CN107964246B - 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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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08L83/04—Polysiloxanes
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/12—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes
- C08F283/124—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polysiloxanes on to polysiloxanes having carbon-to-carbon double bonds
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C08K2201/001—Conductive additives
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- C08L2201/00—Properties
- C08L2201/04—Antistatic
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The invention discloses silicon rubber/ionic liquid composite materials of long-acting antistatic and preparation method thereof.By percentage to the quality, the raw material composition of composite material are as follows: 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 agent 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, and after 1 year, the change in resistance of composite material is unobvious；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, electrical, machinery, chemical industry, prepares various elastic touch panels, key, sheath, rubber roller, casting glue etc..
Description
Technical field
The present invention relates to a kind of silastic mixtures, more particularly to a kind of silicon rubber/ionic liquid of long-acting antistatic
Composite material and preparation method.
Background technique
Silicon rubber has stable-Si-O- backbone structure, shows excellent resistant of high or low temperature, weatherability, electrical insulating property
And physiological inertia, thus silicon rubber is widely applied in the fields such as Aeronautics and Astronautics, electronics, electrical, chemical industry, machinery, medical treatment.Its
In, in electric industry, silicon rubber is mainly used as key, 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
It is easy to produce electrostatic.For example, will affect printing effect as being easy static electrification when printer rubber roller and paper rub.In addition, electrostatic
A large amount of accumulations of lotus may also can cause electrion, or even cause fire.Therefore, the antistatic property research of silicon rubber is very heavy
It wants.
Currently, 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 nanotube, 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 nanotube, 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 fillings 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 higher cost.In addition,
In the long-time use process of composite material, as the oxidation of metal-powder leads to 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, adds 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, is easy to happen between silicon rubber and is mutually separated, 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 have the function of long-acting antistatic.
Summary of the invention
The present invention is directed to then add it to silicone rubber matrix by being first grafted vinyl silicone oil and ionic liquid
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 since the compatibility of vinyl silicone oil grafting ion liquid and silicone rubber matrix is preferable, 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 transparency are not influenced by 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
Composition are as follows:
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 stirs at 60~80 DEG C
12~for 24 hours, vinyl silicone oil and ionic liquid reaction products therefrom are cleaned, part unreacting material is removed, vacuum is dry
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.
To further realize the object of the invention, it is preferable that silicon rubber be dimethyl silicone rubber, methyl vinyl silicone rubber,
One of methyl phenyl vinyl silicone rubber or a variety of mixtures.
Preferably, reinforcing agent is one of precipitated silica and gas-phase silica or a variety of mixtures.
Preferably, constitution controller is one of hydroxy silicon oil and diphenyl silanediol or a variety of mixtures.
Preferably, the ionic liquid is 1- allyl -3- methylimidazole bromide, 1- allyl -3- methylimidazole vinegar
One of hydrochlorate, 1- allyl -3- methylimidazole villaumite and 1- vinyl -3- butyl imidazole villaumite or a variety of mixtures.
Preferably, the crosslinking agent is 2,5- dimethyl -2,5- di-t-butyl hexane peroxide, peroxidating bis- (2,4-
Dichloro-benzoyl), one or more mixtures of cumyl peroxide and dibenzoyl peroxide.
Preferably, the viscosity of the vinyl silicone oil be 200~1000mPas, contents of ethylene be 0.8~
1.9mol%.
Preferably, the organic solvent be one of toluene, dimethylbenzene, petroleum ether, methyl ethyl ketone, carbon tetrachloride or
A variety of mixtures；The mass ratio for controlling vinyl silicone oil and organic solvent is 1:4~1:8.
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.
Silicon rubber/ionic liquid composite material preparation method of the long-acting antistatic: adjusting open mill roll spacing to 1~
Silicon rubber is first added in 2mm, then reinforcing agent and constitution controller is added in packet roller, is uniformly mixed, vinyl silicone oil is added later
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
It is cooling to flow condenser pipe, so that organic solvent is become liquid again, is back in reaction vessel, to guarantee that solvent usage is basically unchanged.
