectra that attached drawing 3 is CNTs, SNTs and SNTs@CNTs.In CNTs spectrograms, two characteristic peaks go out respectively
At present 2 θ=26 ° and 43 °, it is belonging respectively to the diffraction maximum of carbon nanotube (002) and (100) face.Amorphous state is presented in SNTs,
In SNTs spectrograms, there is no apparent characteristic crystalline peaks to occur, and only shows as occurring one in 15 ° to 30 ° diffraction angular regions
A wide and weak amorphous peak, the diffraction maximum of SNTs is consistent with document description in figure.And the XRD spectra of SNTs@CNTs, it is in simultaneously
Show and has come from CNTs and SNTs characteristic peaks.It is worth noting that, the wide and weak amorphous diffraction maximum of SNTs is brilliant with CNTs (002)
The diffraction overlap of peaks in face, and the peak blurring on each crystal faces of CNTs, become wide and weak.By taking SNTs-2@CNTs as an example, spectral line
On show at 2 θ=43 ° diffraction maximum broaden and die down.In one wide and strong diffraction maximum of appearance of 15-30 ° of range, wherein
Nearby there are one the diffraction maximums of the crystal face of CNTs outstanding (100) for 2 θ=26 °, and this diffraction maximum does not have compared to original CNTs
It is so clear.In addition, the intensity of amorphous diffraction maximum is gradual in SNTs-1@CNTs, SNTs-2@CNTs and SNTs-3@CNTs
Enhancing, each crystallographic plane diffraction peaks of CNTs gradually weaken.This may be due to SNTs-1@CNTs, SNTs-2@CNTs and SNTs-3@
SNTs contents in CNTs gradually increase.
TEM figures as shown in drawings, the surfaces CNTs being not decorated are smooth；And the surfaces SNTs@CNTs after coating become
Coarse and particle diameter becomes larger.Energy spectrum analysis has been carried out to SNTs@CNTs series particles.It can be found that three's by EDS pictures
Common feature is that observed C, O, Si and Cu element.Wherein Cu elements are interference elements caused by back end copper mesh, and are received
Rice corpuscles itself is unrelated.As it can be seen that SNTs has been coated on CNTs really.The different characteristic of three is tri- kinds of elements of C, O, Si
Different degrees of variation has occurred in peak intensity.In SNTs-1@CNTs, SNTs-2@CNTs and SNTs-3@tri- kinds of particles of CNTs, Si,
O elements are gradually increased relative to the intensity at C element peak, show that SNTs covering amounts are continuously increased.In order to further analyze SNTs packets
SNTs-1@CNTs, SNTs-2@CNTs and SNTs-3@CNTs are carried out heat under air atmosphere by the specific pattern of coating respectively in experiment
Processing obtains the TEM image of corresponding SNTs particles, as shown in the picture, SNTs-1@CNTs, SNTs-2@CNTs and SNTs-3@
The pipe thickness of the SNTs clads of CNTs particles is continuously increased, respectively 4~5nm, 8~10nm and 13~15nm.
Thermogravimetric curve figure as shown in drawings, (a) are thermal weight loss of the front and back CNTs particles of acidification under ar gas environment
Curve.100 DEG C to 500 DEG C of CNTs particle thermal weight losses are typically that the thermal decomposition of the oxygen-containing functional groups such as carbon pipe surface carboxyl causes
's.In other words, particle directly reflects CNTs acidification success or not and its surface carboxyl groups in 100 DEG C to 500 DEG C of thermal weight loss
How much is content.It is shown by figure (a) curve, minimum quality thermal degradation only has occurred in original CNTs, and residual qualities are up to
97.8%, and CNTs thermal degradations quality greatly improves after acidification, residual qualities drop to 91.9%.As it can be seen that CNTs by
Work(is acidified, and the oxygen-containing functional groups such as surface carboxyl groups content 5.9%.Curve (b) is CNTs, SNTs and three kinds of SNTs@CNTs air
Lower thermogravimetric curve.As seen from the figure, SNTs do not have substantially occur weightlessness, CNTs, SNTs-1@CNTs, SNTs-2@CNTs,
Different degrees of thermal weight loss has occurred in SNTs-3@CNTs successives, and CNTs there is no residual qualities (mf), almost all drop
Solution.Based in thermal weight loss test temperature section, nano-tube quality keeps stablizing, and carbon nanotube is almost thoroughly weightless, because
This, it is believed that in thermal weight loss test, the difference of the residual qualities between SNTs CNTs and CNTs is coated nano-tube
Mass percent.
