CN117700881A - Conductive polypropylene composite material and preparation method thereof - Google Patents
Conductive polypropylene composite material and preparation method thereof Download PDFInfo
- Publication number
- CN117700881A CN117700881A CN202311778866.0A CN202311778866A CN117700881A CN 117700881 A CN117700881 A CN 117700881A CN 202311778866 A CN202311778866 A CN 202311778866A CN 117700881 A CN117700881 A CN 117700881A
- Authority
- CN
- China
- Prior art keywords
- parts
- polypropylene composite
- composite material
- conductive
- cellulose fiber
- 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
- 239000004743 Polypropylene Substances 0.000 title claims abstract description 69
- -1 polypropylene Polymers 0.000 title claims abstract description 69
- 229920001155 polypropylene Polymers 0.000 title claims abstract description 69
- 239000002131 composite material Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 229920001046 Nanocellulose Polymers 0.000 claims abstract description 60
- 239000000835 fiber Substances 0.000 claims abstract description 60
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 44
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 44
- 239000007822 coupling agent Substances 0.000 claims abstract description 24
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 23
- 239000012745 toughening agent Substances 0.000 claims abstract description 16
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 9
- 230000004048 modification Effects 0.000 claims abstract description 9
- 238000012986 modification Methods 0.000 claims abstract description 9
- 239000011256 inorganic filler Substances 0.000 claims abstract description 7
- 229910003475 inorganic filler Inorganic materials 0.000 claims abstract description 7
- 230000002195 synergetic effect Effects 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 238000002156 mixing Methods 0.000 claims description 28
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 26
- 238000001816 cooling Methods 0.000 claims description 24
- 239000003963 antioxidant agent Substances 0.000 claims description 21
- 230000003078 antioxidant effect Effects 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 14
- 238000001125 extrusion Methods 0.000 claims description 13
- 238000001914 filtration Methods 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 13
- 238000010992 reflux Methods 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 11
- 238000005469 granulation Methods 0.000 claims description 11
- 230000003179 granulation Effects 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 9
- 239000002048 multi walled nanotube Substances 0.000 claims description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 8
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 8
- 150000004645 aluminates Chemical class 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- 239000002109 single walled nanotube Substances 0.000 claims description 6
- 239000000314 lubricant Substances 0.000 claims description 5
- 239000010445 mica Substances 0.000 claims description 5
- 229910052618 mica group Inorganic materials 0.000 claims description 5
- 239000000049 pigment Substances 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 4
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 claims description 4
- 239000012969 di-tertiary-butyl peroxide Substances 0.000 claims description 4
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 4
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 4
- 239000010456 wollastonite Substances 0.000 claims description 4
- 229910052882 wollastonite Inorganic materials 0.000 claims description 4
- 229920002943 EPDM rubber Polymers 0.000 claims description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 229920001903 high density polyethylene Polymers 0.000 claims description 3
- 239000004700 high-density polyethylene Substances 0.000 claims description 3
- 229920001684 low density polyethylene Polymers 0.000 claims description 3
- 239000004702 low-density polyethylene Substances 0.000 claims description 3
- 229920001935 styrene-ethylene-butadiene-styrene Polymers 0.000 claims description 3
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 239000000155 melt Substances 0.000 claims description 2
- 229910052623 talc Inorganic materials 0.000 claims description 2
- 239000000454 talc Substances 0.000 claims 1
- 239000011159 matrix material Substances 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 7
- 239000011347 resin Substances 0.000 abstract description 6
- 229920005989 resin Polymers 0.000 abstract description 6
- 239000002861 polymer material Substances 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 12
- 239000004594 Masterbatch (MB) Substances 0.000 description 10
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 9
- 239000008116 calcium stearate Substances 0.000 description 9
- 235000013539 calcium stearate Nutrition 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 6
- 239000000945 filler Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- 125000001165 hydrophobic group Chemical group 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229920003043 Cellulose fiber Polymers 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 2
- 238000007306 functionalization reaction Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000012612 commercial material Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229960003638 dopamine Drugs 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
Abstract
The invention discloses a conductive polypropylene composite material and a preparation method thereof, belonging to the technical field of high polymer materials; the conductive polypropylene composite material comprises the following raw materials in parts by mass: 37-90 parts of polypropylene, 0-20 parts of toughening agent, 0-40 parts of inorganic filler, 1-6 parts of compatilizer, 4-10 parts of modified nano cellulose fiber and 0.5-2 parts of other auxiliary agents; the modified nano cellulose fiber is formed by carrying out surface modification on the nano cellulose fiber by a carbon nano tube under the synergistic effect of a coupling agent and a cross-linking agent; the carbon nanotubes are uniformly distributed on the surfaces of the nano cellulose fibers, the interface conductive effect is better, the modified nano cellulose fibers are uniformly dispersed in the polypropylene resin matrix under the synergistic effect of the compatilizer, the dispersibility of the carbon nanotubes and the polypropylene resin matrix is improved, and the fibers are crisscrossed vertically and horizontally to form a complete conductive network, so that the conductive polypropylene composite material has excellent conductive function under the condition of small carbon nanotube addition amount and has excellent mechanical properties.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a conductive polypropylene composite material and a preparation method thereof.
