CN107955179B - Hyperbranched polymer modified graphene oxide in water phase and preparation method thereof - Google Patents
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Abstract
A hyperbranched polymer modified graphene oxide in a water phase and a preparation method thereof belong to the technical field of modification of graphene materials. The method comprises the following steps: ultrasonically dispersing graphene oxide, adding a diamine monomer, stirring at constant temperature, and fully reacting the diamine monomer with the graphene oxide; and adding a diene monomer into the reaction system, continuously stirring at constant temperature, polymerizing the two monomers, and polymerizing part of the monomers in situ on the graphene oxide lamella to modify the graphene oxide. And removing the hyperbranched polymer through dialysis to obtain the modified graphene oxide. The process method is simple, mild in operation condition, easy to control and free from adding other components or carrying out multi-step reaction. The modified graphene and the composite material thereof prepared by the method can be used in the fields of preparation of novel separation membranes, novel drug loading materials, novel adsorption materials and the like.
Description
Technical Field
The invention relates to a modification technology of a graphene material, and provides a method for preparing hyperbranched polymer modified graphene oxide and a composite material thereof in a water phase by adopting an in-situ polymerization mode.
Background
The graphene is formed by a layer of dense sp wrapped on a honeycomb crystal lattice2The monolayer two-dimensional crystal formed by the hybridized carbon atom arrangement is the thinnest material known in the world at present and has the thickness of only one carbon atom. The unique two-dimensional structure of the material enables the material to have excellent mechanical, thermal, electrical and optical properties. The graphene oxide is used as an important derivative of graphene, has a simple preparation method, and can be obtained by oxidizing graphite with potassium permanganate/concentrated sulfuric acid and then carrying out ultrasonic treatment. The edge of the graphene oxide contains a large number of oxygen-containing groups, so that the graphene oxide has good hydrophilicity and dispersibility, and can be modified through interaction between functional groups, so that the structure and the property of the graphene oxide can be regulated and controlled, and different functionalized graphene materials can be prepared.
Based on the unique chemical structure of the graphene material, the graphene material can be modified through pi-pi conjugation, electrostatic attraction, covalent bonds and other effects, and a large number of related reports on graphene material modification research are reported. The hyperbranched polymer has a highly branched structure, good solubility, low viscosity, a large number of terminal functional groups and a simpler synthesis method than that of a dendrimer, and is widely applied to modification research of graphene materials. The hyperbranched polymer is adopted to modify the graphene material, and the dispersity and the functionalization degree of the graphene sheet layer and the compatibility with the polymer can be obviously improved through the unique molecular structure and the physicochemical property of the hyperbranched polymer.
Covalent functional modification of graphene sheets by polymers in general includes two methods of "grafting to" (graft-from) and "grafting to" (graft-to). The term "grafting to" refers to grafting the hyperbranched macromolecule to the graphene sheet layer by utilizing the direct reaction of the terminal group functional group on the hyperbranched macromolecule and the active functional group on the graphene sheet layer, and the term "grafting to" refers to firstly bonding an initiator on the surface of the graphene, then initiating the polymerization of a monomer, and grafting a polymer on the surface of the graphene. In order to improve the success rate of the grafting reaction, the graphene oxide is often required to be modified to improve the activity thereof. And the polymerization or grafting reaction is often carried out in an organic phase or a system with a relatively high temperature, which is not favorable for large-scale application.
Disclosure of Invention
In order to solve the above problems, the present invention provides a method for modifying a graphene material with a hyperbranched polymer in an aqueous phase. The hyperbranched polymer modified graphene/hyperbranched polymer composite material can be obtained through a one-pot method, and the hyperbranched polymer modified graphene material can be obtained by removing the polymer through a subsequent dialysis process.
A preparation method of hyperbranched polymer modified graphene oxide in an aqueous phase is characterized by comprising the following steps:
a) carrying out ultrasonic treatment on graphene oxide powder to uniformly disperse the graphene oxide powder in a water phase to prepare a stable graphene oxide dispersion liquid;
b) adding a diamine monomer into the graphene oxide dispersion liquid obtained in the step a), and stirring at a constant temperature of 10-60 ℃ for 1-120 hours to modify graphene oxide by using a monomer containing amino;
c) adding another diene monomer into the mixed system prepared in the step b), and continuously stirring for 6-240 hours at a constant temperature of 10-60 ℃;
d) dialyzing, precipitating and drying the solution obtained in the step c) to obtain the hyperbranched polymer modified graphene oxide.
The concentration of the graphene oxide in the graphene oxide dispersion liquid in the step a) of the invention is 10-6～10mg/mL。
The diamine monomer in the present invention is one of 1- (2-aminoethyl) piperazine, 4-aminomethyl piperidine, N-methylethylenediamine, N-ethylethylenediamine, or N-hexyldiamine, which can react with an oxygen-containing functional group such as a carboxyl group on graphene oxide.
