CN107964246A - Silicon rubber/ionic liquid composite material of long-acting antistatic and preparation method thereof - Google Patents
Silicon rubber/ionic liquid composite material of long-acting antistatic and preparation method thereof Download PDFInfo
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Abstract
Silicon rubber/ionic liquid composite material the invention discloses long-acting antistatic and preparation method thereof.By percentage to the quality, the raw material composition of composite material is：Raw-silastic continuously 55~90%, reinforcing agent 5~35%, constitution controller 1~5%, vinyl silicone oil grafting ion liquid 2~8%, crosslinking agent 1~5%.Antistatic additive dosage is few in the silicon rubber of long-acting antistatic of the present invention/ionic liquid composite material formula, the mechanical property of silicon rubber, color and the transparency are influenced little, the antistatic property of gained silicon rubber rubber composite material is stablized, after 1 year, the change in resistance unobvious of composite material；Anti-static composite material preparation process of the present invention is simple, safety and environmental protection, can be widely used for the fields such as electronics, electric, machinery, chemical industry, prepares various elastic contact panels, button, sheath, rubber roller, casting glue etc..
Description
Technical field
The present invention relates to a kind of silastic mixture, more particularly to a kind of silicon rubber/ionic liquid of long-acting antistatic
Composite material and preparation method thereof.
Background technology
Silicon rubber has stable-Si-O- backbone structures, shows excellent resistant of high or low temperature, weatherability, electrical insulating property
And physiological inertia, thus silicon rubber is in the field extensive use such as Aeronautics and Astronautics, electronics, electric, chemical industry, machinery, medical treatment.Its
In, in electric industry, silicon rubber is mainly used as button, sheath, rubber roller, insulator and casting glue etc..Due to silicon rubber
It is a kind of electrically insulating material, volume resistivity is typically larger than 1013Ω m, thus silicon rubber is when with other object CONTACT WITH FRICTIONs
Hold easy to produce static electricity.For example, such as easy static electrification when printer rubber roller and paper rub, printing effect can be influenced.In addition, electrostatic
A large amount of accumulations of lotus may also can cause electrion, or even trigger fire.Therefore, the antistatic property research of silicon rubber is very heavy
Will.
At present, the main method for improving silicon rubber antistatic or conductivity is to add various conductions in silicone rubber matrix to fill out
Material, such as conductive black, carbon fiber, carbon nanotubes, graphene and metallic particles (such as silver powder, copper powder), pass through conductive filler
Between contact with each other and accumulate to form conductive path with physics, improve the electric conductivity of silicon rubber.But the conduction of black is filled out
Expect such as conductive black, carbon fiber, carbon nanotubes, graphene, the color of silicon rubber can be substantially change, reduce the transparent of silicon rubber
Property, thus be not suitable for doing the conductive silicon rubber product of colourful transparent.And the silastic material of the filling such as silver powder or copper powder, although its
Electric conductivity is preferable, but the dosage of metallic particles is also more, can change the transparency of silicon rubber, and cost is higher.In addition,
During the long-time use of composite material, as the oxidation of metal-powder causes the antistatic property or conduction of silicon rubber
Property decline.
Ionic liquid is a kind of chemical property stabilization, high temperature resistant, the room with organic cation and inorganic anion structure
Warm fuse salt.Chinese invention patent 201610695485.X describes a kind of conductive silicon rubber, is added in silicone rubber matrix
The ionic liquid (such as tetrafluoroborate) of (0.01-10) wt% is used as conductive agent, for making conductive rubber roller.But these
Ionic liquid is added directly in silicone rubber matrix, it is easily separated between silicon rubber, i.e., ionic liquid holds
It is easy to migrate to arrive silastic surface, with the extension of time, ionic liquid constantly loses, thus the antistatic property or conduction of silicon rubber
Property can be gradually reduced, and therefore, this antistatic silicone rubber does not possess the function of long-acting antistatic.
The content of the invention
It is contemplated that by being first grafted vinyl silicone oil and ionic liquid, silicone rubber matrix is then added it to
In, a kind of silicon rubber/ionic liquid composite material with long-acting antistatic is prepared, the antistatic property of composite material is stablized,
Resistivity is without significant change after 1 year.
