CN106009424B - A kind of preparation method of graphene/fluoroether rubber of fluoride ion liquid covalent bond modification - Google Patents
A kind of preparation method of graphene/fluoroether rubber of fluoride ion liquid covalent bond modification Download PDFInfo
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- CN106009424B CN106009424B CN201610362804.5A CN201610362804A CN106009424B CN 106009424 B CN106009424 B CN 106009424B CN 201610362804 A CN201610362804 A CN 201610362804A CN 106009424 B CN106009424 B CN 106009424B
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Abstract
The present invention relates to graphene/fluoroether rubber of a kind of fluoride ion liquid covalent bond modification and preparation method thereof, ionic liquid is set to graft on graphite oxide surface using the chemical reaction between organo-functional group, and heat-treated to obtain functional stuffing, filler is mixed with fluorine ether rubber and compounding ingredient, sulfidization molding obtains final product, graphene/the fluoroether rubber effectively overcomes the easy self aggregation of graphene and the defects of with rubber molecule poor compatibility, there is good mechanical property by the use of the fluoroether rubber that functional graphene of the present invention is filled as filler, wear resistance, resistance to elevated temperatures；And preparation method of the present invention is simple and easy, has a good application prospect.
Description
Technical field
The present invention relates to graphene and fluorubber field, more particularly to a kind of graphite of fluoride ion liquid covalent bond modification
The preparation method of alkene/fluoroether rubber.
Background technology
Fluoroether rubber is a kind of high molecular polymer containing a large amount of carbon fluorine and fluoroalkyl ether molecular structure.It is excellent because having
High-low temperature resistant, powerful oxidation corrosion resistance agent and resistant to many chemical mediator performance, used as the encapsulant under extreme condition.Filler
It is the important component in fluoroether rubber, the filler of excellent performance can improve the performance of fluoroether rubber material to a certain extent.Pass
Fluoroether rubber system of uniting is using carbon black as filler, and loading is big and lacks the features such as electricity, calorifics, and it is special to have met
Performance requirement of the air-proof condition to material.Therefore, designing a kind of new function filler improves fluoroether rubber performance as being badly in need of.
Graphene is a kind of emerging two-dimensional sheet carbon nanomaterial, and density is low, specific surface area is big, mechanics, electricity and heat
Excellent performance is learned, is had a good application prospect.But the defects of easy self aggregation and rubber Polymer material poor compatibility,
Make graphene be filled directly into elastomeric material to be difficult to reach estimated performance.To solve above-mentioned problem, some researchers use table
The method modified graphene of face modification, as Jia Hongbing et al. utilizes polyvinyl pyrrolidone modified graphene oxide filled rubber material
Material, improve the thermal conductivity coefficient and mechanical property (Chinese patent, the patent No. of rubber：CN201510025703.4)；Wu et al. is adopted
With silane coupler surface modification graphene oxide, obtained filler can improve the crosslink density of rubber, and strengthen rubber
Mechanical property and gas barrier property (Jinrong Wu, Guangsu 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).Value
Obtain it is noted that the matrix used in these reports is the glue kind such as natural rubber, property and fluoroether rubber difference are larger, and fluorine ether
The processing of rubber and temperature in use are far above natural rubber, and most organic matters have decomposed in this temperature, gas caused by decomposition
Body impurity can make generation loose structure inside rubber, influence rubber performance.Therefore need to find a kind of high temperature resistant and there is surface
The grapheme modified filling fluoroether rubber of special organic matter of activity.
Ionic liquid is a kind of chemical property stabilization, high temperature resistant, the room with organic cation and inorganic anion structure
Warm fuse salt.Existing Physical interaction power, makes ionic liquid between the carbon materials such as the cationic structural and graphene of ionic liquid
Body can be adsorbed in graphenic surface, improve the performance of graphene.Jia Hong soldier et al. reports one kind makes ionic liquid using ball milling
Between body and graphene oxide non-covalent bond combination surface modified graphene oxide and filling natural rubber method (Chinese patent,
The patent No.：CN201310035966.4).But the Physical interaction power between this method intermediate ion liquid and graphene oxide
Weaker, the structure of surface modification is easily destroyed, and graphene oxide does not carry out sequential reduction, make the carrier performance after modification by
To influence.To solve the above problems, propose a kind of freshly prepared side of the grapheme modified filling fluoroether rubber of ionic liquid covalent bond
Method is particularly significant.
