CN111961297A - High-flame-retardancy soft PVC (polyvinyl chloride) antistatic material and preparation method thereof - Google Patents

High-flame-retardancy soft PVC (polyvinyl chloride) antistatic material and preparation method thereof Download PDF

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CN111961297A
CN111961297A CN202010905388.5A CN202010905388A CN111961297A CN 111961297 A CN111961297 A CN 111961297A CN 202010905388 A CN202010905388 A CN 202010905388A CN 111961297 A CN111961297 A CN 111961297A
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flame
weight
parts
graphene
retardancy
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庄鹏程
张凌
李怡霏
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Shanghai Xigu Energy Technology Co ltd
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Shanghai Xigu Energy Technology Co ltd
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions 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; Compositions of derivatives of such polymers
    • C08L27/02—Compositions 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; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/04—Compositions 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; Compositions of derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
    • C08L27/06—Homopolymers or copolymers of vinyl chloride
    • 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
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/223—Packed additives
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    • 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
    • C08J2327/02—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 not modified by chemical after-treatment
    • C08J2327/04—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 not modified by chemical after-treatment containing chlorine atoms
    • C08J2327/06—Homopolymers or copolymers of vinyl chloride
    • C—CHEMISTRY; METALLURGY
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2423/04—Homopolymers or copolymers of ethene
    • C08J2423/06—Polyethene
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    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2423/26—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment
    • C08J2423/30—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers modified by chemical after-treatment by oxidation
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
    • C08K2003/322—Ammonium phosphate
    • C08K2003/323—Ammonium polyphosphate
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    • C08K2201/001—Conductive additives
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    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L2205/00—Polymer mixtures characterised by other features
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Abstract

The invention discloses a high-flame-retardancy soft PVC (polyvinyl chloride) antistatic material and a preparation method thereof. The preparation method comprises the following steps: uniformly mixing graphene, carbon nanotubes, oxidized polyethylene wax, EBS wax and stearic acid to form a graphene master batch material; and uniformly mixing the graphene master batch material, the PVC resin, the plasticizer, the heat stabilizer, the impact modifier and the flame retardant, and then carrying out melting treatment to obtain the high-flame-retardancy soft PVC antistatic material. The preparation method of the invention fully exerts the multi-space synergistic flame-retardant effect among the graphene, the carbon nano tube, the flame retardant and the PVC, greatly reduces the dosage of the flame retardant and improves the flame-retardant effect. In addition, due to the synergistic conductive effect of the graphene and the carbon nano tube, the using amount of conductive filler can be greatly reduced on the basis of achieving the antistatic property, the hardness of the material is reduced, the using amount of a plasticizer is further reduced, the using amount of a flame retardant is further reduced, the flame retardance is improved, and the application of the flame retardant is expanded.

Description

High-flame-retardancy soft PVC (polyvinyl chloride) antistatic material and preparation method thereof
Technical Field
The invention relates to an antistatic material, in particular to a novel high-flame-retardancy soft PVC antistatic material and a preparation method thereof, belonging to the technical field of graphene/polymer composite materials.
Background
PVC has long been one of the most important polymer products in people's production and life, and has become the second largest plastic consumer product with the amount of PVC second to that of polyethylene in the world. Wherein the soft PVC is mainly used for preparing pipes, sheets and films. Along with the development of society, the requirements of people on the performance of soft PVC are higher and higher, although the soft PVC has outstanding performance, the original flame-retardant advantage of PVC is lost due to the addition of a large amount of plasticizer, and the surface resistance of the soft PVC is as high as 1014-1017Omega, which is easy to generate electrostatic hazard, and the further development of the soft PVC is severely limited.
The PVC composite antistatic material prepared by the method of blending, filling and composite modification of the soft PVC and the conductive filler can achieve the antistatic effect, but the hardness of the soft PVC is increased by the huge filling amount of the conductive filler, and if the softness required by the performance is achieved, the dosage of the plasticizer needs to be increased, which can cause the flame retardance to be reduced and the mechanical property to be poor. This creates a contradiction between antistatic properties, flame retardancy, and flexibility. How to improve the flame retardance of the soft antistatic PVC becomes a difficult problem in the industry.
