CN106009424A - Preparation method of grapheme/fluoroether rubber modified by covalent bond of fluorine-containing ionic liquid - Google Patents
Preparation method of grapheme/fluoroether rubber modified by covalent bond of fluorine-containing ionic liquid Download PDFInfo
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Abstract
The invention relates to grapheme/fluoroether rubber modified by a covalent bond of fluorine-containing ionic liquid, and a preparation method of the grapheme/fluoroether rubber. A chemical reaction between organic functional groups is utilized to enable ionic liquid to be grafted on the surface of graphite oxide, thermal recovery is performed to obtain functional filler, and the filler fluoroether raw rubber and a compounding agent are mixed, vulcanized and molded to obtain a final product. The grapheme/fluoroether rubber effectively overcomes the defects that grapheme can easily self-aggregate and the compatibility with rubber molecules is poor, and the fluoroether rubber filled with the functional grapheme provided by the invention has excellent mechanical properties, friction resistance, wear resistance, and high temperature resistance; moreover, the preparation method is easy and simple, and has a good application prospect.
Description
Technical field
The present invention relates to Graphene and fluorubber field, particularly to a kind of fluoride ion liquid covalent bond
The preparation method of the Graphene/fluoroether rubber modified.
Background technology
Fluoroether rubber is a kind of containing a large amount of carbon fluorine and the high molecular polymer of fluoroalkyl ether molecular structure.
Because having high-low temperature resistant, powerful oxidation corrosion resistance agent and the resistant to many chemical mediator performance of excellence, by as extreme
Under the conditions of encapsulant use.Filler is the important component in fluoroether rubber, the filler of excellent performance
The performance of fluoroether rubber material can be improved to a certain extent.Tradition fluoroether rubber system uses white carbon black to make
For filler, loading is big and shortage electricity, calorifics etc. is functional, cannot meet special seal condition
Performance requirement to material.Therefore, a kind of new function filler of design improves fluoroether rubber performance becomes
It is badly in need of.
Graphene is a kind of emerging two-dimensional sheet carbon nanomaterial, and density is low, specific surface area is big, power
, electricity and thermal property are excellent, have a good application prospect.But easily self aggregation and rubber
Deng defects such as macromolecular material poor compatibility, make Graphene be filled directly in elastomeric material and be difficult to reach
Estimated performance.For solving an above-mentioned difficult problem, some researcheres use the method modified graphene that surface is modified,
As Jia Hongbing et al. utilizes polyvinyl pyrrolidone modified graphene oxide filled rubber material, improve
The thermal conductivity coefficient of rubber and mechanical property (Chinese patent, the patent No.: CN201510025703.4)；
Wu et al. uses silane coupler surface to modify graphene oxide, and the filler obtained can improve rubber
Crosslink density, and strengthen mechanical property and gas barrier property (Jinrong Wu, the Guangsu of rubber
Huang,Hui Li,et al.Enhanced mechanical and gas barrier properties of
rubber nanocomposites with surface functionalized graphene oxide at low
content[J].Polymer,2013,54:1930-1937).It should be noted that in these reports and adopt
Matrix be the glue kinds such as natural rubber, character and fluoroether rubber difference are relatively big, and the adding of fluoroether rubber
Work and use temperature are far above natural rubber, and most Organic substance has decomposed in this temperature, decomposes and produces
Raw gaseous impurity can make rubber be internally generated loose structure, affects rubber performance.It is thus desirable to find
A kind of high temperature resistant and have surface activity special organic matter modified Graphene fill fluoroether rubber.
Ionic liquid be a kind of stable chemical nature, high temperature resistant, have organic cation and inorganic the moon from
The room temperature molten salt of minor structure.Exist between the material with carbon elements such as the cationic structural of ionic liquid and Graphene
Physical interaction power, makes ionic liquid can be adsorbed in graphenic surface, improves the performance of Graphene.
Jia Hongbing et al. reports one and utilizes ball milling to make non-covalent bond between ionic liquid with graphene oxide be combined
The method of surface modification graphene oxide filling natural rubber (Chinese patent, the patent No.:
CN201310035966.4).But the physics phase between this method intermediate ion liquid with graphene oxide
Interreaction force is more weak, and the structure that surface is modified easily is destroyed, and graphene oxide does not carry out follow-up going back
Former, make the carrier performance after modification be affected.For solving the problems referred to above, a kind of ionic liquid is proposed
The new preparation process of covalent bond grapheme modified filling fluoroether rubber is particularly significant.
Summary of the invention
It is an object of the invention to overcome the above-mentioned deficiency of prior art, it is provided that a kind of fluoride ion liquid
The preparation method of Graphene/fluoroether rubber that covalent bond is modified, the Graphene that the method prepares/fluorine ether
Rubber effectively overcomes the easy self aggregation of Graphene and the defect with rubber molecule poor compatibility, utilizes this
Bright functional graphene has good mechanical property, rub resistance abrasion as the fluoroether rubber that filler is filled
Performance, resistance to elevated temperatures, and preparation method of the present invention is simple, has a good application prospect.
