CN117511068A - Halogen-free flame-retardant antistatic modified plastic and preparation method thereof - Google Patents
Halogen-free flame-retardant antistatic modified plastic and preparation method thereof Download PDFInfo
- Publication number
- CN117511068A CN117511068A CN202311846124.7A CN202311846124A CN117511068A CN 117511068 A CN117511068 A CN 117511068A CN 202311846124 A CN202311846124 A CN 202311846124A CN 117511068 A CN117511068 A CN 117511068A
- Authority
- CN
- China
- Prior art keywords
- graphene oxide
- carbon nano
- flame
- halogen
- retardant antistatic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003063 flame retardant Substances 0.000 title claims abstract description 81
- 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 title claims abstract description 80
- 239000004033 plastic Substances 0.000 title claims abstract description 38
- 229920003023 plastic Polymers 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 143
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 104
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 99
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 59
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000002216 antistatic agent Substances 0.000 claims abstract description 26
- 239000002131 composite material Substances 0.000 claims abstract description 25
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 23
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 23
- 239000004925 Acrylic resin Substances 0.000 claims abstract description 11
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 10
- 239000004014 plasticizer Substances 0.000 claims abstract description 8
- 238000005469 granulation Methods 0.000 claims abstract description 4
- 230000003179 granulation Effects 0.000 claims abstract description 4
- 239000000843 powder Substances 0.000 claims description 74
- 239000001509 sodium citrate Substances 0.000 claims description 41
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 41
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 36
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 36
- 239000002091 nanocage Substances 0.000 claims description 29
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 27
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 25
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 22
- 238000001291 vacuum drying Methods 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 17
- BRMDATNYMUMZLN-UHFFFAOYSA-N Piloty's Acid Chemical compound ONS(=O)(=O)C1=CC=CC=C1 BRMDATNYMUMZLN-UHFFFAOYSA-N 0.000 claims description 16
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 238000000498 ball milling Methods 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 11
- 239000012535 impurity Substances 0.000 claims description 11
- 239000011261 inert gas Substances 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000000967 suction filtration Methods 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 7
- MIMDHDXOBDPUQW-UHFFFAOYSA-N dioctyl decanedioate Chemical compound CCCCCCCCOC(=O)CCCCCCCCC(=O)OCCCCCCCC MIMDHDXOBDPUQW-UHFFFAOYSA-N 0.000 claims description 7
- 238000005530 etching Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 235000012424 soybean oil Nutrition 0.000 claims description 4
- 239000003549 soybean oil Substances 0.000 claims description 4
- QMMJWQMCMRUYTG-UHFFFAOYSA-N 1,2,4,5-tetrachloro-3-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=C(Cl)C(Cl)=CC(Cl)=C1Cl QMMJWQMCMRUYTG-UHFFFAOYSA-N 0.000 claims description 3
- 238000010000 carbonizing Methods 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
- 238000000643 oven drying Methods 0.000 claims description 3
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims 2
- 239000004743 Polypropylene Substances 0.000 abstract description 14
- 229920001155 polypropylene Polymers 0.000 abstract description 14
- -1 polypropylene Polymers 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 7
- 230000002195 synergetic effect Effects 0.000 abstract description 5
- 239000011159 matrix material Substances 0.000 abstract description 4
- 239000006185 dispersion Substances 0.000 abstract description 2
- 239000012757 flame retardant agent Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 64
- 239000000463 material Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- 229910052736 halogen Inorganic materials 0.000 description 6
- 150000002367 halogens Chemical class 0.000 description 6
- 239000010410 layer Substances 0.000 description 6
- 238000003763 carbonization Methods 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 3
- 239000000779 smoke Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 210000004400 mucous membrane Anatomy 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 230000000638 stimulation Effects 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- ZGHZSTWONPNWHV-UHFFFAOYSA-N 2-(oxiran-2-yl)ethyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCC1CO1 ZGHZSTWONPNWHV-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 239000012796 inorganic flame retardant Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
Abstract
The invention provides halogen-free flame-retardant antistatic modified plastic and a preparation method thereof, comprising the following steps: s1: graphene oxide prepared by Hummers method, S2: preparing a carbon nano cage-graphene oxide composite material, and S3: modifying nano aluminum hydroxide by adopting a silane coupling agent, and S4: preparing a flame-retardant antistatic agent, S5: according to the weight proportion, 100 parts of polyacrylic resin, 8-12 parts of flame-retardant antistatic agent, 2-5 parts of plasticizer and 0.5-0.8 part of antioxidant are evenly mixed and extruded for granulation to obtain the halogen-free flame-retardant antistatic modified plastic. The invention solves the problem of uneven dispersion of antistatic agent graphene and flame retardant nano aluminum hydroxide in a matrix, and simultaneously further improves the flame retardant property through the synergistic effect of carbon nano cage-graphene oxide and nano aluminum hydroxide. Therefore, the addition amount of the flame retardant and antistatic agent in polypropylene is reduced, and the flame retardant and antistatic effect is achieved under the condition that the mechanical property of the polypropylene is not affected.
Description
Technical Field
The invention relates to halogen-free flame-retardant antistatic modified plastic, and belongs to halogen-free flame-retardant antistatic modified plastic and a preparation method thereof.
Background
Polypropylene (PP) is one of the universal plastics with the greatest global usage, has the advantages of light weight, no toxicity, easy processing, excellent mechanical property, chemical corrosion resistance, good electrical insulation property and the like, and is widely applied to the fields of electronic appliances, automobiles, buildings, packaging and the like. However, PP is extremely easy to burn, limiting Oxygen Index (LOI) is only 17% -18%, heat release is large during burning, and molten drops are often accompanied, flame is extremely easy to spread, fire is caused, and life and property safety of people is seriously threatened. Therefore, flame retardant modification of polypropylene is particularly important.
The existing polypropylene material has poor antistatic effect although being applied in various fields, and static electricity can be generated on the surface in the friction, stripping or use processes, so that the material is subjected to dust collection when the material is light, and the material is damaged even fire disaster and human body injury caused by static discharge when the material is heavy. And the polypropylene material is inflammable, and releases a large amount of heat during combustion, and is accompanied by smoke and toxic gas.
