CN115386179A - Preparation method of polyvinyl chloride composite material with electromagnetic shielding and cold resistance - Google Patents
Preparation method of polyvinyl chloride composite material with electromagnetic shielding and cold resistance Download PDFInfo
- Publication number
- CN115386179A CN115386179A CN202211058990.5A CN202211058990A CN115386179A CN 115386179 A CN115386179 A CN 115386179A CN 202211058990 A CN202211058990 A CN 202211058990A CN 115386179 A CN115386179 A CN 115386179A
- Authority
- CN
- China
- Prior art keywords
- parts
- polyvinyl chloride
- filler
- mwcnt
- electromagnetic shielding
- 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
- 239000004800 polyvinyl chloride Substances 0.000 title claims abstract description 71
- 229920000915 polyvinyl chloride Polymers 0.000 title claims abstract description 68
- 239000002131 composite material Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000000945 filler Substances 0.000 claims abstract description 56
- 239000011347 resin Substances 0.000 claims abstract description 37
- 229920005989 resin Polymers 0.000 claims abstract description 37
- 239000002048 multi walled nanotube Substances 0.000 claims abstract description 32
- 239000000463 material Substances 0.000 claims abstract description 24
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 23
- 238000002156 mixing Methods 0.000 claims abstract description 23
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000004381 surface treatment Methods 0.000 claims abstract description 15
- 239000004014 plasticizer Substances 0.000 claims abstract description 12
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 claims abstract description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000006084 composite stabilizer Substances 0.000 claims abstract description 11
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 11
- 235000021355 Stearic acid Nutrition 0.000 claims abstract description 10
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims abstract description 10
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000008117 stearic acid Substances 0.000 claims abstract description 10
- 239000006229 carbon black Substances 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 18
- 238000001125 extrusion Methods 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000003607 modifier Substances 0.000 abstract description 6
- 238000005457 optimization Methods 0.000 abstract description 2
- 239000004698 Polyethylene Substances 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 239000011159 matrix material Substances 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 238000013329 compounding Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 238000004891 communication Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 2
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000005670 electromagnetic radiation Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- 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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
- C08L2203/202—Applications use in electrical or conductive gadgets use in electrical wires or wirecoating
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to a preparation method of a polyvinyl chloride composite material with electromagnetic shielding and cold resistance, which comprises the steps of adding CB, MWCNT, stearic acid and PE wax into a mixing type torque rheometer, and carrying out surface treatment on a filler by using a silane coupling agent after blending to obtain an MWCNT @ CB filler; 90-110 parts of polyvinyl chloride resin SG-3; 40-60 parts of an o-benzene plasticizer; 10-20 parts of impact modified resin; 0.5-1.5 parts of calcium-zinc composite stabilizer; 1-2 parts of ARC resin; 1-2 parts of titanium dioxide; 0-0.5 part of toner; 10-30 parts of MWCNT @ CB filler is extruded and blended by an extruder to obtain the polyvinyl chloride composite material with electromagnetic shielding and cold resistance. According to the invention, the uniform and stable industrial-grade low-cost carbon-series filler MWCNT @ CB is prepared firstly, the MWCNT @ CB can be uniformly dispersed in the polyvinyl chloride material, the electromagnetic shielding capability of the polyvinyl chloride material is improved, and the optimization of the high cold resistance of the composite material is realized by adding the reinforced cold-resistant modifier.
Description
Technical Field
The invention relates to the field of polyvinyl chloride modification and reinforcement, in particular to a preparation method of a polyvinyl chloride composite material which has electromagnetic shielding and cold resistance and can be used as a communication cable material.
Background
Polyvinyl chloride (PVC) resin is a plastic product widely used in current industrial production and people's life, and has abundant raw material sources, strong processability, excellent transparency, electrical insulation and excellent mechanical properties. However, polyvinyl chloride is an amorphous structure, has small branching degree and poor light stability and thermal stability, and a polyvinyl chloride material without any additive can generate oxidative decomposition reaction under the action of illumination and oxygen, and is easy to generate thermal decomposition reaction at a certain temperature so as to lose use value, and a polyvinyl chloride product has the defects of easy embrittlement, poor toughness, poor aging resistance and poor cold resistance and the like. Therefore, polyvinyl chloride is modified to have wider application, so that the polyvinyl chloride is widely applied to the fields of food packaging, pipeline lines, medical instruments and the like.
