CN109354879A - A kind of semiconductive polymer composite material and preparation method of low-voltage correlation - Google Patents
A kind of semiconductive polymer composite material and preparation method of low-voltage correlation Download PDFInfo
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
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Abstract
The present invention relates to semiconductive technical field of composite preparation, specifically provide a kind of semiconductive polymer composite material and preparation method of low-voltage correlation.The composite material is made of the raw material comprising following parts by weight: 50~90 parts of methyl vinyl silicone rubber；10~50 parts of ethylene propylene diene rubber；10~20 parts of conductive agglomerate；1~5 part of crosslinking agent.The volume resistivity of the semiconductive polymer composite material of the low-voltage correlation is in 0.32*106~0.47*106Ω cm is in semiconductor regions (i.e. about 105~109Ω cm) range, and its resistance is sufficiently stable, under hot and humid environment, does not ooze out the chemical substance of pollution photosensitive drums.
Description
Technical field
The present invention relates to semiconductive technical field of composite preparation, and in particular to a kind of semiconductive of low-voltage correlation
Polymer composites and preparation method thereof.
Background technique
In recent years, it is set using offices such as the laser printer, laser integrated machines of electron image (electrofax) image-forming principle
It is standby to have obtained large-scale popularization and application.The semiconductives such as charging roller (PCR), developer roll (DVR), transfer roll, clearer, transfer belt
Rubber manufactured goods are cooperated with photosensitive drums, carbon dust, magnetic roller as key components and parts, constitute commonly known as " toner cartridge "
Drum powder box.
Since charging roller, developer roll are directly contacted with photosensitive drums, preciousness specific to the rubber material in polymer material
Elasticity makes it become only choosing.In order to restore the image of clear exquisiteness, charging roller, developer roll volume resistivity be in half
Conductive region (i.e. about 105~109Ω cm) range, and the variation degree of resistance is the smaller the better, it is smaller to show that material property is steady
It is fixed.
The electrically conducting manner of rubber material is broadly divided into two major classes, and one kind is Ionic conductivity, another kind of to lead for electron type
Electricity.
Ionic conductivity rubber carries out conduction by the ion coordination of high probability, since this is from certain types of rubber
The characteristic that material itself has, electric conductivity is naturally relatively stable, and external alive correlation is also weaker, is currently
The mainstream electrically conducting manner of electron image imaging device.Such as representative epichlorohydrin rubber (epichlorohydrin rubber), volume electricity
Resistance rate is inherently 107~1010Ω cm range, commercialization is universal rapidly in recent years.In general ion can also be added to lead
Electric agent adjusts resistivity.In order to improve certain disadvantages of ionic conduction rubber, have been developed based on ionic conduction rubber, then mix
Close the way of the dual electrically conducting manner of electronic conductive material (such as conductive black).But ionic conduction rubber substrate is right first
Water has natural compatibility, is easy to wet, and surface adhesion degree rises, to adhere to carbon dust and its additive, seriously affects
Print quality.Secondly, especially sensitive to humidity variation, the variation degree of resistance is very big, and material property is unstable.
Third, ionic conductive agent is easy to happen surface migration, photosensitive drums are contaminated.Representative epichlorohydrin rubber is vulcanizing
Acid product can be also generated in reaction, it is necessary to acid absorbent neutralization be added, in order to adjust rubber hardness, the use of softening agent is also compared
Generally.The chemical complexing agent for participating in reaction is numerous, such as: vulcanizing agent, acid absorbent, softening agent, anti-aging agent, is prevented vulcanization accelerator
Burnt agent etc..The dedicated chemical complexing agent in part has a degree of toxicity to environment and human body.
