CN109942890B - Graphene-based antistatic agent with smoke suppression function and preparation method thereof - Google Patents
Graphene-based antistatic agent with smoke suppression function and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 70
- 239000002216 antistatic agent Substances 0.000 title claims abstract description 41
- 239000000779 smoke Substances 0.000 title claims abstract description 17
- 230000001629 suppression Effects 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 27
- -1 graphene ferrocene compound Chemical class 0.000 claims description 26
- 238000000227 grinding Methods 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 10
- 239000012948 isocyanate Substances 0.000 claims description 6
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 3
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- 239000002253 acid Substances 0.000 claims description 3
- 238000000498 ball milling Methods 0.000 claims description 3
- 239000003638 chemical reducing agent Substances 0.000 claims description 3
- GPRSOIDYHMXAGW-UHFFFAOYSA-N cyclopenta-1,3-diene cyclopentanecarboxylic acid iron Chemical compound [CH-]1[CH-][CH-][C-]([CH-]1)C(=O)O.[CH-]1C=CC=C1.[Fe] GPRSOIDYHMXAGW-UHFFFAOYSA-N 0.000 claims description 3
- BFUZANWGLHWYKK-UHFFFAOYSA-N cyclopenta-1,3-diene iron(2+) 5-methylcyclopenta-1,3-dien-1-ol Chemical compound [Fe++].c1cc[cH-]c1.C[c-]1cccc1O BFUZANWGLHWYKK-UHFFFAOYSA-N 0.000 claims description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 3
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 3
- 238000006011 modification reaction Methods 0.000 claims description 3
- 238000006722 reduction reaction Methods 0.000 claims description 3
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 claims description 2
- MYCZBBOLTYBTCX-UHFFFAOYSA-N cyclopenta-2,4-dien-1-amine;cyclopenta-1,3-diene;iron(2+) Chemical compound [Fe+2].C=1C=C[CH-]C=1.NC1=CC=C[CH-]1 MYCZBBOLTYBTCX-UHFFFAOYSA-N 0.000 claims 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 11
- 239000003063 flame retardant Substances 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 7
- 239000004566 building material Substances 0.000 abstract description 3
- 239000011159 matrix material Substances 0.000 description 13
- 229920000642 polymer Polymers 0.000 description 13
- 239000004800 polyvinyl chloride Substances 0.000 description 13
- 229920000915 polyvinyl chloride Polymers 0.000 description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 239000002131 composite material Substances 0.000 description 8
- 230000004048 modification Effects 0.000 description 7
- 238000012986 modification Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical class [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000005325 percolation Methods 0.000 description 4
- 239000002861 polymer material Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 230000003712 anti-aging effect Effects 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
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- 239000003381 stabilizer Substances 0.000 description 2
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- 238000009825 accumulation Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
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- 239000008029 phthalate plasticizer Substances 0.000 description 1
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Abstract
The invention discloses a graphene-based antistatic agent with a smoke suppression function and a preparation method thereof. The graphene antistatic modified PVC prepared by the invention has the advantages of good flame-retardant smoke-suppression effect, high mechanical strength, good antistatic property and the like, and widens the application range of PVC materials in the industries of electronic appliances, green building materials, new energy automobiles, cables and the like.
Description
Technical Field
The invention belongs to the technical field of preparation of graphene-based antistatic agents, and particularly relates to a graphene-based antistatic agent with a smoke suppression function and a preparation method thereof.
Background
The conventional method for preparing the antistatic high molecular material is to add a certain amount of organic molecular antistatic agent into a polymer base material to reduce the surface resistance and the volume resistance of a polymer, increase the conductivity and achieve the aim of preventing charge accumulation on a product. However, the organic molecular antistatic agent has poor compatibility with a matrix and is easy to migrate, and the organic molecular antistatic agent is easy to precipitate from the matrix in the high-temperature processing and using processes, so that the antistatic performance of the material is not durable enough. Although conventional inorganic antistatic agents such as carbon black, metal powder and the like can effectively improve the conductivity of antistatic materials, due to poor compatibility of the additives and matrix materials, the precious mechanical properties of the matrix materials are seriously damaged on the premise of high addition amount, and the application range of the matrix materials is limited. Therefore, it is a common problem in the industry today to improve the conductivity of antistatic materials and develop new high performance antistatic materials.
