CN106589589A - Anti-static polypropylene composite material based on graphene and preparation method thereof - Google Patents
Anti-static polypropylene composite material based on graphene and preparation method thereof Download PDFInfo
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- CN106589589A CN106589589A CN201611107836.7A CN201611107836A CN106589589A CN 106589589 A CN106589589 A CN 106589589A CN 201611107836 A CN201611107836 A CN 201611107836A CN 106589589 A CN106589589 A CN 106589589A
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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
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
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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
- C08L2201/00—Properties
- C08L2201/04—Antistatic
Abstract
The invention relates to an anti-static polypropylene composite material based on graphene and a preparation method thereof. The anti-static polypropylene composite material is prepared by a polypropylene matrix, modified graphene, carbon fiber, modified zinc oxide, a filler, a compatibilizer and an antioxidant, wherein the modified graphene is graphene oxide and silver nitrate solution processed by a co-reduction reaction, the filler is obtained by mixing silver-loaded hollow glass bead and carbon black; the method comprises the following steps: uniformly mixing the polypropylene matrix, modified graphene, carbon fiber, modified zinc oxide, the filler, the compatibilizer and the antioxidant in a blender mixer, and then pelleting a mixture by an extruding machine top obtain the final product. According to the invention, the modified graphene, carbon fiber, modified zinc oxide, and the filler are mutually effected, the mechanical usability of the composite material can be ensured, the composite material has anti-static performance, can satisfy that the polypropylene composite material can be used in the special field, and expands the application of polypropylene.
Description
Technical field
The invention belongs to polymer composites field, particularly relates to a kind of multiple based on Graphene Antistatic type polypropylene
Condensation material and preparation method thereof.
Background technology
Polypropylene is polymerized by propylene monomer as universal thermoplastic, because its have little density, easy processing,
It is nontoxic, there are good mechanical performance, endurance surrender property and stress cracking resistance, and can reclaim and reuse, thus
The aspects such as auto industry, electrical equipment industry, article of everyday use and packaging industry have a wide range of applications.But polypropylene shrinkage factor is big, table
Face easily scratches, easily aging, and its strand contains methyl, increases whole molecule chain rigidity, reduces its impact property, so as to
Purposes of the polypropylene material in special dimension is limited, therefore to expand the use territory of polypropylene material, is needed to poly-
Propylene is modified process.
Two-dimentional carbon element crystal of the Graphene as discovered in recent years, with prominent and excellent heat conductivility, mechanical property
And electric property, its nanostructured is also very unique, and Graphene has larger specific surface area, and a small amount of addition just can be right
Polymeric matrix performance produces significant impact.But graphenic surface and inert state, it is compatible with the interface of other media
Property it is poor, and Graphene has stronger Van der Waals force between layers, easily produces aggregation each other, and Graphene strengthens polymer
The raising of composite property depends on the raising of interface bond strength, and the factor of the most critical of controlling interface bond strength is right
Graphene is surface-treated, and increases the effective functional group of graphenic surface, and Graphene is effectively improved by being modified with polymer
Interface cohesion.Graphene forms nanoscale dispersion in polymeric matrix, is improving hot property, mechanical property and the electricity of polymer
Learn the aspects such as performance and there are bigger potentiality.The appropriate Graphene of addition can be such that the mechanical property of matrix resin obtains significantly
Improve, overcome general inorganic filler usage amount greatly, and rigidity, thermostability, dimensional stability and toughness can not be taken into account while carrying
High shortcoming.Graphene relies on its excellent electric conductivity and extremely low addition, becomes a kind of conductive modified agent of great potential.
Therefore, there is good application prospect by the polymer-modified nano composite material for preparing of Graphene.
The content of the invention
The purpose of the present invention is to propose to a kind of based on Graphene Antistatic type PP composite material and preparation method thereof, pin
To above-mentioned technical problem, requirement of the PP composite material at the aspect such as antistatic effect and mechanical strength is met.
