CN107083055A - Conductive PA6/PPO alloy materials and preparation method thereof - Google Patents

Conductive PA6/PPO alloy materials and preparation method thereof Download PDF

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Publication number
CN107083055A
CN107083055A CN201710375743.0A CN201710375743A CN107083055A CN 107083055 A CN107083055 A CN 107083055A CN 201710375743 A CN201710375743 A CN 201710375743A CN 107083055 A CN107083055 A CN 107083055A
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conductive
antioxidant
alloy materials
ppo alloy
cnt
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孙静
韦良强
黄安荣
董珈豪
石敏
刘小箐
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Guizhou Material Industrial Technology Research Institute
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Guizhou Material Industrial Technology Research Institute
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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
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
    • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08L71/12—Polyphenylene oxides
    • C08L71/126—Polyphenylene oxides modified by chemical after-treatment
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/20—Conductive material dispersed in non-conductive organic material
    • H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/001—Conductive additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/08—Polymer mixtures characterised by other features containing additives to improve the compatibility between two polymers

Abstract

The invention discloses a kind of conductive PA6/PPO alloy materials and preparation method thereof, calculate according to the mass fraction, including 35~60 parts of nylon 6,40~65 parts of Noryls, 2~8 parts of toughener, 0.5~5 part of CNT, 1~10 part of conductive black, 0.1~5 part of compatilizer part and 0.1~3.0 part of antioxidant are preparing raw material.The conductive filler that the present invention is added is relatively fewer, and conductive filler is uniformly dispersed in the base, without agglomeration；Obtained conductive PA6/PPO alloy materials have excellent electric conductivity and its mechanical performance, and processing method is simple, and properties of product are controllable and stably, it is easy to industrialized production.Extensively, with low cost, using effect is good for material source of the present invention.

