CN108002377B - Preparation method of organosilane oligomer modified graphene - Google Patents
Preparation method of organosilane oligomer modified graphene Download PDFInfo
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- CN108002377B CN108002377B CN201711186739.6A CN201711186739A CN108002377B CN 108002377 B CN108002377 B CN 108002377B CN 201711186739 A CN201711186739 A CN 201711186739A CN 108002377 B CN108002377 B CN 108002377B
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Abstract
The invention relates to a preparation method of organosilane oligomer modified graphene, which fully utilizes various oxygen-containing functional groups contained on the surface of graphene oxide, selects chlorosilane to modify the graphene oxide, and utilizes a hydrolytic condensation method to obtain an organosilane oligomer grafted graphene material. The structure and polymerization degree of grafting can be controlled by controlling the input ratio of chlorosilane raw materials with different functionalities. The invention realizes the purpose of preparing the organosilane oligomer modified graphene through one-pot reaction.
Description
Technical Field
The invention discloses a preparation method of organosilane oligomer modified graphene, and belongs to the technical field of graphene and surface treatment.
Background
The silicon rubber is a special semi-organic and semi-inorganic high polymer material, and has outstanding thermal stability and weather aging resistance; the rubber has good chain flexibility and can still keep elasticity at low temperature; in addition, the silicon rubber has excellent performance in the aspects of ultraviolet light resistance and solvent resistance, and is widely applied to high and new technical fields of aviation, aerospace, electronics, communication and the like. Graphene is a material which is popular in recent years, has excellent electrical, thermal conductivity and mechanical properties, but cannot be used as a functional assistant for preparing high-performance silicon rubber products because of easy agglomeration and poor compatibility with silicon rubber. Therefore, in order to fully exert the excellent performance of graphene in silicone rubber, achieving good dispersion in silicone rubber is a key step.
From research literature at home and abroad, more and more researchers pay attention to the compatibility problem of graphene and silicone rubber, and add graphene subjected to surface treatment to silicone rubber, but the processing idea adopted by the researchers is to treat the surface of a graphene material by using organic matters, and the treating agent is basically a silane coupling agent containing carbon functionality or carbon chains, such as maddan, yolin, and yodongdong and the like, and adopts a silane coupling agent KH-550 (gamma-aminopropyltriethoxysilane) to treat graphene (polymer material science and engineering, 2013,29 (10): 138-141), and also adopts a silane coupling agent KH-550 or diphenylmethane-4, 4' -diisocyanate to treat graphene (patent number CN 1056944661A), and the obtained treated graphene is added to prepare the silicone rubber. The documents and work achieve the improvement of the compatibility of the modified graphene and the silicone rubber to a certain extent, but the graphene surface grafting groups obtained by the methods are organic silicon small molecular compounds, and the improvement of the compatibility with the silicone rubber is limited.
Disclosure of Invention
The invention aims to provide a preparation method of organosilane oligomer modified graphene aiming at the defects in the prior art, and aims to enable the prepared organosilane oligomer modified graphene to have a silicon-oxygen repeating unit which is the same as that of common silicon rubber, so that the obtained modified graphene has higher compatibility with silicon rubber.
The purpose of the invention is realized by the following technical scheme:
the preparation method of the organosilane oligomer modified graphene comprises the following steps:
step one, synthesis preparation
Adding 10 parts by mass of graphene oxide prepared by an oxidation-reduction method into a three-mouth reaction bottle, wherein the thickness of a lamella of the graphene oxide is 0.5-10 nm, adding a fully dried anhydrous solvent, sealing, performing ultrasonic dispersion on a mixed system for 40-90 min to obtain a 1-50 g/L dispersion system, installing a stirring device at the middle mouth of the three-mouth reaction bottle, and respectively installing a reflux condenser tube and a constant-pressure dropping device at the side mouth;
the anhydrous solvent is tetrahydrofuran, methyltetrahydrofuran or cyclohexane;
step two, chlorosilane modification reaction and hydrolysis condensation of graphene oxide
2.1 dropwise adding 5-100 parts by mass of chlorosilane into a three-mouth reaction bottle through a constant-pressure dropping device, heating to reflux reaction, and reacting for 24-48 h to complete chlorosilane modification of graphene oxide;
2.2 adding a mixed solution of 0.5-15 parts by mass of deionized water and 10-100 parts by mass of tetrahydrofuran into a three-mouth reaction bottle within 10-15 min by using a constant-pressure dropping funnel, and continuously reacting for 1.0-2.0 h to obtain an organosilane oligomer modified graphene dispersion solution;
step three, separating and purifying components in the organosilane oligomer modified graphene dispersion liquid
And cooling the organosilane oligomer modified graphene dispersion liquid to room temperature, carrying out vacuum filtration and washing, and then carrying out reduced pressure distillation and drying on the obtained solid.
The molecular formula of the chlorosilane is as follows: RnSiCl (4-n), wherein: r is one or more of methyl, vinyl or phenyl, and n is a positive integer not greater than 3.
In the step 2.2, when the mass of the deionized water is not more than 2 parts by mass, adding excessive water or ammonia water into the silane oligomer modified graphene dispersion liquid for end group hydroxylation, or adding methanol or ethanol for end group alkoxylation, and replacing an end-capping group.
Compared with the prior art, the invention has the following advantages:
1. the oligomeric organic silane graft modification of the graphene oxide is realized;
2. the graphene modification method is simple and easy to operate, the number of intermediate steps is small, and all reactions are carried out in the same reaction vessel;
3. the structure and the polymerization degree of the grafted organosilane can be controlled by controlling the input amount of chlorosilane with different functionalities and the addition amount of deionized water during hydrolysis;
4. the blocking group can be adjusted by hydrolysis or alcoholysis.