The above-mentioned purpose of the present invention is mainly achieved by following technical solution:
The preparation method of Graphene/fluoroether rubber that a kind of fluoride ion liquid covalent bond is modified, including such as
Lower step:
(1), fluoride ion liquid, graphite oxide and catalyst being mixed in organic solvent, water-bath surpasses
Sonication is dispersed to graphite oxide, carries out low-temp reaction afterwards, obtain fluorine-containing in nitrogen atmosphere
Ionic liquid grafting graphite oxide；Described fluoride ion liquid with the mass ratio of graphite oxide is: 1:
0.2～5；
(2), fluoride ion liquid graft graphite oxide is carried out reduction treatment, obtain fluoride ion liquid
Graft grapheme；
(3), using fluoride ion liquid graft Graphene as functional stuffing and fluoroether rubber rubber, suction acid
Agent, vulcanizing agent and auxiliary curing agent mixing, and carry out hot-press vulcanization and post vulcanization respectively, obtain graphite
Alkene/fluoroether rubber, wherein hot-press vulcanization temperature is 150 DEG C-200 DEG C, and sulfide stress is
5MPa-20MPa, the time is 5-30min；Post vulcanization temperature is 210 DEG C-260 DEG C, and the time is
5-24h。
In the preparation method of the Graphene/fluoroether rubber of above-mentioned fluoride ion liquid covalent bond modification, step
Suddenly in (1), fluoride ion liquid is 1-amine propyl group-3-Methylimidazole. hexafluorophosphate, 1-amine propyl group-3-
Methyl imidazolium tetrafluoroborate, 1-amine propyl imidazole-3-Methylimidazole. fluoroform sulfimide salt, 1-carboxylic
Propyl group-3-methyl imidazolium tetrafluoroborate, 1-carboxylic propyl group-3-Methylimidazole. hexafluorophosphate or 1-carboxylic propyl group
One in-3-Methylimidazole. fluoroform sulfimide salt or combination.
In the preparation method of the Graphene/fluoroether rubber of above-mentioned fluoride ion liquid covalent bond modification, step
Suddenly in (1) catalyst be N, N'-Dicyclohexylcarbodiimide or to the one in dimethylamino naphthyridine or
Combination；In described step (1), organic solvent is ethanol, acetone, oxolane, N, N-dimethyl methyl
Any one in amide or N-Methyl pyrrolidone.
In the preparation method of the Graphene/fluoroether rubber of above-mentioned fluoride ion liquid covalent bond modification, step
Suddenly in (1), the water bath sonicator process time is 1-4h；In described step (1), reaction temperature is 40 DEG C-60 DEG C,
Response time is 6-48h.
In the preparation method of the Graphene/fluoroether rubber of above-mentioned fluoride ion liquid covalent bond modification, step
Suddenly after (1) carries out low-temp reaction in nitrogen atmosphere, product is purified process, removes not
Participate in ionic liquid and the catalyst of reaction, product drying after purification is processed, wherein purification process
Method is the one in centrifuge washing, filtration under diminished pressure washing or decompression distillation or combination.
In the preparation method of the Graphene/fluoroether rubber of above-mentioned fluoride ion liquid covalent bond modification, step
Suddenly in (2), the reduction temperature of reduction treatment is 150 DEG C-300 DEG C, and heat treatment time is 1-6h.
In the preparation method of the Graphene/fluoroether rubber of above-mentioned fluoride ion liquid covalent bond modification, step
Suddenly in (3), the mass fraction of each component is as follows:
In the preparation method of the Graphene/fluoroether rubber of above-mentioned fluoride ion liquid covalent bond modification, institute
Stating acid-acceptor is the one in magnesium oxide, calcium oxide, calcium hydroxide, zinc oxide or lead oxide or combination.
In the preparation method of the Graphene/fluoroether rubber of above-mentioned fluoride ion liquid covalent bond modification, institute
Stating vulcanizing agent is 2,5-dimethyl-2,5-two (t-butylperoxy) hexane, cumyl peroxide, N, N-
One in double Cortex Cinnamomis fork-1,6-hexamethylene diamine, hydroquinone or dibenzoyl peroxide or combination.
In the preparation method of the Graphene/fluoroether rubber of above-mentioned fluoride ion liquid covalent bond modification, institute
Stating auxiliary curing agent is triallylcyanurate, Triallyl isocyanurate, divinylbenzene, neighbour
In dially phthalate, trimethylolpropane tris first acrylate or ethylene glycol dimethacrylate
One or combination.
