WO2022110665A1 - Flame-retardant antistatic polyamide composite material, preparation method therefor, and use thereof - Google Patents
Flame-retardant antistatic polyamide composite material, preparation method therefor, and use thereof Download PDFInfo
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- WO2022110665A1 WO2022110665A1 PCT/CN2021/092777 CN2021092777W WO2022110665A1 WO 2022110665 A1 WO2022110665 A1 WO 2022110665A1 CN 2021092777 W CN2021092777 W CN 2021092777W WO 2022110665 A1 WO2022110665 A1 WO 2022110665A1
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- flame
- composite material
- antistatic
- retardant
- polyamide composite
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- 239000002131 composite material Substances 0.000 title claims abstract description 55
- 239000003063 flame retardant Substances 0.000 title claims abstract description 46
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 239000004952 Polyamide Substances 0.000 title claims abstract description 36
- 229920002647 polyamide Polymers 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 239000002216 antistatic agent Substances 0.000 claims abstract description 29
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 24
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 24
- 239000012779 reinforcing material Substances 0.000 claims abstract description 9
- 239000006057 Non-nutritive feed additive Substances 0.000 claims abstract description 6
- 239000003245 coal Substances 0.000 claims abstract description 6
- 238000005065 mining Methods 0.000 claims abstract description 4
- GGRIQDPLLHVRDU-UHFFFAOYSA-M potassium;2-(benzenesulfonyl)benzenesulfonate Chemical compound [K+].[O-]S(=O)(=O)C1=CC=CC=C1S(=O)(=O)C1=CC=CC=C1 GGRIQDPLLHVRDU-UHFFFAOYSA-M 0.000 claims description 12
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- 238000007605 air drying Methods 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000005469 granulation Methods 0.000 claims description 2
- 230000003179 granulation Effects 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 12
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 abstract description 2
- LRCFKTLRJZCYCS-UHFFFAOYSA-N C1(=CC=CC=C1)C(C1=CC=CC=C1)S(=O)(=O)C(C1=CC=CC=C1)C1=CC=CC=C1.[K] Chemical compound C1(=CC=CC=C1)C(C1=CC=CC=C1)S(=O)(=O)C(C1=CC=CC=C1)C1=CC=CC=C1.[K] LRCFKTLRJZCYCS-UHFFFAOYSA-N 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 14
- 238000012360 testing method Methods 0.000 description 6
- 239000003963 antioxidant agent Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000000314 lubricant Substances 0.000 description 4
- 239000003094 microcapsule Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- -1 3-tert-butyl-4-hydroxy-5-methylphenyl Chemical group 0.000 description 3
- OKOBUGCCXMIKDM-UHFFFAOYSA-N Irganox 1098 Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)NCCCCCCNC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 OKOBUGCCXMIKDM-UHFFFAOYSA-N 0.000 description 3
- 230000003078 antioxidant effect Effects 0.000 description 3
- 229920006242 ethylene acrylic acid copolymer Polymers 0.000 description 3
- 239000004611 light stabiliser Substances 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 description 3
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000000194 fatty acid Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- QSRJVOOOWGXUDY-UHFFFAOYSA-N 2-[2-[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCCOCCOCCOC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 QSRJVOOOWGXUDY-UHFFFAOYSA-N 0.000 description 1
- BBJZBUKUEUXKDJ-UHFFFAOYSA-N 3-(3,5-ditert-butyl-4-hydroxyphenyl)-n-[1-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoylamino]hexyl]propanamide Chemical compound C=1C(C(C)(C)C)=C(O)C(C(C)(C)C)=CC=1CCC(=O)NC(CCCCC)NC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 BBJZBUKUEUXKDJ-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000004594 Masterbatch (MB) Substances 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- NZIAIWFZXLGIQB-UHFFFAOYSA-N benzenesulfonylbenzene;potassium Chemical group [K].C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 NZIAIWFZXLGIQB-UHFFFAOYSA-N 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 125000000816 ethylene group Chemical group [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000011152 fibreglass Substances 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- 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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
-
- 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
-
- 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
-
- 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
-
- 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
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/41—Compounds containing sulfur bound to oxygen
- C08K5/42—Sulfonic acids; Derivatives thereof
-
- 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
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
-
- 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
- C08K2003/026—Phosphorus
-
- 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
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
-
- 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
- C08K2201/002—Physical properties
- C08K2201/004—Additives being defined by their length
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/04—Antistatic
Definitions
- the present invention relates to the technical field of engineering plastics, and more particularly, to a flame-retardant and antistatic polyamide composite material and a preparation method and application thereof.
- Polyamide has excellent mechanical properties, heat resistance, wear resistance, oil resistance, etc., and is widely used in the machinery industry, automobiles, power tools, electronic appliances, transportation and other fields. Polyamide is often used as a flame retardant material. Although it has strong polarity and strong water absorption, it still has a high surface resistance (above 10 10 ⁇ ) and is used in the occasions where gas gas is generated. The surface resistance should reach (10 8 ⁇ ) The following) can meet the requirements of use, otherwise it is easy to cause fire and explosion. Therefore, in the application of coal mining equipment, it is necessary to develop materials with both flame retardant and antistatic functions.
