CN111040432A - Conductive and flame-retardant polyamide 6 composite material and preparation method thereof - Google Patents

Conductive and flame-retardant polyamide 6 composite material and preparation method thereof Download PDF

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CN111040432A
CN111040432A CN201911278671.3A CN201911278671A CN111040432A CN 111040432 A CN111040432 A CN 111040432A CN 201911278671 A CN201911278671 A CN 201911278671A CN 111040432 A CN111040432 A CN 111040432A
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conductive
composite material
modifier
raw materials
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屈小汉
罗芳
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Shenzhen Hansem New Material Co Ltd
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Shenzhen Hansem New Material Co Ltd
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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
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2217—Oxides; Hydroxides of metals of magnesium
    • C08K2003/2224—Magnesium hydroxide
    • 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
    • C08K3/38—Boron-containing compounds
    • C08K2003/387—Borates
    • 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
    • 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
    • C08L2201/22—Halogen free composition
    • 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
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • 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
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • 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

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  • Health & Medical Sciences (AREA)
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  • Polymers & Plastics (AREA)
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  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses a conductive and flame-retardant polyamide 6 composite material and a preparation method thereof, wherein the adopted raw materials comprise the following components in parts by weight: 120-150 parts of polyamide 6, 25-35 parts of halogen-free flame retardant, 10-14 parts of conductive modifier, 5-10 parts of toughening agent, 1.5-2.0 parts of compatilizer and 0.2-0.4 part of antioxidant, and the obtained polyamide 6 composite material not only has excellent conductivity and flame retardant property, but also can still keep excellent mechanical property, wear resistance, self-lubricating property, oil resistance, impact resistance and the like.

Description

Conductive and flame-retardant polyamide 6 composite material and preparation method thereof
Technical Field
The invention relates to the technical field of polymer composite materials, in particular to a conductive and flame-retardant nylon 6 composite material and a preparation method thereof.
Background
Polyamide (PA) is an engineering plastic and is available in a wide variety of varieties, including PA6, PA66, PA11, PA12, PA46, PA610, PA612, PA1010 and the like. Among them, PA6 (polyamide 6 or nylon 6) is widely used in the fields of automobiles, machinery, electronics, instruments and the like because of its good mechanical properties, wear resistance, self-lubricity, oil resistance, impact resistance and the like. However, with the continuous development of society, the existing PA6 composite material cannot meet the use requirements in terms of conductivity and flame retardant property, so that the development of a novel polyamide 6 composite material is needed.
In order to improve the flame retardant property of PA6, a flame retardant is required to be added, the conventional flame retardants are mainly halogen flame retardants and halogen-free flame retardants, the halogen flame retardants can generate a large amount of smoke and corrosive gas to cause death of people when being heated or combusted, and some bromine flame retardants such as polybrominated diphenyl ethers are decomposed at high temperature to generate polybrominated dioxin and polybrominated furan, so that the flame retardant has a carcinogenic effect; the halogen-free flame retardant has poor actual flame retardant effect and cannot achieve ideal flame retardant effect.
The PA6 is an insulating material with the volume resistivity of about 1014 omega cm, and in order to increase the conductivity and expand the application field, the conductive modification is needed; however, at present, conductive modification is mostly realized by adding conductive Carbon Black (CB), graphite or carbon nanotubes, but the existing conductive filler has large dosage and poor dispersibility, and can seriously affect the mechanical properties and the like of PA 6.
Accordingly, it would be an urgent need to solve the problems of the art to provide a conductive and flame retardant polyamide 6 composite material and a method for preparing the same.
Disclosure of Invention
In view of the above, the invention provides an electrically conductive and flame retardant polyamide 6 composite material and a preparation method thereof, and the obtained polyamide 6 composite material not only has excellent electrical conductivity and flame retardant property, but also can maintain excellent mechanical properties, wear resistance, self-lubricity, oil resistance, impact resistance and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
the conductive and flame-retardant polyamide 6 composite material is characterized by comprising the following raw materials in parts by weight: 120-150 parts of polyamide 6, 25-35 parts of halogen-free flame retardant, 10-14 parts of conductive modifier, 5-10 parts of toughening agent, 1.5-2.0 parts of compatilizer and 0.2-0.4 part of antioxidant; the halogen-free flame retardant adopts the following raw materials: active magnesium hydroxide, microcapsule red phosphorus, antimony trioxide, zinc borate and chlorinated paraffin; the raw materials adopted by the conductive modifier comprise the following components: conductive mica powder, aluminum borate whiskers, conductive carbon black, lubricating oil base oil and a silane coupling agent.
