CN109575467B - Preparation method of graphene-PVC composite material - Google Patents

Preparation method of graphene-PVC composite material Download PDF

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CN109575467B
CN109575467B CN201811241411.4A CN201811241411A CN109575467B CN 109575467 B CN109575467 B CN 109575467B CN 201811241411 A CN201811241411 A CN 201811241411A CN 109575467 B CN109575467 B CN 109575467B
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pvc
graphene
stirring
slurry
composite material
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CN109575467A (en
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闫业海
申玉海
王纲
高虎
朱峰云
李乃朋
冯继凡
张�成
姚中成
高歌
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Graphene Polymer Composites R&d Center Shandong Lutai Holding Group Co ltd
Qingdao University of Science and Technology
Shandong Lutai Holding Group Co Ltd
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Graphene Polymer Composites R&d Center Shandong Lutai Holding Group Co ltd
Qingdao University of Science and Technology
Shandong Lutai Holding Group Co Ltd
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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
    • 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
    • C08K3/042—Graphene or derivatives, e.g. graphene oxides

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

The invention relates to a method for preparing a graphene-PVC composite material by a one-pot method, which comprises the steps of adding PVC slurry into a 500ml three-neck round-bottom flask at room temperature, and mechanically stirring to uniformly suspend PVC particles in a water phase; adding GO slurry, and stirring and mixing uniformly; heating, adding L-ascorbic acid according to a certain mass ratio of the L-ascorbic acid to GO, and stirring for reaction; after the reaction is finished, the temperature is reduced to 50 DEG oCCentrifuging or standing; drying and screening to obtain the functionalized graphene/PVC resin. The graphene oxide slurry and the PVC slurry are used in the method, the aggregation of graphene and PVC is inhibited, and the dispersion is more uniform, so that the graphene-PVC composite material with excellent antistatic and stretch-resistant properties is prepared. Meanwhile, the preparation method starts from raw materials, and directly obtains the high molecular polymer with a complex structure without separation of an intermediate. The whole preparation process is simple to operate, economic and environment-friendly. Is suitable for industrial production.