- Chinese patent CN 1752142A discloses a preparation method of nylon 6/polyelectrolyte antistatic composite material. effect polyamide composite.
- the processing temperature of PA66 is 230 ⁇ 280°C.
- the antistatic additive will degrade, resulting in a significant deterioration of the composite material properties and a decrease in mechanical properties of more than 30%. It is impossible to obtain both good antistatic properties and Mechanical properties of flame retardant polyamide material.
- the technical problem to be solved by the present invention is to overcome the defects and deficiencies that the existing flame retardant polyamide materials cannot have good antistatic properties and mechanical properties at the same time, and provide a flame retardant and antistatic polyamide composite material, which has good antistatic properties at the same time. performance and mechanical properties.
- Another object of the present invention is to provide a method for preparing a flame retardant and antistatic polyamide composite material.
- Another object of the present invention is to provide the application of a flame retardant and antistatic polyamide composite material.
- a flame retardant and antistatic polyamide composite material comprising the following components calculated in parts by mass:
- the composite antistatic agent is a compound of potassium diphenylsulfone sulfonate and carbon nanotubes, wherein the mass ratio of potassium diphenylsulfonesulfonate to carbon nanotubes is 1:1.5-2.5; the diameter of carbon nanotubes It is 8 to 15 nm, and the length is 10 to 70 ⁇ m.
- the invention uses PA66 as the matrix material, which has excellent flame retardant performance, and adds a specific proportion of potassium diphenylsulfone sulfonate and carbon nanotubes of a certain size for compounding as a composite antistatic agent.
- One is diphenylsulfone Potassium sulfonate itself has an antistatic effect.
- potassium diphenylsulfone sulfonate can promote the dispersion of carbon nanotubes in PA66, improve the compatibility of carbon nanotubes in the system, and is conducive to the construction of a charge transfer network.
- the obtained flame-retardant polyamide composite material can obtain good antistatic properties, and can still have good mechanical properties at the processing temperature of PA66 (230-280° C.).
- the mass ratio of the potassium diphenylsulfone sulfonate to the carbon nanotubes is 1:2-2.5.
- the mass ratio of potassium diphenylsulfone sulfonate to carbon nanotubes is 1:2.
- the carbon nanotubes have a diameter of 10-12 nm and a length of 30-60 ⁇ m.
- the number average molecular weight of the PA66 is 12000-30000.
- the relative viscosity of the PA66 is 1.8-3.5.
- the relative viscosity of the PA66 is 2.2-2.8.
- test method for the relative viscosity of PA66 test standard ISO 307-2007, 96% sulfuric acid solution, sample concentration 0.005g/mL, test temperature 25°C.
- the reinforcing material of the present invention includes, but is not limited to, one or more of glass fibers, carbon fibers, aramid fibers, and ceramic fibers.
- the flame retardant is red phosphorus masterbatch.
- the flame retardant is microcapsule red phosphorus masterbatch.
- the mass content of red phosphorus in the microcapsule red phosphorus master batch is 40% to 60%.
- the processing aids of the present invention include, but are not limited to, one or more of antioxidants, lubricants, light stabilizers, and colorants.
- the antioxidants described in the present invention include but are not limited to N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexanediamine (1098), triethylenediamine Alcohol ether-bis(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate (antioxidant 245), tetrakis[beta-(3,5-di-tert-butyl-4-hydroxybenzene base) propionic acid] pentaerythritol ester (antioxidant 1010), tris[2.4-di-tert-butylphenyl] phosphite (antioxidant 168), phosphite antioxidant P-EPQ, copper salt antioxidant One or more of the agent (a compound of potassium iodide, cuprous iodide, and zinc stearate, with a mass ratio of 8:1:1).
- the agent a compound of potassium iodide
- the lubricant of the present invention includes, but is not limited to, one or more of calcium stearate, modified ethylene bis-fatty acid amide, aliphatic fatty acid ester, and ethylene-acrylic acid copolymer.
- the light stabilizer of the present invention includes, but is not limited to, benzotriazole light stabilizer.
- the colorants of the present invention include, but are not limited to, black masterbatch.
- the present invention protects the preparation method of the above-mentioned flame retardant and antistatic polyamide composite material, comprising the following steps:
- a twin-screw extruder with side feeding is used for the melt blending, and the feeding port includes a main feeding port and a side feeding port; the uniformly mixed material is fed from the main feeding port, and the reinforcing material is fed from the main feeding port.
- Side feeding port feeding is used for the melt blending, and the feeding port includes a main feeding port and a side feeding port; the uniformly mixed material is fed from the main feeding port, and the reinforcing material is fed from the main feeding port.
- Side feeding port feeding is used for the melt blending, and the feeding port includes a main feeding port and a side feeding port; the uniformly mixed material is fed from the main feeding port, and the reinforcing material is fed from the main feeding port.
- the temperature of the melt blending is 230-280°C.
- the invention also protects the application of the above flame-retardant and antistatic polyamide composite material in coal mine equipment.
- the flame retardant and antistatic polyamide composite material of the invention has excellent flame retardant performance, reaches V-0 level, the surface resistivity is 10 8 and below, the tensile strength reaches 133MPa and above, and the impact strength reaches 8.5kJ/m 2 and above, with good antistatic properties and mechanical properties.