The content of the invention
It is an object of the invention to overcome the above-mentioned deficiency of prior art, there is provided a kind of fluoride ion liquid covalent bond modification
Graphene/fluoroether rubber preparation method, it is easy that graphene/fluoroether rubber that this method is prepared effectively overcomes graphene
Self aggregation and the defects of with rubber molecule poor compatibility, the fluoroether rubber tool filled by the use of functional graphene of the present invention as filler
There are good mechanical property, wear resistance, resistance to elevated temperatures, and preparation method of the present invention is simple and easy, has good
Application prospect.
What the above-mentioned purpose of the present invention was mainly achieved by following technical solution：
A kind of preparation method of graphene/fluoroether rubber of fluoride ion liquid covalent bond modification, comprises the following steps：
(1), fluoride ion liquid, graphite oxide and catalyst are mixed in organic solvent, water bath sonicator is handled to oxygen
Graphite is dispersed, carries out low-temp reaction in nitrogen atmosphere afterwards, obtains fluoride ion liquid graft graphite oxide；It is described
The mass ratio of fluoride ion liquid and graphite oxide is：1:0.2~5；
(2) reduction treatment, is carried out to fluoride ion liquid graft graphite oxide, obtains fluoride ion liquid graft graphite
Alkene；
(3), using fluoride ion liquid graft graphene as functional stuffing and fluoroether rubber rubber, acid-acceptor, vulcanizing agent
Mixed with 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 5MPa-20MPa, time 5-30min；Post vulcanization temperature is 210 DEG C -260
DEG C, time 5-24h.
In the preparation method of graphene/fluoroether rubber of above-mentioned fluoride ion liquid covalent bond modification, step contains in (1)
Fluorine ion liquid is 1- amine propyl group -3- methylimidazoles hexafluorophosphate, 1- amine propyl group -3- methyl imidazolium tetrafluoroborates, 1- amine
Propyl imidazole -3- methylimidazole trifluoros sulfonamide, 1- carboxylic propyl group -3- methyl imidazolium tetrafluoroborates, 1- carboxylic propyl group -3-
Methylimidazole hexafluorophosphate or one kind in 1- carboxylic propyl group -3- methylimidazole trifluoro sulfonamides or combination.
In the preparation method of graphene/fluoroether rubber of above-mentioned fluoride ion liquid covalent bond modification, step is urged in (1)
Agent is N, N'- Dicyclohexylcarbodiimides or to one kind in dimethylamino naphthyridine or combination；It is organic molten in the step (1)
Agent is any one in ethanol, acetone, tetrahydrofuran, N,N-dimethylformamide or 1-METHYLPYRROLIDONE.
In the preparation method of graphene/fluoroether rubber of above-mentioned fluoride ion liquid covalent bond modification, step (1) reclaimed water
Bath sonication treatment time is 1-4h；Reaction temperature is 40 DEG C -60 DEG C in the step (1), reaction time 6-48h.
In the preparation method of graphene/fluoroether rubber of above-mentioned fluoride ion liquid covalent bond modification, step (1) is in nitrogen
After carrying out low-temp reaction in gas atmosphere, purification process is carried out to reaction product, removes ionic liquid and the catalysis for having neither part nor lot in reaction
Agent, by after purification product drying handle, wherein purification treating method be centrifuge washing, be filtered under diminished pressure washing or be evaporated under reduced pressure in
One kind or combination.
In the preparation method of graphene/fluoroether rubber of above-mentioned fluoride ion liquid covalent bond modification, in step (2) also
The reduction temperature of original place reason is 150 DEG C -300 DEG C, heat treatment time 1-6h.
It is each in step (3) in the preparation method of graphene/fluoroether rubber of above-mentioned fluoride ion liquid covalent bond modification
The mass fraction of component is as follows：
In the preparation method of graphene/fluoroether rubber of above-mentioned fluoride ion liquid covalent bond modification, the acid-acceptor
For one kind in magnesia, calcium oxide, calcium hydroxide, zinc oxide or lead oxide or combination.
