CN114316565A - Scratch-resistant antistatic polyphenyl ether alloy material - Google Patents
Scratch-resistant antistatic polyphenyl ether alloy material Download PDFInfo
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Abstract
The invention relates to a scraping-resistant antistatic polyphenyl ether alloy material which is prepared by uniformly mixing 55-70% of polyphenyl ether, 20-40% of HIPS, 1-10% of PE grafted styrene copolymer, 0.3-1% of interface modifier and 1-5% of conductive agent in a high-speed mixer, discharging, and then feeding the mixed material from a main feeding port of a double-screw machine for extrusion and granulation; wherein the interfacial modifier is PTFE with the weight-average molecular weight of 400-600 w; the scratch-resistant antistatic polyphenyl ether alloy material disclosed by the invention has excellent antistatic property and scratch resistance as well as excellent dimensional stability and heat resistance, and can be applied to parts such as precision electronic component trays and the like.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and relates to a scratch-resistant antistatic polyphenyl ether alloy material.
Background
The polyphenyl ether is a thermoplastic engineering plastic with excellent performance, has higher mechanical property and heat resistance, good dimensional stability and low moisture absorption rate, and is particularly suitable for precise injection molding parts with higher requirements on the dimension. The polyphenyl ether alloy has particularly excellent electrical insulation property, is widely applied to high-voltage resistant components such as ignition coils, display screen transformers and the like, and in order to prevent static electricity from damaging electronic components, electronic and electrical appliance packages such as wafer boxes, module trays and the like require antistatic property and even conductive property on materials, and cannot have abrasion pollution in the transfer process, the materials must have higher scratch resistance simultaneously, and the PPO alloy materials must be subjected to antistatic modification.
Chinese patent CN 109096730A discloses a high-temperature-resistant conductive PPO/PS alloy material and a preparation method thereof, which is prepared from the following raw materials in percentage by mass: the alloy material is composed of 30-60% of PPO, 5-25% of GPPS, 1-10% of compatilizer, 1-10% of SMA, 3-15% of SEBS, 15-30% of conductive carbon black, 0.2-1% of antioxidant, 0.2-3% of lubricant and 1-5% of surface treating agent. The material has the characteristics of high temperature resistance, permanent stable conductivity, antistatic performance and the like, but the scheme uses conductive carbon black as a conductive agent, the threshold value of antistatic or conductive level is required to be higher, the addition amount of the conductive carbon black is particularly large, the processing is difficult, and simultaneously, because the surface polarity difference is large, the compatibility is poor, a large amount of carbon powder falls off in a scraping test, the surface cleanliness of a precision electrical appliance is influenced, and the conductive carbon black is not suitable for application of precision parts with the scraping resistance requirement.
Disclosure of Invention
The invention aims to provide a scratch-resistant antistatic polyphenyl ether alloy material and a preparation method thereof aiming at the defects in the prior art. The scratch-resistant antistatic polyphenyl ether alloy material disclosed by the invention has excellent scratch resistance, excellent high-temperature resistance, excellent antistatic performance and dimensional stability, and can be applied to packaging materials for precise electronic and electric appliances.
In order to achieve the purpose, the invention adopts the following scheme:
a scratch-resistant antistatic polyphenyl ether alloy material comprises the following components in percentage by mass:
55-70% of polyphenyl ether;
20-40% of polystyrene;
1-10% of a scratch-resistant modifier;
0.3-1% of an interface modifier;
1-5% of a conductive agent;
the polystyrene is HIPS;
the scratch-resistant modifier is a PE grafted styrene copolymer;
the interfacial modifier is PTFE with the weight-average molecular weight of 400-600 w.
As a preferred technical scheme:
the scratch-resistant antistatic polyphenyl ether alloy material has the specific viscosity of 0.3-0.5 dl/g of polyphenyl ether in chloroform at 25 ℃.
The scratch-resistant antistatic polyphenyl ether alloy material has the advantages that the PE grafted styrene copolymer is PE-g-AS or PE-g-PS.
The scratch-resistant antistatic polyphenyl ether alloy material has the advantages that the conductive agent is the carbon nano tube.
In the scraping-resistant antistatic polyphenyl ether alloy material, the carbon nanotubes are multi-walled carbon nanotubes with an array structure in which the carbon nanotubes are arranged in parallel.
The scraping-resistant antistatic polyphenyl ether alloy material has the advantages that the average particle size of the carbon nano tube is 5-15 nm, and the specific surface area is 200-400 m2/g。
The invention also provides a preparation method of the scraping-resistant antistatic polyphenyl ether alloy material, which comprises the steps of uniformly mixing polyphenyl ether, polystyrene, a scraping-resistant modifier, an interface modifier and a conductive agent in a high-speed mixer, discharging, feeding the mixed material from a main feeding port of a double-screw machine, and extruding and granulating to obtain the scraping-resistant antistatic polyphenyl ether alloy composite material.
