CN107057192A - Functionalization graphene strengthens the preparation method of composite polyolefine material - Google Patents
Functionalization graphene strengthens the preparation method of composite polyolefine material Download PDFInfo
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- CN107057192A CN107057192A CN201710339294.4A CN201710339294A CN107057192A CN 107057192 A CN107057192 A CN 107057192A CN 201710339294 A CN201710339294 A CN 201710339294A CN 107057192 A CN107057192 A CN 107057192A
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
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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
- C08K9/00—Use of pretreated ingredients
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
Abstract
The invention provides the preparation method that a kind of functionalization graphene strengthens composite polyolefine material, the preparation method includes：S1, graphene or graphene oxide pre-processed, obtain functionalization graphene；S2, functionalization graphene and polyolefin substrate be subjected to high speed premix, obtain mixed material；S3, the water cooling granulation after combination process by mixed material, obtain graphene compound polyolefin particle；Graphene compound polyolefin particle is molded or compression molding, graphene enhancing composite polyolefine material is made.The present invention provides direct method for preparation of industrialization High performance polyolefin base graphene composite material, and it is difficult to solve graphene modification simultaneously, the problem of twin-screw composite diffusion is poor, eventually through the preparation method of this high efficiency continuously, the polyolefin functional composite material of different field adaptive type has been obtained.
Description
Technical field
The present invention relates to the preparation method of composite, in particular it relates to which a kind of functionalization graphene enhancing polyolefin is answered
The preparation method of condensation material.
Background technology
Graphene nanocomposite material is using polymeric matrix as continuous phase, using graphene as dispersed phase, by appropriate
Preparation method graphene uniform is scattered in polymeric matrix material, form the compound system containing nano-sized materials.
Graphene nanocomposite material not only has skin effect, the quantum size effect of nano material, and by the firm of Nano filling
Property, toughness, processability, the dielectric properties of dimensional stability, heat endurance and polymer blend together it is many excellent so as to produce
Different in nature energy.The main polymeric matrix of graphene nanocomposite material has：Nylon-6, makrolon, epoxy resin, polyurethane,
Polystyrene, polymethyl methacrylate, SIS etc..And on graphene/poly-
The research report of olefin nanocomposite is less.
Publication No. CN104926960A patent of invention, disclose it is a kind of by in-situ polymerization technique prepare graphene/
Magnesium chloride is the method for the method for manufacturing diolefine polymerization catalyst of carrier.Publication No. CN105504469A patent of invention, discloses one
Plant the preparation method that graphene/polyolefin elastomer masterbatch, graphene anti-static composite material are prepared by solution combined technique.
But, in-situ polymerization technique and solution combined technique all have the shortcomings that discharge is high, efficiency is low, be difficult scale.
Publication No. CN104098816A patent of invention, propose a kind of polyolefin/graphene nanocomposite material and its
Comparatively preparation section is various for the functionalized modification method of graphene in preparation method, this method, and modification efficiency is low, cost phase
To higher；Publication No. CN105570560A patent of invention, mentions a kind of graphene increased thermal conductivity compound polyolefin pipe
A kind of high semi-conductive screen of polyolefin of cable graphene-containing is proposed in material, Publication No. CN103739929A patent of invention
Material and preparation method thereof, uses melting combination process, but the dispersion effect of the composite prepared in the two patents
It is not good, it is not easy to be directly realized by the preparation of industrialization and application of polyolefin-based graphene composite material.
The content of the invention
For defect of the prior art, it is combined it is an object of the invention to provide a kind of functionalization graphene enhancing polyolefin
The preparation method of material.
The present invention is achieved by the following technical solutions：
The present invention, which provides a kind of functionalization graphene, strengthens the preparation method of composite polyolefine material, the preparation method bag
Include：
S1, graphene or graphene oxide pre-processed, obtain functionalization graphene；
S2, functionalization graphene and polyolefin substrate premixed and (premixed at a high speed), obtain mixed material；
S3, the water cooling granulation after combination process by mixed material, obtain graphene compound polyolefin particle；Graphene is answered
Polyolefin particles processing and forming (being molded or compression molding) is closed, graphene enhancing composite polyolefine material is made.