Description

Conductive PA6/PPO alloy materials and preparation method thereof
Technical field
The present invention relates to technical field of polymer materials, especially a kind of conductive PA6/PPO alloy materials and its preparation side Method.
Background technology
Nylon 6 is a kind of engineering plastics of excellent performance, and it is widely used in automobile, electronic apparatus, machinery, Aero-Space Field is to daily living article such as silk stocking, clothing, carpet etc..It has excellent mechanical property, preferable electrical property and resistance to Mill, oil resistant, self-lubricating and good processing characteristics etc..But the electrical insulation capability of nylon 6 causes it easily to produce electrostatic, so that Limit its application.Polyphenylene oxide (PPO) is one of big general engineering plastic in the world five, and it has, and rigidity is big, heat resistance is high, difficult The advantages of combustion, higher intensity, excellent electrical properties.In addition, PPO also has the advantages that wear-resisting, nontoxic, anti-pollution.PPO dielectric is normal Number and dielectric loss are one of minimum kind in engineering plastics, are hardly influenceed by temperature, humidity, available for it is low, in, High-frequency electric field field；PPO load deformation temperature is up to more than 190 DEG C, and brittle temperature is -170 DEG C.Therefore conduction PA6/PPO Alloy material can take into account simultaneously both excellent properties and PPO materials resistance to elevated temperatures.
Conductive additive in current polymer conducting material mainly has metal powder, carbon black, graphite, CNT.Although Metal powder, carbon black or graphite are added into polymer can also prepare conducting polymer composite material, but filler is in matrix material Easily reunite, so that the mechanical property of material declines to a great extent.
The content of the invention
It is an object of the present invention to provide a kind of conductive PA6/PPO alloy materials and preparation method thereof, it can improve well The dispersiveness of conductive filler in the base, and the conductive filler used is relatively fewer, with excellent electric conductivity and its power machine Tool performance, and processing method is simple, properties of product are controllable and stably.
What the present invention was realized in：Conductive PA6/PPO alloy materials, are calculated according to the mass fraction, including 35~60 parts of Buddhist nuns Imperial 6,40~65 parts of Noryls, 2~8 parts of toughener, 0.5~5 part of CNT, 1~10 part of conductive black, 0.1~5 part Compatilizer part and 0.1~3.0 part of antioxidant are preparing raw material.
The inherent viscosity of described nylon 6 is more than 2.0dL/g.
Described toughener is maleic anhydride grafted ethene -1- octene copolymers or methacrylic acid-butadiene-styrene One or both of copolymer is combined.
Described CNT is multi-walled carbon nanotube, and 8~15nm of external diameter, length is 9~14 μm, and purity is more than 94%.
Described conductive black is the conductive black that oil factor is more than 150ml/100g.
Described compatilizer is the epoxy resin that molecular weight 100~120, epoxide equivalent are 30~550g/eq or modified ring Any combination of one or both of oxygen tree fat.
The antioxidant is antioxidant 1010, antioxidant 1076, antioxidant 1098, irgasfos 168, antioxidant B215, anti- It is one or more of in oxygen agent B225, antioxidant 2246, antioxidant 330, antioxidant BHT, anti-oxidant DLTP or antioxidant DSTP Any combination.
The preparation method of conductive PA6/PPO alloy materials, each component is taken by above-mentioned mass fraction, by nylon 6, is modified and is gathered Phenylate, CNT, conductive black, compatilizer, toughener and antioxidant are well mixed, are then added in double screw extruder Extruded, obtain conduction PA6/PPO alloy materials.
By ultrasonic vibration device to carrying out ultrasonic vibration by the material of head at cross-head.
Nylon 6 and Noryl are dried 4~10h by raw material at a temperature of 80~100 DEG C respectively before being extruded, CNT dries 5~8h with conductive black at a temperature of 75~90 DEG C.
Compared with prior art, the conductive filler that the present invention is added is relatively fewer, and conductive filler disperses in the base Uniformly, without agglomeration；Obtained conductive PA6/PPO alloy materials have excellent electric conductivity and its mechanical performance, and Processing method is simple, and properties of product are controllable and stably, it is easy to industrialized production.Material source of the present invention is extensively, with low cost, makes It is good with effect.
Embodiment
Embodiments of the invention 1：Conductive PA6/PPO alloy materials, are calculated according to the mass fraction, including 700g nylon 6,300g Noryl (commercially available modification MPPO), 50g toughener MBS, 35g CNT, 50g conductive blacks, 10g compatilizers part with And 5g antioxidant 1010s are preparing raw material；The inherent viscosity of described nylon 6 is more than 2.0dL/g；Described CNT is many Wall carbon nano tube, 8~15nm of external diameter, length is 9~14 μm, and purity is more than 94%；Described conductive black is that oil factor is More than 150ml/100g conductive black；Described compatilizer is that molecular weight 100~120, epoxide equivalent are 30~550g/eq's Epoxy resin.
The preparation method of conductive PA6/PPO alloy materials, each component is taken by above-mentioned quality, by nylon 6, modified polyphenyl Ether, CNT, conductive black, compatilizer, toughener and antioxidant are well mixed, are then added in double screw extruder Row extrusion, extrusion temperature is 275 DEG C, obtains conduction PA6/PPO alloy materials；Raw material is before being extruded, by nylon 6 with being modified Polyphenylene oxide dries 4~10h at a temperature of 80~100 DEG C respectively, and CNT dries 5 with conductive black at a temperature of 75~90 DEG C ~8h.