Significant data in air atmosphere on CNTs, SNTs and SNTs@CNTs thermogravimetric curves
Upper table is the significant data on CNTs, SNTs and SNTs@CNTs thermogravimetric curves in air atmosphere.In TG curves
In, incipient degradation temperature (Ti indicates thermal degradation temperature corresponding when particle thermal weight loss mass fraction is 5%) is to weigh material
One important indicator of thermal stability.By table as it can be seen that the cladding of nano-tube particle, is greatly improved the heat of carbon nanotube
Oxidative stability energy, and be continuously improved with the increase Ti of nano-tube covering amount, SNTs-2 is increased to by SNTs-1 in covering amount
When, Ti increases by 33.71 DEG C, and increasing degree is maximum.By mf it can be calculated that being coated in carbon nanotube in SNTs@CNTs
Nano-tube content be respectively：42.47wt% (SNTs-1@CNTs), 53.11wt% (SNTs-2@CNTs) and 69.74wt%
(SNTs-3@CNTs)。
(a) is the SEM photograph of CNTs/SR composite materials, fracture in Fracture scan (SEM) photo of silicon rubber composite material
There is agglomeration in surface；(b-d) it is respectively SNTs-1@CNTs/SR, SNTs-2@CNTs/SR and SNTs-3@CNTs/SR multiple
There is not agglomeration, favorable dispersibility in the SEM photograph of condensation material, SNTs@CNTs nano-particles.As it can be seen that after SNTs claddings,
The dispersibilities of CNTs in the composite improve.
Embodiment 1
Step 1：The accurate raw-silastic continuously for weighing 100 parts by weight, is added in appropriate ethyl acetate, 60 DEG C of heating water baths
And continue stirring to obtain raw rubber solution.
Step 2：It weighs 1 parts by weight SNTs-1@CNTs nano-particles to be placed in ethyl acetate solution, is ultrasonically treated and obtains
Even dispersion liquid.It is added in raw rubber solution made from step 1, stirs evenly, 90 DEG C are evaporated while stirring, 60 DEG C of vacuum drying
48h removes solvent, obtains SNTs-1@CNTs/ raw-silastic continuouslies.
Step 3：By raw rubber made from 100 parts by weight steps 2 in the double roller of 40 DEG C of temperature, it is kneaded 6min, makes it uniformly
Roll banding.
Step 4：2,5- dimethyl -2,5- di-t-butyl hexane peroxides of 0.4 parts by weight are added, continue to be kneaded 13min,
It is kneaded and uniformly obtains rubber compound.
Step 5：Rubber compound prepared by step 4 is fitted into mold, temperature is 180 ± 1 DEG C, heat under conditions of pressure 7MPa
10min sulfidization moldings are pressed, sulfide film is obtained after cooling；
Embodiment 2
Step 1：The accurate raw-silastic continuously for weighing 100 parts by weight, is added in appropriate ethyl acetate, 61 DEG C of heating water baths
And continue stirring to obtain raw rubber solution.
Step 2：It weighs 2 parts by weight SNTs-2@CNTs nano-particles to be placed in ethyl acetate solution, is ultrasonically treated and obtains
Even dispersion liquid.It is added in raw rubber solution made from step 1, stirs evenly, 90 DEG C are evaporated while stirring, 60 DEG C of vacuum drying
47h removes solvent, obtains SNTs-2@CNTs/ raw-silastic continuouslies.
Step 3：By raw rubber made from 100 parts by weight steps 2 in the double roller of 42 DEG C of temperature, it is kneaded 8min, makes it uniformly
Roll banding.
Step 4：2,5- dimethyl -2,5- di-t-butyl hexane peroxides of 0.4 parts by weight are added, continue to be kneaded 13min,
It is kneaded and uniformly obtains rubber compound.
Step 5：Rubber compound prepared by step 4 is fitted into mold, temperature is 180 ± 1 DEG C, heat under conditions of pressure 8MPa
10min sulfidization moldings are pressed, sulfide film is obtained after cooling；
Embodiment 3
Step 1：The accurate raw-silastic continuously for weighing 100 parts by weight, is added in appropriate ethyl acetate, 62 DEG C of heating water baths
And continue stirring to obtain raw rubber solution.
