CN106117949B - High-density polyethylene resin based nano composite material and preparation method thereof - Google Patents
High-density polyethylene resin based nano composite material and preparation method thereof Download PDFInfo
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- CN106117949B CN106117949B CN201610547518.6A CN201610547518A CN106117949B CN 106117949 B CN106117949 B CN 106117949B CN 201610547518 A CN201610547518 A CN 201610547518A CN 106117949 B CN106117949 B CN 106117949B
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- 229920001903 high density polyethylene Polymers 0.000 title claims abstract description 57
- 239000004700 high-density polyethylene Substances 0.000 title claims abstract description 57
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 55
- 239000011347 resin Substances 0.000 title claims abstract description 45
- 229920005989 resin Polymers 0.000 title claims abstract description 45
- 239000000463 material Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 102
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 52
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 34
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 34
- 239000000945 filler Substances 0.000 claims abstract description 27
- 238000002156 mixing Methods 0.000 claims abstract description 18
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims abstract description 9
- 230000020477 pH reduction Effects 0.000 claims description 22
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 21
- 239000000203 mixture Substances 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 229910002804 graphite Inorganic materials 0.000 claims description 13
- 239000010439 graphite Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 10
- 239000002048 multi walled nanotube Substances 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 239000007800 oxidant agent Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 7
- 229910021382 natural graphite Inorganic materials 0.000 claims description 7
- 229910017604 nitric acid Inorganic materials 0.000 claims description 7
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 238000013019 agitation Methods 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 229960000549 4-dimethylaminophenol Drugs 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 3
- 239000005457 ice water Substances 0.000 claims description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 3
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Inorganic materials [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 3
- 238000002525 ultrasonication Methods 0.000 claims description 3
- 238000002604 ultrasonography Methods 0.000 claims description 3
- 238000004898 kneading Methods 0.000 claims description 2
- 238000006396 nitration reaction Methods 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 239000012286 potassium permanganate Substances 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 239000004575 stone Substances 0.000 claims 3
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims 2
- 150000001336 alkenes Chemical class 0.000 claims 2
- 150000008064 anhydrides Chemical class 0.000 claims 1
- 239000000843 powder Substances 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 12
- 239000011159 matrix material Substances 0.000 abstract description 7
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 2
- 238000005728 strengthening Methods 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 239000003921 oil Substances 0.000 description 5
- 238000001069 Raman spectroscopy Methods 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 238000001938 differential scanning calorimetry curve Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000012856 packing Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- 206010054949 Metaplasia Diseases 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- -1 because its is cheap Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052901 montmorillonite Inorganic materials 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- VDGJOQCBCPGFFD-UHFFFAOYSA-N oxygen(2-) silicon(4+) titanium(4+) Chemical compound [Si+4].[O-2].[O-2].[Ti+4] VDGJOQCBCPGFFD-UHFFFAOYSA-N 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- C08K3/04—Carbon
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/22—Expanded, porous or hollow particles
- C08K7/24—Expanded, porous or hollow particles inorganic
-
- 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
- C08K9/02—Ingredients treated with inorganic substances
-
- 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
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
本发明涉及高密度聚乙烯材料的复合材料，尤其是高密度聚乙烯树脂基纳米复合材料及其制备方法。高密度聚乙烯树脂基纳米复合材料，由填料和高密度聚乙烯接枝马来酸酐树脂按以下质量份数熔融共混制得：填料0.25～1份，高密度聚乙烯接枝马来酸酐树脂99.75～99份；所述填料为石墨烯和碳纳米管。该纳米复合材料成本低廉，制备方法简单，易操作、实用性广；充分发挥石墨烯和碳纳米管的协同作用，并对HDPE基体产生明显的协同增强增韧作用，所得纳米复合材料拥有比单种填料改性时更优异的性能；具有优异的力学性能和热性能，在满足性能要求的同时，所需填料的量较少。
The invention relates to a composite material of high-density polyethylene material, in particular to a high-density polyethylene resin-based nanocomposite material and a preparation method thereof. High-density polyethylene resin-based nanocomposite material is prepared by melt blending filler and high-density polyethylene-grafted maleic anhydride resin according to the following parts by mass: 0.25-1 part of filler, high-density polyethylene-grafted maleic anhydride resin 99.75-99 parts; the fillers are graphene and carbon nanotubes. The nanocomposite material has low cost, simple preparation method, easy operation and wide practicability; fully exerts the synergistic effect of graphene and carbon nanotubes, and has obvious synergistic strengthening and toughening effect on the HDPE matrix. It has more excellent performance when modified with various fillers; it has excellent mechanical properties and thermal properties, and the amount of filler required is less while meeting the performance requirements.
