CN109836664A - A kind of preparation method of polyethylene/graphene master batch - Google Patents
A kind of preparation method of polyethylene/graphene master batch Download PDFInfo
- Publication number
- CN109836664A CN109836664A CN201910064065.5A CN201910064065A CN109836664A CN 109836664 A CN109836664 A CN 109836664A CN 201910064065 A CN201910064065 A CN 201910064065A CN 109836664 A CN109836664 A CN 109836664A
- Authority
- CN
- China
- Prior art keywords
- polyethylene
- graphene
- master batch
- preparation
- graphene master
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 131
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 108
- -1 polyethylene Polymers 0.000 title claims abstract description 93
- 229920000573 polyethylene Polymers 0.000 title claims abstract description 92
- 239000004698 Polyethylene Substances 0.000 title claims abstract description 91
- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000007788 liquid Substances 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000002245 particle Substances 0.000 claims abstract description 20
- 239000000725 suspension Substances 0.000 claims abstract description 20
- 239000000839 emulsion Substances 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000006722 reduction reaction Methods 0.000 claims abstract description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 24
- 239000010439 graphite Substances 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 11
- 238000002604 ultrasonography Methods 0.000 claims description 11
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 9
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 6
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 6
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 6
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 claims description 5
- 229930003268 Vitamin C Natural products 0.000 claims description 5
- 239000011718 vitamin C Substances 0.000 claims description 5
- 235000019154 vitamin C Nutrition 0.000 claims description 5
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 4
- 241001122767 Theaceae Species 0.000 claims description 4
- 150000008442 polyphenolic compounds Chemical class 0.000 claims description 4
- 235000013824 polyphenols Nutrition 0.000 claims description 4
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 claims description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 3
- 239000001263 FEMA 3042 Substances 0.000 claims description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 3
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 claims description 3
- 235000011132 calcium sulphate Nutrition 0.000 claims description 3
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 3
- 239000011780 sodium chloride Substances 0.000 claims description 3
- 239000001509 sodium citrate Substances 0.000 claims description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 3
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 claims description 3
- 229940033123 tannic acid Drugs 0.000 claims description 3
- 235000015523 tannic acid Nutrition 0.000 claims description 3
- 229920002258 tannic acid Polymers 0.000 claims description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 239000001175 calcium sulphate Substances 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 235000001727 glucose Nutrition 0.000 claims description 2
- 230000009467 reduction Effects 0.000 claims description 2
- 235000011083 sodium citrates Nutrition 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 235000013616 tea Nutrition 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 239000003960 organic solvent Substances 0.000 abstract description 4
- 230000001681 protective effect Effects 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 29
- 238000001914 filtration Methods 0.000 description 8
- 150000001336 alkenes Chemical class 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000002114 nanocomposite Substances 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical class Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000006210 lotion Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000001458 anti-acid effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000006353 environmental stress Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Landscapes
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a kind of preparation methods of polyethylene/graphene master batch, the following steps are included: first graphene oxide water solution is blended with aqueous polyethylene wax emulsion, it is demulsified after mixing, form polyethylene/graphene oxide particle suspension liquid, then reducing agent is added into polyethylene/graphene oxide particle suspension liquid, after carrying out reduction reaction, using filter, polyethylene/graphene master batch is obtained after drying, it is evenly dispersed in base polyethylene that the method achieve graphene oxides, and do not use organic solvent, it is environmentally protective, polyethylene/graphene master batch obtained is suitable for large-scale industrial production.
Description
Technical field
The invention belongs to polymer/graphene technical fields, and in particular to a kind of preparation side of polyethylene/graphene master batch
Method.
Background technique
Polyethylene is with nontoxic, tasteless, density is small, excellent resistance to water soak, excellent antiacid caustic corrosion, excellent antilysis
The advantages that, it is widely used in auto industry, household electrical appliance, tubing, machine components production etc. as a kind of general-purpose plastics.
