CN110551378A - Halogen-free flame-retardant PC/carbon nano tube conductive material and product thereof - Google Patents
Halogen-free flame-retardant PC/carbon nano tube conductive material and product thereof Download PDFInfo
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- CN110551378A CN110551378A CN201810555293.8A CN201810555293A CN110551378A CN 110551378 A CN110551378 A CN 110551378A CN 201810555293 A CN201810555293 A CN 201810555293A CN 110551378 A CN110551378 A CN 110551378A
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- carbon nanotube
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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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
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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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
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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
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
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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
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
- C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
-
- 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
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
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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
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/016—Additives defined by their aspect ratio
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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
-
- 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
Abstract
The invention relates to the technical field of high polymer materials, in particular to a halogen-free flame-retardant PC/carbon nano tube conductive material and a product thereof, wherein the halogen-free flame-retardant PC/carbon nano tube conductive material comprises, by weight, 65-96.9 parts of PC resin, 0.1-5 parts of hypophosphite flame retardant, 1-20 parts of phosphate flame retardant, 0-3 parts of organosilicon flame retardant and 2-7 parts of carbon nano tube, wherein the product is a product formed by molding the halogen-free flame-retardant PC/carbon nano tube conductive material, the hypophosphite flame retardant, the phosphate flame retardant and the organosilicon flame retardant are added into the material, the flame retardant grade can reach 1.6mmV-0 grade, and the volume resistance of the conductive material can be reduced to 10 3 ohm.cm-10 5 ohm.cm by adding the carbon nano tube.
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 PC/carbon nanotube conductive material and a product thereof.
[ background of the invention ]
The carbon nano tube has high modulus, high strength and high toughness, so that the mechanical property of the material can be greatly improved when the carbon nano tube is added into a high polymer material.
In electronic and electric products, the conductive plastic material can mask harmful signals, eliminate accumulated charges through dissipation, and have wide application. In plastic conductive materials applied to electronic and electric appliances, flame retardant requirements are met, but when carbon nanotubes are used as a conductive medium, the material has a candlewick effect during combustion due to the structure of the carbon nanotube, and the V-0 flame retardant grade is difficult to achieve. The carbon nano tube is easy to adsorb oily substances, so that the ester flame retardant is difficult to play a role in a PC resin phase in a formula and difficult to reach the flame retardant grade of V-0.
In view of the above, there is a need to develop a halogen-free flame retardant PC/carbon nanotube conductive material to solve the problem that the conductive material combined with PC and carbon nanotube in the prior art cannot achieve high flame retardancy.
[ summary of the invention ]
Therefore, the present invention aims to provide a halogen-free flame retardant PC/carbon nanotube conductive material to obtain a PC/carbon nanotube conductive material with high flame retardant property.
In order to achieve the above object, the halogen-free flame retardant PC/carbon nanotube conductive material of the present invention comprises, in parts by weight:
optionally, the PC resin is at least one of bisphenol a polycarbonate, polyester polycarbonate, silicone copolymer polycarbonate, cyclohexane bisphenol a polycarbonate, bisphenol a-organosiloxane copolymer polycarbonate, bisphenol TMC synthesized polycarbonate.
Optionally, the silicone copolymerized polycarbonate content in the PC resin is 0-94 parts.
alternatively, the PC resin may have a melt mass flow rate of 3 to 50g/10min at a temperature of 300 ℃ under a load of 1.2 Kg.
Optionally, the hypophosphite flame retardant is a vinyl aluminum hypophosphite flame retardant.
Optionally, the phosphate flame retardant is at least one of 2, 6-tolyl 1,3 phenylene phosphate, tetraphenyl bisphenol a diphosphate (BDP), tetraphenyl Resorcinol Diphosphate (RDP), triphenyl phosphate (TPP).
Optionally, the silicone flame retardant is at least one of polysilazane, polymethoxyphenylsilane, hydroxymethylsilane, cross-linked Polydimethylsiloxane (PDMS).
