CN112920587A - Halogen-free flame-retardant antistatic PC material and product thereof - Google Patents
Halogen-free flame-retardant antistatic PC material and product thereof Download PDFInfo
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- CN112920587A CN112920587A CN201911242439.4A CN201911242439A CN112920587A CN 112920587 A CN112920587 A CN 112920587A CN 201911242439 A CN201911242439 A CN 201911242439A CN 112920587 A CN112920587 A CN 112920587A
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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
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/001—Conductive additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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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
- C08L2201/02—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
- C08L2205/02—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
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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 antistatic PC material and a product thereof. Every 100 parts by mass of a finished PC material product comprises 93.7-97.4 parts of polycarbonate, 1-2 parts of carbon nano tubes, 1-3 parts of carbon fibers and 0.6-1.3 parts of a flame retardant. The halogen-free flame-retardant antistatic PC material and the product thereof have good antistatic property, flame retardance and impact resistance.
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 antistatic PC material and a product thereof.
[ background of the invention ]
In the existing antistatic plastic products, the antistatic medium usually adopted is carbon fiber, carbon black and carbon nano tube. The carbon nano tube has the largest specific surface area and the length-diameter ratio, so the carbon nano tube is added in the least mass part on the premise of reaching the same conductive grade. For this reason, carbon nanotubes are gradually replacing carbon fibers and carbon black as an antistatic medium.
However, due to the small size of the carbon nanotubes, a large mass fraction of the carbon nanotubes needs to be added to form the current path of the product, and particularly, more than 5% of the carbon nanotubes need to be added to form the current path in a pure PC material. However, this can seriously affect the basic properties of PC materials. In addition, the PC material product has high surface energy and wick effect during burning, so that the product has low flame retardant grade.
Therefore, there is a need to develop a halogen-free flame retardant antistatic PC material to solve the above problems.
[ summary of the invention ]
The invention aims to provide a halogen-free flame-retardant antistatic PC material and a product thereof, which have better antistatic property, flame retardance and impact resistance.
In order to achieve the purpose, the invention adopts the following technical scheme:
every 100 parts by mass of a finished PC material product comprises the following components in parts by mass:
93.7-97.4 parts of polycarbonate;
1-2 parts of carbon nano tubes;
1-3 parts of carbon fiber; and
0.6-1.3 parts of a flame retardant.
Preferably, the polycarbonate is a compound of two or more of bisphenol A polycarbonate, polyester polycarbonate, cyclohexane bisphenol A polycarbonate and high temperature resistant polycarbonate synthesized by bisphenol TMC.
In the present invention, the polycarbonate preferably has a melt mass flow rate of 3g/10min to 50g/10min under a temperature of 300 ℃ and a load of 1.2 Kg.
In a preferred embodiment of the present invention, the carbon nanotube is at least one of a single-walled carbon nanotube, a double-walled carbon nanotube, and a multi-walled carbon nanotube.
Preferably, the carbon nanotubes have a diameter of 0.7 to 7nm, and 50% or more of the carbon nanotubes have a diameter of 0.7 to 1 nm; the length-diameter ratio of the carbon nano tube is more than or equal to 500, the oil absorption value is more than or equal to 300ml/100g, and the nitrogen adsorption specific surface area is more than or equal to 250m2(ii) the iodine adsorption value is more than or equal to 400 mg/g.
In the present invention, the carbon fiber preferably has a filament number of 3K to 60K, a monofilament diameter of 1 μm to 20 μm, and a short-cut length of 1mm to 15 mm.
Further, the content of the carbon nanotube is 1 part, 1.1 parts, 1.2 parts, 1.3 parts, 1.4 parts, 1.5 parts, 1.6 parts, 1.7 parts, 1.8 parts, 1.9 parts or 2 parts per 100 parts by mass of the finished PC material; the carbon fiber content is 1 part, 1.2 parts, 1.4 parts, 1.5 parts, 1.6 parts, 1.8 parts, 2 parts, 2.2 parts, 2.4 parts, 2.5 parts, 2.6 parts, 2.8 parts or 3 parts.
Preferably, the flame retardant is a silicone flame retardant and a sulfonate flame retardant, and the ratio of the flame retardant is 1: 1-1: 3, and the components are compounded in proportion.