Compared with prior art, the invention has the following advantages that
1) antistatic silicon rubber/ionic liquid composite material provided by the invention, first with vinyl silicone oil and from
The double bond activity of sub- liquid realizes the grafting of vinyl silicone oil and ionic liquid, the vinyl silicon of preparation by radical reaction
Oily grafting ion liquid and silicone rubber matrix have good interface compatibility, and silicon rubber composite material is made to be able to maintain 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 that long-acting antistatic, composite material still keep good antistatic property after 1 year, effectively extend 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, have the function of 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 fields such as electronics, electrical, machinery, chemical industry.
Specific embodiment
For a better understanding of the invention, the features of the present invention and advantage are further illustrated combined with specific embodiments below, but
Embodiment does not constitute a limitation on the scope of protection of the present invention.
The manufacturer of each raw material in embodiment are as follows: silicon rubber, Guangdong Charming Co., Ltd. produce；Ionic liquid, woods
State city Ke Neng material Science and Technology Ltd. produces；Precipitated silica, model TOKUSIL 255, Nan Ji Chemical Co., Ltd. produce；Gas phase
White carbon black, model QS 20, moral mountain chemical industry (Zhejiang) Co., Ltd produce；The limited public affairs of standing grain new chemical materials are moistened in vinyl silicone oil, Zhejiang
Department produces；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, Jiaxing Ke Rui organosilicon Co., Ltd produce.Raw material described in embodiment with
Mass percentage.
Wherein the Mechanics Performance Testing (referring to GB/T 528-2009) of silicon rubber carries out on universal testing machine, electricity
Resistance rate test (referring to GB/T 1692-2008, test voltage 1000V) carries out in high insulation leakagel volume leakage flow gauge.
Embodiment 1
Silicon rubber/ionic liquid composite material each group distribution ratio of long-acting antistatic are as follows:
The vinyl silicone oil that viscosity is 200mPas and contents of ethylene is 0.8mol% is dissolved in toluene (ethylene
Base silicone oil and toluene mass ratio are 1:4), ionic liquid is added, AIBN (vinyl silicone oil, ionic liquid and AIBN is then added
Mass ratio be 100:5:1), stirred at 60 DEG C for 24 hours, nitrogen protection, toluene evaporation, after be cooled by water be back to reaction hold
The reaction product of vinyl silicone oil and ionic liquid is cleaned 3 times with ethyl alcohol, then to guarantee that toluene dosage is basically unchanged by device
By product, dry 6h, obtained vinyl silicone oil are grafted 1- allyl -3- methylimidazole bromide 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 is added and is grafted 1- allyl -3- methylimidazole bromide, is eventually adding 2,5- dimethyl -2,5- di-t-butyl peroxide
Change hexane, be uniformly mixed, rubber compound is vulcanized using vulcanizing press, and conditions of vulcanization is 160 DEG C × 20min, and it is multiple that silicon rubber is made
Condensation material.The mechanical property of silicon rubber composite material, surface resistivity and volume resistivity are as shown in table 1.
Embodiment 2
Silicon rubber/ionic liquid composite material each group distribution ratio of long-acting antistatic are as follows:
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), ionic liquid is added, be then added AIBN (vinyl silicone oil, ionic liquid and
The mass ratio of AIBN is 100:5:1), stir 12h at 80 DEG C, nitrogen protection, dimethylbenzene evaporation, after be cooled by water be back to it is anti-
Container is answered, to guarantee that dimethylbenzene dosage is basically unchanged, the reaction product of vinyl silicone oil and ionic liquid is cleaned 6 with ethyl alcohol
Secondary, then by product, dry 2h, obtained vinyl silicone oil are grafted 1- allyl -3- methylimidazole bromide 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 is added and is grafted 1- allyl -3- methylimidazole bromide, is eventually adding 2,5- dimethyl -2,5- di-t-butyl peroxide
Change hexane, be uniformly mixed, rubber compound is vulcanized using vulcanizing press, and conditions of vulcanization is 160 DEG C × 20min, and it is multiple that silicon rubber is made
Condensation material.The mechanical property of silicon rubber composite material, surface resistivity and volume resistivity are as shown in table 1.