Optionally, the halogen-free flame-retardant PC/carbon nanotube conductive material further comprises at least one of an anti-dripping agent, an antibacterial agent, an ultraviolet absorber and a release agent.
Optionally, the halogen-free flame-retardant conductive material comprises 0-1 part of the anti-dripping agent by weight.
Optionally, the carbon nanotube is at least one of a single-walled carbon nanotube, a double-walled carbon nanotube, and a multi-walled carbon nanotube.
Optionally, the diameter of the single-walled carbon nanotube, the double-walled carbon nanotube or the multi-walled carbon nanotube is 0.7nm-7 nm.
Optionally, the carbon nanotubes with the diameter of 0.7nm-7nm account for at least 50% of the total amount of the carbon nanotubes in parts by weight.
Optionally, the aspect ratio L/D of the carbon nanotubes is above 500.
Optionally, the carbon nanotube has an oil absorption value of 300ml/100g or more, a nitrogen adsorption BET specific surface area of 250m 2/g or more, and an iodine adsorption value of 400mg/g or more.
in addition, the invention also provides a product which is produced after the halogen-free flame-retardant PC/carbon nano tube conductive material is molded.
Compared with the prior art, the halogen-free flame-retardant PC/carbon nanotube conductive material has the advantages that the flame retardant grade can reach 1.6mmV-0 grade by adding the hypophosphite flame retardant, the phosphate flame retardant and the organic silicon flame retardant into the material, and the volume resistance of the conductive material can be reduced to 10 3 ohm-10 5 ohm-cm by adding the carbon nanotube.
[ detailed description ] embodiments
the halogen-free flame-retardant PC/carbon nano tube conductive material comprises the following components in parts by weight:
65-96.9 parts of PC resin, wherein the PC resin is at least one of bisphenol A polycarbonate, polyester polycarbonate, organosilicon copolymerization polycarbonate, cyclohexane bisphenol A polycarbonate, bisphenol A-organosiloxane copolymerization polycarbonate and polycarbonate synthesized by bisphenol TMC, the melt mass flow rate of the PC is 3-50g/10min at the temperature of 300 ℃ and the load of 1.2Kg, and the content of the organosilicon copolymerization polycarbonate in the PC resin is 0-94 parts.
2-7 parts of carbon nanotubes, wherein the carbon nanotubes are at least one of single-wall carbon nanotubes, double-wall carbon nanotubes and multi-wall carbon nanotubes, the diameters of the single-wall carbon nanotubes, the double-wall carbon nanotubes and the multi-wall carbon nanotubes are 0.7nm-7nm, the carbon nanotubes with the diameters of 0.7nm-7nm account for at least 50% of the total amount of the carbon nanotubes in parts by weight, the length-diameter ratio L/D of the carbon nanotubes is more than 500, the oil absorption value of the carbon nanotubes is more than 300ml/100g, the nitrogen adsorption BET specific surface area is more than 250m 2/g, and the iodine adsorption value is more than 400 mg/g.
0.1-5 parts of hypophosphite flame retardant, wherein the hypophosphite flame retardant can be vinyl aluminum hypophosphite flame retardant.
1-20 parts of phosphate flame retardant, wherein the phosphate flame retardant is at least one of 1,3 phenylene phosphoric acid (2, 6-methylphenyl) tetraester, tetraphenyl bisphenol A diphosphate (BDP for short), tetraphenyl resorcinol diphosphate (RDP for short) and triphenyl phosphate (TPP for short).
0-3 parts of an organic silicon flame retardant, wherein the organic silicon flame retardant is at least one of polysilane, polymethoxyphenyl silane, hydroxymethyl silane and crosslinked Polydimethylsiloxane (PDMS).
Wherein, in order to obtain the functional composite material, the halogen-free flame-retardant PC/carbon nano tube conductive material also comprises at least one of an anti-dripping agent, an antibacterial agent, an ultraviolet absorbent and a release agent on the premise of not influencing the functional effect.
