CN115368757B - Preparation process of high-strength high-barrier high-thermal-stability modified graphene powder - Google Patents
Preparation process of high-strength high-barrier high-thermal-stability modified graphene powder Download PDFInfo
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- CN115368757B CN115368757B CN202211066339.2A CN202211066339A CN115368757B CN 115368757 B CN115368757 B CN 115368757B CN 202211066339 A CN202211066339 A CN 202211066339A CN 115368757 B CN115368757 B CN 115368757B
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
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- C09C1/46—Graphite
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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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
- 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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- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/08—Treatment with low-molecular-weight non-polymer organic compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/22—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers modified by chemical after-treatment
- C08J2327/24—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers modified by chemical after-treatment halogenated
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
Abstract
The invention discloses a preparation process of high-strength high-barrier high-thermal stability modified graphene powder, which relates to the technical field of graphene materials, and comprises the steps of preparing a flame retardant modifier by reacting dibenzyl phosphoramidate and 1- (2, 3-epoxypropyl) -4-tert-butoxycarbonyl piperazine, and then carrying out non-covalent modification on graphene oxide by using the flame retardant modifier to obtain modified graphene; the modified graphene prepared by the method is applied to processing of plastic products, so that the problem of poor dispersibility between the conventional graphene and the high-molecular polymer due to poor compatibility can be solved, the mechanical property and flame retardant property of the high-molecular polymer can be obviously improved, and the problem that the conventional flame retardant can enhance the flame retardant property of the high-molecular polymer but affect the mechanical property of the high-molecular polymer can be solved.
Description
Technical field:
the invention relates to the technical field of graphene materials, in particular to a preparation process of modified graphene powder with high strength, high barrier and high thermal stability.
The background technology is as follows:
graphene is a kind of graphene with sp 2 The hybridized and connected carbon atoms are closely stacked to form a single-layer two-dimensional honeycomb lattice structure material, which has the characteristics of ultrahigh strength, super conductivity, super heat conductivity, super specific surface area, super light transmittance and the like, and can be widely applied to the preparation of composite materials. And the graphene has the characteristics of high stability, strong barrier, large surface adsorption and the like, and can effectively reduce material combustionThe heat transfer and mass transfer in the process can be used as flame retardant to enhance the flame retardant property of the high polymer material.
Therefore, when the plastic product is prepared, the mechanical property and the flame retardant property of the plastic product can be improved by adding a proper amount of graphene into the high-molecular polymer. However, since graphene is an inorganic substance and has a problem of poor compatibility with a polymer, the dispersibility of graphene in the polymer is affected, and the effect of graphene is further affected.
According to the invention, graphene oxide is used as a raw material, and the surface modification is carried out to improve the compatibility between the graphene oxide and a high polymer, and enhance the action effect of the graphene, so that the application value of the graphene is improved.
The invention comprises the following steps:
the invention aims to solve the technical problem of providing a preparation process of high-strength high-barrier high-thermal-stability modified graphene powder, which comprises the steps of preparing a flame retardant modifier through chemical reaction, and then carrying out non-covalent modification on graphene oxide by using the flame retardant modifier, so that the prepared modified graphene has the advantages of high strength, high barrier and high thermal stability.
The invention aims to provide a preparation process of modified graphene powder, which comprises the steps of preparing a flame retardant modifier by reacting dibenzyl phosphoramidate and 1- (2, 3-epoxypropyl) -4-tert-butoxycarbonyl piperazine, and then carrying out non-covalent modification on graphene oxide by using the flame retardant modifier to obtain modified graphene.
Preferably, the molar ratio of dibenzyl phosphoramidate to 1- (2, 3-epoxypropyl) -4-tert-butoxycarbonylpiperazine is (1-1.1): 1.
The conversion of 1- (2, 3-epoxypropyl) -4-t-butoxycarbonylpiperazine may be increased by a suitable excess of dibenzyl phosphoramidate. The introduction of the 1- (2, 3-epoxypropyl) -4-tert-butoxycarbonyl piperazine molecular chain in the flame retardant modifier is not only for realizing the anchoring of dibenzyl phosphoramidate on graphene oxide and indirectly enhancing the flame retardant effect of the graphene oxide, but also for directly enhancing the flame retardant effect of the graphene oxide and improving the compatibility between the graphene oxide and a high polymer by utilizing the introduced functional group.
