A method for controlling the wall thickness of hyper-crosslinked polymer nanotubes

Abstract

The present invention discloses a method for controlling the wall thickness of a super-crosslinked polymer nanotube, comprising: S1, placing a beaker into a closed reaction device, exhausting the air in the reaction device and the pipeline; S2, introducing nitrogen, adjusting the airflow speed to stabilize the reaction conditions; S3, using a syringe to measure the monomer and injecting it into the flask, reselecting a syringe to weigh the polymerization monomer and injecting it into the flask, and vibrating it to fully mix it; S4, opening the bottle stopper and quickly pouring in the catalyst prepared in proportion, then tightening the bottle stopper, clamping the flask and immersing it in a silicone oil bath, heating and maintaining the speed, and maintaining the pressure of nitrogen during the reaction; S5, after the reaction is completely completed, filtering the turbid product after the reaction with filter paper, using anhydrous ethanol for preliminary rinsing during filtration, and then placing the product in a Soxhlet extractor for cleaning, and placing the cleaned product in a drying oven for drying, and finally obtaining a relatively pure super-crosslinked polymer nanotube. According to the present invention, the use of noble metal catalysts and templates is avoided, and the synthesis method is simple, the reagent cost is low, and the operating conditions are mild.

Description

Technical Field

[0001] The invention relates to the technical field of new materials, and in particular to a method for controlling the wall thickness of a super-crosslinked polymer nanotube. Background Art

[0002] Carbon nanotubes have a wide range of applications in conductive films, fuel cells, solar cells, supercapacitors and sensors due to their unique one-dimensional (1D) structure. Compared with porous carbon nanotubes, they have attracted widespread attention due to their ultra-high specific surface area. The methods that have been reported to prepare PCNTs are:

[0003] (1) CN202110103254.6 discloses a method for preparing a catalyst precursor NiO / Ti by a deposition-precipitation method using nickel nitrate hexahydrate and titanium powder as raw materials in a certain mass ratio, placing NiO / Ti in a tubular furnace with hydrogen as a reducing gas, nitrogen or argon as a carrier gas and methane as a reaction gas, and synthesizing carbon nanotubes by an in-situ chemical vapor deposition method under different reaction conditions. Although the obtained carbon nanotubes have good dispersion and uniform size, the reaction temperature is between 100 and 600°C, requiring multiple heating and the use of Ti / Ni precious metals as catalysts.

[0004] (2) CN202011042458.5 invented and disclosed a method for preparing PCNTs by template method, which specifically comprises the following steps: dissolving the template agent (methyl orange) in deionized water, then adding an oxidant and ferrocene-modified multi-walled carbon nanotubes (hydroxylated multi-walled carbon nanotubes MWCNTs-OH or carboxylated multi-walled carbon nanotubes MWCNTs-COOH), stirring and dispersing; then injecting pyrrole monomer, stirring and reacting at room temperature under the action of the oxidant; and successively filtering, washing, drying, etc. to obtain ferrocene-modified multi-walled carbon nanotube-polypyrrole nanotube absorbing material. Although this method can synthesize PCNTs with special functions, due to the use of a template, the wall thickness of the PCNTs cannot be controlled, and it is not easy to produce on a large scale.

[0005] (3) CN202010315883.0 proposes a method for preparing carbon nanotubes by using a catalyst to catalyze and crack a carbon source (including methane and multi-carbon alkanes, with the content of iso-carbon alkanes being 5% to 63% of the total carbon source gas). The main operation is to increase the temperature to crack the carbon source. Its advantage is that it can effectively improve the production efficiency of carbon nanotubes and reduce production costs. Similarly, this method cannot control the tube wall thickness of PCNTs.