- the invention takes PA66 as the matrix material, adds a certain proportion of reinforcing materials, flame retardants, processing aids, and a certain proportion of potassium diphenylsulfone sulfonate and carbon nanotubes of a certain size to be compounded as a composite antistatic agent.
- the flame retardant and antistatic polyamide composite material can not only obtain good antistatic properties, but also obtain good mechanical properties at the processing temperature of PA66, and has good flame retardant properties. It can be used in applications requiring antistatic properties, such as coal mines. equipment, etc.
- the raw material reagents used in the examples of the present invention are conventionally purchased raw material reagents.
- PA66 the grade is EPR24, the number average molecular weight is 13700, the relative viscosity is 2.4, purchased from Pingdingshan Shenma Group;
- Reinforcing material glass fiber, grade ECS10-03-568H, purchased from Jushi Group;
- Microcapsule red phosphorus masterbatch the brand is FR9950KF, the mass content of red phosphorus is 50%, purchased from Tongcheng Xinde New Materials Co., Ltd.;
- antistatic agent the name is polyether antistatic agent, the brand name is PELESTAT-6500, purchased from Sanyo Chemicals in Japan;
- Conductive carbon black purchased from Yiborui (Tianjin) Chemical Co., Ltd.;
- KSS Potassium Diphenylsulfone Sulfonate
- Carbon nanotube A the grade is LUCAN CP1002M, purchased from LG Chem; the diameter of the carbon nanotube is 8-12 nm, and the length is 50-70 ⁇ m.
- Carbon nanotube B the grade is GC-21, purchased from Shandong Dazhan Nanomaterials Co., Ltd.; the diameter of the carbon nanotube is 12-15 nm, and the length is 10-50 ⁇ m;
- Black mother the grade is N54/1044, purchased from Colly Plastics, UK;
- Antioxidant 1098 N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexamethylenediamine, commercially available;
- Lubricant ethylene-acrylic acid copolymer (EAA), trade name A-C540A, available from Honeywell.
- Table 2 shows the components and mass parts of the flame-retardant and antistatic polyamide composite materials of each embodiment and comparative example.
- a preparation method of a flame retardant and antistatic polyamide composite material comprising the following steps:
- Composite antistatic agent 3 1 2.5 Composite antistatic agent 4 1 1 Composite antistatic agent 5 1 3 Composite antistatic agent 6 1 2
- the flame retardant and antistatic polyamide composite material prepared by the present invention has high antistatic effect, the surface resistivity is 10 8 and below, and also has good notched impact strength, tensile strength and flame retardancy. performance, can be used in applications requiring antistatic, such as coal mining equipment.
- Comparative Example 1 no composite antistatic agent was added, and its surface resistivity increased significantly.
- Comparative Example 2 and Comparative Example 3 conductive carbon black and commercially available antistatic agent PELESTAT-6500 were used as substitutes for the composite antistatic agent. The ratio is still greater than 10 8 , and the mechanical properties such as notched impact strength and tensile strength are significantly reduced.
- the existing conventional antistatic agent cannot reduce the surface resistivity of the material well, and will cause adverse effects on the mechanical properties of the material.
- the composite antistatic agent used in Comparative Example 4 reduces the amount of carbon nanotubes, and the composite antioxidant in Comparative Example 5 increases the amount of carbon nanotubes, and the surface resistivity of the obtained material is still large, still 10 8 Above, the antistatic performance is not good enough, and the mechanical properties also have a certain degree of decline.
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Abstract
Disclosed are a flame-retardant antistatic polyamide composite material, a preparation method therefor, and the use thereof. PA66 is used as a base material, and a certain proportion of a reinforcing material, a flame retardant, a processing aid, a special proportion of potassium diphenylmethylsulfone sulfonate and a certain size of carbon nanotube are added to be compounded as a composite antistatic agent, which is used to prepare the flame-retardant antistatic polyamide composite material, such that the flame-retardant antistatic polyamide composite material has a good antistatic performance and excellent mechanical properties and flame retardant properties, and can be applied to occasions requiring an antistatic performance, such as in coal mining equipment.
Description
本发明涉及工程塑料技术领域，更具体地，涉及一种阻燃抗静电聚酰胺复合材料及其制备方法和应用。The present invention relates to the technical field of engineering plastics, and more particularly, to a flame-retardant and antistatic polyamide composite material and a preparation method and application thereof.
聚酰胺具有杰出的机械性能、耐热性能、耐磨性能、耐油性能等，广泛应用于机械行业、汽车、电动工具、电子电器、交通运输等领域。聚酰胺常用作阻燃材料，虽然本身极性很强，而且吸水性比较强，但仍具有较高的表面电阻(10
10Ω以上)产生瓦斯气体的场合使用，表面电阻要达到(10
8Ω以下)才能满足使用的要求，否则很容易引起火灾和爆炸，因此在煤矿设备这种应用场合，需要开发既具有阻燃又具有抗静电功能的材料。
Polyamide has excellent mechanical properties, heat resistance, wear resistance, oil resistance, etc., and is widely used in the machinery industry, automobiles, power tools, electronic appliances, transportation and other fields. Polyamide is often used as a flame retardant material. Although it has strong polarity and strong water absorption, it still has a high surface resistance (above 10 10 Ω) and is used in the occasions where gas gas is generated. The surface resistance should reach (10 8 Ω) The following) can meet the requirements of use, otherwise it is easy to cause fire and explosion. Therefore, in the application of coal mining equipment, it is necessary to develop materials with both flame retardant and antistatic functions.