Background
Polypropylene is one of the most widely used general plastics due to its high comprehensive cost performance, and can be used as electromagnetic shielding and wave absorbing material after conducting functional modification in various fields such as military, communication, aerospace and the like. The carbon-filled filler and the metal fiber powder are the main means for realizing the conductive functionalization. However, the carbon filler polymer matrix often has the problems of difficult dispersion and low conductive efficiency, and the metal filler has excellent conductive performance compared with the carbon filler, but the addition of the conductive filler greatly reduces the mechanical strength of the material, particularly has great influence on the toughness and elongation at break of the material, and greatly limits the application of the metal filler in conductive functionalization of the polymer due to the high density and high price of the metal filler.
In order to solve the problem, CN101759918A discloses a conductive polypropylene composite material, which can improve the conductivity of the polypropylene composite material, but the method needs to take linear low-density polyethylene as matrix resin and adopt silane coupling agent to carry out surface modification to prepare carbon black master batch, and then mix the carbon black master batch with the rest raw materials, so that the process is complex. CN 110256768A discloses a light high-toughness conductive polypropylene composite material, which uses conductive carbon black treated by dopamine surface modification to carry out surface modification, and improves the surface activity of the conductive carbon black, thereby enhancing the dispersion effect of the conductive carbon black in a polypropylene matrix; however, in order to achieve a good conductive effect, the addition amount is 5-20 parts, and the addition amount is still more.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a conductive polypropylene composite material and a preparation method thereof, which solve the problems in the prior art.
The aim of the invention can be achieved by the following technical scheme:
the conductive polypropylene composite material comprises the following raw materials in parts by mass: 37-89 parts of polypropylene, 0-20 parts of toughening agent, 0-40 parts of inorganic filler, 1-6 parts of compatilizer, 4-10 parts of modified nano cellulose fiber and 0.5-2 parts of other auxiliary agents;
the modified nano cellulose fiber is formed by carrying out surface modification on the nano cellulose fiber under the synergistic effect of a coupling agent and a crosslinking agent by using a carbon nano tube.
Further, the preparation process of the modified nano cellulose fiber comprises the following steps: firstly, a coupling agent, a cross-linking agent, a carbon nano tube and nano cellulose fiber are mixed according to the mass ratio of (1-5): (0.1-0.5): (1-5): (85.6-97.9) and evenly mixing, wherein the mass ratio is 2:5, placing the mixture in a carbon tetrachloride solvent, setting the temperature to be 80-100 ℃, stirring, refluxing and heating for 40-50min, cooling, filtering, washing with water and airing to obtain the product.
Further, the coupling agent is at least one of aluminate, titanate, KH550, KH560 and KH 570; the cross-linking agent is at least one of DCP, DTBP, TPB; the carbon nanotube is one of a single-walled carbon nanotube or a multi-walled carbon nanotube.
Further, the toughening agent is at least one of POE, EPDM, HDPE, LDPE, SEBS.
Further, the inorganic filler is at least one of talcum powder, calcium carbonate, wollastonite, magnesium sulfate whisker and mica.
Further, the compatilizer is at least one of PP-g-MAH, POE-g-MAH and SEBS-g-MAH.
Further, the other auxiliary agent is at least one of an antioxidant, a lubricant, a UV resistant agent and a pigment.