With the vigorous development of the 5G industry, the matched cable material is increasingly in vigorous demand. In order to reduce or inhibit the harm of electromagnetic radiation, the prepared polyvinyl chloride material with excellent electromagnetic shielding performance has excellent production prospect. However, the unmodified polyvinyl chloride material has little shielding effect on electromagnetic waves, and the polyvinyl chloride material has poor toughness at a lower temperature and is difficult to meet the use requirement of an extreme environment.
Therefore, in order to expand the application range of the polyvinyl chloride-based composite material in 5G system engineering and obtain a functional composite material with high performance and low cost, the polyvinyl chloride is generally required to be functionally modified. For example, the cold resistance of the polyvinyl chloride material can be obviously improved by adding a plasticizer and a modifier such as styrene and pre-crosslinked block nitrile rubber into the polyvinyl chloride. Meanwhile, the metal filler, the intrinsic conductive polymer or the carbon filler is compounded with the polymer matrix, so that the material can be endowed with electromagnetic shielding capability. Metal-filled shielding materials such as silver-based, copper-based, and nickel-based materials have been widely used for electromagnetic shielding because of their excellent conductivity. However, it has problems of high price, poor oxidation resistance, easy sinking in the polymer matrix, uneven dispersion and the like. The carbon filler has the advantages of wide source, light weight, relatively low cost, excellent mechanical property, easy molding and processing, high temperature resistance, excellent conductivity, unique photoelectric characteristics (such as conductive carbon black, carbon nano tubes and graphene) and the like, and the carbon filler can endow the polymer with excellent conductivity and simultaneously give the composite material with excellent comprehensive mechanical properties when being filled into a polymer matrix. The multi-wall carbon nano-tube (MWCNT) has a one-dimensional tubular structure and a larger length-diameter ratio, and is particularly suitable for being used as a conductive filler of an electromagnetic shielding material. But the problems of easy agglomeration of nano-filler, narrow shielding frequency band, reflection loss of a shielding mechanism and the like still exist at present.
Disclosure of Invention
The invention aims to provide a preparation method of a polyvinyl chloride composite material with electromagnetic shielding and cold resistance, which is characterized in that a uniform and stable industrial-grade low-price carbon-based filler MWCNT @ CB is prepared by a hybrid compounding technology, the MWCNT @ CB can be uniformly dispersed in the polyvinyl chloride material, the electromagnetic shielding capability of the polyvinyl chloride material is improved, meanwhile, a strengthening cold-resistant modifier is added, and the high-efficiency electromagnetic shielding and the optimization of the high cold resistance of the polyvinyl chloride composite material are realized through the improvement of equipment process and material composition.
The invention is realized by the following technical scheme, and the preparation method of the polyvinyl chloride composite material with electromagnetic shielding and cold resistance provided by the invention specifically comprises the following steps:
(1) Adding Carbon Black (CB), a multi-walled carbon nanotube (MWCNT), stearic acid and PE wax into a mixing type torque rheometer, and after blending, carrying out surface treatment on the filler by using a silane coupling agent to obtain the MWCNT @ CB filler;
(2) 90-110 parts of polyvinyl chloride (PVC) resin SG-3; 40-60 parts of an o-benzene plasticizer; 10-20 parts of impact modified resin; 0.5-1.5 parts of calcium-zinc composite stabilizer; 1-2 parts of ARC resin; 1-2 parts of titanium dioxide; 0-0.5 part of toner; 10-30 parts of MWCNT @ CB filler is extruded and blended by an extruder to obtain the polyvinyl chloride composite material with electromagnetic shielding and cold resistance.