In the prior art, the halogen-containing flame retardant is generally added to improve the flame retardant performance, but the potential hazard of the halogen-containing flame retardant is relatively large. On one hand, the halogen flame retardant material can generate a great deal of smoke toxicity in the combustion process, so that the escape risk of personnel is increased. Meanwhile, the hydrogen chloride has a strong stimulation effect on the mucous membranes of eyes and respiratory tracts, and the hydrogen bromide can cause the stimulation or burn of the skin and mucous membranes. After the halogen flame retardant material is used, if the halogen flame retardant material is not effectively classified and mixed with household garbage for incineration treatment, the halogen flame retardant material can become one of sources of PM 2.5 pollution and groundwater environment pollution. Meanwhile, excessive addition of the flame retardant can affect the mechanical properties of polypropylene, and limit the application of the polypropylene in the field of automobiles.
Disclosure of Invention
The invention aims to provide halogen-free flame-retardant antistatic modified plastic and a preparation method thereof, which are used for solving the problems in the background technology.
In order to achieve the above purpose, the present invention provides the following technical solutions:
the preparation method of the halogen-free flame-retardant antistatic modified plastic comprises the following steps:
s1: graphene oxide prepared by adopting a Hummers method,
s2: preparing a carbon nano cage-graphene oxide composite material, firstly ball-milling sodium citrate powder, and then carbonizing the ball-milled sodium citrate powder at a high temperature under the protection of inert gas; adding carbonized sodium citrate powder into hydrochloric acid solution, and etching away impurities except carbon; filtering, washing and drying to obtain the three-dimensional porous carbon nano cage powder;
the carbon nano cage powder and the graphene oxide are prepared according to the weight ratio of 1:0.2 to 0.5 of the carbon nano cage-graphene oxide solution is added into dimethylbenzene, uniformly mixed, and then added with N-hydroxy benzene sulfonamide and stirred to obtain the carbon nano cage-graphene oxide solution;
placing the carbon nano cage-graphene oxide solution into a vacuum drying oven, and vacuum drying to obtain powder of the carbon nano cage-graphene oxide composite material;
s3: modifying the nano aluminum hydroxide by adopting a silane coupling agent to obtain modified nano aluminum hydroxide;
s4: preparing a flame-retardant antistatic agent, namely, according to the weight components, mixing the modified nano aluminum hydroxide with the carbon nano cage-graphene oxide composite material according to the weight components of 1:3-5, dissolving in dimethylbenzene, uniformly stirring at 80-100 ℃, slowly dripping sulfuric acid, reacting for 6-10h, and vacuum drying to obtain the flame-retardant antistatic agent;
s5: according to the weight components, 100 parts of polyacrylic resin, 8-12 parts of flame-retardant antistatic agent, 2-5 parts of plasticizer and 0.5-0.8 part of antioxidant are uniformly mixed and extruded for granulation to obtain the halogen-free flame-retardant antistatic modified plastic.
Preferably, the specific process of step S2 is: firstly ball-milling sodium citrate powder for 4-8h, and then heating the ball-milled sodium citrate powder at 700-1000 ℃ for 2-5h under the protection of inert gas so as to carbonize the sodium citrate powder; adding carbonized sodium citrate powder into 15-20wt% hydrochloric acid solution, reacting for 24-48h, and etching impurities except carbon; filtering, washing and drying to obtain the three-dimensional porous carbon nano cage powder;
the carbon nano cage powder and the graphene oxide are prepared according to the weight ratio of 1:0.2 to 0.5 of the carbon nano cage-graphene oxide solution is added into dimethylbenzene, uniformly mixed, and then added with N-hydroxy benzene sulfonamide and stirred for 4 to 6 hours to obtain the carbon nano cage-graphene oxide solution;
and placing the carbon nano cage-graphene oxide solution into a vacuum drying oven, vacuumizing and heating to 140-150 ℃, and keeping for 50-70h to sufficiently dry to obtain the powder of the carbon nano cage-graphene oxide composite material.
Preferably, the inert gas is one of argon or nitrogen.
Preferably, the specific process of the step S3 comprises the steps of dispersing 10 parts of nanometer aluminum hydroxide in ethanol solution by using ultrasonic waves according to the molar components, gradually dripping 5-8 parts of silane coupling agent into the ethanol solution, uniformly stirring the reaction solution for 60-80min, washing the product with N, N-dimethylformamide and deionized water for 2 times alternately, carrying out suction filtration, and finally drying at room temperature to obtain the modified aluminum hydroxide.
Preferably, the silane coupling agent is one of KH-550, KH-560 and KH-570.
Preferably, in the step S5, the uniform mixing is performed in a high-pressure homogenizer at the mixing temperature of 60-80 ℃ for 10-20min, and the pressure in the high-pressure homogenizer is 15-20Mpa;
preferably, in step S5, the extrusion is performed in a twin-screw extruder, at each stage of which the temperature is: the temperature of the first area is 160-180 ℃, the temperature of the second area is 180-200 ℃, the temperature of the third area is 200-220 ℃, the temperature of the fourth area is 220-260 ℃, and the temperature of the fifth area is 170-180 ℃.
Preferably, in step S5, the plasticizer is one of dioctyl sebacate, epoxidized soybean oil, and epoxidized butyl stearate.
Preferably, the antioxidant in step S5 is one or more of 1010 antioxidant, BHT antioxidant and 1076 antioxidant.
The halogen-free flame-retardant antistatic modified plastic is prepared by adopting the preparation method and is applied to the field of automobile industry.
The principle of the invention is as follows:
according to the invention, the carbon nano cage-graphene oxide composite material is used as the antistatic agent, so that the interlayer spacing of graphene oxide can be effectively opened, and the problem that graphene oxide sheets are easy to stack in a matrix and are unevenly distributed is solved. And more surface active sites and functional groups are exposed at the same time, so that the subsequent combination with nano aluminum hydroxide is facilitated.
The nanometer aluminum hydroxide generally contains crystal water or components capable of generating water, absorbs a large amount of latent heat at 300-350 ℃ to dehydrate, reduces the actual flame temperature on the surface of the material to degrade the polymer into low molecules, and reduces the occurrence of combustibles. The aluminum hydroxide is dehydrated to generate active alumina to promote dehydrogenation reaction, generate a protective carbon layer, catalyze carbon precipitation and oxidation reaction of corresponding carbon, and reduce the generation amount of flame-retardant smoke.