The preparation method of the conductive polypropylene composite material comprises the following steps:
s1, a coupling agent, a cross-linking agent, a carbon nano tube and nano cellulose fiber are mixed according to the mass ratio of (1-5): (0.1-0.5): (1-5): (85.6-97.9) and uniformly mixing, wherein the mass ratio is 2:5, placing the mixture in a carbon tetrachloride solvent, setting the temperature to be 80-100 ℃, stirring, refluxing and heating for 40-50min, cooling, filtering, washing with water and airing to obtain the modified nano cellulose fiber with the carbon nano tubes attached to the surface;
s2, fully blending 37-90 parts of polypropylene, 0-20 parts of toughening agent, 0-40 parts of inorganic filler, 1-6 parts of compatilizer, 4-10 parts of modified nano cellulose fiber and 0.5-2 parts of other auxiliary agents, adding into a main feeding port of a double-screw extruder, and carrying out melt extrusion, granulation, cooling and drying to obtain the modified nano cellulose.
Further, the other auxiliary agents comprise at least one of antioxidants, lubricants, UV-resistant agents and pigments.
Further, the screw rotating speed of the double-screw extruder is 300-500r/min, the double-screw extruder comprises one region to ten regions, wherein the one region is a blanking region, and the temperatures of the two regions to ten regions are respectively controlled as follows: the melt extrusion temperature is 190-220 ℃.
The invention has the beneficial effects that:
according to the conductive polypropylene composite material provided by the invention, the hydroxyl (-OH) on the surface of the carbon nano tube and the hydrophilic group of the coupling agent are subjected to chemical reaction to form firm chemical bonds, the hydrophobic group at the other end is of a long-chain structure, and the crosslinking reaction is carried out with the nano cellulose fiber under the action of the crosslinking agent, so that the carbon nano tube is uniformly distributed on the surface of the nano cellulose fiber, the conductive effect of an interface is better, the modified nano cellulose fiber is uniformly dispersed in a polypropylene resin matrix under the synergistic effect of the compatilizer, the dispersibility of the carbon nano tube and the fibers is improved, and the fibers are crisscrossed to form a complete conductive network, so that the conductive polypropylene composite material has an excellent conductive function under the condition of small carbon nano tube addition, and in addition, the prepared conductive polypropylene composite material has excellent mechanical property under the reinforcing effect of the nano cellulose fiber.
Detailed Description
The technical solutions of the present invention will be clearly and completely described below in conjunction with examples of the present invention and comparative examples, and it is apparent that the described examples are only some of the examples of the present invention, but not all of the examples. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the following examples and comparative examples, the polypropylene brand is M60RHC and the manufacturer is Yanshan petrochemical; the brand of nano cellulose fiber (CNF for short) is MFC, and the manufacturer is Zhejiang Hangzhou new material science and technology Co., ltd; the brand of the multiwall carbon nanotube is LUCAN BT1001M, and the manufacturer is LG chemistry; the brand of the single-wall carbon nano tube is MATRIX 808, and the manufacturer is OCSIAl; the talcum powder brand is AHCP250, and the manufacturer is Liaoning Ai Hai talcum Co., ltd; the brand of calcium carbonate is VS-625C, and the manufacturer is Dongguan brand five-plastic rubber products limited company; the mica powder has the brand name of AY-03N, the manufacturer is Jiangmen Jingda mica materials limited company, the wollastonite has the brand name of EP-215, and the manufacturer is Ningboenpi new materials science and technology limited company; the brand of the magnesium sulfate whisker is WS-1S, and the manufacturer is Yingkouweisi chemical Co., ltd; the coupling agent, the cross-linking agent, the toughening agent, the compatilizer, the antioxidant, the lubricant, the pigment and the weather-proof agent are all conventional commercial materials.
In addition, the parts referred to in examples and comparative examples are parts by mass.
Example 1
The preparation method of the conductive polypropylene composite material comprises the following steps:
s1, a coupling agent KH550, a cross-linking agent DCP, a single-walled carbon nanotube and a nano cellulose fiber are mixed according to a mass ratio of 1:0.1:1:97.9, and mixing evenly according to the mass ratio of 2: and 5, placing the mixture in a carbon tetrachloride solvent, setting the temperature to 90 ℃, stirring, refluxing and heating for 40min, cooling, filtering, washing with water and airing to obtain the modified nano cellulose fiber with the carbon nano tubes attached to the surface.