Requirement after the PA6/PPO pellets of preparation are dried according to GB/T17037-1997 in injection machine carries out sample preparation, Then the test of tensile property is carried out according to GB/T 1040-2006, impact strength test is carried out according to GB/T1843-2008, presses Bending property test is carried out according to GB/T9341-2008, while carrying out specific insulation test according to GB/T1410-2006, and is remembered Record corresponding test result.
Embodiments of the invention 2：Raw material be the same as Example 1.
The preparation method of conductive PA6/PPO alloy materials, each component is taken by above-mentioned quality, by nylon 6, modified polyphenyl Ether, CNT, conductive black, compatilizer, toughener and antioxidant are well mixed, are then added in double screw extruder Row extrusion, extrusion temperature is 275 DEG C, by ultrasonic vibration device to carrying out ultrasound by the material of head at cross-head Vibrations, the power setting of Vltrasonic device is 200W, finally obtains conduction PA6/PPO alloy materials；Raw material, will before being extruded Nylon 6 dries 4~10h at a temperature of 80~100 DEG C respectively with Noryl, and CNT is with conductive black at 75~90 DEG C At a temperature of dry 5~8h.
Enter after conductive PA6/PPO pellets drying prepared by ultrasound in injection machine according to GB/T17037-1997 requirement Row sample preparation, then carries out the test of tensile property according to GB/T 1040-2006, and impact strength is carried out according to GB/T1843-2008 Test, bending property test is carried out according to GB/T9341-2008, while carrying out specific insulation survey according to GB/T1410-2006 Examination, and record corresponding test result.
Embodiments of the invention 3：Conductive PA6/PPO alloy materials, are calculated according to the mass fraction, including 600g nylon 6,400g Noryl, 50g toughener POE-MAH, 35g CNT, 50g conductive blacks, 25g compatilizers part and 9g antioxidant 1010 be preparing raw material；The inherent viscosity of described nylon 6 is more than 2.0dL/g；Described CNT is multi-walled carbon nanotube, 8~15nm of external diameter, length is 9~14 μm, and purity is more than 94%；Described conductive black is that oil factor is more than 150ml/100g Conductive black；Described compatilizer is the epoxy resin that molecular weight 100~120, epoxide equivalent are 30~550g/eq.
The preparation method of conductive PA6/PPO alloy materials, each component is taken by above-mentioned quality, by nylon 6, modified polyphenyl Ether, CNT, conductive black, compatilizer, toughener and antioxidant are well mixed, are then added in double screw extruder Row extrusion, extrusion temperature is 275 DEG C, by ultrasonic vibration device to carrying out ultrasound by the material of head at cross-head Vibrations, the power setting of Vltrasonic device is 300W, finally obtains conduction PA6/PPO alloy materials；Raw material, will before being extruded Nylon 6 dries 4~10h at a temperature of 80~100 DEG C respectively with Noryl, and CNT is with conductive black at 75~90 DEG C At a temperature of dry 5~8h.
Enter after conductive PA6/PPO pellets drying prepared by ultrasound in injection machine according to GB/T17037-1997 requirement Row sample preparation, then carries out the test of tensile property according to GB/T 1040-2006, and impact strength is carried out according to GB/T1843-2008 Test, bending property test is carried out according to GB/T9341-2008, while carrying out specific insulation survey according to GB/T1410-2006 Examination, and record corresponding test result.
Embodiments of the invention 4：Conductive PA6/PPO alloy materials, are calculated according to the mass fraction, including 400g nylon 6,400g Noryl, 50g toughener POE-MAH, 40g CNT, 60g conductive blacks, 32g compatilizers part and 10.2g antioxygens Agent 1010 is preparing raw material；The inherent viscosity of described nylon 6 is more than 2.0dL/g；Described CNT is multi-wall carbon nano-tube Pipe, 8~15nm of external diameter, length is 9~14 μm, and purity is more than 94%；Described conductive black is that oil factor is 150ml/100g Conductive black above；Described compatilizer is the epoxy resin that molecular weight 100~120, epoxide equivalent are 30~550g/eq.
The preparation method of conductive PA6/PPO alloy materials, each component is taken by above-mentioned quality, by nylon 6, modified polyphenyl Ether, CNT, conductive black, compatilizer, toughener and antioxidant are well mixed, are then added in double screw extruder Row extrusion, extrusion temperature is 275 DEG C, by ultrasonic vibration device to carrying out ultrasound by the material of head at cross-head Vibrations, the power setting of Vltrasonic device is 600W, finally obtains conduction PA6/PPO alloy materials；Raw material, will before being extruded Nylon 6 dries 4~10h at a temperature of 80~100 DEG C respectively with Noryl, and CNT is with conductive black at 75~90 DEG C At a temperature of dry 5~8h.
Enter after conductive PA6/PPO pellets drying prepared by ultrasound in injection machine according to GB/T17037-1997 requirement Row sample preparation, then carries out the test of tensile property according to GB/T 1040-2006, and impact strength is carried out according to GB/T1843-2008 Test, bending property test is carried out according to GB/T9341-2008, while carrying out specific insulation survey according to GB/T1410-2006 Examination, and record corresponding test result.
Each embodiment Experimental comparison of table 1
Index Embodiment 1 Embodiment 2 Embodiment 3 Embodiment 4
Tensile strength (MPa) 56.8 71.7 75.7 84.8
Bending strength (MPa) 86.2 111.5 125.5 132.4
Bending modulus (MPa) 2481 2745 2969 3333
Notch impact strength (KJ/m2) 9.1 12.5 14.2 15.4
Specific insulation (Ω cm) 7.23×106 5.82×104 5.13×104 4.32×103
Comparative example 1 is understood with embodiment 2, and ultrasonic vibration is added in PA6/PPO alloy materials melting preparation process After device, ultrasound can greatly improve the electric conductivity and its mechanical property of PA6/PPO alloy materials.