The beneficial effects of the preferred technical scheme are as follows: according to the invention, the polyamide 6 matrix material is modified by adopting the halogen-free flame retardant, the halogen-free flame retardant is matched with other auxiliary agents, so that the flame retardant can exert excellent flame retardant performance and has excellent durability, and the flame retardant effect cannot be obviously reduced after long-term use; the combined conductive modifier is adopted, the raw materials are mutually matched to play a synergistic effect, so that the use amount of the conductive modifier can be obviously reduced, the dispersibility of the conductive modifier can be obviously improved through the interaction of the raw materials, and the prepared polyamide 6 composite material has excellent mechanical properties; and the physical and mechanical properties, the oxidation resistance and the like of the polyamide 6 composite material can be improved by matching with a toughening agent, a compatilizer and an antioxidant.
Preferably, the halogen-free flame retardant adopts the following raw materials in parts by weight: 100 parts of active magnesium hydroxide, 10-20 parts of microcapsule red phosphorus, 5-15 parts of antimony trioxide, 5-15 parts of zinc borate and 4-10 parts of chlorinated paraffin.
The beneficial effects of the preferred technical scheme are as follows: according to the invention, the synergistic effect is achieved by the mutual cooperation of the active magnesium hydroxide, the microcapsule red phosphorus, the antimony trioxide, the zinc borate and the chlorinated paraffin, so that the active magnesium hydroxide, the microcapsule red phosphorus, the antimony trioxide, the zinc borate and the chlorinated paraffin are matched with PA6 and the like, the flame retardant property of the composite material is improved, the raw material cost is reduced, and the harm to a human body and the environment is avoided.
Preferably, the raw materials adopted by the conductive modifier comprise the following components in parts by weight: 42-48 parts of conductive mica powder, 6-8 parts of aluminum borate whisker, 25-28 parts of conductive carbon black, 0.5-1.0 part of lubricating oil base oil and 0.8-1.6 parts of silane coupling agent.
The beneficial effects of the preferred technical scheme are as follows: according to the invention, the conductive modifier is prepared by mutually matching the conductive mica powder, the aluminum borate whisker, the conductive carbon black, the lubricating oil base oil and the silane coupling agent, the conductive effect of PA6 can be obviously improved, and the raw materials are matched to play a synergistic effect, so that the consumption of the conductive filler can be reduced, and the conductive modifier has excellent dispersion performance, thereby reducing the influence on the mechanical property of PA 6.
Preferably, the toughening agent comprises one or more of maleic anhydride grafted high density polyethylene, maleic anhydride grafted low density polyethylene, maleic anhydride grafted linear low density polyethylene, maleic anhydride grafted polypropylene, maleic anhydride grafted ethylene octene copolymer and maleic anhydride grafted ethylene propylene copolymer.
The beneficial effects of the preferred technical scheme are as follows: the toughening agent and the compatilizer provided by the invention are matched with each other, so that the mutual mixing action of the raw materials can be promoted, and the mechanical property of the composite material is improved.
Preferably, the compatilizer comprises one or more of maleic anhydride grafted ethylene-1-octene copolymer, maleic anhydride grafted thermoplastic elastomer and ethylene propylene diene monomer.
The beneficial effects of the preferred technical scheme are as follows: according to the invention, maleic anhydride grafted ethylene-1-octene copolymer (POE-g-MAH), maleic anhydride grafted thermoplastic elastomer (TPE-g-MAH) and ethylene propylene diene monomer (EPDM-g-MAH) are matched with each other, so that the compatibility is improved, and the mechanical property of the composite material is improved.
Preferably, the oxidant comprises one or more of metallic titanium powder, antioxidant B215, antioxidant B225, antioxidant 1010 and antioxidant 1076.
The beneficial effects of the preferred technical scheme are as follows: the antioxidant disclosed by the invention is matched with matrix resin and other fillers, so that the antioxidant performance of the composite material can be obviously improved, and the service life of the composite material is prolonged.
The invention also provides a preparation method of the conductive and flame-retardant polyamide 6 composite material, which comprises the following steps:
(1) weighing the raw materials according to the composite material, and drying the solid raw materials for later use;
(2) preparing a conductive modifier from a conductive modifier raw material;
(3) adding the raw materials except the conductive modifier into a high-speed mixer, and uniformly mixing to obtain a mixed material;
(4) and adding the mixed material and the conductive modifier into a double-screw extruder, and performing melt blending extrusion, cooling, air drying and granulation to obtain the conductive halogen-free flame-retardant PA6 composite material.
Preferably, the step (2) specifically comprises:
(a) weighing 42-48 parts of conductive mica powder, 6-8 parts of aluminum borate whisker, 25-28 parts of conductive carbon black, 0.5-1.0 part of lubricating oil base oil and 0.8-1.6 parts of silane coupling agent for later use;
(b) uniformly mixing conductive mica powder and aluminum borate whiskers, roasting for 4-5 hours in a vacuum furnace at the temperature of 1000-1200 ℃, cooling a roasted product to the temperature of 15-25 ℃, dispersing the roasted product with a chitosan aqueous solution, filtering, and drying a filtered product;
(c) and stirring and reacting the filtrate, the conductive carbon black, the silane coupling agent and the lubricating oil base oil at the temperature of 60-70 ℃ for 65-75 min to obtain the conductive modifier.