Preferably, the parts by weight of the stearic acid and the PE wax in the step (1) are 10 parts, and the sum of the parts by weight of the Carbon Black (CB) and the multi-wall carbon nanotube (MWCNT) is 80 parts.
Preferably, the mass ratio of the multi-walled carbon nanotubes (MWCNT) to the Carbon Black (CB) in the step (1) is (1-5): (5-9).
Preferably, the temperature of the mixing type torque rheometer in step (1) is set to 180 ℃, the rotation speed of the rotor is 60 revolutions per minute, and the blending time is 10 minutes.
Preferably, the specific method for surface treatment of the filler with the silane coupling agent in the step (1) is as follows: adding the filler into a high-speed mixer, dropwise adding a silane coupling agent, wherein the adding mass of the silane coupling agent accounts for 5% of the mass of the filler, uniformly mixing in the high-speed mixer after the adding is finished, and then placing the treated filler into a vacuum oven to dry for 24 hours at 130 ℃. The silane coupling agent can be selected from one of A151 (vinyl triethoxysilane), A171 (vinyl trimethoxysilane) and A172 (vinyl tri (beta-methoxyethoxy) silane).
Preferably, the weight parts of the raw materials in the step (2) are as follows: 100 parts of PVC resin SG-3; 48 parts of an o-benzene plasticizer; 15 parts of impact modified resin; 0.9 part of calcium-zinc composite stabilizer; 1.5 parts of ARC resin; 1.5 parts of titanium dioxide; 0.2 part of toner; 20 parts of MWCNT @ CB filler.
Preferably, the extrusion process parameters in step (2) are: the average temperature of the inner tube is 175 ℃, the average temperature of the outer tube is 190 ℃, the oven temperature is 415 ℃, and the length-diameter ratio of the extruder screw is 1.
The invention also provides the polyvinyl chloride composite material obtained by the preparation method and application of the polyvinyl chloride composite material in manufacturing of cable outer sheath materials, especially communication cable outer sheath materials.
Compared with the prior art, the invention has obvious advantages and beneficial effects. By means of the technical scheme, the preparation method of the polyvinyl chloride composite material with electromagnetic shielding and cold resistance can achieve considerable technical progress and practicability, has wide utilization value, and at least has the following advantages:
the invention uses a nano material hybridization compounding technology to carry out large-scale compounding on industrial-grade cheap multi-walled carbon nanotubes (MWCNT) and cheap conductive Carbon Black (CB) according to different proportions, and prepares the MWCNT @ CB electromagnetic shielding filler of the one-dimensional carbon filler and the zero-dimensional carbon filler in batches. Meanwhile, the invention selects the commercially available acrylate-MMA copolymer (ARC) as the cold-resistant modifier, and adopts extrusion equipment to process and extrude polyvinyl chloride, the cold-resistant modifier ARC, the compounded surface-modified MWCNT @ CB nano powder and other raw materials, so that the MWCNT @ CB filler modified polyvinyl chloride composite material is prepared under specific conditions, the MWCNT @ CB is uniformly dispersed in a polyvinyl chloride matrix, the problem that the MWCNT is easy to agglomerate is solved, the dispersibility of the MWCNT @ CB electromagnetic shielding filler in the polyvinyl chloride matrix is improved, and the finally prepared polyvinyl chloride composite material has excellent electromagnetic shielding performance and cold resistance, can be applied to preparation of cable materials, and the electromagnetic shielding effect and the cold resistance of the cable materials are improved.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical means of the present invention more clearly understood, the present invention may be implemented in accordance with the content of the description, and in order to make the above and other objects, features, and advantages of the present invention more clearly understood, the following preferred embodiments are specifically described below with reference to the accompanying drawings.
Drawings
FIG. 1 is TEM image of MWCNT @ CB filler of different compounding ratios of example 3 and example 6, wherein, (a) represents MWCNT @ CB filler with mass ratio of MWCNT to CB of 1;
FIG. 2 is SEM topographic cross-section of the polyvinyl chloride composite material with electromagnetic shielding and cold resistance obtained in example 6 at different magnifications, wherein (a) is SEM topographic cross-section at low magnification and (b) is SEM topographic cross-section at high magnification;
FIG. 3 is a graph showing the electromagnetic shielding properties of the polyvinyl chloride composites obtained in examples 1 to 6.