However, nano aluminum hydroxide is easy to agglomerate and difficult to uniformly disperse in a polypropylene matrix due to the nano size, so that the flame retardant property of the nano aluminum hydroxide is reduced. On one hand, the compatibility of nano aluminum hydroxide and organic matters is improved so as to be better dispersed and stabilized in a polypropylene matrix, on the other hand, the nano aluminum hydroxide is coupled with carbon nano cage-graphene oxide, the carbon nano cage can form an effective interface with the nano aluminum hydroxide, the nano aluminum hydroxide reacts with combustible matters at high temperature to generate a carbonization layer, the carbonization layer plays a role of isolating air, the carbon nano cage can play a role of a framework in the carbonization layer, the generated carbonization layer has better rigidity and strength, the generated carbonization layer can resist air flow generated by flue gas flow in a fire house, and furthermore, the carbon nano cage also has a high specific surface area, can provide more surface area to interact with flame and thermal decomposition products, so that the flame retardant effect is improved.
Meanwhile, the graphene has excellent heat conduction performance, and can conduct heat rapidly. The heat can be effectively absorbed and dispersed during the combustion reaction, thereby reducing the temperature of flame and reducing the heat release of the fire source. And secondly, the graphene shows stability at high temperature, can form an effective thermal stability barrier with nano aluminum hydroxide, can slow down the propagation speed of flame, prevents the expansion of fire, and further has the effect of synergistic flame retardance.
The synergistic effect of the nanometer aluminum hydroxide and the carbon nanometer cage-graphene oxide ensures that the flame retardant effect is obviously improved, thereby reducing the addition amount of the nanometer aluminum hydroxide in polypropylene and achieving the flame retardant and antistatic effect under the condition of not affecting the mechanical property of the polypropylene.
Compared with the prior art, the invention has the beneficial effects that:
the inorganic flame retardant in the prior art has low flame retardant efficiency, the filler accounts for 40 percent of the weight of the polymer, and the mechanical property is seriously influenced.
The foregoing description is only an overview of the present invention, and is intended to provide a more thorough understanding of the present invention, and is to be accorded the full scope of the present invention.
Drawings
FIG. 1 is a schematic flow chart of the preparation method of the invention.
Detailed Description
The technical solution of the present invention will be further described with reference to specific embodiments, but the present invention should not be limited to these embodiments, and other equivalent or alternative features having similar purposes may be substituted unless specifically stated. Each feature is one example only of a generic series of equivalent or similar features, unless expressly stated otherwise. The terms used in the present invention generally have meanings commonly understood by those of ordinary skill in the art unless otherwise indicated. In the examples below, the concentration% is, unless otherwise indicated, the mass% of the substances used are all commercially available. The technical solution of the present invention will be further described with reference to specific embodiments, but the present invention should not be limited to these embodiments, and other equivalent or alternative features having similar purposes may be substituted unless specifically stated. Each feature is one example only of a generic series of equivalent or similar features, unless expressly stated otherwise. The terms used in the present invention generally have meanings commonly understood by those of ordinary skill in the art unless otherwise indicated.
The nano aluminum hydroxide used in all examples and comparative examples of the present invention had a purity of 99.9% and an average particle diameter of 40nm, and was purchased from Shanghai super Wei nanotechnology Co.
The polyacrylic resin used was R7021-50RNA, dow chemical in America. (tensile Strength 27.6MPa, flexural modulus 1070 MPa)
Other materials such as antioxidant plasticizers used can be obtained commercially.
The sample test items and criteria are as follows:
surface resistance: according to the test method for detecting the surface resistance in GB/T1410-2006 solid insulating material volume resistivity and surface resistivity test method.
Vertical combustion progression: tested according to GB/T2408 standard.
Tensile strength: tested according to GB/T1040.2 standard.
FIG. 1 shows a schematic flow chart of the preparation method of the invention, which is a preparation method of halogen-free flame-retardant antistatic modified plastic and comprises the following steps:
s1: graphene oxide was prepared using a Hummers method.
In all examples and comparative examples of the present invention, the specific procedure for preparing graphene oxide by Hummers method is as follows:
adding 3.9g of graphite powder and 1.95g of sodium nitrate into 90mL of concentrated sulfuric acid under the stirring of an ice water bath, then slowly adding 12g of potassium permanganate into the mixed solution for three times, wherein the temperature of the mixed solution is not more than 20 ℃ in the whole process, and the potassium permanganate is added in 2 hours; then heating the mixed solution to 35 ℃, and continuously stirring and reacting for 28 hours to obtain a reaction solution; 180mL of deionized water was added to the reaction solution and stirring was continued for 15min. 650mL of deionized water was then added, followed by slow dropwise addition of 26mL of hydrogen peroxide (35%), and finally 260mL of 1M hydrochloric acid solution. The product was filtered and washed multiple times to remove metal ions and excess acid, and the resulting solid was dispersed in deionized water and sonicated for 2 hours. The brown dispersion was centrifuged at 4500rpm for 20min, the precipitate was removed, the supernatant was collected, dialyzed for 7 days, and freeze-dried to obtain graphene oxide powder.
S2: preparing a carbon nano cage-graphene oxide composite material, firstly ball-milling sodium citrate powder, and then carbonizing the ball-milled sodium citrate powder at a high temperature under the protection of inert gas; adding carbonized sodium citrate powder into hydrochloric acid solution, and etching away impurities except carbon; and filtering, washing and drying to obtain the three-dimensional porous carbon nano cage powder.
The carbon nano cage powder and the graphene oxide are prepared according to the weight ratio of 1: and 0.2-0.5 of the carbon nano cage-graphene oxide solution is added into dimethylbenzene, uniformly mixed, and then added with N-hydroxy benzene sulfonamide and stirred to obtain the carbon nano cage-graphene oxide solution.
And placing the carbon nano cage-graphene oxide solution into a vacuum drying oven, and vacuum drying to obtain powder of the carbon nano cage-graphene oxide composite material.
S3: and modifying the nano aluminum hydroxide by adopting a silane coupling agent to obtain the modified nano aluminum hydroxide.
S4: preparing a flame-retardant antistatic agent, namely, according to the weight components, mixing the modified nano aluminum hydroxide with the carbon nano cage-graphene oxide composite material according to the weight components of 1:3-5, dissolving in dimethylbenzene, uniformly stirring at 80-100 ℃, slowly dripping sulfuric acid, reacting for 6-10h, and vacuum drying to obtain the flame-retardant antistatic agent.