With the recent development of graphene and carbon nanotubes, there has been a search for applications of graphene and carbon nanotubes to antistatic materials and flame retardant materials. However, due to the characteristic that graphene is difficult to disperse and the complexity of matching graphene in a soft PVC system, no mature scheme is provided for solving the problems of antistatic flame-retardant soft PVC at present.
Disclosure of Invention
The invention provides a novel high-flame-retardance soft PVC antistatic material and a preparation method thereof, aiming at the problems that the antistatic property, the flame retardance and the flexibility of antistatic flame-retardance soft PVC are mutually restricted, the more the conductive filler is used, the larger the plasticizer and the flame retardant are used, and the problems that graphene serving as a novel material is difficult to disperse and has poor matching effect in the soft PVC.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides a preparation method of a high-flame-retardancy soft PVC antistatic material, which comprises the following steps:
uniformly mixing graphene, carbon nanotubes, oxidized polyethylene wax, EBS wax and stearic acid to form a graphene master batch material;
and uniformly mixing the graphene master batch material, the PVC resin, the plasticizer, the heat stabilizer, the impact modifier and the flame retardant, and then carrying out melting treatment to obtain the high-flame-retardancy soft PVC antistatic material.
In some embodiments, the preparation method specifically comprises: uniformly mixing 0.5-1 part of graphene, 2-5 parts of carbon nano tubes, 0.2-1 part of oxidized polyethylene wax, 0.2-0.5 part of polyethylene wax, 0.3-1 part of EBS wax and 0.2-0.5 part of stearic acid in parts by weight to form the graphene master batch material.
In some embodiments, the preparation method specifically comprises: uniformly mixing 5-10 parts of graphene master batch material, 100 parts of PVC resin, 40-60 parts of plasticizer, 6-8 parts of heat stabilizer, 4-5 parts of impact modifier, 2-3 parts of antimony trioxide and 3-5 parts of ammonium polyphosphate in parts by weight, and then carrying out melting treatment to obtain the high-flame-retardancy soft PVC antistatic material.
The embodiment of the invention also provides the high-flame-retardancy soft PVC antistatic material prepared by the method.
Furthermore, the flame retardant grade of the high-flame-retardant soft PVC antistatic material is V-0 grade, and the limiting oxygen index is 36-40.
Further, the surface resistivity of the high-flame-retardancy soft PVC antistatic material is 103～109Ω。
Furthermore, the Shore A hardness of the high-flame-retardancy soft PVC antistatic material is 50-60.
Compared with the prior art, the invention has the advantages that:
1) the preparation method of the high-flame-retardancy soft PVC antistatic material provided by the invention fully utilizes the multi-space synergistic flame-retardant effect of graphene, carbon nano tubes, ammonium polyphosphate, antimony trioxide and PVC, the one-dimensional structure of the carbon nano tubes forms a network structure in the soft PVC, the two-dimensional structure of the graphene is attached to the structural network formed by the carbon nano tubes, and the ammonium polyphosphate and the antimony trioxide are filled in the network structure to form a multi-space flame-retardant system with a PVC substrate, so that the barrier effect can be exerted to the greatest extent during combustion, the heat and oxygen are prevented from entering, the flame retardant dosage is greatly reduced, and the flame retardancy of the soft antistatic PVC material is greatly improved;
2) in addition, due to the synergistic conductive effect of the graphene and the carbon nano tube, the addition amount of conductive fillers can be reduced on the basis of ensuring the antistatic effect on the basis of achieving the antistatic effect, so that the hardness of the material is reduced, the consumption of a plasticizer is reduced, the consumption of a flame retardant is further reduced, and the flame retardance is improved;
3) according to the preparation method of the high-flame-retardancy soft PVC antistatic material, provided by the invention, the mechanical property is improved due to the fact that the addition amounts of the conductive filler, the plasticizer and the flame retardant are reduced, the problem of difficulty in processing and forming is solved, the performance of the flame-retardancy antistatic soft PVC material is improved, and the application of the flame-retardancy antistatic soft PVC material is expanded.