In the preparation method of graphene/fluoroether rubber of above-mentioned fluoride ion liquid covalent bond modification, the vulcanizing agent
For 2,5- dimethyl -2,5- two (t-butylperoxy) hexane, cumyl peroxide, the double Chinese cassia tree fork -1,6- hexamethylene diamines of N, N-,
One kind or combination in hydroquinones or dibenzoyl peroxide
It is described to help vulcanization in the preparation method of graphene/fluoroether rubber of above-mentioned fluoride ion liquid covalent bond modification
Agent is triallylcyanurate, Triallyl isocyanurate, divinylbenzene, diallyl phthalate, three hydroxyl first
Base propane front three acrylate or one kind in ethylene glycol dimethacrylate or combination.
The present invention has the advantages that compared with prior art：
(1), the present invention utilizes the chemical reaction between organo-functional group ionic liquid is grafted on graphite oxide surface, goes forward side by side
Row thermal reduction obtains functional stuffing, filler is mixed with fluorine ether rubber and compounding ingredient, sulfidization molding obtains final product, the graphite
Alkene/fluoroether rubber effectively overcomes the easy self aggregation of graphene and the defects of with rubber molecule poor compatibility；
(2), the fluoroether rubber product prepared using the inventive method has excellent mechanical property, wear resistance
And resistance to elevated temperatures, can meet space industry applies needs；
(3) each component and content are carried out preferred during, the present invention is standby to course of reaction and rubber system, while to preparing work
Skill condition optimizes design so that the functional stuffing yield that is prepared is high, purity is high, has more excellent comprehensive
Energy；
(4), preparation method of the present invention is simple and easy, it is easy to accomplish, this method can be with further genralrlization to other fillers
System, application prospect are good.
Brief description of the drawings
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 for the ionic liquid grafting that the embodiment of the present invention 1 is prepared；
Fig. 4 is the graphene-structured formula for the ionic liquid grafting that the embodiment of the present invention 1 is prepared；
Fig. 5 is that graphite oxide in the embodiment of the present invention 1, the graphite oxide of ionic liquid grafting and thermal reduction ionic liquid connect
The infrared spectrum curve figure of the graphene of branch；
Fig. 6 is graphite oxide in the embodiment of the present invention 1, the graphite oxide of ionic liquid grafting and middle thermal reduction ionic liquid
The x-ray photoelectron spectrum curve figure of graphene after grafting；
Fig. 7 is that graphite oxide in the embodiment of the present invention 1, the graphite oxide of ionic liquid grafting and thermal reduction ionic liquid connect
Thermogravimetric curve figure of the graphene in nitrogen atmosphere after branch.
Fig. 8 is graphene after thermal reduction ionic liquid grafting in the embodiment of the present invention 1, embodiment 4 and embodiment 5 in air
Under the conditions of thermogravimetric curve comparison diagram；
Fig. 9 is thermogravimetric of the fluoroether rubber prepared in the embodiment of the present invention 4, embodiment 6 and embodiment 7 in air atmosphere
Curve comparison figure；
Figure 10 is the scanning electron microscopic picture of the fluoroether rubber stretching fracture prepared in the embodiment of the present invention 7.
Embodiment
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 of fluoride ion liquid covalent bond modification of the present invention, is specifically included as follows
Step：
(1), fluoride ion liquid graft graphite oxide
Fluoride ion liquid, graphite oxide and catalyst are mixed in organic solvent, water bath sonicator handles 1-4h to oxygen
Graphite is dispersed, carries out low-temp reaction in nitrogen atmosphere afterwards, and reaction temperature is 40 DEG C -60 DEG C, reaction time 6-
48h.Purification process is carried out to reaction product, the ionic liquid and catalyst for having neither part nor lot in reaction is removed, sample after purification is done
Dry processing, obtains fluoride ion liquid graft graphite oxide, wherein purification treating method be centrifuge washing, be filtered under diminished pressure washing or
One kind or combination in vacuum distillation.The mass ratio of the fluoride ion liquid and graphite oxide is：1:0.2~5.
Fluoride ion liquid is 1- amine propyl group -3- methylimidazoles hexafluorophosphate, 1- amine propyl group -3- methylimidazole tetrafluoro boron
Hydrochlorate, 1- amine propyl imidazole -3- methylimidazole trifluoros sulfonamide, 1- carboxylic propyl group -3- methyl imidazolium tetrafluoroborates, 1-
One kind or group in carboxylic propyl group -3- methylimidazoles hexafluorophosphate or 1- carboxylic propyl group -3- methylimidazole trifluoro sulfonamides
Close.