Embodiment 3
Silicon rubber/ionic liquid composite material each group distribution ratio of long-acting antistatic are as follows:
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 be 1:5) is added ionic liquid, AIBN (vinyl silicone oil, ionic liquid is then added
The mass ratio of body and AIBN are 100:5:1), stir 12h at 65 DEG C, nitrogen protection, carbon tetrachloride evaporation, after be cooled by water back
It is flow to reaction vessel, to guarantee 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- allyl -3- methylimidazole 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 is added and is grafted 1- allyl -3- methylimidazole bromide, is eventually adding 2,5- dimethyl -2,5- di-t-butyl peroxide
Change hexane, be uniformly mixed, rubber compound is vulcanized using vulcanizing press, and conditions of vulcanization is 160 DEG C × 20min, and it is multiple that silicon rubber is made
Condensation material.The mechanical property of silicon rubber composite material, surface resistivity and volume resistivity are as shown in table 1.
Embodiment 4
Silicon rubber/ionic liquid composite material each group distribution ratio of long-acting antistatic are as follows:
The vinyl silicone oil that viscosity is 200mPas and contents of ethylene is 0.8mol% is dissolved in toluene (ethylene
Base silicone oil and toluene mass ratio are 1:5), ionic liquid is added, AIBN (vinyl silicone oil, ionic liquid and AIBN is then added
Mass ratio be 100:5:1), stir 12h at 65 DEG C, nitrogen protection, toluene evaporation, after be cooled by water and be back to reaction and hold
The reaction product of vinyl silicone oil and ionic liquid is cleaned 3 times with ethyl alcohol, then to guarantee that toluene dosage is basically unchanged by device
By product, dry 2h, obtained vinyl silicone oil are grafted 1- allyl -3- methylimidazole bromide 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 is added and is grafted 1- allyl -3- methylimidazole bromide, is eventually adding 2,5- dimethyl -2,5- di-t-butyl peroxide
Change hexane, be uniformly mixed, rubber compound is vulcanized using vulcanizing press, and conditions of vulcanization is 160 DEG C × 20min, and it is multiple that silicon rubber is made
Condensation material.The mechanical property of silicon rubber composite material, surface resistivity and volume resistivity are as shown in table 1.
Embodiment 5
Silicon rubber/ionic liquid composite material each group distribution ratio of long-acting antistatic are as follows:
The vinyl silicone oil that viscosity is 200mPas and contents of ethylene is 0.8mol% is dissolved in toluene (ethylene
Base silicone oil and toluene mass ratio are 1:5), ionic liquid is added, AIBN (vinyl silicone oil, ionic liquid and AIBN is then added
Mass ratio be 100:5:1), stirred at 65 DEG C for 24 hours, nitrogen protection, toluene evaporation, after be cooled by water be back to reaction hold
The reaction product of vinyl silicone oil and ionic liquid is cleaned 3 times with ethyl alcohol, then to guarantee that toluene dosage is basically unchanged by device
By product, dry 2h, obtained vinyl silicone oil are grafted 1- allyl -3- methylimidazole bromide 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 is added and is grafted 1- allyl -3- methylimidazole bromide, is eventually adding 2,5- dimethyl -2,5- di-t-butyl
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
Silicon rubber/ionic liquid composite material each group distribution ratio of long-acting antistatic are as follows:
The vinyl silicone oil that viscosity is 200mPas and contents of ethylene is 0.8mol% is dissolved in toluene (ethylene
Base silicone oil and toluene mass ratio are 1:5), ionic liquid is added, AIBN (vinyl silicone oil, ionic liquid and AIBN is then added
Mass ratio be 100:2.5:1), stir 12h at 65 DEG C, nitrogen protection, toluene evaporation, after be cooled by water and be back to reaction and hold
The reaction product of vinyl silicone oil and ionic liquid is cleaned 3 times with ethyl alcohol, then to guarantee that toluene dosage is basically unchanged by device
By product, dry 2h, obtained vinyl silicone oil are grafted 1- allyl -3- methylimidazole bromide 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 is added and is grafted 1- allyl -3- methylimidazole bromide, is eventually adding 2,5- dimethyl -2,5- di-t-butyl peroxide
Change hexane, be uniformly mixed, rubber compound is vulcanized using vulcanizing press, and conditions of vulcanization is 160 DEG C × 20min, and it is multiple that silicon rubber is made
Condensation material.The mechanical property of silicon rubber composite material, surface resistivity and volume resistivity are as shown in table 1.