S2: 89 parts of polypropylene, 1 part of compatilizer PP-g-MAH, 10 parts of modified nano cellulose fiber with carbon nano tubes attached to the surface, 10100.2 parts of antioxidant, 1680.2 parts of antioxidant and 0.1 part of calcium stearate; fully blending, adding into a main feeding port of a double-screw extruder, and performing melt extrusion, granulation, cooling and drying to obtain the conductive polypropylene composite material;
wherein, the screw rod rotational speed of twin-screw extruder is 400r/min, and twin-screw extruder includes one district to ten district, and wherein one district is the unloading district, and two district to ten district's temperatures control respectively as: 190 ℃, 200 ℃, 210 ℃, 200 ℃.
Example 2
The preparation method of the conductive polypropylene composite material comprises the following steps:
s1: coupling agent KH560, cross-linking agent DTBP, single-wall carbon nano-tube and nano-cellulose fiber according to the mass ratio of 5:0.5:5:89.5, mixing uniformly, and mixing according to the mass ratio of 2: and 5, placing the mixture in a carbon tetrachloride solvent, setting the temperature to be 100 ℃, stirring, refluxing and heating for 50min, cooling, filtering and airing to obtain the modified nano cellulose fiber with the carbon nano tubes attached to the surface.
S2: 77 parts of polypropylene, 5 parts of toughening agent EPDM, 5 parts of calcium carbonate, 6 parts of compatilizer PP-g-MAH 2, 6 parts of modified nano cellulose fiber with carbon nano tubes attached to the surface, 10100.25 parts of antioxidant 1680.25 parts of antioxidant, 0.3 part of calcium stearate, 3808PP50.2 parts of UV-resistant agent and 1 part of black masterbatch are fully blended and then added into a main feeding port of a double-screw extruder, and the conductive polypropylene composite material is obtained through melt extrusion, granulation, cooling and drying;
wherein, the screw rod rotational speed of twin-screw extruder is 500r/min, and twin-screw extruder includes one district to ten district, and wherein one district is the unloading district, and two district to ten district's temperatures control respectively as: 190 ℃, 200 ℃, 210 ℃, 220 ℃, 210 ℃, 200 ℃.
Example 3
The preparation method of the conductive polypropylene composite material comprises the following steps:
s1: coupling agent KH570, cross-linking agent TPB, single-wall carbon nano-tube and nano-cellulose fiber according to mass ratio of 2:0.2:2:95.8, mixing evenly, and then mixing according to the mass ratio of 2: and 5, placing the mixture in a carbon tetrachloride solvent, setting the temperature to 80 ℃, stirring, refluxing and heating for 50min, cooling, filtering and airing to obtain the modified nano cellulose fiber with the carbon nano tubes attached to the surface.
S2: 64 parts of polypropylene, 10 parts of toughener HDPE, 15 parts of wollastonite, 3 parts of compatilizer POE-g-MAH, 8 parts of modified nano cellulose fiber with carbon nano tubes attached to the surface, 10100.25 parts of antioxidant 1680.25 parts of antioxidant, 0.3 part of calcium stearate and 1 part of black masterbatch are fully blended, and then added into a main feeding port of a double-screw extruder, and the conductive polypropylene composite material is obtained through melt extrusion, granulation, cooling and drying;
wherein, the screw rod rotational speed of twin-screw extruder is 300r/min, and twin-screw extruder includes one district to ten district, and wherein one district is the unloading district, and two district to ten district's temperatures control respectively as: 190 ℃, 210 ℃, 220 ℃, 210 ℃, 200 ℃.
Example 4
The preparation method of the conductive polypropylene composite material comprises the following steps:
the method comprises the steps of (1) mixing an aluminate coupling agent, a cross-linking agent DTBP, a multi-wall carbon nano tube and nano cellulose fiber according to a mass ratio of 3:0.3:3:93.7, and mixing evenly according to the mass ratio of 2: and 5, placing the mixture in a carbon tetrachloride solvent, setting the temperature to 80 ℃, stirring, refluxing and heating for 50min, cooling, filtering and airing to obtain the modified nano cellulose fiber with the carbon nano tubes attached to the surface.
