TWI728731B - Halogen-free flame retardant antistatic pc material and product thereof - Google Patents

Abstract

A halogen-free flame retardant antistatic PC material and product thereof are disclosed, which are related to polymer materials. The halogen-free flame retardant antistatic PC material includes 93.7~97.4 parts by weight of a polycarbonate, 1~2 parts by weight of a nanotube, 1~3 parts by weight of a carbon fiber, and 0.6~1.3 parts by weight of a flame retardant based on 100 parts by weight of the halogen-free flame retardant antistatic. The halogen-free flame retardant antistatic has better antistatic properties, flame retardancy, and impact resistance.

Description

Halogen-free flame-retardant and antistatic PC materials and their products

The invention relates to the technical field of polymer materials, in particular to a halogen-free flame-retardant antistatic PC material and its products.

In the existing antistatic plastic products, the commonly used antistatic media are carbon fiber, carbon black, and carbon nanotubes. Among them, carbon nanotubes have the largest specific surface area and a length-to-diameter ratio. Therefore, under the premise of achieving the same conductivity level, the amount of carbon nanotubes added is the least. Because of this, carbon nanotubes, as an antistatic medium, have a tendency to gradually replace carbon fiber and carbon black.

However, due to the small size of carbon nanotubes, a larger mass of carbon nanotubes must be added to form the current path of the product. Especially in pure PC materials, it needs to be added to more than 5% to form a current path. However, this will seriously affect the basic properties of PC materials. In addition, the surface energy of this kind of PC material products is higher, which will produce a wick effect when burning, which makes the products have a lower flame retardant grade.

Therefore, it is necessary to develop a halogen-free flame-retardant antistatic PC material to solve the above problems.

The purpose of the present invention is to provide a halogen-free flame-retardant antistatic PC material and its products, which have good antistatic properties, flame retardancy and impact resistance.

In order to achieve the above objective, the present invention adopts the following technical solution: a halogen-free flame-retardant antistatic PC material. For every 100 parts by mass of the finished PC material, it includes the following parts by mass: polycarbonate (PC), 93.7-97.4 Parts; carbon nanotubes, 1-2 parts; carbon fiber, 1-3 parts; and flame retardants, 0.6-1.3 parts.

In a preferred embodiment of the present invention, the polycarbonate is bisphenol A polycarbonate, polyester polycarbonate, cyclohexane bisphenol A polycarbonate, and high temperature resistant synthetic bisphenol TMC Two or more compound formulas in polycarbonate.

In a preferred embodiment of the present invention, under the conditions of a temperature of 300° C. and a load of 1.2 Kg, the melt mass flow rate of the polycarbonate is 3 g/10 min to 50 g/10 min.

In a preferred embodiment of the present invention, the carbon nanotubes are at least one of single-wall carbon nanotubes, double-wall carbon nanotubes, and multi-wall carbon nanotubes.

In a preferred embodiment of the present invention, the diameter of the carbon nanotubes is 0.7nm~7nm, and more than 50% of the carbon nanotubes have a diameter of 0.7nm~1nm; the carbon nanotubes The aspect ratio is greater than or equal to 500, the oil absorption value is greater than or equal to 300ml/100g, the nitrogen adsorption specific surface area is greater than or equal to 250m ² /g, and the iodine adsorption value is greater than or equal to 400mg/g.

In a preferred embodiment of the present invention, the carbon fiber has a filament number of 3K-60K, a single filament diameter of 1 μm-20 μm, and a chopped length of 1 mm-15 mm.

Further, per 100 parts by mass of the finished PC material, the content of the carbon nanotubes 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. Parts or 2 parts; the content of the carbon fiber 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.

In a preferred embodiment of the present invention, the flame retardant is an organosilicon flame retardant and a sulfonate flame retardant prepared in a ratio of 1:1 to 1:3.

In a preferred embodiment of the present invention, the organosilicon flame retardant is polysilborane and its derivative flame retardant, polymethoxyphenylsilane and its derivative, hydroxymethylsilane and its derivative At least one of derivatives, cross-linked polydimethylsiloxane (PDMS) and its derivative flame retardants.