But polyethylene there is also mechanical strengths not enough, the disadvantages of sensitive for environmental stress to heat-resistant aging is poor, limit it and answer
Use range.The study found that when using graphene as reinforced phase, when additive amount is lower, the performance of polyethylene can substantially enhance.But
It is that, since graphene specific surface area is huge, and there are intrinsic Van der Waals force between graphene sheet layer, graphene sheet layer holds very much
It is easy to reunite.Therefore, the graphene of nano-scale is evenly dispersed in base polyethylene is to prepare high performance polyethylene/graphite
The key technology of alkene nanocomposite.
Currently, polyethylene/graphene nanocomposite can be prepared by following three kinds of methods: solution composite approach melts
Melt blending method and situ aggregation method.Although these methods can prepare better performances polyethylene/graphene nanocomposite,
It is all the presence of some disadvantages.If solution blended process needs a large amount of solvent, at high cost, environmental pollution is big；Melt-blending process is difficult to
Realize that fine dispersion of the graphene in polyethylene, obtained polyethylene/graphene nanocomposite performance improve unobvious；
Situ aggregation method is more complicated, it is difficult to industrialized production.
Solution-melting composite algorithm appearance then very good solution these problems, first prepare graphene content with solwution method
Higher polyethylene/graphene master batch, it is then by the method for melt blending that master batch and large quantities of weight northylens is compound, both considered
It has arrived the dispersibility of graphene and has taken into account the feasibility of composite material actual production.There are reports uses solution-melting
Compound thinking prepares polymer/graphene master batch, such as ZL201110282093.8, and graphene oxide is first reduced into stone
Black alkene, then disperse graphene in a small amount of organic solvent, it is then sufficiently mixed, is removed organic molten with polymer solution
After agent, polymer/graphene master batch is obtained, graphene mass percent in master batch is 1%~50%.But this first general
Graphene oxide is reduced into after graphene again with the method for mixed with polymers, and graphene inevitably reassociates, unfavorable
In redisperse, and organic solvent is used, it is larger to environmental hazard.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation method of polyethylene/graphene master batch, this method is able to achieve graphite
Alkene is evenly dispersed in base polyethylene, and does not use organic solvent, environmentally protective.
Above-mentioned purpose of the invention is achieved through the following technical solutions:
A kind of preparation method of polyethylene/graphene master batch, comprising the following steps:
(1) graphite oxide is added to the water, is successively dispersed and removed by stirring and ultrasound, graphene oxide is made
Aqueous polyethylene wax emulsion is added in graphene oxide water solution, through ultrasound or is uniformly mixed, adds brokenly by aqueous solution
Emulsion is demulsified, and polyethylene/graphene oxide particle suspension liquid is made；
(2) reducing agent is added into polyethylene made from step (1)/graphene oxide particle suspension liquid restore instead
Answer, using filter, it is dry after obtain polyethylene/graphene master batch.
The present invention is during the preparation of polyethylene/graphene master batch, by the method restored afterwards that is first demulsified, can first by
Graphene oxide is dispersed in base polyethylene and restores, and occurs after effectively graphene oxide being avoided to be reduced into graphene
Agglomeration.
In the preparation method of above-mentioned polyethylene/graphene master batch:
Preferably, the proportion by weight of step (1) graphite oxide and water is 1:50~500.
Preferably, revolving speed is 100~300rpm when step (1) stirs, and mixing time is 0.5~2h, and temperature is 20~40
DEG C, in ultrasonic procedure, 100~500W of power, temperature is 20~80 DEG C, and ultrasonic time is 10~60min.
Preferably, the solid content of step (1) the aqueous polyethylene wax emulsion is 10~50%, the aqueous polyethylene wax
The proportion by weight of polyethylene and graphite oxide in lotion is 1~9:1.
Preferably, demulsifier described in step (1) is that sodium chloride solution, Klorvess Liquid, magnesium chloride solution, calcium chloride are molten
One of liquid, metabisulfite solution, calcium sulphate soln and polymeric aluminum chlorides solution are a variety of.