Electronic conduction rubber is exactly the material that electronic conduction type is added to ionic conductivity rubber clone, so that rubber obtains
Obtain electric conductivity.Most of rubber almost insulate or semi-insulating, due to the limitation of electronic image system image-forming principle, should not use
Metal class conductive material, so, in fact conductive carbon black is the preferred electronic conductive material being particularly suitable for.In comparative maturity
Conduction field (volume resistivity about 10 completely-3~103Ω cm), have been carried out for conductive carbon black largely has for a long time
Effect research, but the method that these researchs are related to simply can not directly be diverted to semiconductive field, because of the conduction of the two
Mechanism has marked difference, and semiconductive field question is complicated and sensitive.Simple says, complete conduction generally requires that big component is added
The conductive carbon black of (more than tens of parts) obtains very high distributed density, and electrical conduction mechanism belongs to " closely to be connect between conducting particles
Touching forms conductive channel ".Semiconductive then needs to be added the conductive carbon black of appropriate component, component more to a certain degree, conductive machine
Reason tendency " contact is conductive "；Component is few to a certain extent, electrical conduction mechanism then tend to quantum mechanics scope " electron tunnel is worn
More, electron channel is formed "；Reducing again is exactly insulator " non-conductive ".Since semiconductor regions electrical conduction mechanism is complicated, mutual shadow
It rings, within this range, volume resistivity can occur six, seven the huge of the order of magnitude and be widely varied.Following factors can half-and-half be led
Volume resistivity in electric range affects: the fine difference (due to weighing difference or dust collector) of carbon black loading, carbon black
Structural damage (in refining glue process, structure caused by by shearing force is destroyed) degree is inconsistent, and carbon black is in sizing material
Middle bad or even material charge number the difference of dispersion also brings along fluctuation.So the variation degree that obtain resistance is small, performance is steady
Fixed material not a duck soup, in addition electrical conduction mechanism is complicated, the lifting of applied voltage will lead to the variation conversion of conductive path, with
And the factors such as durability dielectric loss are also not easily solved so that significant change occurs therewith for volume resistivity.
Summary of the invention
Technology matter of utmost importance to be solved by this invention is to provide a kind of semiconductive of the low-voltage correlation of resistance stabilization
Polymer composites.
Above-mentioned technical problem to be solved by this invention is achieved by following technical solution:
A kind of semiconductive polymer composite material of low-voltage correlation, is made of the raw material comprising following parts by weight:
50~90 parts of methyl vinyl silicone rubber；10~50 parts of ethylene propylene diene rubber；10~20 parts of conductive agglomerate；Crosslinking agent
1~5 part.
The present inventor conducts extensive research, and in all rubber, silicon rubber is strongest insulator (1015
~1016Ω cm), ethylene propylene diene rubber (1013~1015Ω cm) it is more slightly lower, both rubber are widely applied respectively
In insulation situations.In general, in preparing semiconductive polymer composite material, it is contemplated that reduce conduction is added as far as possible
The component (including reduce cost, reduce softening agent dosage) of carbon black, it is reasonable for selecting the rubber for having certain conductive capability, such as
Highly polar nitrile rubber (NBR, 1010~1011Ω cm), neoprene (CR, 1011~1013Ω cm), it is a large amount of to study
Exploitation is carried out around this direction of strong conductive base.But only consider that this direction is inertia.Inventor has carried out " reverse "
Thinking selects opposite thinking, the i.e. methyl vinyl silicone rubber of the ethylene propylene diene rubber of selection weakly conducting and nonpolarity insulation
As substrate；Inventor is it has furthermore been found that using ethylene propylene diene rubber and methyl vinyl silicone rubber as substrate, from substrate itself
For, though cannot directly make contributions to conduction, the condition that " electron tunnel passes through " occurs between conductive black can be made
Can be more loose, in other words, is conducive to " electron tunnel passes through, and forms electron channel " and realizes conduction.
Preferably, the semiconductive polymer composite material of the low-voltage correlation, by including following parts by weight
Raw material is made:
60~80 parts of methyl vinyl silicone rubber；20~40 parts of ethylene propylene diene rubber；10~20 parts of conductive agglomerate；Crosslinking agent
1~5 part.
