CN111117183A - Antistatic, low-smoke, halogen-free and flame-retardant PC/ABS blending material and preparation method thereof - Google Patents
Antistatic, low-smoke, halogen-free and flame-retardant PC/ABS blending material and preparation method thereof Download PDFInfo
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- CN111117183A CN111117183A CN201911274035.3A CN201911274035A CN111117183A CN 111117183 A CN111117183 A CN 111117183A CN 201911274035 A CN201911274035 A CN 201911274035A CN 111117183 A CN111117183 A CN 111117183A
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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
- C08K2201/002—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
- C08K2201/002—Physical properties
- C08K2201/004—Additives being defined by their length
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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
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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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
- C08K2201/017—Additives being an antistatic agent
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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
Abstract
The invention relates to an antistatic, low-smoke, halogen-free and flame-retardant PC/ABS blending material and a preparation method thereof, and the PC/ABS blending material is specifically composed of the following raw materials in parts by weight: 40-70 parts of PC resin, 5-20 parts of ABS resin, 5-20 parts of aromatic polyphosphate compound flame retardant, 0.5-5 parts of functionalized carbon nanotube, 0.5-1 part of coupling agent and 0.5-1 part of antioxidant. The PC/ABS alloy material obtained by the technical scheme of the invention has excellent flame retardant property, and the addition of the carbon nano tube ensures that the alloy material obtains excellent long-term antistatic effect and the surface resistivity can reach 103‑1012Omega; the halogen-free aromatic polyphosphate compound flame retardant is adopted to synergistically improve the oxygen index and smoke density of the flame-retardant PC/ABS, and can be applied to interior materials of passenger cars. The antistatic, low-smoke, halogen-free and flame-retardant PC/ABS alloy material prepared by the invention has permanent antistatic property, low cost, high mechanical property and stable flame retardance, and the production process is simple, so that the PC/ABS alloy material can be widely applied to large-scale production.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to an antistatic, low-smoke, halogen-free and flame-retardant PC/ABS blending material and a preparation method thereof.
Background
The PC/ABS alloy material is a polymer composite material containing a plurality of components, utilizes the structural compatibility between PC and ABS, and can obtain a series of PC/ABS composite materials with different performance indexes by adjusting the component proportion between PC and ABS. PC/ABS as a two-phase alloy blending material has good physical properties, high fluidity and high insulation, and is widely used in the fields of automobile industry, electronic appliances, electric tools and the like.
In recent years, with the improvement of awareness of fire safety, flame retardant polymer materials are becoming a hot point of development. Although PC has a certain flame retardancy, the flame retardancy is seriously deteriorated when PC is mixed with ABS. Generally, flame retardance of polymer materials is realized by adding a small amount of flame retardant into a resin matrix, and with the increasing requirements on environmental protection, halogen-free flame-retardant PC/ABS alloy materials are rapidly developed, and particularly for interior flame-retardant materials of passenger cars, the flame-retardant PC/ABS alloy materials have the advantages of high oxygen index, low smoke density and good flame retardance. However, due to the high insulation of the PC/ABS, when used in an electrical connector or rubbed with other materials, the PC/ABS plastic may be charged with static electricity, which may cause static electricity accumulation and signal interference, which are not favorable for the application of the PC/ABS material in the fields of vehicle electrical equipment housing and signal connector.
In order to enable PC/ABS to achieve an antistatic effect, antistatic or conductive materials such as carbon black, carbon fiber and the like are often added, however, the addition amount of the carbon black is large, so that the flowability of the material is reduced, the processability is affected, and the flame retardant effect is also negatively affected by the carbon black; although a small amount of carbon fiber can be added to obtain a good antistatic effect, the appearance of the product is obvious in fiber floating, and the product with the appearance is not easy to prepare.