Preferably, reducing agent described in step (2) is vitamin C, sodium citrate, glucose, tannic acid and tea polyphenols
One of or it is a variety of, above-mentioned reducing agent is environmentally protective, and toxicity is lower.
Preferably, the proportion by weight of reducing agent described in step (2) and graphite oxide is 1~20:1.
The reduction 1~for 24 hours under the conditions of 25~90 DEG C when carrying out reduction reaction in step (2).
Dry in step (2) using vacuum drying, vacuum degree is 0.01~0.1MPa, temperature is 40~80 DEG C, when dry
Between for 10~for 24 hours.
Preferably, in polyethylene/graphene master batch obtained in step (2) graphene mass percentage be 10~
50%.
The method of the present invention is mixed by making oxidized graphite into graphene oxide water solution, and with aqueous polyethylene wax emulsion
At being demulsified, being restored, filtration drying again after lotion, point of the graphene in polyethylene is reinforced by the method for solution dispersion
Dissipate property.Compared with prior art, the invention has the following advantages:
(1) present invention is using being first demulsified the method restored afterwards, and it is evenly dispersed in base polyethylene to realize graphene,
The polyethylene/graphene master batch of high graphene content is obtained；
(2) water as solvent is used only in the present invention, and the reducing agent of selection is environmentally protective, preparation process green non-pollution, cost
It is low, simple process, it is easy to accomplish large-scale industrial production.
Detailed description of the invention
Below by way of attached drawing, the present invention is further illustrated.
POM figure of the polypropylene/graphene master batch that Fig. 1 graphene content is 20% at 200 DEG C.
Specific embodiment
Below by way of specific embodiment, the present invention is further illustrated.Graphite oxide used in following embodiments is
The graphite oxide of Nanjing Xian Feng Nono-material Science & Technology Ltd. production.
Embodiment 1
(1) it by 1g graphite oxide, is added in the water of 200g, stirs 0.5h under conditions of 100rpm, 20 DEG C, then 500W
Power, ultrasound 30min under the conditions of 60 DEG C, are dispersed and are removed, and graphene oxide water solution is made；
The 50% aqueous polyethylene wax emulsion containing 1g polyethylene is added in graphene oxide water solution, agitated mixing
Uniformly, the calcium chloride solution for adding 2g 10% is demulsified, and polyethylene/graphene oxide particle suspension liquid is made；
(2) 5g vitamin C is added into polyethylene made from step (1)/graphene oxide particle suspension liquid, in 80 DEG C of items
10h is restored under part, after filtering, drying obtains graphite afterwards for 24 hours in the vacuum drying oven that vacuum degree is 0.01MPa, temperature is 60 DEG C
Alkene content is 50% polyethylene/graphene master batch.
Embodiment 2
(1) it by 1g graphite oxide, is added in the water of 100g, stirs 2h under conditions of 200rpm, 40 DEG C, then 100W function
Rate, ultrasound 60min under the conditions of 80 DEG C, are dispersed and are removed, and graphene oxide water solution is made,
The 45% aqueous polyethylene wax emulsion containing 1.5g polyethylene is added in graphene oxide water solution, it is agitated mixed
It closes uniformly, the magnesium chloride solution for adding 5g 15% is demulsified, and polyethylene/graphene oxide particle suspension liquid is made；
(2) 10g vitamin C is added into polyethylene made from step (1)/graphene oxide particle suspension liquid, in 25 DEG C
Under the conditions of reductase 12 4h, after filtering, in the vacuum drying oven that vacuum degree is 0.05MPa, temperature is 40 DEG C drying obtain stone afterwards for 24 hours
Black alkene content is 40% polyethylene/graphene master batch.