S2: 37 parts of polypropylene, 15 parts of toughener LDPE, 40 parts of mica, 4 parts of compatilizer PP-g-MAH 4 parts of modified nano cellulose fiber with carbon nano tubes attached to the surface, 10100.25 parts of antioxidant, 1680.25 parts of antioxidant, 0.3 part of calcium stearate and 1 part of black matrix; fully blending, adding into a main feeding port of a double-screw extruder, and performing melt extrusion, granulation, cooling and drying to obtain the conductive polypropylene composite material;
wherein, the screw rod rotational speed of twin-screw extruder is 300r/min, and twin-screw extruder includes one district to ten district, and wherein one district is the unloading district, and two district to ten district's temperatures control respectively as: 190 ℃, 210 ℃, 220 ℃, 210 ℃, 200 ℃.
Example 5
The preparation method of the conductive polypropylene composite material comprises the following steps:
s1: titanate coupling agent, cross-linking agent TPB, multi-wall carbon nano tube and nano cellulose fiber according to the mass ratio of 4:0.4:4:85.6, mixing uniformly, and mixing according to the mass ratio of 2: and 5, placing the mixture in a carbon tetrachloride solvent, setting the temperature to 80 ℃, stirring, refluxing and heating for 50min, cooling, filtering and airing to obtain the modified nano cellulose fiber with the carbon nano tubes attached to the surface.
S2: 40 parts of polypropylene, 20 parts of a toughening agent SEBS, 30 parts of magnesium sulfate whisker, 5 parts of a compatilizer PP-g-MAH, 4 parts of modified nano cellulose fiber with carbon nano tubes attached to the surface, 10100.25 parts of an antioxidant 1680.25 parts of calcium stearate, 0.3 part of black masterbatch and 1 part of black masterbatch are fully blended and then added into a main feeding port of a double-screw extruder, and the conductive polypropylene composite material is obtained through melt extrusion, granulation, cooling and drying;
wherein, the screw rod rotational speed of twin-screw extruder is 400r/min, and twin-screw extruder includes one district to ten district, and wherein one district is the unloading district, and two district to ten district's temperatures control respectively as: 190 ℃, 210 ℃, 220 ℃, 210 ℃, 200 ℃.
Example 6
The preparation method of the conductive polypropylene composite material comprises the following steps:
s1: the method comprises the following steps of (1) mixing an aluminate coupling agent, a cross-linking agent DCP, multi-wall carbon nanotubes and nano cellulose fibers according to a mass ratio of 2:0.3:4:89.7, mixing evenly, and then mixing according to the mass ratio of 2: and 5, placing the mixture in a carbon tetrachloride solvent, setting the temperature to 80 ℃, stirring, refluxing and heating for 50min, cooling, filtering and airing to obtain the modified nano cellulose fiber with the carbon nano tubes attached to the surface.
S2: 58 parts of polypropylene, 8 parts of a toughening agent POE, 20 parts of talcum powder, 6 parts of a compatilizer SEBS-g-MAH, 8 parts of modified nano cellulose fiber with carbon nano tubes attached to the surface, 10100.25 parts of an antioxidant 1680.25 parts of calcium stearate, 0.3 part of black masterbatch and 1 part of black masterbatch are fully blended, and then added into a main feeding port of a double-screw extruder, and the conductive polypropylene composite material is obtained through melt extrusion, granulation, cooling and drying;
wherein, the screw rod rotational speed of twin-screw extruder is 400r/min, and twin-screw extruder includes one district to ten district, and wherein one district is the unloading district, and two district to ten district's temperatures control respectively as: 190 ℃, 210 ℃, 220 ℃, 210 ℃, 200 ℃.
Comparative example 1
The preparation method of the conductive polypropylene composite material comprises the following steps:
s1: the cross-linking agent DCP, the multi-wall carbon nano tube and the nano cellulose fiber are mixed according to the mass ratio of 0.3:4:89.7, mixing evenly, and then mixing according to the mass ratio of 2: and 5, placing the mixture in a carbon tetrachloride solvent, setting the temperature to 80 ℃, stirring, refluxing and heating for 50min, cooling, filtering and airing to obtain the modified nano cellulose fiber with the carbon nano tubes attached to the surface.
S2: the procedure is as in S2 of example 6.
