CN116925533A - Nylon composition and preparation method and application thereof - Google Patents

Nylon composition and preparation method and application thereof Download PDF

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Publication number
CN116925533A
CN116925533A CN202210317459.9A CN202210317459A CN116925533A CN 116925533 A CN116925533 A CN 116925533A CN 202210317459 A CN202210317459 A CN 202210317459A CN 116925533 A CN116925533 A CN 116925533A
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nylon composition
composition according
parts
nylon
flame retardant
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CN116925533B (en
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解明晨
钟一平
麦杰鸿
姜苏俊
曹民
徐显骏
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Kingfa Science and Technology Co Ltd
Zhuhai Vanteque Speciality Engineering Plastics Co Ltd
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Kingfa Science and Technology Co Ltd
Zhuhai Vanteque Speciality Engineering Plastics Co Ltd
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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
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
    • 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
    • C08K3/38—Boron-containing compounds
    • C08K2003/387—Borates
    • 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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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The application discloses a nylon composition, a preparation method and application thereof, wherein the nylon composition comprises the following components in parts by weight: 40-60 parts of semi-aromatic polyamide; 8-20 parts of halogen-free flame retardant; 10-40 parts of reinforcing filler; 0.3-5 parts of chelating agent; 0.1-1 part of flow modifier; 0.1-3 parts of flame retardant synergist. The nylon composition provided by the application has high CTI and excellent insulativity in a dry-wet state.

Description

Nylon composition and preparation method and application thereof
Technical Field
The application relates to the technical field of modified nylon materials, in particular to a nylon composition, a preparation method and application thereof.
Background
The new energy automobile and mobile phone industry are vigorously developed, so that the design and functional requirements of new products are endless, the requirements for improving the efficiency are higher and higher due to time saving, the new energy automobile and mobile phone industry are both developing in the fast charging direction, the fast charging means higher voltage intensity and current intensity, so that extremely obvious heating phenomenon can be generated, the heating temperature of a short circuit can reach more than 350 ℃ instantaneously, the traditional PBT material can not serve as a core part in metal contact with the fast charging products, and the traditional PBT material starts to turn to an LCP material and a high-temperature nylon material, but the two materials have more defects.
The LCP material is firstly applied to a plurality of workpieces due to the advantages of good recoverability, high fluidity, easiness in processing into thin-wall workpieces and the like, but the bonding line strength of the LCP material is very poor, and a plurality of workpieces have obvious cracking problems, so that the industry starts to select PA46 materials with good fluidity and excellent bonding line strength, but the PA46 materials start to frequently generate charging failure problems along with continuous lifting of charging current, particularly after the charging current of a mobile phone reaches 3A, obvious white precipitate appears on the plastic surface of a connector through factory returning maintenance, meanwhile, a remarkable plastic ablation phenomenon appears between two pin needles with the largest voltage value difference, the phenomenon that the mobile phone with the problem is stored under the conditions of humidity, sweat and the like is called burning, and the problem appears indicates that the material is easy to generate melting ablation after being subjected to electrolyte invasion for a long time.
In addition, the rechargeable battery of the new energy automobile has more electrolyte, and the voltage and the power are higher, so that once the problem of electrolyte leakage occurs, a great fire risk can be generated, and as reports on phenomena such as fire and the like are gradually increased in recent years, a great requirement on the safety of the new energy automobile is also put forward.
The patent 201210247556 proposes to prepare an alloy by using PA612 and PA46 with low water absorption, so as to improve the CTI (CTI is a relative leakage index, generally means that five test samples can withstand the test process of 50 drops of electrolyte without generating the highest voltage value of leakage tracking failure and continuous flame) and wet electrical safety, but the melting point of PA612 is very low, and the heating power of an electronic and electrical related product is very high, so that the alloy product can have remarkable deformation and failure behaviors, and cannot meet the requirements of industry; at present, researches on materials with high CTI are still all concentrated on materials such as PBT and PC, such as patents CN201110263547.7, CN201010172195.X, CN201811332970.6 and the like, which are thoroughly discussed on the PBT and PC with high CTI, but the materials are not high-temperature resistant and have obvious deformation at high temperature, and the current post-manufacturing process with high temperature resistance and SMT in industry has become industry trend, so how to improve the CTI of the high-temperature resistant materials becomes a problem to be solved urgently.