S5: according to the weight components, 100 parts of polyacrylic resin, 8-12 parts of flame-retardant antistatic agent, 2-5 parts of plasticizer and 0.5-0.8 part of antioxidant are uniformly mixed and extruded for granulation to obtain the halogen-free flame-retardant antistatic modified plastic.
In a preferred embodiment, the specific process of step S2 is as follows: firstly ball-milling sodium citrate powder for 4-8h, and then heating the ball-milled sodium citrate powder at 700-1000 ℃ for 2-5h under the protection of inert gas so as to carbonize the sodium citrate powder; adding carbonized sodium citrate powder into 15-20wt% hydrochloric acid solution, reacting for 24-48h, and etching impurities except carbon; and filtering, washing and drying to obtain the three-dimensional porous carbon nano cage powder.
The carbon nano cage powder and the graphene oxide are prepared according to the weight ratio of 1: and 0.2-0.5 of the carbon nano cage-graphene oxide solution is added into dimethylbenzene, uniformly mixed, and then added with N-hydroxy benzene sulfonamide and stirred for 4-6 hours to obtain the carbon nano cage-graphene oxide solution.
And placing the carbon nano cage-graphene oxide solution into a vacuum drying oven, vacuumizing and heating to 140-150 ℃, and keeping for 50-70h to sufficiently dry to obtain the powder of the carbon nano cage-graphene oxide composite material.
In a preferred embodiment, the inert gas is argon, and in other embodiments, nitrogen.
In a preferred embodiment, the specific process of step S3 is that, based on the molar components, 10 parts of nano aluminum hydroxide is ultrasonically dispersed in an ethanol solution, then 5-8 parts of silane coupling agent is gradually added into the ethanol solution, the reaction solution is uniformly stirred for 60-80min, then the product is alternately washed for 2 times by using N, N-dimethylformamide and deionized water, suction filtration is performed, and finally, the modified aluminum hydroxide is obtained by drying at room temperature.
In a preferred embodiment, the silane coupling agent is KH-550. In other embodiments one of KH-560 and KH-570 may be used.
In a preferred embodiment, in step S5, the uniform mixing is performed in a high-pressure homogenizer at a temperature of 60-80 ℃ for a period of 10-20min, and at a pressure of 15-20Mpa.
In a preferred embodiment, in step S5, the extrusion is performed in a twin screw extruder at the following temperatures: the temperature of the first area is 160-180 ℃, the temperature of the second area is 180-200 ℃, the temperature of the third area is 200-220 ℃, the temperature of the fourth area is 220-260 ℃, and the temperature of the fifth area is 170-180 ℃.
In a preferred embodiment, in step S5, the plasticizer is dioctyl sebacate, and in other embodiments, one of epoxidized soybean oil and epoxidized butyl stearate may be used.
In a preferred embodiment, the antioxidant in step S5 is 1010 antioxidant, and in other embodiments one or more of BHT antioxidant and 1076 antioxidant may be used.
The halogen-free flame-retardant antistatic modified plastic is prepared by the preparation method and is applied to the field of automobile industry, such as front and rear bumpers and automotive interiors.
The following is a further explanation and explanation using specific example data.
Example 1
The preparation method of the halogen-free flame-retardant antistatic modified plastic comprises the following steps:
s1: graphene oxide prepared by adopting a Hummers method,
s2: firstly ball-milling sodium citrate powder for 4 hours, and then heating the ball-milled sodium citrate powder for 2 hours at 700 ℃ under the protection of argon so as to carbonize the sodium citrate powder; adding carbonized sodium citrate powder into a 15wt% hydrochloric acid solution, and reacting for 24 hours to etch impurities except carbon; and filtering, washing and drying to obtain the three-dimensional porous carbon nano cage powder.
The carbon nano cage powder and the graphene oxide are prepared according to the weight ratio of 1: and 0.2, adding the mixture into dimethylbenzene, uniformly mixing, adding N-hydroxybenzenesulfonamide, and stirring for 4-6 hours to obtain the carbon nano cage-graphene oxide solution. The addition amount of the N-hydroxy benzene sulfonamide is 0.3 times of the dosage of the graphene oxide.
And placing the carbon nano cage-graphene oxide solution into a vacuum drying oven, vacuumizing and heating to 145 ℃, and keeping for 50 hours to sufficiently dry to obtain the powder of the carbon nano cage-graphene oxide composite material.
S3: based on the molar components, 10 parts of nano aluminum hydroxide is ultrasonically dispersed in an ethanol solution, then 5 parts of KH-550 is gradually added into the ethanol solution in a dropwise manner, the reaction solution is uniformly stirred for 60min, then the product is alternately washed for 2 times by using N, N-dimethylformamide and deionized water, suction filtration is carried out, and finally the modified aluminum hydroxide is obtained by drying at room temperature.
S4: preparing a flame-retardant antistatic agent, namely, according to the weight components, mixing the modified nano aluminum hydroxide with the carbon nano cage-graphene oxide composite material according to the weight components of 1:3 is dissolved in dimethylbenzene, evenly stirred at 80 ℃, and slowly added with 0.3M sulfuric acid in a dropwise manner, wherein the dosage of the sulfuric acid is 0.1 of the dosage of the modified nano aluminum hydroxide. Reacting for 6h, and vacuum drying to obtain the flame-retardant antistatic agent.
S5: 100 parts of polyacrylic resin, 8 parts of flame-retardant antistatic agent, 2 parts of dioctyl sebacate and 0.5 part of 1076 antioxidant are mixed in a high-pressure homogenizer according to the weight components, the mixing temperature is 60 ℃, the mixing time is 10min, and the pressure in the high-pressure homogenizer is 15Mpa; extruding in a double-screw extruder, wherein the temperatures of each section of the double-screw extruder are as follows: the temperature of the first area is 160 ℃, the temperature of the second area is 180 ℃, the temperature of the third area is 200 ℃, the temperature of the fourth area is 220 ℃, and the temperature of the fifth area is 170 ℃. Extruding and granulating to obtain the halogen-free flame-retardant antistatic modified plastic.
Example 2
The preparation method of the halogen-free flame-retardant antistatic modified plastic comprises the following steps:
s1: graphene oxide prepared by adopting a Hummers method,
s2: firstly ball-milling sodium citrate powder for 8 hours, and then heating the ball-milled sodium citrate powder for 5 hours at the temperature of 1000 ℃ under the protection of nitrogen so as to carbonize the sodium citrate powder; adding carbonized sodium citrate powder into a 20wt% hydrochloric acid solution, and reacting for 48 hours to etch impurities except carbon; and filtering, washing and drying to obtain the three-dimensional porous carbon nano cage powder.