Graphene is one of the hot spots in the research field of conductive polymers at present as a new nano additive. The graphene has the characteristics of high conductivity, high modulus, high strength, large specific surface area and other excellent performances, and a good conductive network is easily formed in a polymer matrix, so that the graphene becomes a conductive filler with great potential. When the proportion of the graphene added in the polymer matrix reaches a conductive percolation threshold value, a stable conductive network is formed, and the conductivity of the composite material can be rapidly improved. Foreign scholars prepare graphene/Polystyrene (PS) conductive composite materials with excellent conductivity. The conductive percolation threshold value at room temperature is only 0.1 percent (volume ratio), the conductivity of the graphene/PS conductive composite material with the volume ratio of 1 percent is up to 0.1S/m, and the conductive percolation threshold value can meet the requirement of the conductive percolation threshold value as an antistatic composite material. However, although graphene can effectively improve the electrical properties of polymers, graphene has become a bottleneck difficulty in the application field of polymer modification due to poor dispersibility, high price and the like. Antistatic materials require a certain flame retardant property in engineering applications. The research on the flame retardant property of the polymer/graphene nanocomposite shows that the graphene sheets uniformly dispersed in the polymer in a nanoscale through intercalation or stripping have a barrier effect in a two-dimensional direction, so that the exchange between the matrix material and external heat and mass transfer and combustible gas is effectively isolated, the matrix material is well protected, and the flame retardant property of the material is improved. However, the flame-retardant smoke-suppressing efficiency of the graphene to the polymer is low, so that the graphene is endowed with better flame-retardant smoke-suppressing effect through functional modification, the dispersibility of the graphene in a matrix is improved, the mechanical property of the antistatic material is improved, and the actual requirement of the engineering application of the antistatic material is better met.
Disclosure of Invention
The invention aims to provide a graphene-based antistatic agent with a smoke suppression function.
The technical scheme adopted by the invention for solving the technical problems is as follows:
the graphene-based antistatic agent is prepared by chemically reducing graphene oxide and grafting and modifying ferrocene compounds.
The preparation method of the graphene-based antistatic agent comprises the following steps:
(1) chemical reduction of Graphene Oxide (GO)
Reducing GO to obtain reduced graphene oxide r-GO; for example, GO can be added into Dimethylformamide (DMF), ultrasonic treatment is carried out for 80 minutes at room temperature, hydrazine hydrate and ammonia water are added, the mixture is uniformly mixed and then transferred into an autoclave containing a polytetrafluoroethylene lining, the mixture is sealed and stored in an oven, and the mixture is heated to 110 ℃ to react for 6 hours; after the reaction is finished, carrying out suction filtration, washing the precipitate for 5 times by using anhydrous methanol, and then carrying out vacuum drying to obtain a product reduced graphene (r-GO); (2) reduced graphene ferrocene compound grafting modification reaction
Adding r-GO and a diisocyanate compound into a ball mill, grinding for 30-100 minutes under the condition of introducing dry nitrogen to prepare isocyanate modified graphene, adding a ferrocene compound, and continuously grinding for 60-120 minutes under the condition of introducing dry nitrogen to prepare the graphene-based antistatic agent with the smoke suppression function.
In the scheme, the mass ratio of the r-GO, the diisocyanate compound and the ferrocene compound in the step (2) is 1: 0.05-0.2: 0.1 to 0.4.
The diisocyanate compound in the step (2) is selected from one of the following: diphenylmethane diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, isophorone diisocyanate.
The ferrocene compound in the step (2) is selected from one of the following compounds: ferroceneacetic acid, ferrocenecarboxylic acid, amino ferrocene and hydroxymethyl ferrocene.
In the grinding process conditions in the step (2), the rotating speed of a roller of the ball mill is 100-600 revolutions per minute, the ball milling tank and the grinding balls are made of agate or tungsten carbide, the ball loading amount is 0.2-1.0 kg, and the nitrogen gas flow rate is 0.1-10 liters per minute.