In a preferred embodiment of the present invention, the sulfonate flame retardant is potassium benzenesulfonate.

Further, per 100 parts by mass of the finished PC material, the content of the organosilicon flame retardant is 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part or 1 part; the sulfonate flame retardant The content is 0.1 part, 0.15 part, 0.2 part, 0.25 part or 0.3 part.

A product prepared from the above halogen-free flame-retardant antistatic PC material.

The beneficial effects of the present invention are: the halogen-free flame-retardant antistatic PC material of the present invention, by adding a certain proportion of carbon nanotubes and carbon fibers as conductive media to the PC material, and adding an appropriate amount of flame retardant, it can be achieved by adding Conductive media with a lower added amount can achieve better antistatic performance, high flame retardant grade, and can retain more than 50% of the good physical properties of the PC material itself. The product prepared by using the halogen-free flame-retardant antistatic PC material of the present invention has good antistatic performance, flame retardancy and impact resistance.

A halogen-free flame-retardant antistatic PC material. For every 100 parts by mass of the finished PC material, it includes 93.7-97.4 parts of polycarbonate, 1~2 parts of carbon nanotubes, 1~3 parts of carbon fiber and 0.6~1.3 parts Flame retardant.

Specifically, in the halogen-free flame-retardant antistatic PC material, the polycarbonate is synthesized from bisphenol A polycarbonate, polyester polycarbonate, cyclohexane bisphenol A polycarbonate, and bisphenol TMC Two or more compound formulas in high temperature resistant polycarbonate. At a temperature of 300°C and a load of 1.2Kg, the mass flow rate of the polycarbonate solution is 3g/10min~50g/10min.

In the halogen-free flame-retardant antistatic PC material, the carbon nanotubes are at least one of single-wall carbon nanotubes, double-wall carbon nanotubes, and multi-wall carbon nanotubes. Furthermore, the diameter of carbon nanotubes is 0.7nm~7nm, and the diameter of more than 50% of carbon nanotubes is 0.7nm~1nm; the aspect ratio of carbon nanotubes is greater than or equal to 500, and the oil absorption value is greater than or equal to 300ml/ 100g, nitrogen adsorption specific surface area greater than or equal to 250m ² /g, iodine adsorption value greater than or equal to 400mg/g. The number of carbon fiber filaments is 3K~60K, the single filament diameter is 1μm~20μm, and the chopped length is 1mm~15mm. Using a certain proportion of carbon nanotubes and carbon fibers as the conductive medium of the PC material can reduce the surface resistance of the PC material to 10^9 Ohm~10^11 Ohm; in addition, the notched impact strength of the PC material can reach 20kJ/m^ 2 or more, well retains more than 50% of the original performance of PC materials.

In the halogen-free flame-retardant antistatic PC material, the flame retardant is an organosilicon flame retardant and a sulfonate flame retardant formulated in a ratio of 1:0.1 to 1:0.6. Among them, organic silicon resistance Burning agent is polysilborane and its derivatives, flame retardant, polymethoxyphenylsilane and its derivatives, hydroxymethylsilane and its derivatives, cross-linked polydimethylsiloxane (PDMS) and At least one of its derivative flame retardants. The sulfonate flame retardant is potassium benzenesulfonylbenzenesulfonate.

The technical solution of the present invention will be further explained by specific embodiments below.

[Example 1]

A halogen-free flame-retardant antistatic PC material. For every 100 parts by mass of the finished PC material, it includes 95.8 parts of polycarbonate, 2 parts of carbon nanotubes, 1 part of carbon fiber, 1 part of polyvinylphenylsilane and 0.2 Potassium benzenesulfonylbenzenesulfonate. Among them, polycarbonate is a composite formula of 50 parts of bisphenol A polycarbonate and 45.8 parts of cyclohexane bisphenol A polycarbonate; carbon nanotubes are single-wall carbon nanotubes, and more than 70% The diameter of the carbon nanotubes is 0.7nm~1nm, the aspect ratio is 500, the oil absorption value is 300ml/100g, the nitrogen adsorption specific surface area is 250m ² /g, the iodine adsorption value is 400mg/g; the number of carbon fibers is 60K , The monofilament diameter is 1μm~10μm, and the chopped length is 1mm~8mm.