The technical scheme that adopted for achieving the above object of the present invention for：
It is a kind of to be based on Graphene Antistatic type PP composite material, by polypropylene matrix, modified graphene, carbon fiber,
Modified zinc oxide, filler, compatilizer and antioxidant are made, by weight, polypropylene matrix 60-70 parts, modified graphene 5-8
Part, carbon fiber 10-15 parts, modified zinc oxide 8-15 parts, filler 13-17 parts, compatilizer 5-8 parts and antioxidant 1-2 parts；It is described
Modified graphene be graphene oxide and silver nitrate solution coreduction reaction treatment；Described modified zinc oxide is six hydration nitre
Sour zinc, sodium hydroxide, hexamethylenetetramine and sodium fluoride by weight 7:1:1:2 mixing, then dissolve in deionized water, mix
The ratio of compound and deionized water is 1g：1-1.5h is stirred under 20-25mL, room temperature, then 10h is reacted at 120 DEG C, by product
Sucking filtration, washing, drying, obtain modified zinc oxide, and described filler compares 2- according to weight to carry silver-colored hollow glass micropearl and white carbon black
3：1 mixes.
Described modified graphene step is to weigh silver nitrate first to be dissolved in deionized water and ethylene glycol mixture, three
The ratio of person is 1g:100mL:200mL, then weighs graphene oxide and is dissolved in ethylene glycol, and ratio therebetween is 1g:10mL,
Ultrasonic 1h, then according to volume ratio 1:2-3, adds silver nitrate mixed solution, 50-60 DEG C of water-bath in graphene oxide suspension
Lower stirring 2-3h, mixing speed 400r/min；It is subsequently adding the NaBH that concentration is 0.1mol/L4Solution, and increase reflux,
2-2.5h is heated to reflux at 120 DEG C, is finally filtered, spent ion-cleaning 3-5 time, drying, obtain modified graphene.
Described carbon fiber adopt condensing reflux mode, 70-80 DEG C in acetone soln at soak 48h after, be dried；Then
According to 1g：It is 3 that dry carbon fiber is added volume ratio by 200ml:In 1 concentrated sulphuric acid and concentrated nitric acid nitration mixture, 60-70 DEG C of acidifying 5-
6h, last deionized water wash away surface residual acid, are dried.
1-5 part europium oxides are additionally added in described filler.
1-3 part silver pastes are additionally added in described filler.
The above-mentioned preparation method based on Graphene Antistatic type PP composite material, is first according to aforementioned proportion and weighs original
Material is simultaneously modified process to raw material, then melts modified raw material with polypropylene matrix and other additives in proportion
Mixing, obtains being based ultimately upon Graphene Antistatic type PP composite material, it is characterised in that：Described is processed to raw material
Refer to：First weigh silver nitrate to be dissolved in deionized water and ethylene glycol mixture, the ratio of three is 1g:100mL:200mL, then
Weigh graphene oxide and be dissolved in ethylene glycol, ratio therebetween is 1g:10mL, ultrasonic 1h, then according to volume ratio 1:2-3,
Silver nitrate mixed solution is added in graphene oxide suspension, 2-3h, mixing speed 400r/min under 50-60 DEG C of water-bath, is stirred；
It is subsequently adding the NaBH that concentration is 0.1mol/L4Solution, and increase reflux, 2-2.5h is heated to reflux at 120 DEG C, finally
Filter, spend ion-cleaning 3-5 time, drying, obtain modified graphene.
According to the above ratio, first polypropylene matrix, modified graphene, carbon fiber, modified zinc oxide, filler, compatilizer and
During antioxidant adds batch mixer, mix 0.5h, the compound of mix homogeneously is added into double screw extruder, screw speed then
For 40～50r/min, in extruder barrel, temperature is set to：One 155-160 DEG C of area, 165-170 DEG C of 2nd area, three area 175-180
DEG C, 180-185 DEG C of 4th area, compound extruded machine extrusion is obtained based on Graphene Antistatic type PP composite material.
In the present invention, described polypropylene matrix is isotactic polypropylene or syndiotactic polypropylene, and its molten value is 1-10g/min；
Described carbon fiber length be 3-5mm, 6-7 μm of diameter；The Zinc Oxide bulk density is 0.4-0.6g/mL；It is described to carry silver sky
Heart glass microballoon, commercially available, 20-30 μm of particle diameter, the white carbon black are conductive black, and particle diameter is 20-30nm, the europium oxide and silver paste
It is commercially available.Described compatilizer is maleic anhydride inoculated polypropylene, and described antioxidant is Hinered phenols antioxidant
Using by graphene oxide and the common reduction treatment of silver nitrate in the present invention, it is supported by processing Nano silver grain
In graphene film layer surface, while the presence of silver particles can also prevent graphene oxide reduction process from overlaping, it is ensured that
It is abundant that graphene oxide is reduced, and graphene oxide reduces its surface activity after coreduction, increases which in polypropylene matrix
In degree of scatter, while its area load silver particles also increases its conductivity, reduce the resistivity of composite.