The present invention is preferable due to the compatibility of vinyl silicone oil grafting ion liquid and silicone rubber matrix so that ionic liquid
Migration dies down in silicone rubber matrix, thus this silicon rubber composite material can keep its antistatic property for a long time, and
Its mechanical property and the transparent influence from ionic liquid.
The object of the invention is achieved through the following technical solutions：
A kind of silicon rubber/ionic liquid composite material of long-acting antistatic, by percentage to the quality, the raw material of composite material
Form and be：
The vinyl silicone oil grafting ion liquid is prepared via a method which：Vinyl silicone oil is dissolved in organic solvent
In, ionic liquid is then added, adds initiator azodiisobutyronitrile (AIBN), nitrogen protection, is stirred at 60~80 DEG C
12~24h, vinyl silicone oil and ionic liquid reaction products therefrom are cleaned, remove part unreacting material, vacuum is done
It is dry, vinyl silicone oil grafting ion liquid is made；The mass ratio for controlling vinyl silicone oil, ionic liquid and AIBN is 100:(2.5
~5)：1.
Further to realize the object of the invention, it is preferable that silicon rubber for dimethyl silicone rubber, methyl vinyl silicone rubber,
One or more mixtures in methyl phenyl vinyl silicone rubber.
Preferably, reinforcing agent is one or more mixtures in precipitated silica and gas-phase silica.
Preferably, constitution controller is one or more mixtures in hydroxy silicon oil and diphenyl silanediol.
Preferably, the ionic liquid is 1- pi-allyl -3- methylimidazoles bromide, 1- pi-allyl -3- methylimidazole vinegar
One or more mixtures in hydrochlorate, 1- pi-allyl -3- methylimidazole villaumites and 1- vinyl -3- butyl imidazole villaumites.
Preferably, the crosslinking agent is 2,5- dimethyl -2,5- di-t-butyl hexane peroxide, peroxidating double (2,4-
Dichloro-benzoyl), one or more mixtures of cumyl peroxide and dibenzoyl peroxide.
Preferably, the viscosity of the vinyl silicone oil is 200~1000mPas, contents of ethylene for 0.8~
1.9mol%.
Preferably, the organic solvent for toluene, dimethylbenzene, petroleum ether, methyl ethyl ketone, one kind in carbon tetrachloride or
A variety of mixtures；It is 1 to control the mass ratio of vinyl silicone oil and organic solvent:4~1:8.
Preferably, the cleaning is to clean product in ethanol 3~6 times；The vacuum drying is at 60~100 DEG C
Dry 2~6h in vacuum drying oven.
The preparation method of silicon rubber/ionic liquid composite material of the long-acting antistatic：Adjust open mill roll spacing to 1~
2mm, first adds silicon rubber, and bag roller, then adds reinforcing agent and constitution controller, is uniformly mixed, adds vinyl silicone oil afterwards
Grafting ion liquid, is eventually adding crosslinking agent, is kneaded uniformly, and clot slice, silicon rubber gross rubber vulcanizes on vulcanizing press,
Curing temperature is 160~200 DEG C, and vulcanization time is 5~20min.
In the preparation of vinyl silicone oil grafting ion liquid of the present invention, organic solvent is passed through back by thermal evaporation, the steam of generation
Condenser pipe cooling is flowed, organic solvent is become liquid again, is back in reaction vessel, to ensure that solvent dosage is basically unchanged.
Compared with prior art, the present invention has the following advantages：
1) anlistatig silicon rubber/ionic liquid composite material provided by the invention, first with vinyl silicone oil and from
The double bond activity of sub- liquid, by radical reaction, realizes the grafting of vinyl silicone oil and ionic liquid, the vinyl silicon of preparation
Oily grafting ion liquid has good interface compatibility with silicone rubber matrix, silicon rubber composite material is kept good power
Performance is learned, and the color of gained composite material (silicon rubber) and the transparency do not change with the addition of ionic liquid.