The carbon nano tube belongs to a one-dimensional nano material, has large length-diameter ratio, high specific strength, good toughness and excellent conductivity, and can be widely applied to high molecular polymers as a reinforcing and conductive filler. However, the chemical inertness of the surface of the carbon nanotubes causes poor dispersibility in the resin matrix, and easily agglomerates in the matrix, resulting in poor electrical conductivity. Therefore, the addition of the functionalized carbon nanotube into the PC/ABS blending system can improve the dispersion degree of the carbon nanotube in the resin system, and also realize the effects of permanent antistatic and electric conduction, and the obtained antistatic halogen-free flame-retardant PC/ABS can be widely applied to the fields of automobile industry, electronic appliances and the like.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide an antistatic, low-smoke, halogen-free and flame-retardant PC/ABS blending material.
The purpose of the invention is realized by the following technical scheme:
an antistatic, low-smoke, halogen-free and flame-retardant PC/ABS blending material comprises the following raw materials in parts by weight:
further, the Polycarbonate (PC) resin has a melt index of 5-30 g/10min and a notch impact strength of not less than 50kJ/m under the test conditions of 260 ℃ and 5Kg2。
Further, the styrene-butadiene-Acrylonitrile (ABS) resin has a melt index of 3-20 g/10min and a butadiene content of less than or equal to 18% under the test conditions of 220 ℃ and 10 Kg.
Furthermore, the flame retardant is environment-friendly halogen-free aromatic polyphosphate and has the effect of smoke suppression, and is a solid or liquid phosphate ester compound system or a compound system of RDP, BDP, TPP and HPCTP.
Furthermore, the carbon nano tube is one or more of an ester-based carbon nano tube, an amino carbon nano tube, a hydroxyl carbon nano tube, a carboxyl carbon nano tube and the like with functionalized surfaces.
Further, the coupling agent is a silane coupling agent, a titanate coupling agent or an aluminate coupling agent.
The second purpose of the invention is to provide a preparation method for preparing the antistatic, low-smoke, halogen-free and flame-retardant PC/ABS blending material as described in claim 1, which is characterized by comprising the following steps:
(1) weighing the dried raw materials according to the weight percentage, and dry-mixing the components except the functionalized carbon nanotubes in a high-speed mixer for 3-5min to uniformly mix the components.
(2) Respectively placing the mixed raw materials and the functionalized carbon nano tube in a main feeding port and a side feeding port of a meshing co-rotating double-screw extruder, and carrying out a series of procedures such as melt extrusion, granulation, drying and the like to obtain the antistatic, low-smoke, halogen-free and flame-retardant PC/ABS alloy, wherein the diameter of a screw of the extruder is 35mm, the length-diameter ratio L/D is 40, the rotating speed of the screw is 200-300rpm/min, and the temperature of each section of the extruder is 200-250 ℃.
Compared with the prior art, the invention has the following beneficial effects:
(1) based on the characteristic that the conventional carbon nano tube has fewer functional groups on the surface and weaker bonding force with a resin matrix, so that the carbon nano tube is unevenly dispersed in the resin system, the surface functionalized multi-walled carbon nano tube is selectively adopted, the compatibility of the functionalized carbon nano tube and the resin matrix is improved, the dispersion degree of the carbon nano tube in the resin system is improved, the antistatic uniformity is improved, and meanwhile, the mechanical property of the material is also improved by taking the carbon nano tube as a reinforcing unit.
(2) By adopting an aromatic phosphate flame retardant compounding system with higher phosphorus content, ester groups in phosphate have stronger interaction with functionalized, especially esterified, carbon nano tubes, so that the flame retardant can be uniformly dispersed in a resin matrix, the V0-grade flame retardance can be achieved, the synergistic effect of the flame retardant is fully exerted, and the flame-retardant PC/ABS material with high oxygen index and low smoke density can be obtained.
Detailed Description
The invention is further illustrated by the following specific examples, which are intended to be illustrative only and not limiting.
The raw materials used in the embodiment of the invention are as follows:
PC is a high molecular weight long-chain polycarbonate having a melt index MFR of 5g/10min (260 ℃ C., 5Kg) and a notched impact strength of 58kJ/m, manufactured by Mitsubishi chemical corporation2。
ABS: the conventional grade ABS has medium petrochemical, high petrochemical, melt index MFR of 15g/10min (220 ℃, 10Kg) and effective butadiene content of 27%.
Flame retardant: HPTCP, yake science, Jiangsu, available phosphorus content: 15 to 20 percent.