Preferably, the vacuum degree of the drying in the step (1) is 0.05-0.09Mpa, the temperature is 75-85 ℃, and the time is 6-7 h.
Preferably, the stirring speed of the high-speed mixer in the step (3) is 1000-.
Preferably, the heating temperature of each heating zone passed by the twin-screw extruder from the feed port to the die head in the step (4) is as follows in sequence: t1-150 ℃, T2-160 ℃, T3-170 ℃, T4-180 ℃, T5-190 ℃, T6-200 ℃, T7-210-220 ℃, T8-220-230 ℃, T9-230-240 ℃, T die head 230-240 ℃ and
the rotation speed of the feeder is 430-800 rpm, and the rotation speed of the twin screw is 300-600 rpm.
Preferably, the molding process of the conductive halogen-free flame-retardant PA6 composite material prepared in the step (3) comprises the steps of drying the obtained granules at 105-115 ℃ for 6-7 hours, and performing injection molding on an injection molding machine to obtain standard tensile and impact sample strips, wherein the injection molding temperature is 240-250 ℃; pressing the particles into a plate on a flat vulcanizing machine, wherein the hot pressing temperature is 235-240 ℃, the pressing gauge pressure is 10MPa, the hot pressing time is 2-3 min, and the cold pressing time is 2 min.
According to the technical scheme, compared with the prior art, the invention discloses the conductive and flame-retardant polyamide 6 composite material and the preparation method thereof, and the conductive and flame-retardant polyamide 6 composite material has the following beneficial effects:
(1) the preparation method disclosed by the invention is simple to operate, and raw materials are uniformly mixed, so that the composite material with uniform and stable properties can be prepared;
(2) the prepared polyamide 6 composite material not only has excellent conductivity and flame retardance, but also can still maintain excellent mechanical property, wear resistance, self-lubrication, oil resistance, impact resistance and the like.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The embodiment of the invention discloses a conductive and flame-retardant polyamide 6 composite material, which is characterized by comprising the following raw materials in parts by weight: 120-150 parts of polyamide 6, 25-35 parts of halogen-free flame retardant, 10-14 parts of conductive modifier, 5-10 parts of toughening agent, 1.5-2.0 parts of compatilizer and 0.2-0.4 part of antioxidant; the halogen-free flame retardant adopts the following raw materials: active magnesium hydroxide, microcapsule red phosphorus, antimony trioxide, zinc borate and chlorinated paraffin; the raw materials adopted by the conductive modifier comprise the following components: conductive mica powder, aluminum borate whiskers, conductive carbon black, lubricating oil base oil and a silane coupling agent.
In order to further optimize the technical scheme, the halogen-free flame retardant adopts the following raw materials in parts by weight: 100 parts of active magnesium hydroxide, 10-20 parts of microcapsule red phosphorus, 5-15 parts of antimony trioxide, 5-15 parts of zinc borate and 4-10 parts of chlorinated paraffin.
In order to further optimize the technical scheme, the raw materials adopted by the conductive modifier comprise the following components in parts by weight: 42-48 parts of conductive mica powder, 6-8 parts of aluminum borate whisker, 25-28 parts of conductive carbon black, 0.5-1.0 part of lubricating oil base oil and 0.8-1.6 parts of silane coupling agent.
For further optimization, the toughening agent comprises one or more of maleic anhydride grafted high-density polyethylene, maleic anhydride grafted low-density polyethylene, maleic anhydride grafted linear low-density polyethylene, maleic anhydride grafted polypropylene, maleic anhydride grafted ethylene octene copolymer and maleic anhydride grafted ethylene propylene copolymer.
For further optimization, the compatilizer comprises one or more of maleic anhydride grafted ethylene-1-octene copolymer, maleic anhydride grafted thermoplastic elastomer and ethylene propylene diene monomer.
For further optimization, the oxidant comprises one or more of metallic titanium powder, antioxidant B215, antioxidant B225, antioxidant 1010 and antioxidant 1076.
The embodiment of the invention also provides a preparation method of the conductive and flame-retardant polyamide 6 composite material, which is characterized by comprising the following steps:
(1) weighing the raw materials according to the composite material, and drying the solid raw materials for later use;
(2) preparing a conductive modifier from a conductive modifier raw material;
(3) adding the raw materials except the conductive modifier into a high-speed mixer, and uniformly mixing to obtain a mixed material;
(4) and adding the mixed material and the conductive modifier into a double-screw extruder, and performing melt blending extrusion, cooling, air drying and granulation to obtain the conductive halogen-free flame-retardant PA6 composite material.