中国专利CN 1752142A(公开日2006.3.29)公开了一种尼龙6/聚电解质抗静电复合材料的制备方法，通过添加碱金属盐或烷基苯二苯甲砜磺酸钾制备了具有良好抗静电效果的聚酰胺复合材料。然而PA66的加工温度为230～280℃，在如此高的加工温度下，抗静电助剂会发生降解，导致复合材料性能显著劣化，力学性能降低30％以上，无法获得同时具有良好抗静电性能和力学性能的阻燃聚酰胺材料。Chinese patent CN 1752142A (published on March 29, 2006) discloses a preparation method of nylon 6/polyelectrolyte antistatic composite material. effect polyamide composite. However, the processing temperature of PA66 is 230~280℃. At such a high processing temperature, the antistatic additive will degrade, resulting in a significant deterioration of the composite material properties and a decrease in mechanical properties of more than 30%. It is impossible to obtain both good antistatic properties and Mechanical properties of flame retardant polyamide material.
发明内容SUMMARY OF THE INVENTION
本发明要解决的技术问题是克服现有阻燃聚酰胺材料无法同时具有良好的抗静电性能和力学性能的缺陷和不足，提供一种阻燃抗静电聚酰胺复合材料，同时具有良好的抗静电性能和力学性能。The technical problem to be solved by the present invention is to overcome the defects and deficiencies that the existing flame retardant polyamide materials cannot have good antistatic properties and mechanical properties at the same time, and provide a flame retardant and antistatic polyamide composite material, which has good antistatic properties at the same time. performance and mechanical properties.
本发明的又一目的是提供一种阻燃抗静电聚酰胺复合材料的制备方法。Another object of the present invention is to provide a method for preparing a flame retardant and antistatic polyamide composite material.
本发明的另一目的是提供一种阻燃抗静电聚酰胺复合材料的应用。Another object of the present invention is to provide the application of a flame retardant and antistatic polyamide composite material.
本发明上述目的通过以下技术方案实现：The above-mentioned purpose of the present invention is achieved through the following technical solutions:
一种阻燃抗静电聚酰胺复合材料，包括如下按照质量份计算的组分：A flame retardant and antistatic polyamide composite material, comprising the following components calculated in parts by mass:
所述复合抗静电剂为二苯甲砜磺酸钾与碳纳米管的复配物，其中二苯甲砜磺酸钾与碳纳米管的质量比为1：1.5～2.5；碳纳米管的直径为8～15nm，长度为10～70μm。The composite antistatic agent is a compound of potassium diphenylsulfone sulfonate and carbon nanotubes, wherein the mass ratio of potassium diphenylsulfonesulfonate to carbon nanotubes is 1:1.5-2.5; the diameter of carbon nanotubes It is 8 to 15 nm, and the length is 10 to 70 μm.
本发明以PA66作为基体材料，具有优异的阻燃性能，并添加选择特定比例的二苯甲砜磺酸钾与一定尺寸的碳纳米管进行复配作为复合抗静电剂，一是二苯甲砜磺酸钾本身具有抗静电效果，二是二苯甲砜磺酸钾能够促进碳纳米管在PA66的分散，提高碳纳米管在体系中的相容性，有利于构建电荷的传递网络，所制得的阻燃聚酰胺复合材料可以获得良好抗静电性能，并且在PA66的加工温度下(230～280℃)，仍能具有较好的力学性能。The invention uses PA66 as the matrix material, which has excellent flame retardant performance, and adds a specific proportion of potassium diphenylsulfone sulfonate and carbon nanotubes of a certain size for compounding as a composite antistatic agent. One is diphenylsulfone Potassium sulfonate itself has an antistatic effect. Second, potassium diphenylsulfone sulfonate can promote the dispersion of carbon nanotubes in PA66, improve the compatibility of carbon nanotubes in the system, and is conducive to the construction of a charge transfer network. The obtained flame-retardant polyamide composite material can obtain good antistatic properties, and can still have good mechanical properties at the processing temperature of PA66 (230-280° C.).
优选地，包括如下按照质量份计算的组分：Preferably, the following components calculated in parts by mass are included:
优选地，所述二苯甲砜磺酸钾与碳纳米管质量比为1：2～2.5。Preferably, the mass ratio of the potassium diphenylsulfone sulfonate to the carbon nanotubes is 1:2-2.5.
更优选地，所述二苯甲砜磺酸钾与碳纳米管质量比为1：2。More preferably, the mass ratio of potassium diphenylsulfone sulfonate to carbon nanotubes is 1:2.
优选地，所述碳纳米管的直径10～12nm，长度30～60μm。Preferably, the carbon nanotubes have a diameter of 10-12 nm and a length of 30-60 μm.
优选地，所述PA66的数均分子量为12000～30000。Preferably, the number average molecular weight of the PA66 is 12000-30000.