Detailed Description
The technical solution of the present invention will be explained in more detail below. It is to be understood, however, that within the scope of the present invention, the above-described features of the present invention and those specifically described below (e.g., in the examples) may be combined with one another to form new or preferred embodiments. Not to be reiterated herein, but to the extent of space.
Aiming at the defects of the prior art, the inventor of the invention provides the technical scheme of the invention through long-term research and massive practice. In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
One aspect of the embodiments of the present invention provides a method for preparing a high flame retardant flexible PVC antistatic material, comprising:
uniformly mixing graphene, carbon nanotubes, oxidized polyethylene wax, EBS wax and stearic acid to form a graphene master batch material;
and uniformly mixing the graphene master batch material, the PVC resin, the plasticizer, the heat stabilizer, the impact modifier and the flame retardant, and then carrying out melting treatment to obtain the high-flame-retardancy soft PVC antistatic material.
In some embodiments, the preparation method of the novel high flame retardant flexible PVC antistatic material comprises: graphene and carbon nanotubes are used as conductive fillers and synergistic flame retardants, a composite dispersing agent of oxidized polyethylene wax, EBS wax and stearic acid is used as an auxiliary material, the graphene master batch is prepared, the graphene master batch, PVC resin, a plasticizer, a heat stabilizer, an impact modifier and a flame retardant are uniformly mixed, and the high-flame-retardancy soft PVC antistatic material is obtained after melting processing.
In some preferred embodiments, the preparation method specifically comprises: uniformly mixing 0.5-1 part of graphene, 2-5 parts of carbon nano tubes, 0.2-1 part of oxidized polyethylene wax, 0.2-0.5 part of polyethylene wax, 0.3-1 part of EBS wax and 0.2-0.5 part of stearic acid in parts by weight to form the graphene master batch material.
Furthermore, the graphene is mechanically stripped graphene, and the sheet diameter is 5-30 microns.
Further, the carbon nanotube is a single-walled carbon nanotube, a multi-walled carbon nanotube, or the like, but is not limited thereto.
Further, the length of the carbon nano tube is 10-50 μm.
Furthermore, the oxidized polyethylene wax has a number average molecular weight of 2000-10000 and an acid value of 5-15.
Further, the number average molecular weight of the polyethylene wax is 2000-8000.
In some embodiments, the flame retardant comprises a combination of antimony trioxide and ammonium polyphosphate.
In some preferred embodiments, the preparation method specifically comprises: uniformly mixing 5-10 parts by weight of graphene master batch material, 100 parts by weight of PVC resin, 40-60 parts by weight of plasticizer, 6-8 parts by weight of heat stabilizer, 4-5 parts by weight of impact modifier, 2-3 parts by weight of antimony trioxide and 3-5 parts by weight of ammonium polyphosphate, and then carrying out melting treatment at 165-180 ℃ for 2-5 min to obtain the high-flame-retardancy soft PVC antistatic material.
Further, the polymerization degree of the PVC resin is 1000-1500.
Further, the plasticizer may include any one or a combination of two or more of phthalic acid plasticizers, such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate (DOP), butyl benzyl phthalate, di (2-ethyl) hexyl phthalate, diisononyl phthalate, and the like, and may also be chlorinated paraffin and vegetable ester plasticizers, such as epoxidized soybean oil, but is not limited thereto.
Further, the heat stabilizer includes any one or a combination of two or more of organic tin laurate, organic tin maleate and organic tin mercaptide, but is not limited thereto.
Further, the heat stabilizer may specifically be any one or a combination of two or more of, for example, dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin laurate maleate, dibutyltin maleate, dioctyltin maleate, tin methyl mercaptide, tin butylmercaptide, tin octylmercaptide, and the like, but is not limited thereto.
Further, the impact modifier includes CPE and acrylate-based compounds, such as MBS and ACR, but not limited thereto.