Detailed Description
To make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions of the present invention will be clearly and completely described below with reference to specific embodiments and accompanying drawings. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without any inventive step, are within the scope of the present invention.
Unless otherwise specified, parts referred to herein are parts by weight.
Example 1
100 portions of PVC resin SG-3; 48 parts of an o-benzene plasticizer; 15 parts of impact modified resin; 0.9 part of calcium-zinc composite stabilizer; 1.5 parts of ARC resin; 1.5 parts of titanium dioxide; and 0.2 part of toner is extruded and blended by an extruder. The temperature of the extrusion process is as follows: average temperature of the inner tube was 175 ℃, average temperature of the outer tube was 190 ℃, oven temperature was 415 ℃, extruder type: the model phi 80 is a model, and the length-diameter ratio of the screw is 1.
TABLE 1 mechanical properties and Low temperature impact Properties of the polyvinyl chloride composite in example 1
| Detecting items | Technical requirements | The result of the detection |
| Tensile Strength (MPa) | ≥16.0 | 20.6 |
| Tensile strain at break (%) | ≥180 | 272 |
| Impact embrittlement performance (-40 ℃ C.) | Not less than 15/30 of the total weight of the steel plate | 24/30 non-breaking |
Table 1 shows the mechanical properties and low-temperature impact resistance of the extrudate obtained by adding the ARC resin in example 1, and it can be seen from Table 1 that the mechanical properties and low-temperature impact resistance of the polyvinyl chloride composite material obtained by adding the ARC resin both meet the technical requirements of national standard GB/T8815-2008, and the material has higher mechanical properties and low-temperature impact resistance after adding the ARC resin.
Example 2
(1) 80 parts of Carbon Black (CB); 10 parts of stearic acid; adding 10 parts of PE wax into a mixing type torque rheometer, setting the temperature to be 180 ℃, rotating the rotor at 60 rpm, blending for 10 minutes, and finally carrying out surface treatment on the obtained filler by using a silane coupling agent to obtain the MWCNT and the MWCNT @ CB (0.
The specific method for carrying out surface treatment on the filler by using the silane coupling agent in the step comprises the following steps: adding the filler into a high-speed mixer, dropwise adding a silane coupling agent, wherein the adding mass of the silane coupling agent accounts for 5% of the mass of the filler, uniformly mixing in the high-speed mixer after the adding is finished, and then placing the treated filler into a vacuum oven to dry for 24 hours at 130 ℃.
The silane coupling agent is selected from but not limited to one of A151 (vinyl triethoxysilane), A171 (vinyl trimethoxysilane) and A172 (vinyl tri (beta-methoxyethoxy) silane).
(2) 100 portions of PVC resin SG-3; 48 parts of an o-benzene plasticizer; 15 parts of impact modified resin; 0.9 part of calcium-zinc composite stabilizer; 1.5 parts of ARC resin; 1.5 parts of titanium dioxide; 0.2 part of toner; MWCNT @ CB (0). The temperature of the extrusion process is as follows: average temperature of the inner tube was 175 ℃, average temperature of the outer tube was 190 ℃, oven temperature was 415 ℃, extruder type: the model phi 80, the length-diameter ratio of the screw is 1. The polyvinyl chloride composite material with electromagnetic shielding and cold resistance is obtained.
Example 3
(1) 72 parts of Carbon Black (CB); 8 parts of multi-wall carbon nano-tube (MWCNT); 10 parts of stearic acid; adding 10 parts of PE wax into a mixing type torque rheometer, setting the temperature at 180 ℃, rotating the rotor at 60 rpm, blending for 10 minutes, and finally carrying out surface treatment on the filler by using a silane coupling agent to obtain the MWCNT @ CB (1. The surface treatment of the filler with the silane coupling agent was carried out in the same manner as in example 2.