Wherein, the pretreatment of graphene plays an important roll in whole process：First, the pretreatment of graphene sheet layer has
Help improve the compatibility between graphene sheet layer and polyolefin substrate；Secondly, the optimization processing direct relation of graphene-structured
Scattered journey of the graphene filler in polyolefin substrate in composite obtained by the twin-screw combination process by serialization
Degree.So will reach that optimal balance is then twin-screw melting combination process between the processing of graphenic surface and the control of structure
Prepare the most important link of composite polyolefine material.
Preferably, in step sl, the method for the pretreatment is method of modifying, the modified graphite oxide of graphene oxide
The physical modification method of the restoring method of alkene, the interim heat treatment method of modified graphene oxide or mechanical stripping graphene.
Wherein, the restoring method of modified graphene oxide, the interim heat treatment method of modified graphene oxide are in the present invention
The further processing carried out on the basis of the modified graphene oxide of preparation.The functionalization graphene is：Modified graphite oxide
Alkene, modified with reduction graphene oxide, interim heat treatment modified graphene oxide or physical modification mechanical stripping graphene.With showing
Some modification technologies are compared, and the maximum advantage of this technology is that reaction rate is fast, cost is low, simultaneously shortens graphene
Matting reduces scavenging period, substantially increases the modification efficiency of graphene.
Preferably, the method for modifying of the graphene oxide is：By graphite oxide in the deionized water system that pH is more than 2
Ultrasonically treated 2-20min, concentration of the graphene oxide in water is 0.05mg-50mg/ml, then adds organic modifiers (pin
To the modifying agent of the functionalization of different compound system addition variety classes and concentration), it is cold finally by flocculate suction filtration, washing
It is dry to produce modified graphene oxide.The modifying agent of difference in functionality, variety classes here are added for different compound systems
Added primarily directed to final polymeric matrix, in such as PP matrixes, we select the strong organic modifiers of hydrophobic performance, such as
Octadecyl dimethyl amine oxide, DDAO etc..
Preferably, the organic modifiers are octadecyl dimethyl amine oxide, DDAO, Gao Ju
Thing electrolyte, PDDA, imidazoline, morpholine guanidine, triazine derivative, polypropylene grafted maleic anhydride, polyacrylamide, low point
One or more in sub- weight polyacrylonitrile.Powered one end ion and surface of graphene oxide in cationic surfactant
Polar group occur electrophilic reaction, so as to rapid modified graphene oxide, so as to reversely be separated out from system.
Preferably, the addition of the organic modifiers is 0.5-2.0 times of graphene oxide quality.Adding proportion is too high
When mainly waste to modifying agent, be unfavorable for sufficient modification when addition is too low, thus influence modified graphene oxide with
The final consistency problem of polymeric matrix.
Preferably, the restoring method of the modified graphene oxide is：The modified graphene oxide of freeze-drying is disperseed
In oiliness organic phase, reducing agent is added, the graphene of certain reducing degree is obtained, then freezed, dry.Certain reduction journey
The graphene of degree can not completely be reduced mainly due to graphene oxide by chemical reaction.Wherein, the modified oxygen
Graphite alkene is equally to adopt to be prepared with the following method：By graphite oxide in the deionized water system that pH is more than 2 at ultrasound
Reason, adds organic modifiers, cold dry to produce then by flocculate suction filtration, washing.
Preferably, the one kind or several of the organic phase in dimethylbenzene, n-butanol, n-hexane, chloroform, atoleine
Kind, the reducing agent is selected from hydrazine hydrate, oxalic acid H2C2O4, potassium borohydride KBH4, sodium borohydride NaBH4In one or more.On
Stating reducing agent has reduction well to modified graphene oxide and improves the effect of Graphene powder bulk conductivity.
Preferably, the addition of the reducing agent is 0.1-2.0 times of modified graphene oxide quality.
Preferably, the reacting furnace temperature of the interim heat treatment method of the modified graphene oxide is 50-350 DEG C, rank
The specific steps of section property heat treatment include：First stage heat treatment is that a period of time, second are incubated in 50-120 DEG C of stove
Phase heat treatment continues to be incubated to be warming up in the range of 120-350 DEG C, finally gives the adjustable functionalization graphene of structure.Work as temperature
When spending high, modifier molecules chain sweeps away in high temperature and can decomposed, so that the modified effect of modified graphene oxide itself is damaged, and
It is unfavorable for the stripping and reduction of modified graphene oxide when temperature is too low, is unfavorable for modified graphene oxide final in the base
It is scattered.Wherein, the modified graphene oxide is equally to adopt to be prepared with the following method：Graphite oxide is more than 2 in pH
It is ultrasonically treated in deionized water system, organic modifiers are added, it is cold dry to produce then by flocculate suction filtration, washing.