Flame retardant: PX220, Zhejiang province chemical industry, with effective phosphorus content of 10-15%.
Flame retardant: TPP, Zhejiang Wansheng chemical industry, has effective phosphorus content of 10-15%.
Carbon nanotube: diameter of 20 + -5 nm and length of 4 μm, Chengdu organic chemistry, Inc
Functionalized carbon nanotubes: self-made
And (3) product performance testing:
tensile property: the test was carried out according to ISO527-2 standard at a rate of 50 mm/min.
Bending property: the test was carried out according to IS178 with a span of 64mm and a test rate of 2 mm/min.
Notched impact strength: the test is carried out on a simple beam impact tester according to ISO179-1 standard, the notch of a sample strip is A type, and the test is carried out at normal temperature (23 ℃).
Flame retardant property: the test was carried out in a Drek DRK-310 horizontal vertical burning tester according to the standard test method for UL94 vertical burning, with a test specimen thickness of 1.6 mm.
Oxygen index: testing according to a standard method of GB/T2406;
smoke density: testing was carried out according to the standard method of GB/T8627
Surface resistance: tested according to IEC 60093 standard, 23 ℃.
Example 1
Weighing the PC resin, the ABS resin, the flame retardant, the coupling agent and the antioxidant according to the weight percentage of the embodiment 1 in the table 1, stirring the mixture in a high-speed mixer for 3 to 5min, and drying the mixture in an oven to obtain the mixed raw material.
Respectively placing the mixed raw materials and the functionalized carbon nano tube in a main feeding port and a side feeding port of a meshing co-rotating double-screw extruder, and carrying out a series of procedures such as melt extrusion, granulation, drying and the like to obtain the antistatic, low-smoke, halogen-free and flame-retardant PC/ABS alloy, wherein the diameter of a screw of the extruder is 35mm, the length-diameter ratio L/D is 40, the rotating speed of the screw is 200-300rpm/min, and the temperature of each section of the extruder is 200-250 ℃.
Example 2
Weighing the PC resin, the ABS resin, the flame retardant, the coupling agent and the antioxidant according to the weight percentage of the embodiment 1 in the table 1, stirring the mixture in a high-speed mixer for 3 to 5min, and drying the mixture in an oven to obtain the mixed raw material.
Respectively placing the mixed raw materials and the functionalized carbon nano tube in a main feeding port and a side feeding port of a meshing co-rotating double-screw extruder, and carrying out a series of procedures such as melt extrusion, granulation, drying and the like to obtain the antistatic, low-smoke, halogen-free and flame-retardant PC/ABS alloy, wherein the diameter of a screw of the extruder is 35mm, the length-diameter ratio L/D is 40, the rotating speed of the screw is 200-300rpm/min, and the temperature of each section of the extruder is 200-250 ℃.
Example 3
Weighing the PC resin, the ABS resin, the flame retardant, the coupling agent and the antioxidant according to the weight percentage of the embodiment 1 in the table 1, stirring the mixture in a high-speed mixer for 3 to 5min, and drying the mixture in an oven to obtain the mixed raw material.
Respectively placing the mixed raw materials and the functionalized carbon nano tube in a main feeding port and a side feeding port of a meshing co-rotating double-screw extruder, and carrying out a series of procedures such as melt extrusion, granulation, drying and the like to obtain the antistatic, low-smoke, halogen-free and flame-retardant PC/ABS alloy, wherein the diameter of a screw of the extruder is 35mm, the length-diameter ratio L/D is 40, the rotating speed of the screw is 200-300rpm/min, and the temperature of each section of the extruder is 200-250 ℃.
Example 4
Weighing the PC resin, the ABS resin, the flame retardant, the coupling agent and the antioxidant according to the weight percentage of the embodiment 1 in the table 1, stirring the mixture in a high-speed mixer for 3 to 5min, and drying the mixture in an oven to obtain the mixed raw material.
Respectively placing the mixed raw materials and the functionalized carbon nano tube in a main feeding port and a side feeding port of a meshing co-rotating double-screw extruder, and carrying out a series of procedures such as melt extrusion, granulation, drying and the like to obtain the antistatic, low-smoke, halogen-free and flame-retardant PC/ABS alloy, wherein the diameter of a screw of the extruder is 35mm, the length-diameter ratio L/D is 40, the rotating speed of the screw is 200-300rpm/min, and the temperature of each section of the extruder is 200-250 ℃.