Preferably, the reaction of dibenzyl phosphoramidate with 1- (2, 3-epoxypropyl) -4-tert-butoxycarbonylpiperazine is carried out in an organic solvent.
The use of water as a solvent can reduce the cost and improve the environmental protection, but the presence of water can cause the ring-opening reaction of 1- (2, 3-epoxypropyl) -4-tert-butoxycarbonyl piperazine, thereby affecting the conversion rate of dibenzyl phosphoramidate.
Preferably, the non-covalent modification is performed under anhydrous conditions.
As the prepared flame retardant modifier belongs to liquid, graphene oxide can be directly added for non-covalent modification, so that the contact area between the flame retardant modifier and the graphene oxide is increased, and the modification effect is enhanced.
Preferably, the non-covalent modification is performed under the action of ultrasound.
The contact area of the flame retardant modifier and the graphene oxide can be increased through the assistance of ultrasonic waves, so that the modification effect is enhanced and the modification time is shortened.
Preferably, the mass ratio of the graphene oxide to the flame retardant modifier is 1 (1-10).
The second object of the present invention is to provide a modified graphene prepared according to the aforementioned preparation process.
The invention further aims to provide an application of the modified graphene in plastic product processing.
The plastic product takes a high molecular polymer as a matrix, and 0.5-5wt% of the modified graphene is added.
The addition amount of the modified graphene can be adjusted according to the inherent characteristics of the high molecular polymer of the applied system and the use performance requirement of the plastic product, so as to control the processing cost of the plastic product.
Preferably, the high molecular polymer is at least one selected from polyvinyl chloride, polycarbonate, polyamide, polyurethane, polyethylene, polypropylene, polystyrene, polyacrylonitrile, polyvinyl alcohol, polyacrylate and epoxy resin.
The polymer is not limited to the above-listed polymer, and may be any polymer having good compatibility with the modified graphene.
Based on the principle that amino and epoxy groups undergo ring-opening reaction, dibenzyl phosphoramidate reacts with 1- (2, 3-epoxypropyl) -4-tert-butoxycarbonyl piperazine to prepare the flame retardant modifier; and then non-covalent modification is carried out on graphene oxide based on the action force of hydrogen bonds between hydroxyl groups in the structure of the flame retardant modifier and hydroxyl groups on the surface of the graphene oxide, the flame retardant modifier is anchored on the graphene oxide, the preparation of nitrogen-phosphorus doped modified graphene is realized, the flame retardant property and the mechanical property of the graphene are enhanced, and meanwhile, the compatibility between the graphene and a high polymer is improved.
The beneficial effects of the invention are as follows: according to the invention, the surface of the graphene oxide is modified in a non-covalent modification mode, so that the prepared modified graphene has the advantages of high strength, high barrier and high thermal stability, and the prepared modified graphene is applied to processing of plastic products, so that the problem of poor dispersibility between the conventional graphene and the high polymer due to poor compatibility can be solved, the mechanical property and flame retardant property of the high polymer can be obviously improved, and the problem that the conventional flame retardant can enhance the flame retardant property of the high polymer but affect the mechanical property of the high polymer can be solved.
The specific embodiment is as follows:
the invention is further described in connection with the following embodiments in order to make the technical means, the creation features, the achievement of the purpose and the effect of the invention easy to understand.
The sources of the raw materials in the following examples and comparative examples are illustrated:
dibenzyl phosphoramidate of the formula:
1- (2, 3-epoxypropyl) -4-tert-butoxycarbonylpiperazine, structural formula:
graphene oxide was purchased from beijing meston technologies development limited with an oxygen content of 46%.
The chlorinated polyvinyl chloride is French Acomat 792.
The MBS resin is Rogowski EXL2690.
Nano calcium carbonate was purchased from Guangzhou thick liter new materials limited, with a particle size of 1250 mesh.
The calcium-zinc composite stabilizer NC-105P is purchased from Hangzhou Furuite chemical engineering Co.