In a preferred embodiment of the present invention, the silicone flame retardant is at least one of a flame retardant of polysilane and its derivatives, a flame retardant of polymethoxyphenylsilane and its derivatives, hydroxymethylsilane and its derivatives, and a flame retardant of crosslinked Polydimethylsiloxane (PDMS) and its derivatives.
Preferably, the sulfonate flame retardant is potassium benzenesulfonyl benzene sulfonate and/or perfluorobutyl sulfonate.
Further, the content of the silicone flame retardant is 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts or 1 part per 100 parts by mass of the finished PC material; the content of the sulfonate flame retardant is 0.1 part, 0.15 part, 0.2 part, 0.25 part or 0.3 part.
The product is prepared from the halogen-free flame-retardant antistatic PC material.
The invention has the beneficial effects that: according to the halogen-free flame-retardant antistatic PC material, the carbon nano tubes and the carbon fibers are added into the PC material in a certain proportion to serve as a conductive medium, and a proper amount of flame retardant is added, so that the good antistatic performance is obtained by adding the conductive medium with a low addition amount, the flame retardant grade is high, and more than 50% of good physical properties of the PC material can be reserved. The product prepared from the halogen-free flame-retardant antistatic PC material has good antistatic performance, flame retardance and impact resistance.
[ detailed description ] embodiments
Every 100 parts by mass of a finished PC material product comprises 93.7-97.4 parts of polycarbonate, 1-2 parts of carbon nanotubes, 1-3 parts of carbon fibers and 0.6-1.3 parts of a flame retardant.
Specifically, in the halogen-free flame-retardant antistatic PC material, the polycarbonate is a compound of two or more of bisphenol A polycarbonate, polyester polycarbonate, cyclohexane bisphenol A polycarbonate and high-temperature resistant polycarbonate synthesized by bisphenol TMC. The melt mass flow rate of the polycarbonate is 3g/10 min-50 g/10min under the conditions that the temperature is 300 ℃ and the load is 1.2 Kg.
In the halogen-free flame-retardant antistatic PC material, the carbon nano tube is at least one of a single-wall carbon nano tube, a double-wall carbon nano tube and a multi-wall carbon nano tube. Further, the diameter of the carbon nano tube is 0.7 nm-7 nm, and the diameter of more than 50% of the carbon nano tubes is 0.7 nm-1 nm; the length-diameter ratio of the carbon nano tube is more than or equal to 500, the oil absorption value is more than or equal to 300ml/100g, and the nitrogen adsorption specific surface area is more than or equal to 250m2(ii) the iodine adsorption value is more than or equal to 400 mg/g. The number of the filaments of the carbon fiber is 3K-60K, the diameter of the monofilament is 1 mu m-20 mu m, and the chopped length is 1 mm-15 mm. The carbon nano tube and the carbon fiber in a certain proportion are used as a conductive medium of the PC material, so that the surface resistance of the PC material can be reduced to 10^9 Ohm-10 ^11 Ohm; in addition, the notch impact strength of the PC material can reach more than 20kJ/m ^2, and more than 50 percent of the original performance of the PC material is well reserved.
In the halogen-free flame-retardant antistatic PC material, the flame retardant is an organic silicon flame retardant and a sulfonate flame retardant according to the weight ratio of 1: 1-1: 3, and the components are compounded in proportion. Wherein the organosilicon flame retardant is at least one of flame retardants of polyborosilazane and derivatives thereof, polymethoxyphenyl silane and derivatives thereof, hydroxymethyl silane and derivatives thereof, and cross-linked Polydimethylsiloxane (PDMS) and derivatives thereof. The sulfonate flame retardant is potassium benzenesulfonyl benzene sulfonate and/or perfluorobutyl sulfonate.
The technical solution of the present invention is further explained by the following embodiments.
Example 1
Every 100 parts by mass of a finished PC material product comprises 95.8 parts of polycarbonate, 2 parts of carbon nano tubes, 1 part of carbon fibers, 1 part of polyvinyl phenyl silane and 0.2 part of potassium benzenesulfonyl benzene sulfonate. Wherein the polycarbonate is 50 parts of bisphenol A polycarbonate andcompounding 45.8 parts of cyclohexane bisphenol A polycarbonate; the carbon nano tube is a single-walled carbon nano tube, more than 70 percent of the carbon nano tubes have the diameter of 0.7nm to 1nm, the length-diameter ratio of 500, the oil absorption value of 300ml/100g and the nitrogen adsorption specific surface area of 250m2The iodine adsorption value is 400 mg/g; the number of filaments of the carbon fiber is 60K, the diameter of the monofilament is 1-10 mu m, and the short-cut length is 1-8 mm.