Disclosure of Invention
In order to overcome the defects in the prior art, the application provides a nylon composition, and a preparation method and application thereof. The application improves CTI of nylon composition and insulativity under dry and wet state by compounding chelating agent and synergist. The chelating agent complexes metal ions, so that the chelating agent complexes metal ions, free metal ions are reduced, and damage of plastic after being affected by the metal ions is reduced, thereby improving CTI under severe conditions, reducing precipitation of flame retardant under the condition of damp and heat by the synergist, reducing corrosiveness to metal parts, and radically solving the invasion of the metal ions. Whereas the insulation in the dry and wet state depends on the amount of water absorption of nylon and the content of internal metal ions, PA10T has the most excellent electrical insulation property due to the lowest water absorption; when the metal ions are complexed with the chelating agent, the amount of free metal ions in the material decreases, and the conductivity decreases, so that the insulation increases.
The method is realized by the following technical scheme:
the nylon composition comprises the following components in parts by weight:
preferably, the composition comprises the following components in parts by weight:
further, the chelating agent is an arylamine chelating agent, and the molecular weight of the arylamine chelating agent is more than 2000, preferably 2000-5000. The macromolecular arylamine chelating agent has good thermal stability, can be suitable for high-temperature nylon with the processing temperature of up to 350 ℃, and the other types of chelating agents can not be suitable for high-temperature nylon because of serious degradation of a system caused by easy decomposition at high temperature.
The semiaromatic polyamide is derived from the following repeating units: 50mol% of recurring units based on terephthalic acid and 50mol% of recurring units based on diamine.
The diamine-based repeating unit is selected from NH (C 2 H 4 NH 2 ) 2 、H 2 N[C 2 H 4 NH] 2 C 2 H 4 NH 2 、H 2 N[C 2 H 4 NH] 3 C 2 H 4 NH 2 、NH[(CH 2 ) 4 NH 2 ] 2 、NH[(CH 2 ) 5 NH 2 ] 2 、NH[(CH 2 ) 6 NH 2 ] 2 、NH[(CH 2 ) 7 NH 2 ] 2 、NH[(CH 2 ) 8 NH 2 ] 2 、NH[(CH 2 ) 9 NH 2 ] 2 、NH[(CH 2 ) 10 NH2] 2 、NH[(CH 2 ) 11 NH 2 ] 2 、N[(CH 2 ) 12 NH 2 ] 2 、NH[(CH 2 ) 13 NH 2 ] 2 、NH[(CH 2 )14NH 2 ) 2 、NH[(CH 2 ) 15 NH 2 ] 2 、NH[(CH 2 ) 16 NH 2 ] 2 、NH[(CH 2 ) 17 NH 2 ] 2 、NH[(CH 2 ) 18 NH 2 ] 2 、H 2 N(H 2 C) 10 NH(CH 2 ) 5 NH 2 、H 2 N(H 2 C) 10 NH(CH 2 ) 6 NH 2 、H 2 N(H 2 C) 10 NH(CH 2 ) 7 NH 2 、H 2 N(H 2 C) 10 NH(CH 2 ) 8 NH 2 、H 2 N(H 2 C) 10 NH(CH 2 ) 9 NH 2 、H 2 N(H 2 C) 10 NH(CH 2 ) 11 NH 2 、H 2 N(H 2 C) 10 NH(CH 2 ) 12 NH 2 、H 2 N(H 2 C) 9 NH(CH 2 ) 6 CH(CH 3 )CH 2 NH 2 、H 2 N(H 2 C) 9 NHCH 2 CH(CH 3 )(CH 2 ) 6 NH 2 、NH[(CH 2 ) 6 CH(CH 3 )CH 2 NH 2 ] 2 、NH[CH 2 CH(CH 3 )(CH 2 ) 6 NH 2 ] 2 One or more of them.