The present invention compared with prior art has the advantages that
(1), the present invention utilizes the chemical reaction between organo-functional group to make ionic liquid graft on graphite oxide
Surface, and carry out thermal reduction and obtain functional stuffing, by filler and fluorine ether rubber and compounding ingredient mixes, sulfur
Chemical conversion type obtains end product, this Graphene/fluoroether rubber effectively overcome the easy self aggregation of Graphene and with
The defect of rubber molecule poor compatibility；
(2), the fluoroether rubber product using the inventive method to prepare has the mechanical property of excellence, antifriction
Wipe polishing machine and resistance to elevated temperatures, the application needs of space industry can be met；
(3), each component and content in course of reaction and rubber preparation process are carried out preferably, together by the present invention
Time preparation process condition is optimized design so that the functional stuffing productivity for preparing is high, purity
Height, has more excellent combination property；
(4), preparation method of the present invention is simple, it is easy to accomplish, the method can be with further genralrlization
To other filler systems, application prospect is good.
Accompanying drawing explanation
Fig. 1 is the preparation flow schematic diagram in the preparation method step 1 of Graphene/fluoroether rubber of the present invention；
Fig. 2 is the preparation flow schematic diagram in the preparation method step 2 of Graphene/fluoroether rubber of the present invention；
Fig. 3 is the graphite oxide structural formula of the ionic liquid grafting that the embodiment of the present invention 1 prepares；
Fig. 4 is the graphene-structured formula of the ionic liquid grafting that the embodiment of the present invention 1 prepares；
Fig. 5 is that graphite oxide in the embodiment of the present invention 1, the graphite oxide of ionic liquid grafting and heat are gone back
The infrared spectrum curve chart of the Graphene of former ionic liquid grafting；
Fig. 6 is graphite oxide in the embodiment of the present invention 1, the graphite oxide of ionic liquid grafting and middle heat
The x-ray photoelectron spectrum curve figure of Graphene after reduction ionic liquid grafting；
Fig. 7 is that graphite oxide in the embodiment of the present invention 1, the graphite oxide of ionic liquid grafting and heat are gone back
Graphene thermogravimetric curve figure in nitrogen atmosphere after the grafting of former ionic liquid.
Fig. 8 is thermal reduction ionic liquid grafting in the embodiment of the present invention 1, embodiment 4 and embodiment 5
Rear Graphene thermogravimetric curve comparison diagram under air conditions；
Fig. 9 is that the fluoroether rubber prepared in the embodiment of the present invention 4, embodiment 6 and embodiment 7 is at sky
Thermogravimetric curve comparison diagram in gas atmosphere；
Figure 10 is the scanning electron microscopic picture of the fluoroether rubber stretching fracture of preparation in the embodiment of the present invention 7.
Detailed description of the invention
The present invention is described in further detail with specific embodiment below in conjunction with the accompanying drawings:
The preparation method of Graphene/fluoroether rubber that fluoride ion liquid covalent bond of the present invention is modified, specifically
Comprise the steps:
(1), fluoride ion liquid graft graphite oxide
Fluoride ion liquid, graphite oxide and catalyst are mixed in organic solvent, at water bath sonicator
1-4h is dispersed to graphite oxide for reason, carries out low-temp reaction, reaction temperature afterwards in nitrogen atmosphere
Being 40 DEG C-60 DEG C, the response time is 6-48h.Product is purified process, and removing has neither part nor lot in
The ionic liquid of reaction and catalyst, process sample drying after purification, obtain fluoride ion liquid
Grafting graphite oxide, wherein purification treating method is centrifuge washing, filtration under diminished pressure washing or decompression distillation
In one or combination.Described fluoride ion liquid with the mass ratio of graphite oxide is: 1:0.2～5.
Fluoride ion liquid is 1-amine propyl group-3-Methylimidazole. hexafluorophosphate, 1-amine propyl group-3-methyl miaow
Azoles tetrafluoroborate, 1-amine propyl imidazole-3-Methylimidazole. fluoroform sulfimide salt, 1-carboxylic propyl group-3-
Methyl imidazolium tetrafluoroborate, 1-carboxylic propyl group-3-Methylimidazole. hexafluorophosphate or 1-carboxylic propyl group-3-methyl
One in imidazoles fluoroform sulfimide salt or combination.
Catalyst is N, N'-Dicyclohexylcarbodiimide or to the one in dimethylamino naphthyridine or combination.
Organic solvent is ethanol, acetone, oxolane, N,N-dimethylformamide or N-methylpyrrole
Any one in alkanone.
It is illustrated in figure 1 the preparation flow in the preparation method step 1 of Graphene/fluoroether rubber of the present invention
Schematic diagram, wherein A is COOH or NH2；X is (CF3SO2)2N、—BF4Or PF6；
M is COO or CO-NH.