It is further preferred that the semiconductive polymer composite material of the low-voltage correlation, by comprising weighing as follows
The raw material of amount part is made:
70 parts of methyl vinyl silicone rubber；30 parts of ethylene propylene diene rubber；10~20 parts of conductive agglomerate；1~5 part of crosslinking agent.
Preferably, the conductive agglomerate is prepared by the inclusion of the method for following steps:
(1) preparation of modified carbon black: carbon black is placed in the mixed acid solution of the concentrated sulfuric acid and concentrated nitric acid composition, 70~90
5~10h of back flow reaction is carried out at DEG C, must be acidified carbon black after washing is dry；Then acidification carbon black is mixed with nano-titanium dioxide
It is placed on progress 4~6h of ball milling in dehydrated alcohol, is modified carbon black to obtain the final product after removing ethyl alcohol drying；
(2) up to conductive female after the modification carbon black that step (1) is prepared and methyl vinyl silicone rubber melt blending
Grain；
Wherein, the amount ratio of carbon black and mixed acid solution is 1g:20~50mL, dense sulphur in mixed acid solution in step (1)
The volume ratio of acid and concentrated nitric acid is 1~3:1~3；The weight ratio for being acidified carbon black and nano-titanium dioxide is 1:1~3；It is acidified carbon black
It is 1g:8~20mL with the total weight of nano-titanium dioxide and the amount ratio of dehydrated alcohol；Modified carbon black and methyl in step (2)
The weight ratio of vinylsiloxane rubber is 1:1~3.
It is further preferred that the amount ratio of carbon black and mixed acid solution is 1g:20~30mL in step (1), mixed acid is molten
The volume ratio of the concentrated sulfuric acid and concentrated nitric acid is 1:2 in liquid.
It is further preferred that the weight ratio of acidification carbon black and nano-titanium dioxide is 1:1 in step (1)；Be acidified carbon black with
The total weight of nano-titanium dioxide and the amount ratio of dehydrated alcohol are 1g:10~15mL.
It is further preferred that the weight ratio of modified carbon black and methyl vinyl silicone rubber is 1:2 in step (2).
It is further preferred that 6~8h of back flow reaction in step (1)；Ball-milling Time is 5~6h.
The present invention also provides a kind of preparation method of the semiconductive polymer composite material of above-mentioned low-voltage correlation, packets
Containing following steps:
Methyl vinyl silicone rubber, ethylene propylene diene rubber, conductive agglomerate and crosslinking agent are placed in two-roll mill or turned
The uniformly semiconductive polymer composite material up to the low-voltage correlation is kneaded in sub- mixer.
Preferably, 3 times or more thin logical processing are carried out in mixing process.
The utility model has the advantages that (1) the present invention provides the semiconductive polymer of low-voltage correlation that one kind completely newly forms is compound
Material；The volume resistivity of the semiconductive polymer composite material is in 0.32*106~0.47*106Ω cm is in and partly leads
Electric region (i.e. about 105~109Ω cm) range；(2) the semiconductive polymer composite material of the low-voltage correlation described in is with three
First EP rubbers and methyl vinyl silicone rubber as substrate can that " electron tunnel passes through " occurs between conductive black
Condition can be more loose, in other words, is conducive to " electron tunnel passes through, and forms electron channel " and realizes conduction；(2) institute of the present invention
The conductive black stated is used to prepare semiconductive polymer composite material, phase after the method is prepared into conductive agglomerate through the invention
For other modes, volume resistivity on the one hand can be further decreased；On the other hand its resistance is sufficiently stable, embodiment experiment
It proves, R250Relative to R500Variation degree and R1000Relative to R500Variation degree from the point of view of, in 15~32% ranges；
Far smaller than other modes；(3) in addition, the semiconductive polymer composite material of low-voltage correlation of the present invention is in high temperature
Under high humidity environment, the chemical substance of pollution photosensitive drums is not oozed out.