Compared with the prior art, the beneficial effects of the invention are embodied in the following aspects:
1. the graphene-based antistatic agent prepared by the invention not only can improve the flame-retardant and smoke-suppression performance of the high polymer material, but also can improve the mechanical property of the high polymer material. Chemically modifying graphene by utilizing surface grafting modification and the like, and grafting the ferrocene compound smoke suppressant on the surface of the graphene to endow the graphene with flame retardant and smoke suppressant functions. Meanwhile, the organic modification of the graphene surface increases the compatibility and the dispersibility with a polymer matrix, enhances the interaction of the interface of the graphene and the polymer matrix, and uniformly disperses the graphene-based antistatic agent in the polymer matrix by a melt blending method, an in-situ polymerization method and the like, thereby improving the mechanical property and the conductivity of the antistatic polymer composite material;
2. according to the graphene-based antistatic agent prepared by the invention, the synergistic effect of smoke suppression of the condensed phase of the graphene and the ferrocene is adopted, so that the flame-retardant smoke suppression effect of the graphene-based antistatic agent is greatly improved, meanwhile, the ferrocene micromolecules anchored on the surface of the graphene are not easy to separate out in the use process, and the secondary pollution of the smoke suppression agent is reduced;
3. the graphene-based antistatic agent disclosed by the invention adopts a preparation method of a solvent-free solid-phase ball-milling reaction, so that the preparation process is simple, the production cost is low, and the energy consumption and the pollutant emission are reduced;
4. the graphene-based antistatic agent prepared by the invention has the characteristics of modification functions of self-enhancement, flame retardance, smoke suppression, electric conduction and the like, is suitable for antistatic, flame retardance and smoke suppression modification of various high polymer materials, and widens the application range of the high polymer materials in the industries of electronic appliances, green building materials, new energy automobiles, cables and the like.
Detailed Description
The technical solution of the present invention is illustrated by the following specific examples, but the scope of the present invention is not limited thereto:
example 1
Preparation of graphene-based antistatic agent:
(1) chemical reduction of Graphene Oxide (GO)
Adding 1g of GO into 100g of DMF, carrying out ultrasonic treatment at room temperature for 80 minutes, adding 1.6mL of hydrazine hydrate and 7mL of concentrated ammonia water (the concentration is 28 percent), uniformly mixing, transferring to a high-pressure kettle with a polytetrafluoroethylene lining, sealing and storing in an oven, and heating to 110 ℃ for reaction for 6 hours; washing the precipitate with anhydrous methanol for 5 times, and then vacuumizing and drying to obtain the product reduced graphene (r-GO).
(2) Reduced graphene ferrocene compound grafting modification reaction
Adding 1g r-GO and 0.05g of diphenylmethane diisocyanate into a high-energy planetary ball mill (model: F-P2000, manufacturer: Hunan Fukas laboratory instruments Co., Ltd.), grinding for 30 minutes under the condition of introducing 10 liters/minute of dry nitrogen flow rate to prepare isocyanate modified graphene, adding 0.1g of ferroceneacetic acid, continuously grinding for 60 minutes under the condition of introducing 10 liters/minute of dry nitrogen flow rate, and separating to prepare the target product graphene-based antistatic agent.
Example 2
The procedure for preparing reduced graphene (r-GO) was the same as in step (1) of example 1. Adding 1g r-GO and 0.2g of toluene diisocyanate into a high-energy planetary ball mill, grinding for 100 minutes under the condition of introducing a dry nitrogen flow rate of 0.1 liter/minute at the rotating speed of the ball mill of 100 revolutions/minute to prepare isocyanate modified graphene, adding 0.4g of amino ferrocene, continuously grinding for 120 minutes under the condition of introducing a dry nitrogen flow rate of 0.1 liter/minute, and separating to prepare the target product graphene-based antistatic agent.
Example 3
The procedure for preparing reduced graphene (r-GO) was the same as in step (1) of example 1. Adding 1g r-GO and 0.1g of isophorone diisocyanate into a high-energy planetary ball mill, grinding for 60 minutes under the condition of introducing dry nitrogen flow rate of 1.5 liters/minute at the rotating speed of the ball mill of 300 revolutions/minute to prepare isocyanate modified graphene, adding 0.25g of hydroxymethyl ferrocene, continuously grinding for 80 minutes under the condition of introducing dry nitrogen flow rate of 1.5 liters/minute, and separating to prepare the target product graphene-based antistatic agent.
Example 4
The procedure for preparing reduced graphene (r-GO) was the same as in step (1) of example 1. Adding 1g r-GO and 0.15g hexamethylene diisocyanate into a high-energy planetary ball mill, grinding for 50 minutes under the condition of introducing a dry nitrogen flow rate of 2.8 liters/minute at the rotating speed of the ball mill of 250 revolutions/minute to prepare isocyanate modified graphene, adding 0.28g ferrocenecarboxylic acid, continuously grinding for 100 minutes under the condition of introducing a dry nitrogen flow rate of 3.5 liters/minute, and separating to prepare the target product graphene-based antistatic agent.