Step 2：It weighs 3 mass parts SNTs-3@CNTs nano-particles to be placed in ethyl acetate solution, is ultrasonically treated and obtains
Even dispersion liquid.It is added in raw rubber solution made from step 1, stirs evenly, 92 DEG C are evaporated while stirring, 63 DEG C of vacuum drying
48h removes solvent, obtains SNTs@CNTs-3/ raw-silastic continuouslies.
Step 3：By raw rubber made from 100 parts by weight steps 2 in the double roller of 43 DEG C of temperature, it is kneaded 9min, makes it uniformly
Roll banding.
Step 4：2,5- dimethyl -2,5- di-t-butyl hexane peroxides of 0.4 mass parts are added, continue to be kneaded 15min,
It is kneaded and uniformly obtains rubber compound.
Step 5：Rubber compound prepared by step 4 is fitted into mold, temperature is 180 ± 1 DEG C, heat under conditions of pressure 6MPa
10min sulfidization moldings are pressed, sulfide film is obtained after cooling；
Embodiment 4
Step 1：The accurate raw-silastic continuously for weighing 100 parts by weight, is added in appropriate ethyl acetate, 64 DEG C of heating water baths
And continue stirring to obtain raw rubber solution.
Step 2：It weighs 1 mass parts SNTs-3@CNTs nano-particles to be placed in ethyl acetate solution, is ultrasonically treated and obtains
Even dispersion liquid.It is added in raw rubber solution made from step 1, stirs evenly, be evaporated while stirring at 90 DEG C, 59 DEG C of vacuum are dry
Dry 48h removes solvent, obtains SNTs@CNTs/ raw-silastic continuouslies.
Step 3：By raw rubber made from 100 parts by weight steps 2 in the double roller of 44 DEG C of temperature, it is kneaded 9min, makes it uniformly
Roll banding.
Step 4：2,5- dimethyl -2,5- di-t-butyl hexane peroxides of 0.2 mass parts are added, continue to be kneaded 14min,
It is kneaded and uniformly obtains rubber compound.
Step 5：Rubber compound prepared by step 4 is fitted into mold, temperature is 180 ± 1 DEG C, heat under conditions of pressure 5MPa
10min sulfidization moldings are pressed, sulfide film is obtained after cooling.
Embodiment 5
Step 1：The accurate raw-silastic continuously for weighing 100 parts by weight, is added in appropriate ethyl acetate, 61 DEG C of heating water baths
And continue stirring to obtain raw rubber solution.
Step 2：It weighs 2 mass parts SNTs-1@CNTs nano-particles to be placed in ethyl acetate solution, is ultrasonically treated and obtains
Even dispersion liquid.It is added in raw rubber solution made from step 1, stirs evenly, be evaporated while stirring at 90 DEG C, 58 DEG C of vacuum are dry
Dry 48h removes solvent, obtains SNTs@CNTs/ raw-silastic continuouslies.
Step 3：By raw rubber made from 100 parts by weight steps 2 in the double roller of 40 DEG C of temperature, it is kneaded 10min, makes it uniformly
Roll banding.
Step 4：2,5- dimethyl -2,5- di-t-butyl hexane peroxides of 0.5 mass parts are added, continue to be kneaded 15min,
It is kneaded and uniformly obtains rubber compound.
Step 5：Rubber compound prepared by step 4 is fitted into mold, temperature is 180 ± 1 DEG C, heat under conditions of pressure 8MPa
9min sulfidization moldings are pressed, sulfide film is obtained after cooling.
Simultaneously using blank sample is made, each parts by weight are 1g
Step 1：The accurate raw-silastic continuously for weighing 100 parts by weight, is added in appropriate ethyl acetate, 60 DEG C of heating water baths
And continue stirring to obtain raw rubber solution.
Step 2：It in raw rubber solution made from step 1, stirs evenly, is evaporated while stirring at 90 DEG C, 60 DEG C of vacuum drying
48h removes solvent, obtains raw-silastic continuously.