Preferably, the physical modification method of the mechanical stripping graphene is the graphene ultrasound for preparing Physical
It is dispersed in water, ethanol or methyl pyrrolidone solvent, adds after macromolecule modifier processing, centrifuge the modification modified
Graphene, after finally solvent is replaced by the aqueous solution, cools down, dries.Wherein, the graphene one that Physical is prepared
As the graphene that obtains for mechanical stripping and supercritical expansion method, feature is that graphene-structured is complete, and heap density is of a relatively high.
Preferably, the macromolecule modifier is that macromolecule modifier gathers including sodium alginate, cellulose, lignin, shell
Sugar, PEO, PDDA, the PVDF of the PAA of low molecule amount or low molecule amount.Macromolecule modifier disperses to be formed to divide in a solvent first
The scattered Polymer Solution of sub- rank, these Gao Fen Duan also can be between graphene film while interaction and entanglement
Interacted, and then mutually tangled by Van der Waals for, simultaneously the specific surface area of graphene film super large is in solution body
Belong to upper state in system, thus it is unstable.And the trend of solution system is then to tend to lower state, and then stable state is reached, institute
Strong active force mutually tangles/attracted so as to obtain stable state, finally between connecting section by macromolecule with graphene film
Entanglement of the macromolecular chain on graphene film, realizes the physical modification to graphene film.
Preferably, the addition of the macromolecule modifier is 0.1-5.0 times of graphene quality, and too low addition is not
The modification to graphene can be completely realized, and the proportion of graphene powder is equally influenceed when too high, finally in the composite
When the interface composition of graphene and matrix is too high, stress/carrier etc. can not be effectively transmitted, so as to influence composite
The combination properties such as mechanics/calorifics/electricity.
Preferably, in step s 2, the polyolefin substrate is a kind of in polypropylene, polyethylene；The polypropylene bag
Include atactic copolymerized polypropene (PPR).
Preferably, in step s 2, functionalization graphene addition in polyolefin substrate is 0.5wt%-
10wt%；The functionalization graphene needs before premix to be dried with polyolefin substrate, and the time of the premix is 2-
15min.The time in each stage must be effectively controlled in whole process.For high speed pre-mix stage：Incorporation time is too short,
Graphene then fails equably to be attached in polyolefin particles, uneven after causing later stage twin-screw compound, and during mixed at high speed
Between it is long, high energy impact effect under, polyolefin particles can decompose influence end-use properties first, secondly, graphene premix
It can be stacked for a long time under machine high energy impact, it is scattered in polyolefin substrate that this is unfavorable for graphene sheet layer, ultimately results in material
The decline of combination property.
Preferably, in step s3, at least one in the blended melting equipment choosing double screw extruder, banbury
Kind.
Preferably, in step s3, the process conditions of the double screw extruder are that twin-screw warm area temperature is 160-260
DEG C, charging rate is 10-40g/min, and screw speed is 10-35r/min.For the twin-screw process segment：Charging rate is too fast
And screw speed it is too high when, graphene and polyolefin only have the extruding and shearing of short time high speed in screw rod, cause pre-
The graphene of processing is fully rubbed and peeled off by polymeric matrix, so as to influence graphene film in the base scattered.And enter
When material and screw speed are too low, screw rod only has slight extruding and shearing to matrix and graphene, is equally also unfavorable for graphene
Piece is scattered in polyolefin substrate, and then eventually affects the combination property of composite polyolefine material.
Preferably, in step s3, the graphene compound polyolefin particle be molded or compression molding before need into
Row drying.
Graphenic surface and structure are modified and optimized first in the present invention, then is cut by high speed mixing smelting machine in high energy
The effect of cutting is lower so that graphene uniform and be fully attached in polyolefin particles, eventually passes through twin-screw melt-processed, passes through
The shearing and extruding of screw rod, graphene is while being fully stripped it is also possible that molecular polyolefin arrangement and winding well
On graphene sheet layer.Under the influence of linkage effects, and then improve the mechanical performance and heat endurance of composite.Work as in addition
When increasing the concentration of graphene filler, graphene sheet layer is reached after threshold value, realizes that physical contact formula is conductive, due to passing through this hair
The conductivity threshold concentration for the graphene compound polyolefin material that bright method is obtained is not high, so such functional composite material
The combination property of (electromagnetic shielding material) do not significantly decrease, thus further the width application field of function element and
Use condition.