Weighing the components with the corresponding weight, uniformly stirring the components, and adding the components into a double-screw extruder for melt extrusion granulation.
Example 2
Every 100 parts by mass of a finished PC material product comprises 96 parts of polycarbonate, 2 parts of carbon nano tubes, 1 part of carbon fibers, 0.8 part of polyvinyl phenyl silane and 0.2 part of potassium benzenesulfonyl benzene sulfonate. Wherein the polycarbonate is the compound of 50 parts of bisphenol A polycarbonate and 45.8 parts of cyclohexane bisphenol A polycarbonate; the carbon nano tube is a single-walled carbon nano tube, more than 70 percent of the carbon nano tubes have the diameter of 0.7nm to 1nm, the length-diameter ratio of 500, the oil absorption value of 300ml/100g and the nitrogen adsorption specific surface area of 250m2The iodine adsorption value is 400 mg/g; the number of filaments of the carbon fiber is 60K, the diameter of the monofilament is 1-10 mu m, and the short-cut length is 1-8 mm.
Weighing the components with the corresponding weight, uniformly stirring the components, and adding the components into a double-screw extruder for melt extrusion granulation.
Example 3
Every 100 parts by mass of a finished PC material product comprises 96.3 parts of polycarbonate, 2 parts of carbon nano tubes, 1 part of carbon fibers, 0.5 part of polyethylene phenyl silane and 0.2 part of potassium benzenesulfonyl benzene sulfonate. Wherein the polycarbonate is the compound of 50 parts of bisphenol A polycarbonate and 45.8 parts of cyclohexane bisphenol A polycarbonate; the carbon nano tube is a single-walled carbon nano tube, more than 70 percent of the carbon nano tubes have the diameter of 0.7nm to 1nm, the length-diameter ratio of 500, the oil absorption value of 300ml/100g and the nitrogen adsorption specific surface area of 250m2The iodine adsorption value is 400 mg/g; the number of filaments of the carbon fiber is 60K, the diameter of the monofilament is 1-10 mu m, and the short-cut length is 1-8 mm.
Weighing the components with the corresponding weight, uniformly stirring the components, and adding the components into a double-screw extruder for melt extrusion granulation.
Example 4
Every 100 parts by mass of a finished PC material product comprises 95.9 parts of polycarbonate, 2 parts of carbon nano tubes, 1 part of carbon fibers, 1 part of polyvinyl phenyl silane and 0.1 part of potassium benzenesulfonyl benzene sulfonate. Wherein the polycarbonate is the compound of 50 parts of bisphenol A polycarbonate and 45.8 parts of cyclohexane bisphenol A polycarbonate; the carbon nano tube is a single-walled carbon nano tube, more than 70 percent of the carbon nano tubes have the diameter of 0.7nm to 1nm, the length-diameter ratio of 500, the oil absorption value of 300ml/100g and the nitrogen adsorption specific surface area of 250m2The iodine adsorption value is 400 mg/g; the number of filaments of the carbon fiber is 60K, the diameter of the monofilament is 1-10 mu m, and the short-cut length is 1-8 mm.
Weighing the components with the corresponding weight, uniformly stirring the components, and adding the components into a double-screw extruder for melt extrusion granulation.
Example 5
Every 100 parts by mass of a finished PC material product comprises 95.7 parts of polycarbonate, 2 parts of carbon nano tubes, 1 part of carbon fibers, 1 part of polyvinyl phenyl silane and 0.3 part of potassium benzenesulfonyl benzene sulfonate. Wherein the polycarbonate is the compound of 50 parts of bisphenol A polycarbonate and 45.8 parts of cyclohexane bisphenol A polycarbonate; the carbon nano tube is a single-walled carbon nano tube, more than 70 percent of the carbon nano tubes have the diameter of 0.7nm to 1nm, the length-diameter ratio of 500, the oil absorption value of 300ml/100g and the nitrogen adsorption specific surface area of 250m2The iodine adsorption value is 400 mg/g; the number of filaments of the carbon fiber is 60K, the diameter of the monofilament is 1-10 mu m, and the short-cut length is 1-8 mm.