(2), the reduction of fluoride ion liquid graft graphite oxide
Fluoride ion liquid graft graphite oxide is carried out reduction treatment, obtains fluoride ion liquid graft
Graphene；The reduction temperature of reduction treatment is 150 DEG C-300 DEG C, and heat treatment time is 1-6h.
It is illustrated in figure 2 the preparation flow in the preparation method step 2 of Graphene/fluoroether rubber of the present invention
Schematic diagram, wherein X is (CF3SO2)2N、—BF4Or PF6；M is COO or CO-NH
One.
(3), the mixing of functional graphene and fluoroether rubber and molding
Using fluoride ion liquid graft Graphene as functional stuffing and fluoroether rubber rubber, acid-acceptor, sulfur
Agent and auxiliary curing agent mixing, and carry out hot-press vulcanization and post vulcanization respectively, obtain Graphene/fluorine ether
Rubber.
The mass fraction of each component is as follows:
Wherein hot-press vulcanization temperature is 150 DEG C-200 DEG C, and sulfide stress is 5MPa-20MPa, and the time is
5-30min；Post vulcanization temperature is 210 DEG C-260 DEG C, and the time is 5-24h.
Acid-acceptor is the one in magnesium oxide, calcium oxide, calcium hydroxide, zinc oxide or lead oxide or group
Close.
Vulcanizing agent be 2,5-dimethyl-2,5-two (t-butylperoxy) hexane, cumyl peroxide,
One in N, N-double Cortex Cinnamomi fork-1,6-hexamethylene diamine, hydroquinone or dibenzoyl peroxide or combination.
Auxiliary curing agent be triallylcyanurate, Triallyl isocyanurate, divinylbenzene,
Diallyl phthalate, trimethylolpropane tris first acrylate or ethylene glycol dimethacrylate
In one or combination.
Embodiment 1
1. ionic liquid grafting graphite oxide
Weigh graphite oxide 1g, 1-amine propyl group-3-Methylimidazole. fluoroform sulfimide salt 1g, N, N'-
Dicyclohexylcarbodiimide 1g, to dimethylamino naphthyridine 50mg, weighing 200mL has N, N-dimethyl methyl
Amide is placed in flask.After water bath sonicator processes 2h, temperature control 50 DEG C reaction 24h in nitrogen atmosphere.Right
Product uses centrifuge washing to be purified process, removes unreacted ionic liquid and catalyst,
Vacuum drying product.
It is illustrated in figure 3 the graphite oxide knot of the ionic liquid grafting that the embodiment of the present invention 1 prepares
Structure formula.
2. the reduction of ionic liquid grafting graphite oxide
Weigh the graphite oxide 1g after grafting to be placed in crucible, heat treatment 1h under the conditions of 230 DEG C of baking oven,
Obtain the oxidoreduction functional graphene product of fluffy cotton-shaped Ionic Liquid Modified.
It is illustrated in figure 4 the graphene-structured of the ionic liquid grafting that the embodiment of the present invention 1 prepares
Formula.
3. the mixing of functional graphene and fluoroether rubber and molding
Weigh 100g fluoroether rubber rubber, 1g functional graphene, 3g magnesium oxide, 4g 2,5-dimethyl-2,5-
Two (t-butylperoxy) hexane, 4g Triallyl isocyanurate, on a mill until mix homogeneously.Will
Mix products 175 DEG C, under the conditions of 10MPa after sulfidization molding 20min, at 220 DEG C of post vulcanization 5h,
Obtain rubber product.
It is illustrated in figure 5 graphite oxide in the embodiment of the present invention 1, the graphite oxide of ionic liquid grafting
And the infrared spectrum of the rear ink alkene of thermal reduction ionic liquid grafting；Fig. 6 is oxygen in the embodiment of the present invention 1
After the graphite oxide of graphite, ionic liquid grafting and the grafting of thermal reduction ionic liquid, the X of Graphene penetrates
Photoelectron spectra；Fig. 7 is graphite oxide in the embodiment of the present invention 1, the oxidation of ionic liquid grafting
Graphene thermogravimetric curve figure in nitrogen atmosphere after graphite and the grafting of thermal reduction ionic liquid.Fig. 8
Bent for Graphene thermogravimetric under air conditions after thermal reduction ionic liquid grafting in the embodiment of the present invention 1
Line chart.
As seen from the figure, the present invention is to native oxide graphite, the graphite oxide of ionic liquid grafting and heat also
The Graphene of former ionic liquid grafting carries out element, group and hot analysis and characterization, it was demonstrated that ionic liquid
Successfully it is grafted on graphenic surface and reduction effective to graphite oxide.