Weigh the above-mentioned components with corresponding weights, mix them evenly, and add them to the twin-screw extruder for melt extrusion and granulation.

[Example 2]

A halogen-free flame-retardant and antistatic PC material. For every 100 parts by mass of the finished PC material, it includes 96 parts of polycarbonate, 2 parts of carbon nanotubes, 1 part of carbon fiber, 0.8 parts of polyvinylphenylsilane and 0.2 parts of PC material. Potassium benzenesulfonylbenzenesulfonate. Among them, polycarbonate is a composite formula of 50 parts of bisphenol A polycarbonate and 45.8 parts of cyclohexane bisphenol A polycarbonate; carbon nanotubes are single-wall carbon nanotubes, and more than 70% The diameter of the carbon nanotubes is 0.7nm~1nm, the aspect ratio is 500, the oil absorption value is 300ml/100g, the nitrogen adsorption specific surface area is 250m ² /g, the iodine adsorption value is 400mg/g; the number of carbon fibers is 60K , The monofilament diameter is 1μm~10μm, and the chopped length is 1mm~8mm.

Weigh the above-mentioned components with corresponding weights, mix them evenly, and add them to the twin-screw extruder for melt extrusion and granulation.

[Example 3]

A halogen-free flame-retardant and antistatic PC material. For every 100 parts by mass of the finished PC material, it includes 96.3 parts of polycarbonate, 2 parts of carbon nanotubes, 1 part of carbon fiber, 0.5 parts of polyvinylphenylsilane and 0.2 parts Potassium benzenesulfonylbenzenesulfonate. Among them, polycarbonate is a composite formula of 50 parts of bisphenol A polycarbonate and 45.8 parts of cyclohexane bisphenol A polycarbonate; carbon nanotubes are single-wall carbon nanotubes, and more than 70% The diameter of the carbon nanotubes is 0.7nm~1nm, the aspect ratio is 500, the oil absorption value is 300ml/100g, the nitrogen adsorption specific surface area is 250m ² /g, the iodine adsorption value is 400mg/g; the number of carbon fibers is 60K , The monofilament diameter is 1μm~10μm, and the chopped length is 1mm~8mm.

Weigh the above-mentioned components with corresponding weights, mix them evenly, and add them to the twin-screw extruder for melt extrusion and granulation.

[Example 4]

A halogen-free flame-retardant and antistatic PC material. For every 100 parts by mass of the finished PC material, it includes 95.9 parts of polycarbonate, 2 parts of carbon nanotubes, 1 part of carbon fiber, 1 part of polyvinylphenylsilane and 0.1 Potassium benzenesulfonylbenzenesulfonate. Among them, polycarbonate is a composite formula of 50 parts of bisphenol A polycarbonate and 45.8 parts of cyclohexane bisphenol A polycarbonate; carbon nanotubes are single-wall carbon nanotubes, and more than 70% The diameter of the carbon nanotubes is 0.7nm~1nm, the aspect ratio is 500, the oil absorption value is 300ml/100g, the nitrogen adsorption specific surface area is 250m ² /g, the iodine adsorption value is 400mg/g; the number of carbon fibers is 60K , The monofilament diameter is 1μm~10μm, and the chopped length is 1mm~8mm.

Weigh the above-mentioned components with corresponding weights, mix them evenly, and add them to the twin-screw extruder for melt extrusion and granulation.

[Example 5]

A halogen-free flame-retardant and antistatic PC material. For every 100 parts by mass of the finished PC material, it includes 95.7 parts of polycarbonate, 2 parts of carbon nanotubes, 1 part of carbon fiber, 1 part of polyvinylphenylsilane and 0.3 Potassium benzenesulfonylbenzenesulfonate. Among them, polycarbonate is a composite formula of 50 parts of bisphenol A polycarbonate and 45.8 parts of cyclohexane bisphenol A polycarbonate; carbon nanotubes are single-wall carbon nanotubes, and more than 70% The diameter of the carbon nanotubes is 0.7nm~1nm, the aspect ratio is 500, the oil absorption value is 300ml/100g, the nitrogen adsorption specific surface area is 250m ² /g, the iodine adsorption value is 400mg/g; the number of carbon fibers is 60K , The monofilament diameter is 1μm~10μm, and the chopped length is 1mm~8mm.