Description

Preparation method of graphene-PVC composite material
Technical Field
The invention belongs to the field of polymer composite materials, and relates to a preparation method of a graphene-PVC composite material.
Background
Graphene (graphene) is a two-dimensional nanomaterial, which is a single-layer two-dimensional material formed by connecting carbon atoms in sp2 hybridization. Due to the special structure, the graphene has excellent performances which are not possessed by many other nano materials, such as extremely high mechanical strength, excellent electric and heat conduction performances, extremely large specific surface area and the like. These properties make graphene an ideal two-dimensional nanofiller for the preparation of high performance polymer nanocomposites. Can improve the conductivity, mechanical property and thermal stability of the polymer, and has higher application value in the field of polymer composite materials. Polyvinyl chloride (PVC) is one of five general-purpose plastics and is widely applied to various fields such as pipes, plates, sectional materials, wires and cables, artificial leather and the like. The production of PVC resin in our province has a leading position in the whole country, and five major producers such as Shandong Tutai chemical, Shandong Texas Shihua, chat on the Xin and Taian salinization, etc. have the proportion of the yield of vinyl chloride accounting for the total amount of the whole country about 20%. However, the SG5 type resin produced by the rutai chemical method is limited in practical application due to poor thermal stability and processability and low degree of functionalization. This results in lower added value for most products. In the beginning of the new year, the Shandong province makes reports for promoting the conversion of new and old kinetic energies, and the reports require 'accelerating the development of basic dominant materials'. Can be made into advanced high polymer materials such as strong fluorine-silicon materials, novel polyurethane, special rubber, functional plastics, synthetic resin and the like. Therefore, the latest scientific and technological achievements in the field of new materials at home and abroad are adopted to transform the traditional PVC industry and develop the new energy-saving, environment-friendly and high-performance PVC material, so that the PVC material is not only policy-oriented, but also is a practical market demand, and has very important practical significance.
At present, the preparation methods of the graphene/polymer composite material mainly include 3 methods: solution blending, melt blending and in situ polymerization. The solvent of the solution blending method is easy to adsorb between graphene sheets and is difficult to remove, so that the performance of the composite material is reduced; meanwhile, the organic solvent is easy to pollute the environment, has high preparation and recovery cost, is difficult to carry out large-scale industrial production, and is only used for small and medium-scale experiments in laboratories generally. Compared with a solvent blending method, the melt blending method does not need to use an organic solvent, is more environment-friendly and is easy for industrial large-scale production. However, the method always has the problem that graphene is difficult to disperse in PVC, and the product performance is not ideal. Therefore, the performance of the PVC/graphene composite material is further improved, the simple physical blending is difficult to realize, the interface combination of graphene and PVC is enhanced by starting from a chemical bond surface organic modification mode, the effective compounding of graphene and macromolecules is realized by an in-situ polymerization means, and the comprehensive performances of the material such as mechanics, heat resistance, electric conduction and the like are expected to be greatly improved. The in-situ polymerization method can keep the graphene in a delamination state, so that the graphene is easily uniformly dispersed in a polymer matrix, the interface interaction between the graphene and the matrix is enhanced, and the mechanical property, the electrical property and the like of the PVC are obviously improved. Graphene/nano calcium carbonate/PVC composite resin is prepared through laboratory pilot scale reaction in-situ polymerization reaction in China. The results show that the particle regularity of the synthesized composite resin is not high due to the direct addition of the particles into the suspension polymerization system, the yield is very low due to the low oil-water ratio, the utilization rate of the free radical initiator is low, the final production consumption is very high, and the product quality is poor.
In conclusion, in order to effectively utilize graphene in the PVC composite material and fully exert the excellent potential of the graphene, and simultaneously overcome the defects of the existing composite material preparation method and reduce the investment cost, the invention innovatively adopts an industrial solution for preparing the graphene/PVC in-situ polymerization composite material by using a one-pot method. The method not only can thoroughly solve the challenging problem that common graphene is easy to agglomerate in matrix resin, achieves the purpose of achieving high performance of the composite material by using as few graphene as possible, but also can fully utilize the existing PVC polymerization production line, greatly reduce the investment of equipment and other fixed assets, and has complete large-scale production and application potential. The invention is pioneering at home and abroad.
Disclosure of Invention
The invention provides a method for preparing a graphene-PVC composite material by a one-pot method, aiming at the problems, and the method specifically comprises the following steps:
1) a500 ml three-neck round-bottom flask is adopted, 100-200 ml of PVC slurry is added at room temperature, and mechanical stirring is carried out to enable PVC particles to be uniformly suspended in the water phase.
2) Adding 50-100 ml GO pulp, and stirring uniformly.
3) Heating to 60-90 deg.C oCAccording to the mass ratio of 1 to GO: 1-10: 1, adding a reducing agent, and stirring for reaction for 1-3 h.
4) After the reaction is finished, the temperature is reduced to 50 DEG oCHereinafter, centrifugation or standing is performed.
5) Drying and screening to obtain the functionalized graphene/PVC resin.
Preferably, the mechanical stirring in step 1) is performed by using a high-speed homogenizer. The rotating speed is 3500r/min, and the stirring time is 10 min.
Preferably, the GO slurry is added in the step 2) and then is uniformly stirred. The rotating speed of the stirrer is 700 r/min, and the time is 10 min.
Preferably, the heating temperature in the step 3) is 80 ℃; the reducing agent is L-ascorbic acid, and the mass ratio of the reducing agent to GO is 4:1, the stirring speed is 700 r/min.
Preferably, the centrifugation time in the step 4) is 20min, and the rotating speed is 1000 r/min.
Compared with the prior art, the invention has the advantages and positive effects that,
1. the preparation method provided by the invention is simple and convenient to operate, does not separate an intermediate, and directly obtains the polymer composite material with a complex structure. Is economical and has no pollution.