Embodiment 3
(1) it by 1g graphite oxide, is added in the water of 100g, stirs 1h under conditions of 300rpm, 30 DEG C, then 300W function
Rate, ultrasound 10min under the conditions of 40 DEG C, are dispersed and are removed, and graphene oxide water solution is made,
The 30% aqueous polyethylene wax emulsion containing 2.3g polyethylene is added in graphene oxide water solution, it is agitated mixed
It closes uniformly, the liquor alumini chloridi for adding 1g 10% is demulsified, and polyethylene/graphene oxide particle suspension liquid is made；
(2) 10g glucose is added into polyethylene made from step (1)/graphene oxide particle suspension liquid, in 80 DEG C of items
Reductase 12 4h under part after filtering, obtains graphite after dry 15h in the vacuum drying oven that vacuum degree is 0.07MPa, temperature is 70 DEG C
Alkene content is 30.3% polyethylene/graphene master batch.
Embodiment 4
(1) it by 1g graphite oxide, is added in the water of 50g, stirs 1.2h under conditions of 150rpm, 25 DEG C, then 400W
Power, ultrasound 30min under the conditions of 50 DEG C, are dispersed and are removed, and graphene oxide water solution is made,
The 25% aqueous polyethylene wax emulsion containing 4g polyethylene is added in graphene oxide water solution, agitated mixing
Uniformly, the sodium chloride and potassium chloride mixed solution for adding 10g 25% are demulsified, and polyethylene/graphene oxide particle is made
Suspension；
(2) 5g sodium citrate is added into polyethylene made from step (1)/graphene oxide particle suspension liquid, in 90 DEG C
Under the conditions of restore 10h, after filtering, obtain graphite after dry 20h in the vacuum drying oven that vacuum degree is 0.1MPa, temperature is 50 DEG C
Alkene content is 20% polyethylene/graphene master batch.
The polarised light MIcrosope image of polyethylene/graphene master batch obtained as shown in Figure 1, in figure as it can be seen that color compared with
Deep graphene has been uniformly distributed.
Embodiment 5
(1) it by 1g graphite oxide, is added in the water of 500g, stirs 1.8h under conditions of 250rpm, 20 DEG C, then 400W
Power, ultrasound 15min under the conditions of 30 DEG C, are dispersed and are removed, and graphene oxide water solution is made,
The 10% aqueous polyethylene wax emulsion containing 9g polyethylene is added in graphene oxide water solution, agitated mixing
Uniformly, the metabisulfite solution for adding 50g 10% is demulsified, and polyethylene/graphene oxide particle suspension liquid is made；
(2) 20g tea polyphenols are added into polyethylene made from step (1)/graphene oxide particle suspension liquid, in 85 DEG C of items
1h is restored under part, after filtering, drying obtains graphene afterwards for 24 hours in the vacuum drying oven that vacuum degree is 0.01MPa, temperature is 60 DEG C
Content is 10% polyethylene/graphene master batch.
Embodiment 6
(1) it by 1g graphite oxide, is added in the water of 300g, stirs 1h under conditions of 300rpm, 30 DEG C, then 300W function
Rate, ultrasound 10min under the conditions of 40 DEG C, are dispersed and are removed, and graphene oxide water solution is made,
The 20% aqueous polyethylene wax emulsion containing 7g polyethylene is added in graphene oxide water solution, agitated mixing
Uniformly, the polymeric aluminum chlorides solution for adding 20g 15% is demulsified, and polyethylene/graphene oxide particle suspension liquid is made；
(2) 1g tannic acid is added into polyethylene made from step (1)/graphene oxide particle suspension liquid, in 40 DEG C of items
Reductase 12 0h under part after filtering, obtains graphite after dry 10h in the vacuum drying oven that vacuum degree is 0.03MPa, temperature is 80 DEG C
Alkene content is 12.5% polyethylene/graphene master batch.