Weighing the components with the corresponding weight, uniformly stirring the components, and adding the components into a double-screw extruder for melt extrusion granulation.
Example 6
Every 100 parts by mass of a finished PC material product comprises 96.4 parts of polycarbonate, 2 parts of carbon nano tubes and 1 part of PCCarbon fiber, 0.5 part of polyvinyl phenyl silane and 0.1 part of potassium benzenesulfonyl benzene sulfonate. Wherein the polycarbonate is the compound of 50 parts of bisphenol A polycarbonate and 45.8 parts of cyclohexane bisphenol A polycarbonate; the carbon nano tube is a single-walled carbon nano tube, more than 70 percent of the carbon nano tubes have the diameter of 0.7nm to 1nm, the length-diameter ratio of 500, the oil absorption value of 300ml/100g and the nitrogen adsorption specific surface area of 250m2The iodine adsorption value is 400 mg/g; the number of filaments of the carbon fiber is 60K, the diameter of the monofilament is 1-10 mu m, and the short-cut length is 1-8 mm.
Weighing the components with the corresponding weight, uniformly stirring the components, and adding the components into a double-screw extruder for melt extrusion granulation.
Example 7
Every 100 parts by mass of a finished PC material product comprises 96.3 parts of polycarbonate, 2 parts of carbon nano tubes, 1 part of carbon fibers, 0.5 part of polyethylene phenyl silane and 0.2 part of potassium benzenesulfonyl benzene sulfonate. Wherein the polycarbonate is the compound of 50 parts of bisphenol A polycarbonate and 45.8 parts of cyclohexane bisphenol A polycarbonate; the carbon nano tube is a single-walled carbon nano tube, more than 70 percent of the carbon nano tubes have the diameter of 0.7nm to 1nm, the length-diameter ratio of 500, the oil absorption value of 300ml/100g and the nitrogen adsorption specific surface area of 250m2The iodine adsorption value is 400 mg/g; the number of filaments of the carbon fiber is 60K, the diameter of the monofilament is 1-10 mu m, and the short-cut length is 1-8 mm.
Weighing the components with the corresponding weight, uniformly stirring the components, and adding the components into a double-screw extruder for melt extrusion granulation.
Example 8
Every 100 parts by mass of a finished PC material product comprises 96.2 parts of polycarbonate, 2 parts of carbon nano tubes, 1 part of carbon fibers, 0.5 part of polyethylene phenyl silane and 0.3 part of potassium benzenesulfonyl benzene sulfonate. Wherein the polycarbonate is the compound of 50 parts of bisphenol A polycarbonate and 45.8 parts of cyclohexane bisphenol A polycarbonate; the carbon nano tube is a single-walled carbon nano tube, more than 70 percent of the carbon nano tubes have the diameter of 0.7nm to 1nm, the length-diameter ratio of 500, the oil absorption value of 300ml/100g and the nitrogen adsorption specific surface area of 250m2The iodine adsorption value is 400 mg/g; the number of filaments of the carbon fiber is 60K, the diameter of the monofilament is 1-10 mu m, and the short-cut length is 1-8 mm.
Weighing the components with the corresponding weight, uniformly stirring the components, and adding the components into a double-screw extruder for melt extrusion granulation.
Comparative example 1
Every 100 parts by mass of a finished PC material product comprises 94.8 parts of polycarbonate, 4 parts of carbon nano tubes, 1 part of polyvinyl phenyl silane and 0.2 part of potassium benzenesulfonyl benzene sulfonate. In comparative example 1 and example 1, two halogen-free flame retardant antistatic PC materials are different: in comparative example 1, the content of carbon nanotubes was different, and carbon fibers were not added.
Weighing the components with the corresponding weight, uniformly stirring the components, and adding the components into a double-screw extruder for melt extrusion granulation.
Comparative example 2
Every 100 parts by mass of a finished PC material product comprises 90.8 parts of polycarbonate, 8 parts of carbon fiber, 1 part of polyvinyl phenyl silane and 0.2 part of potassium benzenesulfonyl benzene sulfonate. In comparative example 2 and example 1, two halogen-free flame retardant antistatic PC materials are different: in comparative example 2, the content of carbon fibers was different and carbon nanotubes were not added.