Step 3：Raw rubber made from 100 parts by weight steps 2 is mixed in the double roller of 40 DEG C of temperature, 10min is kneaded, makes it
2,5- dimethyl -2,5- di-t-butyl hexane peroxides of 0.5 parts by weight are added in even roll banding, continue to be kneaded 14min, are kneaded equal
Even acquisition rubber compound.
Step 4：Rubber compound prepared by step 3 is fitted into mold, temperature is 180 ± 1 DEG C, heat under conditions of pressure 8MPa
10min sulfidization moldings are pressed, sulfide film is obtained after cooling；
According to the formula of embodiment 2, by SNTs-2@CNTs replace with respectively carboxylic carbon nano-tube (CNTs-COOH) and
It is standby that three kinds of SNTs@CNTs carry out rubber system.
Using punching experimental machine, print cutting makes it be similar to dumbbell shaped (with reference to GB/T 528-2009).It is relatively narrow flat in sample
At row, two parallel lines easy to identify for not influencing sample physical property are spread in painting, and line and center are equidistant (25.0 ± 0.5mm).
According to GB/T528-2009 and GB/T529-2008 requirements, vulcanizate is tested with TestometricM350-20KN electronic tensile machines
Mechanical property.Sample is placed in the center of clamper, is machined, with the speed tensile batten of 500mm/min and passes through survey
Stretch the label of pointers track sample working portion.Record load data value when each sample is pulled apart, and averaged.
Silicon rubber based composites mechanical property
| Title | Tensile strength (MPa) | Elongation at break (%) |
| Blank | 0.30±0.027 | 167.54±14.17 |
| CNTs-COOH/SR | 0.36±0.031 | 234.12±21.31 |
| SNTs-1@CNTs/SR | 0.47±0.037 | 299.43±28.50 |
| SNTs-2@CNTs/SR | 0.61±0.041 | 317.71±29.64 |
| SNTs-3@CNTs/SR | 0.50±0.035 | 306.68±26.94 |
The adjustment of technological parameter is carried out according to the content of present invention can prepare nano-tube enveloped carbon nanometer tube modified silicon rubber
Glue simultaneously has good mechanical property.Illustrative description is done to the present invention above, it should which explanation is not departing from the present invention
Core in the case of, it is any it is simple deformation, modification or other skilled in the art can not spend creative work
Equivalent replacement each fall within protection scope of the present invention.
Claims (9)
1. a kind of method improving methyl vinyl silicone rubber mechanical property, it is characterised in that steps are as follows：
Step 1, the raw-silastic continuously of 100 mass parts is added in ethyl acetate, 60~64 DEG C of heating water baths simultaneously continue to stir
Obtain raw rubber solution；
Step 2, the silicon-carbon composite nano tube for weighing 1~3 mass parts is placed in ethyl acetate solution, is ultrasonically treated and is obtained uniformly
Dispersion liquid；Then mixed liquor is added in raw rubber solution made from step 1, stir evenly and at 90~92 DEG C while stirring
It is evaporated, SNTs@CNTs/ raw-silastic continuouslies is obtained after vacuum drying；
Step 3, it by SNTs@CNTs/ raw-silastic continuouslies made from 100 mass parts steps 3 in the double roller of 40~44 DEG C of temperature, mixes
6~10min is refined, its uniform roll banding is made；Then 2,5- dimethyl -2,5- di-tert-butyl peroxides of 0.1~0.5 mass parts are added
Hexane continues 13~15min of mixing, is kneaded and uniformly obtains rubber compound；
Step 4, rubber compound prepared by step 3 is fitted into mold, it is hot under conditions of 180 ± 1 DEG C of temperature, 5~8MPa of pressure
9~10min sulfidization moldings are pressed, sulfide film is obtained after cooling；
The raw-silastic continuously is methyl vinyl silicone rubber；
Silicon dioxide layer, institute is arranged using carbon nanotube as inner tube in the silicon-carbon composite nano tube on the outer wall of carbon nanotube
The silicon dioxide layer stated forms Silica Nanotube on the outside of carbon nanotube；In the structure of silicon-carbon composite nano tube, carbon is received
Mitron and Silica Nanotube form coaxial sleeve structure, and inner tube is carbon nanotube, and outer tube is Silica Nanotube；
The preparation method of the silicon-carbon composite nano tube is by the evenly dispersed formation suspension of carboxylic carbon nano-tube and to adjust
PH value is alkalinity, then ethyl orthosilicate is added in the suspension of carboxylic carbon nano-tube, is sufficiently mixed and evenly dispersed；Point
From solid matter, 550~650 DEG C are heated to from room temperature in an inert atmosphere and are heat-treated, then cooled to room temperature.