Catalyst is N, N'- Dicyclohexylcarbodiimides or to one kind in dimethylamino naphthyridine or combination.
Organic solvent is any in ethanol, acetone, tetrahydrofuran, N,N-dimethylformamide or 1-METHYLPYRROLIDONE
It is a kind of.
It is as shown in Figure 1 the preparation flow schematic diagram in the preparation method step 1 of graphene/fluoroether rubber of the present invention, its
Middle A is-COOH or-NH2；X is-(CF3SO2)2N、—BF4Or PF6；M for-COO-or-CO-NH-.
(2), the reduction of fluoride ion liquid graft graphite oxide
Reduction treatment is carried out to fluoride ion liquid graft graphite oxide, obtains fluoride ion liquid graft graphene；Also
The reduction temperature of original place reason is 150 DEG C -300 DEG C, heat treatment time 1-6h.
The preparation flow schematic diagram being illustrated in figure 2 in the preparation method step 2 of graphene/fluoroether rubber of the present invention, its
Middle X is-(CF3SO2)2N、—BF4Or PF6；M is-COO-or-CO-NH mono-.
(3), the mixing and shaping of functional graphene and fluoroether rubber
Fluoride ion liquid graft graphene as functional stuffing and fluoroether rubber rubber, acid-acceptor, vulcanizing agent and is helped
Vulcanizing agent mixes, and carries out hot-press vulcanization and post vulcanization respectively, obtains graphene/fluoroether rubber.
The mass fraction of each component is as follows：
Wherein hot-press vulcanization temperature is 150 DEG C -200 DEG C, sulfide stress 5MPa-20MPa, time 5-30min；Two sections
Curing temperature is 210 DEG C -260 DEG C, time 5-24h.
Acid-acceptor is one kind or combination in magnesia, calcium oxide, calcium hydroxide, zinc oxide or lead oxide.
Vulcanizing agent is 2,5- dimethyl -2,5- two (t-butylperoxy) hexane, cumyl peroxide, the double Chinese cassia trees of N, N-
Fork -1,6- hexamethylene diamines, hydroquinones or one kind or combination in dibenzoyl peroxide
Auxiliary curing agent is triallylcyanurate, Triallyl isocyanurate, divinylbenzene, phthalic acid two
Allyl ester, trimethylolpropane tris first acrylate or one kind in ethylene glycol dimethacrylate or combination.
Embodiment 1
1. ionic liquid is grafted graphite oxide
Weigh graphite oxide 1g, 1- amine propyl group -3- methylimidazole trifluoro sulfonamide 1g, N, N'- dicyclohexyl carbon
Acid imide 1g, to dimethylamino naphthyridine 50mg, weighing 200mL has DMF to be placed in flask.At water bath sonicator
After managing 2h, 50 DEG C of reaction 24h of temperature control in nitrogen atmosphere.Purification process is carried out using centrifuge washing to reaction product, removed not
The ionic liquid and catalyst of reaction, it is dried in vacuo product.
It is illustrated in figure 3 the graphite oxide structural formula for the ionic liquid grafting that the embodiment of the present invention 1 is prepared.
2. ionic liquid is grafted the reduction of graphite oxide
Weigh the graphite oxide 1g after grafting to be placed in crucible, be heat-treated 1h under the conditions of 230 DEG C of baking oven, obtain fluffy
The redox functional graphene product of cotton-shaped Ionic Liquid Modified.
It is illustrated in figure 4 the graphene-structured formula for the ionic liquid grafting that the embodiment of the present invention 1 is prepared.
3. the mixing and shaping of functional graphene and fluoroether rubber
Weigh 100g fluoroether rubber rubbers, 1g functional graphenes, 3g magnesia, 4g 2, (the tertiary fourth of 5- dimethyl -2,5- bis-
Base peroxy) hexane, 4g Triallyl isocyanurates, be well mixed on a mill.By mix products in 175 DEG C, 10MPa
Under the conditions of after sulfidization molding 20min, in 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 thermal reduction ion
The infrared spectrum of the rear black alkene of liquid graft；Fig. 6 is graphite oxide in the embodiment of the present invention 1, the oxidation stone of ionic liquid grafting
The x-ray photoelectron power spectrum of graphene after ink and thermal reduction ionic liquid grafting；Fig. 7 be the embodiment of the present invention 1 in graphite oxide,
Thermogravimetric curve figure of the graphene in nitrogen atmosphere after the graphite oxide of ionic liquid grafting and thermal reduction ionic liquid grafting.