Embodiment 7
Silicon rubber/ionic liquid composite material each group distribution ratio of long-acting antistatic are as follows:
The vinyl silicone oil that viscosity is 200mPas and contents of ethylene is 0.8mol% is dissolved in toluene (ethylene
Base silicone oil and toluene mass ratio are 1:5), ionic liquid is added, AIBN (vinyl silicone oil, ionic liquid and AIBN is then added
Mass ratio be 100:2.5:1), stir 12h at 65 DEG C, nitrogen protection, toluene evaporation, after be cooled by water and be back to reaction and hold
The reaction product of vinyl silicone oil and ionic liquid is cleaned 3 times with ethyl alcohol, then to guarantee that toluene dosage is basically unchanged by device
By product, dry 2h, obtained vinyl silicone oil are grafted 1- allyl -3- methylimidazole bromide 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 is added and is grafted 1- allyl -3- methylimidazole bromide, is 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
Silicon rubber/ionic liquid composite material each group distribution ratio of long-acting antistatic are as follows:
The vinyl silicone oil that viscosity is 200mPas and contents of ethylene is 0.8mol% is dissolved in toluene (ethylene
Base silicone oil and toluene mass ratio are 1:5), ionic liquid 1- allyl -3- methylimidazole villaumite is added, AIBN (second is then added
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, after be cooled by water and be back to reaction vessel, to guarantee that toluene dosage is basically unchanged, by the anti-of vinyl silicone oil and ionic liquid
Product is answered to be cleaned 3 times with ethyl alcohol, then dry 2h, obtained vinyl silicone oil are grafted 1- allyl-in 100 DEG C of baking ovens by product
3- methylimidazole villaumite.
First methyl vinyl silicone rubber, gas-phase silica and hydroxy silicon oil are kneaded in rubber mixing mill uniformly, then
Vinyl silicone oil is added and is grafted 1- allyl -3- methylimidazole villaumite, is eventually adding 2,5- dimethyl -2,5- di-t-butyl peroxide
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
Silicon rubber/ionic liquid composite material each group distribution ratio of long-acting antistatic are as follows:
The vinyl silicone oil that viscosity is 200mPas and contents of ethylene is 0.8mol% is dissolved in toluene (ethylene
Base silicone oil and toluene mass ratio are 1:5), ionic liquid 1- allyl -3- methylimidazole acetate is added, AIBN is then added
(mass ratio of vinyl silicone oil, ionic liquid and AIBN is 100:2.5:1), stirs 12h, nitrogen protection, toluene at 65 DEG C
Evaporation, after be cooled by water and be back to reaction vessel, to guarantee that toluene dosage is basically unchanged, by vinyl silicone oil and ionic liquid
Reaction product is cleaned 3 times with ethyl alcohol, and then by product, dry 2h, obtained vinyl silicone oil are grafted 1- allyl 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 is added and is grafted 1- allyl -3- methylimidazole bromide, is eventually adding 2,5- dimethyl -2,5- di-t-butyl peroxide
Change hexane, be uniformly mixed, rubber compound is vulcanized using vulcanizing press, and conditions of vulcanization is 160 DEG C × 20min, and it is multiple that silicon rubber is made
Condensation material.The mechanical property of silicon rubber composite material, surface resistivity and volume resistivity are as shown in table 1.