The carbon nano cage powder and the graphene oxide are prepared according to the weight ratio of 1: and 0.5, adding the mixture into dimethylbenzene, uniformly mixing, adding N-hydroxybenzenesulfonamide, and stirring for 6 hours to obtain the carbon nano cage-graphene oxide solution. The addition amount of the N-hydroxy benzene sulfonamide is 0.3 times of the dosage of the graphene oxide.
And placing the carbon nano cage-graphene oxide solution into a vacuum drying oven, vacuumizing and heating to 150 ℃, and keeping for 70 hours to sufficiently dry to obtain the powder of the carbon nano cage-graphene oxide composite material.
S3: based on the molar components, 10 parts of nano aluminum hydroxide is ultrasonically dispersed in an ethanol solution, then 8 parts of KH-560 are gradually added into the ethanol solution in a dropwise manner, the reaction solution is uniformly stirred for 80min, then the product is alternately washed for 2 times by using N, N-dimethylformamide and deionized water, suction filtration is carried out, and finally the modified aluminum hydroxide is obtained by drying at room temperature.
S4: preparing a flame-retardant antistatic agent, namely, according to the weight components, mixing the modified nano aluminum hydroxide with the carbon nano cage-graphene oxide composite material according to the weight components of 1:5 is dissolved in dimethylbenzene, evenly stirred at 100 ℃, and slowly added with 0.3M sulfuric acid in a dropwise manner, wherein the dosage of the sulfuric acid is 0.1 of that of the modified nano aluminum hydroxide. Reacting for 10h, and vacuum drying to obtain the flame-retardant antistatic agent.
S5: according to the weight components, 100 parts of polyacrylic resin, 12 parts of flame-retardant antistatic agent, 5 parts of epoxidized soybean oil and 0.8 part of BHT antioxidant are mixed in a high-pressure homogenizer at the mixing temperature of 80 ℃ for 20min, and the pressure in the high-pressure homogenizer is 20Mpa; extruding in a double-screw extruder, wherein the temperatures of each section of the double-screw extruder are as follows: the temperature of the first area is 180 ℃, the temperature of the second area is 200 ℃, the temperature of the third area is 220 ℃, the temperature of the fourth area is 260 ℃, and the temperature of the fifth area is 180 ℃. Extruding and granulating to obtain the halogen-free flame-retardant antistatic modified plastic.
Example 3
The preparation method of the halogen-free flame-retardant antistatic modified plastic comprises the following steps:
s1: graphene oxide prepared by adopting a Hummers method,
s2: firstly ball-milling sodium citrate powder for 6 hours, and then heating the ball-milled sodium citrate powder for 3.5 hours at 850 ℃ under the protection of argon so as to carbonize the sodium citrate powder; adding carbonized sodium citrate powder into 17.5wt% hydrochloric acid solution, and reacting for 36h to etch impurities except carbon; and filtering, washing and drying to obtain the three-dimensional porous carbon nano cage powder.
The carbon nano cage powder and the graphene oxide are prepared according to the weight ratio of 1: and 0.35 of the carbon nano cage-graphene oxide solution is added into dimethylbenzene, uniformly mixed, and then added with N-hydroxybenzenesulfonamide and stirred for 5 hours to obtain the carbon nano cage-graphene oxide solution. The addition amount of the N-hydroxy benzene sulfonamide is 0.3 times of the dosage of the graphene oxide.
And placing the carbon nano cage-graphene oxide solution into a vacuum drying oven, vacuumizing and heating to 145 ℃, and keeping for 60 hours to sufficiently dry to obtain the powder of the carbon nano cage-graphene oxide composite material.
S3: based on the molar components, 10 parts of nano aluminum hydroxide is ultrasonically dispersed in an ethanol solution, 7 parts of KH-570 is gradually added into the ethanol solution in a dropwise manner, the reaction solution is uniformly stirred for 70min, the product is alternately washed for 2 times by using N, N-dimethylformamide and deionized water, suction filtration is performed, and finally the modified aluminum hydroxide is obtained by drying at room temperature.
S4: preparing a flame-retardant antistatic agent, namely, according to the weight components, mixing the modified nano aluminum hydroxide with the carbon nano cage-graphene oxide composite material according to the weight components of 1:4 is dissolved in dimethylbenzene, evenly stirred at the temperature of 80-100 ℃, and slowly added with 0.3M sulfuric acid in a dropwise manner, wherein the dosage of the sulfuric acid is 0.1 of the dosage of the modified nano aluminum hydroxide. Reacting for 8h, and vacuum drying to obtain the flame-retardant antistatic agent.
S5: 100 parts of polyacrylic resin, 10 parts of flame-retardant antistatic agent, 4 parts of epoxy butyl stearate and 0.7 part of 1010 antioxidant are mixed in a high-pressure homogenizer according to the weight components, the mixing temperature is 70 ℃, the mixing time is 15min, and the pressure in the high-pressure homogenizer is 17.5Mpa; extruding in a double-screw extruder, wherein the temperatures of each section of the double-screw extruder are as follows: the first zone temperature is 170 ℃, the second zone temperature is 190 ℃, the third zone temperature is 210 ℃, the fourth zone temperature is 240 ℃, and the fifth zone temperature is 175 ℃. Extruding and granulating to obtain the halogen-free flame-retardant antistatic modified plastic.
Example 4
The preparation method of the halogen-free flame-retardant antistatic modified plastic comprises the following steps:
s1: graphene oxide prepared by adopting a Hummers method,
s2: firstly ball-milling sodium citrate powder for 5 hours, and then heating the ball-milled sodium citrate powder for 3 hours at 800 ℃ under the protection of argon so as to carbonize the sodium citrate powder; adding carbonized sodium citrate powder into a 16wt% hydrochloric acid solution, and reacting for 35 hours to etch impurities except carbon; and filtering, washing and drying to obtain the three-dimensional porous carbon nano cage powder.
The carbon nano cage powder and the graphene oxide are prepared according to the weight ratio of 1: and 0.25 of the carbon nano cage-graphene oxide solution is added into dimethylbenzene, uniformly mixed, and then added with N-hydroxybenzenesulfonamide and stirred for 4 hours to obtain the carbon nano cage-graphene oxide solution. The addition amount of the N-hydroxy benzene sulfonamide is 0.3 times of the dosage of the graphene oxide.