Furthermore, condensing reflux mode is adopted to the carbon fiber in the present invention, with acetone soln process, carbon fiber processing is removed
The slurry on process surface, and etched with concentrated sulphuric acid and concentrated nitric acid nitration mixture, surface roughness is improved, surface activity is reduced, is increased which
Dispersibility in the base, and improve adhesion between carbon fiber and basal body interface.Carbon fiber and modified graphite in the composite
Alkene is mutually overlapped to form three-dimensional network, and three-dimensional network can not only play a part of Stress Transfer, while three-dimensional network can also be made
For conductive path.The silver-colored filler such as hollow glass micropearl and white carbon black is carried by addition in the base, silver-colored hollow glass micropearl and charcoal is carried
It is black to be filled into from different-grain diameter in three-dimensional network skeleton, increase the overlapped points of carbon fiber and modified graphene, improve conductive logical
Way amount, reduces composite material resistance rate, in addition composite when being acted on by extraneous stress, carry silver-colored hollow glass micropearl and
White carbon black can absorb transmission energy, have certain strengthening action to composite, furthermore in the course of processing, in shear action
Under, carry and interact between silver-colored hollow glass micropearl and white carbon black and other additives, improve from matrices of composite material
In dispersion.
Furthermore, modified zinc oxide in the present invention, compared with commercially available Zinc Oxide, modified zinc oxide surface activity in the present invention
It is low, without being just dispersed in very well in PP composite material matrix, to composite power by other surfaces activating agent is modified
The raising for learning performance has good potentiation.
Additionally, europium oxide can also be added in the present invention, europium oxide has special 4f electron configuration energy levels, and electronics is easy
Generation transition, produces activation energy, is added in the three-dimensional net structure of composite, due to its special energy level, Ke Yixian
Write the electric conductivity for improving composite；Furthermore a small amount of silver paste added in filler, in mixing process, a small amount of silver paste can be carried
High additive and PP GRANULES adhesive force, improve additive dispersibility in the base during being conducive to post-production.
Beneficial effect：1st, graphene oxide is adopted and silver nitrate coreduction, Nano silver grain is supported on into graphite oxide
Alkene sheet surfaces, not only reduce graphenic surface activity, while improving the steering capability of Graphene；
2nd, adopt and carry silver-colored hollow glass micropearl and white carbon black can increase carbon fiber and modified graphene for filler, on the one hand
Overlapped points, improve conductive path quantity, reduce composite material resistance rate, on the other hand when being acted on by extraneous stress, carry silver
Hollow glass micropearl and white carbon black can absorb transmission energy, have certain strengthening action to composite, simultaneously because carrying silver
Hollow glass micropearl has certain ball effect, can improve the flowing of Composite Melt during composite processing
Property, be conducive to the optimization of working process parameter；
3rd, europium oxide can also be added in the present invention, using the special energy level of europium oxide, electronics is susceptible to transition, produces work
Change energy E, the electric conductivity of carbon fiber and modified graphene three-dimensional net structure can be significantly improved；
4th, preparation process is simple of the present invention, is not polluted to environment using additive, and the product of the present invention can be by poly- third
Alkene composite is applied to some special dimensions, expands the polyacrylic scope of application.
Specific embodiment
With reference to specific embodiment, the present invention is further elaborated, and in following embodiment, raw material used is
The conventional raw material in this area or from can be commercially available on the market.