In order to further optimize the technical scheme, the step (2) specifically comprises the following steps:
(a) weighing 42-48 parts of conductive mica powder, 6-8 parts of aluminum borate whisker, 25-28 parts of conductive carbon black, 0.5-1.0 part of lubricating oil base oil and 0.8-1.6 parts of silane coupling agent for later use;
(b) uniformly mixing conductive mica powder and aluminum borate whiskers, roasting for 4-5 hours in a vacuum furnace at the temperature of 1000-1200 ℃, cooling a roasted product to the temperature of 15-25 ℃, dispersing the roasted product with a chitosan aqueous solution, filtering, and drying a filtered product;
(c) and stirring and reacting the filtrate, the conductive carbon black, the silane coupling agent and the lubricating oil base oil at the temperature of 60-70 ℃ for 65-75 min to obtain the conductive modifier.
In order to further optimize the technical scheme, the vacuum degree of the drying in the step (1) is 0.05-0.09Mpa, the temperature is 75-85 ℃, and the time is 6-7 hours.
In order to further optimize the technical scheme, the stirring speed of the high-speed mixer in the step (3) is 1000-1500r/min, and the time is 5-8 min.
In order to further optimize the technical solution, the method for preparing the conductive and flame retardant polyamide 6 composite material according to claim 7 is characterized in that the heating temperature of the twin-screw extruder in the step (4) from the feed port to each heating zone of the die is as follows: t1 ═ 150 ℃ to 160 ℃, T2 ═ 160 ℃ to 170 ℃, T3 ═ 170 ℃ to 180 ℃, T4 ═ 180 ℃ to 190 ℃, T5 ═ 190 ℃ to 200 ℃, T6 ═ 200 ℃ to 210 ℃, T7 ═ 210 ℃ to 220 ℃, T8 ═ 220 ℃ to 230 ℃, T9 ═ 230 ℃ to 240 ℃, T die head ═ 230 ℃ to 240 ℃; the rotation speed of the feeder is 430-800 rpm, and the rotation speed of the twin screw is 300-600 rpm.
In order to further optimize the technical scheme, the forming process of the conductive halogen-free flame-retardant PA6 composite material prepared in the step (3) comprises the steps of blowing and drying the obtained granules for 4-5 hours at 110-120 ℃, and performing injection molding on the granules on an injection molding machine to form standard tensile and impact sample strips, wherein the injection molding temperature is 235-245 ℃; pressing the particles into a plate on a flat vulcanizing machine, wherein the hot pressing temperature is 230-240 ℃, the pressing gauge pressure is 10MPa, the hot pressing time is 2-3 min, and the cold pressing time is 2 min.
Example 1
The embodiment 1 of the invention discloses a conductive and flame-retardant polyamide 6 composite material, which comprises the following raw materials in parts by weight: 1200g of polyamide 6, 250g of halogen-free flame retardant, 100g of conductive modifier, 50g of toughening agent, 15g of compatilizer and 2g of antioxidant;
the halogen-free flame retardant adopts the following raw materials in parts by weight: 100 parts of active magnesium hydroxide, 10 parts of microcapsule red phosphorus, 5 parts of antimony trioxide, 5 parts of zinc borate and 4 parts of chlorinated paraffin;
the conductive modifier adopts the following raw materials in parts by weight: 42 parts of conductive mica powder, 6 parts of aluminum borate whisker, 25 parts of conductive carbon black, 0.5 part of lubricating oil base oil and 0.8 part of silane coupling agent.
The toughening agent is maleic anhydride grafted high-density polyethylene.
The compatilizer is maleic anhydride grafted ethylene-1-octene copolymer.
The oxidant comprises metallic titanium powder and an antioxidant B215.
The embodiment 1 of the invention also provides a preparation method of the conductive and flame-retardant polyamide 6 composite material, which is characterized by comprising the following steps:
(1) weighing the raw materials according to the composite material, and drying the solid raw materials for later use, wherein the drying vacuum degree is 0.05Mpa, the temperature is 75 ℃, and the time is 7 hours;
(2) preparation of conductive modifier from conductive modifier raw material
(a) Weighing 42 parts of conductive mica powder, 6 parts of aluminum borate whisker, 25 parts of conductive carbon black, 0.5 part of lubricating oil base oil and 0.8 part of silane coupling agent for later use;
(b) uniformly mixing conductive mica powder and aluminum borate whiskers, roasting for 5 hours in a 1000 ℃ vacuum furnace, cooling a roasted product to 25 ℃, dispersing the roasted product with a chitosan aqueous solution, filtering, and drying a filtrate;
(c) and stirring and reacting the filtrate, the conductive carbon black, the silane coupling agent and the lubricating oil base oil at 70 ℃ for 65min to obtain the conductive modifier.
(3) Adding the raw materials except the conductive modifier into a high-speed mixer, and uniformly mixing to obtain a mixed material, wherein the stirring speed of the high-speed mixer is 1000r/min, and the stirring time is 8 min;
(4) adding the mixed material and the conductive modifier into a double-screw extruder, and performing melt blending extrusion, cooling, air drying and granulation to obtain the conductive halogen-free flame-retardant PA6 composite material;
the heating temperature of each heating zone from the feed inlet to the die head of the double-screw extruder is as follows in sequence: t1 ═ 150 ℃, T2 ═ 160 ℃, T3 ═ 170 ℃, T4 ═ 180 ℃, T5 ═ 190 ℃, T6 ═ 200 ℃, T7 ═ 210 ℃, T8 ═ 220 ℃, T9 ═ 230 ℃, T die ═ 230 ℃; the feeder speed was 430rpm and the twin screw speed was 300 rpm.