2) vinyl silicone oil grafting ion liquid stability in silicone rubber matrix of the present invention is preferable, makes silicon rubber composite wood
Material has the function of long-acting antistatic, and composite material still kept good antistatic property after 1 year, effectively extended antistatic silicon
The service life of rubber composite material.
3) preparation process of silicon rubber/ionic liquid composite material of the present invention is simple, safety and environmental protection.
4) silicon rubber/ionic liquid composite material of the present invention due to its mechanical property it is good, color and the transparency not with ion
The addition of liquid and change, there is long-acting antistatic, excellent combination property, and preparation process is simple, safety and environmental protection, because
And it is with a wide range of applications in the field such as electronics, electric, machinery, chemical industry.
Embodiment
To more fully understand the present invention, the features of the present invention and advantage are further illustrated with reference to specific embodiment, but
Embodiment does not form limiting the scope of the invention.
The manufacturer of each raw material is in embodiment：Silicon rubber, Guangdong Charming Co., Ltd.'s production；Ionic liquid, woods
State city Ke Neng materials Science and Technology Ltd. produces；Precipitated silica, model TOKUSIL 255, the production of Nan Ji Chemical Co., Ltd.s；Gas phase
White carbon, model QS 20, the production of moral mountain chemical industry (Zhejiang) Co., Ltd；Vinyl silicone oil, the Zhejiang profit limited public affairs of standing grain new chemical materials
Department's production；2,5- dimethyl -2,5- di-t-butyl hexane peroxides, cumyl peroxide, Dongguan City coloured silk source organosilicon material have
Limit company produces；Hydroxy silicon oil and diphenyl silanediol, the production of Jiaxing Ke Rui organosilicons Co., Ltd.Raw material described in embodiment with
Mass percentage.
The Mechanics Performance Testing (with reference to GB/T 528-2009) of wherein silicon rubber carries out on universal testing machine, electricity
The test of resistance rate carries out (with reference to GB/T 1692-2008, test voltage 1000V) in high insulation leakagel volume leakage flow gauge.
Embodiment 1
The each group distribution ratio of silicon rubber/ionic liquid composite material of long-acting antistatic is：
The vinyl silicone oil that viscosity is 200mPas and contents of ethylene is 0.8mol% is dissolved in toluene (ethene
Base silicone oil and toluene mass ratio are 1:4) ionic liquid, is added, then adds AIBN (vinyl silicone oil, ionic liquid and AIBN
Mass ratio be 100:5:1) 24h, is stirred at 60 DEG C, nitrogen protection, toluene evaporation, is back to reaction by water cooling and holds
Device, to ensure that toluene dosage is basically unchanged, cleans 3 times, then by the reaction product of vinyl silicone oil and ionic liquid with ethanol
By product, dry 6h, obtained vinyl silicone oil are grafted 1- pi-allyl -3- methylimidazole bromides in 60 DEG C of baking ovens.
First methyl vinyl silicone rubber, gas-phase silica and hydroxy silicon oil are kneaded in rubber mixing mill uniformly, then
Vinyl silicone oil grafting 1- pi-allyl -3- methylimidazole bromides are added, are eventually adding 2,5- dimethyl -2,5- di-t-butyl peroxides
Change hexane, be uniformly mixed, rubber compound is vulcanized using vulcanizing press, and conditions of vulcanization is 160 DEG C × 20min, and obtained silicon rubber is answered
Condensation material.The mechanical property of silicon rubber composite material, surface resistivity and volume resistivity are as shown in table 1.
Embodiment 2
The each group distribution ratio of silicon rubber/ionic liquid composite material of long-acting antistatic is：
The vinyl silicone oil that viscosity is 200mPas and contents of ethylene is 0.8mol% is dissolved in dimethylbenzene (second
Alkenyl silicone oil and xylene mass ratio are 1:8), add ionic liquid, then add AIBN (vinyl silicone oil, ionic liquid and
The mass ratio of AIBN is 100:5:1) 12h, is stirred at 80 DEG C, nitrogen protection, dimethylbenzene evaporation, is back to instead by water cooling
Container is answered, to ensure that dimethylbenzene dosage is basically unchanged, the reaction product of vinyl silicone oil and ionic liquid is cleaned 6 with ethanol
Secondary, then by product, dry 2h, obtained vinyl silicone oil are grafted 1- pi-allyl -3- methylimidazole bromides in 100 DEG C of baking ovens.