Embodiment 1
It is a kind of to be based on Graphene Antistatic type PP composite material, by polypropylene matrix, modified graphene, carbon fiber,
Modified zinc oxide, filler, compatilizer and antioxidant are made, by weight, 60 parts of polypropylene matrix, 5 parts of modified graphene, carbon
10 parts of fiber, 8 parts of modified zinc oxide, 13 parts of filler, compatilizer account for 1 part of part and antioxidant；Described modified graphene is oxygen
Graphite alkene and silver nitrate solution coreduction reaction treatment；Described modified zinc oxide be zinc nitrate hexahydrate, sodium hydroxide, six
Methenamine and sodium fluoride by weight 7:1:1:2 mixing, are then dissolved in deionized water, mixture and deionized water
Than for 1g：1h being stirred under 20mL, room temperature, then 10h being reacted at 120 DEG C, product sucking filtration, washing, drying are modified
Zinc Oxide, described filler are to carry silver-colored hollow glass micropearl and white carbon black according to 2：1 mixes.
The above-mentioned preparation method based on Graphene Antistatic type PP composite material, is first according to aforementioned proportion and weighs original
Material is simultaneously modified process to raw material, then melts modified raw material with polypropylene matrix and other additives in proportion
Mixing, obtains being based ultimately upon Graphene Antistatic type PP composite material, it is characterised in that：Described is processed to raw material
Refer to：First weigh silver nitrate to be dissolved in deionized water and ethylene glycol mixture, the ratio of three is 1g:100mL:200mL, then
Weigh graphene oxide and be dissolved in ethylene glycol, ratio therebetween is 1g:10mL, ultrasonic 1h, then according to volume ratio 1:2, in oxygen
Silver nitrate mixed solution is added in graphite alkene suspension, under 50 DEG C of water-baths, 2h, mixing speed 400r/min is stirred；It is subsequently adding
NaBH of the concentration for 0.1mol/L4Solution, and increase reflux, is heated to reflux 2h at 120 DEG C, finally filter, spend from
Seed detergent 3 times, drying, obtain modified graphene.
According to the above ratio, first polypropylene matrix, modified graphene, carbon fiber, modified zinc oxide, filler, compatilizer and
During antioxidant adds batch mixer, mix 0.5h, the compound of mix homogeneously is added into double screw extruder, screw speed then
For 40r/min, in extruder barrel, temperature is set to：One 155 DEG C of area, 167 DEG C of 2nd area, 175 DEG C of 3rd area, 180 DEG C of 4th area, mixing
Expect extruded machine extrusion, be obtained based on Graphene Antistatic type PP composite material.
Above for the present embodiment basic embodiment, can more than on the basis of further improved, optimized and limited：
Such as, the modification procedure of described modified graphene, weighs silver nitrate first and is dissolved in deionized water and ethylene glycol mixing
In liquid, the ratio of three is 1g:100mL:200mL, then weighs graphene oxide and is dissolved in ethylene glycol, and ratio therebetween is
1g:10mL, ultrasonic 1h, then according to volume ratio 1:2, the addition silver nitrate mixed solution in graphene oxide suspension, 50 DEG C
2h, mixing speed 400r/min are stirred under water-bath；It is subsequently adding the NaBH that concentration is 0.1mol/L4Solution, and increase backflow dress
Put, 2h is heated to reflux at 120 DEG C, finally filter, spend ion-cleaning 3 times, drying, obtain modified graphene；
Such as, described carbon fiber adopt condensing reflux mode, 70-80 DEG C in acetone soln at soak 48h after, be dried；
Then according to 1g：It is 3 that dry carbon fiber is added volume ratio by 200ml:In 1 concentrated sulphuric acid and concentrated nitric acid nitration mixture, 60 DEG C of acidifyings
5h, last deionized water wash away surface residual acid, are dried；
For another example, 1 part of europium oxide is additionally added in described filler；
Finally, 1 part of silver paste is additionally added in described filler.
Embodiment 2
It is a kind of to be based on Graphene Antistatic type PP composite material, by polypropylene matrix, modified graphene, carbon fiber,
Modified zinc oxide, filler, compatilizer and antioxidant are made, by weight, 65 parts of polypropylene matrix, 7 parts of modified graphene, carbon
1 part of 13 parts of fiber, 11 parts of modified zinc oxide, 15 parts of filler, 6 parts of compatilizer and antioxidant；Described modified graphene is oxygen
Graphite alkene and silver nitrate solution coreduction reaction treatment；Described modified zinc oxide be zinc nitrate hexahydrate, sodium hydroxide, six
Methenamine and sodium fluoride mixing by weight 7:1:1:2 mixing, are then dissolved in deionized water, mixture and deionization
The ratio of water is 1g：1.5h being stirred under 23mL, room temperature, then 10h being reacted at 120 DEG C, product sucking filtration, washing, drying are obtained
To modified zinc oxide, described filler is to carry silver-colored hollow glass micropearl and white carbon black according to 3：1 mixes.