Weigh the above-mentioned components with corresponding weights, mix them evenly, and add them to the twin-screw extruder for melt extrusion and granulation.

[Example 6]

A halogen-free flame-retardant and antistatic PC material. For every 100 parts by mass of the finished PC material, it includes 96.4 parts of polycarbonate, 2 parts of carbon nanotubes, 1 part of carbon fiber, 0.5 parts of polyvinylphenylsilane and 0.1 parts Potassium benzenesulfonylbenzenesulfonate. Among them, polycarbonate is a composite formula of 50 parts of bisphenol A polycarbonate and 45.8 parts of cyclohexane bisphenol A polycarbonate; carbon nanotubes are single-wall carbon nanotubes, and more than 70% The diameter of the carbon nanotubes is 0.7nm~1nm, the aspect ratio is 500, the oil absorption value is 300ml/100g, the nitrogen adsorption specific surface area is 250m ² /g, the iodine adsorption value is 400mg/g; the number of carbon fibers is 60K , The monofilament diameter is 1μm~10μm, and the chopped length is 1mm~8mm.

Weigh the above-mentioned components with corresponding weights, mix them evenly, and add them to the twin-screw extruder for melt extrusion and granulation.

[Example 7]

A halogen-free flame-retardant and antistatic PC material. For every 100 parts by mass of the finished PC material, it includes 96.3 parts of polycarbonate, 2 parts of carbon nanotubes, 1 part of carbon fiber, 0.5 parts of polyvinylphenylsilane and 0.2 parts Potassium benzenesulfonylbenzenesulfonate. Among them, polycarbonate is a composite formula of 50 parts of bisphenol A polycarbonate and 45.8 parts of cyclohexane bisphenol A polycarbonate; carbon nanotubes are single-wall carbon nanotubes, and more than 70% The diameter of the carbon nanotubes is 0.7nm~1nm, the aspect ratio is 500, the oil absorption value is 300ml/100g, the nitrogen adsorption specific surface area is 250m ² /g, the iodine adsorption value is 400mg/g; the number of carbon fibers is 60K , The monofilament diameter is 1μm~10μm, and the chopped length is 1mm~8mm.

Weigh the above-mentioned components with corresponding weights, mix them evenly, and add them to the twin-screw extruder for melt extrusion and granulation.

[Example 8]

A halogen-free flame-retardant antistatic PC material. For every 100 parts by mass of the finished PC material, it includes 96.2 parts of polycarbonate, 2 parts of carbon nanotubes, 1 part of carbon fiber, 0.5 parts of polyvinylphenylsilane and 0.3 Potassium benzenesulfonylbenzenesulfonate. Among them, polycarbonate is a composite formula of 50 parts of bisphenol A polycarbonate and 45.8 parts of cyclohexane bisphenol A polycarbonate; carbon nanotubes are single-wall carbon nanotubes, and more than 70% The diameter of the carbon nanotubes is 0.7nm~1nm, the aspect ratio is 500, the oil absorption value is 300ml/100g, the nitrogen adsorption specific surface area is 250m ² /g, the iodine adsorption value is 400mg/g; the number of carbon fibers is 60K , The monofilament diameter is 1μm~10μm, and the chopped length is 1mm~8mm.

Weigh the above-mentioned components with corresponding weights, mix them evenly, and add them to the twin-screw extruder for melt extrusion and granulation.

[Comparative Example 1]

A halogen-free flame-retardant and antistatic PC material. For every 100 parts by mass of the finished PC material, it includes 94.8 parts of polycarbonate, 4 parts of carbon nanotubes, 1 part of polyvinylphenylsilane and 0.2 Potassium benzenesulfonylbenzenesulfonate. In Comparative Example 1 and Example 1, the difference between the two halogen-free flame-retardant and antistatic PC materials is that in Comparative Example 1, the content of carbon nanotubes is different, and no carbon fiber is added.