Comparative example 2
The preparation method of the conductive polypropylene composite material comprises the following steps:
s1: the method comprises the following steps of (1) mixing an aluminate coupling agent, a multi-wall carbon nano tube and nano cellulose fiber according to a mass ratio of 2:4:89.7, mixing evenly, and then mixing according to the mass ratio of 2: and 5, placing the mixture in a carbon tetrachloride solvent, setting the temperature to 80 ℃, stirring, refluxing and heating for 50min, cooling, filtering and airing to obtain the modified nano cellulose fiber with the carbon nano tubes attached to the surface.
S2: the procedure is as in S2 of example 6.
Comparative example 3
A preparation method of a polypropylene composite material comprises the following steps:
s1: uniformly mixing an aluminate coupling agent, a cross-linking agent DCP and nano cellulose fibers according to the mass ratio of 2/5 after being uniformly mixed according to the mass ratio of 2/0.3/89.7, placing the mixture in a carbon tetrachloride solvent, setting the temperature to 80 ℃, stirring, refluxing and heating for 50min, cooling, filtering and airing to obtain the surface modified nano cellulose fibers.
S2: 58 parts of polypropylene, 8 parts of a toughening agent POE, 20 parts of talcum powder, 6 parts of a compatilizer SEBS-g-MAH, 8 parts of surface modified nano cellulose fiber, 10100.25 parts of an antioxidant, 1680.25 parts of an antioxidant, 0.3 part of calcium stearate and 1 part of black masterbatch are fully blended and then added into a main feeding port of a double-screw extruder, and the polypropylene composite material is obtained through melt extrusion, granulation, cooling and drying;
wherein, the screw rod rotational speed of twin-screw extruder is 400r/min, and twin-screw extruder includes one district to ten district, and wherein one district is the unloading district, and two district to ten district's temperatures control respectively as: 190 ℃, 210 ℃, 220 ℃, 210 ℃, 200 ℃.
Comparative example 4
A preparation method of a polypropylene composite material comprises the following steps:
58 parts of polypropylene, 8 parts of a toughening agent POE, 20 parts of talcum powder, 6 parts of a compatilizer SEBS-g-MAH, 8 parts of unmodified nano cellulose fiber, 10100.25 parts of an antioxidant, 1680.25 parts of an antioxidant, 0.3 part of calcium stearate and 1 part of black masterbatch; fully blending, adding into a main feeding port of a double-screw extruder, and performing melt extrusion, granulation, cooling and drying to obtain a polypropylene composite material;
wherein, the screw rod rotational speed of twin-screw extruder is 400r/min, and twin-screw extruder includes one district to ten district, and wherein one district is the unloading district, and two district to ten district's temperatures control respectively as: 190 ℃, 210 ℃, 220 ℃, 210 ℃, 200 ℃.
Comparative example 5
The preparation method of the conductive polypropylene composite material comprises the following steps:
58 parts of polypropylene, 8 parts of a toughening agent POE, 20 parts of talcum powder, 6 parts of a compatilizer SEBS-g-MAH, 10100.25 parts of an antioxidant 1680.25 parts of an antioxidant, 0.3 part of calcium stearate, 1 part of a black matrix and 8 parts of a system (mass ratio of an aluminate coupling agent, a cross-linking agent DCP and a multi-wall carbon nano tube 2:0.3:4); fully blending, adding into a main feeding port of a double-screw extruder, and performing melt extrusion, granulation, cooling and drying to obtain the modified polypropylene composite material; wherein, the screw rod rotational speed of twin-screw extruder is 400r/min, and twin-screw extruder includes one district to ten district, and wherein one district is the unloading district, and two district to ten district's temperatures control respectively as: 190 ℃, 210 ℃, 220 ℃, 210 ℃, 200 ℃.
The polypropylene composites prepared in examples 1 to 6 and comparative examples 1 to 5 were subjected to mechanical properties and surface resistivity tests, and the results are shown in Table 1.