In some more preferred embodiments, the preparation method of the high flame retardant flexible PVC antistatic material comprises the following steps:
mixing 0.5-1 part by weight of graphene, 2-5 parts by weight of carbon nanotubes, 0.2-1 part by weight of oxidized polyethylene wax, 0.2-0.5 part by weight of polyethylene wax, 0.3-1 part by weight of EBS wax and 0.2-0.5 part by weight of stearic acid to prepare a graphene master batch material;
uniformly mixing 5-10 parts by weight of graphene master batch material, 100 parts by weight of PVC resin, 40-60 parts by weight of plasticizer, 6-8 parts by weight of heat stabilizer, 4-5 parts by weight of impact modifier, 2-3 parts by weight of antimony trioxide and 3-5 parts by weight of ammonium polyphosphate, and then carrying out melting processing to obtain the high-flame-retardancy soft PVC antistatic material.
In another aspect of the embodiments of the present invention, there is also provided a flexible PVC antistatic material with high flame retardancy prepared by the foregoing method.
Furthermore, the flame retardant grade of the high-flame-retardant soft PVC antistatic material is V-0 grade, and the limiting oxygen index is 36-40.
Further, the surface resistivity of the high-flame-retardancy soft PVC antistatic material is 103～109Ω。
Furthermore, the Shore A hardness of the high-flame-retardancy soft PVC antistatic material is 50-60.
In conclusion, the preparation method provided by the invention fully exerts the multi-space synergistic flame-retardant effect among the graphene, the carbon nano tube, the flame retardant and the PVC, greatly reduces the dosage of the flame retardant and improves the flame-retardant effect. In addition, due to the synergistic conductive effect of the graphene and the carbon nano tube, the using amount of conductive filler can be greatly reduced on the basis of achieving the antistatic property, the hardness of the material is reduced, the using amount of a plasticizer is further reduced, the using amount of a flame retardant is further reduced, and the flame retardance is improved. Meanwhile, the addition amounts of the conductive filler, the plasticizer and the flame retardant are reduced, so that the mechanical property of the flame-retardant antistatic flexible PVC material is improved, the problem of difficult processing and forming is solved, the performance of the flame-retardant antistatic flexible PVC material is improved, and the application of the flame-retardant antistatic flexible PVC material is expanded.
In order to make the objects, technical solutions and advantages of the present invention clearer, the technical solutions of the present invention are described in detail below with reference to several preferred embodiments, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
The conditions used in the following examples may be further adjusted as necessary, and the conditions used in the conventional experiments are not generally indicated.
Comparative example 1
100 parts by weight of PVC resin, 40 parts by weight of DOP, 6 parts by weight of organotin, 4 parts by weight of ACR, 2 parts by weight of antimony trioxide and 3 parts by weight of ammonium polyphosphate were weighed, the raw materials were banburied for 5 minutes, and then taken out, tabletted and subjected to performance tests, and the results are shown in Table 1.
Comparative example 2
100 parts by weight of PVC resin, 40 parts by weight of DOP, 6 parts by weight of organotin, 4 parts by weight of ACR, 2 parts by weight of antimony trioxide, 3 parts by weight of ammonium polyphosphate and 25 parts by weight of conductive carbon black are weighed, the raw materials are banburied for 5 minutes, and then taken out, pressed into sheets and subjected to performance tests, and the results are shown in Table 1.
Comparative example 3
Weighing 0.5 part by weight of graphene with the sheet diameter of 10-15 mu m, 2 parts by weight of multi-wall carbon nano-tubes with the length of 20-30 mu m, 0.2 part by weight of oxidized polyethylene wax with the average molecular weight of 5000-6000, 0.2 part by weight of polyethylene wax with the average molecular weight of 3000-4000, 0.3 part by weight of EBS wax and 0.2 part by weight of stearic acid, and mixing to prepare a master batch material;
100 parts by weight of PVC resin, 40 parts by weight of DOP, 6 parts by weight of organotin, 4 parts by weight of ACR and 5 parts by weight of master batch material are weighed, the raw materials are banburied for 5 minutes, then taken out, tabletted and subjected to performance test.
Comparative example 4
Weighing 2 parts by weight of multi-wall carbon nano-tube with the length of 20-30 mu m, 0.2 part by weight of oxidized polyethylene wax with the average molecular weight of 5000-6000, 0.2 part by weight of polyethylene wax with the average molecular weight of 3000-4000, 0.3 part by weight of EBS wax and 0.2 part by weight of stearic acid, and mixing to prepare a master batch material;
weighing 100 parts by weight of PVC resin, 40 parts by weight of DOP, 6 parts by weight of organotin, 4 parts by weight of ACR, 2 parts by weight of antimony trioxide, 3 parts by weight of ammonium polyphosphate and 5 parts by weight of master batch material, banburying the raw materials for 5 minutes, taking out, tabletting and carrying out performance test.