Example 1
Preparation of flame retardant modifier: dibenzyl phosphoramidate (30.5 g,0.11 mol) and 1- (2, 3-epoxypropyl) -4-tert-butoxycarbonyl piperazine (24.2 g,0.1 mol) were added to DMF, heated to 80℃for reaction for 5 hours, after the dibenzyl phosphoramidate had reacted completely, heating was stopped, DMF was distilled off under reduced pressure, diethyl ether was added to the residue and stirred, and the mixture was allowed to stand for delamination, and the lower layer liquid was taken to give a flame retardant modifier in a yield of 92.18% and a purity of 99.35%.
Example 2
Preparation of modified graphene: and adding 100g of graphene oxide into 200g of the prepared flame retardant modifier, performing ultrasonic treatment for 5 hours, filtering, washing with water, and drying to obtain the modified graphene.
Example 3
Preparation of modified graphene: and adding 100g of graphene oxide into 400g of the prepared flame retardant modifier, performing ultrasonic treatment for 5 hours, filtering, washing with water, and drying to obtain the modified graphene.
Example 4
Preparation of modified graphene: and adding 100g of graphene oxide into 600g of the prepared flame retardant modifier, performing ultrasonic treatment for 8 hours, filtering, washing with water, and drying to obtain the modified graphene.
Example 5
Preparation of modified graphene: and adding 100g of graphene oxide into 800g of the prepared flame retardant modifier, performing ultrasonic treatment for 8 hours, filtering, washing with water, and drying to obtain the modified graphene.
Example 6
Processing a decorative film: mixing chlorinated polyvinyl chloride, MBS resin, tributyl citrate, nano calcium carbonate and calcium zinc composite stabilizer NC-105P according to the mass ratio of 100:15:20:8:5, adding 5wt% of modified graphene prepared in example 2, carrying out melt extrusion at 150-200 ℃, and cooling and granulating to obtain a polyvinyl chloride/graphene composite material; and (3) calendaring the prepared polyvinyl chloride/graphene composite material at 180 ℃ to form a film, wherein the linear speed of a roller is 10m/min, and thus the decorative film is obtained.
Example 7
Processing a decorative film: mixing chlorinated polyvinyl chloride, MBS resin, tributyl citrate, nano calcium carbonate and calcium zinc composite stabilizer NC-105P according to the mass ratio of 100:15:20:8:5, adding 4wt% of modified graphene prepared in example 3, carrying out melt extrusion at 150-200 ℃, and cooling and granulating to obtain a polyvinyl chloride/graphene composite material; and (3) calendaring the prepared polyvinyl chloride/graphene composite material at 180 ℃ to form a film, wherein the linear speed of a roller is 10m/min, and thus the decorative film is obtained.
Example 8
Processing a decorative film: mixing chlorinated polyvinyl chloride, MBS resin, tributyl citrate, nano calcium carbonate and calcium zinc composite stabilizer NC-105P according to the mass ratio of 100:15:20:8:5, adding 3wt% of modified graphene prepared in example 4, carrying out melt extrusion at 150-200 ℃, and cooling and granulating to obtain a polyvinyl chloride/graphene composite material; and (3) calendaring the prepared polyvinyl chloride/graphene composite material at 180 ℃ to form a film, wherein the linear speed of a roller is 10m/min, and thus the decorative film is obtained.
Example 9
Processing a decorative film: mixing chlorinated polyvinyl chloride, MBS resin, tributyl citrate, nano calcium carbonate and calcium zinc composite stabilizer NC-105P according to the mass ratio of 100:15:20:8:5, adding 3wt% of modified graphene prepared in example 5, carrying out melt extrusion at 150-200 ℃, and cooling and granulating to obtain a polyvinyl chloride/graphene composite material; and (3) calendaring the prepared polyvinyl chloride/graphene composite material at 180 ℃ to form a film, wherein the linear speed of a roller is 10m/min, and thus the decorative film is obtained.
Comparative example 1
The modified graphene in example 9 was replaced with graphene oxide, and the rest of the preparation steps were the same as in example 9.