优选地，所述PA66的相对粘度为1.8～3.5。Preferably, the relative viscosity of the PA66 is 1.8-3.5.
优选地，所述PA66的相对粘度在2.2～2.8。Preferably, the relative viscosity of the PA66 is 2.2-2.8.
其中上述PA66相对粘度的测试方法：测试标准ISO 307-2007，96％的硫酸溶液，样品浓度0.005g/mL，测试温度25℃。Among them, the test method for the relative viscosity of PA66: test standard ISO 307-2007, 96% sulfuric acid solution, sample concentration 0.005g/mL, test temperature 25°C.
本发明所述增强材料包括但不限于玻璃纤维、碳纤维、芳纶纤维、陶瓷纤维中一种或几种。The reinforcing material of the present invention includes, but is not limited to, one or more of glass fibers, carbon fibers, aramid fibers, and ceramic fibers.
优选地，所述阻燃剂为红磷母粒。Preferably, the flame retardant is red phosphorus masterbatch.
优选地，所述阻燃剂为微胶囊红磷母粒。Preferably, the flame retardant is microcapsule red phosphorus masterbatch.
优选地，所述微胶囊红磷母粒中红磷的质量含量为40％～60％。Preferably, the mass content of red phosphorus in the microcapsule red phosphorus master batch is 40% to 60%.
本发明所述加工助剂包括但不限于抗氧剂、润滑剂、光稳定剂、着色剂中的一种或几种。The processing aids of the present invention include, but are not limited to, one or more of antioxidants, lubricants, light stabilizers, and colorants.
本发明所述抗氧剂包括但不限于N,N'-双-(3-(3,5-二叔丁基-4-羟基苯基)丙酰基)己二胺(1098)、三乙二醇醚-二(3-叔丁基-4-羟基-5-甲基苯基)丙酸酯(抗氧剂245)、四[β-(3，5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯(抗氧剂1010)、三[2.4-二叔丁基苯基]亚磷酸酯(抗氧剂168)、亚磷酸酯类抗氧剂P-EPQ、铜盐抗氧剂(碘化钾、碘化亚铜、硬脂酸锌的复配物，质量比为8:1:1)中的一种或几种。The antioxidants described in the present invention include but are not limited to N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexanediamine (1098), triethylenediamine Alcohol ether-bis(3-tert-butyl-4-hydroxy-5-methylphenyl) propionate (antioxidant 245), tetrakis[beta-(3,5-di-tert-butyl-4-hydroxybenzene base) propionic acid] pentaerythritol ester (antioxidant 1010), tris[2.4-di-tert-butylphenyl] phosphite (antioxidant 168), phosphite antioxidant P-EPQ, copper salt antioxidant One or more of the agent (a compound of potassium iodide, cuprous iodide, and zinc stearate, with a mass ratio of 8:1:1).
本发明所述润滑剂包括但不限于硬脂酸钙、改性乙撑双脂肪酸酰胺、脂肪族脂肪酸酯、乙烯-丙烯酸共聚物中的一种或几种。The lubricant of the present invention includes, but is not limited to, one or more of calcium stearate, modified ethylene bis-fatty acid amide, aliphatic fatty acid ester, and ethylene-acrylic acid copolymer.
本发明所述光稳定剂包括但不限于苯并三唑类光稳定剂。The light stabilizer of the present invention includes, but is not limited to, benzotriazole light stabilizer.
本发明所述着色剂包括但不限于黑色母。The colorants of the present invention include, but are not limited to, black masterbatch.
本发明保护上述阻燃抗静电聚酰胺复合材料的制备方法，包括如下步骤：The present invention protects the preparation method of the above-mentioned flame retardant and antistatic polyamide composite material, comprising the following steps:
将PA66、增强材料、阻燃剂、复合抗静电剂、加工助剂混合均匀，熔融共混后，经过冷却、风干、造粒制得阻燃抗静电聚酰胺复合材料。Mixing PA66, reinforcing material, flame retardant, compound antistatic agent and processing aid evenly, after melt blending, cooling, air-drying and granulation, the flame retardant and antistatic polyamide composite material is obtained.
优选地，所述熔融共混选用带侧喂的双螺杆挤出机，喂料口包括主喂料口、侧喂料口；将混合均匀的物料从主喂料口喂入，将增强材料从侧喂料口喂入。Preferably, a twin-screw extruder with side feeding is used for the melt blending, and the feeding port includes a main feeding port and a side feeding port; the uniformly mixed material is fed from the main feeding port, and the reinforcing material is fed from the main feeding port. Side feeding port feeding.
优选地，所述熔融共混的温度为230～280℃。Preferably, the temperature of the melt blending is 230-280°C.
本发明还保护上述阻燃抗静电聚酰胺复合材料在煤矿设备中的应用。本发明的阻燃抗静电聚酰胺复合材料具有优异的阻燃性能，达到V-0级，表面电阻率在10
8及其以下，拉伸强度达到133MPa及其以上，冲击强度达到8.5kJ/m
2及其以上，具有良好的抗静电性能和力学性能。
The invention also protects the application of the above flame-retardant and antistatic polyamide composite material in coal mine equipment. The flame retardant and antistatic polyamide composite material of the invention has excellent flame retardant performance, reaches V-0 level, the surface resistivity is 10 8 and below, the tensile strength reaches 133MPa and above, and the impact strength reaches 8.5kJ/m 2 and above, with good antistatic properties and mechanical properties.