First methyl vinyl silicone rubber, gas-phase silica and hydroxy silicon oil are kneaded in rubber mixing mill uniformly, then
Vinyl silicone oil grafting 1- pi-allyl -3- methylimidazole bromides are added, are eventually adding 2,5- dimethyl -2,5- di-t-butyl peroxides
Change hexane, be uniformly mixed, rubber compound is vulcanized using vulcanizing press, and conditions of vulcanization is 160 DEG C × 20min, and obtained silicon rubber is answered
Condensation material.The mechanical property of silicon rubber composite material, surface resistivity and volume resistivity are as shown in table 1.
Embodiment 3
The each group distribution ratio of silicon rubber/ionic liquid composite material of long-acting antistatic is：
The vinyl silicone oil that viscosity is 1000mPas and contents of ethylene is 1.9mol% is dissolved in carbon tetrachloride
(vinyl silicone oil and carbon tetrachloride mass ratio are 1:5) ionic liquid, is added, then adds AIBN (vinyl silicone oil, ionic liquid
The mass ratio of body and AIBN are 100:5:1) 12h, is stirred at 65 DEG C, nitrogen protection, carbon tetrachloride evaporation, is returned by water cooling
Reaction vessel is flow to, to ensure that carbon tetrachloride dosage is basically unchanged, by the reaction product second of vinyl silicone oil and ionic liquid
Alcohol cleans 3 times, and then by product, dry 2h, obtained vinyl silicone oil are grafted 1- pi-allyl -3- methylimidazoles in 100 DEG C of baking ovens
Bromide.
First methyl vinyl silicone rubber, gas-phase silica and hydroxy silicon oil are kneaded in rubber mixing mill uniformly, then
Vinyl silicone oil grafting 1- pi-allyl -3- methylimidazole bromides are added, are eventually adding 2,5- dimethyl -2,5- di-t-butyl peroxides
Change hexane, be uniformly mixed, rubber compound is vulcanized using vulcanizing press, and conditions of vulcanization is 160 DEG C × 20min, and obtained silicon rubber is answered
Condensation material.The mechanical property of silicon rubber composite material, surface resistivity and volume resistivity are as shown in table 1.
Embodiment 4
The each group distribution ratio of silicon rubber/ionic liquid composite material of long-acting antistatic is：
The vinyl silicone oil that viscosity is 200mPas and contents of ethylene is 0.8mol% is dissolved in toluene (ethene
Base silicone oil and toluene mass ratio are 1:5) ionic liquid, is added, then adds AIBN (vinyl silicone oil, ionic liquid and AIBN
Mass ratio be 100:5:1) 12h, is stirred at 65 DEG C, nitrogen protection, toluene evaporation, is back to reaction by water cooling and holds
Device, to ensure that toluene dosage is basically unchanged, cleans 3 times, then by the reaction product of vinyl silicone oil and ionic liquid with ethanol
By product, dry 2h, obtained vinyl silicone oil are grafted 1- pi-allyl -3- methylimidazole bromides in 100 DEG C of baking ovens.
First methyl vinyl silicone rubber, gas-phase silica and hydroxy silicon oil are kneaded in rubber mixing mill uniformly, then
Vinyl silicone oil grafting 1- pi-allyl -3- methylimidazole bromides are added, are eventually adding 2,5- dimethyl -2,5- di-t-butyl peroxides
Change hexane, be uniformly mixed, rubber compound is vulcanized using vulcanizing press, and conditions of vulcanization is 160 DEG C × 20min, and obtained silicon rubber is answered
Condensation material.The mechanical property of silicon rubber composite material, surface resistivity and volume resistivity are as shown in table 1.