Embodiment 10
Silicon rubber/ionic liquid composite material each group distribution ratio of long-acting antistatic are as follows:
The vinyl silicone oil that viscosity is 200mPas and contents of ethylene is 0.8mol% is dissolved in toluene (ethylene
Base silicone oil and toluene mass ratio are 1:5), ionic liquid 1- vinyl -3- butyl imidazole villaumite is added, AIBN (second is then added
The mass ratio of alkenyl silicone oil, ionic liquid and AIBN is 100:2.5:1), it is stirred at 65 DEG C for 24 hours, nitrogen protection, toluene steams
Hair, after be cooled by water and be back to reaction vessel, to guarantee that toluene dosage is basically unchanged, by the anti-of vinyl silicone oil and ionic liquid
Product is answered to be cleaned 3 times with ethyl alcohol, then dry 2h, obtained vinyl silicone oil are grafted 1- vinyl-in 100 DEG C of baking ovens by product
3- butyl imidazole villaumite.
First methyl vinyl silicone rubber, gas-phase silica and hydroxy silicon oil are kneaded in rubber mixing mill uniformly, then
Vinyl silicone oil is added and is grafted 1- vinyl -3- butyl imidazole villaumite, is eventually adding 2,5- dimethyl -2,5- di-t-butyl peroxide
Change hexane, be uniformly mixed, rubber compound is vulcanized using vulcanizing press, and conditions of vulcanization is 160 DEG C × 20min, and it is multiple that silicon rubber is made
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- allyl -3- methylimidazole bromide
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 that vinyl silicone oil is grafted 1- allyl -3- methylimidazole bromide increases
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
It applies 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- allyl -3- methylimidazole 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 decline causes vinyl silicone oil to be grafted 1- allyl -3- methylimidazole bromide since reinforcing agent dosage increases in composite material
Ion transport in silicone rubber matrix reduces, thus the resistivity of composite material increases.In embodiment 5, when using precipitating
When white carbon black replaces gas-phase silica, the tensile strength and elongation at break of composite material reduce, and change in resistance is little.It is real
It applies in example 6, increases the proportion of vinyl silicone oil and 1- allyl -3- methylimidazole bromide, i.e. 1- allyl -3- methylimidazole bromine
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 is unobvious.Embodiment 8~10
In, 1- allyl -3- methylimidazole villaumite, 1- allyl -3- methylimidazole acetate and 1- vinyl -3- butyl is respectively adopted
Imidazoles villaumite replaces 1- allyl -3- methylimidazole bromide, it is found that the change in resistance of composite material is little, all meet antistatic
Performance requirement.In Examples 1 to 10, composite material park 1 year after surface resistivity and volume resistivity and preparation initial stage
It compares, amplitude of variation very little, is 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 usually conductive filler such as carbon black, carbon nanotube, the graphene for adding black
Deng, often will cause color and transparency of silicon rubber etc. change, limit the use scope of conductive silicon rubber.And add silver powder
Or the metal-powders such as copper powder will increase dramatically the density of silicon rubber into silicon rubber, reduce the transparency of silicon rubber, and compound
Material is in long-time use process, as the oxidation of metal-powder causes the antistatic property of silicon rubber or electric conductivity significant
Decline.Ionic liquid is directly added in silicon rubber, although the antistatic property of rubber increases, ionic liquid be will 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
Has long-acting antistatic.Because the continuous decrease of existing antistatic silicone rubber product antistatic property, will lead to product in power
It learns in the good situation of property retention, due to losing antistatic property, must be replaced in advance on various electronic and electrical equipments.