Fig. 8 is that thermogravimetric curve figure of the graphene under air conditionses after ionic liquid grafting is heat-treated in the embodiment of the present invention 1.
As seen from the figure, the present invention is to native oxide graphite, the graphite oxide of ionic liquid grafting and thermal reduction ionic liquid
The graphene of grafting enters row element, group and heat analysis characterize, it was demonstrated that ionic liquid is successfully grafted on graphenic surface and right
Graphite oxide effectively reduces.
The tensile strength of the fluoroether rubber prepared in the inventive method embodiment 1 is 11.8MPa, hardness 60.1Shore
A, elongation rate of tensile failure 290%.The fluoroether rubber prepared in the inventive method embodiment 1 is in 5N load, 6cm/s rate conditions
Under, using the coefficient of friction after ball disc type instrument friction 20min, wear rate is 2.78 × 10 for 1.36- 7cm3/Nm。
Embodiment 2
1. ionic liquid is grafted graphite oxide
Weigh graphite oxide 1g, 1- amine propyl group -3- methyl imidazolium tetrafluoroborates 2g, N, N'- Dicyclohexylcarbodiimide
1g, to dimethylamino naphthyridine 50mg, weighing 200mL has DMF to be placed in flask.After water bath sonicator processing 1h,
40 DEG C of reaction 36h of temperature control in nitrogen atmosphere.To reaction product using centrifuge washing carry out purification process, remove it is unreacted from
Sub- liquid and catalyst, it is dried in vacuo product.
2. ionic liquid is grafted the reduction of graphite oxide
Weigh the graphite oxide 1g after grafting to be placed in crucible, be heat-treated 1h under the conditions of 250 DEG C of baking oven, obtain fluffy
The redox functional graphene product of cotton-shaped Ionic Liquid Modified.
3. the mixing and shaping of functional graphene and fluoroether rubber
Weigh 100g fluoroether rubber rubbers, 1g functional graphenes, 4g magnesia, 3g 2, (the tertiary fourth of 5- dimethyl -2,5- bis-
Base peroxy) hexane, 3g Triallyl isocyanurates, be well mixed on a mill.By mix products in 155 DEG C, 20MPa
Under the conditions of after sulfidization molding 20min, in 250 DEG C of post vulcanization 5h, obtain rubber product.
The tensile strength of the fluoroether rubber prepared in the inventive method embodiment 1 is 11.5MPa, hardness 59.8Shore
A, elongation rate of tensile failure 287%.
Embodiment 3
1. ionic liquid is grafted graphite oxide
Weigh graphite oxide 1g, 1- amine propyl group -3- methylimidazole hexafluorophosphate 0.5g, N, N'- dicyclohexyls phosphinylidyne Asia
Amine 1g, to dimethylamino naphthyridine 50mg, weighing 200mL has DMF to be placed in flask.Water bath sonicator handles 4h
Afterwards, 60 DEG C of reaction 6h of temperature control in nitrogen atmosphere.Purification process is carried out using centrifuge washing to reaction product, removed unreacted
Ionic liquid and catalyst, it is dried in vacuo product.
2. the reduction of the graphite oxide of ionic liquid grafting
Weigh the graphite oxide 1g after grafting to be placed in crucible, be heat-treated 6h under the conditions of 210 DEG C of baking oven, obtain fluffy
The redox functional graphene product of cotton-shaped Ionic Liquid Modified.
3. the mixing and shaping of functional graphene and fluoroether rubber
Weigh 100g fluoroether rubber rubbers, 1g functional graphenes, 5g magnesia, 3g 2, (the tertiary fourth of 5- dimethyl -2,5- bis-
Base peroxy) hexane, 5g Triallyl isocyanurates, be well mixed on a mill.By mix products in 165 DEG C, 15MPa
Under the conditions of after sulfidization molding 30min, in 240 DEG C of post vulcanization 10h, obtain rubber product.