Specific embodiment
The present invention is explained further below in conjunction with specific embodiment, but embodiment does not do any type of limit to the present invention
It is fixed.
The preparation of the semiconductive polymer composite material of 1 low-voltage correlation of embodiment
Parts by weight of raw materials composition: 70 parts of methyl vinyl silicone rubber；30 parts of ethylene propylene diene rubber；15 parts of conductive agglomerate；It hands over
3 parts of agent DCP of connection；
The conductive agglomerate is prepared via a method which to obtain: (1) carbon black the preparation of modified carbon black: being placed in the concentrated sulfuric acid
In the mixed acid solution of concentrated nitric acid composition, back flow reaction 6h is carried out at 80 DEG C, must be acidified carbon black after washing is dry；Then will
Acidification carbon black is mixed with nano-titanium dioxide is placed on progress ball milling 5h in dehydrated alcohol, up to carbon modified after removing ethyl alcohol is dry
It is black；(2) up to conductive agglomerate after the modification carbon black that step (1) is prepared and methyl vinyl silicone rubber melt blending；Its
In, the amount ratio of carbon black and mixed acid solution is 1g:25mL in step (1), the body of the concentrated sulfuric acid and concentrated nitric acid in mixed acid solution
Product is than being 1:2；The weight ratio for being acidified carbon black and nano-titanium dioxide is 1:1；It is acidified the total weight of carbon black and nano-titanium dioxide
Amount ratio with dehydrated alcohol is 1g:15mL；The weight ratio of modified carbon black and methyl vinyl silicone rubber is 1:2 in step (2)；
The preparation method of the semiconductive polymer composite material of low-voltage correlation: by methyl vinyl silicone rubber, ternary
EP rubbers, conductive agglomerate and crosslinking agent, which are placed in two-roll mill, to be kneaded uniformly up to the half of the low-voltage correlation
Conducting polymer composite material；It is sufficiently mixed to realize, 3 times thin logical processing is carried out in mixing process.
The preparation of the semiconductive polymer composite material of 2 low-voltage correlation of embodiment
Parts by weight of raw materials composition: 60 parts of methyl vinyl silicone rubber；40 parts of ethylene propylene diene rubber；10 parts of conductive agglomerate；It hands over
2 parts of agent DCP of connection；
The conductive agglomerate is prepared via a method which to obtain: (1) carbon black the preparation of modified carbon black: being placed in the concentrated sulfuric acid
In the mixed acid solution of concentrated nitric acid composition, back flow reaction 8h is carried out at 70 DEG C, must be acidified carbon black after washing is dry；Then will
Acidification carbon black is mixed with nano-titanium dioxide is placed on progress ball milling 6h in dehydrated alcohol, up to carbon modified after removing ethyl alcohol is dry
It is black；(2) up to conductive agglomerate after the modification carbon black that step (1) is prepared and methyl vinyl silicone rubber melt blending；Its
In, the amount ratio of carbon black and mixed acid solution is 1g:30mL in step (1), the body of the concentrated sulfuric acid and concentrated nitric acid in mixed acid solution
Product is than being 1:3；The weight ratio for being acidified carbon black and nano-titanium dioxide is 1:1；It is acidified the total weight of carbon black and nano-titanium dioxide
Amount ratio with dehydrated alcohol is 1g:20mL；The weight ratio of modified carbon black and methyl vinyl silicone rubber is 1:3 in step (2)；
The preparation method of the semiconductive polymer composite material of low-voltage correlation: by methyl vinyl silicone rubber, ternary
EP rubbers, conductive agglomerate and crosslinking agent, which are placed in two-roll mill, to be kneaded uniformly up to the half of the low-voltage correlation
Conducting polymer composite material；It is sufficiently mixed to realize, 3 times thin logical processing is carried out in mixing process.