[0006] According to the above-mentioned several existing schemes, whether it is the flame method, chemical vapor deposition method or template method, none of them can get rid of the expensive noble metal-based catalysts, or the one-dimensional polymer precursors with harsh preparation conditions and complex processes, and at the same time, it is also impossible to make the carbon nanotubes contain specific functional groups. Summary of the invention

[0007] In view of the shortcomings of the prior art, the purpose of the present invention is to provide a method for controlling the wall thickness of hyper-crosslinked polymer nanotubes, which avoids the use of precious metal catalysts and templates, has the advantages of simple synthesis method, low reagent cost, mild operating conditions and significant advantages. In order to achieve the above-mentioned purpose and other advantages according to the present invention, a method for controlling the wall thickness of hyper-crosslinked polymer nanotubes is provided, comprising:

[0008] S1. Place the beaker into a closed reaction device and exhaust all the air in the reaction device and pipelines;

[0009] S2, introduce nitrogen and adjust the gas flow rate to stabilize the reaction conditions;

[0010] S3, using a syringe to measure the monomer and inject it into the flask, reselecting a syringe to weigh the polymerization monomer and inject it into the flask, vibrating to fully mix;

[0011] S4. Open the bottle stopper and quickly pour in the catalyst prepared in proportion, then tighten the bottle stopper, clamp the flask and immerse it in a silicone oil bath, heat it at a high speed and maintain the nitrogen pressure;

[0012] S5. After the reaction is completely completed, the turbid product after the reaction is filtered with filter paper. Anhydrous ethanol is used for preliminary rinsing during filtration. The product is then placed in a Soxhlet extractor for cleaning. The cleaned product is placed in a drying oven for drying, and finally relatively pure hyper-cross-linked polymer nanotubes are obtained.

[0013] Preferably, the monomer type in step S1 may be an alcohol containing a benzene functional group, specifically, 1-naphthalenemethanol, 9-anthracenemethanol, 1-pyrenemethanol, etc., which have a methanol structure with multiple benzene rings connected.

[0014] Preferably, the monomer-solvent ratio in step S1 is adjusted according to the required nanotube wall thickness.

[0015] Preferably, the monomer concentration is 0.005-1 mol / L, and the molar ratio of the anhydrous FeCl3 catalyst to the monomer substance is 2:1.

[0016] Preferably, the temperature of the speed heating in step S4 is 20° C. to 90° C., the time is 8 to 48 hours, the speed is 0 to 500 r / min, and the ultrasound is 20 to 50 kHz.

[0017] Preferably, aromatic hydrocarbons are dissolved in DCE to synthesize a series of one-dimensional hyper-crosslinked polymer nanotubes through a Lewis acid-catalyzed Friedel-Crafts crosslinking reaction, and the wall thickness of the nanotubes is controlled by controlling the concentration of various monomers or monomers of different sizes.

[0018] Compared with the prior art, the present invention has the following beneficial effects:

[0019] (1) The wall thickness of the nanotubes can be controlled by controlling the concentration of various monomers, and polymer nanotubes with higher stability and hydroxyl functionalization can be prepared using different monomers.

[0020] (2) Compared with HNTs prepared by traditional template method and solvothermal method, this simple and easy HNTs preparation strategy avoids the use of precious metal catalysts and templates. In particular, their controllable tube diameter and high specific surface area make these HNTs have potential application prospects in gas storage, pollutant removal, drug release, and other energy and environmental fields.

[0021] (3) This method has significant advantages such as simple synthesis method, low reagent cost, and mild operating conditions. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 TEM image of benzyl alcohol-HNTs according to the method for controlling the wall thickness of hyper-crosslinked polymer nanotubes of the present invention;

[0023] Figure 2 TEM image of 1-naphthalenemethanol-HNTs according to the method for controlling the wall thickness of hyper-crosslinked polymer nanotubes of the present invention;

[0024] Figure 3 TEM image of 9-anthracenemethanol-HNTs according to the method for controlling the wall thickness of hyper-crosslinked polymer nanotubes of the present invention. DETAILED DESCRIPTION

[0025] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0026] Reference Figure 1-3 , a method for controlling the wall thickness of a hyper-crosslinked polymer nanotube, comprising: S1, at room temperature, selecting a suitable flask, placing a rotor in it, adding a polymerization monomer and 1,2-dichloroethane solvent therein, using the Friedel-Crafts crosslinking reaction principle catalyzed by Lewis acid, adding a catalyst, placing the beaker in a closed reaction device, and exhausting the air in the reaction device and the pipeline;

[0027] S2, introduce nitrogen and adjust the gas flow rate to stabilize the reaction conditions;

