CN111100453A - Halogen-free flame-retardant PA antistatic material and product thereof - Google Patents
Halogen-free flame-retardant PA antistatic material and product thereof Download PDFInfo
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- CN111100453A CN111100453A CN201811255755.0A CN201811255755A CN111100453A CN 111100453 A CN111100453 A CN 111100453A CN 201811255755 A CN201811255755 A CN 201811255755A CN 111100453 A CN111100453 A CN 111100453A
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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
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
-
- 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
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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
- C08L2201/00—Properties
- C08L2201/04—Antistatic
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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
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The invention relates to the technical field of high polymer materials, and particularly discloses a halogen-free flame-retardant PA antistatic material and a product thereof. The halogen-free flame-retardant PA antistatic material comprises, by mass, 44.5-82.8 parts of PA, 2-25 parts of a conductive medium, 2-5 parts of a toughening agent, 0.2-0.5 part of an anti-dripping agent and a flame retardant, relative to 100 parts of a finished material product, wherein the flame retardant is a compound of 12-20 parts of a hypophosphite flame retardant and 1-5 parts of an ester flame retardant. The halogen-free flame-retardant PA antistatic material can meet the requirements of antistatic property and high flame retardance, and has good mechanical property.
Description
[ technical field ] A method for producing a semiconductor device
The invention relates to the technical field of high polymer materials, in particular to a halogen-free flame-retardant PA antistatic material.
[ background of the invention ]
Polyamide (PA) is a high polymer whose main chain contains polar amide groups (-CO-NH-). The PA is originally used as a raw material for manufacturing fibers, and later becomes an engineering plastic widely applied in the industry at present due to the advantages of toughness, wear resistance, self lubrication, wide use temperature range and the like.
In order to meet the antistatic property of electronic and electric products, PA antistatic material is usually adopted to prepare accessories of the electronic and electric products. However, in the existing PA antistatic material, since carbon black or carbon nanotubes are added to the PA material as a conductive medium, the mechanical properties of the material are reduced as a whole; in addition, the wick effect of carbon black and carbon nanotubes can make it difficult to achieve high flame retardant ratings for the material.
Therefore, there is a need to develop a halogen-free flame retardant PA antistatic material to solve the above problems.
[ summary of the invention ]
The invention aims to provide a halogen-free flame-retardant PA antistatic material which can meet the requirements of antistatic property and high flame retardance and has good mechanical property.
In order to achieve the purpose, the invention adopts the following technical scheme:
the halogen-free flame-retardant PA antistatic material comprises the following components in parts by mass relative to 100 parts by mass of a finished material product:
44.5-82.8 parts by mass of PA;
2-25 parts by mass of a conductive medium;
2-5 parts by mass of a toughening agent;
0.2-0.5 parts by mass of an anti-dripping agent; and
the flame retardant is a compound of 12-20 parts by mass of hypophosphite flame retardant and 1-5 parts by mass of ester flame retardant.
Preferably, the anti-dripping agent is 0.2 part by mass, 0.3 part by mass, 0.4 part by mass or 0.5 part by mass; the hypophosphite flame retardant is 12 parts by mass, 13 parts by mass, 14 parts by mass, 15 parts by mass, 16 parts by mass, 17 parts by mass, 18 parts by mass, 19 parts by mass and 20 parts by mass; the ester flame retardant is 1 part by mass, 2 parts by mass, 3 parts by mass, 4 parts by mass or 5 parts by mass.
Wherein the hypophosphite flame retardant is a vinyl aluminum hypophosphite flame retardant or an aluminum methyl hypophosphite flame retardant; the ester flame retardant is melamine polyphosphate (MCA) or melamine cyanurate (MPP).
Wherein the PA is an aliphatic polyamide or an aromatic polyamide. Preferably, the aliphatic polyamide is PA6 or PA 66; the aramid is PA6T or PA 1212.
Wherein the toughening agent is one or more of propylene grafted maleic anhydride (PP-g-MAH), styrene-butadiene-styrene copolymer grafted maleic anhydride (SBS-g-MAH) and styrene-ethylene-butyl copolymer grafted maleic anhydride (SEBS-g-MAH). Preferably, the toughening agent is 2 parts by mass, 3 parts by mass, 4 parts by mass or 5 parts by mass.
Wherein the conductive medium is carbon black and/or carbon nanotubes. Wherein the carbon nano tube accounts for 0-4 parts by mass. Preferably, the carbon nanotube is 0 part by mass, 1 part by mass, 2 parts by mass, 3 parts by mass, or 4 parts by mass.