Comparative example 5
Weighing 0.5 part by weight of graphene with the sheet diameter of 10-15 mu m, 0.2 part by weight of oxidized polyethylene wax with the average molecular weight of 5000-6000, 0.2 part by weight of polyethylene wax with the average molecular weight of 3000-4000, 0.3 part by weight of EBS wax and 0.2 part by weight of stearic acid, and mixing to prepare a master batch material;
weighing 100 parts by weight of PVC resin, 40 parts by weight of DOP, 6 parts by weight of organotin, 4 parts by weight of ACR, 2 parts by weight of antimony trioxide, 3 parts by weight of ammonium polyphosphate and 5 parts by weight of master batch material, banburying the raw materials for 5 minutes, taking out, tabletting and carrying out performance test.
Example 1
Weighing 0.5 part by weight of graphene with the sheet diameter of 10-15 mu m, 2 parts by weight of multi-wall carbon nano tubes with the length of 20-30 mu m, 0.2 part by weight of oxidized polyethylene wax with the average molecular weight of 5000-6000, 0.2 part by weight of polyethylene wax with the average molecular weight of 3000-4000, 0.3 part by weight of EBS wax and 0.2 part by weight of stearic acid, and mixing to prepare a graphene master batch material;
weighing 100 parts by weight of PVC resin with the polymerization degree of 1200, 40 parts by weight of DOP, 6 parts by weight of dibutyltin dilaurate, 4 parts by weight of ACR, 2 parts by weight of antimony trioxide, 3 parts by weight of ammonium polyphosphate and 5 parts by weight of graphene master batch material, banburying the raw materials at 165 ℃ for 5 minutes, taking out, tabletting to obtain the high-flame-retardancy soft PVC antistatic material, and carrying out performance test, wherein the results are shown in Table 1.
Example 2
Weighing 0.8 part by weight of graphene with the sheet diameter of 10-15 mu m, 3 parts by weight of multi-wall carbon nano tubes with the length of 20-30 mu m, 0.5 part by weight of oxidized polyethylene wax with the average molecular weight of 5000-6000, 0.3 part by weight of polyethylene wax with the average molecular weight of 3000-4000, 0.6 part by weight of EBS wax and 0.3 part by weight of stearic acid, and mixing to prepare a graphene master batch material;
weighing 100 parts by weight of PVC resin with the polymerization degree of 1500, 50 parts by weight of dimethyl phthalate, 7 parts by weight of dioctyltin maleate, 4.5 parts by weight of ACR, 2.5 parts by weight of antimony trioxide, 4 parts by weight of ammonium polyphosphate and 7 parts by weight of graphene master batch material, banburying the raw materials at 170 ℃ for 2 minutes, taking out, tabletting to obtain the high-flame-retardancy soft PVC antistatic material, and carrying out performance test, wherein the results are shown in Table 1.
Example 3
Weighing 1 part by weight of graphene with the sheet diameter of 10-15 mu m, 5 parts by weight of multi-wall carbon nano tubes with the length of 20-30 mu m, 1 part by weight of oxidized polyethylene wax with the average molecular weight of 5000-6000, 0.5 part by weight of polyethylene wax with the average molecular weight of 3000-4000, 1 part by weight of EBS wax and 0.5 part by weight of stearic acid, and mixing to prepare a graphene master batch material;
weighing 100 parts by weight of PVC resin with the polymerization degree of 1000, 60 parts by weight of di (2-ethyl) hexyl phthalate, 8 parts by weight of tin methyl mercaptide, 5 parts by weight of MBS, 3 parts by weight of antimony trioxide, 5 parts by weight of ammonium polyphosphate and 10 parts by weight of graphene master batch material, banburying the raw materials at 180 ℃ for 2 minutes, taking out, tabletting to obtain the high-flame-retardancy soft PVC antistatic material, and carrying out performance test, wherein the results are shown in Table 1.