Embodiment 5
The each group distribution ratio of silicon rubber/ionic liquid composite material of long-acting antistatic is：
The vinyl silicone oil that viscosity is 200mPas and contents of ethylene is 0.8mol% is dissolved in toluene (ethene
Base silicone oil and toluene mass ratio are 1:5) ionic liquid, is added, then adds AIBN (vinyl silicone oil, ionic liquid and AIBN
Mass ratio be 100:5:1) 24h, is stirred at 65 DEG C, nitrogen protection, toluene evaporation, is back to reaction by water cooling and holds
Device, to ensure that toluene dosage is basically unchanged, cleans 3 times, then by the reaction product of vinyl silicone oil and ionic liquid with ethanol
By product, dry 2h, obtained vinyl silicone oil are grafted 1- pi-allyl -3- methylimidazole bromides in 100 DEG C of baking ovens.
First methyl vinyl silicone rubber, precipitated silica and diphenyl silanediol are kneaded in rubber mixing mill uniformly,
Then vinyl silicone oil grafting 1- pi-allyl -3- methylimidazole bromides are added, are eventually adding 2,5- dimethyl -2,5- di-t-butyls
Butylperoxyhexane, is uniformly mixed, and rubber compound is vulcanized using vulcanizing press, and conditions of vulcanization is 160 DEG C × 20min, and silicon rubber is made
Glue composite material.The mechanical property of silicon rubber composite material, surface resistivity and volume resistivity are as shown in table 1.
Embodiment 6
The each group distribution ratio of silicon rubber/ionic liquid composite material of long-acting antistatic is：
The vinyl silicone oil that viscosity is 200mPas and contents of ethylene is 0.8mol% is dissolved in toluene (ethene
Base silicone oil and toluene mass ratio are 1:5) ionic liquid, is added, then adds AIBN (vinyl silicone oil, ionic liquid and AIBN
Mass ratio be 100:2.5:1) 12h, is stirred at 65 DEG C, nitrogen protection, toluene evaporation, is back to reaction by water cooling and holds
Device, to ensure that toluene dosage is basically unchanged, cleans 3 times, then by the reaction product of vinyl silicone oil and ionic liquid with ethanol
By product, dry 2h, obtained vinyl silicone oil are grafted 1- pi-allyl -3- methylimidazole bromides in 100 DEG C of baking ovens.
First methyl vinyl silicone rubber, gas-phase silica and hydroxy silicon oil are kneaded in rubber mixing mill uniformly, then
Vinyl silicone oil grafting 1- pi-allyl -3- methylimidazole bromides are added, are eventually adding 2,5- dimethyl -2,5- di-t-butyl peroxides
Change hexane, be uniformly mixed, rubber compound is vulcanized using vulcanizing press, and conditions of vulcanization is 160 DEG C × 20min, and obtained silicon rubber is answered
Condensation material.The mechanical property of silicon rubber composite material, surface resistivity and volume resistivity are as shown in table 1.
Embodiment 7
The each group distribution ratio of silicon rubber/ionic liquid composite material of long-acting antistatic is：
The vinyl silicone oil that viscosity is 200mPas and contents of ethylene is 0.8mol% is dissolved in toluene (ethene
Base silicone oil and toluene mass ratio are 1:5) ionic liquid, is added, then adds AIBN (vinyl silicone oil, ionic liquid and AIBN
Mass ratio be 100:2.5:1) 12h, is stirred at 65 DEG C, nitrogen protection, toluene evaporation, is back to reaction by water cooling and holds
Device, to ensure that toluene dosage is basically unchanged, cleans 3 times, then by the reaction product of vinyl silicone oil and ionic liquid with ethanol
By product, dry 2h, obtained vinyl silicone oil are grafted 1- pi-allyl -3- methylimidazole bromides in 100 DEG C of baking ovens.
First methyl phenyl vinyl silicone rubber, gas-phase silica and hydroxy silicon oil are kneaded in rubber mixing mill uniformly,
Then vinyl silicone oil grafting 1- pi-allyl -3- methylimidazole bromides are added, are eventually adding cumyl peroxide, mixing is equal
Even, rubber compound is vulcanized using vulcanizing press, and conditions of vulcanization is 160 DEG C × 20min, and silicon rubber composite material is made.Silicon rubber
The mechanical property of composite material, surface resistivity and volume resistivity are as shown in table 1.