For further understanding of the objects, effects and technical means of the present invention, the following description is given with reference to the comparative examples and specific examples.
Example 1
The PC resin-1 is a PC resin other than the silicone copolymer polycarbonate. Weighing the components in corresponding weight; then, stirring the components by using a single-shaft stirring barrel; and respectively adding the mixture into a double-screw extruder to perform melt extrusion granulation.
Example 2
PC resin-1 is a PC resin other than silicone copolymer polycarbonate; the PC resin-2 is organic silicon copolymerization type polycarbonate. Weighing the components in corresponding weight; then, stirring the components by using a single-shaft stirring barrel; and respectively adding the mixture into a double-screw extruder to perform melt extrusion granulation.
Comparative example 1
The PC resin-1 is a PC resin other than the silicone copolymer polycarbonate. Weighing the components in corresponding weight; then, stirring the components by using a single-shaft stirring barrel; and respectively adding the mixture into a double-screw extruder to perform melt extrusion granulation.
Comparative example 2
PC resin-1 is a PC resin other than silicone copolymer polycarbonate; the PC resin-2 is organic silicon copolymerization type polycarbonate. Weighing the components in corresponding weight; then, stirring the components by using a single-shaft stirring barrel; and respectively adding the mixture into a double-screw extruder to perform melt extrusion granulation.
After melt extrusion granulation of the above examples and comparative examples, the particles in each example were injection molded into standard test bars on an injection molding machine, and the mechanical properties of the resulting materials were tested according to the standard, with the test results shown in table 1:
Table 1: test results of examples and comparative examples
From the above, it can be seen that: compared with the comparative example 1 and the comparative example 2, in the example 2, the flame retardant property is greatly improved by adding the hypophosphite flame retardant, the phosphate flame retardant and the organic silicon flame retardant into the PC resin, and the V grade can be improved to 1.6mm V-0 grade. In addition, compared with example 2, in example 1, when the silicone-containing copolymerized polycarbonate was added to the material, the elongation at break, the flexural strength, and the flexural modulus were improved, and the impact strength was greatly improved.
In addition, the invention also provides a product which is produced by molding the halogen-free flame-retardant conductive material, and the product can be widely applied to electronic and electrical products, such as printers, computer CPU conductive parts and other fields.
Claims (14)
1. The halogen-free flame-retardant PC/carbon nano tube conductive material is characterized by comprising the following components in parts by weight:
2. The halogen-free flame retardant PC/carbon nanotube conductive material of claim 1, wherein the carbon nanotube is at least one of a single-walled carbon nanotube, a double-walled carbon nanotube, and a multi-walled carbon nanotube.
3. The halogen-free flame-retardant PC/carbon nanotube conductive material of claim 2, wherein the diameters of the single-walled carbon nanotube, the double-walled carbon nanotube and the multi-walled carbon nanotube are 0.7nm-7 nm.
4. The halogen-free flame-retardant PC/carbon nanotube conductive material of claim 1, wherein the carbon nanotubes with a diameter of 0.7nm-7nm account for at least 50% of the total amount of the carbon nanotubes in parts by weight.
5. The halogen-free flame retardant PC/carbon nanotube conductive material of claim 1, wherein the aspect ratio L/D of the carbon nanotube is above 500.
6. The halogen-free flame-retardant PC/carbon nanotube conductive material of claim 1, wherein the carbon nanotube has an oil absorption value of 300ml/100g or more, a nitrogen adsorption BET specific surface area of 250m 2/g or more, and an iodine adsorption value of 400mg/g or more.
7. The halogen-free flame retardant PC/carbon nanotube conductive material of claim 1, wherein the PC resin is at least one of bisphenol A polycarbonate, polyester polycarbonate, silicone copolymer polycarbonate, cyclohexane bisphenol A polycarbonate, bisphenol A-organosiloxane copolymer polycarbonate, and polycarbonate synthesized by bisphenol TMC.