(2) 100 portions of PVC resin SG-3; 48 parts of an o-benzene plasticizer; 15 parts of impact modified resin; 0.9 part of calcium-zinc composite stabilizer; 1.5 parts of ARC resin; 1.5 parts of titanium dioxide; 0.2 part of toner; 20 parts of MWCNT @ CB (1). The temperature of the extrusion process is as follows: average temperature of the inner tube was 175 ℃, average temperature of the outer tube was 190 ℃, oven temperature was 415 ℃, extruder type: the model phi 80, the length-diameter ratio of the screw is 1. The polyvinyl chloride composite material with electromagnetic shielding and cold resistance is obtained.
Example 4
(1) 64 parts of Carbon Black (CB); 16 parts of multi-wall carbon nano-tube (MWCNT); 10 parts of stearic acid; adding 10 parts of PE wax into a mixing type torque rheometer, setting the temperature to be 180 ℃, rotating the rotor at 60 rpm, blending for 10 minutes, and finally carrying out surface treatment on the filler by using a silane coupling agent to obtain the MWCNT @ CB (2. The surface treatment of the filler with the silane coupling agent was carried out in the same manner as in example 2.
(2) 100 parts of PVC resin SG-3; 48 parts of an o-benzene plasticizer; 15 parts of impact modified resin; 0.9 part of calcium-zinc composite stabilizer; 1.5 parts of ARC resin; 1.5 parts of titanium dioxide; 0.2 part of toner; MWCNT @ CB (2. The temperature of the extrusion process is as follows: average temperature of the inner tube was 175 ℃, average temperature of the outer tube was 190 ℃, oven temperature was 415 ℃, extruder model: the model phi 80, the length-diameter ratio of the screw is 1. The polyvinyl chloride composite material with electromagnetic shielding and cold resistance is obtained.
Example 5
(1) 56 parts of Carbon Black (CB); 24 parts of multi-wall carbon nanotubes (MWCNT); 10 parts of stearic acid; adding 10 parts of PE wax into a mixing type torque rheometer, setting the temperature at 180 ℃, rotating the rotor at 60 rpm, blending for 10 minutes, and finally carrying out surface treatment on the filler by using a silane coupling agent to obtain the MWCNT @ CB (3. The surface treatment of the filler with the silane coupling agent was carried out in the same manner as in example 2.
(2) 100 portions of PVC resin SG-3; 48 parts of an o-benzene plasticizer; 15 parts of impact modified resin; 0.9 part of calcium-zinc composite stabilizer; 1.5 parts of ARC resin; 1.5 parts of titanium dioxide; 0.2 part of toner; MWCNT @ CB (3). The temperature of the extrusion process is as follows: average temperature of the inner tube was 175 ℃, average temperature of the outer tube was 190 ℃, oven temperature was 415 ℃, extruder type: the model phi 80, the length-diameter ratio of the screw is 1. The polyvinyl chloride composite material with electromagnetic shielding and cold resistance is obtained.
Example 6
(1) 40 parts of Carbon Black (CB); 40 parts of multi-wall carbon nano-tube (MWCNT); 10 parts of stearic acid; adding 10 parts of PE wax into a mixing type torque rheometer, setting the temperature at 180 ℃, rotating the rotor at 60 rpm, blending for 10 minutes, and finally carrying out surface treatment on the filler by using a silane coupling agent to obtain the MWCNT @ CB (5). The surface treatment of the filler with the silane coupling agent was carried out in the same manner as in example 2.
(2) 100 portions of PVC resin SG-3; 48 parts of an o-benzene plasticizer; 15 parts of impact modified resin; 0.9 part of calcium-zinc composite stabilizer; 1.5 parts of ARC resin; 1.5 parts of titanium dioxide; 0.2 part of toner; MWCNT @ CB (5). The temperature of the extrusion process is as follows: average temperature of the inner tube was 175 ℃, average temperature of the outer tube was 190 ℃, oven temperature was 415 ℃, extruder type: phi 80 model, the length-diameter ratio of the screw is 1:30. the polyvinyl chloride composite material with electromagnetic shielding and cold resistance is obtained.