Wherein the carbon nanotube is a single-walled carbon nanotube, a double-walled carbon nanotube or a multi-walled carbon nanotube; the diameter of the carbon nano tube is 0.7 nm-7 nm, and the length-diameter ratio of the carbon nano tube is more than or equal to 500. The carbon nano tube has an oil absorption value of more than or equal to 300ml/100g and a nitrogen adsorption BET specific surface area of more than or equal to 250m2(ii) the iodine adsorption value is more than or equal to 400 mg/g.
Wherein the carbon black is 0 to 25 parts by mass. Preferably, the carbon black is 0 part by mass, 2 parts by mass, 4 parts by mass, 6 parts by mass, 8 parts by mass, 10 parts by mass, 12 parts by mass, 14 parts by mass, 16 parts by mass, 18 parts by mass, 20 parts by mass, 22 parts by mass, 24 parts by mass, or 25 parts by mass.
Wherein the carbon black is acetylene carbon black. The oil absorption value of the carbon black is more than or equal to 150ml/100g, and the nitrogen adsorption BET specific surface area is more than or equal to 50m2The volume resistance is less than or equal to 10ohm.
The halogen-free flame-retardant PA antistatic material product is prepared from the halogen-free flame-retardant PA antistatic material.
The invention has the beneficial effects that: according to the halogen-free flame-retardant PA antistatic material and the product thereof, 2-25 parts by mass of a conductive medium, 2-5 parts by mass of a toughening agent, 0.2-0.5 part by mass of an anti-dripping agent, 12-20 parts by mass of a hypophosphite flame retardant and 1-5 parts by mass of an ester flame retardant are added into 44.5-82.8 parts by mass of PA, so that the tensile, bending and impact mechanical properties of the material are improved while the antistatic property and high flame retardance of the material are met, and the application range of the material is expanded.
[ detailed description ] embodiments
The invention provides a halogen-free flame-retardant PA antistatic material which comprises, by mass, 44.5-82.8 parts of PA, 2-25 parts of a conductive medium, 2-5 parts of a toughening agent, 0.2-0.5 part of an anti-dripping agent and a flame retardant, wherein the flame retardant is a compound of 12-20 parts of a hypophosphite flame retardant and 1-5 parts of an ester flame retardant, relative to 100 parts of a finished material.
Specifically, in the halogen-free flame-retardant PA antistatic material, PA is aliphatic polyamide or aromatic polyamide. Preferably, the aliphatic polyamide is PA6 or PA 66; the aramid is PA6T or PA 1212. The conductive medium is carbon black and/or carbon nano tubes; wherein the mass of the carbon nano tube is 0-4 parts; 0 to 25 parts by mass of carbon black. Further, the carbon nanotube is a single-walled carbon nanotube, a double-walled carbon nanotube or a multi-walled carbon nanotube; the diameter of the carbon nano tube is 0.7 nm-7 nm, and the length-diameter ratio of the carbon nano tube is more than or equal to 500. The carbon nano tube has an oil absorption value of 300ml/100g or more and a nitrogen adsorption BET specific surface area of 250m or more2(ii) the iodine adsorption value is more than or equal to 400 mg/g. The carbon black is acetylene black. The carbon black has an oil absorption value of 150ml/100g or more and a nitrogen adsorption BET specific surface area of 50m or more2The volume resistance is less than or equal to 10ohm. The toughening agent is one or more of propylene grafted maleic anhydride (PP-g-MAH), styrene-butadiene-styrene copolymer grafted maleic anhydride (SBS-g-MAH) and styrene-ethylene-butyl copolymer grafted maleic anhydride (SEBS-g-MAH). The hypophosphite flame retardant is an ethylene aluminum hypophosphite flame retardant or an aluminum methyl hypophosphite flame retardant; the ester flame retardant is melamine polyphosphate (MCA) or melamine cyanurate (MPP).
To further illustrate the technical means and effects of the present invention adopted to achieve the predetermined objects, the following detailed description is given with reference to the preferred embodiments.
Example 1
Relative to 100 parts by mass of a finished material product, the halogen-free flame-retardant PA antistatic material comprises 24 parts by mass of PA6, 50 parts by mass of PA66, 20 parts by mass of vinyl aluminum hypophosphite, 1 part by mass of melamine polyphosphate (MCA), 2 parts by mass of propylene grafted maleic anhydride (PP-g-MAH), 2.5 parts by mass of carbon nanotubes and 0.5 part by mass of an anti-dripping agent.
Weighing the corresponding components in proportion; firstly, adding a conductive medium, a toughening agent, an anti-dripping agent and a flame retardant of each component into a PA material in proportion, and fully and uniformly stirring by using a high-speed mixer; and then melting, mixing, extruding and granulating the mixed materials.