Silicon rubber/ionic liquid composite material the mechanical property and antistatic property of long-acting antistatic of the present invention are good, and antistatic property
Can for a long time holdings in (1 year) stabilization, can significantly extend the service life of antistatic silicone rubber product.The present invention simultaneously
Mechanical property, color and the transparency of gained composite material (silicon rubber) are not influenced substantially by 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 (7)
1. silicon rubber/ionic liquid composite material of long-acting antistatic, which is characterized in that by percentage to the quality, composite material
Raw material composition are as follows:
The vinyl silicone oil grafting ion liquid is prepared via a method which: in organic solvent by vinyl silicone oil dissolution,
Then ionic liquid is added, adds initiator A IBN, nitrogen protection, stir 12 at 60~80 DEG C~for 24 hours, by vinyl silicon
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；
The silicon rubber is one of dimethyl silicone rubber, methyl vinyl silicone rubber, methyl phenyl vinyl silicone rubber
Or a variety of mixtures；
The ionic liquid is 1- allyl -3- methylimidazole bromide, 1- allyl -3- methylimidazole acetate, 1- allyl
One of base -3- methylimidazole villaumite and 1- vinyl -3- butyl imidazole villaumite or a variety of mixtures；
The crosslinking agent be 2,5- dimethyl -2,5- di-t-butyl hexane peroxide, peroxidating bis- (2,4 dichloro benzene formyls),
One or more mixtures of cumyl peroxide and dibenzoyl peroxide.
2. silicon rubber/ionic liquid composite material of long-acting antistatic according to claim 1, which is characterized in that reinforcement
Agent is one of precipitated silica and gas-phase silica or a variety of mixtures.
3. silicon rubber/ionic liquid composite material of long-acting antistatic according to claim 1, which is characterized in that structure
Controlling agent is one of hydroxy silicon oil and diphenyl silanediol or a variety of mixtures.
4. silicon rubber/ionic liquid composite material of long-acting antistatic according to claim 1, which is characterized in that described
The viscosity of vinyl silicone oil is 200~1000mPas, and contents of ethylene is 0.8~1.9mol%.
5. silicon rubber/ionic liquid composite material of long-acting antistatic according to claim 1, which is characterized in that described
Organic solvent is one of toluene, dimethylbenzene, petroleum ether, methyl ethyl ketone, carbon tetrachloride or a variety of mixtures；Control second
The mass ratio of alkenyl silicone oil and organic solvent is 1:4~1:8.
6. silicon rubber/ionic liquid composite material of long-acting antistatic according to claim 1, which is characterized 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。
7. silicon rubber/ionic liquid composite material preparation method of any one of the claim 1-6 long-acting antistatic, special
Sign is: adjusting open mill roll spacing to 1~2mm, silicon rubber is first added, then reinforcing agent and constitution controller is added in packet roller, mix
It closes uniformly, vinyl silicone oil grafting ion liquid is added later, be eventually adding crosslinking agent, be kneaded uniformly, clot slice, silicon rubber
Rubber compound vulcanizes on vulcanizing press, and curing temperature is 160~200 DEG C, and vulcanization time is 5~20min.
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| US20210363326A1 (en) * | 2020-05-22 | 2021-11-25 | P.T. Medisafe Technologies | Synthetic rubber latex compositions with ionic liquid for elastomeric gloves |
| CN112608689B (en) * | 2020-12-03 | 2022-05-20 | 浙江工业大学 | Antistatic organic silicon pressure-sensitive adhesive containing electron transport material and preparation method thereof |
| CN114479473A (en) * | 2022-01-24 | 2022-05-13 | 镇江高美新材料有限公司 | Antistatic liquid silicone rubber and preparation method thereof |
| CN115044045A (en) * | 2022-06-24 | 2022-09-13 | 上海睿思畅科技发展有限公司 | Silicon-containing ionic liquid flame retardant and preparation method thereof |
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