Description
Technical field
The present invention relates to the composite material of high-density polyethylene material, especially high-density polyethylene resin base is nano combined
Material and preparation method thereof.
Background technique
High density polyethylene (HDPE) (HDPE) is one of five big general-purpose plastics, because its is cheap, chemical stability is high, is easy to add
Work forms and is widely used in the fields such as film, pipeline and packaging.However the tensile strength of HDPE is low, hardness is insufficient and Heat-resistant stable
Property difference etc. limits it in the application in certain fields.In order to widen the application field of HDPE, the added value of HDPE is improved, in fact
Apply the main direction of studying that modification is current HDPE.Wherein, melt blending have it is technically simple, be suitable for large-scale industry metaplasia
It produces and becomes the modified major technique mode of HDPE.In the method for numerous HDPE melt blendings, high-performance is added in HDPE
Nanofiller is the hot spot in the composite modified research of current HDPE.Traditional nanofiller, such as nanometer calcium carbonate, nanometer titanium dioxide
Silicon, montmorillonite etc. and high performance nanofiller, such as (expansion) graphite, carbon nanotube, fiber are added in PP and have obtained
Obtained a large amount of research.But traditional filler and the compatibility of HDPE are poor, interface bond strength is low, cause the dispersion of filler equal
Even property is poor, and the preferable composite material of performance could be obtained by needing to improve additive amount.
Currently, by graphene and its derivative with HDPE is compound can give full play to the excellent mechanics of graphene, calorifics, electricity
And other functional characteristics provide new thinking for preparation high-performance HDPE based nano composite material.But because of graphene and its
The nanometer size effect of derivative and high specific surface energy cause it easily to reunite in HDPE matrix, cannot not only give full play to
The excellent properties of graphene can also reduce the performance of matrix resin.Therefore, point for improving graphene in HDPE matrix is explored
It dissipates, the interface cohesion for improving it with HDPE has important engineering significance.
Summary of the invention
The present invention provides that a kind of production cost is low, use scope is wide, highly dense with excellent mechanical property and heat resistance
Polyvinyl resin based nano composite material is spent, the specific technical proposal is:
High-density polyethylene resin based nano composite material is pressed by filler and high-density polycthylene grafted maleic anhydride resin
Following mass fraction melt blending is made: 0.25~1 part of filler, high-density polycthylene grafted maleic anhydride resin 99.75~99
Part；The filler is graphene and carbon nanotube.
The graphene and carbon nanotube are respectively graphene oxide and acidification carbon nanotube；Graphene oxide and acidification carbon
The mass ratio of nanotube is 1:1.
The graphene oxide is the ethylenediamine grafted graphene oxide being grafted through ethylenediamine.
The graphene oxide is made by the following method:
(1) natural graphite is aoxidized to obtain graphite oxide using strong oxidizer；
(2) graphite oxide obtains graphene oxide after ultrasonic wave disperses.
The graphite oxide specific the preparation method comprises the following steps:
Strong oxidizer is added in dry beaker, strong oxidizer includes the concentrated sulfuric acid, concentrated nitric acid, sodium nitrate and potassium permanganate
Deng.It is cooled to ice-water bath not higher than 4 DEG C；Simultaneously natural graphite powder and NaNO is added in high degree of agitation3Mixture, then again slowly
KMnO is added4, and the control of the temperature of reaction system is being not higher than 20 DEG C；Continue to rise to system temperature after being stirred to react 5min
35 ± 3 DEG C, constant temperature stirs 30min；Then high degree of agitation and deionized water is added, and temperature of reaction system is controlled at 98 DEG C,
Keep 15min；Deionized water is added and carries out pyrohydrolysis；It is eventually adding H2O2Unreacted strong oxidizer is neutralized, is filtered while hot simultaneously
It is sufficiently washed with dilute hydrochloric acid and deionized water, is dried in a vacuum drying oven, obtain graphite oxide.