The preparation of the semiconductive polymer composite material of 3 low-voltage correlation of embodiment
Parts by weight of raw materials composition: 50 parts of methyl vinyl silicone rubber；50 parts of ethylene propylene diene rubber；20 parts of conductive agglomerate；It hands over
5 parts of agent DCP of connection；
The conductive agglomerate is prepared via a method which to obtain: (1) carbon black the preparation of modified carbon black: being placed in the concentrated sulfuric acid
In the mixed acid solution of concentrated nitric acid composition, back flow reaction 5h is carried out at 90 DEG C, must be acidified carbon black after washing is dry；Then will
Acidification carbon black is mixed with nano-titanium dioxide is placed on progress ball milling 5h in dehydrated alcohol, up to carbon modified after removing ethyl alcohol is dry
It is black；(2) up to conductive agglomerate after the modification carbon black that step (1) is prepared and methyl vinyl silicone rubber melt blending；Its
In, the amount ratio of carbon black and mixed acid solution is 1g:20mL in step (1), the body of the concentrated sulfuric acid and concentrated nitric acid in mixed acid solution
Product is than being 1:1；The weight ratio for being acidified carbon black and nano-titanium dioxide is 1:3；It is acidified the total weight of carbon black and nano-titanium dioxide
Amount ratio with dehydrated alcohol is 1g:10mL；The weight ratio of modified carbon black and methyl vinyl silicone rubber is 1:2 in step (2)；
The preparation method of the semiconductive polymer composite material of low-voltage correlation: by methyl vinyl silicone rubber, ternary
EP rubbers, conductive agglomerate and crosslinking agent, which are placed in two-roll mill, to be kneaded uniformly up to the half of the low-voltage correlation
Conducting polymer composite material；It is sufficiently mixed to realize, 3 times thin logical processing is carried out in mixing process.
The preparation of the semiconductive polymer composite material of 1 low-voltage correlation of comparative example
Parts by weight of raw materials composition: 70 parts of methyl vinyl silicone rubber；30 parts of ethylene propylene diene rubber；15 parts of conductive agglomerate；It hands over
3 parts of agent DCP of connection；
The conductive agglomerate is prepared via a method which to obtain: after carbon black and methyl vinyl silicone rubber melt blending
Up to conductive agglomerate；Wherein, the weight ratio of carbon black and methyl vinyl silicone rubber is 1:2；
The preparation method of the semiconductive polymer composite material of low-voltage correlation: by methyl vinyl silicone rubber, ternary
EP rubbers, conductive agglomerate and crosslinking agent, which are placed in two-roll mill, to be kneaded uniformly up to the half of the low-voltage correlation
Conducting polymer composite material；It is sufficiently mixed to realize, 3 times thin logical processing is carried out in mixing process.
Comparative example 1 the difference from embodiment 1 is that, conductive agglomerate do not use by modified carbon black as described in the present invention with
Ethylene propylene diene rubber melt blending forms, but directlys adopt carbon black and ethylene propylene diene rubber melt blending forms.For comparing
It is polymerize using the semiconductive for the low-voltage correlation being prepared by modified carbon black as described in the present invention with non-modified carbon black
Difference of the object composite material in performance.
