CN115216145A - High-impact-resistance conductive polyamide composite material - Google Patents
High-impact-resistance conductive polyamide composite material Download PDFInfo
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- CN115216145A CN115216145A CN202110848340.XA CN202110848340A CN115216145A CN 115216145 A CN115216145 A CN 115216145A CN 202110848340 A CN202110848340 A CN 202110848340A CN 115216145 A CN115216145 A CN 115216145A
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- 239000004952 Polyamide Substances 0.000 title claims abstract description 56
- 229920002647 polyamide Polymers 0.000 title claims abstract description 56
- 239000002131 composite material Substances 0.000 title claims abstract description 51
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 31
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 31
- 239000000835 fiber Substances 0.000 claims abstract description 30
- 239000000314 lubricant Substances 0.000 claims abstract description 19
- 229920006122 polyamide resin Polymers 0.000 claims abstract description 9
- 239000012763 reinforcing filler Substances 0.000 claims abstract description 9
- 239000003365 glass fiber Substances 0.000 claims description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 239000002109 single walled nanotube Substances 0.000 claims description 9
- 239000002079 double walled nanotube Substances 0.000 claims description 8
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 8
- 239000002048 multi walled nanotube Substances 0.000 claims description 8
- -1 PA56 Polymers 0.000 claims description 5
- 239000003063 flame retardant Substances 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 239000004953 Aliphatic polyamide Substances 0.000 claims description 4
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- 229920006152 PA1010 Polymers 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 229920003231 aliphatic polyamide Polymers 0.000 claims description 4
- 150000001413 amino acids Chemical class 0.000 claims description 4
- 150000004985 diamines Chemical class 0.000 claims description 4
- 239000000945 filler Substances 0.000 claims description 4
- 150000003951 lactams Chemical class 0.000 claims description 4
- 229920006119 nylon 10T Polymers 0.000 claims description 4
- 229920006111 poly(hexamethylene terephthalamide) Polymers 0.000 claims description 4
- 229920006012 semi-aromatic polyamide Polymers 0.000 claims description 4
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 claims description 3
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 3
- 229920002292 Nylon 6 Polymers 0.000 claims description 3
- 229920002302 Nylon 6,6 Polymers 0.000 claims description 3
- 239000004917 carbon fiber Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 238000001746 injection moulding Methods 0.000 claims description 3
- 239000005995 Aluminium silicate Substances 0.000 claims description 2
- 229920002748 Basalt fiber Polymers 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- 241000208202 Linaceae Species 0.000 claims description 2
- 235000004431 Linum usitatissimum Nutrition 0.000 claims description 2
- 229920003189 Nylon 4,6 Polymers 0.000 claims description 2
- 229920006153 PA4T Polymers 0.000 claims description 2
- 239000012963 UV stabilizer Substances 0.000 claims description 2
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- 150000008431 aliphatic amides Chemical class 0.000 claims description 2
- 235000012211 aluminium silicate Nutrition 0.000 claims description 2
- 239000003963 antioxidant agent Substances 0.000 claims description 2
- 229960000892 attapulgite Drugs 0.000 claims description 2
- 239000011324 bead Substances 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- 150000007942 carboxylates Chemical class 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
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- 238000000748 compression moulding Methods 0.000 claims description 2
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- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- 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 claims description 2
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 150000004665 fatty acids Chemical class 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 239000012760 heat stabilizer Substances 0.000 claims description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- 239000003607 modifier Substances 0.000 claims description 2
- 239000006082 mold release agent Substances 0.000 claims description 2
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 2
- 229910052625 palygorskite Inorganic materials 0.000 claims description 2
- 229920006131 poly(hexamethylene isophthalamide-co-terephthalamide) Polymers 0.000 claims description 2
- 229920006396 polyamide 1012 Polymers 0.000 claims description 2
- 229920006123 polyhexamethylene isophthalamide Polymers 0.000 claims description 2
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 2
- 229920006024 semi-aromatic copolyamide Polymers 0.000 claims description 2
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 2
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 2
- 239000000344 soap Substances 0.000 claims description 2
- 239000010456 wollastonite Substances 0.000 claims description 2
- 229910052882 wollastonite Inorganic materials 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- 239000012765 fibrous filler Substances 0.000 claims 2
- 238000006068 polycondensation reaction Methods 0.000 claims 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims 1
- 125000001931 aliphatic group Chemical group 0.000 claims 1
- 229920001296 polysiloxane Polymers 0.000 claims 1
- 230000001105 regulatory effect Effects 0.000 abstract description 5
- 230000001276 controlling effect Effects 0.000 abstract description 3
- 239000012745 toughening agent Substances 0.000 description 15