The ethylenediamine grafted graphene oxide the preparation method comprises the following steps:
(1) graphene oxide powder is put in beaker, is added according to the ratio column that 1mL solvent corresponds to 1mg graphene oxide
Dimethylformamide, ultrasound 1h inside supersonic wave cleaning machine is put into after slightly shaking up makes graphene oxide be evenly dispersed in solvent
In；
(2) beaker is transferred in oil bath pan, is slowly heated up, the pH of concentrated ammonia liquor adjustment system is added when temperature reaches 90 DEG C
Value；
(3) DCC and DMAP reagent is added, after temperature rises to 95 DEG C, ethylenediamine, the reaction was continued 6h is added；
(4) it filters, is washed 5 times with dehydrated alcohol while hot after reaction, it is dry at 80 DEG C, then be ground up, sieved to obtain second
Diamines grafted graphene oxide.
The acidification carbon nanotube is acidified through nitration mixture by multi-walled carbon nanotube and is made, and preparation step is as follows:
(1) multi-walled carbon nanotube is placed in flask, concentrated nitric acid is added, then with the concentrated sulfuric acid and concentrated nitric acid volume ratio for 3:
The concentrated sulfuric acid is added in 1 ratio；
(2) by beaker ultrasonication 40min, it is dispersed in multi-walled carbon nanotube in acid solution；
(3) beaker is put into oil bath pan again, the acidification 6h at 60 DEG C；
(4) drying for 24 hours, obtains acidification carbon nanotube at 80 DEG C after being filtered, washed.
The preparation method of high-density polyethylene resin based nano composite material, includes the following steps:
(1) after mixing by filler and high-density polycthylene grafted maleic anhydride resin particle, it is put into kneading machine；
(2) melt blending temperature is 160 DEG C, and the blending time is 15min, and the revolving speed of rotor is 50r/min.
Filler of the present invention is graphene and carbon nanotube.Graphene is aoxidized simultaneously by natural graphite through strong oxidizer
It is obtained through strength ultrasonic disperse.During natural graphite oxidation prepares graphite oxide, it can draw on the surface of graphite oxide
Enter a large amount of polarity oxygen-containing functional group (such as hydroxyl, carboxyl and epoxy group)；Meanwhile carbon nanotube it is acidified after taken carboxylic
Base group.High-density polycthylene grafted Maleic Anhydride Surface also contains a large amount of carboxyls, these oxygen-containing groups can mutually be changed
It learns reaction and generates amido bond.Based on this, between filler and polymer formed chemistry key connection can effectively reinforcing filler with
Interface bond strength between matrix.Three-D space structure can be formed between quasi-one-dimensional carbon nanotube and two-dimensional graphene,
This structure can obstruct each other, inhibit the reunion of graphene or carbon nanotube itself, to promote its dispersibility in the base.
The present invention uses cheap, widely used thermoplastic high density polyvinyl resin grafted maleic anhydride for base
Body prepares nanocomposite using melt-blending process using graphene and carbon nanotube as filler.Preparation process mistake of the invention
Journey is simple, and the content of filler can be controlled in 0.25~1% in composite material, the composite material of acquisition mechanical property with higher
And hot property.
Compared with prior art, the invention has the following beneficial effects:
(1) abundance of polymeric matrix and filler used in the present invention, it is low in cost.Technically in order to inhibit filler
Reunion in the base promotes dispersion, uses graphene and carbon nanotube as the modifying agent of polymer, give full play to graphene with
The synergistic effect of carbon nanotube, and apparent collaboration activeness and quietness effect is generated to HDPE matrix, gained nanocomposite is gathered around
Superior performance when having more filler modified than single；
(2) nanocomposite preparation method of the invention is simple, easy to operate, practicability is wide；
(3) present invention gained nanocomposite has excellent mechanical property and hot property, is meeting performance requirement
Meanwhile the amount of required filler is less.
Detailed description of the invention
Fig. 1 is the mechanism of action signal between oxidation, grafting process and HDPE-g-MAH and the filler of natural graphite
Figure；
Influence of the content of Fig. 2 compounded mix to nanocomposite tensile strength；
Influence of the content of Fig. 3 compounded mix to nanocomposite impact strength；
The heating curve of the DSC curve of Fig. 4 composite material；
The temperature lowering curve of the DSC curve of Fig. 5 composite material；
The Raman map of Fig. 6 GO and GO-EDA；
The Raman map of Fig. 7 MWCNTs and MWCNTs-COOH；
The TG curve of nanocomposite under Fig. 8 difference filer content；
The DTG curve of nanocomposite under Fig. 9 difference filer content；
The impact fracture surface SEM photograph of nanocomposite under Figure 10 difference filer content；
The storage modulus of the DMA curve of nanocomposite under Figure 11 difference filer content；
The loss modulus of the DMA curve of nanocomposite under Figure 12 difference filer content.