Example 2
The embodiment 2 of the invention discloses a conductive and flame-retardant polyamide 6 composite material, which comprises the following raw materials in parts by weight: 1500g of polyamide 6, 350g of halogen-free flame retardant, 140g of conductive modifier, 100g of toughening agent, 20g of compatilizer and 4g of antioxidant;
the halogen-free flame retardant adopts the following raw materials in parts by weight: 100 parts of active magnesium hydroxide, 20 parts of microcapsule red phosphorus, 15 parts of antimony trioxide, 15 parts of zinc borate and 10 parts of chlorinated paraffin;
the conductive modifier adopts the following raw materials in parts by weight: 48 parts of conductive mica powder, 8 parts of aluminum borate whisker, 28 parts of conductive carbon black, 1.0 part of lubricating oil base oil and 1.6 parts of silane coupling agent.
The toughening agent comprises a combination of maleic anhydride grafted low density polyethylene and maleic anhydride grafted linear low density polyethylene.
The compatilizer comprises one or more of maleic anhydride grafted ethylene-1-octene copolymer and ethylene propylene diene monomer.
The oxidant comprises metal titanium powder, antioxidant B225 and antioxidant 1010.
The embodiment 2 of the invention also provides a preparation method of the conductive and flame-retardant polyamide 6 composite material, which is characterized by comprising the following steps:
(1) weighing the raw materials according to the composite material, and drying the solid raw materials for later use, wherein the vacuum degree of drying is 0.09Mpa, the temperature is 85 ℃, and the time is 6 hours;
(2) preparation of conductive modifier from conductive modifier raw material
(a) Weighing 48 parts of conductive mica powder, 8 parts of aluminum borate whisker, 28 parts of conductive carbon black, 1.0 part of lubricating oil base oil and 1.6 parts of silane coupling agent for later use;
(b) uniformly mixing conductive mica powder and aluminum borate whiskers, roasting for 4 hours in a 1200 ℃ vacuum furnace, cooling a roasted product to 15 ℃, dispersing the roasted product with a chitosan aqueous solution, filtering, and drying a filtrate;
(c) and stirring and reacting the filtrate, the conductive carbon black, the silane coupling agent and the lubricating oil base oil at the temperature of 60 ℃ for 75min to obtain the conductive modifier.
(3) Adding the raw materials except the conductive modifier into a high-speed mixer, and uniformly mixing to obtain a mixed material, wherein the stirring speed of the high-speed mixer is 1500r/min, and the stirring time is 5 min;
(4) adding the mixed material and the conductive modifier into a double-screw extruder, and performing melt blending extrusion, cooling, air drying and granulation to obtain the conductive halogen-free flame-retardant PA6 composite material;
the heating temperature of each heating zone from the feed inlet to the die head of the double-screw extruder is as follows in sequence: t1 ═ 160 ℃, T2 ═ 170 ℃, T3 ═ 180 ℃, T4 ═ 190 ℃, T5 ═ 200 ℃, T6 ═ 210 ℃, T7 ═ 220 ℃, T8 ═ 230 ℃, T9 ═ 240 ℃, T die ═ 240 ℃; the rotation speed of the feeder is 800rpm, and the rotation speed of the twin screw is 600 rpm.
Example 3
The embodiment 3 of the invention discloses a conductive and flame-retardant polyamide 6 composite material, which comprises the following raw materials in parts by weight: 1350g of polyamide 6, 280g of halogen-free flame retardant, 130g of conductive modifier, 70g of toughening agent, 18g of compatilizer and 3g of antioxidant;
the halogen-free flame retardant adopts the following raw materials in parts by weight: 100 parts of active magnesium hydroxide, 18 parts of microcapsule red phosphorus, 8 parts of antimony trioxide, 9 parts of zinc borate and 7 parts of chlorinated paraffin;
the conductive modifier adopts the following raw materials in parts by weight: 45 parts of conductive mica powder, 7 parts of aluminum borate whisker, 26 parts of conductive carbon black, 0.8 part of lubricating oil base oil and 1.0 part of silane coupling agent.
The toughening agent includes a combination of maleic anhydride grafted polypropylene, maleic anhydride grafted ethylene octene copolymer, and maleic anhydride grafted ethylene propylene copolymer.
The compatibilizer comprises a combination of maleic anhydride grafted thermoplastic elastomer and ethylene propylene diene monomer.
The oxidizing agent includes one or more of metallic titanium powder and an antioxidant 1076.