In the inventive method embodiment 1, the hot strength of the fluoroether rubber of preparation is 11.8MPa, hardness
For 60.1Shore A, elongation rate of tensile failure is 290%.The fluorine ether of preparation in the inventive method embodiment 1
Rubber, under 5N load, 6cm/s rate conditions, uses rubbing after ball disc type instrument friction 20min
Wiping coefficient is 1.36, and wear rate is 2.78 × 10-7cm3/Nm。
Embodiment 2
1. ionic liquid grafting graphite oxide
Weigh graphite oxide 1g, 1-amine propyl group-3-methyl imidazolium tetrafluoroborate 2g, N, N'-dicyclohexyl
Carbimide 1g, to dimethylamino naphthyridine 50mg, weighing 200mL has DMF to be placed in
In flask.After water bath sonicator processes 1h, temperature control 40 DEG C reaction 36h in nitrogen atmosphere.To product
Use centrifuge washing to be purified process, remove unreacted ionic liquid and catalyst, vacuum drying
Product.
2. the reduction of ionic liquid grafting graphite oxide
Weigh the graphite oxide 1g after grafting to be placed in crucible, heat treatment 1h under the conditions of 250 DEG C of baking oven,
Obtain the oxidoreduction functional graphene product of fluffy cotton-shaped Ionic Liquid Modified.
3. the mixing of functional graphene and fluoroether rubber and molding
Weigh 100g fluoroether rubber rubber, 1g functional graphene, 4g magnesium oxide, 3g 2,5-dimethyl-2,5-
Two (t-butylperoxy) hexane, 3g Triallyl isocyanurate, on a mill until mix homogeneously.Will
Mix products 155 DEG C, under the conditions of 20MPa after sulfidization molding 20min, at 250 DEG C of post vulcanization 5h,
Obtain rubber product.
In the inventive method embodiment 1, the hot strength of the fluoroether rubber of preparation is 11.5MPa, and hardness is
59.8Shore A, elongation rate of tensile failure is 287%.
Embodiment 3
1. ionic liquid grafting graphite oxide
Weigh graphite oxide 1g, 1-amine propyl group-3-Methylimidazole. hexafluorophosphate 0.5g, N, N'-bis-hexamethylene
Base carbimide 1g, to dimethylamino naphthyridine 50mg, weighing 200mL has DMF to put
In flask.After water bath sonicator processes 4h, temperature control 60 DEG C reaction 6h in nitrogen atmosphere.Reaction is produced
Thing uses centrifuge washing to be purified process, removes unreacted ionic liquid and catalyst, and vacuum is done
Dry product.
2. the reduction of the graphite oxide of ionic liquid grafting
Weigh the graphite oxide 1g after grafting to be placed in crucible, heat treatment 6h under the conditions of 210 DEG C of baking oven,
Obtain the oxidoreduction functional graphene product of fluffy cotton-shaped Ionic Liquid Modified.
3. the mixing of functional graphene and fluoroether rubber and molding
Weigh 100g fluoroether rubber rubber, 1g functional graphene, 5g magnesium oxide, 3g 2,5-dimethyl-2,5-
Two (t-butylperoxy) hexane, 5g Triallyl isocyanurate, on a mill until mix homogeneously.Will
Mix products 165 DEG C, under the conditions of 15MPa after sulfidization molding 30min, at 240 DEG C of post vulcanization 10h,
Obtain rubber product.
In the inventive method embodiment 1, the hot strength of the fluoroether rubber of preparation is 11.3MPa, and hardness is
59.5Shore A, elongation rate of tensile failure is 281%.
Embodiment 4
1. ionic liquid grafting graphite oxide
Weigh graphite oxide 1g, 1-amine propyl group-3-Methylimidazole. fluoroform sulfimide salt 0.5g, N, N'-
Dicyclohexylcarbodiimide 1g, to dimethylamino naphthyridine 50mg, weighing 200mL has N, N-dimethyl methyl
Amide is placed in flask.After water bath sonicator processes 2h, temperature control 40 DEG C reaction 48h in nitrogen atmosphere.Right
Product uses centrifuge washing to be purified process, removes unreacted ionic liquid and catalyst,
Vacuum drying product.
2. the reduction of ionic liquid grafting graphite oxide
Weigh the graphite oxide 1g after grafting to be placed in crucible, heat treatment 2h under the conditions of 230 DEG C of baking oven,
Obtain the oxidoreduction functional graphene product of fluffy cotton-shaped Ionic Liquid Modified.
3. the mixing of functional graphene and fluoroether rubber and molding
Weigh 100g fluoroether rubber rubber, 1g functional graphene, 3g magnesium oxide, 2g 2,5-dimethyl-2,5-
Two (t-butylperoxy) hexane, 4g Triallyl isocyanurate, on a mill until mix homogeneously.Will
Mix products 190 DEG C, under the conditions of 5MPa after sulfidization molding 5min, at 210 DEG C of post vulcanization 24h,
Obtain rubber product.