Specific embodiment
In conjunction with the embodiments with Detailed description of the invention a specific embodiment of the invention.
Embodiment 1
The preparation of graphite oxide: the concentrated sulfuric acid of 115mL98% is added in dry beaker, is cooled to 4 DEG C with ice-water bath
Hereinafter, 5gNGP and 2.5gNaNO is added under high degree of agitation3Mixture, be then slow added into the KMnO of 15g4, and will reaction
The temperature of system controls at 20 DEG C hereinafter, continuing to be stirred to react after 5min system temperature rising to 35 ± 3 DEG C, constant temperature stirring
After 30min, 230mL deionized water is added under vigorous stirring.Above-mentioned system is transferred to the oil bath pan of heating, system reaction temperature
At 98 DEG C, 15min is kept, then plus the deionized water of 355mL heat carries out pyrohydrolysis, adds the H of 30mL2O2It neutralizes unreacted
Strong oxidizer filters while hot, and is sufficiently washed with 5% hydrochloric acid and deionized water, and drying for 24 hours, obtains in 90 DEG C of vacuum ovens
To graphite oxide.Graphite oxide obtains graphene oxide after ultrasonic disperse.
The preparation of ethylenediamine grafted graphene oxide (GO-EDA): graphene oxide powder made from a certain amount of upper step is weighed
Dimethylformamide (DMF) is added in beaker, then in the ratio that 1mL solvent corresponds to 1mg graphene oxide, first slightly shakes manually
Ultrasound 1h inside supersonic wave cleaning machine is put into after even is evenly dispersed in graphene oxide in solvent；Then the system is turned
Enter in oil bath pan, be slowly warming up to 95 DEG C, reaches 90 DEG C of pH value that concentrated ammonia liquor adjustment system is added to temperature, be subsequent grafting
Reaction provides reaction condition；It is subsequently added into suitable DCC and DMAP reagent, after temperature rises to 95 DEG C, ethylenediamine is added,
The reaction was continued 6h；It filters, is washed 5 times with dehydrated alcohol while hot after reaction, it is dry at 80 DEG C, then be ground up, sieved to obtain
GO-EDA。
It is acidified the preparation of carbon nanotube: weighing 2g multi-walled carbon nanotube in flask, the concentrated nitric acid of 20ml is first added, then
With the concentrated sulfuric acid: the 60ml concentrated sulfuric acid is added in concentrated nitric acid=3:1 ratio.By flask through ultrasonication 40min, make multi-wall carbon nano-tube
Pipe is dispersed in acid solution, then flask is put into oil bath pan the acidification 6h at 60 DEG C；In 80 DEG C after being filtered, washed
Lower drying obtains acidification carbon nanotube for 24 hours.
The preparation of high-density polyethylene resin based nano composite material: by the ethylenediamine grafted graphene oxide of 0.0375g
With acidification carbon nanotube mixture and 14.9625g HDPE-g-MAH after mixing, add mixture to melting mixing
15min, rotor speed 50r/min are kneaded in machine at 160 DEG C, the high density that the mass content for obtaining filler is 0.25% is poly-
Vinyl based nano composite material.
For convenient for comparison, pure HDPE-g-MAH is prepared using melt blending condition same as described above.
Resulting high-density polyethylene resin based nano composite material uses vulcanizing press tabletting.By sample preparation at mute
Bell-shaped sample (62.5 × 3.25 × 0.7mm3) does extension test, and sample preparation is done impact at cuboid (10 × 1.5mm2) and is surveyed
Examination.Wherein tensile speed is 50mm/min, impact pendulnm 4J.
It stretches and shock-testing result is as shown in Fig. 2, Fig. 3 and table 1.As can be seen that being used compared with pure HDPE-g-MAH
Ethylenediamine grafted graphene oxide and acidification carbon nanotube mixture are nano combined as the high-density polyethylene resin base of filler
The tensile strength and impact strength of material all improve, and 10.7% and 3.3% has been respectively increased.