Embodiment 3 of the present invention further provides a preparation method of a conductive and flame retardant polyamide 6 composite material, which is characterized by specifically comprising the following steps:
(1) weighing the raw materials according to the composite material, and drying the solid raw materials for later use, wherein the drying vacuum degree is 0.07Mpa, the temperature is 80 ℃, and the time is 7 hours;
(2) preparation of conductive modifier from conductive modifier raw material
(a) Weighing 45 parts of conductive mica powder, 7 parts of aluminum borate whisker, 26 parts of conductive carbon black, 0.8 part of lubricating oil base oil and 1.0 part of silane coupling agent for later use;
(b) uniformly mixing conductive mica powder and aluminum borate whisker, roasting for 4.5 hours in a vacuum furnace at 1100 ℃, cooling a roasted product to 20 ℃, dispersing the roasted product with a chitosan aqueous solution, filtering, and drying a filtered substance;
(c) and stirring and reacting the filtrate, the conductive carbon black, the silane coupling agent and the lubricating oil base oil at 65 ℃ for 70min to obtain the conductive modifier.
(3) Adding the raw materials except the conductive modifier into a high-speed mixer, and uniformly mixing to obtain a mixed material, wherein the stirring speed of the high-speed mixer is 1200r/min, and the stirring time is 6 min;
(4) adding the mixed material and the conductive modifier into a double-screw extruder, and performing melt blending extrusion, cooling, air drying and granulation to obtain the conductive halogen-free flame-retardant PA6 composite material;
the heating temperature of each heating zone from the feed inlet to the die head of the double-screw extruder is as follows in sequence: t1 ═ 155 ℃, T2 ═ 168 ℃, T3 ═ 176 ℃, T4 ═ 185 ℃, T5 ═ 197 ℃, T6 ═ 205 ℃, T7 ═ 214 ℃, T8 ═ 226 ℃, T9 ═ 233 ℃, T die ═ 234 ℃; the rotation speed of the feeder is 600rpm, and the rotation speed of the twin screw is 400 rpm.
Example 4
The embodiment 4 of the invention discloses a conductive and flame-retardant polyamide 6 composite material, which comprises the following raw materials in parts by weight: 1450g of polyamide 6, 320g of halogen-free flame retardant, 130g of conductive modifier, 60g of toughening agent, 12g of compatilizer and 3.5g of antioxidant;
the halogen-free flame retardant adopts the following raw materials in parts by weight: 100 parts of active magnesium hydroxide, 17 parts of microcapsule red phosphorus, 6 parts of antimony trioxide, 9 parts of zinc borate and 9 parts of chlorinated paraffin;
the conductive modifier adopts the following raw materials in parts by weight: 44 parts of conductive mica powder, 7 parts of aluminum borate whisker, 28.1 parts of conductive carbon black, 0.8 part of lubricating oil base oil and 0.9 part of silane coupling agent.
The toughening agent is maleic anhydride grafted ethylene octene copolymer.
The compatilizer is ethylene propylene diene monomer.
The oxidant is metallic titanium powder.
Embodiment 4 of the present invention further provides a preparation method of a conductive and flame retardant polyamide 6 composite material, which is characterized by specifically comprising the following steps:
(1) weighing the raw materials according to the composite material, and drying the solid raw materials for later use, wherein the drying vacuum degree is 0.07Mpa, the temperature is 79 ℃, and the time is 6.7 hours;
(2) preparation of conductive modifier from conductive modifier raw material
(a) Weighing 44 parts of conductive mica powder, 7 parts of aluminum borate whisker, 28.1 parts of conductive carbon black, 0.8 part of lubricating oil base oil and 0.9 part of silane coupling agent for later use;
(b) uniformly mixing conductive mica powder and aluminum borate whisker, roasting for 5 hours in a 1050 ℃ vacuum furnace, cooling a roasted product to 22 ℃, dispersing the roasted product with a chitosan water solution, filtering, and drying a filtered substance;
(c) and (3) stirring and reacting the filtrate, the conductive carbon black, the silane coupling agent and the lubricating oil base oil at 67 ℃ for 67min to obtain the conductive modifier.
(3) Adding the raw materials except the conductive modifier into a high-speed mixer, and uniformly mixing to obtain a mixed material, wherein the stirring speed of the high-speed mixer is 1450r/min, and the stirring time is 7 min;
(4) adding the mixed material and the conductive modifier into a double-screw extruder, and performing melt blending extrusion, cooling, air drying and granulation to obtain the conductive halogen-free flame-retardant PA6 composite material;
the heating temperature of each heating zone from the feed inlet to the die head of the double-screw extruder is as follows in sequence: t1 ═ 158 ℃, T2 ═ 163 ℃, T3 ═ 171 ℃, T4 ═ 184 ℃, T5 ═ 195 ℃, T6 ═ 206 ℃, T7 ═ 217 ℃, T8 ═ 227 ℃, T9 ═ 238 ℃, T die ═ 238 ℃; the feeding speed is 700rpm, and the twin-screw speed is 580 rpm.