Compared with prior art, the present invention also has following beneficial effect：
1st, the present invention provides direct method for preparation of industrialization High performance polyolefin base graphene composite material, and together
When solve graphene and be modified difficult, the problem of twin-screw composite diffusion is poor, eventually through the preparation side of this high efficiency continuously
Formula, has obtained the polyolefin functional composite material of different field adaptive type.
2nd, in contrast to in-situ polymerization technique and solution combined technique, this method has the spy of zero-emission, high efficiency, scale
Point, has the characteristics of dispersion effect height can be prepared continuously in contrast to other melting combination process, thus can be directly realized by polyolefin
The preparation of industrialization and application of base graphene composite material.
3rd, the present invention in graphene pretreatment modification method, compared to existing method of modifying have prepare cost it is low, after
Phase process cycle is short, the characteristics of blowdown flow rate is low, so as to directly solve the big of graphene during composite prepare with scale
The problem of demand, and then provide raw materials requirement guarantor for the preparation of industrialization of functional polyolefin base graphene composite material
Barrier.
Brief description of the drawings
By reading the detailed description made with reference to the following drawings to non-limiting example, further feature of the invention,
Objects and advantages will become more apparent upon：
Fig. 1 is the SEM photograph of functionalization graphene in embodiment 1；
Fig. 2 is the TEM photos of functionalization graphene in embodiment 1；
Fig. 3 is the photo in kind that graphene is combined PPR；
Fig. 4 is the mechanical experimental results of graphene/composite polyolefine material；
Fig. 5 is the uvioresistant performance result of graphene/composite polyolefine material.
Embodiment
With reference to specific embodiment, the present invention is described in detail.Following examples will be helpful to the technology of this area
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that to the ordinary skill of this area
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection domain.
Embodiment 1
The present embodiment, which is related to a kind of functionalization graphene, strengthens the preparation method of composite polyolefine material.
It is heat-treated, graphene is pre-processed, specific preparation process is by the stage to modified graphene oxide：
First, processing is modified to graphene oxide, including 10g graphene oxide is dispersed in 5L large beakers, simple ultrasound
Scattered 5min, is then heated to 40 degree, and the solution of the octadecyl dimethyl amine oxide of 5g solid contents is added under mechanical stirring,
Suction filtration is dried after reversely separating out, and is pulverized after heat drying, is noted crushing, prevent unexpected generation.Then will be dried then,
After 100 degree of modified graphene oxide preheating 10min, then it is warming up to 200 degree, 200 degree of post-modification graphite oxides are quickly peeled off, and are obtained
Functionalization graphene.
Premix at a high speed is carried out in premixing machine and obtains mixture with polypropylene particles after functionalization graphene is dried
Material；Wherein, functionalization graphene addition in polypropylene matrix is 0.5wt%, and the time of premix is 10min at a high speed,
Graphene is set to be attached on completely in polyolefin particles.After premix processing, mixed material is put into twin screw compounder, double spiral shells
Bar warm area temperature is 230 DEG C, and charging rate is 40g/min, and screw speed is 10rpm, then by water cooling granulation.The stone granulated
It is molded or compression molding after black alkene compound polyolefin particle redrying, different structure is prepared according to different demands
Graphene/composite polyolefine material.
The SEM photograph after interim heat treatment is carried out in this implementation to modified graphene oxide as shown in figure 1, TEM photos
As shown in Figure 2.
Embodiment 2
The present embodiment, which is related to a kind of functionalization graphene, strengthens the preparation method of composite polyolefine material.
By the reduction to modified graphene oxide, graphene is pre-processed, specific preparation process is：First, it is right
Graphene oxide is modified consistent in the step of processing, graphene oxide modification and embodiment 1；Then, will be cold
Freeze dry modified graphene oxide to be dispersed in oiliness organic phase, reducing agent is added under the conditions of 80 DEG C of oil baths, reducing agent is
Hydrazine hydrate, the addition of reducing agent is 0.2 times of graphene quality, and reduction 1.0h obtains the graphene of certain reducing degree, then
Freeze, dry, obtain functionalization graphene.