Embodiment 7
(1) it by 1g graphite oxide, is added in the water of 400g, stirs 1.5h under conditions of 100rpm, 35 DEG C, then 120W
Power, ultrasound 35min under the conditions of 55 DEG C, are dispersed and are removed, and graphene oxide water solution is made,
The aqueous polyethylene wax emulsion of 40% containing 6g polyethylene is added in graphene oxide water solution, it is agitated mixed
It closes uniformly, the mixed solution of the calcium sulfate and sodium sulphate that add 15g 23% is demulsified, and polyethylene/graphene oxide is made
Particle suspension liquid；
(2) vitamin C is added into polyethylene made from step (1)/graphene oxide particle suspension liquid and tea polyphenols are total
15g restores 5h under the conditions of 90 DEG C, after filtering, the dry 18h in the vacuum drying oven that vacuum degree is 0.08MPa, temperature is 55 DEG C
After obtain graphene content be 14.3% polyethylene/graphene master batch.
It should be pointed out that the above embodiments are only illustrated the present invention rather than limit, of the invention suitable
Meaning and scope in any change, be all considered as including within the scope of the present invention.
Claims (10)
1. a kind of preparation method of polyethylene/graphene master batch, which comprises the following steps:
(1) graphite oxide is added to the water, is successively dispersed and removed by stirring and ultrasound, it is water-soluble that graphene oxide is made
Aqueous polyethylene wax emulsion is added in graphene oxide water solution, through ultrasound or is uniformly mixed, adds demulsifier by liquid
It is demulsified, polyethylene/graphene oxide particle suspension liquid is made；
(2) reducing agent is added into polyethylene made from step (1)/graphene oxide particle suspension liquid and carries out reduction reaction, then
Filtered, dry after obtain polyethylene/graphene master batch.
2. the preparation method of polyethylene/graphene master batch according to claim 1, which is characterized in that step (1) described oxygen
The proportion by weight of graphite and water is 1:50~500.
3. the preparation method of polyethylene/graphene master batch according to claim 1, which is characterized in that when step (1) stirs
Revolving speed is 100~300rpm, and mixing time is 0.5~2h, and temperature is 20~40 DEG C, in ultrasonic procedure, 100~500W of power,
Temperature is 20~80 DEG C, and ultrasonic time is 10~60min.
4. the preparation method of polyethylene/graphene master batch according to claim 1, which is characterized in that step (1) described water
Property polythene wax emulsion solid content be 10~50%, the matter of polyethylene and graphite oxide in the aqueous polyethylene wax emulsion
Measuring part proportion is 1~9:1.
5. the preparation method of polyethylene/graphene master batch according to claim 1, which is characterized in that described in step (1)
Demulsifier is sodium chloride solution, Klorvess Liquid, magnesium chloride solution, calcium chloride solution, metabisulfite solution, calcium sulphate soln and gathers
Close one of liquor alumini chloridi or a variety of.
6. the preparation method of polyethylene/graphene master batch according to claim 1, which is characterized in that described in step (2)
Reducing agent be one of vitamin C, sodium citrate, glucose, tannic acid and tea polyphenols or a variety of.
7. the preparation method of polyethylene/graphene master batch according to claim 1 or 6, which is characterized in that in step (2)
The proportion by weight of the reducing agent and graphite oxide is 1~20:1.
8. the preparation method of polyethylene/graphene master batch according to claim 1, which is characterized in that carried out in step (2)
When reduction reaction under the conditions of 25~90 DEG C reduction 1~for 24 hours.
9. the preparation method of polyethylene/graphene master batch according to claim 1, which is characterized in that dry in step (2)
Using vacuum drying, vacuum degree is 0.01~0.1MPa, temperature is 40~80 DEG C, drying time be 10~for 24 hours.