As a preferred technical scheme:
the scraping-resistant antistatic polyphenyl ether alloy material has the advantages that the rotating speed of a double-screw machine is 300-600 revolutions per minute, and the extrusion temperature is 240-300 ℃.
The scratch-resistant antistatic polyphenyl ether alloy material disclosed by the invention has excellent antistatic performance and scratch-resistant characteristic:
(1) PPO cannot be used alone, and must be alloyed with other resins, most commonly with PA, PP and the like, and has the following problems: on one hand, the compatibility of PP, PA and PPO is poor, and corresponding compatilizers must be added, on the other hand, both PP and PA belong to crystalline materials, and the problem of shrinkage deformation caused by recrystallization can occur during high and low temperature experiments, and extreme conditions such as stress concentration cracking and the like also exist. According to the scraping-resistant antistatic polyphenyl ether alloy material disclosed by the invention, PPO/HIPS is selected as an alloy matrix, a continuous polystyrene phase structure in the HIPS is better in compatibility with the PPO, and better compatibility can be achieved without adding an additional compatilizer.
(2) The PE grafted styrene copolymer is selected as a scratch-resistant modifier, the styrene section of the PE grafted styrene copolymer is arranged in matrix resin, and the PE section is exposed on the surface of a workpiece as a soft section due to low melting point to form a smooth and compact scratch-resistant 'buffer' structure, so that the PE grafted styrene copolymer is not easy to rub and fall off due to poor compatibility when contacting a hard object. On the other hand, the HIPS has a discontinuous butadiene rubber phase, the compatibility with a benzene ring structure is poor, and under the action of an interfacial repulsive force of the HIPS and the benzene ring structure, the interfacial gap between the carbon nanotube and resin is further compressed, so that a conductive network chain is more easily formed, and the addition amount of the carbon nanotube can be reduced.
(3) The general conductive carbon black/carbon fiber has a higher conductive threshold value, a conductive path can be realized by a high addition amount, a general high-molecular antistatic agent is generally a polyamide structure embedded with polyether, the temperature resistance is poor, the compatibility with PPO is poor, an antistatic effect can be realized by a very large addition amount, the deterioration of the mechanical property and the high temperature resistance of a material is serious, a multi-walled carbon nanotube is selected as a conductive agent, a conductive network chain is easier to form due to the fact that the multi-walled carbon nanotube has a large specific surface area, and meanwhile, compared with an array type carbon nanotube, the winding type carbon nanotube has lower hardness, better dispersion can be formed under the action of low shear, the addition amount is small, the cost performance is high, and the industrial commercialization is easier.
(4) The high molecular weight polytetrafluoroethylene is selected as the interface modifier, and besides excellent lubricating resistance, the polytetrafluoroethylene is mainly arranged in a fibrous shape under high-temperature shearing, orientation of benzene rings in a PPO/HIPS structure is enhanced, conductive carbon nanotubes are arranged along the radial direction, so that a more stable and continuous conductive network chain is formed, the addition of the conductive agent can be greatly reduced, and stable antistatic and conductive effects are achieved.
Advantageous effects
The scratch-resistant antistatic polyphenyl ether alloy material disclosed by the invention has excellent antistatic property and scratch resistance as well as excellent dimensional stability and heat resistance, and can be applied to parts such as precision electronic component trays and the like.
Detailed Description
The invention will be further illustrated with reference to specific embodiments. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
The polyphenylene ether has the intrinsic viscosity of 0.3-0.5 dl/g in chloroform at 25 ℃, and is derived from LXR035 (viscosity of 0.35), LXR040 (viscosity of 0.4) and LXR045 (viscosity of 0.45) of New blue-star chemical material Co.
The polystyrene in the invention is HIPS (high impact polystyrene) which is derived from HIPS 425TV of Han brocade lake petrochemical company.
The scratch-resistant modifier in the invention is PE-g-AS (polyethylene grafted styrene acrylonitrile copolymer, from Japan Co., Ltd., A1401) or PE-g-PS (polyethylene grafted styrene, from Japan Co., Ltd., A1100).
The interface improver is PTFE (polytetrafluoroethylene) with the weight-average molecular weight of 400-600 w, and is derived from TF-1645 of American 3M company.
The conductive agent in the invention is an array-type multi-wall carbon nano-tube with carbon nano-tubes arranged in parallel, and the carbon nano-tube is flatThe average particle diameter is 5-15 nm, and the specific surface area is 200-400 m2(ii) in terms of/g. LUCAN CP1002M from LG corporation.