Embodiment 8
The each group distribution ratio of silicon rubber/ionic liquid composite material of long-acting antistatic is：
The vinyl silicone oil that viscosity is 200mPas and contents of ethylene is 0.8mol% is dissolved in toluene (ethene
Base silicone oil and toluene mass ratio are 1:5) ionic liquid 1- pi-allyl -3- methylimidazole villaumites, are added, then add AIBN (second
The mass ratio of alkenyl silicone oil, ionic liquid and AIBN is 100:2.5:1) 12h, nitrogen protection, are stirred at 65 DEG C, toluene steams
Hair, reaction vessel is back to by water cooling, to ensure that toluene dosage is basically unchanged, by the anti-of vinyl silicone oil and ionic liquid
Answer product to clean 3 times with ethanol, then by product in 100 DEG C of baking ovens dry 2h, be made vinyl silicone oil grafting 1- pi-allyls-
3- methylimidazole villaumites.
First methyl vinyl silicone rubber, gas-phase silica and hydroxy silicon oil are kneaded in rubber mixing mill uniformly, then
Vinyl silicone oil grafting 1- pi-allyl -3- methylimidazole villaumites are added, are eventually adding 2,5- dimethyl -2,5- di-t-butyl peroxides
Change hexane, be uniformly mixed, rubber compound is vulcanized using vulcanizing press, and conditions of vulcanization is 200 DEG C × 5min, and it is compound that silicon rubber is made
Material.The mechanical property of silicon rubber composite material, surface resistivity and volume resistivity are as shown in table 1.
Embodiment 9
The each group distribution ratio of silicon rubber/ionic liquid composite material of long-acting antistatic is：
The vinyl silicone oil that viscosity is 200mPas and contents of ethylene is 0.8mol% is dissolved in toluene (ethene
Base silicone oil and toluene mass ratio are 1:5) ionic liquid 1- pi-allyl -3- methylimidazole acetate, is added, then adds AIBN
(mass ratio of vinyl silicone oil, ionic liquid and AIBN is 100:2.5:1) 12h, nitrogen protection, toluene, are stirred at 65 DEG C
Evaporation, reaction vessel is back to by water cooling, to ensure that toluene dosage is basically unchanged, by vinyl silicone oil and ionic liquid
Reaction product is cleaned 3 times with ethanol, and then by product, dry 2h, obtained vinyl silicone oil are grafted 1- allyls in 100 DEG C of baking ovens
Base -3- methylimidazole acetate.
First methyl vinyl silicone rubber, gas-phase silica and hydroxy silicon oil are kneaded in rubber mixing mill uniformly, then
Vinyl silicone oil grafting 1- pi-allyl -3- methylimidazole bromides are added, are eventually adding 2,5- dimethyl -2,5- di-t-butyl peroxides
Change hexane, be uniformly mixed, rubber compound is vulcanized using vulcanizing press, and conditions of vulcanization is 160 DEG C × 20min, and obtained silicon rubber is answered
Condensation material.The mechanical property of silicon rubber composite material, surface resistivity and volume resistivity are as shown in table 1.
Embodiment 10
The each group distribution ratio of silicon rubber/ionic liquid composite material of long-acting antistatic is：
The vinyl silicone oil that viscosity is 200mPas and contents of ethylene is 0.8mol% is dissolved in toluene (ethene
Base silicone oil and toluene mass ratio are 1:5) ionic liquid 1- vinyl -3- butyl imidazole villaumites, are added, then add AIBN (second
The mass ratio of alkenyl silicone oil, ionic liquid and AIBN is 100:2.5:1) 24h, nitrogen protection, are stirred at 65 DEG C, toluene steams
Hair, reaction vessel is back to by water cooling, to ensure that toluene dosage is basically unchanged, by the anti-of vinyl silicone oil and ionic liquid
Answer product to clean 3 times with ethanol, then by product in 100 DEG C of baking ovens dry 2h, be made vinyl silicone oil grafting 1- vinyl-
3- butyl imidazole villaumites.