TABLE 1 mechanical Properties and surface resistivity test Table for Polypropylene composite materials
As can be seen from Table 1, according to examples 1 to 6, the surface resistivity of the nanocellulose fibers after being surface-modified by carbon nanotubes, coupling agents and crosslinking agents is less than or equal to 10 < -5 > ohm/sq; the surface resistivity requirement of the conductive material is met, hydroxyl (-OH) on the surface of the carbon nano tube and hydrophilic groups of the coupling agent are subjected to chemical reaction to form firm chemical bonds, hydrophobic groups at the other end are of long-chain structures, and the hydrophobic groups and the nano cellulose fibers are subjected to crosslinking reaction under the action of the crosslinking agent, so that the carbon nano tube is uniformly distributed on the surface of the nano cellulose fibers, the surface conductive effect is better, the modified nano cellulose fibers are uniformly dispersed in the polypropylene resin matrix under the synergistic effect of the compatilizer, the dispersibility of the carbon nano tube and the hydrophilic groups of the coupling agent is improved, and the fibers are crisscrossed to form a complete conductive network, so that the conductive material has excellent conductive function under the condition of small carbon nano tube addition.
Example 6 and comparative examples 1 to 2 show that when the nanocellulose has not been sufficiently modified, the surface resistivity thereof cannot meet the requirement of 10 < -5 > ohm/sq, because the lack of the coupling agent does not allow the carbon nanotubes to have good compatibility with the nanocellulose and the polypropylene resin when the surface modification is performed on the carbon nanotubes and the nanocellulose, thereby affecting the dispersion of the carbon nanotubes as a conductive medium; when the cross-linking agent is absent, the carbon nano-tube cannot be well attached to the surface of the nano-cellulose, and the dispersion of the carbon nano-tube is also affected; so that the surface resistivity cannot be effectively reduced. As can be seen from examples 6 and comparative example 4, the unmodified nanocellulose fibers have limited enhancement of the mechanical properties of the whole system. As can be seen from comparative example 5, when carbon nanotubes were directly added, even if a large amount of carbon nanotubes were added, the powder particles were too small to be well dispersed, and thus the effect of reducing the surface resistivity could not be well exerted.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing has shown and described the basic principles, principal features and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, and that the above embodiments and descriptions are merely illustrative of the principles of the present invention, and various changes and modifications may be made without departing from the spirit and scope of the invention, which is defined in the appended claims.
Claims (10)
1. The conductive polypropylene composite material is characterized by comprising the following raw materials in parts by mass: 37-89 parts of polypropylene, 0-20 parts of toughening agent, 0-40 parts of inorganic filler, 1-6 parts of compatilizer, 4-10 parts of modified nano cellulose fiber and 0.5-2 parts of other auxiliary agents;
the modified nano cellulose fiber is formed by carrying out surface modification on the nano cellulose fiber under the synergistic effect of a coupling agent and a crosslinking agent by using a carbon nano tube.
2. The conductive polypropylene composite material according to claim 1, wherein the modified nanocellulose fibers are prepared by the following steps: firstly, a coupling agent, a cross-linking agent, a carbon nano tube and nano cellulose fiber are mixed according to the mass ratio of (1-5): (0.1-0.5): (1-5): (85.6-97.9) and evenly mixing, wherein the mass ratio is 2:5, placing the mixture in a carbon tetrachloride solvent, setting the temperature to be 80-100 ℃, stirring, refluxing and heating for 40-50min, cooling, filtering, washing with water and airing to obtain the product.
3. The conductive polypropylene composite according to claim 1 or 2, wherein the coupling agent is at least one of aluminate, titanate, KH550, KH560, KH 570; the cross-linking agent is at least one of DCP, DTBP, TPB; the carbon nanotube is one of a single-walled carbon nanotube or a multi-walled carbon nanotube.
4. The electrically conductive polypropylene composite material of claim 1, wherein the toughening agent is at least one of POE, EPDM, HDPE, LDPE, SEBS.
5. The conductive polypropylene composite material according to claim 1, wherein the inorganic filler is at least one of talc, calcium carbonate, wollastonite, magnesium sulfate whisker, and mica.
6. The conductive polypropylene composite of claim 1, wherein the compatibilizer is at least one of PP-g-MAH, POE-g-MAH, SEBS-g-MAH.
7. The conductive polypropylene composite according to claim 1, wherein the other auxiliary agent is at least one of an antioxidant, a lubricant, a UV resistant agent, and a pigment.