The tensile strength of the fluoroether rubber prepared in the inventive method embodiment 1 is 11.3MPa, hardness 59.5Shore
A, elongation rate of tensile failure 281%.
Embodiment 4
1. ionic liquid is grafted graphite oxide
Weigh graphite oxide 1g, 1- amine propyl group -3- methylimidazole trifluoro sulfonamide 0.5g, N, N'- dicyclohexyls
Carbimide 1g, to dimethylamino naphthyridine 50mg, weighing 200mL has DMF to be placed in flask.Water bath sonicator
After handling 2h, 40 DEG C of reaction 48h of temperature control in nitrogen atmosphere.Purification process is carried out using centrifuge washing to reaction product, removed
Unreacted ionic liquid and catalyst, it is dried in vacuo product.
2. ionic liquid is grafted the reduction of graphite oxide
Weigh the graphite oxide 1g after grafting to be placed in crucible, be heat-treated 2h under the conditions of 230 DEG C of baking oven, obtain fluffy
The redox functional graphene product of cotton-shaped Ionic Liquid Modified.
3. the mixing and shaping of functional graphene and fluoroether rubber
Weigh 100g fluoroether rubber rubbers, 1g functional graphenes, 3g magnesia, 2g 2, (the tertiary fourth of 5- dimethyl -2,5- bis-
Base peroxy) hexane, 4g Triallyl isocyanurates, be well mixed on a mill.By mix products in 190 DEG C, 5MPa
Under the conditions of after sulfidization molding 5min, in 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 under air conditionses
Thermogravimetric curve figure.Thermogravimetric curve of the fluoroether rubber prepared in the embodiment of the present invention 4 in air atmosphere is as shown in Figure 9.
The tensile strength of the fluoroether rubber prepared in the inventive method embodiment 4 is 12.3MPa, hardness 60.8Shore
A, elongation rate of tensile failure 284%.The fluoroether rubber prepared in the inventive method embodiment 4 is in 5N load, 6cm/s rate conditions
Under, using the coefficient of friction after ball disc type instrument friction 20min, wear rate is 2.63 × 10 for 1.32-7cm3/Nm。
Embodiment 5
1. ionic liquid is grafted graphite oxide
Weigh graphite oxide 1g, 1- amine propyl group -3- methylimidazole trifluoro sulfonamide 0.5g, N, N'- dicyclohexyls
Carbimide 1g, to dimethylamino naphthyridine 50mg, weighing 200mL has DMF to be placed in flask.Water bath sonicator
After handling 1h, 60 DEG C of reaction 24h of temperature control in nitrogen atmosphere.Purification process is carried out using centrifuge washing to reaction product, removed
Unreacted ionic liquid and catalyst, it is dried in vacuo product.
2. ionic liquid is grafted the reduction of graphite oxide
Weigh the graphite oxide 1g after grafting to be placed in crucible, be heat-treated 6h under the conditions of 230 DEG C of baking oven, obtain fluffy
The redox functional graphene product of cotton-shaped Ionic Liquid Modified.
3. the mixing and shaping of functional graphene and fluoroether rubber
Weigh 100g fluoroether rubber rubbers, 1g functional graphenes, 4g magnesia, 6g 2, (the tertiary fourth of 5- dimethyl -2,5- bis-
Base peroxy) hexane, 6g Triallyl isocyanurates, be well mixed on a mill.By mix products in 180 DEG C, 10MPa
Under the conditions of after sulfidization molding 10min, in 260 DEG C of post vulcanization 8h, obtain rubber product.
It is illustrated in figure 8 in the embodiment of the present invention 5 and heat-treats heat of the graphene under air conditionses after ionic liquid is grafted
Weight curve map.
The tensile strength of the fluoroether rubber prepared in the inventive method embodiment 5 is 12.1MPa, hardness 61.0Shore
A, elongation rate of tensile failure 257%.
Embodiment 6
1. ionic liquid is grafted graphite oxide
Weigh graphite oxide 1g, 1- amine propyl group -3- methylimidazole trifluoro sulfonamide 0.5g, N, N'- dicyclohexyls
Carbimide 1g, to dimethylamino naphthyridine 50mg, weighing 200mL has DMF to be placed in flask.Water bath sonicator
After handling 3h, 50 DEG C of reaction 36h of temperature control in nitrogen atmosphere.Purification process is carried out using centrifuge washing to reaction product, removed
Unreacted ionic liquid and catalyst, it is dried in vacuo product.