First methyl vinyl silicone rubber, gas-phase silica and hydroxy silicon oil are kneaded in rubber mixing mill uniformly, then
Vinyl silicone oil grafting 1- vinyl -3- butyl imidazole villaumites are added, are eventually adding 2,5- dimethyl -2,5- di-t-butyl peroxides
Change hexane, be uniformly mixed, rubber compound is vulcanized using vulcanizing press, and conditions of vulcanization is 160 DEG C × 20min, and obtained silicon rubber is answered
Condensation material.The mechanical property of silicon rubber composite material, surface resistivity and volume resistivity are as shown in table 1.
As shown in Table 1, in embodiment 1, when the quality percentage of vinyl silicone oil grafting 1- pi-allyl -3- methylimidazole bromides
When content is 2%, the surface resistivity and volume resistivity of silicon rubber composite material are below 1011The order of magnitude, reaches antistatic
It is required that.Compared with Example 1, in embodiment 2, the content increase of vinyl silicone oil grafting 1- pi-allyl -3- methylimidazole bromides
To 8%, the surface resistivity and volume resistivity of composite material reduce 2 orders of magnitude, and the antistatic property of composite material improves.It is real
Apply in example 3, when silicon oil viscosity is improved to 1000mPas, when contents of ethylene increases to 1.9mol%, vinyl silicone oil grafting
Ionic liquid (1- pi-allyl -3- methylimidazoles bromide) content improve, thus composite material resistivity decline, antistatic property
It can improve.In embodiment 4, gas-phase silica dosage increases to 35% from 5%, and the tensile strength of silicon rubber improves, extension at break
Rate declines, and since reinforcing agent dosage increases in composite material, causes vinyl silicone oil to be grafted 1- pi-allyl -3- methylimidazole bromides
Ion transport in silicone rubber matrix reduces, thus the resistivity rise of composite material.In embodiment 5, when using precipitation
When white carbon replaces gas-phase silica, the tensile strength and elongation at break of composite material reduce, and change in resistance is little.It is real
Apply in example 6, increase the proportioning of vinyl silicone oil and 1- pi-allyl -3- methylimidazole bromides, i.e. 1- pi-allyls -3- methylimidazole bromines
The percentage composition of salt reduces, thus the resistivity of composite material slightly increases.In embodiment 7, with methyl phenyl vinyl silicon rubber
Glue replaces methyl vinyl silicone rubber, and the mechanical property of composite material increases, and change in resistance unobvious.Embodiment 8~10
In, 1- pi-allyl -3- methylimidazole villaumites, 1- pi-allyls -3- methylimidazoles acetate and 1- vinyl -3- butyl is respectively adopted
Imidazoles villaumite replaces 1- pi-allyl -3- methylimidazole bromides, it is found that the change in resistance of composite material is little, all meet antistatic
Performance requirement.In embodiment 1~10, composite material park 1 year after surface resistivity and volume resistivity and preparation initial stage
Compare, amplitude of variation very little, no more than 5%, show that silicon rubber composite material has long-acting antistatic.
Mechanical property, surface resistivity and the volume resistivity of 1 silicon rubber composite material of table
In the prior art, conductive silicon rubber is typically conductive filler such as carbon black, carbon nanotubes, the graphene for adding black
Deng often causing color and transparency of silicon rubber etc. to change, limit the use scope of conductive silicon rubber.And add silver powder
Or the density of silicon rubber can be significantly increased into silicon rubber in the metal-powder such as copper powder, reduce the transparency of silicon rubber, and it is compound
Material is during long-time use, as the oxidation of metal-powder causes the antistatic property of silicon rubber or electric conductivity notable
Decline.Ionic liquid is directly added in silicon rubber, although the antistatic property of rubber increases, ionic liquid can cause
The mechanical property of silicon rubber is decreased obviously, or even changes the color of silicon rubber；And the silicon rubber of ionic liquid is directly added, by
In ionic liquid fast transferring to the surface of silicon rubber, cause the easy loss of ionic liquid, make silicon rubber composite material not
Possesses long-acting antistatic.Because the continuous decrease of existing antistatic silicone rubber product antistatic property, can cause product in power
In the case that property retention is good, due to losing antistatic property, it must be replaced in advance on various electronic and electrical equipments.