High speed is carried out in premixing machine and is premixed with atactic copolymerized polypropene particle after functionalization graphene is dried
To mixed material；Wherein, functionalization graphene addition in atactic copolymerized polypropene matrix is 2wt%, is premixed at a high speed
Time be 10min, graphene is attached on completely in polyolefin particles.After premix processing, mixed material is put into double spiral shells
In bar kneading machine, twin-screw warm area temperature is 260 DEG C, and charging rate is 15g/min, and screw speed is 20rpm, then by water cooling
Granulation.It is molded or compression molding after the graphene compound polyolefin particle redrying granulated, according to different need
Seek the graphene/composite polyolefine material for preparing different structure.
Embodiment 3
The present embodiment, which is related to a kind of functionalization graphene, strengthens the preparation method of composite polyolefine material.
Organic modification processing is carried out to graphene oxide, concretely comprised the following steps：First prepare and simply cleaning Hummers methods are obtained
The graphite oxide arrived, then in pH>Direct ultrasonically treated 30min obtains graphene oxide dispersion under 2 acid condition, then directly
Addition modifying agent PDDA under agitation, and 10g graphene oxide correspondence 10-20g PDDA are met, finally suction filtration is obtained
Modified graphene oxide, freezing, dry.
Premix at a high speed is carried out with polyethylene in premixing machine obtain mixture after above-mentioned pretreated graphene is dried
Material；Wherein, above-mentioned functions graphite alkene addition in base polyethylene is 3wt%, and mixing 10min obtains mixed material, made
Graphene is dispersed in base polyethylene and adhere to each other.After premix processing, mixed material is put into twin-screw
It is combined in kneading machine, charging rate is 10g/min, screw rod warm area is 260 degree, and engine speed is 20rpm, then will be compound
Material enters water cooling and granulated, and the compound particle granulated goes water process through row drying immediately.The graphene granulated is compound poly-
It is molded after olefin particles redrying or compression molding, the graphene of different structure/poly- is prepared according to different demands
Alkene composite.
Embodiment 4
The present embodiment, which is related to a kind of functionalization graphene, strengthens the preparation method of composite polyolefine material.
The pretreatment of physical modification is carried out to mechanical stripping graphene, is concretely comprised the following steps：The stone that Physical is prepared
Black alkene ultrasonic disperse adds macromolecule modifier PVDF (vinylidene) processing in ethanol or methyl pyrrolidone solvent,
PVDF amount is 1.5 times of graphene quality, centrifuges the modified graphene modified, finally replaces solvent by the aqueous solution
Cool down, dry afterwards.
Premixed after above-mentioned pretreated graphene is dried with dried polyethylene in high speed mixing smelting machine, stone
Functionalization graphene addition in polyvinyl resin is 5wt%, and mixing 15min obtains mixed material so that function graphite
Alkene is dispersed in base polyethylene and adheres to each other.After premix processing, mixed material is put into twin screw compounder
Middle to be combined, screw rod warm area temperature is set as 250 degree, and screw speed is 35rpm, and charging rate is 20g/min, then by water
Cold granulation.It is molded or compression molding after the graphene compound polyolefin particle redrying granulated, according to different
Demand prepares graphene/composite polyolefine material of different structure.
Comparative example 1
This comparative example, which is related to a kind of functionalization graphene, strengthens the preparation method of composite polyolefine material, the preparation method
Basically identical with embodiment 1, difference is：Using unmodified graphene oxide.
Comparative example 2
This comparative example, which is related to a kind of functionalization graphene, strengthens the preparation method of composite polyolefine material.The preparation method
Basically identical with embodiment 1, difference is：Using unmodified mechanical stripping graphene.
Performance test
Performance test is carried out to graphene compound polyolefin composite made from above-described embodiment, comparative example, joined respectively
Carried out according to following method：Mechanical property (GB1040-79), uvioresistant absorb (GB2410-80), anti-microbial property (JIS Z 2801-
2000), conductance (GB1410-78, GB1672-81), the test of heat endurance (GB/T 14837-1993), as a result as follows：
Heat endurance refers to the temperature that thermal decomposition starts in table 1, is usually temperature when weightlessness reaches 5%.Each reality in table 1
The result for applying electrical conductivity in example and comparative example be due to different graphenes by different modified condition and processing mode, and
Matrix is also different, so the distribution mode of its conductive filler is different after compound, and with different electric property.
Fig. 4 answers for polypropylene composite materials stage heat treatment modified graphene oxide in embodiment 1 with polypropylene in comparative example 1
The stress-strain curve diagram of graphene oxide is closed, is had no it can be seen that being combined unmodified graphene oxide after-drawing performance
It is obviously improved, its yield strength and fracture strength have obvious increasing after compound interim heat treatment modified graphene oxide
Plus, fracture strength improves 22%.