Example 5
The embodiment 5 of the invention discloses a conductive and flame-retardant polyamide 6 composite material, which comprises the following raw materials in parts by weight: 1450g of polyamide 6, 310g of halogen-free flame retardant, 135g of conductive modifier, 78g of toughening agent, 19g of compatilizer and 2.8g of antioxidant;
the halogen-free flame retardant adopts the following raw materials in parts by weight: 100 parts of active magnesium hydroxide, 16.5 parts of microcapsule red phosphorus, 8.5 parts of antimony trioxide, 9.7 parts of zinc borate and 67 parts of chlorinated paraffin;
the conductive modifier adopts the following raw materials in parts by weight: 46 parts of conductive mica powder, 7 parts of aluminum borate whisker, 26 parts of conductive carbon black, 0.8 part of lubricating oil base oil and 0.9 part of silane coupling agent.
The toughening agents include combinations of maleic anhydride grafted high density polyethylene, maleic anhydride grafted linear low density polyethylene, maleic anhydride grafted polypropylene, and maleic anhydride grafted ethylene propylene copolymers.
The compatibilizer comprises a combination of maleic anhydride grafted thermoplastic elastomer and ethylene propylene diene monomer.
The oxidizer includes a combination of metallic titanium powder, antioxidant 1010 and antioxidant 1076.
Embodiment 5 of the present invention further provides a preparation method of a conductive and flame retardant polyamide 6 composite material, specifically including the following steps:
(1) weighing the raw materials according to the composite material, and drying the solid raw materials for later use, wherein the drying vacuum degree is 0.08Mpa, the temperature is 82 ℃, and the time is 7 hours;
(2) preparation of conductive modifier from conductive modifier raw material
(a) Weighing 46 parts of conductive mica powder, 7 parts of aluminum borate whisker, 26 parts of conductive carbon black, 0.7 part of lubricating oil base oil and 0.9 part of silane coupling agent for later use;
(b) uniformly mixing conductive mica powder and aluminum borate whisker, roasting for 5 hours in a 1100 ℃ vacuum furnace, cooling a roasted product to 25 ℃, dispersing the roasted product with a chitosan water solution, filtering, and drying a filtered substance;
(c) and stirring and reacting the filtrate, the conductive carbon black, the silane coupling agent and the lubricating oil base oil at 70 ℃ for 75min to obtain the conductive modifier.
(3) Adding the raw materials except the conductive modifier into a high-speed mixer, and uniformly mixing to obtain a mixed material, wherein the stirring speed of the high-speed mixer is 1400r/min, and the stirring time is 8 min;
(4) adding the mixed material and the conductive modifier into a double-screw extruder, and performing melt blending extrusion, cooling, air drying and granulation to obtain the conductive halogen-free flame-retardant PA6 composite material;
the heating temperature of each heating zone from the feed inlet to the die head of the double-screw extruder is as follows in sequence: t1 ═ 158 ℃, T2 ═ 164 ℃, T3 ═ 175 ℃, T4 ═ 185 ℃, T5 ═ 194 ℃, T6 ═ 206 ℃, T7 ═ 215 ℃, T8 ═ 225 ℃, T9 ═ 237 ℃, T die ═ 238 ℃; the feeder speed was 650rpm and the twin screw speed was 450 rpm.
Comparative example 1
The halogen-free flame retardant component in example 5 was omitted and the other steps and technical parameters were unchanged.
Comparative example 2
The conductivity modifier component of example 5 was removed and the other steps and technical parameters were unchanged.
The performance test is carried out on the conductive halogen-free flame retardant PA6 composite materials prepared in the above examples 1-5 and comparative examples 1-2.
Respectively carrying out forced air drying on the granules of the conductive halogen-free flame-retardant PA6 composite material prepared in the embodiments 1-5 at 116 ℃ for 5h, and carrying out injection molding on the granules on an injection molding machine to form standard tensile and impact sample strips, wherein the injection molding temperature is 238 ℃; pressing the particles into plates on a flat vulcanizing machine, wherein the hot pressing temperature is 232 ℃, the pressing gauge pressure is 10MPa, the hot pressing time is 3min, and the cold pressing time is 2 min.
The resulting bars were tested for properties and the results are shown in Table 1 below.
TABLE 1
Figure BSA0000197398230000121
Figure BSA0000197398230000131
From the results in table 1 above, it is evident that: compared with a comparative example, the flame retardant property and the conductivity of the conductive and flame retardant polyamide 6 composite material prepared in the embodiments 1-5 of the invention are obviously improved, and the mechanical properties such as tensile strength, bending strength, port impact strength and the like are also obviously improved.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other. The device disclosed by the embodiment corresponds to the method disclosed by the embodiment, so that the description is simple, and the relevant points can be referred to the method part for description.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims (10)

1. The conductive and flame-retardant polyamide 6 composite material is characterized by comprising the following raw materials in parts by weight: 120-150 parts of polyamide 6, 25-35 parts of halogen-free flame retardant, 10-14 parts of conductive modifier, 5-10 parts of toughening agent, 1.5-2.0 parts of compatilizer and 0.2-0.4 part of antioxidant; the halogen-free flame retardant adopts the following raw materials: active magnesium hydroxide, microcapsule red phosphorus, antimony trioxide, zinc borate and chlorinated paraffin; the raw materials adopted by the conductive modifier comprise the following components: conductive mica powder, aluminum borate whiskers, conductive carbon black, lubricating oil base oil and a silane coupling agent.