Weighing the components with the corresponding weight, uniformly stirring the components, and adding the components into a double-screw extruder for melt extrusion granulation.
After the halogen-free flame-retardant antistatic PC materials of the above examples and comparative examples are melt extruded and pelletized, the particles in the examples and comparative examples are injection molded on an injection molding machine to form standard test sample strips, the mechanical properties of the obtained materials are tested according to the standards, and the test results are shown in Table 1:
TABLE 1 test results
Comparing the above examples 1-8 with comparative examples 1 and 2, it can be seen that adding a certain proportion of carbon nanotubes and carbon fibers as conductive media to a PC material and adding a compounded flame retardant can make the PC material have better antistatic property, flame retardant property and higher impact resistance, mainly because the compounding of carbon nanotubes and carbon fibers as conductive media of the PC material is adopted, so that the addition amount of the conductive media in the PC material is lower, not only can the PC material obtain better antistatic property and flame retardant property, but also more than 50% of the physical properties of the PC material itself can be retained.
The invention also provides a product which is prepared from the halogen-free flame-retardant antistatic PC material. The product has good antistatic performance, high flame retardant grade and strong impact resistance.
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 antistatic PC material is characterized in that each 100 parts by mass of a PC material finished product comprises the following components in parts by mass:
93.7-97.4 parts of polycarbonate;
1-2 parts of carbon nano tubes;
1-3 parts of carbon fiber; and
0.6-1.3 parts of a flame retardant.
2. The halogen-free flame-retardant antistatic PC material according to claim 1, wherein the polycarbonate is a compound of two or more of bisphenol A polycarbonate, polyester polycarbonate, cyclohexane bisphenol A polycarbonate and high temperature resistant polycarbonate synthesized by bisphenol TMC.
3. The halogen-free flame-retardant antistatic PC material according to claim 2, wherein the polycarbonate has a melt mass flow rate of 3g/10min to 50g/10min at a temperature of 300 ℃ and a load of 1.2 Kg.
4. The halogen-free flame retardant antistatic PC material of claim 1, wherein the carbon nanotubes are at least one of single-walled carbon nanotubes, double-walled carbon nanotubes and multi-walled carbon nanotubes.
5. The halogen-free flame-retardant antistatic PC material according to claim 4, wherein the diameter of the carbon nanotubes is 0.7nm to 7nm, and more than 50% of the carbon nanotubes have a diameter of 0.7nm to 1 nm; the length-diameter ratio of the carbon nano tube is more than or equal to 500, the oil absorption value is more than or equal to 300ml/100g, and the nitrogen adsorption specific surface area is more than or equal to 250m2(ii) the iodine adsorption value is more than or equal to 400 mg/g.
6. The halogen-free flame-retardant antistatic PC material according to claim 1, wherein the carbon fiber has a filament number of 3K-60K, a monofilament diameter of 1 μm-20 μm, and a chopped length of 1 mm-15 mm.
7. The halogen-free flame-retardant antistatic PC material according to claim 1, wherein the flame retardant is an organosilicon flame retardant and a sulfonate flame retardant according to a ratio of 1: 1-1: 3, and the components are compounded in proportion.
8. The halogen-free flame retardant antistatic PC material according to claim 7, wherein the organosilicon-based flame retardant is at least one of a flame retardant of polysilazane and its derivatives, a flame retardant of polymethoxyphenylsilane and its derivatives, hydroxymethylsilane and its derivatives, a flame retardant of crosslinked Polydimethylsiloxane (PDMS) and its derivatives.
9. The halogen-free flame-retardant antistatic PC material according to claim 7, wherein the sulfonate flame retardant is potassium benzenesulfonyl benzene sulfonate and/or perfluorobutyl sulfonate.
10. An article, characterized in that the article is prepared by using the halogen-free flame retardant antistatic PC material according to any one of claims 1 to 9.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114621573A (en) * | 2022-03-15 | 2022-06-14 | 金发科技股份有限公司 | Halogen-free flame-retardant carbon fiber reinforced polycarbonate composition and preparation method and application thereof |
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