8. The preparation method of the conductive polypropylene composite material is characterized by comprising the following steps of:
s1, a coupling agent, a cross-linking agent, a carbon nano tube and nano cellulose fiber are mixed according to the mass ratio of (1-5): (0.1-0.5): (1-5): (85.6-97.9) and uniformly mixing, wherein the mass ratio is 2:5, placing the mixture in a carbon tetrachloride solvent, setting the temperature to be 80-100 ℃, stirring, refluxing and heating for 40-50min, cooling, filtering, washing with water and airing to obtain the modified nano cellulose fiber with the carbon nano tubes attached to the surface;
s2, fully blending 37-90 parts of polypropylene, 0-20 parts of toughening agent, 0-40 parts of inorganic filler, 1-6 parts of compatilizer, 4-10 parts of modified nano cellulose fiber and 0.5-2 parts of other auxiliary agents, adding into a main feeding port of a double-screw extruder, and carrying out melt extrusion, granulation, cooling and drying to obtain the modified nano cellulose.
9. The method for preparing a conductive polypropylene composite according to claim 8, wherein the other auxiliary agent comprises at least one of an antioxidant, a lubricant, a UV-resistant agent, and a pigment.
10. The method for preparing a conductive polypropylene composite material according to claim 8, wherein the screw speed of the twin-screw extruder is 300-500r/min, the twin-screw extruder comprises one region to ten regions, wherein the one region is a blanking region, and the temperatures of the two regions to ten regions are respectively controlled as follows: the melt extrusion temperature is 190-220 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311778866.0A CN117700881A (en) | 2023-12-22 | 2023-12-22 | Conductive polypropylene composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311778866.0A CN117700881A (en) | 2023-12-22 | 2023-12-22 | Conductive polypropylene composite material and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117700881A true CN117700881A (en) | 2024-03-15 |
Family
ID=90151358
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311778866.0A Pending CN117700881A (en) | 2023-12-22 | 2023-12-22 | Conductive polypropylene composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117700881A (en) |
-
2023
- 2023-12-22 CN CN202311778866.0A patent/CN117700881A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US7566749B2 (en) | Conductive thermosets by extrusion | |
| CN102585348B (en) | Toughened conducting material and preparation method for toughened conducting material | |
| CN102585349A (en) | Antistatic material, preparation method and applications of antistatic material | |
| CN104513410A (en) | Preparation method of pre-dispersed carbon nano-tube rubber masterbatches | |
| CN106674825B (en) | A kind of preparation method and masterbatch of graphene/PVC composite material masterbatch | |
| KR101183016B1 (en) | Carbon Nanotube-polymer Nanocomposite Improved In Electrical Conductivity And Preparation Method Thereof | |
| CN112538219A (en) | Polypropylene composition and preparation method thereof | |
| CN111732778B (en) | Preparation method of high-thermal-conductivity composite material | |
| KR101164287B1 (en) | Carbon Nanotube-polymer Nanocomposite Improved In Electrical Conductivity And Preparation Method Thereof | |
| CN111286108B (en) | Anti-sagging master batch for plastic pipes and preparation method and application thereof | |
| CN112724512A (en) | Preparation method of nano-cellulose polypropylene master batch | |
| CN1704447A (en) | Conductive composite materials with positive temperature coefficient effect and process for making same | |
| CN111073040B (en) | Preparation method of HGM-CNTs bonding substance and light antistatic polypropylene material | |
| CN112080067B (en) | High-filling filler modified polyolefin composite material and preparation method and application thereof | |
| CN117700881A (en) | Conductive polypropylene composite material and preparation method thereof | |
| CN115850851B (en) | Modified polypropylene composite material and preparation method thereof | |
| CN106751332A (en) | A kind of high conductivity degradable plastic sheeting composite of carbon nanotubes and preparation method thereof | |
| CN111748188A (en) | Ultrahigh-conductivity nano carbon master batch and preparation method and application thereof | |
| CN112341747A (en) | Carbon nanotube modified permanent antistatic ABS material and preparation method thereof | |
| CN106589866A (en) | PCL conductive shapable material and preparation method thereof | |
| CN112500635B (en) | Polypropylene-carbon-based composite material capable of being subjected to microwave self-repairing and preparation method thereof | |
| CN112552581A (en) | Conductive thermoplastic elastomer composite material and preparation method thereof | |
| CN101928401A (en) | Method for preparing polyolefin/carbon nano tube composite material by water cross-linking reaction | |
| CN115678170A (en) | Conductive TPV (thermoplastic vulcanizate) elastic material and preparation method thereof | |
| CN117304609A (en) | Polypropylene composite material with high yield and elongation and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination |