CN106046632B - A kind of graphene is modified fluorubber and preparation method thereof - Google Patents
A kind of graphene is modified fluorubber and preparation method thereof Download PDFInfo
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- CN106046632B CN106046632B CN201610700237.XA CN201610700237A CN106046632B CN 106046632 B CN106046632 B CN 106046632B CN 201610700237 A CN201610700237 A CN 201610700237A CN 106046632 B CN106046632 B CN 106046632B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/02—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type
- B29B7/22—Component parts, details or accessories; Auxiliary operations
- B29B7/28—Component parts, details or accessories; Auxiliary operations for measuring, controlling or regulating, e.g. viscosity control
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/02—Mixing; Kneading non-continuous, with mechanical mixing or kneading devices, i.e. batch type
- B29B7/22—Component parts, details or accessories; Auxiliary operations
- B29B7/28—Component parts, details or accessories; Auxiliary operations for measuring, controlling or regulating, e.g. viscosity control
- B29B7/286—Component parts, details or accessories; Auxiliary operations for measuring, controlling or regulating, e.g. viscosity control measuring properties of the mixture, e.g. temperature, density
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
- B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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Abstract
A kind of graphene is modified fluorubber, it is characterized in that include graphene carbon black alumina composite particle, the graphene carbon black alumina composite particle is that graphene and carbon black are each carried out surface preparation before rubber is added in, then it is co-precipitated again with aluminium hydroxide, and sediment is calcined, form graphene carbon black alumina composite particle；In the refining process of rubber, the composite particles are directly added into.The present invention solves the agglomeration traits of graphene in rubber mixing process, obtain the fluororubber compounded rubber haveing excellent performance, tensile strength improves more than 20%, wear volume reduces by more than 30%, the present invention can promote extensive use of the graphene in fluorubber field, and technical merit has reached domestically leading level.
Description
Technical field
The invention belongs to rubber materials, refer specifically to the processing method that a kind of graphene is modified fluorubber
Background technology
Fluorubber (FKM) refers to a kind of synthesis macromolecular elastomer that fluorine atom is connected on the carbon atom of main chain or side chain.
The radius of fluorine atom is small, electronegativity is extremely strong, can be closely arranged in around carbon atom, the very high fluorine carbon key of generation bond energy,
Good shielding action is generated to carbon-carbon bond.Thus fluorubber has very high thermal stability and chemical inertness, is used as sealing
Material is widely used in the fields such as national defence, military project, space flight and aviation, automobile, petrochemical industry.Fluorubber is used as grinding roller sealing ring, tool
The advantage for having other rubber incomparable：High temperature resistant, fuel oil resistance, powerful oxidation corrosion resistance agent, resistance to natural weathering etc..But existing skill
The wear-resisting property of fluorubber grinding roller sealing ring in art is poor, especially under high temperature, high velocity environment, can not meet real need
It asks.
Dilute graphite is as made from the Andre Geim of Univ Manchester UK in 2004 earliest.Graphite is dilute to be considered
It is the basic structural unit of fowler coal, carbon nanotubes, graphite, because its mechanics, quantum and electrical properties are special, is subject to physics and material
Expect that educational circles pays high attention to.The dilute stretch modulus of graphite and ultimate strength receive suitable, the light weight that carrys out pipe with single armed carbon, and thermal conductivity is good
And large specific surface area.Dilute graphite is mono-layer graphite, and raw material is easy to get, is cheap, is expected to break nano combined material as polymer matrix
The new key function material of material.
Graphite is dilute/and polymer nanocomposites have a good application prospect, and people, which prepare it, grind extensively
Study carefully.Prepare at present graphite it is dilute/methods of polymer nanocomposites mainly includes melt-blending process, situ aggregation method, solution
Mixing method and lotion mixing method.The current dilute nanocomposite of graphite directly prepared is simultaneously few, and it is dilute both to be primarily due to graphite
It is not hydrophilic that oleophylic, reactivity be not high yet so that it is modified it is relatively difficult, so as to cause compound with other materials
It is relatively difficult.It prepares dilute receive of graphite to carry out composite material can first to prepare graphite oxide dilute (graphene oxide), allows oxidation stone
Ink is dilute compound with other polymeric materials, then the dilute reduction of graphite oxide therein is obtained the dilute nanocomposite of graphite.
At present much in relation to by graphene, for improving the research of rubber performance, but graphene is due to the change of itself
Learn performance, there is being easy to reunite, dispersion performance is bad in rubber material, it is with high costs the problem of.