[0028] S3, use a syringe to measure the monomer and inject it into the flask, select a syringe again to weigh the polymerization monomer and inject it into the flask, vibrate to mix it thoroughly, use a syringe to measure 30ml of 1,2-dichloroethane and inject it into the flask, select a syringe again to weigh 1.5mmol of benzene

[0029] Pour the alcohol monomer into the flask and vibrate to mix it thoroughly;

[0030] S4, open the bottle stopper and quickly pour in the catalyst prepared in proportion, then tighten the bottle stopper, clamp the flask and immerse it in a silicone oil bath, open the bottle stopper and quickly pour in 3mmol of anhydrous FeCl3 catalyst prepared in proportion, then tighten the bottle stopper. Clamp the flask and immerse it in a silicone oil bath, select a speed of 350r / min, heat to 80℃ and maintain for 24h, during which time keep the atmospheric pressure gas N2;

[0031] S5. After the reaction is completely completed, the turbid product after the reaction is filtered with filter paper. Anhydrous ethanol is used for preliminary rinsing during filtration. The product is then placed in a Soxhlet extractor for cleaning. The cleaned product is placed in a drying oven for drying, and finally relatively pure hyper-cross-linked polymer nanotubes are obtained.

[0032] Furthermore, the monomer type in step S1 may be an alcohol containing a benzene functional group, specifically, 1-naphthalenemethanol, 9-anthracenemethanol, 1-pyrenemethanol, etc., which have a methanol structure with multiple benzene rings connected.

[0033] Furthermore, the ratio of monomer to solvent in step S1 is adjusted according to the required nanotube wall thickness.

[0034] Furthermore, the monomer concentration is between 0.005 and 1 mol / L, and the molar ratio of the anhydrous FeCl3 catalyst to the monomer substance is 2:1.

[0035] Furthermore, in step S4, the temperature of the speed heating is 20° C. to 90° C., the time is 8 to 48 hours, the speed is 0 to 500 r / min, and the ultrasound is 20 to 50 kHz.

[0036] Furthermore, aromatic hydrocarbons are dissolved in DCE to synthesize a series of one-dimensional hyper-crosslinked polymer nanotubes through a Lewis acid-catalyzed Friedel-Crafts crosslinking reaction, and the wall thickness of the nanotubes is controlled by controlling the concentration of various monomers or monomers of different sizes. Taking BA monomer as an example, its concentration range is 0.005-1 mol / L. When different monomers are replaced, the concentration and other conditions will change to a certain extent, including but not limited to 0.1 mol / L. The synthesis of a series of one-dimensional hyper-crosslinked polymer nanotubes under the monomer concentration condition of 0.005-1 mol-1.L is the main innovation of the invention, and a series of one-dimensional hyper-crosslinked polymer nanotubes with controllable morphology and wall thickness can be obtained according to the adjustment of different monomer reaction conditions.

[0037] Figure 1 a is a scanning electron microscope (SEM) image of HNTs synthesized from benzyl alcohol in the scheme of the present application, Figure 1 b is a transmission electron microscope (TEM) image. The wall length of HNTs synthesized by benzyl alcohol can reach 10μm and the thickness is about 35nm.

[0038] Figure 2 a is a scanning electron microscope (SEM) image of HNTs synthesized from 1-naphthalene methanol in the scheme of the present application, Figure 2 b is the thickness of the transmission electron microscope (TEM) image. The wall length of HNTs synthesized from 1-naphthalene methanol can reach 10 μm and the thickness is about 45 nm.

[0039] Figure 3 a is a scanning electron microscope (SEM) image of HNTs synthesized from 9-anthracene methanol in the scheme of the present application, Figure 3 b is the thickness of the transmission electron microscope (TEM) image. The wall length of HNTs synthesized by 9-anthracene methanol can reach 1 μm and the thickness is about 15 nm.

[0040] Comparison plan 1

[0041] At room temperature, select a suitable flask, place a rotor in it, add the polymerization monomer and 1,2-dichloro

[0042] Ethane solvent, using the principle of Friedel-Crafts cross-linking reaction catalyzed by Lewis acid, add catalyst, close the reaction device, exhaust the air in the reaction device and pipelines, then introduce gas N2, and adjust the gas flow rate to stabilize the reaction conditions.