The above-mentioned preparation method based on Graphene Antistatic type PP composite material, is first according to aforementioned proportion and weighs original
Material is simultaneously modified process to raw material, then melts modified raw material with polypropylene matrix and other additives in proportion
Mixing, obtains being based ultimately upon Graphene Antistatic type PP composite material, described to carry out process to raw material and refer to：First weigh
Silver nitrate is dissolved in deionized water and ethylene glycol mixture, and the ratio of three is 1g:100mL:200mL, then weighs oxidation stone
Black alkene is dissolved in ethylene glycol, and ratio therebetween is 1g:10mL, ultrasonic 1h, then according to volume ratio 1:3, it is outstanding in graphene oxide
Silver nitrate mixed solution is added in supernatant liquid, under 60 DEG C of water-baths, 2.5h, mixing speed 400r/min is stirred；Being subsequently adding concentration is
The NaBH of 0.1mol/L4Solution, and increase reflux, 2.5h is heated to reflux at 120 DEG C, is finally filtered, washed with deionization
5 times, drying are washed, modified graphene is obtained.
According to the above ratio, first polypropylene matrix, modified graphene, carbon fiber, modified zinc oxide, filler, compatilizer and
During antioxidant adds batch mixer, mix 0.5h, the compound of mix homogeneously is added into double screw extruder, screw speed then
For 40～50r/min, in extruder barrel, temperature is set to：One 160 DEG C of area, 168 DEG C of 2nd area, 177 DEG C of 3rd area, 183 DEG C of 4th area,
The extruded machine extrusion of compound, is obtained based on Graphene Antistatic type PP composite material.
Above for the present embodiment basic embodiment, can more than on the basis of further improved, optimized and limited：
Such as, described modified graphene modification procedure, weighs silver nitrate first and is dissolved in deionized water and ethylene glycol mixture
In, the ratio of three is 1g:100mL:200mL, then weighs graphene oxide and is dissolved in ethylene glycol, and ratio therebetween is 1g:
10mL, ultrasonic 1h, then according to volume ratio 1:3, silver nitrate mixed solution, 60 DEG C of water-baths are added in graphene oxide suspension
Lower stirring 2.5h, mixing speed 400r/min；It is subsequently adding the NaBH that concentration is 0.1mol/L4Solution, and increase reflux,
2.5h is heated to reflux at 120 DEG C, is finally filtered, spent ion-cleaning 5 times, drying, obtain modified graphene；
Such as, described carbon fiber adopts condensing reflux mode, after soaking 48h, is dried in acetone soln at 80 DEG C；Then
According to 1g：It is 3 that dry carbon fiber is added volume ratio by 200ml:In 1 concentrated sulphuric acid and concentrated nitric acid nitration mixture, 70 DEG C of acidifying 6h, most
Deionized water washes away surface residual acid afterwards, and is dried；
For another example, 3 parts of europium oxides are additionally added in described filler；
Finally, 2 parts of silver pastes are additionally added in described filler.
Embodiment 3
It is a kind of to be based on Graphene Antistatic type PP composite material, by polypropylene matrix, modified graphene, carbon fiber,
Modified zinc oxide, filler, compatilizer and antioxidant are made, by weight, 70 parts of polypropylene matrix, 8 parts of modified graphene, carbon
2 parts of 15 parts of fiber, 15 parts of modified zinc oxide, 17 parts of filler, 8 parts of compatilizer and antioxidant；Described modified graphene is oxygen
Graphite alkene and silver nitrate solution coreduction reaction treatment；Described modified zinc oxide be zinc nitrate hexahydrate, sodium hydroxide, six
Methenamine and sodium fluoride by weight 7:1:1:2 mixing, then re-dissolved in deionized water, mixture and deionized water
Ratio be 1g：1.5h being stirred under 25mL, room temperature, then 10h being reacted at 120 DEG C, product sucking filtration, washing, drying are obtained
Modified zinc oxide, described filler are to carry silver-colored hollow glass micropearl and white carbon black according to 3：1 mixes.