CN103275368A discloses a kind of mechanical blending and prepares graphene oxide/white carbon black/rubber nanocomposite
Method.Since graphene and white carbon intert mutually effective aggregation for inhibiting two kinds of fillers itself in the composite material,
So as to the composite material for obtaining high degree of dispersion, height is removed and disperseed in nanoscale.Not only there is higher modulus and relatively low
Rolling resistance while, also significantly improve the wear-resisting property of rubber material, and further improve the modulus of composite material
And tear resistance, simultaneously because the lamellar structure of graphene oxide and good automatic recovery ability, also impart rubber material
Expect good gas barrier property and self-healing capability, the advantage for having conventional filler incomparable.
CN104845009A discloses a kind of fluororesin/graphene composite material and preparation method and application, wherein stone
Black alkene is isolated by fluororesin, is distributed in three-dimensional isolation network shape, and fluororesin size is 50nm-500 μm, and fluororesin is full of in graphite
In alkene three-dimensional network, volume content of the graphene in fluororesin/graphene composite material is 0.01%~10%.The material has
There is relatively low exceeding to ooze concentration and higher electrical conductivity, preparation method is simple, easily operated, low energy consumption, reproducible, at low cost
It is honest and clean, it can be widely used in the preparation of conductive material.
The content of the invention
It is an object of the invention to：The processing method that a kind of graphene is modified fluorubber is provided.In the prior art when in fluorine
When graphene is added in rubber, surface modification first usually is carried out to graphene so that graphene itself has higher divide
Property is dissipated, is then processed in the addition open mill together with other granular materials such as carbon black, solid-filling agent.But this Shen
Ask someone to find, surface treated graphene mixed with other granular materials directly enter be processed in open mill when, it is past
Toward due to the charge of itself or dispersion degree of granular material it is not uniform enough, cause dispersion degree of the graphene in fluorubber not
Ideal, so as to which the fluorubber properties of product for affecting final further improve.
The present inventor is put forward for the first time, and graphene and carbon black are surface-treated together, and forms composite particles so as to subtract
Few unclassified stores obtains the more excellent rubber product of performance for the adverse effect of graphene dispersion degree.The present invention is right first
Grapheme material has carried out surface modification, and polyacrylamide is introduced on the molecule border of graphene, by the introducing of organic group,
So that graphene realizes semimetal property on the nanostructure, improved graphene metastable can be present in organic molten
In agent.Then carbon black is pre-processed with sodium carboxymethylcellulose, added after the carbon black by pretreatment and graphene are mixed
Enter in aluminate, and be co-precipitated, form graphene-carbon black-aluminium hydroxide co-precipitation, stone is further obtained after calcining
Black alkene-carbon black-alumina composite particle.Compared with directly graphene is added in rubber in the prior art, the present invention is protecting
While demonstrate,proving the raising of rubber quality, the dosage of graphene is also reduced, reduces cost.And this composite particles can be very good
It is scattered in rubber material, and there is good heat conductivility, improve the ductility of rubber.
A kind of graphene is modified fluorubber, it is characterised in that include graphene-carbon black-alumina composite particle, it is described
Graphene-carbon black-alumina composite particle is that graphene and carbon black are each carried out surface preparation before rubber is added in, so
It is co-precipitated again with aluminium hydroxide afterwards, and sediment is calcined, form graphene-carbon black-alumina composite particle；In rubber
Refining process in, be directly added into the composite particles, dosage is that every 100 parts of crude fluororubbers add in 10-30 parts this compound
Grain.
The preparation method of the graphene-carbon black-alumina composite particle, comprises the following steps：(1) graphene oxide point
It dissipates in deionized water, adds in surfactant and polyacrylamide solution, be heated to 60-80 DEG C；(2) it is clear to add in acid solution for carbon black
Sodium carboxymethylcellulose is added in after washing；(3) solution for obtaining step (1) and (2) mixes, and adds in sodium aluminate solution, and slowly
PH value is adjusted to 10-12, obtains the suspension；(4) filter, wash；(5) 1-6h is calcined at 200-300 DEG C, obtained described
Modified graphene；Wherein step (1)-(3) are stirred with ultrasonic wave.
Spray shaping may be employed in the step (4), i.e., the suspension obtained step (3) passes through spray-drying installation,
Atomization forms small complex liquid drop, and moisture is removed in dried medium, obtains modified graphene particle.
The surfactant is dodecyl ethyoxyl sulfobetaines, dodecyl hydroxypropyl sulfobetaines, gathers
One kind in ethylene glycol.