The diene monomer in the invention is N, N-methylene bisacrylamide or N, N' -bis (acryloyl) cystamine.
The molar ratio of the diamine monomer to the diene monomer is 2: 1-1: 2.
The dialysis in the invention adopts a dialysis bag with the molecular weight of 8-30kDa and carries out dialysis in deionized water.
The technical principle of the invention is as follows: adding a diamine monomer into the graphene oxide dispersion liquid and stirring for a long time to enable the diamine monomer to react with carboxylic acid groups on graphene oxide sheet layers. Then adding diene monomer, and carrying out polymerization reaction between diamine monomer and diene monomer and between diene monomer and diamine monomer modified graphene sheets. The hyperbranched polymer and the graphene material modified by the hyperbranched polymer are obtained simultaneously through one-step reaction, the composite material can be directly applied in the next step, and the graphene material modified by the hyperbranched polymer can be obtained by removing the polymer through dialysis.
The specific scheme provided by the invention has mild reaction conditions and simple and easy reaction process, and the prepared composite material or graphene material can be applied to the fields of preparation of separation membrane materials, adsorption materials, drug controlled release materials and the like.
Drawings
FIG. 1 is an infrared spectrum of graphene oxide and hyperbranched polymer-modified graphene oxide prepared by the method of the present invention.
Fig. 2 is a raman spectrum of graphene oxide and hyperbranched polymer-modified graphene oxide prepared by the method of the present invention.
Fig. 3 is an AFM image of hyperbranched polymer-modified graphene oxide prepared by using the method of the present invention for graphene oxide groups, and thicknesses of sheets before and after modification (a is graphene oxide, and b is hyperbranched polymer-modified graphene oxide).
Detailed Description
The present invention will be described in detail with reference to specific examples, but the present invention is not limited to the following examples.
Example 1
The specific method for modifying graphene oxide by hyperbranched polymer is as follows:
(1) taking 30mg of graphene oxide powder, adding 30mL of deionized water, and performing ultrasonic treatment for 4 hours to obtain a stably dispersed 1mg/mL graphene oxide dispersion liquid;
(2) 2.584g of 1- (2-aminoethyl) piperazine was added to the dispersion prepared in step (1), and stirred at a constant temperature of 30 ℃ for 24 hours;
(3) adding 3.083g N, N-methylene bisacrylamide into the reaction system in the step (2), and continuing stirring at constant temperature of 30 ℃ for 60 hours to obtain a mixed solution of 1mg/mL hyperbranched polymer/hyperbranched polymer modified graphene oxide;
(4) putting the reaction solution prepared in the step (3) into an 8-14kDa dialysis bag, and dialyzing for one week to obtain hyperbranched polymer modified graphene oxide;
the prepared graphene oxide material is characterized, and FIG. 1 is an infrared spectrum of the graphene oxide material before and after modification, wherein the infrared spectrum is 2920cm-1The peak value is a characteristic peak of a C-H bond, and the peak value is obviously enhanced after the hyperbranched polymer is modified, which indicates the introduction of hydrocarbons on a graphene sheet layer; FIG. 2 is a Raman spectrum of the graphene oxide material before and after modification, and I of the modified materialD/IGThe regularity of the graphene sheet layer is obviously reduced due to the fact that a covalent bond is formed on the graphene sheet layer after modification, the regularity is reduced, and the result also verifies the successful implementation of the modification; fig. 3 is a representation of the oxidized graphene AFM before and after modification, and a large amount of hyperbranched polymer is generated by in-situ polymerization on the graphene lamella through modification, so that the thickness of the lamella is obviously increased.
Example 2
The specific method for modifying graphene oxide by hyperbranched polymer is as follows:
(1) preparing 1mg/mL graphene oxide dispersion liquid by ultrasonic treatment for 4 hours, and adding 1mL of dispersion liquid into deionized water to dilute the dispersion liquid to 30 mL;
(2) 2.584g of 1- (2-aminoethyl) piperazine was added to the dispersion prepared in step (1), and stirred at a constant temperature of 30 ℃ for 24 hours;
(3) adding 3.083g N, N-methylene bisacrylamide into the reaction system in the step (2), and continuously stirring for 48 hours at the constant temperature of 30 ℃;
(4) and (4) adding deionized water into the solution obtained in the step (3), and diluting to 500mL to obtain a mixed solution of the hyperbranched polymer/hyperbranched polymer modified graphene oxide with the graphene oxide concentration of 2 mg/L.