8. The halogen-free flame retardant PC/carbon nanotube conductive material of claim 7, wherein the content of the silicone copolymerized polycarbonate in the PC resin is 0-94 parts.
9. The halogen-free flame-retardant PC/carbon nanotube conductive material according to claim 1, wherein the melt mass flow rate of the PC resin is 3-50g/10min at 300 ℃ and under a load of 1.2 Kg.
10. The halogen-free flame retardant PC/carbon nanotube conductive material of claim 1, wherein the hypophosphite flame retardant is an ethylene aluminum hypophosphite flame retardant.
11. The halogen-free flame retardant PC/carbon nanotube conductive material of claim 1, wherein the phosphate ester flame retardant is at least one of 1,3 phenylene phosphoric acid (2, 6-tolyl) tetraester, tetraphenyl bisphenol A diphosphate, tetraphenyl resorcinol diphosphate and triphenyl phosphate.
12. The halogen-free flame-retardant PC/carbon nanotube conductive material according to claim 1, wherein the organosilicon flame retardant is at least one of polysilazane, polymethoxyphenylsilane, hydroxymethylsilane, and cross-linked polydimethylsiloxane.
13. The halogen-free flame retardant PC/carbon nanotube conductive material of claim 1, wherein the high performance halogen-free flame retardant PC conductive material further comprises at least one of an anti-dripping agent, an antibacterial agent, an ultraviolet absorber and a mold release agent.
14. A product produced by molding the halogen-free flame-retardant PC/carbon nanotube conductive material according to any one of claims 1 to 13.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810555293.8A CN110551378A (en) | 2018-06-01 | 2018-06-01 | Halogen-free flame-retardant PC/carbon nano tube conductive material and product thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201810555293.8A CN110551378A (en) | 2018-06-01 | 2018-06-01 | Halogen-free flame-retardant PC/carbon nano tube conductive material and product thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111875943A (en) * | 2020-08-07 | 2020-11-03 | 宁波耀众模塑科技有限公司 | Carbon-containing high polymer material mixture for flame retardant for polyurethane foaming product |
Citations (4)
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|---|---|---|---|---|
| CN104341762A (en) * | 2013-07-26 | 2015-02-11 | 三星Sdi株式会社 | Conductive Sheet Composition |
| CN106221035A (en) * | 2016-08-29 | 2016-12-14 | 四川金开特种电线电缆有限公司 | A kind of flame-retardant cable material |
| CN107541034A (en) * | 2016-06-27 | 2018-01-05 | 汉达精密电子(昆山)有限公司 | High tenacity fire-retardant polycarbonate thin-film material and its products formed |
| CN107722586A (en) * | 2016-08-11 | 2018-02-23 | 汉达精密电子(昆山)有限公司 | CNT polycarbafil/carbon fibre composite and its products formed |
-
2018
- 2018-06-01 CN CN201810555293.8A patent/CN110551378A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104341762A (en) * | 2013-07-26 | 2015-02-11 | 三星Sdi株式会社 | Conductive Sheet Composition |
| CN107541034A (en) * | 2016-06-27 | 2018-01-05 | 汉达精密电子(昆山)有限公司 | High tenacity fire-retardant polycarbonate thin-film material and its products formed |
| CN107722586A (en) * | 2016-08-11 | 2018-02-23 | 汉达精密电子(昆山)有限公司 | CNT polycarbafil/carbon fibre composite and its products formed |
| CN106221035A (en) * | 2016-08-29 | 2016-12-14 | 四川金开特种电线电缆有限公司 | A kind of flame-retardant cable material |
Non-Patent Citations (1)
| Title |
|---|
| 《化工百科全书》编辑委员会: "《化工百科全书》", 30 June 1995 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111875943A (en) * | 2020-08-07 | 2020-11-03 | 宁波耀众模塑科技有限公司 | Carbon-containing high polymer material mixture for flame retardant for polyurethane foaming product |
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Application publication date: 20191210 |