Weigh the above-mentioned components with corresponding weights, mix them evenly, and add them to the twin-screw extruder for melt extrusion and granulation.

[Comparative Example 2]

A halogen-free flame-retardant antistatic PC material. For every 100 parts by mass of the finished PC material, it includes 90.8 parts of polycarbonate, 8 parts of carbon fiber, 1 part of polyvinyl phenyl silane and 0.2 benzenesulfonyl benzene sulfonate potassium . In Comparative Example 2 and Example 1, the difference between the two halogen-free flame-retardant and antistatic PC materials is that in Comparative Example 2, the content of carbon fiber is different, and carbon nanotubes are not added.

Weigh the above-mentioned components with corresponding weights, mix them evenly, and add them to the twin-screw extruder for melt extrusion and granulation.

After melt-extrusion and granulation of the halogen-free flame-retardant and antistatic PC materials of the above examples and comparative examples, the particles in the examples and comparative examples were injection molded into standard test specimens on an injection molding machine, and the obtained materials were tested according to the standards The mechanical properties of the test results are shown in Table 1:

Comparing the foregoing Examples 1-8 with Comparative Example 1 and Comparative Example 2, it can be seen that a certain proportion of carbon nanotubes and carbon fibers are added as conductive media to the PC material, and a composite compound is added. Fang’s flame retardant can make the PC material have better antistatic performance, flame retardant performance and higher impact resistance. This is mainly because the composite formula of carbon nanotube and carbon fiber is used as the conductive medium of the PC material. , So that the amount of conductive medium added in the PC material is lower, not only makes the PC material obtain better antistatic and flame retardant properties, but also retains more than 50% of the physical properties of the PC material itself.

The present invention further provides a product which is made of the above 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 conjunction with specific embodiments. These descriptions are only for explaining the principles of the present invention and cannot be construed as limiting the protection scope of the present invention in any way. Based on the explanation here, those skilled in the art can think of other specific implementation manners of the present invention without creative work, and these manners will fall within the protection scope of the present invention.

Claims (6)

A halogen-free flame-retardant and antistatic PC material, in which, for every 100 parts by mass of the finished PC material, the following components are included: polycarbonate, 93.7-97.4 parts; carbon nanotubes, 1-2 parts; carbon fiber, 1 to 3 parts; and flame retardant, 0.6 to 1.3 parts, and the flame retardant is polyvinyl phenyl silane and potassium benzenesulfonyl benzene sulfonate prepared in a ratio of 1:0.1 to 1:0.6. The halogen-free flame-retardant antistatic PC material according to claim 1, wherein the polycarbonate is bisphenol A polycarbonate, polyester polycarbonate, cyclohexane bisphenol A polycarbonate, Two or more compound formulas in high temperature resistant polycarbonate synthesized by bisphenol TMC. The halogen-free flame-retardant antistatic PC material according to claim 2, wherein, under the conditions of a temperature of 300°C and a load of 1.2Kg, the melt mass flow rate of the polycarbonate is 3g/10min~50g/ 10min. The halogen-free flame-retardant antistatic PC material according to claim 1, wherein the carbon nanotubes are at least one of single-wall carbon nanotubes, double-wall carbon nanotubes, and multi-wall carbon nanotubes. The halogen-free flame-retardant antistatic PC material according to claim 4, wherein the diameter of the carbon nanotubes is 0.7nm~7nm, and the diameter of more than 50% of the carbon nanotubes is 0.7nm~1nm The aspect ratio of the carbon nanotubes is greater than or equal to 500, the oil absorption value is greater than or equal to 300 ml/100g, the nitrogen adsorption specific surface area is greater than or equal to 250 m ² /g, and the iodine adsorption value is greater than or equal to 400 mg/g. The halogen-free flame-retardant antistatic PC material according to claim 1, wherein the number of filaments of the carbon fiber is 3K~60K, the diameter of single filament is 1μm~20μm, and the chopped length is 1mm~15mm.