If the Graphene that Fig. 8 is the thermal reduction ionic liquid grafting prepared in the embodiment of the present invention 4 is at air
Under the conditions of thermogravimetric curve figure.The fluoroether rubber of preparation heat in air atmosphere in the embodiment of the present invention 4
Weight curve is as shown in Figure 9.
In the inventive method embodiment 4, the hot strength of the fluoroether rubber of preparation is 12.3MPa, hardness
For 60.8Shore A, elongation rate of tensile failure is 284%.The fluorine ether of preparation in the inventive method embodiment 4
Rubber, under 5N load, 6cm/s rate conditions, uses rubbing after ball disc type instrument friction 20min
Wiping coefficient is 1.32, and wear rate is 2.63 × 10-7cm3/Nm。
Embodiment 5
1. ionic liquid grafting graphite oxide
Weigh graphite oxide 1g, 1-amine propyl group-3-Methylimidazole. fluoroform sulfimide salt 0.5g, N, N'-
Dicyclohexylcarbodiimide 1g, to dimethylamino naphthyridine 50mg, weighing 200mL has N, N-dimethyl methyl
Amide is placed in flask.After water bath sonicator processes 1h, temperature control 60 DEG C reaction 24h in nitrogen atmosphere.Right
Product uses centrifuge washing to be purified process, removes unreacted ionic liquid and catalyst,
Vacuum drying product.
2. the reduction of ionic liquid grafting graphite oxide
Weigh the graphite oxide 1g after grafting to be placed in crucible, heat treatment 6h under the conditions of 230 DEG C of baking oven,
Obtain the oxidoreduction functional graphene product of fluffy cotton-shaped Ionic Liquid Modified.
3. the mixing of functional graphene and fluoroether rubber and molding
Weigh 100g fluoroether rubber rubber, 1g functional graphene, 4g magnesium oxide, 6g 2,5-dimethyl-2,5-
Two (t-butylperoxy) hexane, 6g Triallyl isocyanurate, on a mill until mix homogeneously.Will
Mix products 180 DEG C, under the conditions of 10MPa after sulfidization molding 10min, at 260 DEG C of post vulcanization 8h,
Obtain rubber product.
After being illustrated in figure 8 in the embodiment of the present invention 5 grafting of thermal reduction ionic liquid, Graphene is at air
Under the conditions of thermogravimetric curve figure.
In the inventive method embodiment 5, the hot strength of the fluoroether rubber of preparation is 12.1MPa, and hardness is
61.0Shore A, elongation rate of tensile failure is 257%.
Embodiment 6
1. ionic liquid grafting graphite oxide
Weigh graphite oxide 1g, 1-amine propyl group-3-Methylimidazole. fluoroform sulfimide salt 0.5g, N, N'-
Dicyclohexylcarbodiimide 1g, to dimethylamino naphthyridine 50mg, weighing 200mL has N, N-dimethyl methyl
Amide is placed in flask.After water bath sonicator processes 3h, temperature control 50 DEG C reaction 36h in nitrogen atmosphere.Right
Product uses centrifuge washing to be purified process, removes unreacted ionic liquid and catalyst,
Vacuum drying product.
2. the reduction of ionic liquid grafting graphite oxide
Weigh the graphite oxide 1g after grafting to be placed in crucible, heat treatment 1h under the conditions of 280 DEG C of baking oven,
Obtain the oxidoreduction functional graphene product of fluffy cotton-shaped Ionic Liquid Modified.
3. the mixing of functional graphene and fluoroether rubber and molding
Weighing 100g fluoroether rubber rubber, 2g functional graphene, 4g calcium hydroxide, 3g peroxidating two are different
Propyl benzene alkane, 4g triallylcyanurate, on a mill until mix homogeneously.By mix products 180 DEG C,
Sulfidization molding 10min under the conditions of 20MPa, at 230 DEG C of post vulcanization 15h, obtains rubber product.
In the inventive method embodiment 6, the hot strength of the fluoroether rubber of preparation is 13.6MPa, and hardness is
63.1Shore A, elongation rate of tensile failure is 300%.The fluoroether rubber of preparation in the inventive method embodiment 6
Under 5N load, 6cm/s rate conditions, the coefficient of friction after employing ball disc type instrument friction 20min is
1.23, wear rate is 2.31 × 10-7cm3/Nm。
The fluoroether rubber of preparation thermogravimetric curve such as Fig. 5 institute in air atmosphere in the embodiment of the present invention 6
Show.