The preparation of the semiconductive polymer composite material of 2 low-voltage correlation of comparative example
Parts by weight of raw materials composition: 70 parts of methyl vinyl silicone rubber；30 parts of ethylene propylene diene rubber；15 parts of conductive agglomerate；It hands over
3 parts of agent DCP of connection；
The conductive agglomerate is prepared via a method which to obtain: (1) carbon black the preparation of modified carbon black: being placed in the concentrated sulfuric acid
In the mixed acid solution of concentrated nitric acid composition, back flow reaction 6h is carried out at 80 DEG C, must be acidified carbon black after washing is dry；(2) will
Up to conductive agglomerate after acidification carbon black and methyl vinyl silicone rubber melt blending that step (1) is prepared；Wherein, step
(1) amount ratio of carbon black and mixed acid solution is 1g:25mL in, and the volume ratio of the concentrated sulfuric acid and concentrated nitric acid is 1 in mixed acid solution:
2；The amount ratio of the total weight and dehydrated alcohol that are acidified carbon black and nano-titanium dioxide is 1g:15mL；Carbon black is acidified in step (2)
Weight ratio with methyl vinyl silicone rubber is 1:2；
The preparation method of the semiconductive polymer composite material of low-voltage correlation: by methyl vinyl silicone rubber, ternary
EP rubbers, conductive agglomerate and crosslinking agent, which are placed in two-roll mill, to be kneaded uniformly up to the half of the low-voltage correlation
Conducting polymer composite material；It is sufficiently mixed to realize, 3 times thin logical processing is carried out in mixing process.
Comparative example 2 the difference from embodiment 1 is that, simultaneously nano titanium dioxide ball mill is added in modified carbon black in conductive agglomerate
Step.It is poly- for the semiconductive than the low-voltage correlation being less prepared according to the method for modifying of carbon black of the present invention
Difference of the compound composite material in performance.
The preparation of the semiconductive polymer composite material of 3 low-voltage correlation of comparative example
Parts by weight of raw materials composition: 70 parts of methyl vinyl silicone rubber；30 parts of ethylene propylene diene rubber；15 parts of carbon black；Crosslinking agent
3 parts of DCP；
The preparation method of the semiconductive polymer composite material of low-voltage correlation: by methyl vinyl silicone rubber, ternary
EP rubbers, carbon black and crosslinking agent, which are placed in two-roll mill, is kneaded the uniformly semiconductive up to the low-voltage correlation
Polymer composites；It is sufficiently mixed to realize, 3 times thin logical processing is carried out in mixing process.
Comparative example 3 the difference from embodiment 1 is that, carbon black is not to be added in the form of conductive agglomerate during the preparation process
Enter, but is directly added into.For compare carbon black be directly added into the present invention it is modified prepare conductive agglomerate form be added after make
Difference of the semiconductive polymer composite material of standby obtained low-voltage correlation in performance.
Experimental example 1
The semiconductive polymer composite wood for the low-voltage correlation that Examples 1 to 3 and comparative example 1~3 are prepared
The development roller sample that installation is equipped with is prepared in material, and (rubber outside diameter 20mm, metal core axle diameter are 10mm, rubber part length
235.5mm), hereinafter abbreviated as 1~3 sample of Examples 1 to 3 sample and comparative example；Following performance, tool are tested in applied voltage
Body the results are shown in Table 1.
(1) volume resistivity is tested: development roller sample to be evaluated adds outside under 500V voltage, is tested using volume resistivity
Instrument test volume resistivity；
(2) voltage dependence is tested: development roller sample to be evaluated is at standard test environment (23 DEG C, relative humidity 55%)
Under, apply 250 volts 500 volts and 1000 volts of DC voltages respectively, measurement resistance is respectively R250,R500And R1000.Using R500 as base
Quasi- value.Test test specimens R250Relative to R500Variation degree；And test specimens R1000Relative to R500Variation degree.Resistance
Variation degree it is the smaller the better, it is smaller show material property stablize.Office machine needs not be provided multiple voltage output or compensation, letter
Change structure and reduces cost.The value belongs to preferable less than 100% in test.Above-mentioned " variation degree " is used to express the stabilization of resistance
Property, it is defined as follows: the quasi- ╳ 100% of the variation degree=∣ quasi- ∣/R Ji of R variation-R Ji
(3) photosensitive drums test for contamination: development roller sample is mounted in a whole set of toner cartridge, set environment chamber condition: temperature
50 DEG C, relative humidity 80%.Standing time: 7 days.After printing set original text, detecting the presence of test roller has low molecular compound precipitation, feels
Light drum is without contaminated phenomenon.