2. The method not only can thoroughly solve the challenging problem that common graphene is easy to agglomerate in matrix resin, achieves the purpose of achieving high performance of the composite material by using as little graphene as possible, but also can fully utilize the existing PVC polymerization production line, greatly reduces the investment of equipment and other fixed assets, and has complete large-scale production and application potential.
Drawings
In order to more clearly illustrate the preparation technical route of the invention, the drawings required in the embodiments are described below, the drawings in the following description are only examples of the invention, and for those skilled in the art, other drawings can be obtained according to the drawings of the embodiments of the invention without creative efforts. Wherein: fig. 1 and 2 are Scanning Electron Microscopes (SEM) of functionalized graphene/PVC resin.
Detailed Description
In order that the above objects, features and advantages of the present invention can be more clearly understood, the present invention will be further described with reference to the following examples. It should be noted that the embodiments and features of the embodiments of the present application may be combined with each other without conflict.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, however, the present invention may be practiced in other ways than those specifically described herein, and thus the present invention is not limited to the specific embodiments of the present disclosure.
Example 1:
the invention aims to provide a method for preparing a graphene-PVC composite material by a one-pot method, which can directly obtain molecules with complex structures from relatively simple and easily-obtained raw materials without separation of intermediates. Such a preparation is clearly economically and environmentally advantageous. The aim of improving the high performance of the PVC composite material is fulfilled by adding the graphene oxide slurry.
The preparation method comprises the steps of adding 100 ml of PVC slurry into a 500ml three-neck round-bottom flask at room temperature, and mechanically stirring to uniformly suspend PVC particles in a water phase at 3500r/min for 10 min; adding 80 ml of GO slurry, stirring and mixing uniformly at the rotating speed of 700 r/min for 10 min; heating to 80 deg.CoC, adding L-ascorbic acid according to the mass ratio of the L-ascorbic acid to GO being 4:1, and stirring for reacting for 2 hours; after the reaction is finished, the temperature is reduced to 50 DEG oCCentrifuging at 1000r/min for 20min or standing for 24 h; drying and screening to obtain the functionalized graphene/PVC resin.
Example 2:
the invention aims to provide a method for preparing a graphene-PVC composite material by a one-pot method, which comprises the steps of adding 150 ml of PVC slurry into a 500ml three-mouth round-bottom flask at room temperature, mechanically stirring to enable PVC particles to be uniformly suspended in a water phase at 3500r/min for 10 min; adding 80 ml of GO slurry, stirring and mixing uniformly at the rotating speed of 700 r/min for 10 min; heating to 80 deg.CoC, adding L-ascorbic acid according to the mass ratio of the L-ascorbic acid to GO being 4:1, and stirring for reacting for 2 hours; after the reaction is finished, the temperature is reduced to 50 DEG oCCentrifuging at 1000r/min for 20min or standing for 24 h; drying and screening to obtain the functionalized graphene/PVC resin.
Example 3:
the invention aims to provide a method for preparing a graphene-PVC composite material by a one-pot method, which comprises the steps of adding 200 ml of PVC slurry into a 500ml three-mouth round-bottom flask at room temperature, mechanically stirring to enable PVC particles to be uniformly suspended in a water phase at 3500r/min for 10 min; adding 80 ml of GO slurry, stirring and mixing uniformly at the rotating speed of 700 r/min for 10 min; heating to 80 deg.CoC, adding L-ascorbic acid according to the mass ratio of the L-ascorbic acid to GO being 4:1, and stirring for reacting for 2 hours; after the reaction is finished, the temperature is reduced to 50 DEG oCCentrifuging at 1000r/min for 20min or standing for 24 h; drying and screening to obtain the functionalized graphene/PVC resin.
Example 4:
the invention aims to provide a method for preparing a graphene-PVC composite material by a one-pot method, which comprises the steps of adopting a 500ml three-neck round-bottom flask,adding 100 ml of PVC slurry at room temperature, mechanically stirring to enable PVC particles to be uniformly suspended in the water phase at 3500r/min for 10 min; adding 80 ml of GO slurry, stirring and mixing uniformly at the rotating speed of 700 r/min for 10 min; heating to 80 deg.CoAdding hydrazine hydrate according to the mass ratio of 4:1 to GO, and stirring for reaction for 2 hours; after the reaction is finished, the temperature is reduced to 50 DEG oCCentrifuging at 1000r/min for 20min or standing for 24 h; drying and screening to obtain the functionalized graphene/PVC resin.
Example 5:
the invention aims to provide a method for preparing a graphene-PVC composite material by a one-pot method, which comprises the steps of adding 150 ml of PVC slurry into a 500ml three-mouth round-bottom flask at room temperature, mechanically stirring to enable PVC particles to be uniformly suspended in a water phase at 3500r/min for 10 min; adding 80 ml of GO slurry, stirring and mixing uniformly at the rotating speed of 700 r/min for 10 min; heating to 80 deg.CoAdding hydrazine hydrate according to the mass ratio of 4:1 to GO, and stirring for reaction for 2 hours; after the reaction is finished, the temperature is reduced to 50 DEG oCCentrifuging at 1000r/min for 20min or standing for 24 h; drying and screening to obtain the functionalized graphene/PVC resin.
Example 6:
the invention aims to provide a method for preparing a graphene-PVC composite material by a one-pot method, which comprises the steps of adding 200 ml of PVC slurry into a 500ml three-mouth round-bottom flask at room temperature, mechanically stirring to enable PVC particles to be uniformly suspended in a water phase at 3500r/min for 10 min; adding 80 ml of GO slurry, stirring and mixing uniformly at the rotating speed of 700 r/min for 10 min; heating to 80 deg.CoAdding hydrazine hydrate according to the mass ratio of 4:1 to GO, and stirring for reaction for 2 hours; after the reaction is finished, the temperature is reduced to 50 DEG oCCentrifuging at 1000r/min for 20min or standing for 24 h; drying and screening to obtain the functionalized graphene/PVC resin.
Obviously, the raw materials of the PVC slurry and the graphene oxide slurry used in the present invention, as well as the stirring speed and time, can be modified by those skilled in the art without departing from the meaning and the scope of the present invention. Thus, it is intended that the present invention cover the modifications of this invention provided they come within the scope of the appended claims and their equivalents.
The above description is only a preferred embodiment of the present invention, and not intended to limit the present invention in other forms, and any person skilled in the art may apply the above modifications or changes to the equivalent embodiments with equivalent changes, without departing from the technical spirit of the present invention, and any simple modification, equivalent change and change made to the above embodiments according to the technical spirit of the present invention still belong to the protection scope of the technical spirit of the present invention.