Detailed description of the invention
The technical solution of the present invention will be further described with reference to the following examples:
example 1:
the preparation method of the organosilane oligomer modified graphene comprises the following steps:
adding 2g of graphene oxide into a three-mouth reaction bottle, adding 250g of fully dried anhydrous tetrahydrofuran, and sealing; and carrying out ultrasonic dispersion on the mixed system for 90 min. A stirring device is arranged at the middle port of the three-port reaction bottle, and a reflux condenser pipe and a constant-pressure liquid dropping device are respectively arranged at the side ports of the three-port reaction bottle;
5g of dimethyldichlorosilane is dripped into a three-mouth reaction bottle through a constant pressure dripping device, and the reaction is carried out for 36 hours after the temperature is raised to a micro reflux reaction. After 1.0h of reaction, 15ml of a deionized water-tetrahydrofuran mixture containing 0.3g of deionized water was added dropwise to the system over 12 min. And after continuously reacting for 2h, adding excessive deionized water for hydrolysis to obtain the hydroxyl-terminated organosilane oligomer modified graphene. And cooling the reaction system to room temperature, carrying out vacuum filtration and washing, and carrying out reduced pressure distillation and drying on the obtained solid substance.
Example 2:
the preparation method of the organosilane oligomer modified graphene comprises the following steps:
the difference from example 1 is that 5g of methyl phenyl dichlorosilane and 1g of trimethyl monochlorosilane are dropped into a three-mouth reaction bottle by a constant pressure dropping device, and then the temperature is raised to a micro reflux reaction for 40 hours. After the reaction is carried out for 1.0h, 10ml of deionized water-tetrahydrofuran mixed solution containing 0.6g of deionized water is dripped into the system within 10min, and the reaction is continued for 2h to obtain the organosilane oligomer modified graphene terminated by trimethylsilane. And cooling the reaction system to room temperature, carrying out vacuum filtration and washing, and carrying out reduced pressure distillation and drying on the obtained solid substance.
Example 3:
the preparation method of the organosilane oligomer modified graphene comprises the following steps:
the difference from example 2 is that 5g of dimethyldichlorosilane, 1g of trimethylchlorosilane and 0.2g of monomethyltrichlorosilane are added dropwise into a three-neck reaction flask by a constant pressure dropping device, and then the temperature is raised to a micro reflux reaction for 48 hours. After the reaction is carried out for 1.0h, 40ml of deionized water-tetrahydrofuran mixed solution containing 0.5g of deionized water is dripped into the system within 14min, and the reaction is continued for 2h to obtain the trimethylsilyl terminated organosilane oligomer modified graphene containing the branched chain.
Example 4:
the preparation method of the organosilane oligomer modified graphene comprises the following steps:
the difference from example 1 is that an excess of ammonia water was added for hydrolysis to give hydroxyl-terminated organosilane oligomer-modified graphene.
Example 5:
the preparation method of the organosilane oligomer modified graphene comprises the following steps:
the difference from example 1 is that ethanol is added in excess for alcoholysis to finally obtain the ethoxy-terminated organosilane oligomer-modified graphene.
Claims (2)
1. A preparation method of organosilane oligomer modified graphene is characterized by comprising the following steps: the method comprises the following steps:
step one, synthesis preparation
Adding 10 parts by mass of graphene oxide prepared by an oxidation-reduction method into a three-mouth reaction bottle, wherein the thickness of a lamella of the graphene oxide is 0.5-10 nm, adding a fully dried anhydrous solvent, sealing, performing ultrasonic dispersion on a mixed system for 40-90 min to obtain a 1-50 g/L dispersion system, installing a stirring device at the middle mouth of the three-mouth reaction bottle, and respectively installing a reflux condenser tube and a constant-pressure dropping device at the side mouth;
the anhydrous solvent is tetrahydrofuran, methyltetrahydrofuran or cyclohexane;
step two, chlorosilane modification reaction and hydrolysis condensation of graphene oxide
2.1 dropwise adding 5-100 parts by mass of chlorosilane into a three-mouth reaction bottle through a constant-pressure dropping device, heating to reflux reaction, and reacting for 24-48 h to complete chlorosilane modification of graphene oxide;
2.2 adding a mixed solution of 0.5-15 parts by mass of deionized water and 10-100 parts by mass of tetrahydrofuran into a three-mouth reaction bottle within 10-15 min by using a constant-pressure dropping funnel, and continuously reacting for 1.0-2.0 h to obtain an organosilane oligomer modified graphene dispersion solution;
step three, separating and purifying components in the organosilane oligomer modified graphene dispersion liquid
Cooling the organosilane oligomer modified graphene dispersion liquid to room temperature, carrying out vacuum filtration and washing, and then carrying out reduced pressure distillation and drying on the obtained solid;
the molecular formula of the chlorosilane is as follows: rnSiCl(4-n)Wherein: r is one or more of methyl, vinyl or phenyl, and n is a positive integer not greater than 3.
2. The method for producing an organosilane oligomer-modified graphene according to claim 1, wherein: in the step 2.2, when the mass of the deionized water is not more than 2 parts by mass, adding excessive water or ammonia water into the organosilane oligomer modified graphene dispersion liquid for end group hydroxylation, or adding methanol or ethanol for end group alkoxylation, and replacing an end capping group.
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