Embodiment 7
1. ionic liquid grafting graphite oxide
Weigh graphite oxide 1g, 1-amine propyl group-3-Methylimidazole. fluoroform sulfimide salt 0.5g, N, N'-
Dicyclohexylcarbodiimide 1g, to dimethylamino naphthyridine 50mg, weighing 200mL has N, N-dimethyl methyl
Amide is placed in flask.After water bath sonicator processes 2h, temperature control 40 DEG C reaction 48h in nitrogen atmosphere.Right
Product uses centrifuge washing to be purified process, removes unreacted ionic liquid and catalyst,
Vacuum drying product.
2. the reduction of ionic liquid grafting graphite oxide
Weigh the graphite oxide 1g after grafting to be placed in crucible, heat treatment 6h under the conditions of 170 DEG C of baking oven,
Obtain the oxidoreduction functional graphene product of fluffy cotton-shaped Ionic Liquid Modified.
3. the mixing of functional graphene and fluoroether rubber and molding
Weigh 100g fluoroether rubber rubber, 4g functional graphene, 3g magnesium oxide, 2g 2,5-dimethyl-2,5-
Two (t-butylperoxy) hexane, 4g Triallyl isocyanurate, on a mill until mix homogeneously.Will
Mix products 190 DEG C, under the conditions of 15MPa after sulfidization molding 20min, at 250 DEG C of post vulcanization 20h,
Obtain rubber product.
In the inventive method embodiment 7, the hot strength of the fluoroether rubber of preparation is 14.8MPa, and hardness is
66.0Shore A, elongation rate of tensile failure is 253%.The fluoroether rubber of preparation in the inventive method embodiment 7
Under 5N load, 6cm/s rate conditions, the coefficient of friction after employing ball disc type instrument friction 20min is
1.23, wear rate is 2.31 × 10-7cm3/Nm。
The fluoroether rubber of preparation thermogravimetric curve such as Fig. 9 institute in air atmosphere in the embodiment of the present invention 7
Show.In the embodiment of the present invention 7, the surface sweeping Electronic Speculum morphology characterization result of the fluoroether rubber stretching fracture of preparation is such as
Shown in Figure 10.
As seen from the figure, Graphene and the fluoroether rubber of thermal reduction ionic liquid grafting has good compatible
Property.
The above, the detailed description of the invention that only present invention is optimal, but protection scope of the present invention is also
Be not limited to this, any those familiar with the art in the technical scope that the invention discloses,
The change that can readily occur in or replacement, all should contain within protection scope of the present invention.
The content not being described in detail in description of the invention belongs to the known of professional and technical personnel in the field
Technology.
Claims (10)
1. the preparation method of the Graphene/fluoroether rubber of a fluoride ion liquid covalent bond modification, it is characterised in that: comprise the steps:
(1), fluoride ion liquid, graphite oxide and catalyst being mixed in organic solvent, water bath sonicator processes dispersed to graphite oxide, carries out low-temp reaction afterwards, obtain fluoride ion liquid graft graphite oxide in nitrogen atmosphere；Described fluoride ion liquid with the mass ratio of graphite oxide is: 1:0.2～5；
(2), fluoride ion liquid graft graphite oxide is carried out reduction treatment, obtain fluoride ion liquid graft Graphene；
(3), fluoride ion liquid graft Graphene is mixed as functional stuffing with fluoroether rubber rubber, acid-acceptor, vulcanizing agent and auxiliary curing agent, and carry out hot-press vulcanization and post vulcanization respectively, obtain Graphene/fluoroether rubber, wherein hot-press vulcanization temperature is 150 DEG C-200 DEG C, sulfide stress is 5MPa-20MPa, and the time is 5-30min；Post vulcanization temperature is 210 DEG C-260 DEG C, and the time is 5-24h.
The preparation method of Graphene/fluoroether rubber that a kind of fluoride ion liquid covalent bond the most according to claim 1 is modified, it is characterised in that: the one during fluoride ion liquid is 1-amine propyl group-3-Methylimidazole. hexafluorophosphate, 1-amine propyl group-3-methyl imidazolium tetrafluoroborate, 1-amine propyl imidazole-3-Methylimidazole. fluoroform sulfimide salt, 1-carboxylic propyl group-3-methyl imidazolium tetrafluoroborate, 1-carboxylic propyl group-3-Methylimidazole. hexafluorophosphate or 1-carboxylic propyl group-3-Methylimidazole. fluoroform sulfimide salt in described step (1) or combination.
The preparation method of Graphene/fluoroether rubber that a kind of fluoride ion liquid covalent bond the most according to claim 1 is modified, it is characterized in that: in described step (1), catalyst is N, N'-Dicyclohexylcarbodiimide or to the one in dimethylamino naphthyridine or combination；In described step (1), organic solvent is any one in ethanol, acetone, oxolane, N,N-dimethylformamide or N-Methyl pyrrolidone.