And placing the carbon nano cage-graphene oxide solution into a vacuum drying oven, vacuumizing and heating to 147 ℃, and keeping for 65 hours to sufficiently dry to obtain the powder of the carbon nano cage-graphene oxide composite material.
S3: based on the molar components, 10 parts of nano aluminum hydroxide is ultrasonically dispersed in an ethanol solution, 7 parts of KH-550 is gradually added into the ethanol solution in a dropwise manner, the reaction solution is uniformly stirred for 75min, the product is alternately washed for 2 times by using N, N-dimethylformamide and deionized water, suction filtration is performed, and finally the modified aluminum hydroxide is obtained by drying at room temperature.
S4: preparing a flame-retardant antistatic agent, namely, according to the weight components, mixing the modified nano aluminum hydroxide with the carbon nano cage-graphene oxide composite material according to the weight components of 1:3 is dissolved in dimethylbenzene, evenly stirred at 85 ℃, and slowly added with 0.3M sulfuric acid in a dropwise manner, wherein the dosage of the sulfuric acid is 0.1 of the dosage of the modified nano aluminum hydroxide. And (3) reacting for 7h, and vacuum drying to obtain the flame-retardant antistatic agent.
S5: 100 parts of polyacrylic resin, 12 parts of flame-retardant antistatic agent, 4 parts of dioctyl sebacate and 0.6 part of 1076 antioxidant are mixed in a high-pressure homogenizer according to the weight components, the mixing temperature is 65 ℃, the mixing time is 18min, and the pressure in the high-pressure homogenizer is 19Mpa; extruding in a double-screw extruder, wherein the temperatures of each section of the double-screw extruder are as follows: the first zone temperature is 175 ℃, the second zone temperature is 195 ℃, the third zone temperature is 210 ℃, the fourth zone temperature is 235 ℃, and the fifth zone temperature is 175 ℃. Extruding and granulating to obtain the halogen-free flame-retardant antistatic modified plastic.
Comparative example 1
The preparation method of the halogen-free flame-retardant antistatic modified plastic comprises the following steps:
s1: graphene oxide prepared by adopting a Hummers method,
s2: firstly ball-milling sodium citrate powder for 5 hours, and then heating the ball-milled sodium citrate powder for 3 hours at 800 ℃ under the protection of argon so as to carbonize the sodium citrate powder; adding carbonized sodium citrate powder into a 16wt% hydrochloric acid solution, and reacting for 35 hours to etch impurities except carbon; and filtering, washing and drying to obtain the three-dimensional porous carbon nano cage powder.
The carbon nano cage powder and the graphene oxide are prepared according to the weight ratio of 1: and 0.25 of the carbon nano cage-graphene oxide solution is added into dimethylbenzene, uniformly mixed, and then added with N-hydroxybenzenesulfonamide and stirred for 4 hours to obtain the carbon nano cage-graphene oxide solution. The addition amount of the N-hydroxy benzene sulfonamide is 0.3 times of the dosage of the graphene oxide.
And placing the carbon nano cage-graphene oxide solution into a vacuum drying oven, vacuumizing and heating to 147 ℃, and keeping for 65 hours to sufficiently dry to obtain the powder of the carbon nano cage-graphene oxide composite material.
S3: based on the molar components, 10 parts of nano aluminum hydroxide is ultrasonically dispersed in an ethanol solution, 7 parts of KH-550 is gradually added into the ethanol solution in a dropwise manner, the reaction solution is uniformly stirred for 75min, the product is alternately washed for 2 times by using N, N-dimethylformamide and deionized water, suction filtration is performed, and finally the modified aluminum hydroxide is obtained by drying at room temperature.
S5: according to the weight components, 100 parts of polyacrylic resin, 12 parts of carbon nano cage-graphene oxide composite material, 12 parts of modified aluminum hydroxide, 4 parts of dioctyl sebacate and 0.6 part of 1076 antioxidant are mixed in a high-pressure homogenizer at the mixing temperature of 65 ℃ for 18min, and the pressure in the high-pressure homogenizer is 19Mpa; extruding in a double-screw extruder, wherein the temperatures of each section of the double-screw extruder are as follows: the first zone temperature is 175 ℃, the second zone temperature is 195 ℃, the third zone temperature is 210 ℃, the fourth zone temperature is 235 ℃, and the fifth zone temperature is 175 ℃. Extruding and granulating to obtain the halogen-free flame-retardant antistatic modified plastic.
Compared with example 4, the step of reacting the modified nano aluminum hydroxide with the carbon nano cage-graphene oxide composite material is omitted, and the rest steps are the same.
Comparative example 2
The preparation method of the halogen-free flame-retardant antistatic modified plastic comprises the following steps:
s1: graphene oxide prepared by adopting a Hummers method,
s3: based on the molar components, 10 parts of nano aluminum hydroxide is ultrasonically dispersed in an ethanol solution, 7 parts of KH-550 is gradually added into the ethanol solution in a dropwise manner, the reaction solution is uniformly stirred for 75min, the product is alternately washed for 2 times by using N, N-dimethylformamide and deionized water, suction filtration is performed, and finally the modified aluminum hydroxide is obtained by drying at room temperature.
S5: according to the weight components, 100 parts of polyacrylic resin, 12 parts of graphene oxide, 12 parts of modified nano aluminum hydroxide, 4 parts of dioctyl sebacate and 0.6 part of 1076 antioxidant are mixed in a high-pressure homogenizer at the mixing temperature of 65 ℃ for 18min, and the pressure in the high-pressure homogenizer is 19Mpa; extruding in a double-screw extruder, wherein the temperatures of each section of the double-screw extruder are as follows: the first zone temperature is 175 ℃, the second zone temperature is 195 ℃, the third zone temperature is 210 ℃, the fourth zone temperature is 235 ℃, and the fifth zone temperature is 175 ℃. Extruding and granulating to obtain the halogen-free flame-retardant antistatic modified plastic.
Compared with example 4, the reaction of the carbon nanocages with graphene oxide and aluminum hydroxide was omitted, and the rest steps were the same.