2. ionic liquid is grafted the reduction of graphite oxide
Weigh the graphite oxide 1g after grafting to be placed in crucible, be heat-treated 1h under the conditions of 280 DEG C of baking oven, obtain fluffy
The redox functional graphene product of cotton-shaped Ionic Liquid Modified.
3. the mixing and shaping of functional graphene and fluoroether rubber
Weigh 100g fluoroether rubber rubbers, 2g functional graphenes, 4g calcium hydroxides, 3g cumyl peroxides alkane, 4g tri-
Pi-allyl cyanurate, is well mixed on a mill.By mix products under the conditions of 180 DEG C, 20MPa sulfidization molding 10min,
In 230 DEG C of post vulcanization 15h, rubber product is obtained.
The tensile strength of the fluoroether rubber prepared in the inventive method embodiment 6 is 13.6MPa, hardness 63.1Shore
A, elongation rate of tensile failure 300%.The fluoroether rubber prepared in the inventive method embodiment 6 is in 5N load, 6cm/s rate conditions
Under, using the coefficient of friction after ball disc type instrument friction 20min, wear rate is 2.31 × 10 for 1.23- 7cm3/Nm。
Thermogravimetric curve of the fluoroether rubber prepared in the embodiment of the present invention 6 in air atmosphere is as shown in Figure 5.
Embodiment 7
1. ionic liquid is grafted graphite oxide
Weigh graphite oxide 1g, 1- amine propyl group -3- methylimidazole trifluoro sulfonamide 0.5g, N, N'- dicyclohexyls
Carbimide 1g, to dimethylamino naphthyridine 50mg, weighing 200mL has DMF to be placed in flask.Water bath sonicator
After handling 2h, 40 DEG C of reaction 48h of temperature control in nitrogen atmosphere.Purification process is carried out using centrifuge washing to reaction product, removed
Unreacted ionic liquid and catalyst, it is dried in vacuo product.
2. ionic liquid is grafted the reduction of graphite oxide
Weigh the graphite oxide 1g after grafting to be placed in crucible, be heat-treated 6h under the conditions of 170 DEG C of baking oven, obtain fluffy
The redox functional graphene product of cotton-shaped Ionic Liquid Modified.
3. the mixing and shaping of functional graphene and fluoroether rubber
Weigh 100g fluoroether rubber rubbers, 4g functional graphenes, 3g magnesia, 2g 2, (the tertiary fourth of 5- dimethyl -2,5- bis-
Base peroxy) hexane, 4g Triallyl isocyanurates, be well mixed on a mill.By mix products in 190 DEG C, 15MPa
Under the conditions of after sulfidization molding 20min, in 250 DEG C of post vulcanization 20h, obtain rubber product.
The tensile strength of the fluoroether rubber prepared in the inventive method embodiment 7 is 14.8MPa, hardness 66.0Shore
A, elongation rate of tensile failure 253%.The fluoroether rubber prepared in the inventive method embodiment 7 is in 5N load, 6cm/s rate conditions
Under, using the coefficient of friction after ball disc type instrument friction 20min, wear rate is 2.31 × 10 for 1.23- 7cm3/Nm。
Thermogravimetric curve of the fluoroether rubber prepared in the embodiment of the present invention 7 in air atmosphere is as shown in Figure 9.It is of the invention real
The surface sweeping Electronic Speculum morphology characterization result for applying the fluoroether rubber stretching fracture prepared in example 7 is as shown in Figure 10.
As seen from the figure, the graphene for heat-treating ionic liquid grafting has good compatibility with fluoroether rubber.
It is described above, it is only the optimal embodiment of the present invention, but protection scope of the present invention is not limited thereto,
Any one skilled in the art the invention discloses technical scope in, the change or replacement that can readily occur in,
It should all be included within the scope of the present invention.
The content not being described in detail in description of the invention belongs to the known technology of professional and technical personnel in the field.