Claims (2)

1. A method for preparing a graphene-PVC composite material is characterized by comprising the following steps:
adding 100-200 ml of PVC slurry into a 500ml three-mouth round-bottom flask at room temperature, and mechanically stirring to uniformly suspend PVC particles in a water phase;
adding 50-100 ml of GO slurry, and uniformly stirring;
heating to 60-90 ℃, and mixing the obtained product with GO according to the mass ratio of 1: 1-10: 1, adding a reducing agent, and stirring for reaction for 1-3 h;
after the reaction is finished, cooling to below 50 ℃, and centrifuging or standing;
drying and screening to obtain functionalized graphene/PVC resin;
mechanically stirring to uniformly suspend PVC particles in the water phase, wherein the rotating speed of the high-speed homogenizer is 3500r/min, and the stirring time is 10 min;
adding GO slurry, and stirring uniformly;
the rotating speed of the stirrer is 700 r/min, and the time is 10 min;
after the reaction is finished, the temperature is reduced to below 50 ℃, the centrifugal speed is 1000r/min, and the time is 20min or the standing is 24 h.
2. The method of preparing graphene-PVC composite according to claim 1, wherein: the reducing agent is any one of L-ascorbic acid or hydrazine hydrate.
CN201811241411.4A 2018-10-24 2018-10-24 Preparation method of graphene-PVC composite material Active CN109575467B (en)

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Publication number Priority date Publication date Assignee Title
CN112226021A (en) * 2020-10-30 2021-01-15 江苏理工学院 Preparation method of graphene/polyvinyl chloride composite material
CN113603193B (en) * 2021-07-05 2023-01-17 常州大学 Preparation method of graphene electrode for capacitive deionization

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106674825A (en) * 2017-02-09 2017-05-17 济宁利特纳米技术有限责任公司 Preparation method of master batch for graphene/PVC (Polyvinyl Chloride) composite material and master batch
CN106809822A (en) * 2017-01-22 2017-06-09 戴天元 A kind of preparation method of super-elasticity graphene aerogel
CN108425239A (en) * 2018-06-19 2018-08-21 哈尔滨工业大学 A method of in the growing mixed graphene aerogel of fiber surface

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106809822A (en) * 2017-01-22 2017-06-09 戴天元 A kind of preparation method of super-elasticity graphene aerogel
CN106674825A (en) * 2017-02-09 2017-05-17 济宁利特纳米技术有限责任公司 Preparation method of master batch for graphene/PVC (Polyvinyl Chloride) composite material and master batch
CN108425239A (en) * 2018-06-19 2018-08-21 哈尔滨工业大学 A method of in the growing mixed graphene aerogel of fiber surface

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
"Self-assembly of graphene aerogel on carbon fiber for improvement of interfacial properties with epoxy resin";Liu Liu et al.;《Materials Letters》;20180220;第218卷;第44-46页 *

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