Claims (10)

1. a kind of conductive PA6/PPO alloy materials, it is characterised in that：Calculate according to the mass fraction, including 35~60 parts of nylon 6,40 ~65 parts of Noryls, 2~8 parts of toughener, 0.5~5 part of CNT, 1~10 part of conductive black, 0.1~5 part of compatilizer Part and 0.1~3.0 part of antioxidant are preparing raw material.
2. conductive PA6/PPO alloy materials according to claim 1, it is characterised in that：The inherent viscosity of described nylon 6 More than 2.0dL/g.
3. conductive PA6/PPO alloy materials according to claim 1, it is characterised in that：Described toughener is maleic acid Any group of one or both of acid anhydride grafted ethene -1- octene copolymers or Methacrylate-butadiene-styrene Close.
4. conductive PA6/PPO alloy materials according to claim 1, it is characterised in that：Described CNT is many walls CNT, 8~15nm of external diameter, length is 9~14 μm, and purity is more than 94%.
5. conductive PA6/PPO alloy materials according to claim 1, it is characterised in that：Described conductive black is oil suction It is worth the conductive black for more than 150ml/100g.
6. conductive PA6/PPO alloy materials according to claim 1, it is characterised in that：Described compatilizer is molecular weight 100~120, epoxide equivalent is 30~550g/eq epoxy resin or any group of one or both of modified epoxy Close.
7. conductive PA6/PPO alloy materials according to claim 1, it is characterised in that：The antioxidant is antioxidant 1010th, antioxidant 1076, antioxidant 1098, irgasfos 168, antioxidant B215, antioxidant B225, antioxidant 2246, antioxidant 330th, any combination one or more of in antioxidant BHT, anti-oxidant DLTP or antioxidant DSTP.
8. a kind of preparation method of conductive PA6/PPO alloy materials as claimed in claim 1, it is characterised in that：By above-mentioned Mass fraction takes each component, and nylon 6, Noryl, CNT, conductive black, compatilizer, toughener and antioxidant are mixed Close uniform, be then added in double screw extruder and extruded, obtain conduction PA6/PPO alloy materials.
9. preparation method according to claim 8, it is characterised in that：Pass through ultrasonic vibration device pair at cross-head Ultrasonic vibration is carried out by the material of head.
10. preparation method according to claim 8, it is characterised in that：Raw material is before being extruded, by nylon 6 with being modified Polyphenylene oxide dries 4~10h at a temperature of 80~100 DEG C respectively, and CNT dries 5 with conductive black at a temperature of 75~90 DEG C ~8h.
CN201710375743.0A 2017-05-25 2017-05-25 Conductive PA6/PPO alloy materials and preparation method thereof Pending CN107083055A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111019320A (en) * 2020-01-03 2020-04-17 无锡巨旺塑化材料有限公司 CNT (carbon nano tube) conductive PPO (polyphenylene oxide)/PA (polyamide) alloy and preparation method thereof
CN111073277A (en) * 2019-12-19 2020-04-28 上海普利特伴泰材料科技有限公司 PA/PPO alloy plastic capable of being sprayed on line and preparation method thereof
CN116925534A (en) * 2022-03-29 2023-10-24 珠海万通特种工程塑料有限公司 Nylon composition with adjustable dielectric constant and preparation method and application thereof

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CN102311633A (en) * 2011-04-29 2012-01-11 深圳市科聚新材料有限公司 PPO/PA66 (poly phenylene oxide/polyamide 66) alloy material as well as preparation method and application thereof
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CN102311633A (en) * 2011-04-29 2012-01-11 深圳市科聚新材料有限公司 PPO/PA66 (poly phenylene oxide/polyamide 66) alloy material as well as preparation method and application thereof
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111073277A (en) * 2019-12-19 2020-04-28 上海普利特伴泰材料科技有限公司 PA/PPO alloy plastic capable of being sprayed on line and preparation method thereof
CN111019320A (en) * 2020-01-03 2020-04-17 无锡巨旺塑化材料有限公司 CNT (carbon nano tube) conductive PPO (polyphenylene oxide)/PA (polyamide) alloy and preparation method thereof
CN116925534A (en) * 2022-03-29 2023-10-24 珠海万通特种工程塑料有限公司 Nylon composition with adjustable dielectric constant and preparation method and application thereof

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Application publication date: 20170822