FIG. 1 is a TEM image of MWCNT @ CB fillers of examples 3 and 6 having different compounding ratios, wherein (a) is MWCNT @ CB filler having a MWCNT/CB mass ratio of 1: although the dispersibility of the filler in the matrix decreases with increasing content of multi-walled carbon nanotubes, the dispersibility is still better.
Fig. 2 is SEM topographic cross-sections of the pvc composite material with electromagnetic shielding and cold resistance obtained in example 6 at different magnifications, wherein (a) is SEM topographic cross-section at low magnifications, and (b) is SEM topographic cross-section at high magnifications, as shown in fig. 2: the MWCNT @ CB filler is well dispersed in the polyvinyl chloride matrix, and no obvious agglomeration phenomenon exists.
Fig. 3 is an electromagnetic shielding performance diagram of the polyvinyl chloride composite material obtained in examples 1-6, and it can be seen from fig. 3 that the electromagnetic shielding effect of the composite material added with the mwcnt @ cb filler is greatly improved, the electromagnetic shielding effect of the composite material is gradually increased along with the increase of the mass of the carbon nanotubes in the mwcnt @ cb filler, and the excellent electromagnetic shielding performance further illustrates that the mwcnt @ cb filler has excellent dispersibility in the composite material.
According to the invention, industrial-grade low-cost multi-walled carbon nanotubes (MWCNTs) and low-cost conductive Carbon Black (CB) are compounded in a large scale according to different proportions, MWCNT @ CB electromagnetic shielding fillers are prepared in batches, a commercially available acrylate-MMA copolymer (ARC) is selected as a cold-resistant modifier, raw materials are processed and extruded by adopting extrusion equipment, and the polyvinyl chloride composite material with electromagnetic shielding and high cold resistance is prepared under specific conditions, so that the dispersibility of the MWCNT @ CB electromagnetic shielding fillers in a polyvinyl chloride matrix is improved, the problem that the nano fillers are easy to agglomerate is solved, the finally prepared polyvinyl chloride composite material has excellent electromagnetic shielding performance and cold resistance, and the polyvinyl chloride composite material can be applied to preparation of a cable sheath material, and the electromagnetic shielding effect and the cold resistance of the cable sheath material are improved.
The above description is only an embodiment of the present invention, and is not intended to limit the present invention in any way, and the present invention may also have other embodiments according to the above structures and functions, and is not listed again. Therefore, any simple modification, equivalent change and modification of the above embodiments according to the technical essence of the present invention by those skilled in the art can be made within the technical scope of the present invention.
Claims (9)
1. A preparation method of a polyvinyl chloride composite material with electromagnetic shielding and cold resistance is characterized by comprising the following steps:
(1) Adding Carbon Black (CB), a multi-walled carbon nanotube (MWCNT), stearic acid and PE wax into a mixing type torque rheometer, and after blending, carrying out surface treatment on the filler by using a silane coupling agent to obtain the MWCNT @ CB filler;
(2) 90-110 parts of polyvinyl chloride (PVC) resin SG-3; 40-60 parts of an o-benzene plasticizer; 10-20 parts of impact modified resin; 0.5-1.5 parts of calcium-zinc composite stabilizer; 1-2 parts of ARC resin; 1-2 parts of titanium dioxide; 0-0.5 part of toner; 10-30 parts of MWCNT @ CB filler is extruded and blended by an extruder to obtain the polyvinyl chloride composite material with electromagnetic shielding and cold resistance.
2. The method for preparing polyvinyl chloride composite material with electromagnetic shielding and cold resistance as claimed in claim 1, wherein the weight parts of stearic acid and PE wax are 10 parts, and the sum of the weight parts of Carbon Black (CB) and multi-walled carbon nanotubes (MWCNT) is 80 parts.
3. The method for preparing a polyvinyl chloride composite material having electromagnetic shielding and cold resistance as claimed in claim 2, wherein the mass ratio of the multi-walled carbon nanotubes (MWCNT) to the Carbon Black (CB) is (1-5): (5-9).