The preparation method of Graphene/fluoroether rubber that a kind of fluoride ion liquid covalent bond the most according to claim 1 is modified, it is characterised in that: in described step (1), the water bath sonicator process time is 1-4h；In described step (1), reaction temperature is 40 DEG C-60 DEG C, and the response time is 6-48h.
The preparation method of Graphene/fluoroether rubber that a kind of fluoride ion liquid covalent bond the most according to claim 1 is modified, it is characterized in that: after described step (1) carries out low-temp reaction in nitrogen atmosphere, product is purified process, remove ionic liquid and the catalyst having neither part nor lot in reaction, product drying after purification is processed, the one during wherein purification treating method is centrifuge washing, filtration under diminished pressure washing or decompression distillation or combination.
The preparation method of Graphene/fluoroether rubber that a kind of fluoride ion liquid covalent bond the most according to claim 1 is modified, it is characterised in that: in described step (2), the reduction temperature of reduction treatment is 150 DEG C-300 DEG C, and heat treatment time is 1-6h.
The preparation method of Graphene/fluoroether rubber that a kind of fluoride ion liquid covalent bond the most according to claim 1 is modified, it is characterised in that: in described step (3), the mass fraction of each component is as follows:
8. the preparation method of the Graphene/fluoroether rubber modified according to a kind of fluoride ion liquid covalent bond one of claim 1～7 Suo Shu, it is characterised in that: described acid-acceptor is the one in magnesium oxide, calcium oxide, calcium hydroxide, zinc oxide or lead oxide or combination.
9. the preparation method of the Graphene/fluoroether rubber modified according to a kind of fluoride ion liquid covalent bond one of claim 1～7 Suo Shu, it is characterized in that: described vulcanizing agent is 2,5-dimethyl-2,5-bis-(t-butylperoxy) hexane, cumyl peroxide, N, N-double Cortex Cinnamomi fork-1, the one in 6-hexamethylene diamine, hydroquinone or dibenzoyl peroxide or combination.
10. the preparation method of the Graphene/fluoroether rubber modified according to a kind of fluoride ion liquid covalent bond one of claim 1～7 Suo Shu, it is characterised in that: described auxiliary curing agent is the one in triallylcyanurate, Triallyl isocyanurate, divinylbenzene, diallyl phthalate, trimethylolpropane tris first acrylate or ethylene glycol dimethacrylate or combination.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101985354A (en) * | 2010-09-21 | 2011-03-16 | 中国科学院长春应用化学研究所 | Method for preparing ionic liquid functionalized graphene material |
| CN103102514A (en) * | 2013-01-30 | 2013-05-15 | 南京理工大学 | Ionic liquid modified graphene oxide/natural rubber vulcanized rubber and preparation method thereof |
| CN103626162A (en) * | 2012-08-27 | 2014-03-12 | 海洋王照明科技股份有限公司 | Preparation method of graphene |
| US20140275597A1 (en) * | 2013-03-15 | 2014-09-18 | Washington State University Research Foundation | Methods for producing functionalized graphenes |
| CN104893042A (en) * | 2015-05-26 | 2015-09-09 | 南京理工大学 | Rubber vulcanized rubber containing ionic liquid modified graphene oxide and preparation method of vulcanized rubber |
| CN105255073A (en) * | 2015-10-29 | 2016-01-20 | 中国航空工业集团公司北京航空材料研究院 | Graphene-containing wear-resisting fluororubber and preparation method thereof |
-
2016
- 2016-05-26 CN CN201610362804.5A patent/CN106009424B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101985354A (en) * | 2010-09-21 | 2011-03-16 | 中国科学院长春应用化学研究所 | Method for preparing ionic liquid functionalized graphene material |
| CN103626162A (en) * | 2012-08-27 | 2014-03-12 | 海洋王照明科技股份有限公司 | Preparation method of graphene |
| CN103102514A (en) * | 2013-01-30 | 2013-05-15 | 南京理工大学 | Ionic liquid modified graphene oxide/natural rubber vulcanized rubber and preparation method thereof |
| US20140275597A1 (en) * | 2013-03-15 | 2014-09-18 | Washington State University Research Foundation | Methods for producing functionalized graphenes |
| CN104893042A (en) * | 2015-05-26 | 2015-09-09 | 南京理工大学 | Rubber vulcanized rubber containing ionic liquid modified graphene oxide and preparation method of vulcanized rubber |
| CN105255073A (en) * | 2015-10-29 | 2016-01-20 | 中国航空工业集团公司北京航空材料研究院 | Graphene-containing wear-resisting fluororubber and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| P. TAMILARASAN等: "Amine-rich ionic liquid grafted graphene for sub-ambient carbon dioxide adsorption", 《RSC ADVANCES》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107828165A (en) * | 2017-11-21 | 2018-03-23 | 张文平 | A kind of silicon/fluorine ether/fluorine silicon composite rubber material and preparation method thereof |
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