Preferably, the semiaromatic polyamide is PA6T or PA10T, preferably PA10T.
Further, the halogen-free flame retardant is preferably aluminum diethylphosphinate.
Further, the reinforcing filler is preferably glass fiber.
Further, the flow modifier is one or more of sodium montanate, lithium stearate, sodium stearate, oxidized polyethylene wax or oxidized propylene wax.
Further, the flame retardant synergist is preferably zinc borate.
Further, 0.1-1 part of auxiliary agent is also included. The auxiliary agent is one or more of an antioxidant, a heat-resistant stabilizer, an impact stabilizer, other polymers or a lubricant.
The antioxidant is selected from one or more of hindered phenol antioxidants, hindered amine antioxidants, thioether antioxidants and phosphonite antioxidants.
The other polymer is selected from one or more of other kinds of polyamide, polyester, polysulfone or polyphenylene oxide.
The lubricant is selected from one or more of erucamide, alkali metal montanate, stearate, montan wax, polyethylene wax, polypropylene wax or hyperbranched flow modifier.
The application also provides a preparation method of the nylon composition, which comprises the following steps:
s1, weighing the components according to the proportion, and premixing the reinforcing filler and the components except the halogen-free flame retardant to obtain a premix;
s2: and (2) respectively putting the premix, the reinforcing filler and the halogen-free flame retardant in the step (S1) into an extruder, carrying out melt blending, extruding and granulating to obtain the nylon composition.
Further, the extruder is a double-screw extruder, the premix in the step S1 is put into a feed opening of the double-screw extruder, meanwhile, the reinforcing filler is added into a first side feed opening of the double-screw extruder, the halogen-free flame retardant is added into a second side feed opening, and the nylon composition is obtained by melt blending and extrusion granulation at the processing temperature of 290-330 ℃.
The application also provides application of the nylon composition in preparation of electronic electrical parts, and is particularly suitable for the fields of potential electrolyte contact in new energy automobiles, high-voltage industries and the like.
Compared with the prior art, the application has the beneficial effects that:
by complexing metal ions with the chelating agent, CTI under severe conditions is improved, and damage of plastic after being affected by the metal ions is reduced; by using the flame retardant synergist, the precipitation of the flame retardant under the damp and hot condition is obviously reduced, the corrosiveness to metal parts is reduced, and the invasion of metal ions is radically solved, so that the chelating agent and the flame retardant synergist are compounded for use, and the CTI of the material is improved together. By preferably using PA6T and PA10T resins, the dielectric safety of the material is improved, especially PA10T has the best electrical safety.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings required for the description of the embodiments will be briefly described below, and it is apparent that the drawings in the following description are only some embodiments of the present application, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is the CTI test results of comparative example 2;
FIG. 2 shows the CTI test results of example 1;
FIG. 3 is the CTI test results of example 4;
FIG. 4 is the CTI test results of comparative example 1;
FIG. 5 is the CTI test results of comparative example 3.
Detailed Description
The following description of the embodiments of the present application will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the application. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
At present, no related research aiming at the high CTI (CTI is metal ion resistance) of plastics exists in the industry, no definite research conclusion exists in the whole industry on the invasion of metal ions, and the chelating agent is used in the application, so that the problem can be remarkably improved, and the material has the advantage of long-term use. And the synergist obviously reduces the precipitation of the flame retardant under the condition of damp and hot, reduces the corrosiveness to metal parts, radically solves the invasion of metal ions, and has a synergistic effect with the chelating agent to jointly improve the CTI of the material. In addition, through optimization of the chemical structure of the resin, the electrical properties are greatly improved as a whole by adjusting the chemical structure from PA46 and LCP to PA6T and PA10T, so that the probability of safety problems of the product is reduced; under the condition that no available material exists in the industry at present, the application creatively provides a high CTI scheme, and solves the pain point and the difficult problem in the industry.