4. The method for preparing polyvinyl chloride composite materials with electromagnetic shielding and cold resistance as claimed in claim 1 or 3, wherein the temperature of the mixing type torque rheometer in step (1) is set to 180 ℃, the rotation speed of the rotor is 60 rpm, and the blending time is 10 minutes.
5. The method for preparing polyvinyl chloride composite material with electromagnetic shielding and cold resistance as claimed in claim 4, wherein the specific method of surface treatment of the filler with silane coupling agent in step (1) is: adding the filler into a high-speed mixer, dropwise adding a silane coupling agent, wherein the adding mass of the silane coupling agent accounts for 5% of the mass of the filler, uniformly mixing in the high-speed mixer after the adding is finished, and then placing the treated filler into a vacuum oven to dry for 24 hours at 130 ℃.
6. The preparation method of the polyvinyl chloride composite material with electromagnetic shielding and cold resistance as claimed in claim 1, wherein the weight parts of the raw materials in the step (2) are: 100 parts of PVC resin SG-3; 48 parts of an o-benzene plasticizer; 15 parts of impact modified resin; 0.9 part of calcium-zinc composite stabilizer; 1.5 parts of ARC resin; 1.5 parts of titanium dioxide; 0.2 part of toner; 20 parts of MWCNT @ CB filler.
7. The method for preparing polyvinyl chloride composite material with electromagnetic shielding and cold resistance as claimed in claim 1 or 5, wherein the parameters of the extrusion process in step (2) are: the average temperature of the inner tube is 175 ℃, the average temperature of the outer tube is 190 ℃, the oven temperature is 415 ℃, and the length-diameter ratio of the extruder screw is 1.
8. A polyvinyl chloride composite material obtained by the production method as claimed in claim 1.
9. Use of the polyvinyl chloride composite obtained by the preparation method according to claim 1 in the preparation of cable materials.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211058990.5A CN115386179A (en) | 2022-08-31 | 2022-08-31 | Preparation method of polyvinyl chloride composite material with electromagnetic shielding and cold resistance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211058990.5A CN115386179A (en) | 2022-08-31 | 2022-08-31 | Preparation method of polyvinyl chloride composite material with electromagnetic shielding and cold resistance |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115386179A true CN115386179A (en) | 2022-11-25 |
Family
ID=84125464
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211058990.5A Pending CN115386179A (en) | 2022-08-31 | 2022-08-31 | Preparation method of polyvinyl chloride composite material with electromagnetic shielding and cold resistance |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115386179A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102675718A (en) * | 2012-05-25 | 2012-09-19 | 上海第二工业大学 | Ultralow-resistance organic positive temperature coefficient (PTC) composite material and preparation method thereof |
| CN104893178A (en) * | 2015-06-13 | 2015-09-09 | 合肥和安机械制造有限公司 | Collaborative antistatic cable material with conductive carbon black and CNTs (carbon nano-tubes) added as well as preparation method of cable material |
| CN106752490A (en) * | 2016-11-10 | 2017-05-31 | 无锡市明盛强力风机有限公司 | A kind of broadband electromagnetical shielding material |
| CN106832666A (en) * | 2017-01-22 | 2017-06-13 | 浙江同正管道技术有限公司 | Polyvinyl chloride pipe for electromagnetism interference and preparation method thereof |
| CN107629353A (en) * | 2017-09-18 | 2018-01-26 | 无锡市永兴金属软管有限公司 | A kind of PVC electric wire bellows and preparation method thereof |
| US20180127556A1 (en) * | 2015-04-17 | 2018-05-10 | Polyone - Shanghai, China | Masterbatch containing carbon nanotubes as black pigment |
-
2022
- 2022-08-31 CN CN202211058990.5A patent/CN115386179A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102675718A (en) * | 2012-05-25 | 2012-09-19 | 上海第二工业大学 | Ultralow-resistance organic positive temperature coefficient (PTC) composite material and preparation method thereof |