与现有技术相比，本发明的有益效果是：Compared with the prior art, the beneficial effects of the present invention are:
本发明以PA66为基体材料，添加一定配比的增强材料、阻燃剂、加工助剂以及特定比例的二苯甲砜磺酸钾与一定尺寸的碳纳米管复配作为复合抗静电剂制得阻燃抗静电聚酰胺复合材料，不仅可以获得良好抗静电性能，并且在PA66的加工温度下，仍能获得较好的力学性能，阻燃性能良好，可以应用于要求抗静电的场合，比如煤矿设备等。The invention takes PA66 as the matrix material, adds a certain proportion of reinforcing materials, flame retardants, processing aids, and a certain proportion of potassium diphenylsulfone sulfonate and carbon nanotubes of a certain size to be compounded as a composite antistatic agent. The flame retardant and antistatic polyamide composite material can not only obtain good antistatic properties, but also obtain good mechanical properties at the processing temperature of PA66, and has good flame retardant properties. It can be used in applications requiring antistatic properties, such as coal mines. equipment, etc.
下面结合具体实施方式对本发明作进一步的说明，但实施例并不对本发明做任何形式的限定。除非另有说明，本发明实施例采用的原料试剂为常规购买的原料试剂。The present invention will be further described below in conjunction with specific embodiments, but the embodiments do not limit the present invention in any form. Unless otherwise specified, the raw material reagents used in the examples of the present invention are conventionally purchased raw material reagents.
实施例和对比例中的组分：Components in Examples and Comparative Examples:
PA66：牌号为EPR24，数均分子量为13700，相对粘度2.4，购于平顶山神马集团；PA66: the grade is EPR24, the number average molecular weight is 13700, the relative viscosity is 2.4, purchased from Pingdingshan Shenma Group;
增强材料：玻璃纤维，牌号为ECS10-03-568H，购于巨石集团；Reinforcing material: glass fiber, grade ECS10-03-568H, purchased from Jushi Group;
微胶囊红磷母粒：牌号为FR9950KF，红磷质量含量50％，购于桐城市信得新材料有限公司；Microcapsule red phosphorus masterbatch: the brand is FR9950KF, the mass content of red phosphorus is 50%, purchased from Tongcheng Xinde New Materials Co., Ltd.;
市售抗静电剂：名称为聚醚型抗静电剂，牌号为PELESTAT-6500，购于日本三洋化成；Commercially available antistatic agent: the name is polyether antistatic agent, the brand name is PELESTAT-6500, purchased from Sanyo Chemicals in Japan;
导电炭黑：购于亿博瑞(天津)化工有限公司；Conductive carbon black: purchased from Yiborui (Tianjin) Chemical Co., Ltd.;
二苯甲砜磺酸钾(KSS)：牌号为KSS-KF，购于上海鼎耐化工有限公司；Potassium Diphenylsulfone Sulfonate (KSS): the trade name is KSS-KF, purchased from Shanghai Dingnai Chemical Co., Ltd.;
碳纳米管A：牌号为LUCAN CP1002M，购于LG化学；碳纳米管的直径为8～12nm，长度为50～70μm。Carbon nanotube A: the grade is LUCAN CP1002M, purchased from LG Chem; the diameter of the carbon nanotube is 8-12 nm, and the length is 50-70 μm.
碳纳米管B：牌号为GC-21，购于山东大展纳米材料有限公司；碳纳米管的直径为12～15nm，长度为10～50μm；Carbon nanotube B: the grade is GC-21, purchased from Shandong Dazhan Nanomaterials Co., Ltd.; the diameter of the carbon nanotube is 12-15 nm, and the length is 10-50 μm;
黑色母：牌号为N54/1044，购于英国高莱塑料；Black mother: the grade is N54/1044, purchased from Colly Plastics, UK;
抗氧剂1098：N,N'-双-(3-(3,5-二叔丁基-4-羟基苯基)丙酰基)己二胺，市售；Antioxidant 1098: N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexamethylenediamine, commercially available;
润滑剂：乙烯-丙烯酸共聚物(EAA)，牌号为A-C540A，购于霍尼韦尔。Lubricant: ethylene-acrylic acid copolymer (EAA), trade name A-C540A, available from Honeywell.
实施例1Example 1
各实施例和对比例的阻燃抗静电聚酰胺复合材料，其组分及其质量份如表2所示。Table 2 shows the components and mass parts of the flame-retardant and antistatic polyamide composite materials of each embodiment and comparative example.
一种阻燃抗静电聚酰胺复合材料的制备方法，包括如下步骤：A preparation method of a flame retardant and antistatic polyamide composite material, comprising the following steps:
将PA66、增强材料、阻燃剂、复合抗静电剂、加工助剂投入混合机中进行混合直至均匀，得到混合物料；然后选用带双侧喂的双螺杆挤出机，从主喂下料；再将增强材料从侧喂口下料，然后在280℃下熔融共混、螺杆转速为450rpm，挤出、水冷、风干、造粒；再将材料烘干、注塑成相应的测试样条和样板。Put PA66, reinforcing material, flame retardant, compound antistatic agent, and processing aid into the mixer for mixing until uniform to obtain a mixed material; then select a twin-screw extruder with double-side feeding, and unload the material from the main feed; The reinforcing material is then unloaded from the side feeding port, and then melt-blended at 280 ° C, the screw speed is 450 rpm, extruded, water-cooled, air-dried, and pelletized; then the material is dried and injection-molded into corresponding test strips and samples. .