- 239000000463 material Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 239000011231 conductive filler Substances 0.000 description 6
- 238000011056 performance test Methods 0.000 description 6
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- 238000000465 moulding Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000001143 conditioned effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000004677 Nylon Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000007796 conventional method Methods 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
- 238000001035 drying Methods 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000007373 indentation Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
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- 229920001955 polyphenylene ether Polymers 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
-
- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
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- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/10—Reinforcing macromolecular compounds with loose or coherent fibrous material characterised by the additives used in the polymer mixture
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
- C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- C—CHEMISTRY; METALLURGY
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
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- 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
- C08K7/00—Use of ingredients characterised by shape
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Abstract
The invention discloses a high-impact-resistance conductive polyamide composite material which comprises the following components in parts by weight: 60 to 100 parts of polyamide resin, 0 to 40 parts of reinforcing filler, 3 to 15 parts of conductive fiber, 0.03 to 1 part of carbon nanotube and 0.15 to 10 parts of lubricant; the dosage ratio of the lubricant to the carbon nano tube is 5 to 1. According to the invention, proper carbon nanotubes are introduced into a conductive fiber/polyamide system, and the excellent conductivity and good impact toughness of the polyamide composite material are endowed by regulating and controlling the dosage ratio of the carbon nanotubes and the lubricant, so that the application range of the polyamide composite material is further widened.
Description
Technical Field
The invention relates to the technical field of modification of high polymer materials, in particular to a high-impact-resistance conductive polyamide composite material.
Background
Based on the continuous development of the automobile industry, the polyamide composite material with excellent conductivity and good impact resistance has a wide application prospect, so that how to provide the high-impact-resistance conductive polyamide composite material is a problem to be solved urgently by the technical staff in the field.
The surface resistivity of the polyamide is generally 10 14 ～10 15 Omega, is an excellent insulator. In order to endow the polyamide composite material with excellent electric conductivity and impact resistance, the conventional technical means is to simultaneously introduce conductive fillers and a toughening agent into a polyamide matrix, and when the conductive fillers such as conductive carbon black, carbon fibers, metal powder or carbon nano tubes and the like are added into the polyamide matrix, the reduction of the impact resistance of the polyamide material can be further promoted due to the addition of the conductive fillers, so that the polyamide composite material has good impact resistance, and the addition amount of the toughening agent is relatively large. For example, chinese patent CN111019341A discloses a toughened conductive flame-retardant polyamide 6 composite material, which adopts conductive carbon black and carbon nanotubes (single-walled carbon nanotubes or multi-walled carbon nanotubes) as conductive fillers, adopts POE grafted MAH as a toughening agent, the dosage of the toughening agent is up to 9%, and the impact strength of the prepared polyamide composite material is only 5.5 to 6.5KJ/m 2 . Chinese patent CN102702721AA high-flowability high-toughness conductive polyphenylene ether polyamide composition is prepared through using carbon nanotube as conductive filler, introducing toughening agent to prevent the impact resistance of material from being reduced by adding carbon nanotube, and using 5% of toughening agent to obtain composite material with notch impact strength up to 7.9 KJ/m 2 . Chinese patent CN101870812A discloses a conductive nylon 66 material and a preparation method thereof, wherein carbon nano tubes are used as conductive fillers, a toughening agent is also added to ensure that the material has good impact resistance, and when the dosage of the toughening agent is 4.5%, the notch impact strength of the nylon material is 9.5 KJ/m 2 . However, when the toughening agent is added, the fluidity and the heat resistance of the polyamide composite material are reduced, and the application range of the polyamide composite material is limited.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a high-impact-resistance conductive polyamide composite material which can obviously improve the impact resistance toughness of the material without adding a toughening agent.
The purpose of the invention is realized by the following technical scheme:
a high impact conductive polyamide composite material comprises the following components in parts by weight:
60 to 100 parts of polyamide resin,
0 to 40 parts of a reinforcing filler,
3 to 15 parts of conductive fiber,
0.03 to 1 part of carbon nano tube,
0.15 to 10 portions of lubricant;
wherein the dosage ratio of the lubricant to the carbon nano tube is 5 to 1; the carbon nano tube is selected from one or a plurality of single-wall carbon nano tubes, double-wall carbon nano tubes and multi-wall carbon nano tubes with the length more than 5 mu m.