< preparation of examples and comparative examples >
The raw materials used in the examples and comparative examples of the present application are derived from commercial or homemade sources, but are not limited to these materials:
semi-aromatic polyamide a (PA 10T): homemade, 50mol% terephthalic acid, the remainder being decylenediamine of the diamines described above, the relative viscosity being 2.4; the preparation method comprises the following steps: adding decanediamine, terephthalic acid, a benzoic acid end-capping agent and deionized water into a reaction kettle with nitrogen atmosphere and pressure of 2-4Mpa according to the proportion, heating the reaction kettle to 160-220 ℃ and keeping the temperature for 0.5-1.5 hours, and heating to 230-240 ℃ and keeping the temperature for 10-15 hours to obtain PA10T;
semi-aromatic polyamide B (PA 6T): homemade, 50mol% terephthalic acid, the remainder being hexamethylenediamine of the diamines described above, with a relative viscosity of 2.4; the preparation method comprises the following steps: adding hexamethylenediamine, terephthalic acid, a benzoic acid end-capping agent and deionized water into a reaction kettle with nitrogen atmosphere and pressure of 2-4Mpa, heating the reaction kettle to 160-220 ℃ and keeping the temperature for 0.5-1.5 hours, and heating to 230-240 ℃ and keeping the temperature for 10-15 hours to obtain PA6T;
halogen-free flame retardant: aluminum diethylphosphinate, exolit OP 1230, available from Craien, germany;
chelating agent a: aromatic amine with number average molecular weight distribution range of 2000-5000, and trademark OKAFLEX EM, purchased from Zhuang Jing Chemicals;
chelating agent B: ethylenediamine tetraacetic acid (non-aromatic amines) having a molecular weight of 292 and a trade name ethylenediamine tetraacetic acid, available from a reagent of ala Ding Huaxue;
chelating agent C:4,4' -bis (α, α -dimethylbenzyl) diphenylamine having a molecular weight of 406, and having a brand NAUGARD 445, a family of polymers of the manufacturer.
Flame retardant synergist: zinc borate, brand HT-207, purchased from shandongtaixing;
glass fiber: the chopped round glass fiber is 3mm, and the trade mark ECS301HP is purchased from the International composite material Co., ltd;
flow modifier: sodium montanate, commercially available, was used in parallel experiments using the same commercially available product;
an antioxidant: hindered phenols, commercially available, were used in parallel experiments using the same commercially available product;
the preparation methods of the examples and comparative examples of the present application are as follows:
s1, weighing the components according to the proportion of the table 1 and the table 3, and premixing the components except the reinforcing filler and the halogen-free flame retardant to obtain a premix;
s2: and (3) respectively putting the premix, the reinforcing filler and the halogen-free flame retardant in the step (S1) into a double-screw extruder, carrying out melt blending, extruding and granulating to obtain the nylon composition.
Wherein, the screw length-diameter ratio of the twin-screw extruder is 52:1, the barrel temperature of the twin-screw extruder is 320 ℃, the screw rotating speed of the twin-screw extruder is 200rpm, and the feeding speed is 350Kg/h.
In the present specification, "parts" means "parts by weight" unless specifically stated otherwise.
< test Standard >
The performance test criteria for each of the examples and comparative examples of the present application are as follows:
tensile strength: heating and melting the nylon composition at 290-330 ℃ and performing injection molding to form a tensile sample, and performing tensile property test according to international standard ISO 527-2019 to obtain tensile strength;
CTI test: heating and melting nylon composition at 290-330 deg.c, injection molding to produce square board of 60mm 1mm, and mixing part of the square board with 85 deg.c/85% humidity for 168 hr to form wet state; preparing an ammonium chloride solution with a required concentration according to IEC 60112 Souliton A standard, and performing dry-wet CTI test for a specified time according to a specific time interval; the CTI test is a model for simulating the failure of plastic under the condition that the surface is electrified when the surface is corroded by ions, and the metal ions are too severely corroded on the electrode, so that the test is carried out by adopting an ammonium chloride solution with corrosiveness and corrosiveness closest to each other in the standard.