表1不同配比的复合抗静电剂(质量比)Table 1 Composite antistatic agent (mass ratio) with different proportions
| 二苯甲砜磺酸钾Potassium Diphenylsulfone Sulfonate | 碳纳米管ACarbon Nanotube A | 碳纳米管Bcarbon nanotubes B | |
| 复合抗静电剂1Composite antistatic agent 1 | 11 | 1.51.5 | |
| 复合抗静电剂2Composite antistatic agent 2 | 11 | 22 |
| 复合抗静电剂3Composite antistatic agent 3 | 11 | 2.52.5 | |
| 复合抗静电剂4Composite antistatic agent 4 | 11 | 11 | |
| 复合抗静电剂5Composite antistatic agent 5 | 11 | 33 | |
| 复合抗静电剂6Composite antistatic agent 6 | 11 | 22 |
表2各实施例和对比例中的组分及其质量份Components and their mass parts in each embodiment and comparative example of table 2
| 对比例1Comparative Example 1 | 对比例2Comparative Example 2 | 对比例3Comparative Example 3 | 对比例4Comparative Example 4 | 对比例5Comparative Example 5 | |
| PA66EPR24PA66EPR24 | 58.558.5 | 43.543.5 | 43.543.5 | 54.554.5 | 54.554.5 |
| 微胶囊红磷母粒FR9950KFMicrocapsule Red Phosphorus Masterbatch FR9950KF | 1414 | 1414 | 1414 | 1414 | 1414 |
| 导电炭黑Conductive carbon black | 1515 | ||||
| 市售抗静电剂Commercially available antistatic agents | 1515 |
| PELESTAT-6500PELESTAT-6500 | |||||
| 复合抗静电剂1Composite antistatic agent 1 | |||||
| 复合抗静电剂2Composite antistatic agent 2 | |||||
| 复合抗静电剂3Composite antistatic agent 3 | |||||
| 复合抗静电剂4Composite antistatic agent 4 | 44 | ||||
| 复合抗静电剂5Composite antistatic agent 5 | 44 | ||||
| 复合抗静电剂6Composite antistatic agent 6 | |||||
| 黑色母N54/1044Black female N54/1044 | 1.51.5 | 1.51.5 | 1.51.5 | 1.51.5 | 1.51.5 |
| 玻璃纤维ECS10-03-568HFiberglass ECS10-03-568H | 2525 | 2525 | 2525 | 2525 | 2525 |
| 抗氧剂1098Antioxidant 1098 | 0.50.5 | 0.50.5 | 0.50.5 | 0.50.5 | 0.50.5 |
| 润滑剂A-C0540ALubricant A-C0540A | 0.50.5 | 0.50.5 | 0.50.5 | 0.50.5 | 0.50.5 |
性能测试Performance Testing
1、测试方法1. Test method
(1)拉伸强度：按照GB/T 1040.2-2006标准进行测试；拉伸速度为10mm/min；(2)悬臂梁缺口冲击强度：按照ISO 180进行测试；(1) Tensile strength: tested according to GB/T 1040.2-2006 standard; tensile speed is 10mm/min; (2) Izod notched impact strength: tested according to ISO 180;
(3)阻燃性能：按照UL 94测试，样条规格125×13×0.8mm；(3) Flame retardant performance: tested according to UL 94, the spline size is 125×13×0.8mm;
(4)表面电阻率：GBT 1410-2006，样板规格100*100*3.0mm矩形板。(4) Surface resistivity: GBT 1410-2006, the template size is 100*100*3.0mm rectangular plate.
2、测试结果2. Test results
表3各实施例和对比例产品的测试结果The test result of each embodiment of table 3 and comparative example product
通过表3可以发现，通过本发明制备的阻燃抗静电聚酰胺复合材料具有高效的抗静电效果，表面电阻率在10
8及其以下，还具有良好的缺口冲击强度、拉伸 强度和阻燃性能，可以应用于要求抗静电的场合，比如煤矿设备。但是其中对比例1没有添加复合抗静电剂，其表面电阻率显著增大，对比例2和对比例3分别采用导电炭黑、市售抗静电剂PELESTAT-6500作为替代复合抗静电剂，表面电阻率仍大于10
8，且缺口冲击强度、拉伸强度等力学性能显著下降，可见现有常规的抗静电剂不能很好地降低材料表面电阻率，且对材料的力学性能会造成不良影响。对比例4中使用的复合抗静电剂减少了碳纳米管的用量，对比例5中的复合抗氧化剂增加了碳纳米管的用量，制得的材料的表面电阻率仍较大，仍在10
8以上，抗静电性能不够好，且力学性能也有一定程度的下降。
It can be found from Table 3 that the flame retardant and antistatic polyamide composite material prepared by the present invention has high antistatic effect, the surface resistivity is 10 8 and below, and also has good notched impact strength, tensile strength and flame retardancy. performance, can be used in applications requiring antistatic, such as coal mining equipment. However, in Comparative Example 1, no composite antistatic agent was added, and its surface resistivity increased significantly. In Comparative Example 2 and Comparative Example 3, conductive carbon black and commercially available antistatic agent PELESTAT-6500 were used as substitutes for the composite antistatic agent. The ratio is still greater than 10 8 , and the mechanical properties such as notched impact strength and tensile strength are significantly reduced. It can be seen that the existing conventional antistatic agent cannot reduce the surface resistivity of the material well, and will cause adverse effects on the mechanical properties of the material. The composite antistatic agent used in Comparative Example 4 reduces the amount of carbon nanotubes, and the composite antioxidant in Comparative Example 5 increases the amount of carbon nanotubes, and the surface resistivity of the obtained material is still large, still 10 8 Above, the antistatic performance is not good enough, and the mechanical properties also have a certain degree of decline.