Example 5
Weighing the PC resin, the ABS resin, the flame retardant, the coupling agent and the antioxidant according to the weight percentage of the embodiment 1 in the table 1, stirring the mixture in a high-speed mixer for 3 to 5min, and drying the mixture in an oven to obtain the mixed raw material.
Respectively placing the mixed raw materials and the functionalized carbon nano tube in a main feeding port and a side feeding port of a meshing co-rotating double-screw extruder, and carrying out a series of procedures such as melt extrusion, granulation, drying and the like to obtain the antistatic, low-smoke, halogen-free and flame-retardant PC/ABS alloy, wherein the diameter of a screw of the extruder is 35mm, the length-diameter ratio L/D is 40, the rotating speed of the screw is 200-300rpm/min, and the temperature of each section of the extruder is 200-250 ℃.
Example 6
Weighing the PC resin, the ABS resin, the flame retardant, the coupling agent and the antioxidant according to the weight percentage of the embodiment 1 in the table 1, stirring the mixture in a high-speed mixer for 3 to 5min, and drying the mixture in an oven to obtain the mixed raw material.
Respectively placing the mixed raw materials and the functionalized carbon nano tube in a main feeding port and a side feeding port of a meshing co-rotating double-screw extruder, and carrying out a series of procedures such as melt extrusion, granulation, drying and the like to obtain the antistatic, low-smoke, halogen-free and flame-retardant PC/ABS alloy, wherein the diameter of a screw of the extruder is 35mm, the length-diameter ratio L/D is 40, the rotating speed of the screw is 200-300rpm/min, and the temperature of each section of the extruder is 200-250 ℃.
Comparative example 1
Weighing the PC resin, the ABS resin, the flame retardant, the coupling agent and the antioxidant according to the weight percentage of the comparative example 1 in the table 1, stirring the mixture in a high-speed mixer for 3 to 5min, and drying the mixture in an oven to obtain the mixed raw material.
Respectively placing the mixed raw materials and the carbon black in a main feeding port and a side feeding port of a meshing co-rotating double-screw extruder, and carrying out a series of procedures such as melt extrusion, granulation, drying and the like to obtain the antistatic, low-smoke, halogen-free and flame-retardant PC/ABS alloy, wherein the diameter of a screw of the extruder is 35mm, the length-diameter ratio L/D is 40, the rotating speed of the screw is 200-300rpm/min, and the temperature of each section of the extruder is 200-250 ℃.
TABLE 1 formulation of antistatic, low smoke, halogen-free, flame retardant PC/ABS blend materials (unit:%)
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Comparative example 1 | |
| PC | 80 | 79 | 77 | 78 | 78 | 78 | 64 |
| ABS | 10 | 10 | 10 | 8 | 8 | 8 | 10 |
| PX220 | 3 | 3 | 3 | 3 | |||
| HPCTP | 3 | 3 | 8 | 3 | 3 | 3 | 8 |
| TPP | 3 | ||||||
| Ester-based carbon nanotubes | 1 | 2 | 2 | 5 | 5 | ||
| Amino carbon nanotube | 5 | ||||||
| Carbon black | 15 |
TABLE 2 test results of antistatic, low-smoke, halogen-free, flame-retardant PC/ABS blend materials
From the material performance test data of each example 1-6 in table 2, the PC/ABS filled with carbon nanotubes can achieve 1.6mmV0 flame retardance, the oxygen index and the smoke density both meet the flame retardance standard of interior trim of a passenger car (GB/T38262-2019), and the surface resistance of the material gradually decreases with the increase of the addition amount of the carbon nanotubes. Compared with the comparative example 1, the carbon nano tube used as a conductive agent has better performance than the conductive composite material prepared from carbon black in both flame retardance and mechanical property, namely the carbon nano tube can be used as a conductive and antistatic filler and also can be used as a reinforcing unit to improve the mechanical property of PC/ABS. In addition, the esterified carbon nanotube has better compatibility with PC and phosphate ester flame retardant due to the ester group functional group, and is dispersed in the resin matrix more uniformly, so that the conductive uniformity of the embodiment 4 is better than that of the embodiment 5. Therefore, the invention adopts the functionalized carbon nano tube as the conductive auxiliary agent, can obtain the flame-retardant PC/ABS alloy material with uniform conductivity, can also improve the mechanical property of the alloy, and can be widely applied to the fields of vehicle-mounted electrical appliances, signal connectors and the like.