The semiconductive polymer composite property test result of 1. low-voltage correlation of table
As can be seen that the semiconductive polymer of low-voltage correlation described in Examples 1 to 3 is multiple from 1 experimental data of table
Its volume resistivity of condensation material is in 0.32*106~0.47*106Ω cm is in semiconductor regions (i.e. about 105~109Ω·cm)
Range.
From its R of the semiconductive polymer composite material of Examples 1 to 3 low-voltage correlation250Relative to R500Variation journey
Degree and R1000Relative to R500Variation degree from the point of view of, in 15~32% ranges；In this field the value less than 100% i.e. belong to compared with
It is good, and the sample value being prepared by the semiconductive polymer composite material of low-voltage correlation of the present invention is much small
In 100%, this illustrates that its resistance is sufficiently stable, and effect is very prominent.Wherein it is prepared under the formula of embodiment 1 and method
The semiconductive polymer composite material effect of low-voltage correlation is most significant.
It can be seen that its R of 1~2 sample of comparative example from the data of comparative example 1~2 and embodiment 1250Relative to R500Change
Change degree and R1000Relative to R500Variation degree be all larger than 200%, significantly larger than embodiment 1, resistance reproducibility is bad,
It fluctuates bigger than normal.This explanation is adopted using the semiconductive polymer composite material ratio being prepared by modified carbon black as described in the present invention
The semiconductive for the low-voltage correlation not being prepared with non-modified carbon black or according to the modified carbon black of the method for the invention
The stability of polymer composites resistance value is significantly very much.
It can be seen that directly addition carbon black without preparing using by the method for the present invention from the data of comparative example 3 and embodiment 1
The semiconductive polymer composite material of the form preparation low-voltage correlation of conductive agglomerate, R250Relative to R500Variation degree
And R1000Relative to R500Variation degree be all larger than 1500%, significantly larger than embodiment 1, resistance value is very unstable.
Claims (10)
1. a kind of semiconductive polymer composite material of low-voltage correlation, which is characterized in that by the original comprising following parts by weight
Material is made:
50~90 parts of methyl vinyl silicone rubber；10~50 parts of ethylene propylene diene rubber；10~20 parts of conductive agglomerate；Crosslinking agent 1~5
Part.
2. the semiconductive polymer composite material of low-voltage correlation according to claim 1, which is characterized in that by comprising
The raw material of following parts by weight is made:
60~80 parts of methyl vinyl silicone rubber；20~40 parts of ethylene propylene diene rubber；10~20 parts of conductive agglomerate；Crosslinking agent 1~5
Part.
3. the semiconductive polymer composite material of low-voltage correlation according to claim 1, which is characterized in that by comprising
The raw material of following parts by weight is made:
70 parts of methyl vinyl silicone rubber；30 parts of ethylene propylene diene rubber；10~20 parts of conductive agglomerate；1~5 part of crosslinking agent.
4. the semiconductive polymer composite material of low-voltage correlation according to claim 1, which is characterized in that described
Conductive agglomerate is prepared by the inclusion of the method for following steps:
(1) preparation of modified carbon black: carbon black is placed in the mixed acid solution of the concentrated sulfuric acid and concentrated nitric acid composition, at 70~90 DEG C
5~10h of back flow reaction is carried out, carbon black must be acidified after washing is dry；Then carbon black will be acidified and mix postposition with nano-titanium dioxide
4~6h of ball milling is carried out in dehydrated alcohol, is modified carbon black to obtain the final product after removing ethyl alcohol drying；
(2) up to conductive agglomerate after the modification carbon black that step (1) is prepared and methyl vinyl silicone rubber melt blending；
Wherein, the amount ratio of carbon black and mixed acid solution is 1g:20~50mL in step (1), in mixed acid solution the concentrated sulfuric acid and
The volume ratio of concentrated nitric acid is 1~3:1~3；The weight ratio for being acidified carbon black and nano-titanium dioxide is 1:1~3；It is acidified carbon black and receives
The total weight of rice titanium dioxide and the amount ratio of dehydrated alcohol are 1g:8~20mL；Modified carbon black and ethylene methacrylic in step (2)
The weight ratio of base silicon rubber is 1:1~3.