Fig. 5 is random copolymerization in polypropylene composite materials stage heat treatment modified graphene oxide in embodiment 1 and embodiment 2
The UV-permeable spectrogram of polypropylene composite materials modified with reduction graphene oxide, is as can be seen from the figure combined interim heat treatment and changes
Property graphene oxide after ultraviolet permeability all have decreased to 0.1% from average 10%, have apparent UVResistant effect.
Fig. 3 is the photo in kind that graphene is combined PPR, wherein, leftmost transparent pictorial diagram is PPR base materials, Ran Houcong
Left-to-right pictorial diagram is corresponding in turn to PPR and is combined the compound 0.5wt% modified graphene oxides of 0.5wt% graphene oxides, PPR, PPR
Compound 0.5wt% modified with reduction graphene oxide, PPR are combined 0.5wt% physical modification mechanical stripping graphenes.
In the present invention, addition of the functionalization graphene in polyolefin is 0.5wt%-10wt%, wherein 3wt% additions
The mechanical performance boost rate of the following composite of amount can be more than 18%, and improved thermo stability is at 50-95 DEG C, simultaneously
Each band ultraviolet of the polyolefin sheets of 0.8mm thickness absorbable more than 98%, such composite can be widely used in
Sewage disposal barrier film, bumper, heat conduction tubing, construction material etc..Polyolefin of its addition in 3wt%-10wt%
Composite and according to conductance difference the composite polyolefine material of electrical conductivity can be applied electromagnetic shielding finishing material,
And the composite polyolefine material of slightly higher electrical conductivity can be applicable to electronic device neighborhood, such as PTC temperature-sensitive elements, PTC heating tapes etc. are led
Domain.
The invention provides a kind of preparation of industrialization is surface-functionalized and the controllable polyolefin-based graphene nano of structure and morphology
The method of composite, including equipment complex, the equipment are the melt blending equipment such as twin-screw, banbury；This method is with showing
The industrialized process for preparing for having composite polyolefine material can realize seamless connection, can directly amplify preparation, be polyolefin foundation stone
The preparation of industrialization of black alkene composite provides direct method.
The preparation method of the graphene, the preparation method compared to existing graphene has preparation cost low, at the later stage
The reason cycle is short, the characteristics of blowdown flow rate is low, so as to directly solve the big demand of graphene during composite prepare with scale
The problem of amount, and then preparation of industrialization for functional polyolefin base graphene composite material provides raw materials requirement guarantee.
The specific embodiment of the present invention is described above.It is to be appreciated that the invention is not limited in above-mentioned
Particular implementation, those skilled in the art can make various deformations or amendments within the scope of the claims, this not shadow
Ring the substantive content of the present invention.
Claims (10)
1. a kind of functionalization graphene strengthens the preparation method of composite polyolefine material, it is characterised in that the preparation method bag
Include：
S1, graphene or graphene oxide pre-processed, obtain functionalization graphene；
S2, functionalization graphene and polyolefin substrate premixed, obtain mixed material；
S3, the water cooling granulation after combination process by mixed material, obtain graphene compound polyolefin particle；Graphene is compound poly-
Olefin particles processing and forming, is made graphene enhancing composite polyolefine material.
2. feature graphene according to claim 1 strengthens the preparation method of composite polyolefine material, it is characterised in that
In step sl, the method for the pretreatment is the method for modifying of graphene oxide, the restoring method of modified graphene oxide, changed
The interim heat treatment method or the physical modification method of mechanical stripping graphene of property graphene oxide.
3. feature graphene according to claim 2 strengthens the preparation method of composite polyolefine material, it is characterised in that
The method of modifying of the graphene oxide is：By graphite oxide pH be more than 2 deionized water system in it is ultrasonically treated, addition has
Machine modifying agent, it is cold dry to produce modified graphene oxide then by flocculate suction filtration, washing.
4. feature graphene according to claim 3 strengthens the preparation method of composite polyolefine material, it is characterised in that
The organic modifiers be octadecyl dimethyl amine oxide, DDAO, high polymeric polyelectrolyte, PDDA,
In imidazoline, morpholine guanidine, triazine derivative, polypropylene grafted maleic anhydride, polyacrylamide, low-molecular-weight polypropylene nitrile
One or more；
The addition of the organic modifiers is 0.5-2.0 times of graphene oxide quality.