The polyamide resin is formed by gradually polycondensing diamine and dibasic acid, or by ring-opening polymerization of lactam, or by gradually polycondensing amino acid, or by copolymerization of diamine, dibasic acid, lactam and amino acid.
Preferably, the polyamide resin is selected from one or more of aliphatic polyamide, semi-aromatic polyamide and copolyamide; the aliphatic polyamide is selected from at least one of PA6, PA66, PA46, PA56, PA11, PA12, PA610, PA612, PA1010, PA1012 and PA1212, the semi-aromatic polyamide is selected from at least one of PA4T, PA6T, PA T, PA T, PA6I, MXD, and the copolyamide is selected from at least one of PA66/6, PA6T/6I, PA T/66, PA10T/PA1010, PA6T/PA610 and PA10T/PA 1012.
The reinforcing filler is selected from fiber filler, inorganic mineral powder or a compound of the fiber filler and the inorganic mineral powder; the fiber filler is selected from one or more of glass fiber, basalt fiber, potassium titanate fiber and flax fiber; the inorganic mineral powder is selected from one or more of talcum powder, wollastonite, mica, calcium carbonate, attapulgite, montmorillonite, zeolite, kaolin and glass beads.
The conductive fiber is selected from one or more of metal fiber, carbon fiber, metal-plated boron fiber and metal-plated silicon carbide fiber.
The lubricant is selected from one or more of saturated hydrocarbon, metal soap, aliphatic amide, organosilicon, fatty acid, fatty acetic acid, fatty alcohol and long-chain saturated linear carboxylate lubricant.
The polyamide composite material prepared by the invention has excellent electric conductivity and good impact toughness, and can meet the application requirements of the automobile industry. The inventor surprisingly finds that by introducing appropriate carbon nanotubes into a conductive fiber filled modified polyamide composite material system and regulating the use amounts of the carbon nanotubes and a lubricant, the conductivity of the composite material is improved, and meanwhile, the composite material can be endowed with excellent impact toughness without adding a toughening agent. Compared with a formula system only adding conductive fibers without a toughening agent, the unnotched impact strength of the composite material can be improved by more than 50 percent and even higher; the notch impact strength can be improved by nearly 50 percent.
Preferably, the high-impact-resistance conductive polyamide composite material comprises the following components in parts by weight:
60 to 80 parts of polyamide resin,
20-40 parts of a reinforcing filler,
3 to 15 parts of conductive fiber,
0.03 to 0.5 portion of carbon nano tube,
0.15 to 5 parts of a lubricant;
wherein the reinforcing filler is glass fiber or a compound of the glass fiber and inorganic mineral powder; the dosage ratio of the lubricant to the carbon nano tube is 1 to 5 to 1.
Further preferably, the carbon nanotube is a single-walled carbon nanotube or a double-walled carbon nanotube having a diameter of less than 6 nm.
Introducing a small amount of single-wall carbon nano tubes or double-wall carbon nano tubes with the diameter less than 6nm into a glass fiber reinforced conductive fiber filled modified polyamide system, simultaneously regulating and controlling the using amount and the proportion of a lubricant and the carbon nano tubes, and under the condition of no addition of a toughening agent, the prepared conductive polyamide composite material has the unnotched impact strength as high as 95 KJ/m 2 The notch impact strength can reach 14.1 KJ/m 2 。
The high impact conductive polyamide composite material of the present invention may further comprise other components selected from one or more of flame retardants, flame retardant synergists, anti-dripping agents, flow modifiers, colorants, antioxidants, heat stabilizers, UV stabilizers, and mold release agents, according to the actual performance requirements.
The invention also provides an application of the high-impact-resistance conductive polyamide composite material, and particularly relates to a lightweight product prepared from the high-impact-resistance conductive polyamide composite material through compression molding or injection molding and applied to structural members of automobiles and rail transit.