Through tests, the data of various test indexes of the materials obtained in the above comparative examples 1-5 and examples 1-3 are shown in the following table 1.
TABLE 1 data of various test indexes of the materials obtained in comparative examples 1 to 5 and examples 1 to 3
Item Total content of conductive filler/%) Limiting oxygen index/%) Flame retardant rating Surface resistivity/omega Shore A hardness/° C
Comparative example 1 0 24 V-2 1017 48
Comparative example 2 12 30 V-1 106 80
Comparative example 3 2.3 29 V-1 109 50
Comparative example 4 2.2 32 V-1 1010 49
Comparative example 5 1.1 31 V-1 1012 48
Example 1 2.3 36 V-0 109 50
Example 2 2.8 38 V-0 106 57
Example 3 3.5 40 V-0 103 60
As can be seen from table 1 above, compared to comparative example 1, comparative example 2 has a poor flame retardant effect and a large material hardness although it achieves an antistatic effect; in comparative example 3, antimony trioxide and ammonium polyphosphate which are flame retardants are not added, a multi-space synergistic flame-retardant effect cannot be formed with graphene and carbon nanotubes, and the flame-retardant effect is poor; comparative examples 4 and 5, in which graphene and carbon nanotubes are not added, respectively, also failed to form a multi-element space synergistic flame retardant effect, and had poor flame retardant effect and higher surface resistivity; the use requirements of flame-retardant antistatic soft PVC are not met.
In the embodiments 1 to 3 of the invention, the flame retardance is improved by the multi-element space synergistic flame retardant effect formed by compounding the graphene, the carbon nano tubes, the antimony trioxide and the ammonium polyphosphate, and the dosage of the conductive filler, the hardness and the plasticizer are reduced by the coordination effect of the composite dispersant. The two phases are overlapped, so that the flame retardance is greatly improved, the maximum limit oxygen index reaches 40, and the flame retardance grade reaches V-0. In actual use, the manufacturer can select different addition amounts according to different performance requirements.
In conclusion, the novel high-flame-retardancy soft PVC antistatic material prepared by the preparation method of the novel high-flame-retardancy soft PVC antistatic material has the advantages of remarkable improvement of antistatic performance and flexibility, no reduction of flame retardancy, reasonable design and strong practicability, and is beneficial to wide application of the soft PVC antistatic flame-retardant material.
In addition, the present inventors prepared high flame retardant flexible PVC antistatic materials with different graphene and carbon nanotube ratios, and prepared flexible PVC antistatic materials with excellent mechanical properties and high flame retardancy, referring to the manner of examples 1-3. In actual use, a producer can select different graphene and carbon nanotube ratios according to different performance requirements.
For example, referring to examples 1 to 3, the inventors of the present invention replaced the plasticizer with diethyl phthalate, dibutyl phthalate, butyl benzyl phthalate, diisononyl phthalate, chlorinated paraffin, epoxidized soybean oil, etc., replaced the heat stabilizer with dioctyltin dilaurate, dibutyltin laurate, maleate, butyltin mercaptide, octyltin mercaptide, etc., and replaced the impact modifier with CPE and acrylic compounds, etc., and the obtained flexible PVC antistatic material had test index data substantially identical to those of examples 1 to 3.
The aspects, embodiments, features and examples of the present invention should be considered as illustrative in all respects and not intended to be limiting of the invention, the scope of which is defined only by the claims. Other embodiments, modifications, and uses will be apparent to those skilled in the art without departing from the spirit and scope of the claimed invention.
The use of headings and chapters in this disclosure is not meant to limit the disclosure; each section may apply to any aspect, embodiment, or feature of the disclosure.
Throughout this specification, where a composition is described as having, containing, or comprising specific components or where a process is described as having, containing, or comprising specific process steps, it is contemplated that the composition of the present teachings also consist essentially of, or consist of, the recited components, and the process of the present teachings also consist essentially of, or consist of, the recited process steps.
It should be understood that the order of steps or the order in which particular actions are performed is not critical, so long as the teachings of the invention remain operable. Further, two or more steps or actions may be performed simultaneously.