The composition and mechanical experimental results of 1 high-density polyethylene resin based nano composite material of table
Embodiment 2
The preparation of ethylenediamine grafted graphene oxide and acidification carbon nanotube is same as Example 1.In high-density polyethylene
In the preparation process of olefine resin based nano composite material, by the ethylenediamine grafted graphene oxide of 0.075g and acidification carbon nanotube
Mixture and 14.925g HDPE-g-MAH after the melt blending of process same as Example 1, obtain packing quality content
For 0.5% high-density polyethylene resin based nano composite material.
The test sample of high-density polyethylene resin based nano composite material prepare and test condition with 1 phase of embodiment
Together, the results are shown in Table 1 with shock-testing for stretching.As can be seen that being grafted and being aoxidized using ethylenediamine compared with pure HDPE-g-MAH
The tensile strength of graphene and acidification carbon nanotube mixture as the high-density polyethylene resin based nano composite material of filler
16.1% and 11.2 has been respectively increased with impact strength.
As shown in Fig. 2, Fig. 3 and table 1, the tensile strength of high-density polyethylene resin based nano composite material is than identical at this time
Individually using graphene or the resulting composite material difference high 9.4% and 5.3% of carbon nanotube under content.
The results are shown in Table 2 for thermal performance test.As can be seen that compared with pure HDPE-g-MAH, high-density polyethylene resin
The hot property of based nano composite material also improves, and 11.2 DEG C and 15.4 DEG C have been respectively increased in crystallization enthalpy and melting enthalpy.
The composition and thermal property of 2 high-density polyethylene resin based nano composite material of table
Embodiment 3
The preparation of ethylenediamine grafted graphene oxide and acidification carbon nanotube is same as Example 1.In high-density polyethylene
In the preparation process of olefine resin based nano composite material, by the ethylenediamine grafted graphene oxide of 0.1125g and acidification carbon nanometer
The mixture of pipe and the HDPE-g-MAH of 14.8875g obtain packing quality after the melt blending of process same as Example 1
The high-density polyethylene resin based nano composite material that content is 0.75%.
The test sample of high-density polyethylene resin based nano composite material prepare and test condition with 1 phase of embodiment
Together, the results are shown in Table 1 with shock-testing for stretching.As can be seen that being grafted and being aoxidized using ethylenediamine compared with pure HDPE-g-MAH
The tensile strength and impact of the high-density polyethylene resin based nano composite material of graphene and the mixture of acidification carbon nanotube
11.9% and 20% has been respectively increased in intensity.
The tensile strength and impact strength of high-density polyethylene resin based nano composite material place an order than same amount at this time
Solely using graphene or the resulting composite material difference high 16.5% and 2.2% of carbon nanotube.
The results are shown in Table 2 for thermal performance test.As can be seen that compared with pure HDPE-g-MAH, high-density polyethylene resin
The hot property of based nano composite material all improves, and 9.2 DEG C and 8.7 DEG C have been respectively increased in crystallization enthalpy and melting enthalpy.
Embodiment 4
The preparation of ethylenediamine grafted graphene oxide and acidification carbon nanotube is same as Example 1.In high-density polyethylene
In the preparation process of olefine resin based nano composite material, by the ethylenediamine grafted graphene oxide of 0.15g and acidification carbon nanotube
Mixture and 14.85g HDPE-g-MAH after the melt blending of process same as Example 1, obtain packing quality content
For 1% high-density polyethylene resin based nano composite material.
The test sample of high-density polyethylene resin based nano composite material prepare and test condition with 1 phase of embodiment
Together, it stretches and shock-testing result is as shown in Fig. 2, Fig. 3 and table 1.As can be seen that high density is poly- compared with pure HDPE-g-MAH
The tensile strength of vinyl based nano composite material improves 7.4%.
Other test results of high-density polyethylene resin based nano composite material are as follows:
Such as the heating curve of the DSC curve of Fig. 4 composite material；Such as the temperature lowering curve of the DSC curve of Fig. 5 composite material；Such as
The Raman map of Fig. 6 GO and GO-EDA；Such as the Raman map of Fig. 7 MWCNTs and MWCNTs-COOH；Such as Fig. 8 difference filer content
The TG curve of lower nanocomposite；Such as the DTG curve of nanocomposite under Fig. 9 difference filer content；As Figure 10 difference is filled out
Expect the impact fracture surface SEM photograph of nanocomposite under content；DMA such as nanocomposite under Figure 11 difference filer content is bent
The storage modulus of line；Such as the loss modulus of the DMA curve of nanocomposite under Figure 12 difference filer content.