The above-mentioned preparation method based on Graphene Antistatic type PP composite material, is first according to aforementioned proportion and weighs original
Material is simultaneously modified process to raw material, then melts modified raw material with polypropylene matrix and other additives in proportion
Mixing, obtains being based ultimately upon Graphene Antistatic type PP composite material, described to carry out process to raw material and refer to：First weigh
Silver nitrate is dissolved in deionized water and ethylene glycol mixture, and the ratio of three is 1g:100mL:200mL, then weighs oxidation stone
Black alkene is dissolved in ethylene glycol, and ratio therebetween is 1g:10mL, ultrasonic 1h, then according to volume ratio 1:3, it is outstanding in graphene oxide
Silver nitrate mixed solution is added in supernatant liquid, under 60 DEG C of water-baths, 3h, mixing speed 400r/min is stirred；Being subsequently adding concentration is
The NaBH of 0.1mol/L4Solution, and increase reflux, 2.5h is heated to reflux at 120 DEG C, is finally filtered, washed with deionization
5 times, drying are washed, modified graphene is obtained.
According to the above ratio, first polypropylene matrix, modified graphene, carbon fiber, modified zinc oxide, filler, compatilizer and
During antioxidant adds batch mixer, mix 0.5h, the compound of mix homogeneously is added into double screw extruder, screw speed then
For 40～50r/min, in extruder barrel, temperature is set to：One 160 DEG C of area, 170 DEG C of 2nd area, 180 DEG C of 3rd area, 185 DEG C of 4th area,
The extruded machine extrusion of compound, is obtained based on Graphene Antistatic type PP composite material.
Above for the present embodiment basic embodiment, can more than on the basis of further improved, optimized and limited：
Such as, described modified graphene modification procedure, weighs silver nitrate first and is dissolved in deionized water and ethylene glycol mixture
In, the ratio of three is 1g:100mL:200mL, then weighs graphene oxide and is dissolved in ethylene glycol, and ratio therebetween is 1g:
10mL, ultrasonic 1h, then according to volume ratio 1:3, silver nitrate mixed solution, 60 DEG C of water-baths are added in graphene oxide suspension
Lower stirring 3h, mixing speed 400r/min；It is subsequently adding the NaBH that concentration is 0.1mol/L4Solution, and increase reflux,
2.5h is heated to reflux at 120 DEG C, is finally filtered, spent ion-cleaning 5 times, drying, obtain modified graphene；
Such as, described carbon fiber adopts condensing reflux mode, after soaking 48h, is dried in acetone soln at 80 DEG C；Then
According to 1g：It is 3 that dry carbon fiber is added volume ratio by 200ml:In 1 concentrated sulphuric acid and concentrated nitric acid nitration mixture, 70 DEG C of acidifying 5-6h,
Last deionized water washes away surface residual acid, and is dried；
For another example, 5 parts of europium oxides are additionally added in described filler；
Finally, 3 parts of silver pastes are additionally added in described filler.
Contrast test
Method according to embodiment of the present invention 1-3 prepare respectively three dimensions it is identical resisted based on Graphene it is quiet
Electric type PP composite material sample, and volume is designated as sample 1, sample 2, sample 3, is then prepared using the method for the present invention in addition
It is identical based on Graphene Antistatic type PP composite material sample with sample 1, sample 2,3 dimensions of sample, remember
For sample 4, the difference only graphene oxide of sample 4 and sample 2 is only through conventional Ultrasound 1.5h process；According to the side of the present invention
The weight ratio that method prepares raw material and its filler used in sample 5, and sample 5 is identical with sample 2, and which is distinguished as the oxygen for using
Change zinc is conventional commercial Zinc Oxide, prepares sample 6 according to the method for the present invention, with being distinguished as in sample 6 without addition for sample 2
Europium oxide.