5. the semiconductive polymer composite material of low-voltage correlation according to claim 4, which is characterized in that step
(1) amount ratio of carbon black and mixed acid solution is 1g:20~30mL in, the volume ratio of the concentrated sulfuric acid and concentrated nitric acid in mixed acid solution
For 1:2.
6. the semiconductive polymer composite material of low-voltage correlation according to claim 4, which is characterized in that step
(1) weight ratio of acidification carbon black and nano-titanium dioxide is 1:1 in；Be acidified the total weight of carbon black and nano-titanium dioxide with it is anhydrous
The amount ratio of ethyl alcohol is 1g:10~15mL.
7. the semiconductive polymer composite material of low-voltage correlation according to claim 4, which is characterized in that step
(2) weight ratio of modified carbon black and methyl vinyl silicone rubber is 1:2 in.
8. the semiconductive polymer composite material of low-voltage correlation according to claim 4, which is characterized in that step
(1) 6~8h of back flow reaction in；Ball-milling Time is 5~6h.
9. the preparation method of the semiconductive polymer composite material of low-voltage correlation according to any one of claims 1 to 8,
It is characterized in that, comprises the following steps:
Methyl vinyl silicone rubber, ethylene propylene diene rubber, conductive agglomerate and crosslinking agent are placed in two-roll mill or rotor
Mixer mixing is uniformly up to the semiconductive polymer composite material of the low-voltage correlation.
10. preparation method according to claim 9, which is characterized in that carry out 3 times or more thin logical processing in mixing process.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115895129A (en) * | 2022-11-28 | 2023-04-04 | 株洲时代新材料科技股份有限公司 | Rubber conductive additive, preparation method thereof and conductive rubber |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020128139A1 (en) * | 2000-12-18 | 2002-09-12 | Masayuki Hashimoto | Conductive rubber roller |
| CN101055455A (en) * | 2006-04-14 | 2007-10-17 | 住友橡胶工业株式会社 | Semiconductor rubber member and developing roller composed of semiconductor rubber member |
| CN105968809A (en) * | 2016-03-14 | 2016-09-28 | 安徽电缆股份有限公司 | A soft rubber cable material |
| CN106349707A (en) * | 2016-08-19 | 2017-01-25 | 深圳市乐普泰科技股份有限公司 | Conductive silicone rubber, conductive rubber-covered roller and production method of conductive rubber-covered roller |
-
2018
- 2018-10-12 CN CN201811190068.5A patent/CN109354879B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020128139A1 (en) * | 2000-12-18 | 2002-09-12 | Masayuki Hashimoto | Conductive rubber roller |
| CN101055455A (en) * | 2006-04-14 | 2007-10-17 | 住友橡胶工业株式会社 | Semiconductor rubber member and developing roller composed of semiconductor rubber member |
| CN105968809A (en) * | 2016-03-14 | 2016-09-28 | 安徽电缆股份有限公司 | A soft rubber cable material |
| CN106349707A (en) * | 2016-08-19 | 2017-01-25 | 深圳市乐普泰科技股份有限公司 | Conductive silicone rubber, conductive rubber-covered roller and production method of conductive rubber-covered roller |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115895129A (en) * | 2022-11-28 | 2023-04-04 | 株洲时代新材料科技股份有限公司 | Rubber conductive additive, preparation method thereof and conductive rubber |
| CN115895129B (en) * | 2022-11-28 | 2024-03-29 | 株洲时代新材料科技股份有限公司 | Rubber conductive additive, preparation method thereof and conductive rubber |
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