Claims (7)
1. An antistatic, low-smoke, halogen-free and flame-retardant PC/ABS blending material is characterized in that: the feed comprises the following raw materials in parts by weight:
2. the antistatic, low-smoke, halogen-free and flame-retardant PC/ABS blending material as claimed in claim 1, wherein: the Polycarbonate (PC) resin has a melt index of 5-30 g/10min and a notch impact strength of not less than 50kJ/m under the test conditions of 260 ℃ and 5Kg2。
3. The antistatic, low-smoke, halogen-free and flame-retardant PC/ABS blending material as claimed in claim 1, wherein: the styrene-butadiene-Acrylonitrile (ABS) resin has a melt index of 3-20 g/10min and a butadiene content of less than or equal to 18% under the test conditions of 220 ℃ and 10 Kg.
4. The antistatic, low-smoke, halogen-free and flame-retardant PC/ABS blending material as claimed in claim 1, wherein: the flame retardant is environment-friendly halogen-free aromatic polyphosphate and has a smoke suppression effect, and is a solid or liquid phosphate ester compound system or a compound system of RDP, BDP, TPP and HPCTP.
5. The antistatic, low-smoke, halogen-free and flame-retardant PC/ABS blending material as claimed in claim 1, wherein: the carbon nano tube is one or more of an ester-based carbon nano tube, an amino carbon nano tube, a hydroxyl carbon nano tube, a carboxyl carbon nano tube and the like with functionalized surfaces.
6. The antistatic, low-smoke, halogen-free and flame-retardant PC/ABS blending material as claimed in claim 1, wherein: the coupling agent is a silane coupling agent, a titanate coupling agent or an aluminate coupling agent.
7. The preparation method of the antistatic, low-smoke, halogen-free and flame-retardant PC/ABS blending material according to any one of claims 6, characterized by comprising the following steps:
(1) weighing the dried raw materials according to the weight percentage, and dry-mixing the components except the functionalized carbon nanotubes in a high-speed mixer for 3-5min to uniformly mix the components.
(2) Respectively placing the mixed raw materials and the functionalized carbon nano tube in a main feeding port and a side feeding port of a meshing co-rotating double-screw extruder, and carrying out a series of procedures such as melt extrusion, granulation, drying and the like to obtain the antistatic, low-smoke, halogen-free and flame-retardant PC/ABS alloy, wherein the diameter of a screw of the extruder is 35mm, the length-diameter ratio L/D is 40, the rotating speed of the screw is 200-300rpm/min, and the temperature of each section of the extruder is 200-250 ℃.
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| CN112625359A (en) * | 2020-12-09 | 2021-04-09 | 上海普利特复合材料股份有限公司 | High-impact-resistance flame-retardant polypropylene composite material for interior decoration of passenger car and preparation method thereof |
| CN112625419A (en) * | 2020-12-17 | 2021-04-09 | 重庆科聚孚工程塑料有限责任公司 | High-heat-resistance halogen-free flame-retardant permanent antistatic PC/ABS composite material, preparation method thereof, product thereof and preparation method of product |
| CN112940478A (en) * | 2021-02-03 | 2021-06-11 | 福建新永发塑胶模具有限公司 | PC/ABS anti-aging material special for automobiles and preparation method thereof |
| CN113174121A (en) * | 2021-04-08 | 2021-07-27 | 宁波坚锋新材料有限公司 | Regenerated ABS composite material and preparation method thereof |
| CN113969036A (en) * | 2021-11-26 | 2022-01-25 | 北方华锦化学工业股份有限公司 | Preparation method of functionalized multi-walled carbon nanotube modified ABS resin |
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