The above-mentioned examples 6 to 9 and comparative examples 1 to 2 were prepared as decorative films having a thickness of 0.22mm, and the decorative films were tested for flame retardant properties according to the standards GB/T2406-2008 and GB/T2408-2008, and the decorative films were tested for tensile properties according to the standards GB/T1040.3-2006, and the test results are shown in Table 1.
TABLE 1
| Oxygen index | Vertical combustion grade | Tensile strength MPa | |
| Example 6 | 32.1 | V-0 | 39.8 |
| Example 7 | 34.5 | V-0 | 39.2 |
| Example 8 | 36.5 | V-0 | 38.3 |
| Example 9 | 37.8 | V-0 | 37.6 |
| Comparative example 1 | 28.4 | V-1 | 32.5 |
The foregoing has shown and described the basic principles and main features of the present invention and the advantages of the present invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined in the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (8)
1. A preparation process of modified graphene powder is characterized by comprising the following steps: firstly, preparing a flame retardant modifier by reacting dibenzyl phosphoramidate and 1- (2, 3-epoxypropyl) -4-tert-butoxycarbonyl piperazine, and then carrying out noncovalent modification on graphene oxide by using the flame retardant modifier to obtain modified graphene;
the mole ratio of dibenzyl phosphoramidate to 1- (2, 3-epoxypropyl) -4-tert-butoxycarbonyl piperazine is (1-1.1): 1;
the mass ratio of the graphene oxide to the flame retardant modifier is 1 (1-10).
2. The process according to claim 1, wherein: the reaction of dibenzyl phosphoramidate with 1- (2, 3-epoxypropyl) -4-tert-butoxycarbonylpiperazine is carried out in an organic solvent.
3. The process according to claim 1, wherein: the non-covalent modification is performed under anhydrous conditions.
4. The process according to claim 1, wherein: the non-covalent modification is carried out under the action of ultrasonic waves.
5. The modified graphene prepared by the preparation process according to any one of claims 1 to 4.
6. The use of the modified graphene of claim 5 in the processing of plastic products.
7. The use according to claim 6, wherein: the plastic product takes a high molecular polymer as a matrix, and 0.5-5wt% of the modified graphene is added.
8. The use according to claim 7, wherein: the high molecular polymer is at least one selected from polyvinyl chloride, polycarbonate, polyamide, polyurethane, polyethylene, polypropylene, polystyrene, polyacrylonitrile, polyvinyl alcohol, polyacrylate and epoxy resin.
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| WO2015181982A1 (en) * | 2014-05-30 | 2015-12-03 | グラフェンプラットフォーム株式会社 | Graphene composition and graphene molded article |
| JP2016160430A (en) * | 2015-02-27 | 2016-09-05 | 現代自動車株式会社Ｈｙｕｎｄａｉ Ｍｏｔｏｒ Ｃｏｍｐａｎｙ | Polypropylene-graphene composite body and method for producing the same |
| CN104629496B (en) * | 2015-03-05 | 2017-03-15 | 贵州一当科技有限公司 | A kind of processing method of modified graphene |
| CN106674899A (en) * | 2016-12-21 | 2017-05-17 | 华中科技大学 | Composite material integrating flame retardance and heat conductivity and preparation method thereof |
| CN106883450B (en) * | 2017-02-20 | 2018-10-12 | 无锡市惠山区川大石墨烯应用研究中心 | A kind of richness phosphatization Graphene fire retardant and preparation method thereof |
| CN111440416A (en) * | 2020-05-11 | 2020-07-24 | 林科 | Flame-retardant functionalized graphene modified epoxy resin material and preparation method thereof |
| CN112341804A (en) * | 2020-10-27 | 2021-02-09 | 合肥通融新型材料科技有限公司 | Preparation method of flame-retardant polyamide composite material |
| CN112831165B (en) * | 2021-01-29 | 2022-05-24 | 华南理工大学 | Degradable barrier nano composite film and preparation method and application thereof |
| CN114956065B (en) * | 2022-05-30 | 2023-09-26 | 广东墨睿科技有限公司 | Amino modified graphene, preparation method thereof, amino modified graphene coating and application |
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