Compared with the prior art, the invention has the beneficial effects that: according to the invention, a small amount of proper carbon nano tubes are introduced into a conductive fiber filled modified polyamide system, and the use amounts of the carbon nano tubes and the lubricant are regulated and controlled, so that the conductivity of the polyamide composite material can be greatly improved, the polyamide composite material can be endowed with good impact toughness under the condition of no toughening agent, and the conventional method of improving the toughness of the composite material by adding the toughening agent in the past is abandoned. The prepared polyamide composite material has excellent conductivity and impact toughness, and the application range of the polyamide composite material in the fields of automobiles and rail transit is widened.
Detailed Description
The present invention is further illustrated by the following embodiments, which are preferred embodiments of the present invention, and a person skilled in the art can analyze and understand the embodiments and make a series of modifications and equivalent substitutions on the technical solution provided by the present invention in combination with the prior knowledge, and the new technical solution obtained by the modifications and equivalent substitutions is also included by the present invention.
The examples and comparative examples used the following starting materials:
carbon nanotube 1: the single-walled carbon nanotube (XFS 26) has the diameter of 4 to 5nm and the length of 0.5 to 5 mu m, and is produced by Jiangsu Xiancheng nanometer material science and technology limited.
And (2) carbon nanotube: double-walled carbon nanotubes (CNT 110) having a diameter of 2 to 4nm and a length of 5 to 15 μm, manufactured by Beijing Dekko island gold technologies, ltd.
Carbon nanotube 3: the multi-wall carbon nano-tube (MWNT-10) has the diameter of 7 to 15nm and the length of more than 5 mu m, shenzhen nano-harbor Limited.
And (3) carbon nano tube 4: the multi-walled carbon nano-tube (S-MWNT-1020) has the diameter of 10 to 20nm and the length of less than 2 mu m, shenzhen nano-gang Limited company.
The rest raw materials are all sold in the market.
The present invention will be further described with reference to examples 1 to 11 and comparative examples 1 to 9.
The following examples and comparative examples were prepared according to the following methods for testing the properties of polyamide composite materials:
(1) Surface resistivity: according to IEC60093, disks with a diameter of 100mm and a thickness of 3mm were prepared by moulding, and the surface resistance test was carried out after conditioning the test pieces in a standard environmental climate of 23 ℃ and 50% RH for 12h, at a test voltage of 500V for 1min.
(2) Unnotched impact strength: test specimens 80mm long, 10mm wide and 4mm thick were prepared by moulding according to ISO179, conditioned for 12h in standard ambient climate 23 ℃,50% RH and then subjected to unnotched impact strength test with pendulum energy 4J.
(3) Notched impact strength: test specimens 80mm long, 10mm wide and 4mm thick were prepared by moulding according to ISO179, cut to type A indentations using a notch prototype, conditioned for 12h in standard environmental climate 23 ℃,50% RH and then subjected to unnotched impact strength test with pendulum energy 1J.
Examples 1 to 11
According to the weight portion ratio shown in the table 1, other components except the glass fiber are uniformly mixed, the materials are discharged from a main feeding port of a double-screw extruder, the glass fiber is discharged from a side feeding port of the double-screw extruder, and the materials are melted, mixed, extruded, cooled and granulated through the double-screw extruder to obtain the glass fiber. The length-diameter ratio of the twin-screw extruder is 40, and the screw rotating speed is 280r/min. Drying the prepared finished product particles in a vacuum drying oven at 80 ℃ for 5-8 h, molding and punching corresponding performance test standard sample strips in an injection molding machine, and carrying out performance test, wherein the test results are shown in table 1.
Table 1 examples 1 to 11 formulation components of polyamide composite materials and performance test results
Comparative examples 1 to 9
The raw material components were weighed according to the weight parts ratios described in table 2, and the preparation method and the detection method were the same as in the above examples. The results of the performance tests of comparative examples 1 to 9 are shown in Table 2.
TABLE 2 comparative example 1~9 Polyamide composite formulation and Performance test results
From the results of the performance tests of examples 1 to 11 in Table 1 and comparative example 1~9 in Table 2, it can be seen that: compared with a polyamide system filled with pure conductive fibers and a polyamide system modified by compounding conductive fibers and other conductive agents, a small amount of single-walled carbon nanotubes, double-walled carbon nanotubes or multi-walled carbon nanotubes with the length of more than 5 mu m are introduced into the conductive fiber/polyamide system, so that the polyamide composite material can be endowed with excellent conductive performance, and the impact toughness of the polyamide composite material can be remarkably improved; for a glass fiber reinforced conductive fiber/polyamide composite material system, when a single-wall carbon nano tube, a double-wall carbon nano tube or a multi-wall carbon nano tube with the length more than 5 mu m is introduced, the impact toughness of the prepared polyamide composite material is better than that of a non-conductive glass fiber reinforced polyamide composite material by regulating and controlling the dosage ratio of the carbon nano tube and a lubricant.