Surface resistance performance test: heating and melting nylon composition at 290-330 deg.c, injection molding to produce 100mm×100mm×2mm flat test piece, regulating part of the square board to wet state at 85 deg.c/85% humidity for 168 hr, and measuring dry and wet state resistance with surface resistance meter;
dielectric strength test: heating and melting nylon composition at 290-330 deg.c, injection molding to produce square plate of 60mm x 1mm, and dielectric strength test with dielectric strength tester;
test of the precipitability: the nylon composition (particles) was sealed in a closed container at a ratio of 5g nylon composition particles +50g water, placed in an oven at 70 c for 72 hours, and then tested for phosphine content in aqueous solution to compare the precipitation performance.
TABLE 1 examples 1-7 formulations (parts by weight)
TABLE 2 EXAMPLES 8 to 15 formulations
TABLE 3 Performance test results for examples 1-7
TABLE 4 Performance test results for examples 8-15
Table 5. Comparative examples 1-4 formulations (parts by weight)
Table 6. Comparative examples 5-8 formulations (parts by weight)
TABLE 7 Performance test results for comparative examples 1-4
TABLE 8 Performance test results for comparative examples 5-8
As can be seen from the test results, the PA10T (example 1) material has a higher surface resistance than the PA6T (example 4) material and the PA46 material (comparative example 3), and thus generates less current when energized, and generates less surface heat; the use of chelating agents, whether in dry or wet form, provides a PA10T material with a higher dielectric strength than PA6T and PA46 materials, greatly aiding in the improvement of the wet dielectric strength of the materials (example 1, comparative example 2); the use of chelating agents has no significant negative impact on the mechanical properties of the material.
In addition, dry and wet CTI test and precipitation test were also performed on the examples and some of the comparative examples, and the results are shown in tables 9 to 12.
TABLE 9 Dry and Wet CTI test data for examples 1-8
TABLE 10 Dry and Wet CTI test data for examples 9-15
TABLE 11 Dry and Wet CTI test data for part of the comparative examples
From the experimental results, it can be seen that PA10T (example 1) and PA6T (example 4) have absolute advantages over PA46 (comparative example 3) in CTI performance, especially a significant difference in wet CTI, due to the disadvantages of high water absorption of PA 46;
after CTI testing, the smaller the area of the surface eroded, the shallower the depth the better the CTI performance is represented. One of the flags that CTI test can pass is the condition that the surface has not burned out holes.
The CTI test of part of the samples of the examples and part of the samples of the comparative examples is shown in the drawing, the test is carried out under 600V, the conductivity of the ammonium chloride solution is 0.04 omega.m, one drop is dropped at intervals of 10s for 10min, and the CTI in extremely severe conditions is confirmed by the damage condition of the surface. Fig. 1 is a test result of comparative example 2, fig. 2 is a test result of example 1, and fig. 3 is a test result of example 4. It can be clearly seen that comparative example 2, without the use of a chelating agent, shows a significant trace of ablation, particularly the intermediate destruction is extremely deep, but with the addition of a chelating agent, example 1 can see a significant decrease in intermediate destruction depth, indicating a significant improvement in electrolyte destruction tolerance; FIG. three shows PA6T with a chelating agent, which is more severe than PA10T with the same chelating agent.
From the experimental results (shown in figures 1-3), it is clear that increasing the chelating agent dosage is obviously helpful for improving CTI value under severe conditions, thus demonstrating that the metal ion erosion resistance of plastics is greatly improved; and PA10T has better CTI under severe conditions than PA 6T. It can be stated that the nylon composition provided by the application can be suitable for the fields of potential electrolyte contact such as new energy automobiles and high-voltage industries. As can be seen from fig. 4 and 5, without the use of chelating agents, the surface is eroded to a greater depth and the surface area of disruption is greater; the PA46 is directly perforated very much.