Example 5: application of graphene-based antistatic agent
The graphene-based antistatic agent was prepared in the same manner as in example 4. 100 parts by mass of polyvinyl chloride (PVC), 50 parts by mass of phthalate plasticizer (DOP), 1 part by mass of graphene-based antistatic agent, 20 parts by mass of light calcium carbonate, 2 parts by mass of stearic acid, 6 parts by mass of stabilizer and 2 parts by mass of anti-aging agent are added into a stirrer to be mixed for 30min, the mixture is discharged and added into an extruder, materials are extruded at a processing temperature of 160-180 ℃, then the graphene antistatic modified PVC is prepared by compression molding at a temperature of 180-200 ℃ and under a pressure of 10MPa, and the test results of the material performance are shown below.
TABLE 1
The formula of the PVC antistatic composite material comprises 100 parts of PVC, 50 parts of DOP, 1 part of conductive carbon black, 0.5 part of ferrocene, 20 parts of light calcium carbonate, 2 parts of stearic acid, 6 parts of stabilizer and 2 parts of anti-aging agent, and the preparation process is the same as that of the preparation method of graphene antistatic modified PVC.
Compared with the conductive carbon black modified PVC antistatic composite material, the graphene-based antistatic agent has better reinforcing effect on PVC; from the aspect of conductivity, compared with conventional conductive carbon black, the graphene-based antistatic agent has a better conductive modification effect on PVC, so that a better antistatic effect can be obtained, and the surface resistance of the graphene antistatic modified PVC is one order of magnitude lower than that of a PVC antistatic composite material under the same addition amount; compared with single ferrocene, the graphene-based antistatic agent has better flame-retardant and smoke-suppression effects on PVC. The graphene antistatic modified PVC prepared by the invention has the advantages of good flame-retardant smoke-suppression effect, high mechanical strength, good antistatic property and the like, and widens the application range of PVC materials in the industries of electronic appliances, green building materials, new energy automobiles, cables and the like.
Claims (4)
1. A preparation method of a graphene-based antistatic agent with a smoke suppression function is characterized by comprising the following steps:
(1) chemical reduction of Graphene Oxide (GO)
Reducing GO to obtain reduced graphene oxide r-GO;
(2) reduced graphene ferrocene compound grafting modification reaction
Adding r-GO and a diisocyanate compound into a ball mill, grinding for 30-100 minutes under the condition of introducing dry nitrogen to prepare isocyanate modified graphene, adding a ferrocene compound, and continuously grinding for 60-120 minutes under the condition of introducing dry nitrogen to prepare a graphene-based antistatic agent with a smoke suppression function; the ferrocene compound is selected from one of the following compounds: ferroceneacetic acid, ferrocenecarboxylic acid, aminoferrocene, hydroxymethyl ferrocene;
the grinding in the step (2) means that the rotating speed of a roller of the ball mill is 100-600 r/min, the ball milling tank and the grinding balls are made of agate or tungsten carbide, the ball loading amount is 0.2-1.0 kg, and the nitrogen flow rate is 0.1-10 l/min.
2. The preparation method of the graphene-based antistatic agent with the smoke suppression function according to claim 1, wherein the mass ratio of the r-GO, the diisocyanate compound and the ferrocene compound in the step (2) is 1: 0.05-0.2: 0.1 to 0.4.
3. The method for preparing a graphene-based antistatic agent with a smoke suppressing function according to claim 1, wherein the diisocyanate compound in the step (2) is selected from one of the following: diphenylmethane diisocyanate, hexamethylene diisocyanate, toluene diisocyanate, isophorone diisocyanate.
4. A graphene-based antistatic agent having a smoke-suppressing function, characterized by being obtained by the method according to any one of claims 1 to 3.
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| CN111613454B (en) * | 2020-05-29 | 2021-09-21 | 华南理工大学 | Graphene/metallocene composite supercapacitor electrode material and preparation method and application thereof |
| CN111996611B (en) * | 2020-09-03 | 2022-11-22 | 湖北尚助化学有限公司 | Antistatic agent and preparation method thereof |
| CN115894959B (en) * | 2023-01-03 | 2023-07-28 | 深圳市今朝时代股份有限公司 | Electrode active material for super capacitor and preparation method thereof |
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Denomination of invention: A graphene based antistatic agent with smoke suppression function and its preparation method Effective date of registration: 20231111 Granted publication date: 20210716 Pledgee: Zhejiang Xianju Rural Commercial Bank Co.,Ltd. Pledgor: TAIZHOU BRT PLASTICS ELECTRONICS Co.,Ltd. Registration number: Y2023330002610 |