Claims (9)
- A kind of 1. preparation method of graphene/fluoroether rubber of fluoride ion liquid covalent bond modification, it is characterised in that：Including such as Lower step：(1), fluoride ion liquid, graphite oxide and catalyst are mixed in organic solvent, water bath sonicator is handled to oxidation stone Ink is dispersed, carries out low-temp reaction in nitrogen atmosphere afterwards, obtains fluoride ion liquid graft graphite oxide；It is described fluorine-containing The mass ratio of ionic liquid and graphite oxide is：1:0.2~5；(2) reduction treatment, is carried out to fluoride ion liquid graft graphite oxide, obtains fluoride ion liquid graft graphene；(3), fluoride ion liquid graft graphene as functional stuffing and fluoroether rubber rubber, acid-acceptor, vulcanizing agent and is helped Vulcanizing agent mixes, and carries out hot-press vulcanization and post vulcanization respectively, obtains graphene/fluoroether rubber, wherein hot-press vulcanization temperature For 150 DEG C -200 DEG C, sulfide stress 5MPa-20MPa, time 5-30min；Post vulcanization temperature is 210 DEG C -260 DEG C, when Between be 5-24h；Fluoride ion liquid is 1- amine propyl group -3- methylimidazoles hexafluorophosphate, 1- amine propyl group -3- methyl in the step (1) Tetrafluoroborate, 1- amine propyl imidazole -3- methylimidazole trifluoros sulfonamide, 1- carboxylic propyl group -3- methylimidazoles four In borofluoride, 1- carboxylic propyl group -3- methylimidazoles hexafluorophosphates or 1- carboxylic propyl group -3- methylimidazole trifluoro sulfonamides One kind or combination.
- A kind of 2. preparation side of graphene/fluoroether rubber of fluoride ion liquid covalent bond modification according to claim 1 Method, it is characterised in that：Catalyst is N in the step (1), N'- Dicyclohexylcarbodiimides or in dimethylamino naphthyridine A kind of or combination；Organic solvent is ethanol, acetone, tetrahydrofuran, N,N-dimethylformamide or N- methyl in the step (1) Any one in pyrrolidones.
- A kind of 3. preparation side of graphene/fluoroether rubber of fluoride ion liquid covalent bond modification according to claim 1 Method, it is characterised in that：Water-bath sonication treatment time is 1-4h in the step (1)；Reaction temperature is 40 in the step (1) DEG C -60 DEG C, reaction time 6-48h.
- A kind of 4. preparation side of graphene/fluoroether rubber of fluoride ion liquid covalent bond modification according to claim 1 Method, it is characterised in that：After the step (1) carries out low-temp reaction in nitrogen atmosphere, purification process is carried out to reaction product, removed Remove to have neither part nor lot in the ionic liquid and catalyst of reaction, product drying after purification is handled, wherein purification treating method is centrifugation Wash, be filtered under diminished pressure washing or one kind in vacuum distillation or combination.
- A kind of 5. preparation side of graphene/fluoroether rubber of fluoride ion liquid covalent bond modification according to claim 1 Method, it is characterised in that：The reduction temperature of reduction treatment is 150 DEG C -300 DEG C in the step (2), heat treatment time 1-6h.
- A kind of 6. preparation side of graphene/fluoroether rubber of fluoride ion liquid covalent bond modification according to claim 1 Method, it is characterised in that：The mass fraction of each component is as follows in the step (3)：
- 7. a kind of graphene/fluoroether rubber of fluoride ion liquid covalent bond modification according to one of claim 1~6 Preparation method, it is characterised in that：The acid-acceptor is one kind in magnesia, calcium oxide, calcium hydroxide, zinc oxide or lead oxide Or combination.
- 8. a kind of graphene/fluoroether rubber of fluoride ion liquid covalent bond modification according to one of claim 1~6 Preparation method, it is characterised in that：The vulcanizing agent is 2,5- dimethyl -2,5- two (t-butylperoxy) hexane, peroxidating two Isopropylbenzene, N, the double Chinese cassia tree fork -1,6- hexamethylene diamines of N-, hydroquinones or one kind or combination in dibenzoyl peroxide
- 9. a kind of graphene/fluoroether rubber of fluoride ion liquid covalent bond modification according to one of claim 1~6 Preparation method, it is characterised in that：The auxiliary curing agent is triallylcyanurate, Triallyl isocyanurate, divinyl One in base benzene, diallyl phthalate, trimethylolpropane tris first acrylate or GDMA Kind or combination.
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