Claims (8)
1. high-density polyethylene resin based nano composite material, which is characterized in that by filler and high-density polycthylene grafted Malaysia
Anhydride resin is made by following mass fraction melt blending: 0.25~1 part of filler, high-density polycthylene grafted maleic anhydride resin
99.75~99 parts；The filler is graphene and carbon nanotube.
2. high-density polyethylene resin based nano composite material according to claim 1, which is characterized in that the graphene
It is respectively graphene oxide and acidification carbon nanotube with carbon nanotube；Graphene oxide and the mass ratio of acidification carbon nanotube are 1:
1。
3. high-density polyethylene resin based nano composite material according to claim 2, which is characterized in that the oxidation stone
Black alkene is the ethylenediamine grafted graphene oxide being grafted through ethylenediamine.
4. high-density polyethylene resin based nano composite material according to claim 2, which is characterized in that the oxidation stone
Black alkene is made by the following method:
(1) natural graphite is aoxidized to obtain graphite oxide using strong oxidizer；
(2) graphite oxide obtains graphene oxide after ultrasonic wave disperses.
5. high-density polyethylene resin based nano composite material according to claim 4, which is characterized in that the oxidation stone
Ink it is specific the preparation method comprises the following steps:
Strong oxidizer is added in dry beaker, is cooled to ice-water bath not higher than 4 DEG C；Simultaneously natural graphite is added in high degree of agitation
Powder and NaNO3Mixture, be then slow added into KMnO4, and the control of the temperature of reaction system is being not higher than 20 DEG C；Continue
It is stirred to react after 5min and system temperature is risen to 35 ± 3 DEG C, constant temperature stirs 30min；Then high degree of agitation and deionized water is added,
And control temperature of reaction system at 98 DEG C, keep 15min；Deionized water is added and carries out pyrohydrolysis；It is eventually adding H2O2It neutralizes
Unreacted strong oxidizer, filters while hot, and is sufficiently washed with dilute hydrochloric acid and deionized water, dries, obtains in a vacuum drying oven
To graphite oxide.
6. high-density polyethylene resin based nano composite material according to claim 3, which is characterized in that the ethylenediamine
Grafted graphene oxide the preparation method comprises the following steps:
(1) graphene oxide powder is put in beaker, diformazan is added according to the ratio column that 1mL solvent corresponds to 1mg graphene oxide
Base formamide, ultrasound 1h inside supersonic wave cleaning machine is put into after slightly shaking up is evenly dispersed in graphene oxide in solvent；
(2) beaker is transferred in oil bath pan, is slowly heated up, the pH value of concentrated ammonia liquor adjustment system is added when temperature reaches 90 DEG C；
(3) DCC and DMAP reagent is added, after temperature rises to 95 DEG C, ethylenediamine, the reaction was continued 6h is added；
(4) it filters, is washed 5 times with dehydrated alcohol while hot after reaction, it is dry at 80 DEG C, then be ground up, sieved to obtain ethylenediamine
Grafted graphene oxide.
7. high-density polyethylene resin based nano composite material according to claim 2, which is characterized in that the acidification carbon
Nanotube is acidified through nitration mixture by multi-walled carbon nanotube and is made, and preparation step is as follows:
(1) multi-walled carbon nanotube is placed in flask, concentrated nitric acid is added, then with the concentrated sulfuric acid: concentrated nitric acid volume ratio is the ratio of 3:1
The concentrated sulfuric acid is added in example；
(2) by beaker ultrasonication 40min, it is dispersed in multi-walled carbon nanotube in acid solution；
(3) beaker is put into oil bath pan again, the acidification 6h at 60 DEG C；
(4) drying for 24 hours, obtains acidification carbon nanotube at 80 DEG C after being filtered, washed.
8. the preparation method of high-density polyethylene resin based nano composite material according to claim 1, which is characterized in that
Include the following steps:
(1) after mixing by filler and high-density polycthylene grafted maleic anhydride resin particle, it is put into kneading machine；
(2) melt blending temperature is 160 DEG C, and the blending time is 15min, and the revolving speed of rotor is 50r/min.
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