The solution is used for preparing a pervaporation membrane on the surface of an inorganic ceramic material, and the pretreatment is carried out on an inorganic tubular membrane: immersing the inorganic membrane into 3-amino-triethoxysilane ethanol solution for 2 hours, taking out, and placing into a 110 ℃ oven for high-temperature treatment for 2 two hours; placing the treated tubular membrane in the diluted reaction solution obtained in the step (4), and soaking for 10 minutes under the negative pressure condition of about-0.9 MPa; taking out the membrane, and drying in a 40 ℃ oven for 48 hours to obtain the modified graphene oxide/hyperbranched polymer composite membrane
And (3) carrying out pervaporation performance test on the prepared composite membrane in a pervaporation membrane pool, wherein the test conditions are as follows: the methyl tert-butyl ether/methanol system with the raw liquid material methanol content of 10 wt% has the experimental temperature of 40 ℃ and the pressure of 300Pa at the downstream of the membrane. It has good separation effect on a methyl tert-butyl ether/methanol mixed system, and the flux and the methanol content in the permeate can respectively reach 403g/m2h and 99.51%.
Claims (4)
1. A preparation method of hyperbranched polymer modified graphene oxide in an aqueous phase is characterized by comprising the following steps:
a) carrying out ultrasonic treatment on graphene oxide powder to uniformly disperse the graphene oxide powder in a water phase to prepare a stable graphene oxide dispersion liquid;
b) adding a diamine monomer into the graphene oxide dispersion liquid obtained in the step a), and stirring at a constant temperature of 10-60 ℃ for 1-120 hours to modify graphene oxide by using a monomer containing amino;
c) adding another diene monomer into the mixed system prepared in the step b), and continuously stirring for 6-240 hours at a constant temperature of 10-60 ℃;
d) dialyzing, precipitating and drying the solution obtained in the step c) to obtain hyperbranched polymer modified graphene oxide;
the diamine monomer is 1- (2-aminoethyl) piperazine; the diene monomer is N, N-methylene bisacrylamide, and the molar ratio of the diamine monomer to the diene monomer is 2: 1-1: 2.
2. The method for preparing graphene oxide modified by hyperbranched polymer in aqueous phase according to claim 1, wherein the graphene oxide concentration in the graphene oxide dispersion liquid in the step a) is 10-6～10mg/mL。
3. The preparation method of graphene oxide modified by hyperbranched polymer in aqueous phase according to claim 1, wherein a dialysis bag with molecular weight of 8-30kDa is selected for dialysis, and the dialysis is performed in deionized water.
4. Hyperbranched polymer-modified graphene oxide prepared according to the method of any one of claims 1 to 3.
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| CN108940232B (en) * | 2018-07-11 | 2020-07-28 | 华南理工大学 | Preparation and application of amino-terminated hyperbranched polymer grafted graphene oxide magnetic anion adsorbent |
| CN109406507B (en) * | 2018-12-10 | 2021-09-24 | 鲁东大学 | Method for detecting silver ions in seawater by adopting stabilized gold nanoparticles |
| CN109647514B (en) * | 2019-01-30 | 2020-04-17 | 中国科学院长春应用化学研究所 | High-dispersion palladium catalyst and preparation method and application thereof |
| KR102225469B1 (en) * | 2019-06-19 | 2021-03-10 | 한국과학기술연구원 | Functionalized graphene oxide and preparing method thereof |
| CN110508247A (en) * | 2019-08-30 | 2019-11-29 | 方大炭素新材料科技股份有限公司 | A kind of preparation method of the graphene oxide composite material for Industrial Waste Water Treatments |
| CN113144915B (en) * | 2021-05-13 | 2023-02-28 | 清华大学 | Modified polyamide composite nanofiltration membrane and preparation method thereof |
| CN115491077B (en) * | 2022-09-21 | 2023-09-15 | 武汉易锦包装印务有限公司 | Quick-drying high-stability printing ink and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102390830A (en) * | 2011-08-23 | 2012-03-28 | 华南理工大学 | Method for preparing polyamide-amine in-situ intercalation graphene composite material |
| CN102826539A (en) * | 2012-07-31 | 2012-12-19 | 上海交通大学 | Hyperbranched polyaramide functionalized graphene, as well as preparation method and applications of hyperbranched polyaramide functionalized graphene |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102390830A (en) * | 2011-08-23 | 2012-03-28 | 华南理工大学 | Method for preparing polyamide-amine in-situ intercalation graphene composite material |
| CN102826539A (en) * | 2012-07-31 | 2012-12-19 | 上海交通大学 | Hyperbranched polyaramide functionalized graphene, as well as preparation method and applications of hyperbranched polyaramide functionalized graphene |
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| Title |
|---|
| "Poly(amidoamine) modified graphene oxide as an efficient adsorbent for heavy metal ions";Yang Yuan et al;《Polym.Chem.》;20130212;第4卷(第6期);正文第2164页第2.1节第2-4段 * |
| "多功能超支化聚酰胺-胺的合成及应用";余志强;《中国博士学位论文全文数据库工程科技Ⅰ辑》;20131015;正文第93页第4.2.4节 * |
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