Example 2
The halogen-free flame-retardant PA antistatic material comprises, relative to 100 parts by mass of a finished material product, 30 parts by mass of PA6, 50 parts by mass of PA66, 12 parts by mass of vinyl aluminum hypophosphite, 3 parts by mass of melamine polyphosphate (MCA), 2 parts by mass of propylene grafted maleic anhydride (PP-g-MAH), 2.5 parts by mass of carbon nanotubes and 0.5 part by mass of an anti-dripping agent.
Weighing the corresponding components in proportion; firstly, adding a conductive medium, a toughening agent, an anti-dripping agent and a flame retardant of each component into a PA material in proportion, and fully and uniformly stirring by using a high-speed mixer; and then melting, mixing, extruding and granulating the mixed materials.
Example 3
The halogen-free flame-retardant PA antistatic material comprises, relative to 100 parts by mass of a finished material product, 25 parts by mass of PA6, 50 parts by mass of PA66, 15 parts by mass of vinyl aluminum hypophosphite, 5 parts by mass of melamine polyphosphate (MCA), 2 parts by mass of propylene grafted maleic anhydride (PP-g-MAH), 2.5 parts by mass of carbon nanotubes and 0.5 part by mass of an anti-dripping agent.
Weighing the corresponding components in proportion; firstly, adding a conductive medium, a toughening agent, an anti-dripping agent and a flame retardant of each component into a PA material in proportion, and fully and uniformly stirring by using a high-speed mixer; and then melting, mixing, extruding and granulating the mixed materials.
Comparative example 1
The halogen-free flame-retardant PA antistatic material comprises 45 parts by mass of PA6, 50 parts by mass of PA66, 2 parts by mass of propylene grafted maleic anhydride (PP-g-MAH), 2.5 parts by mass of carbon nanotubes and 0.5 part by mass of an anti-dripping agent, relative to 100 parts by mass of a finished material product.
Weighing the corresponding components in proportion; firstly, adding a conductive medium, a toughening agent, an anti-dripping agent and a flame retardant of each component into a PA material in proportion, and fully and uniformly stirring by using a high-speed mixer; and then melting, mixing, extruding and granulating the mixed materials.
Comparative example 2
The halogen-free flame-retardant PA antistatic material comprises 33 parts by mass of PA6, 50 parts by mass of PA66, 12 parts by mass of vinyl aluminum hypophosphite, 2 parts by mass of propylene grafted maleic anhydride (PP-g-MAH), 2.5 parts by mass of carbon nanotubes and 0.5 part by mass of an anti-dripping agent, relative to 100 parts by mass of a finished material product.
Weighing the corresponding components in proportion; firstly, adding a conductive medium, a toughening agent, an anti-dripping agent and a flame retardant of each component into a PA material in proportion, and fully and uniformly stirring by using a high-speed mixer; and then melting, mixing, extruding and granulating the mixed materials.
The particles of examples 1 to 3 and comparative examples 1 to 2 were injection molded into standard test specimens on an injection molding machine, and mechanical properties were measured according to the relevant standards, and the test results are shown in table 1 below.
TABLE 1 test results
As can be seen from the above table 1, by adding the conductive medium, the toughening agent, the anti-dripping agent, the hypophosphite flame retardant and the ester flame retardant which are corresponding components into the PA, the antistatic property and the high flame retardance of the material can be satisfied, the tensile, bending and impact resistance mechanical properties of the material can be improved, and the application range of the material is expanded.
In addition, the invention also provides a halogen-free flame-retardant PA antistatic material product, which is prepared from the halogen-free flame-retardant PA antistatic material, has high antistatic property, high flame retardance and good tensile property, bending resistance and impact resistance, and can be widely applied to electronic and electric products with higher requirements on the antistatic property, the flame retardance and the mechanical property of the material.
The technical principles of the present invention have been described above in connection with specific embodiments, which are intended to explain the principles of the present invention and should not be construed as limiting the scope of the present invention in any way. Based on the explanations herein, those skilled in the art will be able to conceive of other embodiments of the present invention without inventive effort, which would fall within the scope of the present invention.
Claims (10)
1. The halogen-free flame-retardant PA antistatic material is characterized by comprising the following components in parts by mass relative to 100 parts by mass of a finished material product:
44.5-82.8 parts by mass of PA;
2-25 parts by mass of a conductive medium;
2-5 parts by mass of a toughening agent;
0.2-0.5 parts by mass of an anti-dripping agent; and
the flame retardant is a compound of 12-20 parts by mass of hypophosphite flame retardant and 1-5 parts by mass of ester flame retardant.