Although the above embodiments have described the design idea of the present invention in more detail, these descriptions are only simple descriptions of the design idea of the present invention, and are not limitations of the design idea of the present invention, and any combination, addition, or modification without departing from the design idea of the present invention falls within the protection scope of the present invention.
Claims (10)
1. The high-impact-resistance conductive polyamide composite material is characterized by comprising the following components in parts by weight:
60 to 100 parts of polyamide resin,
0 to 40 parts of a reinforcing filler,
3 to 15 parts of conductive fiber,
0.03 to 1 part of carbon nano tube,
0.15 to 10 portions of lubricant;
wherein the dosage ratio of the lubricant to the carbon nano tube is 5 to 1; the carbon nano tube is selected from one or a plurality of single-wall carbon nano tubes, double-wall carbon nano tubes and multi-wall carbon nano tubes with the length more than 5 mu m.
2. The high impact conductive polyamide composite material according to claim 1, wherein the polyamide resin is prepared by stepwise polycondensation of diamine and dibasic acid, or ring-opening polymerization of lactam, or stepwise polycondensation of amino acid, or copolymerization of diamine, dibasic acid, lactam and amino acid.
3. The high impact conductive polyamide composite material according to claim 2, wherein the polyamide resin is selected from one or more of aliphatic polyamide, semi-aromatic polyamide, and copolyamide; the aliphatic polyamide is selected from at least one of PA6, PA66, PA46, PA56, PA11, PA12, PA610, PA612, PA1010, PA1012 and PA1212, the semi-aromatic polyamide is selected from at least one of PA4T, PA6T, PA T, PA T, PA6I, MXD, and the copolyamide is selected from at least one of PA66/6, PA6T/6I, PA T/66, PA10T/PA1010, PA6T/PA610 and PA10T/PA 1012.
4. The high impact conductive polyamide composite material according to claim 1, wherein the reinforcing filler is selected from a fibrous filler, inorganic mineral powder or a combination of a fibrous filler and inorganic mineral powder; the fiber filler is selected from one or more of glass fiber, basalt fiber, potassium titanate fiber and flax fiber; the inorganic mineral powder is selected from one or more of talcum powder, wollastonite, mica, calcium carbonate, attapulgite, montmorillonite, zeolite, kaolin and glass beads.
5. The high impact conductive polyamide composite material according to claim 1, wherein the conductive fibers are selected from one or more of metal fibers, carbon fibers, metal-plated boron fibers, and metal-plated silicon carbide fibers.
6. The high impact conductive polyamide composite material according to claim 1, wherein the lubricant is one or more selected from the group consisting of saturated hydrocarbon, metal soap, aliphatic amide, silicone, fatty acid, aliphatic acetate, aliphatic alcohol, and long chain saturated linear carboxylate lubricants.
7. The high impact conductive polyamide composite material according to claim 1, characterized by comprising the following components in parts by weight:
60 to 80 parts of polyamide resin,
20-40 parts of a reinforcing filler,
3 to 15 parts of conductive fiber,
0.03 to 0.5 portion of carbon nano tube,
0.15 to 5 parts of a lubricant;
wherein the reinforcing filler is glass fiber or a compound of the glass fiber and inorganic mineral powder; the dosage ratio of the lubricant to the carbon nano tube is 1 to 5 to 1.
8. The high impact conductive polyamide composite of claim 7, characterized in that the carbon nanotubes are single-walled carbon nanotubes or double-walled carbon nanotubes with a diameter < 6 nm.
9. The high impact conductive polyamide composite of any one of claims 1~8 further comprising an additional component selected from one or more of flame retardants, flame retardant synergists, anti-drip agents, flow modifiers, colorants, antioxidants, heat stabilizers, UV stabilizers, mold release agents.
10. The use of the high impact conductive polyamide composite material according to claim 1, wherein the high impact conductive polyamide composite material is prepared into a lightweight product by compression molding or injection molding and is used for structural members of automobiles and rail transit.
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