[0043] Weigh 1.5 mmol of 1-naphthalene methanol monomer, use a syringe to measure 30 ml of 1,2-dichloroethane and inject it into the flask, inject it into the flask, and shake it to mix it thoroughly.

[0044] Open the bottle stopper and quickly pour in 12mmol of anhydrous FeCl3 catalyst prepared in proportion, then tighten the bottle stopper. Clamp the flask and immerse it in a silicone oil bath, select a speed of 400r / min, heat to 80℃ and maintain for 30h, during which time the atmospheric pressure N2 gas is maintained.

[0045] After the reaction is completely completed, the turbid product after the reaction is filtered with filter paper. Anhydrous ethanol is used for preliminary rinsing during filtration. The product is then placed in a Soxhlet extractor for cleaning. The cleaned product is placed in a drying oven for drying, and finally relatively pure hyper-cross-linked polymer nanotubes are obtained.

[0046] Comparison plan 2

[0047] At room temperature, select a suitable flask, put in a rotor, add polymerization monomers and 1,2-dichloroethane solvent, use the principle of Lewis acid-catalyzed Friedel-Crafts cross-linking reaction, add catalyst, close the reaction device, exhaust the air in the reaction device and pipelines, then introduce N2 gas, and adjust the gas flow rate to stabilize the reaction conditions.

[0048] Use a syringe to measure 30 ml of 1,2-dichloroethane and inject it into the flask. Use another syringe to weigh 6 mmol of benzyl alcohol monomer and inject it into the flask. Vibrate to mix thoroughly.

[0049] Open the bottle stopper and quickly pour in 12 mmol of anhydrous FeCl3 catalyst prepared in proportion, then tighten the bottle stopper. Clamp the flask and immerse it in a silicone oil bath, select a speed of 350 r / min, heat to 80°C and maintain for 24 hours, during which time the atmospheric pressure of N2 gas is maintained.

[0050] After the reaction is completely completed, the turbid product after the reaction is filtered with filter paper. Anhydrous ethanol is used for preliminary rinsing during filtration. The product is then placed in a Soxhlet extractor for cleaning. The cleaned product is placed in a drying oven for drying, and finally relatively pure hyper-cross-linked polymer nanotubes are obtained.

[0051] Comparison plan 3

[0052] At room temperature, select a suitable flask, put in a rotor, add polymerization monomers and 1,2-dichloroethane solvent, use the principle of Lewis acid-catalyzed Friedel-Crafts cross-linking reaction, add catalyst, close the reaction device, exhaust the air in the reaction device and pipelines, then introduce N2 gas, and adjust the gas flow rate to stabilize the reaction conditions.

[0053] Use a syringe to measure 30 ml of 1,2-dichloroethane and inject it into the flask. Use another syringe to weigh 15 mmol of benzyl alcohol monomer and inject it into the flask. Vibrate to mix thoroughly.

[0054] Open the bottle stopper and quickly pour in 30mmol of anhydrous FeCl3 catalyst prepared in proportion, then tighten the bottle stopper. Clamp the flask and immerse it in a silicone oil bath, select a speed of 350r / min, heat to 80℃ and maintain for 24h, during which time the atmospheric pressure gas N2 is maintained.

[0055] After the reaction is completely completed, the turbid product after the reaction is filtered with filter paper. Anhydrous ethanol is used for preliminary rinsing during filtration. The product is then placed in a Soxhlet extractor for cleaning. The cleaned product is placed in a drying oven for drying, and finally relatively pure hyper-cross-linked polymer nanotubes are obtained.

[0056] Comparison plan 4

[0057] At room temperature, select a suitable flask, put in a rotor, add polymerization monomers and 1,2-dichloroethane solvent, use the principle of Lewis acid-catalyzed Friedel-Crafts cross-linking reaction, add catalyst, close the reaction device, exhaust the air in the reaction device and pipelines, then introduce N2 gas, and adjust the gas flow rate to stabilize the reaction conditions.

[0058] Use a syringe to measure 30 ml of 1,2-dichloroethane and inject it into the flask. Use another syringe to weigh 3 mmol of benzyl alcohol monomer and inject it into the flask. Vibrate to mix thoroughly.