The addition of the polyacrylamide is the 50-300% of graphene oxide quality, preferably 10-150%.
The addition of the sodium aluminate is with Al2O3Meter, dosage is the 50-100% of graphene oxide quality.
The grain size of the graphene-carbon black-alumina composite particle is 1-200 microns, preferably 10-50 microns.
The mass ratio of graphene and carbon black in the graphene-carbon black-alumina composite particle is 1:20-50, preferably
It is 1:30-40.
The carbon black can also be replaced with barium sulfate.
Acid solution in step (2) refers to the hydrochloric acid or nitric acid that pH value is 3-5.
The fluorubber further includes the rubber chemicals such as carbon black, magnesia, calcium hydroxide, bisphenol AF, BPP, microwax.
The preparation method of the fluorubber comprises the following steps, and 100 parts of crude fluororubbers is placed on open mill, roll-in
Bottom sheet after 10-15min, the wherein plasticating temperature of open mill preliminary roller are 55-60 DEG C, and the plasticating temperature of open mill back roller is 40-50
℃；Crude fluororubber is placed in mixer, sequentially add 0.1-3 parts of microwaxes, 5-25 parts of magnesia, 1-5 parts of calcium hydroxides,
10-30 parts of graphene-carbon black-alumina composite particles, discharge after being kneaded uniformly；Wherein, melting temperature is 60-65 DEG C, is kneaded
Time is 2-3min；Treated, and mixture placement 12-36h is placed in open mill, adds in 0.5-2 parts of bisphenol AFs and 0.1-
0.5 part of BPP is vulcanized, and the curing temperature of one step cure is 150-180 DEG C, and vulcanization time 0.5-1h is continuously heating to
200-210 DEG C of progress post vulcanization 12-24h, bottom sheet is to get the fluorubber after being finally cooled to less than 60-80 DEG C.
Compared with the prior art the present invention has following distinguishing feature and good effect：Solves stone in rubber mixing process
The agglomeration traits of black alkene obtain the fluororubber compounded rubber haveing excellent performance, and tensile strength improves more than 20%, and wear volume reduces
More than 30%, the present invention can promote extensive use of the graphene in fluorubber field, and technical merit has reached domestically leading
It is horizontal.
Specific embodiment
The preparation of graphene-carbon black-alumina composite particle, (1) graphene oxide are scattered in deionized water, add in table
Face activating agent and polyacrylamide solution are heated to 60 DEG C；(2) carbon black adds in sodium carboxymethylcellulose after adding in acid solution cleaning；
(3) solution for obtaining step (1) and (2) mixes, and adds in sodium aluminate solution, and slowly adjusts pH value to 12, obtains described outstanding
Turbid；(4) filter, wash；(5) 2h is calcined at 280 DEG C, obtains the modified graphene；Wherein step (1)-(3) ultrasound
Ripple stirs.
Embodiment 1
| Comparative example 1 | Comparative example 2 | Embodiment 1 | |
| Fluorubber | 100 | 100 | 100 |
| Carbon black N990 | 35 | 35 | 0 |
| Magnesia | 5 | 5 | 5 |
| Calcium hydroxide | 3 | 3 | 3 |
| Microwax | 2 | 2 | 2 |
| Bisphenol AF | 1.5 | 1.5 | 1.5 |
| BPP | 0.3 | 0.3 | 0.3 |
| Common graphite alkene | 0 | 0.5 | 0 |
| Composite particles | 0 | 0 | 35 |
The preparation method of fluorubber according to following steps, 100 parts of crude fluororubbers is placed on open mill, roll-in 10min
Bottom sheet afterwards, the wherein plasticating temperature of open mill preliminary roller are 55 DEG C, and the plasticating temperature of open mill back roller is 50 DEG C；Crude fluororubber is put
In mixer, microwax, magnesia, calcium hydroxide, modified graphene, carbon black are sequentially added, discharge after being kneaded uniformly；Its
In, melting temperature is 50 DEG C, mixing time 3min；Treated, and mixture placement 12h is placed in open mill, adds in bis-phenol
AF and BPP are vulcanized, and the curing temperature of one step cure is 150 DEG C, vulcanization time 0.5h, are continuously heating to 200 DEG C of vulcanizations
12h, bottom sheet is to get the fluorubber after being finally cooled to less than 80 DEG C.
| Comparative example 1 | Comparative example 2 | Embodiment 1 | |
| Tensile strength/MPa | 6.9 | 11.3 | 15.1 |
| Coefficient of friction (method A) | 0.75 | 0.40 | 0.32 |
| Thermal conductivity W/ (M.K) | 0.28 | 0.46 | 0.59 |
| Elongation at break % | 230 | 265 | 276 |
Can be seen that composite particles of the present invention from more than contrast test data can significantly improve the items of rubber
Can, and it is better than performance when graphene is individually added into fluorubber, achieve unexpected technique effect.