The method for testing the tensile strength, the bending strength, the heat distortion temperature and the surface resistance of the material comprises the following steps: drying the material in a blast oven at 90 ℃ for 4 hours, and then performing injection molding by using a plastic injection molding machine to obtain a standard sample strip; placing the injection molded standard sample strip at the relative humidity of 50% and the temperature of 23 ℃ for at least 24 hours and then testing;
(1) tensile strength: according to ISO 527 method, the drawing speed is 5 mm/min;
(2) bending strength: according to the ISO 178 method, the test speed is 2 mm/min;
(3) heat distortion temperature: according to ISO 75 method, the load is 1.8 MPa;
(4) surface resistance: according to the IEC 60093 method;
the scratch resistance of the material of the invention is tested by the following method: the material is injection molded to prepare a square part with the thickness of 150mm x 3.2mm, a glass original sheet with the diameter of 10mm x 2mm is installed to be pressed down to the surface of the part at an angle of 45 degrees, 2N pressure is applied, the stroke is 60mm, the speed is 60mm/s, the surface of the glass original sheet is rubbed, 10 groups of tests are carried out, the vibration abrasion of the electronic tray in the transportation process is simulated, the quantity of foreign matters on the recording lens caused by glass scraping is observed, and the quantity of the foreign matters can be blown off by 3 times of observation through purging by an ear washing ball.
Examples 1 to 6
A preparation method of a scratch-resistant antistatic polyphenyl ether alloy material comprises the following steps:
(1) preparing raw materials: preparing materials according to the components and the mass percentage of the components in the table 1;
(2) mixing the materials prepared in the step (1) in a high-speed mixer for 6-10 min, and discharging;
(3) and (3) feeding the material mixed in the step (2) from a double-screw main feeding port, setting the rotating speed of a double-screw machine to be 300-600 rpm, and performing extrusion granulation at the extrusion temperature of 240-300 ℃ to obtain the scratch-resistant antistatic polyphenyl ether alloy composite material.
Wherein, the components and the mass percentage thereof in the embodiments 1-6 are shown in the following table 1:
TABLE 1
The polyphenylene ether alloy materials prepared in examples 1 to 6 were subjected to tensile strength, bending strength, heat distortion temperature, surface resistance and scratch resistance tests, and the test results are shown in table 2.
TABLE 2
Comparative example 1
A method for preparing a polyphenylene ether alloy material, which comprises the steps substantially the same as those of example 1 except that: the scratch resistance modifier in example 1 was replaced with PE-G-MAH (CMG 5904 from the good easy Polymer (Shanghai) Co., Ltd.). The prepared polyphenylene oxide alloy material is subjected to tensile strength, bending strength, thermal deformation temperature, surface resistance and scratch resistance performance tests, and the test results are shown in Table 3.
Comparative example 2
A method for preparing a polyphenylene ether alloy material, which comprises the steps substantially the same as those of example 1 except that: the conductive agent in example 1 is replaced by multi-wall carbon nanotubes (CNT 103 from Ching-de-Ke island technologies Co., Ltd., Beijing) with 8-15 nm diameter and 200m specific surface area2In terms of/g). The prepared polyphenylene oxide alloy material is subjected to tensile strength, bending strength, thermal deformation temperature, surface resistance and scratch resistance performance tests, and the test results are shown in Table 3.
Comparative example 3
A method for preparing a polyphenylene ether alloy material, which comprises the steps substantially the same as those of example 1 except that: the interface modifier in example 1 was replaced with low molecular weight polytetrafluoroethylene (L-5 (molecular weight 1w) from a general wear-resistant additive) derived from a great-gold chemical. The prepared polyphenylene oxide alloy material is subjected to tensile strength, bending strength, thermal deformation temperature, surface resistance and scratch resistance performance tests, and the test results are shown in Table 3.
TABLE 3
Claims (6)
1. The scratch-resistant antistatic polyphenyl ether alloy material is characterized by comprising the following components in percentage by mass:
55-70% of polyphenyl ether;
20-40% of polystyrene;
1-10% of a scratch-resistant modifier;
0.3-1% of an interface modifier;
1-5% of a conductive agent;
the polystyrene is HIPS;
the scratch-resistant modifier is a PE grafted styrene copolymer;
the interfacial modifier is PTFE with the weight-average molecular weight of 400-600 w.
2. The scratch-resistant antistatic polyphenylene ether alloy material as claimed in claim 1, wherein the specific viscosity of polyphenylene ether in chloroform at 25 ℃ is 0.3-0.5 dl/g.
3. The scraping-resistant antistatic polyphenyl ether alloy material according to claim 1, wherein the PE grafted styrene copolymer is PE-g-AS or PE-g-PS.
4. The scraping-resistant antistatic polyphenyl ether alloy material according to claim 1, wherein the conductive agent is carbon nanotubes.
5. The scraping-resistant antistatic polyphenyl ether alloy material according to claim 4, wherein the carbon nanotubes are multi-walled carbon nanotubes with an array structure of carbon nanotubes arranged in parallel.
6. The scraping-resistant antistatic polyphenyl ether alloy material as claimed in claim 5, wherein the carbon nanotubes have an average particle size of 5-15 nm and a specific surface area of 200-400 m2/g。
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