[0059] Open the bottle stopper and quickly pour in 6 mmol of anhydrous FeCl3 catalyst prepared in proportion, then tighten the bottle stopper. Clamp the flask and immerse it in a silicone oil bath, select a speed of 350 r / min, heat to 80°C and maintain for 24 hours, during which time the atmospheric pressure gas N2 is maintained.

[0060] After the reaction is completely completed, the turbid product after the reaction is filtered with filter paper. Anhydrous ethanol is used for preliminary rinsing during filtration. The product is then placed in a Soxhlet extractor for cleaning. The cleaned product is placed in a drying oven for drying, and finally relatively pure hyper-cross-linked polymer nanotubes are obtained.

[0061] Comparison plan 5

[0062] At room temperature, select a suitable flask, put in a rotor, add polymerization monomers and 1,2-dichloroethane solvent, use the principle of Lewis acid-catalyzed Friedel-Crafts cross-linking reaction, add catalyst, close the reaction device, exhaust the air in the reaction device and pipelines, then introduce N2 gas, and adjust the gas flow rate to stabilize the reaction conditions.

[0063] 1.5 mmol of 9-anthracene methanol was added, and after nitrogen was filled, 30 ml of 1,2-dichloroethane was measured with a syringe and injected into the flask, and the 9-anthracene methanol and 1,2-dichloroethane were thoroughly mixed by vibration.

[0064] Open the bottle stopper and quickly pour in 3 mmol of anhydrous FeCl3 catalyst prepared in proportion, then tighten the bottle stopper. Clamp the flask and immerse it in a silicone oil bath, select a speed of 350 r / min, heat to 80°C and maintain for 24 hours, during which time the atmospheric pressure of N2 gas is maintained.

[0065] After the reaction is completely completed, the turbid product after the reaction is filtered with filter paper. Anhydrous ethanol is used for preliminary rinsing during filtration. The product is then placed in a Soxhlet extractor for cleaning. The cleaned product is placed in a drying oven for drying, and finally relatively pure hyper-cross-linked polymer nanotubes are obtained.

[0066] The number of devices and processing scales described here are used to simplify the description of the present invention, and the application, modification and variation of the present invention will be obvious to those skilled in the art.

[0067] Although the embodiments of the present invention have been disclosed as above, they are not limited to the applications listed in the specification and implementation modes. They can be fully applied to various fields suitable for the present invention. For those familiar with the art, additional modifications can be easily implemented. Therefore, without departing from the general concept defined by the claims and the scope of equivalents, the present invention is not limited to the specific details and the illustrations shown and described herein.

Claims

1. A method for controlling the wall thickness of hyper-crosslinked polymer nanotubes, It is characterized in that The following steps are involved: S1: Place the flask into a closed reaction apparatus and exhaust all the air in the reaction apparatus and pipelines; S2: introduce nitrogen and adjust the gas flow rate to stabilize the reaction conditions; S3: Use a syringe to measure 30 ml of 1,2-dichloroethane and inject it into the flask. Use a syringe again to weigh the monomer and inject it into the flask. Vibrate to mix it thoroughly. The monomers include 1-naphthalenemethanol, 9-anthracenemethanol, and 1-pyrenemethanol. The monomer-solvent ratio is adjusted by the desired nanotube wall thickness, and the monomer concentration is between 0.005 and 1 mol / L; S4: Open the stopper and quickly pour in the catalyst prepared in proportion, then tighten the stopper, clamp the flask and immerse it in a silicone oil bath, open the stopper and quickly pour in the anhydrous FeCl 3 The catalyst is then tightened, the flask is clamped and immersed in a silicone oil bath, and heated at a high speed for a certain period of time, during which the atmospheric pressure gas N 2 ; The anhydrous FeCl 3 The ratio of catalyst to monomer substance is 2:1; S5: After the reaction is completely completed, the turbid product after the reaction is filtered with filter paper. When filtering, anhydrous ethanol-water is used for preliminary filtration. The product is then placed in a Soxhlet extractor for washing. The washed product is placed in a drying oven for drying to finally obtain hyper-crosslinked polymer nanotubes.

2. A method for controlling the wall thickness of hyper-crosslinked polymer nanotubes as claimed in claim 1, It is characterized in that The temperature of the speed heating in step S4 is 20° C. to 90° C., the time is 8 to 48 hours, and the speed is 350 to 500 r / min.

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