While the invention has been described with reference to illustrative embodiments, it will be understood by those skilled in the art that various other changes, omissions and/or additions may be made and substantial equivalents may be substituted for elements thereof without departing from the spirit and scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from its scope. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the appended claims.

Claims (10)

1. A preparation method of a high-flame-retardancy soft PVC antistatic material is characterized by comprising the following steps:
uniformly mixing graphene, carbon nanotubes, oxidized polyethylene wax, EBS wax and stearic acid to form a graphene master batch material;
and uniformly mixing the graphene master batch material, the PVC resin, the plasticizer, the heat stabilizer, the impact modifier and the flame retardant, and then carrying out melting treatment to obtain the high-flame-retardancy soft PVC antistatic material.
2. The production method according to claim 1, characterized by comprising: uniformly mixing 0.5-1 part of graphene, 2-5 parts of carbon nano tubes, 0.2-1 part of oxidized polyethylene wax, 0.2-0.5 part of polyethylene wax, 0.3-1 part of EBS wax and 0.2-0.5 part of stearic acid in parts by weight to form the graphene master batch material.
3. The production method according to claim 1 or 2, characterized in that: the graphene is mechanically stripped graphene, and the sheet diameter is 5-30 mu m.
4. The production method according to claim 1 or 2, characterized in that: the carbon nano tube is a single-wall carbon nano tube and/or a multi-wall carbon nano tube; preferably, the length of the carbon nanotube is 10 to 50 μm.
5. The production method according to claim 1 or 2, characterized in that: the oxidized polyethylene wax has a number average molecular weight of 2000-10000 and an acid value of 5-15.
6. The production method according to claim 1 or 2, characterized in that: the number average molecular weight of the polyethylene wax is 2000-8000.
7. The method of claim 1, wherein: the flame retardant comprises a combination of antimony trioxide and ammonium polyphosphate.
8. The production method according to claim 7, characterized by comprising: uniformly mixing 5-10 parts by weight of graphene master batch material, 100 parts by weight of PVC resin, 40-60 parts by weight of plasticizer, 6-8 parts by weight of heat stabilizer, 4-5 parts by weight of impact modifier, 2-3 parts by weight of antimony trioxide and 3-5 parts by weight of ammonium polyphosphate, and then carrying out melt treatment at 165-180 ℃ for 2-5 min to obtain the high-flame-retardancy soft PVC antistatic material.
9. The method of claim 8, wherein: the polymerization degree of the PVC resin is 1000-1500; and/or the plasticizer comprises any one or the combination of more than two of phthalic acid plasticizers, chlorinated paraffin and plant ester plasticizers; preferably, the phthalic acid plasticizer comprises any one or a combination of more than two of dimethyl phthalate, diethyl phthalate, dibutyl phthalate, dioctyl phthalate, butyl benzyl phthalate, di (2-ethyl) hexyl phthalate and diisononyl phthalate; preferably, the vegetable ester plasticizer comprises epoxidized soybean oil; and/or the heat stabilizer comprises any one or the combination of more than two of organic tin laurate, organic tin maleate and organic tin mercaptide, preferably any one or the combination of more than two of dibutyltin dilaurate, dioctyltin dilaurate, dibutyltin laurate maleate, dibutyltin maleate, dioctyltin maleate, methyltin mercaptide, butyltin mercaptide and octyltin mercaptide; and/or, the impact modifier comprises CPE and an acrylate-based compound, preferably MBS and/or ACR.
10. A high flame retardant flexible PVC antistatic material prepared by the process of any one of claims 1 to 9; preferably, the flame resistance of the high-flame-retardancy soft PVC antistatic materialThe fuel grade is V-0 grade, and the limiting oxygen index is 36-40; preferably, the surface resistivity of the high-flame-retardancy soft PVC antistatic material is 103～109Omega; preferably, the Shore A hardness of the high-flame-retardancy soft PVC antistatic material is 50-60.
CN202010905388.5A 2020-09-01 2020-09-01 High-flame-retardancy soft PVC (polyvinyl chloride) antistatic material and preparation method thereof Pending CN111961297A (en)

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