Comparative examples 5-6 comparative example 5 chelating agent was added too much compared to example 4, resulting in deterioration of tensile strength, dielectric strength and surface resistance properties of comparative example 5; too little chelating agent addition of comparative example 6 resulted in deterioration of the wet dielectric strength properties of comparative example 6.
Comparative examples 7 and 8 the flame retardant synergist of comparative example 7 was added too little compared to example 4, resulting in a reduction in mechanical properties, dielectric strength and wet surface resistance, and the flame retardant synergist of comparative example 8 was added too much, resulting in a reduction in dielectric strength.
Example 15 compared to example 4, the chelating agent used has a molecular weight below 2000, resulting in an overall decrease in all properties.
TABLE 12 comparative precipitation of samples of some examples and comparative examples
Precipitation property Comparative example 8 Example 1 Example 2 Example 4 Comparative example 4
Phosphine content PPM 623 321 248 458 350
From the experimental results, the precipitation performance of the PA10T (example 1) and the PA6T (example 4) is much lower than that of the PA46 (comparative example 3), and on the basis, the use of the synergist in the example 1 reduces the consumption of the flame retardant, can further reduce the precipitation of the flame retardant, is obviously helpful for improving the corrosion of metals after long-term use, and reduces the generation of metal ions, so that the invasion of the metal ions is blocked from the source. As can be seen from comparison of comparative example 4 with example 1, the addition of the flame retardant synergist helps to improve the precipitation of phosphorus-containing substances.
The foregoing description of the preferred embodiments of the application is not intended to limit the application to the precise form disclosed, and any such modifications, equivalents, and alternatives falling within the spirit and scope of the application are intended to be included within the scope of the application.

Claims (10)

1. The nylon composition is characterized by comprising the following components in parts by weight:
2. nylon composition according to claim 1, characterized in that it comprises the following components in parts by weight:
3. nylon composition according to claim 1 or 2, characterized in that the chelating agent is an arylamine chelating agent having a number average molecular weight of more than 2000.
4. A nylon composition according to claim 3, wherein the arylamine chelant has a number average molecular weight of 2000 to 5000.
5. Nylon composition according to claim 1 or 2, characterized in that the semiaromatic polyamide is PA6T or PA10T.
6. Nylon composition according to claim 1 or 2, characterized in that the flow modifier is one or more of sodium montanate, lithium stearate, sodium stearate, oxidized polyethylene wax or oxidized propylene wax.
7. Nylon composition according to claim 1 or 2, characterized in that it further comprises 0.1-1 parts of an auxiliary agent.
8. The nylon composition of claim 7, wherein the auxiliary agent is one or more of an antioxidant, a heat stabilizer, an impact stabilizer, other polymers, or a lubricant.
9. A process for preparing a nylon composition according to any one of claims 1 to 8, comprising the steps of:
s1: weighing the components according to the proportion, and premixing the reinforcing filler and the components except the halogen-free flame retardant to obtain a premix;
s2: and (2) respectively putting the premix, the reinforcing filler and the halogen-free flame retardant in the step (S1) into an extruder, carrying out melt blending, extruding and granulating to obtain the nylon composition with high CTI and excellent insulation property in a dry and wet state.
10. Use of the nylon composition according to any one of claims 1-8 for the preparation of electronic electrical articles.
CN202210317459.9A 2022-03-29 2022-03-29 Nylon composition and preparation method and application thereof Active CN116925533B (en)

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CN111004497A (en) * 2019-12-24 2020-04-14 上海中镭新材料科技有限公司 Electroplating nylon material and preparation method thereof
CN111303623A (en) * 2020-04-29 2020-06-19 泉州永聚兴塑胶原料有限公司 High-toughness high-flame-retardance polyamide composite material and preparation method thereof
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CN111704796A (en) * 2020-06-29 2020-09-25 上海中镭新材料科技有限公司 Electroplating nylon material and preparation method thereof

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