Carry out mechanical strength respectively to above sample under the same conditions and antistatic property is determined, experimental data is as follows：
Claims (7)
- It is 1. a kind of to be based on Graphene Antistatic type PP composite material, it is characterised in that：By polypropylene matrix, modified graphite Alkene, carbon fiber, modified zinc oxide, filler, compatilizer and antioxidant are made, and by weight, polypropylene matrix 60-70 parts, change Property Graphene 5-8 parts, carbon fiber 10-15 parts, modified zinc oxide 8-15 parts, filler 13-17 parts, compatilizer 5-8 parts and antioxidation Agent 1-2 parts；Described modified graphene is graphene oxide and silver nitrate solution coreduction reaction treatment；Described is modified oxidized Zinc is zinc nitrate hexahydrate, sodium hydroxide, hexamethylenetetramine and sodium fluoride by weight 7:1:1:2 mixing, then spend from The ratio of sub- water dissolution, mixture and deionized water is 1g：1-1.5h is stirred under 20-25mL, room temperature, then 120oReact under C 10h, by product sucking filtration, washing, drying, obtains modified zinc oxide, and described filler is the silver-colored hollow glass micropearl of load and charcoal It is black to compare 2-3 according to weight：1 mixes.
- 2. according to claim 1 a kind of based on Graphene Antistatic type PP composite material, it is characterised in that：It is described Modified graphene step be to weigh silver nitrate first to be dissolved in deionized water and ethylene glycol mixture, the ratio of three is 1g: 100mL:200mL, then weighs graphene oxide and is dissolved in ethylene glycol, and ratio therebetween is 1g:10mL, ultrasonic 1h, then presses According to volume ratio 1:2-3, adds silver nitrate mixed solution, 50-60 in graphene oxide suspensiono2-3h is stirred under C water-baths, is stirred Mix speed 400r/min；It is subsequently adding the NaBH that concentration is 0.1mol/L4Solution, and increase reflux, 120oHeat under C Backflow 2-2.5h, finally filters, spends ion-cleaning 3-5 time, drying, obtain modified graphene.
- 3. according to claim 1 a kind of based on Graphene Antistatic type PP composite material, it is characterised in that：It is described Carbon fiber, using condensing reflux mode, the 70-80 in acetone solnoAfter soaking 48h under C, it is dried；Then according to 1g： It is 3 that dry carbon fiber is added volume ratio by 200ml:In 1 concentrated sulphuric acid and concentrated nitric acid nitration mixture, 60-70oC-acid 5-6h, finally Deionized water washes away surface residual acid, is dried.
- 4. according to claim 1 a kind of based on Graphene Antistatic type PP composite material, it is characterised in that：It is described Filler in be additionally added 1-5 part europium oxides.
- 5. according to claim 1 a kind of based on Graphene Antistatic type PP composite material, it is characterised in that：It is described Filler in be additionally added 1-3 part silver pastes.
- 6. a kind of preparation method based on Graphene Antistatic type PP composite material as claimed in claim 1, is pressed first Raw material is weighed according to aforementioned proportion and process is modified to raw material, then by modified raw material and polypropylene matrix and other additions Material carries out melting mixing in proportion, obtains being based ultimately upon Graphene Antistatic type PP composite material, it is characterised in that：It is described Process carried out to raw material refer to：First weigh silver nitrate to be dissolved in deionized water and ethylene glycol mixture, the ratio of three is 1g: 100mL:200mL, then weighs graphene oxide and is dissolved in ethylene glycol, and ratio therebetween is 1g:10mL, ultrasonic 1h, then presses According to volume ratio 1:2-3, adds silver nitrate mixed solution, 50-60 in graphene oxide suspensiono2-3h is stirred under C water-baths, is stirred Mix speed 400r/min；It is subsequently adding the NaBH that concentration is 0.1mol/L4Solution, and increase reflux, 120oHeat under C Backflow 2-2.5h, finally filters, spends ion-cleaning 3-5 time, drying, obtain modified graphene.
- 7. a kind of preparation method based on Graphene Antistatic type PP composite material according to claim 6, which is special Levy and be：According to the above ratio, polypropylene matrix, modified graphene, carbon fiber, modified zinc oxide, filler, compatilizer and anti-first During oxidant adds batch mixer, mix 0.5h, then by the compound addition double screw extruder of mix homogeneously, screw speed is 40 ~ 50r/min, in extruder barrel, temperature is set to：One 155-160 DEG C of area, 165-170 DEG C of 2nd area, 175-180 DEG C of 3rd area, Four 180-185 DEG C of areas, the extruded machine extrusion of compound, are obtained based on Graphene Antistatic type PP composite material.