2. a kind of method improving methyl vinyl silicone rubber mechanical property according to claim 1, it is characterised in that：
In the step 2, carboxylic carbon nano-tube is dispersed in absolute ethyl alcohol and forms suspension, adjusting pH value using ammonium hydroxide is
8~10, it specifically, weighs carboxylic carbon nano-tube and is put into beaker, absolute ethyl alcohol is added, stirring keeps CNTs dispersions abundant；
Dispersion liquid is put into ultrasonic cell disrupte machine, ice-bath ultrasonic process 1h, power 500W, working time 3s, the intermittent time is
2s weighs ammonium hydroxide, is added rapidly to adjust pH value in suspension obtained above to be alkalinity 8~10, strong stirring 0.5h is obtained
The suspension of carboxylic carbon nano-tube.
3. a kind of method improving methyl vinyl silicone rubber mechanical property according to claim 1, it is characterised in that：
In the step 2, ethyl orthosilicate is dispersed in absolute ethyl alcohol, forms the teos solution of stable homogeneous, then
Teos solution is added in the suspension of carboxylic carbon nano-tube, specifically, ethyl orthosilicate is weighed, is put into
In the absolute ethyl alcohol of 300ml, stirring fully obtains the solution of stable homogeneous, solution is rapidly joined in suspension, strong stirring
2h obtains mixed liquor, this mixed liquor is put into ultrasonic cell disrupte machine again, ice-bath ultrasonic process 30min, ultrasonic power 500W,
Working time is 3s, intermittent time 2s, is taken out after the completion of processing, sealing and standing is for 24 hours.
4. a kind of method improving methyl vinyl silicone rubber mechanical property according to claim 1, it is characterised in that：
In the step 2, inert atmosphere is nitrogen, helium or argon gas；It is warming up to from room temperature with 5~10 DEG C/min speed for 20~25 DEG C
550~650 DEG C are heat-treated at least 2 hours, specifically, are filtered after standing, are filtered product and are placed in vacuum drying oven,
It is dried at 60~80 DEG C, after dry, ground solid sample to obtain powder with mortar, powder is placed in Muffle furnace and carries out heat
Processing.
5. a kind of method improving methyl vinyl silicone rubber mechanical property according to claim 5, it is characterised in that：
In the step 2, when heat treatment, is handled 2~5 hours under the conditions of 600~650 DEG C.
6. a kind of method improving methyl vinyl silicone rubber mechanical property according to claim 1, it is characterised in that：
It is bonded using carboxyl and the ethyl orthosilicate realization of carbon nano tube surface in the step 2, then heat up and be heat-treated, so that
Ethyl orthosilicate is in carbon nano tube surface in-situ preparation silica；Pass through the carboxyl-content of carbon nano tube surface, positive silicic acid second
The dosage of ester adjusts the appearance structure of silicon-carbon composite nano tube, can be regulated and controled to silicone tube thickness, silicone tube continuity degree etc..
7. a kind of method improving methyl vinyl silicone rubber mechanical property according to claim 1, it is characterised in that：
In the step 2, the vacuum drying condition is that 46~48h is dried in vacuo at 58~60 DEG C.
8. a kind of method improving methyl vinyl silicone rubber mechanical property according to claim 1, it is characterised in that：
In the step 3,0.2~0.3 parts by weight 2,5- dimethyl -2,5- di-t-butyl hexane peroxides are chosen.
9. a kind of method improving methyl vinyl silicone rubber mechanical property according to claim 1, it is characterised in that：
In the step 4, the die size is 140 × 140 × 2mm3, hot under conditions of 180 ± 1 DEG C of temperature, pressure 7MPa
Press 9min sulfidization moldings.
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| CN114752080A (en) * | 2022-05-16 | 2022-07-15 | 西京学院 | Preparation method and application of hydrogel with interpenetrating network structure |
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| CN105255197A (en) * | 2015-10-25 | 2016-01-20 | 北京化工大学 | Silicone rubber nano composite with high tear resistance and preparation method thereof |
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