2. The halogen-free flame retardant PA antistatic material of claim 1 wherein the hypophosphite flame retardant is a vinyl aluminum hypophosphite flame retardant or an aluminum methyl hypophosphite flame retardant; the ester flame retardant is melamine polyphosphate (MCA) or melamine cyanurate (MPP).
3. The halogen-free flame retardant PA antistatic material of claim 1 wherein the PA is aliphatic polyamide or aromatic polyamide.
4. The halogen-free flame retardant PA antistatic material of claim 1, wherein the toughening agent is one or more of propylene grafted maleic anhydride (PP-g-MAH), styrene-butadiene-styrene copolymer grafted maleic anhydride (SBS-g-MAH), and styrene-ethylene-butyl copolymer grafted maleic anhydride (SEBS-g-MAH).
5. The halogen-free flame retardant PA antistatic material of claim 1 wherein the conductive media is carbon black and/or carbon nanotubes.
6. The halogen-free flame-retardant PA antistatic material as claimed in claim 5, wherein the carbon nanotubes are in an amount of 0 to 4 parts by mass.
7. The halogen-free flame retardant PA antistatic material of claim 6 wherein the carbon nanotubes are single-walled carbon nanotubes, double-walled carbon nanotubes or multi-walled carbon nanotubes; the diameter of the carbon nano tube is 0.7 nm-7 nm, and the length-diameter ratio of the carbon nano tube is more than or equal to 500.
8. The halogen-free flame-retardant PA antistatic material as claimed in claim 5, wherein the carbon black is in an amount of 0 to 25 parts by mass.
9. The halogen-free flame retardant PA antistatic material of claim 8 wherein the carbon black is acetylene carbon black.
10. A halogen-free flame-retardant PA antistatic material product, characterized in that the halogen-free flame-retardant PA antistatic material product is prepared by the halogen-free flame-retardant PA antistatic material of any of claims 1 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811255755.0A CN111100453A (en) | 2018-10-26 | 2018-10-26 | Halogen-free flame-retardant PA antistatic material and product thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811255755.0A CN111100453A (en) | 2018-10-26 | 2018-10-26 | Halogen-free flame-retardant PA antistatic material and product thereof |
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| CN111100453A true CN111100453A (en) | 2020-05-05 |
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| CN201811255755.0A Pending CN111100453A (en) | 2018-10-26 | 2018-10-26 | Halogen-free flame-retardant PA antistatic material and product thereof |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102321367A (en) * | 2011-09-07 | 2012-01-18 | 上海日之升新技术发展有限公司 | High-CTI antistatic fire-retardance-enhanced PA6 composite material and preparation method thereof |
| CN103013105A (en) * | 2012-12-28 | 2013-04-03 | 常州大学 | Conducting halogen-free flame-retardant PA6 (polyamide 6) composite material and preparation method thereof |
| CN103351618A (en) * | 2013-06-28 | 2013-10-16 | 广东威林工程塑料有限公司 | Antistatic, halogen-free, and fire-retardant enhanced master batch dedicated for polyamide and preparation method thereof |
| CN103408929A (en) * | 2013-08-08 | 2013-11-27 | 上海日之升新技术发展有限公司 | Continuous long fiber-reinforced halogen-free flame-retardant PA66 composite material and preparation method thereof |
| CN106967295A (en) * | 2017-05-06 | 2017-07-21 | 广东威林工程塑料股份有限公司 | A kind of halogen-free flame-proof antistatic nylon composite materials and preparation method thereof |
-
2018
- 2018-10-26 CN CN201811255755.0A patent/CN111100453A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102321367A (en) * | 2011-09-07 | 2012-01-18 | 上海日之升新技术发展有限公司 | High-CTI antistatic fire-retardance-enhanced PA6 composite material and preparation method thereof |
| CN103013105A (en) * | 2012-12-28 | 2013-04-03 | 常州大学 | Conducting halogen-free flame-retardant PA6 (polyamide 6) composite material and preparation method thereof |
| CN103351618A (en) * | 2013-06-28 | 2013-10-16 | 广东威林工程塑料有限公司 | Antistatic, halogen-free, and fire-retardant enhanced master batch dedicated for polyamide and preparation method thereof |
| CN103408929A (en) * | 2013-08-08 | 2013-11-27 | 上海日之升新技术发展有限公司 | Continuous long fiber-reinforced halogen-free flame-retardant PA66 composite material and preparation method thereof |
| CN106967295A (en) * | 2017-05-06 | 2017-07-21 | 广东威林工程塑料股份有限公司 | A kind of halogen-free flame-proof antistatic nylon composite materials and preparation method thereof |
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