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Cited By (11)
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| CN107858059A (en) * | 2017-11-21 | 2018-03-30 | 新化县中润化学科技有限公司 | A kind of graphene silver waterborne conductive coating compound and preparation method |
| CN107987510A (en) * | 2017-11-30 | 2018-05-04 | 安徽坤大化学锚固有限公司 | A kind of coal mining Antistatic type polyurethane Anchor Agent and its preparation process |
| CN110117393A (en) * | 2019-04-26 | 2019-08-13 | 集美大学 | A kind of graphene Masterbatch material and preparation method thereof with antistatic property |
| CN110284265A (en) * | 2019-07-09 | 2019-09-27 | 杭州高烯科技有限公司 | A kind of multi-functional graphene modification nonwoven cloth and preparation method thereof |
| CN110885493A (en) * | 2019-11-21 | 2020-03-17 | 万华化学（宁波）有限公司 | Carbon fiber reinforced polypropylene composite material and preparation method thereof |
| CN111995823A (en) * | 2020-08-11 | 2020-11-27 | 清远市宏达环保塑胶材料科技有限公司 | Antistatic corrugated board |
| CN114656722A (en) * | 2022-04-26 | 2022-06-24 | 台州一帆环保设备科技有限公司 | Antistatic air pipe |
| CN115160693A (en) * | 2022-07-21 | 2022-10-11 | 建德市华丰环保科技有限公司 | Three-layer composite polypropylene antistatic material and preparation method thereof |
| CN115232384A (en) * | 2022-08-25 | 2022-10-25 | 青岛优派普环保科技股份有限公司 | Antistatic PE gas pipe and preparation method thereof |
| WO2023123070A1 (en) * | 2021-12-28 | 2023-07-06 | 周菊青 | High-pressure-resistant pipeline plastic and preparation method therefor |
| CN117050427A (en) * | 2023-08-29 | 2023-11-14 | 广州工程技术职业学院 | Fluorescent polypropylene compound for 3D printing and preparation method thereof |
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| CN107858059A (en) * | 2017-11-21 | 2018-03-30 | 新化县中润化学科技有限公司 | A kind of graphene silver waterborne conductive coating compound and preparation method |
| CN107987510A (en) * | 2017-11-30 | 2018-05-04 | 安徽坤大化学锚固有限公司 | A kind of coal mining Antistatic type polyurethane Anchor Agent and its preparation process |
| CN110117393A (en) * | 2019-04-26 | 2019-08-13 | 集美大学 | A kind of graphene Masterbatch material and preparation method thereof with antistatic property |
| CN110284265A (en) * | 2019-07-09 | 2019-09-27 | 杭州高烯科技有限公司 | A kind of multi-functional graphene modification nonwoven cloth and preparation method thereof |
| CN110885493B (en) * | 2019-11-21 | 2022-04-22 | 万华化学（宁波）有限公司 | Carbon fiber reinforced polypropylene composite material and preparation method thereof |
| CN110885493A (en) * | 2019-11-21 | 2020-03-17 | 万华化学（宁波）有限公司 | Carbon fiber reinforced polypropylene composite material and preparation method thereof |
| CN111995823A (en) * | 2020-08-11 | 2020-11-27 | 清远市宏达环保塑胶材料科技有限公司 | Antistatic corrugated board |
| WO2023123070A1 (en) * | 2021-12-28 | 2023-07-06 | 周菊青 | High-pressure-resistant pipeline plastic and preparation method therefor |
| CN114656722A (en) * | 2022-04-26 | 2022-06-24 | 台州一帆环保设备科技有限公司 | Antistatic air pipe |
| CN115160693A (en) * | 2022-07-21 | 2022-10-11 | 建德市华丰环保科技有限公司 | Three-layer composite polypropylene antistatic material and preparation method thereof |
| CN115232384A (en) * | 2022-08-25 | 2022-10-25 | 青岛优派普环保科技股份有限公司 | Antistatic PE gas pipe and preparation method thereof |
| CN115232384B (en) * | 2022-08-25 | 2023-02-10 | 青岛优派普环保科技股份有限公司 | Antistatic PE gas pipe and preparation method thereof |
| CN117050427A (en) * | 2023-08-29 | 2023-11-14 | 广州工程技术职业学院 | Fluorescent polypropylene compound for 3D printing and preparation method thereof |
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