It the above is only the implementation example of the present invention, protection scope of the present invention be not limited in any way.It is every to use this
Equivalent substitution well known to field or the equivalent technical solution for exchanging formation, are within the scope of the present invention.
Claims (9)
1. a kind of graphene is modified fluorubber, it is characterised in that includes graphene-carbon black-alumina composite particle, the stone
Black alkene-carbon black-alumina composite particle is that graphene and carbon black are each carried out surface preparation before rubber is added in, then
It is co-precipitated again with aluminium hydroxide, and sediment is calcined, form graphene-carbon black-alumina composite particle；In rubber
In refining process, the graphene-carbon black-alumina composite particle is directly added into, dosage is that every 100 parts of crude fluororubbers add in
The 10-30 parts of graphene-carbon black-alumina composite particles；The preparation method of the graphene-carbon black-alumina composite particle,
Comprise the following steps：(1) graphene oxide is scattered in deionized water, is added in surfactant and polyacrylamide solution, is added
Heat is to 60-80 DEG C；(2) carbon black adds in sodium carboxymethylcellulose after adding in acid solution cleaning；(3) step (1) and (2) are obtained molten
Liquid mixes, and adds in sodium aluminate solution, and slowly adjusts pH value to 10-12, obtains suspension；(4) filter, wash；(5) in 200-
1-6h is calcined at 300 DEG C, obtains the graphene-carbon black-alumina composite particle；Wherein step (1)-(3) are stirred with ultrasonic wave
It mixes.
2. modified fluorubber as described in claim 1, it is characterised in that in the graphene-carbon black-alumina composite particle
The mass ratio of graphene and carbon black is 1:20-50.
3. modified fluorubber as described in claim 1, it is characterised in that the step (4) uses spray shaping, i.e., by step (3)
Obtained suspension passes through spray-drying installation, and atomization forms small complex liquid drop, moisture is removed in dried medium, is obtained
To graphene-carbon black-alumina composite particle.
4. modified fluorubber as described in claim 1, it is characterised in that the surfactant is dodecyl ethyoxyl sulfo group
One kind in glycine betaine, dodecyl hydroxypropyl sulfobetaines, polyethylene glycol；The addition of the polyacrylamide is oxidation
The 50-300% of graphene quality；Acid solution in step (2) refers to the hydrochloric acid or nitric acid that pH value is 3-5.
5. modified fluorubber as described in claim 1, it is characterised in that the grain of the graphene-carbon black-alumina composite particle
Footpath is 1-200 microns.
6. modified fluorubber as described in claim 1, it is characterised in that the grain of the graphene-carbon black-alumina composite particle
Footpath is 10-50 microns.
7. modified fluorubber as described in claim 1, it is characterised in that the carbon black can also be replaced with barium sulfate.
8. modified fluorubber as described in claim 1, it is characterised in that the fluorubber further includes carbon black, magnesia, hydroxide
Calcium, bisphenol AF, BPP, microwax.
9. the preparation method of modified fluorubber, comprises the following steps, by 100 parts of fluorubber as described in claim any one of 1-8
Raw rubber is placed on open mill, bottom sheet after roll-in 10-15min, and wherein the plasticating temperature of open mill preliminary roller is 55-60 DEG C, open mill
The plasticating temperature of back roller is 40-50 DEG C；Crude fluororubber is placed in mixer, sequentially adds 0.1-3 parts of microwaxes, 5-25 parts of oxygen
Change magnesium, 1-5 parts of calcium hydroxides, 10-30 parts of graphene-carbon black-alumina composite particles, discharge after being kneaded uniformly；Wherein, it is kneaded
Temperature is 60-65 DEG C, mixing time 2-3min；Treated, and mixture placement 12-36h is placed in open mill, is added in
0.5-2 parts of bisphenol AFs and 0.1-0.5 parts of BPP are vulcanized, and the curing temperature of one step cure is 150-180 DEG C, and vulcanization time is
0.5-1h, be continuously heating to 200-210 DEG C progress post vulcanization 12-24h, be finally cooled to less than 60-80 DEG C afterwards bottom sheet to get
The fluorubber.
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