The mechanical property and antistatic property of silicon rubber/ionic liquid composite material of long-acting antistatic of the present invention are good, and antistatic property
It is able to can keep stablizing for (1 year) for a long time, can significantly extend the service life of antistatic silicone rubber product.The present invention at the same time
The mechanical property of gained composite material (silicon rubber), color and the transparency substantially from the influence of ionic liquid, composite material
Simple and convenient processing method is easy, thus being more widely applied in fields such as electronics, electric appliance, machinery, chemical industry.
Claims (10)
1. silicon rubber/ionic liquid composite material of long-acting antistatic, it is characterised in that by percentage to the quality, composite material
Raw material composition be：
The vinyl silicone oil grafting ion liquid is prepared via a method which：By vinyl silicone oil dissolving in organic solvent,
Then ionic liquid is added, adds initiator A IBN, nitrogen protection, stirs 12~24h, by vinyl silicon at 60~80 DEG C
Oil and ionic liquid reaction products therefrom are cleaned, and remove part unreacting material, vacuum drying, obtained vinyl silicone oil connects
Branch ionic liquid；The mass ratio for controlling vinyl silicone oil, ionic liquid and AIBN is 100:(2.5~5)：1.
2. silicon rubber/ionic liquid composite material of long-acting antistatic according to claim 1, it is characterised in that silicon rubber
Glue is dimethyl silicone rubber, one or more mixtures in methyl vinyl silicone rubber, methyl phenyl vinyl silicone rubber.
3. silicon rubber/ionic liquid composite material of long-acting antistatic according to claim 1, it is characterised in that reinforcement
Agent is one or more mixtures in precipitated silica and gas-phase silica.
4. silicon rubber/ionic liquid composite material of long-acting antistatic according to claim 1, it is characterised in that structure
Controlling agent is one or more mixtures in hydroxy silicon oil and diphenyl silanediol.
5. silicon rubber/ionic liquid composite material of long-acting antistatic according to claim 1, it is characterised in that described
Ionic liquid for 1- pi-allyl -3- methylimidazoles bromide, 1- pi-allyl -3- methylimidazoles acetate, 1- pi-allyl -3- methyl
One or more mixtures in imidazoles villaumite and 1- vinyl -3- butyl imidazole villaumites.
6. silicon rubber/ionic liquid composite material of long-acting antistatic according to claim 1, it is characterised in that described
Crosslinking agent be 2,5- dimethyl -2,5- di-t-butyl hexane peroxides, peroxidating double (2,4 dichloro benzene formyl), peroxidating two
One or more mixtures of isopropylbenzene and dibenzoyl peroxide.
7. silicon rubber/ionic liquid composite material of long-acting antistatic according to claim 1, it is characterised in that described
The viscosity of vinyl silicone oil is 200~1000mPas, and contents of ethylene is 0.8~1.9mol%.
8. silicon rubber/ionic liquid composite material of long-acting antistatic according to claim 1, it is characterised in that described
Organic solvent is toluene, one or more mixtures in dimethylbenzene, petroleum ether, methyl ethyl ketone, carbon tetrachloride；Control second
The mass ratio of alkenyl silicone oil and organic solvent is 1:4~1:8.
9. silicon rubber/ionic liquid composite material of long-acting antistatic according to claim 1, it is characterised in that described
Cleaning be to clean product in ethanol 3~6 times；The vacuum drying be dry 2 in 60~100 DEG C of vacuum drying ovens~
6h。
10. the preparation method of silicon rubber/ionic liquid composite material of any one of the claim 1-9 long-acting antistatics, its
It is characterized in that：Open mill roll spacing is adjusted to 1~2mm, first adds silicon rubber, bag roller, then adds reinforcing agent and constitution controller,
It is uniformly mixed, adds vinyl silicone oil grafting ion liquid afterwards, be eventually adding crosslinking agent, is kneaded uniform, clot slice, silicon rubber
Glue rubber compound vulcanizes on vulcanizing press, and curing temperature is 160~200 DEG C, and vulcanization time is 5~20min.
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