5. feature graphene according to claim 2 strengthens the preparation method of composite polyolefine material, it is characterised in that
The restoring method of the modified graphene oxide is：The modified graphene oxide of freeze-drying is dispersed in organic phase, added
Reducing agent, obtains the graphene of certain reducing degree, then freezes, dries.
6. feature graphene according to claim 5 strengthens the preparation method of composite polyolefine material, it is characterised in that
One or more of the organic phase in dimethylbenzene, n-butanol, n-hexane, chloroform, atoleine, the reducing agent is selected from
One or more in hydrazine hydrate, oxalic acid, potassium borohydride, sodium borohydride；The addition of the reducing agent is modified graphite oxide
0.1-2.0 times of alkene quality.
7. feature graphene according to claim 2 strengthens the preparation method of composite polyolefine material, it is characterised in that
The reacting furnace temperature of the interim heat treatment method of the modified graphene oxide is 50-350 DEG C, and it is specific that stage is heat-treated
Step includes：First stage heat treatment is that a period of time is incubated in 50-120 DEG C, and second stage is heat-treated to be warming up to 120-
Continue to be incubated in the range of 350 DEG C, finally give the adjustable functionalization graphene of structure.
8. feature graphene according to claim 2 strengthens the preparation method of composite polyolefine material, it is characterised in that
The physical modification method of the mechanical stripping graphene be the graphene ultrasonic disperse for preparing Physical water, ethanol or
In person's methyl pyrrolidone solvent, add after macromolecule modifier processing, centrifuge the modified graphene modified, finally will be molten
After agent is replaced by the aqueous solution, cool down, dry.
9. feature graphene according to claim 8 strengthens the preparation method of composite polyolefine material, it is characterised in that
The macromolecule modifier includes sodium alginate, cellulose, lignin, chitosan, PEO, PDDA, the PAA of low molecule amount or low
The PVDF of molecular weight；The addition of the macromolecule modifier is 0.1-5.0 times of graphene quality.
10. feature graphene according to claim 1 strengthens the preparation method of composite polyolefine material, its feature exists
In in step s 2, the polyolefin substrate is selected from polypropylene or polyethylene；The functionalization graphene is in polyolefin substrate
Addition is 0.5wt%-10wt%；The pre- of the functionalization graphene and polyolefin substrate is done time as 2-15min.
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| CN201710339294.4A Pending CN107057192A (en) | 2017-05-15 | 2017-05-15 | Functionalization graphene strengthens the preparation method of composite polyolefine material |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107652531A (en) * | 2017-11-06 | 2018-02-02 | 浙江山峪科技股份有限公司 | A kind of graphene modified polyolefine elastomer composite and preparation method thereof |
| CN108164790A (en) * | 2017-12-27 | 2018-06-15 | 浙江大学宁波理工学院 | Composite polyolefine material with high antioxidant and preparation method thereof |
| CN108588883A (en) * | 2018-05-02 | 2018-09-28 | 广州市泽福医疗科技有限公司 | graphene fiber and preparation method and product |
| WO2019153790A1 (en) * | 2018-02-11 | 2019-08-15 | 华南理工大学 | Method for preparing polymer material/graphene nanocomposite material by means of in-situ reduction during continuous mixing and application thereof |
| CN110643116A (en) * | 2019-09-17 | 2020-01-03 | 重庆科林包装制品有限公司 | High-strength polyolefin composite material for packaging bag and preparation method thereof |
| CN110669284A (en) * | 2019-09-30 | 2020-01-10 | 北京石墨烯技术研究院有限公司 | Graphene composite material and preparation method thereof, and prepared product and application thereof |
| CN111484663A (en) * | 2020-06-20 | 2020-08-04 | 上海旗华水上工程建设股份有限公司 | Graphene floating body for aquatic travel floating system |