10. the preparation method of polyethylene/graphene master batch according to claim 1, which is characterized in that in step (2)
To polyethylene/graphene master batch in graphene mass percentage be 10~50%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910064065.5A CN109836664A (en) | 2019-01-23 | 2019-01-23 | A kind of preparation method of polyethylene/graphene master batch |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910064065.5A CN109836664A (en) | 2019-01-23 | 2019-01-23 | A kind of preparation method of polyethylene/graphene master batch |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109836664A true CN109836664A (en) | 2019-06-04 |
Family
ID=66883923
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910064065.5A Pending CN109836664A (en) | 2019-01-23 | 2019-01-23 | A kind of preparation method of polyethylene/graphene master batch |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109836664A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101864098A (en) * | 2010-06-03 | 2010-10-20 | 四川大学 | Preparation method of polymer/graphene composite material through in situ reduction |
| US20120187348A1 (en) * | 2009-09-18 | 2012-07-26 | Basf Se | Polymer- graphite nanocomposites |
-
2019
- 2019-01-23 CN CN201910064065.5A patent/CN109836664A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120187348A1 (en) * | 2009-09-18 | 2012-07-26 | Basf Se | Polymer- graphite nanocomposites |
| CN101864098A (en) * | 2010-06-03 | 2010-10-20 | 四川大学 | Preparation method of polymer/graphene composite material through in situ reduction |
Non-Patent Citations (2)
| Title |
|---|
| YU LIN等: "Radiation resistance of poly(methyl methacrylate)/reduced graphene oxide nanocomposites fabricated through latex mixing and in situ reduction", 《CHEMICAL ENGINEERING JOURNAL》 * |
| 张玉龙主编: "《纳米复合材料手册（第1版）》", 31 July 2005, 中国石化出版社 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103642198B (en) | Graphene/carbon black thermoplastic resin master batch with polymolecularity and preparation method thereof | |
| CN103326001B (en) | The preparation method of core-shell polymers-nano-sulfur particles composite material | |
| CN103525379A (en) | Polymer nano-silica temperature-resistant, salt-tolerant and fluid loss reducing agent and preparation method thereof | |
| CN108559112A (en) | A kind of preparation method of graphene-cellulose conductive composite film | |
| CN105399889A (en) | Hybridization wall material nano-capsules made of phase change energy storage material and preparation method of hybridization wall material nano-capsules | |
| CN103804553A (en) | Preparation method for graphene/polyvinyl chloride composite material | |
| CN109754907B (en) | Carbon nano tube polymer composite conductive material and preparation method thereof | |
| CN104710661A (en) | carboxy terminated nitrile rubber/graphene nanocomposite and preparation method thereof | |
| CN110183731B (en) | Preparation method of polyaniline modified nano carbon material | |
| CN105061650A (en) | Method for in-situ suspension polymerization preparation of polyvinyl chloride/graphene composite material | |
| CN101210053B (en) | Amphiphilic starch derivative fine particles and preparing method thereof | |
| CN105974750B (en) | A kind of color toner and preparation method thereof | |
| CN105693900A (en) | Preparation method of nano calcium carbonate/vinyl chloride in-situ polymerization composite resin | |
| CN109021522A (en) | A kind of preparation method of ultrahigh-strength graphene modified polymer material | |
| CN105968777A (en) | Antistatic composite nano material film and preparation method thereof | |
| CN110734587A (en) | Method for preparing nitrile rubber from modified carbon blacks | |
| CN115304935A (en) | High-dispersion carbon nanotube/carbon black composite carbon material and preparation method thereof | |
| CN104841386A (en) | Preparation method for composite high oil-absorption resin | |
| CN1830788A (en) | Technology of transforming common magnesium hydrexide into hexagonal sheel shaped magnesium hydroxide by hydrothermal method | |
| CN109734938A (en) | A kind of preparation method of polypropylene/graphene master batch | |
| CN108424538B (en) | Preparation method of cellulose/nano-attapulgite composite barrier film | |
| CN109836664A (en) | A kind of preparation method of polyethylene/graphene master batch | |
| CN106608653A (en) | Monodisperse spherical nanometer molybdenum disulfide and preparation method and application thereof | |
| CN102875722B (en) | Preparation method of highly adhesive binder for lithium ion batteries | |
| CN105799078B (en) | It is a kind of to be directly atomized rubber wet method mixing method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190604 |
|
| RJ01 | Rejection of invention patent application after publication |