2. The conductive and flame-retardant polyamide 6 composite material as claimed in claim 1, wherein the halogen-free flame retardant comprises the following raw materials in parts by weight: 100 parts of active magnesium hydroxide, 10-20 parts of microcapsule red phosphorus, 5-15 parts of antimony trioxide, 5-15 parts of zinc borate and 4-10 parts of chlorinated paraffin.
3. The conductive and flame-retardant polyamide 6 composite material as claimed in claim 1, wherein the conductive modifier is prepared from the following raw materials in parts by weight: 42-48 parts of conductive mica powder, 6-8 parts of aluminum borate whisker, 25-28 parts of conductive carbon black, 0.5-1.0 part of lubricating oil base oil and 0.8-1.6 parts of silane coupling agent.
4. The electrically conductive, flame retardant polyamide 6 composite material of claim 1, wherein the toughening agent comprises one or more of maleic anhydride grafted high density polyethylene, maleic anhydride grafted low density polyethylene, maleic anhydride grafted linear low density polyethylene, maleic anhydride grafted polypropylene, maleic anhydride grafted ethylene octene copolymer, and maleic anhydride grafted ethylene propylene copolymer in combination.
5. The electrically conductive, flame retardant polyamide 6 composite of claim 1, wherein the compatibilizer comprises one or more of a combination of maleic anhydride grafted ethylene-1-octene copolymer, maleic anhydride grafted thermoplastic elastomer, and ethylene propylene diene monomer.
6. The electrically conductive, flame retardant polyamide 6 composite material of claim 1, wherein the oxidizing agent comprises one or more of metallic titanium powder, antioxidant B215, antioxidant B225, antioxidant 1010, antioxidant 1076.
7. The preparation method of the conductive and flame-retardant polyamide 6 composite material is characterized by comprising the following steps:
(1) weighing each raw material according to the composite material of any one of claims 1 to 6, and drying the solid raw material for later use;
(2) preparing a conductive modifier from a conductive modifier raw material;
(3) adding the raw materials except the conductive modifier into a high-speed mixer, and uniformly mixing to obtain a mixed material;
(4) and adding the mixed material and the conductive modifier into a double-screw extruder, and performing melt blending extrusion, cooling, air drying and granulation to obtain the conductive halogen-free flame-retardant PA6 composite material.
8. The preparation method of the conductive and flame-retardant polyamide 6 composite material as claimed in claim 7, wherein the step (2) specifically comprises:
(a) weighing 42-48 parts of conductive mica powder, 6-8 parts of aluminum borate whisker, 25-28 parts of conductive carbon black, 0.5-1.0 part of lubricating oil base oil and 0.8-1.6 parts of silane coupling agent for later use;
(b) uniformly mixing conductive mica powder and aluminum borate whiskers, roasting for 4-5 hours in a vacuum furnace at the temperature of 1000-1200 ℃, cooling a roasted product to the temperature of 15-25 ℃, dispersing the roasted product with a chitosan aqueous solution, filtering, and drying a filtered product;
(c) and stirring and reacting the filtrate, the conductive carbon black, the silane coupling agent and the lubricating oil base oil at the temperature of 60-70 ℃ for 65-75 min to obtain the conductive modifier.
9. The method for preparing an electrically conductive and flame retardant polyamide 6 composite material as claimed in claim 7, wherein the stirring speed of the high speed mixer in step (3) is 1000-1500r/min for 5-8 min.
10. The method for preparing an electrically conductive and flame retardant polyamide 6 composite material as claimed in claim 7, wherein the heating temperature of each heating zone passing from the feed inlet to the die of the twin-screw extruder in the step (4) is as follows in sequence: t1 ═ 150 ℃ to 160 ℃, T2 ═ 160 ℃ to 170 ℃, T3 ═ 170 ℃ to 180 ℃, T4 ═ 180 ℃ to 190 ℃, T5 ═ 190 ℃ to 200 ℃, T6 ═ 200 ℃ to 210 ℃, T7 ═ 210 ℃ to 220 ℃, T8 ═ 220 ℃ to 230 ℃, T9 ═ 230 ℃ to 240 ℃, T die head ═ 230 ℃ to 240 ℃; the rotation speed of the feeder is 430-800 rpm, and the rotation speed of the twin screw is 300-600 rpm.
CN201911278671.3A 2019-12-13 2019-12-13 Conductive and flame-retardant polyamide 6 composite material and preparation method thereof Pending CN111040432A (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114525964A (en) * 2022-03-09 2022-05-24 张俊 Conductive ratchet wheel assembly and preparation method thereof

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