| CN111647215A (en) * | 2020-06-20 | 2020-09-11 | 上海旗华水上工程建设股份有限公司 | Graphene floating body for floating system of offshore photovoltaic power station |
| CN112111105A (en) * | 2020-08-28 | 2020-12-22 | 安徽越洋达新能源科技有限公司 | High strength power support |
| CN114316409A (en) * | 2021-12-31 | 2022-04-12 | 南通强生光电科技有限公司 | Functionalized graphene reinforced polyolefin composite material and preparation method thereof |
| CN114702752A (en) * | 2022-04-07 | 2022-07-05 | 中山市华洋塑胶颜料有限公司 | Graphene composite plastic for heat dissipation and preparation method thereof |
| CN115312968A (en) * | 2022-09-09 | 2022-11-08 | 盐城师范学院 | Lithium ion battery based on high-temperature-resistant diaphragm and preparation method thereof |
| CN115433408A (en) * | 2022-08-31 | 2022-12-06 | 方大炭素新材料科技股份有限公司 | Graphene-polypropylene composite antibacterial master batch and preparation method and application thereof |
| CN117510730A (en) * | 2023-10-24 | 2024-02-06 | 上海泽明塑胶有限公司 | Preparation method of polyolefin for nylon production |
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| CN103087411A (en) * | 2013-01-17 | 2013-05-08 | 湖北大学 | High-dispersion alkylated graphene/polypropylene composite material and preparation method thereof |
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| CN103087411A (en) * | 2013-01-17 | 2013-05-08 | 湖北大学 | High-dispersion alkylated graphene/polypropylene composite material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107652531A (en) * | 2017-11-06 | 2018-02-02 | 浙江山峪科技股份有限公司 | A kind of graphene modified polyolefine elastomer composite and preparation method thereof |
| CN108164790A (en) * | 2017-12-27 | 2018-06-15 | 浙江大学宁波理工学院 | Composite polyolefine material with high antioxidant and preparation method thereof |
| WO2019153790A1 (en) * | 2018-02-11 | 2019-08-15 | 华南理工大学 | Method for preparing polymer material/graphene nanocomposite material by means of in-situ reduction during continuous mixing and application thereof |
| CN108588883B (en) * | 2018-05-02 | 2021-03-02 | 广州市泽福医疗科技有限公司 | Graphene fibers, methods of making, and articles |
| CN108588883A (en) * | 2018-05-02 | 2018-09-28 | 广州市泽福医疗科技有限公司 | graphene fiber and preparation method and product |
| CN110643116A (en) * | 2019-09-17 | 2020-01-03 | 重庆科林包装制品有限公司 | High-strength polyolefin composite material for packaging bag and preparation method thereof |
| CN110669284A (en) * | 2019-09-30 | 2020-01-10 | 北京石墨烯技术研究院有限公司 | Graphene composite material and preparation method thereof, and prepared product and application thereof |
| CN111484663A (en) * | 2020-06-20 | 2020-08-04 | 上海旗华水上工程建设股份有限公司 | Graphene floating body for aquatic travel floating system |
| CN111647215A (en) * | 2020-06-20 | 2020-09-11 | 上海旗华水上工程建设股份有限公司 | Graphene floating body for floating system of offshore photovoltaic power station |
| CN112111105A (en) * | 2020-08-28 | 2020-12-22 | 安徽越洋达新能源科技有限公司 | High strength power support |
| CN114316409A (en) * | 2021-12-31 | 2022-04-12 | 南通强生光电科技有限公司 | Functionalized graphene reinforced polyolefin composite material and preparation method thereof |
| CN114702752A (en) * | 2022-04-07 | 2022-07-05 | 中山市华洋塑胶颜料有限公司 | Graphene composite plastic for heat dissipation and preparation method thereof |
| CN114702752B (en) * | 2022-04-07 | 2022-11-18 | 中山市华洋塑胶颜料有限公司 | Graphene composite plastic for heat dissipation and preparation method thereof |
| US11767416B1 (en) | 2022-04-07 | 2023-09-26 | Zhongshan Huayang Plastic Dyestuffs Co., Ltd. | Graphene composite plastic and preparation method thereof |
| CN115433408A (en) * | 2022-08-31 | 2022-12-06 | 方大炭素新材料科技股份有限公司 | Graphene-polypropylene composite antibacterial master batch and preparation method and application thereof |
| CN115312968A (en) * | 2022-09-09 | 2022-11-08 | 盐城师范学院 | Lithium ion battery based on high-temperature-resistant diaphragm and preparation method thereof |
| CN115312968B (en) * | 2022-09-09 | 2023-12-22 | 盐城师范学院 | Lithium ion battery based on high-temperature-resistant diaphragm and preparation method thereof |
| CN117510730A (en) * | 2023-10-24 | 2024-02-06 | 上海泽明塑胶有限公司 | Preparation method of polyolefin for nylon production |
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