显然，本发明的上述实施例仅仅是为清楚地说明本发明所作的举例，而并非是对本发明的实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明权利要求的保护范围之内。Obviously, the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. For those of ordinary skill in the art, changes or modifications in other different forms can also be made on the basis of the above description. There is no need and cannot be exhaustive of all implementations here. Any modifications, equivalent replacements and improvements made within the spirit and principle of the present invention shall be included within the protection scope of the claims of the present invention.
Claims (10)
- 一种阻燃抗静电聚酰胺复合材料，其特征在于，包括如下按照质量份计算的组分：A flame retardant and antistatic polyamide composite material, characterized in that, it comprises the following components calculated in parts by mass:
所述复合抗静电剂为二苯甲砜磺酸钾与碳纳米管的复配物，其中二苯甲砜磺酸钾与碳纳米管的质量比为1：1.5～2.5；碳纳米管的直径为8～15nm，长度为10～70μm。The composite antistatic agent is a compound of potassium diphenylsulfone sulfonate and carbon nanotubes, wherein the mass ratio of potassium diphenylsulfonesulfonate to carbon nanotubes is 1:1.5-2.5; the diameter of carbon nanotubes It is 8 to 15 nm, and the length is 10 to 70 μm. - 根据权利要求1所述阻燃抗静电聚酰胺复合材料，其特征在于，包括如下按照质量份计算的组分：The flame-retardant and antistatic polyamide composite material according to claim 1, characterized in that, it comprises the following components calculated in parts by mass:
- 根据权利要求1或2所述阻燃抗静电聚酰胺复合材料，其特征在于，所述二苯甲砜磺酸钾与碳纳米管的质量比为1：2～2.5。The flame-retardant and antistatic polyamide composite material according to claim 1 or 2, wherein the mass ratio of the potassium diphenylsulfone sulfonate to the carbon nanotubes is 1:2-2.5.
- 根据权利要求1或2所述阻燃抗静电聚酰胺复合材料，其特征在于，所述碳纳米管的直径10～12nm，长度30～60μm。The flame-retardant and antistatic polyamide composite material according to claim 1 or 2, wherein the carbon nanotubes have a diameter of 10-12 nm and a length of 30-60 μm.
- 根据权利要求1所述阻燃抗静电聚酰胺复合材料，其特征在于，所述PA66的数均分子量为15000～40000。The flame-retardant and antistatic polyamide composite material according to claim 1, wherein the number average molecular weight of the PA66 is 15,000-40,000.
- 根据权利要求1所述阻燃抗静电聚酰胺复合材料，其特征在于，所述PA66的相对粘度为1.8～3.5。The flame-retardant and antistatic polyamide composite material according to claim 1, wherein the relative viscosity of the PA66 is 1.8-3.5.
- 根据权利要求1所述阻燃抗静电聚酰胺复合材料，其特征在于，所述阻燃剂为红磷母粒。The flame retardant and antistatic polyamide composite material according to claim 1, wherein the flame retardant is red phosphorus masterbatch.
- 权利要求1～7任一项所述阻燃抗静电聚酰胺复合材料的制备方法，其特征在于，包括如下步骤：The preparation method of the flame retardant and antistatic polyamide composite material according to any one of claims 1 to 7, characterized in that it comprises the following steps:将PA66、增强材料、阻燃剂、复合抗静电剂、加工助剂混合均匀，熔融共 混后，经过冷却、风干、造粒制得阻燃抗静电聚酰胺复合材料。Mix PA66, reinforcing material, flame retardant, composite antistatic agent, and processing aid evenly, and after melt blending, cooling, air-drying, and granulation to obtain flame-retardant and antistatic polyamide composite material.
- 权利要求1～7任一项所述阻燃抗静电聚酰胺复合材料在煤矿设备领域用聚酰胺制品中的应用。Application of the flame retardant and antistatic polyamide composite material according to any one of claims 1 to 7 in polyamide products used in the field of coal mining equipment.
- 一种聚酰胺制品，其特征在于，包括权利要求1～7任一项所述阻燃抗静电聚酰胺复合材料制成。A polyamide product, characterized in that it is made of the flame-retardant and antistatic polyamide composite material according to any one of claims 1 to 7.
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