| US20180127556A1 (en) * | 2015-04-17 | 2018-05-10 | Polyone - Shanghai, China | Masterbatch containing carbon nanotubes as black pigment |
| CN104893178A (en) * | 2015-06-13 | 2015-09-09 | 合肥和安机械制造有限公司 | Collaborative antistatic cable material with conductive carbon black and CNTs (carbon nano-tubes) added as well as preparation method of cable material |
| CN106752490A (en) * | 2016-11-10 | 2017-05-31 | 无锡市明盛强力风机有限公司 | A kind of broadband electromagnetical shielding material |
| CN106832666A (en) * | 2017-01-22 | 2017-06-13 | 浙江同正管道技术有限公司 | Polyvinyl chloride pipe for electromagnetism interference and preparation method thereof |
| CN107629353A (en) * | 2017-09-18 | 2018-01-26 | 无锡市永兴金属软管有限公司 | A kind of PVC electric wire bellows and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| L LIU, 等: "Poly(tannin urethane)-Stabilized Multiwalled Carbon Nanotube Aqueous Dispersion for Antistatic Coating", 《INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH》, vol. 60, no. 33, pages 12353 - 12361 * |
| 刘西文，等: "《塑料挤出工（中、高级）培训教程》", 印刷工业出版社, pages: 21 - 22 * |
| 王婷，等: "碳系导电填料的导电橡胶研究进展", 《橡胶工业》, no. 6 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP6490580B2 (en) | Composite materials with very low content of carbon-based nanofillers, methods for their preparation and their use | |
| US9896564B2 (en) | Use of carbon-based nanofillers at a very low content for the UV stabilization of composite materials | |
| CN102675720A (en) | Macromolecule conductive master batches | |
| CN113105703B (en) | Modified conductive fluororubber, preparation method and conductive medium-resistant fluororubber sealing ring | |
| CN110791103B (en) | Novel conductive liquid silicone rubber and preparation method and application thereof | |
| CN110903531A (en) | Carbon nanotube modified polyolefin double-resistant material and preparation method and application thereof | |
| CN112679844A (en) | High-strength wear-resistant polypropylene composite material and preparation method thereof | |
| CN106279979A (en) | A kind of Graphene is combined shock resistance PP plastics and preparation method thereof | |
| CN106366423B (en) | A kind of antistatic eva foam composite material and preparation method | |
| CN106810878A (en) | A kind of High-performance electroconductive rubber composite and preparation method thereof | |
| CN109401253B (en) | Biodegradable toughened composite material and preparation method thereof | |
| CN102924763B (en) | Preparation method of high-modulus low-heat carbon nano tube/ rubber composite material | |
| CN115386179A (en) | Preparation method of polyvinyl chloride composite material with electromagnetic shielding and cold resistance | |
| CN110452479B (en) | Electric-conduction heat-conduction wear-resistant PVC (polyvinyl chloride) pipe and preparation method thereof | |
| EP3183287A1 (en) | Rubber products based on improved nbr masterbatch | |
| CN112409657A (en) | Improved conductive rubber composition and method for making same | |
| CN111748188A (en) | Ultrahigh-conductivity nano carbon master batch and preparation method and application thereof | |
| CN106221005A (en) | A kind of impact resistance increasing tougheness PP plastics and preparation method thereof | |
| CN111440398B (en) | Special material for ion-crosslinked polyvinyl chloride protection tube | |
| CN113943462A (en) | Conductive polymer composite material and preparation method and application thereof | |
| CN112625326A (en) | Preparation method of micro-crosslinked antistatic graphene-based polyethylene composite material | |
| CN103360678A (en) | Polypropylene/montmorillonite/graphite nanocomposite material and preparation method for same | |
| CN108485023B (en) | Polyethylene material, preparation method and product thereof | |
| CN112266488A (en) | Carbon nanotube/nylon composite material and preparation method and conductive application thereof | |
| CN112011160A (en) | High-toughness polymer-based temperature-sensitive composite material and preparation method and application 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 |