The plastics obtained in examples 1-4 and comparative examples 1-2 were sliced and then subjected to performance tests, the test results of which are shown in Table 1 below:
as shown in Table 1, it can be seen that inventive examples 1-4 have UL94V 0 flame retardant properties, and better antistatic properties and mechanical strength. In comparative example 1, due to the lack of the process of combining nano aluminum hydroxide and carbon nano cage-graphene oxide, the nano aluminum hydroxide and the carbon nano cage-graphene oxide are randomly distributed in the resin, so that the carbon nano cage in the unevenly distributed resin cannot form an interface with the nano aluminum hydroxide to perform synergistic flame retardance, and meanwhile, the graphene lacks of heat absorption and thermal stability, and the flame retardant is insufficient in flame retardance due to low addition amount of the flame retardant, so that the UL94V-1 grade is only reached. In comparative example 2, due to the lack of the carbon nanocages, the graphene oxide sheets are accumulated, so that the antistatic performance of the graphene oxide sheets is reduced, the surface resistance is increased, the mechanical property is reduced, and the synergistic effect of the carbon nanocages, graphene oxide and nano aluminum hydroxide is lacked, so that the flame retardant property is also greatly reduced. Significantly lower than examples 1-4 of the present invention.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.
Claims (10)
1. The preparation method of the halogen-free flame-retardant antistatic modified plastic is characterized by comprising the following steps of:
s1: graphene oxide prepared by adopting a Hummers method;
s2: preparing a carbon nano cage-graphene oxide composite material, firstly ball-milling sodium citrate powder, and then carbonizing the ball-milled sodium citrate powder at a high temperature under the protection of inert gas; adding carbonized sodium citrate powder into hydrochloric acid solution, and etching away impurities except carbon; filtering, washing and drying to obtain the three-dimensional porous carbon nano cage powder;
the carbon nano cage powder and the graphene oxide are prepared according to the weight ratio of 1:0.2 to 0.5 of the carbon nano cage-graphene oxide solution is added into dimethylbenzene, uniformly mixed, and then added with N-hydroxy benzene sulfonamide and stirred to obtain the carbon nano cage-graphene oxide solution;
placing the carbon nano cage-graphene oxide solution into a vacuum drying oven, and vacuum drying to obtain powder of the carbon nano cage-graphene oxide composite material;
s3: modifying the nano aluminum hydroxide by adopting a silane coupling agent to obtain modified nano aluminum hydroxide;
s4: preparing a flame-retardant antistatic agent, namely, according to the weight components, mixing the modified nano aluminum hydroxide with the carbon nano cage-graphene oxide composite material according to the weight components of 1:3-5, dissolving in dimethylbenzene, uniformly stirring at 80-100 ℃, slowly dripping sulfuric acid, reacting for 6-10h, and vacuum drying to obtain the flame-retardant antistatic agent;
s5: according to the weight components, 100 parts of polyacrylic resin, 8-12 parts of flame-retardant antistatic agent, 2-5 parts of plasticizer and 0.5-0.8 part of antioxidant are uniformly mixed and extruded for granulation to obtain the halogen-free flame-retardant antistatic modified plastic.
2. The preparation method of the halogen-free flame-retardant antistatic modified plastic according to claim 1, wherein the specific process of the step S2 is as follows: firstly ball-milling sodium citrate powder for 4-8h, and then heating the ball-milled sodium citrate powder at 700-1000 ℃ for 2-5h under the protection of inert gas so as to carbonize the sodium citrate powder; adding carbonized sodium citrate powder into 15-20wt% hydrochloric acid solution, reacting for 24-48h, and etching impurities except carbon; filtering, washing and drying to obtain the three-dimensional porous carbon nano cage powder;
the carbon nano cage powder and the graphene oxide are prepared according to the weight ratio of 1:0.2 to 0.5 of the carbon nano cage-graphene oxide solution is added into dimethylbenzene, uniformly mixed, and then added with N-hydroxy benzene sulfonamide and stirred for 4 to 6 hours to obtain the carbon nano cage-graphene oxide solution;
and placing the carbon nano cage-graphene oxide solution into a vacuum drying oven, vacuumizing and heating to 140-150 ℃, and keeping for 50-70h to sufficiently dry to obtain the powder of the carbon nano cage-graphene oxide composite material.
3. The method for preparing halogen-free flame-retardant antistatic modified plastic according to claim 1 or 2, wherein the inert gas is one of argon and nitrogen.
4. The preparation method of the halogen-free flame-retardant antistatic modified plastic according to claim 1, wherein the specific process of the step S3 is that 10 parts of nanometer aluminum hydroxide is ultrasonically dispersed in ethanol solution by counting the mole components, then 5-8 parts of silane coupling agent is gradually dripped into the ethanol solution, the reaction solution is uniformly stirred for 60-80min, then the product is alternately washed for 2 times by using N, N-dimethylformamide and deionized water, suction filtration is carried out, and finally the modified aluminum hydroxide is obtained by drying at room temperature.
5. The method for preparing halogen-free flame retardant antistatic modified plastic according to claim 1 or 4, wherein the silane coupling agent is one of KH-550, KH-560 and KH-570.
6. The method for preparing halogen-free flame-retardant antistatic modified plastic according to claim 1, wherein in step S5, the uniform mixing is performed in a high-pressure homogenizer at 60-80 ℃ for 10-20min, and the pressure in the high-pressure homogenizer is 15-20Mpa.
7. The method for preparing halogen-free flame-retardant antistatic modified plastic according to claim 1, wherein in step S5, the extrusion is performed in a twin-screw extruder, and the temperatures of each section of the twin-screw extruder are as follows: the temperature of the first area is 160-180 ℃, the temperature of the second area is 180-200 ℃, the temperature of the third area is 200-220 ℃, the temperature of the fourth area is 220-260 ℃, and the temperature of the fifth area is 170-180 ℃.
8. The method for preparing halogen-free flame-retardant antistatic modified plastic according to claim 1, wherein in the step S5, the plasticizer is one of dioctyl sebacate, epoxidized soybean oil and epoxidized butyl stearate.
9. The method for preparing halogen-free flame retardant antistatic modified plastic according to claim 1, wherein the antioxidant in the step S5 is one or more of 1010 antioxidant, BHT antioxidant and 1076 antioxidant.
10. A halogen-free flame-retardant antistatic modified plastic, which is characterized by being prepared by the preparation method of any one of claims 1-9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311846124.7A CN117511068A (en) | 2023-12-29 | 2023-12-29 | Halogen-free flame-retardant antistatic modified plastic and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311846124.7A CN117511068A (en) | 2023-12-29 | 2023-12-29 | Halogen-free flame-retardant antistatic modified plastic and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117511068A true CN117511068A (en) | 2024-02-06 |
Family
ID=89749731
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311846124.7A Pending CN117511068A (en) | 2023-12-29 | 2023-12-29 | Halogen-free flame-retardant antistatic modified plastic and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117511068A (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103694615A (en) * | 2013-12-18 | 2014-04-02 | 江苏悦达墨特瑞新材料科技有限公司 | Antistatic halogen-free environment-friendly flame-retardant sheet moulding compound and preparation method thereof |
| CN108467547A (en) * | 2018-04-04 | 2018-08-31 | 宁波福天新材料科技有限公司 | A kind of converter environment-protection flame-proof electrostatic resistance polypropylene composition and preparation method thereof |
| CN109265828A (en) * | 2018-09-20 | 2019-01-25 | 大连裕丰塑料制品有限公司 | A kind of anti-static plastic and its production technology |
| CN109627574A (en) * | 2018-11-28 | 2019-04-16 | 广州市宇艺包装材料有限公司 | A kind of heat-resistant fireproof packaging material and preparation method thereof |
| CN109836996A (en) * | 2017-09-22 | 2019-06-04 | 北京大学深圳研究生院 | Aqueous thermally conductive anticorrosive paint of one kind and preparation method thereof |
| CN113174187A (en) * | 2021-05-27 | 2021-07-27 | 深圳市华必达科技有限公司 | Nano cage flame retardant modified epoxy resin floor paint and preparation method thereof |
| CN113346054A (en) * | 2021-04-23 | 2021-09-03 | 西交利物浦大学 | Preparation method and application of MXene-carbon nanocage-sulfur composite material |
| CN113522287A (en) * | 2021-06-24 | 2021-10-22 | 中科合成油技术有限公司 | Carbon-supported metal catalyst with hierarchical pore structure, preparation method and application thereof |
-
2023
- 2023-12-29 CN CN202311846124.7A patent/CN117511068A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103694615A (en) * | 2013-12-18 | 2014-04-02 | 江苏悦达墨特瑞新材料科技有限公司 | Antistatic halogen-free environment-friendly flame-retardant sheet moulding compound and preparation method thereof |
| CN109836996A (en) * | 2017-09-22 | 2019-06-04 | 北京大学深圳研究生院 | Aqueous thermally conductive anticorrosive paint of one kind and preparation method thereof |
| CN108467547A (en) * | 2018-04-04 | 2018-08-31 | 宁波福天新材料科技有限公司 | A kind of converter environment-protection flame-proof electrostatic resistance polypropylene composition and preparation method thereof |
| CN109265828A (en) * | 2018-09-20 | 2019-01-25 | 大连裕丰塑料制品有限公司 | A kind of anti-static plastic and its production technology |
| CN109627574A (en) * | 2018-11-28 | 2019-04-16 | 广州市宇艺包装材料有限公司 | A kind of heat-resistant fireproof packaging material and preparation method thereof |
| CN113346054A (en) * | 2021-04-23 | 2021-09-03 | 西交利物浦大学 | Preparation method and application of MXene-carbon nanocage-sulfur composite material |
| CN113174187A (en) * | 2021-05-27 | 2021-07-27 | 深圳市华必达科技有限公司 | Nano cage flame retardant modified epoxy resin floor paint and preparation method thereof |
| CN113522287A (en) * | 2021-06-24 | 2021-10-22 | 中科合成油技术有限公司 | Carbon-supported metal catalyst with hierarchical pore structure, preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110218401B (en) | Flame-retardant smoke-inhibiting soft polyvinyl chloride composite material with good mechanical property and preparation method thereof | |
| CN108976588B (en) | Flame-retardant antistatic EVA foam composite material and preparation method thereof | |
| CN100412124C (en) | Flame-proof polyethylene material and its preparation method | |
| CN113292777B (en) | Fireproof flame-retardant sheath material, and preparation method and application thereof | |
| CN112812435A (en) | Normal-temperature heat-conducting high-temperature flame-retardant polymer composite material and preparation method thereof | |
| Xu et al. | The effect of ammonium polyphosphate on the mechanism of phosphorous-containing hydrotalcite synergism of flame retardation of polypropylene | |
| CN110483880B (en) | Halogen-free flame-retardant low-voltage electrothermal film and preparation method thereof | |
| CN107236185A (en) | A kind of novel flame-retardant cable material and preparation method thereof | |
| CN111690202A (en) | High-flame-retardance high-crust-forming low-smoke halogen-free flame-retardant oxygen-insulating layer cable material | |
| Tian et al. | Mechanical, flammability, and thermal properties of polyvinyl chloride‐wood composites with carbide slag | |
| CN115011078A (en) | Flame-retardant environment-friendly PET plastic and preparation method thereof | |
| CN112063163B (en) | Antistatic heat-conducting flame-retardant composite material and preparation method thereof | |
| CN108034126B (en) | Halogen-free flame-retardant polyolefin composite material and preparation method thereof | |
| CN117511068A (en) | Halogen-free flame-retardant antistatic modified plastic and preparation method thereof | |
| Tian et al. | Metal chelates as flame retardants and smoke suppressants for flexible poly (vinyl chloride) | |
| CN109988411B (en) | Flame-retardant smoke-suppression thermoplastic polyurethane antistatic composite material and preparation method thereof | |
| CN1487014A (en) | Antistatic fireproof composite polyethylene pipe and its production process | |
| CN111690197A (en) | Melamine-containing direct intercalation g-C3N4Flame-retardant cable material and preparation method thereof | |
| Zhan et al. | Ma Lao-like structural fireproof aramid nanofiber@ Ag nanocomposite film enhanced with MXene for advanced thermal management applications | |
| CN115368673A (en) | Graphene modified flame-retardant polypropylene material and preparation method thereof | |
| CN109535638B (en) | Flame-retardant smoke-suppression ABS for electronic equipment shell and preparation method thereof | |
| CN110483941B (en) | Low-smoke environment-friendly 5 VA-grade flame-retardant ABS material and preparation method thereof | |
| CN113480802A (en) | High-performance flame-retardant antistatic polypropylene | |
| CN112898754A (en) | Preparation method and application of polylactic acid nano composite material with easy crystallinity, antistatic property and flame retardance | |
| CN117229569B (en) | Efficient composite flame retardant for polypropylene and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |