Tetrachloromethane corrosion resistant composite material as well as preparation method and application thereof

Abstract

The invention discloses a tetrachloromethane corrosion resistant composite material and a preparation method and application thereof, and belongs to the technical field of high polymer materials, the tetrachloromethane corrosion resistant composite material provided by the invention is prepared from the following components by mass: 20%-40% of alkali-free glass fiber, 3%-10% of a toughening agent, 10%-20% of polytetrafluoroethylene, 0.2%-1% of an antioxidant, 0.2%-0.7% of a lubricant, 1%-3% of a coloring agent, and 0.1%-0.5% of a heat stabilizer. And the balance of polyamide resin. According to the invention, PA612 is adopted as basic resin, and proper glass fiber and flexibilizer are selected, so that the corrosion resistance to tetrachloromethane is effectively improved, the attenuation rates of tensile strength and notch impact strength of the material soaked in tetrachloromethane for 3000 hours are both lower than 10%, the material has no crack or pulverization phenomenon, meets the requirement of transporting tetrachloromethane, and is low in cost and suitable for industrial production. Meanwhile, the manufacturing efficiency is greatly improved, the original complex manufacturing process of a metal part is changed into injection molding integral forming, the weight of the product is obviously reduced, and the weight of a single piece is only about half of that of the original metal part.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of high polymer materials, and particularly relates to a composite material resistant to tetrachloromethane corrosion and a preparation method and application thereof. BACKGROUND

[0002] Tetrachloromethane is widely used in chemical industry, pharmaceutical industry, electronics industry and other industrial fields as an important organic synthesis raw material, solvent and refrigerant. In the actual material conveying link of industrial production, tetrachloromethane has certain corrosiveness, so the conveying pipeline usually uses corrosion-resistant soft rubber pipe, and the joint required for pipeline connection directly affects the stability and safety of the conveying system as a key component. In the prior art, in order to adapt to the corrosive environment of tetrachloromethane, the joint material is usually selected from metal materials such as stainless steel and brass. Although such metal joints can meet the corrosion resistance requirement to a certain extent, the production of metal joints needs to go through multiple complex processes such as smelting, forging, mechanical processing and surface corrosion prevention treatment, the production process is long, the processing precision is high, which leads to high preparation cost, and the density of metal material is large, so that the overall weight of the joint is heavy, which not only increases the labor intensity of pipeline installation and maintenance, but also may affect the connection and sealing performance of the soft rubber pipe and the joint due to long-term gravity effect; in addition, the production cycle of the metal joint is long, which is difficult to quickly respond to the large quantity and low cost demand of the joint in industrial production. Therefore, developing a new joint material with corrosion resistance, low cost and easy processing characteristics has become the key to solving the pain points of the prior art. Based on this, the present application provides a composite material resistant to tetrachloromethane corrosion and a preparation method and application thereof. SUMMARY

[0003] This section aims to summarize some aspects of the embodiments of the present application and briefly introduce some preferred embodiments. Some simplifications or omissions may be made in this section and the abstract and title of the specification to avoid obscuring the purpose of this section, abstract and title, and such simplifications or omissions cannot be used to limit the scope of the present application.

[0004] In view of the above and / or problems existing in the prior art, the present application is proposed.

[0005] Therefore, the purpose of the present application is to overcome the deficiencies in the prior art, and to provide a composite material resistant to tetrachloromethane corrosion and a preparation method and application thereof.

[0006] To solve the above technical problems, the present application provides the following technical scheme: the composite material resistant to tetrachloromethane corrosion is prepared from the following components according to mass fraction: Alkali-free glass fiber 20%~40%, toughening agent 3%~10%, polytetrafluoroethylene 10%~20%, antioxidant 0.2%~1%, lubricant 0.2%~0.7%, colorant 1%~3%, heat stabilizer 0.1%~0.5%, balance polyamide resin; The alkali-free glass fiber contains less than 0.5% alkali metal oxides, has a diameter of 10~16μm, and a length of 3~5mm.

[0007] Furthermore, the polyamide resin is PA612 with a relative viscosity of 2.2~2.5.

[0008] Furthermore, the polytetrafluoroethylene has a diameter of 12~18μm and a molecular weight of 4×10⁻⁶. 4 ~6×10 4 .

[0009] Furthermore, the lubricant includes at least one of PETS, OP wax, silicone masterbatch, and mesoamide.

[0010] Furthermore, the colorant includes at least one of nylon-carrier aniline black masterbatch and PE-carrier black masterbatch.

[0011] Furthermore, the heat stabilizer includes at least one of the following: inorganic copper salt nylon heat stabilizer, organic copper salt nylon heat stabilizer, inorganic phosphate nylon heat stabilizer, and a compound heat stabilizer of aluminum silicate treated with titanate and dipentaerythritol propionate.

[0012] Furthermore, the antioxidant includes a primary antioxidant and a secondary antioxidant; The primary antioxidant includes at least one of antioxidant 245, antioxidant 1010, and antioxidant 1098. The auxiliary antioxidant includes at least one of antioxidant 168, antioxidant 626, and antioxidant 9228.

[0013] Furthermore, the toughening agent includes at least one of grafted POE, grafted LLDPE, grafted PP, and grafted EPDM.

[0014] This invention also proposes a method for preparing a composite material resistant to tetrachloromethane corrosion, comprising the following steps: S1: After mixing polyamide resin, toughening agent, and colorant evenly, add lubricant, polytetrafluoroethylene, heat stabilizer, primary antioxidant, and secondary antioxidant and mix evenly to obtain a mixture; S2: The mixture is added to the main feed port of the twin-screw extruder. Alkali-free glass fiber is added via a side feeder after loss of weight. After melting, extrusion, cooling, air drying, and pelletizing, a composite material resistant to tetrachloromethane corrosion is obtained. The temperature of the double screw extruder is 180 DEG C, 225 DEG C, 230 DEG C, 230 DEG C, 230 DEG C, 230 DEG C, 230 DEG C, 230 DEG C, 230 DEG C, 230 DEG C, 230 DEG C, 240 DEG C from the first zone to the head in sequence, the screw rotation speed is 280 rpm, and the feeding rotation speed is 10-20 rpm The application also provides application of the composite material resistant to tetrachloromethane corrosion to a conveying system.

[0015] The application has the following beneficial effects: The application adopts PA612 as a base resin, utilizes polytetrafluoroethylene resistant to tetrachloromethane, and the characteristics that polytetrafluoroethylene is incompatible with polyurethane resin and the surface tension of polytetrafluoroethylene is much greater than that of polyamide resin, so that the polytetrafluoroethylene is more easily floated on the outer surface of the alloy to form a natural protective film. The glass fiber with alkali metal oxide content less than 0.5%, diameter of 10-16 microns and length of 3-5 mm, and maleic anhydride grafted EPDM as a toughening agent, and suitable antioxidants, lubricants, heat stabilizers and colorants are selected, so that the corrosion resistance to tetrachloromethane is effectively improved. The attenuation rates of the tensile strength and the notched impact strength of the material after soaking in tetrachloromethane for 3000 hours are both less than 10%, and there is no crack and no powdering phenomenon, which meets the requirements of transporting tetrachloromethane, and the cost is low. Meanwhile, the manufacturing efficiency is greatly improved from the complex manufacturing process of the original metal parts to the integrated molding by injection molding, and the product weight is obviously reduced, and the single piece weight is only about half of the original metal parts. DETAILED DESCRIPTION

[0016] In order to make the above objectives, characteristics and advantages of the present application more obvious and easy to understand, the specific embodiments of the present application will be described in detail below with reference to the embodiments of the present application.

[0017] In the following description, a large number of specific details are set forth in order to provide a thorough understanding of the present application, but the present application can also be implemented in other ways different from those described herein, and those skilled in the art can make similar extensions without departing from the concept of the present application, so the present application is not limited to the specific embodiments disclosed below.

[0018] Secondly, the "one embodiment" or "embodiment" referred to herein means that the specific features, structures or characteristics can be included in at least one implementation of the present application. "In one embodiment" appearing in different places in the specification does not mean the same embodiment, nor is it an embodiment that is separate or alternative to other embodiments.

[0019] In the present application, the lubricant is silicone master granules, the production factory is Dow Corning, and the model number is MB50-002; The main antioxidant is antioxidant 1098, and the production factory is Tianjin Li'anlong; The auxiliary antioxidant is antioxidant 168, and the manufacturer is Tianjin Li'anlong; The toughening agent is KT-8 produced by Guotong. The alkali-free glass fiber is T435TM produced by Taishan Glass Fiber. The polytetrafluoroethylene is F5AEX produced by Solvay. The colorant is N1033 produced by Gaoli. The thermal stabilizer is H3336 produced by Bruggemann. The PA612 adhesive resin is HB30 produced by Huitong Special Material, and the relative viscosity is 2.4. The materials used in the present application are all commercially available conventional products.

[0020] Example 1 The present embodiment provides a preparation method of a tetrachloromethane corrosion-resistant composite material, and the preparation steps are as follows: 1) PA612 resin HB30 is dried at 80℃ for 4h for standby, and the raw materials are weighed according to the following proportions: 20 parts of alkali-free glass fiber, 0.3 parts of lubricant, 0.2 parts of main antioxidant, 0.2 parts of auxiliary antioxidant, 3 parts of toughening agent, 10 parts of polytetrafluoroethylene, 64.8 parts of PA612 resin, 0.3 parts of thermal stabilizer, and 1.2 parts of colorant; 2) The PA612 resin, the toughening agent and the colorant are mixed at high speed for 5min, and then the lubricant, the polytetrafluoroethylene, the thermal stabilizer, the main antioxidant and the auxiliary antioxidant are continuously mixed at high speed for 5min to obtain a mixture; 3) The mixture is added to the main feeding port of the double-screw extruder, and the alkali-free glass fiber is added through the loss weight scale side feeding. After melting, extrusion, cooling, air drying and granulation, the tetrachloromethane corrosion-resistant composite material is obtained. The temperature of the double-screw extruder is 180℃, 225℃, 230℃, 230℃, 230℃, 230℃, 230℃, 230℃, 230℃, 230℃, 230℃ and 240℃ from the first zone to the head, the screw speed is 280rpm, and the feeding speed is 10-20rpm.

[0021] Example 2 The difference between the present embodiment and example 1 is that the alkali-free glass fiber is 40 parts and the PA612 resin is 44.8 parts in step 1), and the rest of the process is completely consistent with example 1, so that the tetrachloromethane corrosion-resistant composite material of example 2 is obtained.

[0022] Example 3 The difference between this embodiment and embodiment 1 is that in step 1), 20 parts of polytetrafluoroethylene and 54.8 parts of PA612 resin are used, and the rest of the process is the same as that of embodiment 1, thereby obtaining the tetrachloromethane corrosion resistant composite material of embodiment 3.

[0023] Example 4 The difference between this embodiment and embodiment 1 is that in step 1), 10 parts of toughening agent and 57.8 parts of PA612 resin are used, and the rest of the process is the same as that of embodiment 1, thereby obtaining the tetrachloromethane corrosion resistant composite material of embodiment 4.

[0024] Example 5 The difference between this embodiment and embodiment 1 is that in step 1), 10 parts of toughening agent, 40 parts of alkali-free glass fiber and 37.8 parts of PA612 resin are used, and the rest of the process is the same as that of embodiment 1, thereby obtaining the tetrachloromethane corrosion resistant composite material of embodiment 4.

[0025] Comparative Example 1 Comparative Example 1 is based on embodiment 1, and the difference between comparative example 1 and embodiment 1 is that in step 1), 19 parts of alkali-free glass fiber and 65.8 parts of PA612 resin are used, and the rest of the process is the same as that of embodiment 1, thereby obtaining the composite material of this comparative example.

[0026] Comparative Example 2 Comparative Example 2 is based on embodiment 1, and the difference between comparative example 2 and embodiment 1 is that in step 1), 41 parts of alkali-free glass fiber and 43.8 parts of PA612 resin are used, and the rest of the process is the same as that of embodiment 1, thereby obtaining the composite material of this comparative example.

[0027] Comparative Example 3 Comparative Example 3 is based on embodiment 1, and the difference between comparative example 3 and embodiment 1 is that in step 1), 40 parts of alkali-free glass fiber, 9 parts of polytetrafluoroethylene and 45.8 parts of PA612 resin are used, and the rest of the process is the same as that of embodiment 1, thereby obtaining the composite material of this comparative example.

[0028] Comparative Example 4 Comparative Example 4 is based on embodiment 1, and the difference between comparative example 4 and embodiment 1 is that in step 1), 2 parts of toughening agent and 65.8 parts of PA612 resin are used, and the rest of the process is the same as that of embodiment 1, thereby obtaining the composite material of this comparative example.

[0029] Comparative Example 5 Comparative Example 5 is based on embodiment 1, and the difference between comparative example 5 and embodiment 1 is that in step 1), 40 parts of alkali-free glass fiber, 2 parts of toughening agent and 45.8 parts of PA612 resin are used, and the rest of the process is the same as that of embodiment 1, thereby obtaining the composite material of this comparative example.

[0030] The composite materials prepared in Examples 1-5 and Comparative Examples 1-5 were subjected to performance tests, the test methods and conditions are shown in Table 1, and the test results are shown in Table 2.

[0031] Table 1

[0032] Table 2

[0033] As can be seen from the results in Table 2, by using PA612 as the base resin, supplemented with suitable toughening agents and alkali-free glass fibers, and optimally matching suitable antioxidants, lubricants, thermal stabilizers and colorants, the corrosion resistance to tetrachloromethane is effectively improved. When the alkali-free glass fiber is 20 parts, the toughening agent is 3 parts, and the polytetrafluoroethylene is 10 parts in the raw materials, the attenuation rates of the tensile strength and the notched impact strength of the prepared composite material after immersion in tetrachloromethane for 3000h are both less than 10%, and there is no cracking or powdering phenomenon, meeting the requirements for transporting tetrachloromethane, and the cost is relatively low. At the same time, the manufacturing efficiency is greatly improved, from the complex manufacturing process of metal parts to injection molding integrated molding, and the product weight is significantly reduced, with a single piece weight of only about half of the original metal parts.

[0034] Compared with Examples 1-2, the addition amount of polytetrafluoroethylene in Example 3 is increased from 10% to 20%, and the attenuation rates of the tensile strength and the notched impact strength after immersion in tetrachloromethane for 3000h are greatly reduced. However, the price of polytetrafluoroethylene is relatively high, and the formulation of Examples 1-2 is more economical and more suitable for large-scale industrial production requirements. The attenuation rates of the tensile strength and the notched impact strength of the product prepared in Example 3 after immersion in tetrachloromethane for 3000h are lower, showing more excellent tetrachloromethane swelling resistance and mechanical property stability, and are more suitable for special scenarios such as the preparation of high-pressure sealing elements; As can be seen from the test results of Examples 4-5, increasing the content of the toughening agent or the alkali-free glass fiber can increase the notched impact strength of the prepared composite material, and the low-temperature performance is excellent, and the attenuation rates of the tensile strength and the notched impact strength after immersion in tetrachloromethane for 3000h can also meet the use requirements. However, the appearance of the actual injection molded product appears fiber floating, and the equipment current is large during the extrusion process, and the product has a softening trend, which cannot achieve the ideal effect in the plug-in test; In Comparative Examples 1-2, when the alkali-free glass fiber is less than 20%, the reinforcing effect of the glass fiber is reduced, the attenuation rates of the tensile strength and the notched impact strength after immersion in tetrachloromethane for 3000 hours cannot meet the use requirements, and when assembling the joint, the joint is found to be soft and there is a risk of bending; when the alkali-free glass fiber is more than 40%, the attenuation rates of the tensile strength and the notched impact strength after immersion in tetrachloromethane for 3000 hours can meet the use requirements, but the density of the prepared composite material is too high, which affects the shrinkage rate of the final product, resulting in that the size of the prepared finished joint is too large, the rubber pipe is difficult to assemble, and the product cannot be put into actual use. In Comparative Example 3, when the amount of polytetrafluoroethylene is reduced to 9%, the attenuation rates of the tensile strength and the notched impact strength after immersion in tetrachloromethane for 3000 hours do not meet the actual use requirements. In Comparative Examples 4-5, when the addition amount of the toughening agent is 2%, the attenuation rates of the tensile strength and the notched impact strength after immersion in tetrachloromethane for 3000 hours meet the customer requirements, but the low-temperature notched impact strength is 5 KJ / M2, there is a risk of fracture when assembling the joint, and in the high-low temperature cycle test, there is a cracking rate of 10%, which cannot meet the actual application requirements.

[0035] In summary, the tetrachloromethane corrosion-resistant composite material prepared by the application has better corrosion resistance, low raw material cost, easy availability, excellent processing performance, and can be prepared into a joint through integrated forming processes such as injection molding and mold pressing, without the need for complex mechanical processing and surface corrosion prevention treatment processes, further reducing production energy consumption and manufacturing cost, meeting the needs of industrialized mass production, and having significant technical advantages and economic value.

[0036] It should be noted that the above examples are only used to illustrate the technical solutions of the application and are not limiting, although the application has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the application can be modified or replaced by equivalents without departing from the spirit and scope of the technical solutions of the application, which should be covered in the scope of the claims of the application.

Claims

1. A composite material resistant to tetrachloromethane corrosion, characterized in that: It is prepared from the following components in parts by mass: Alkali-free glass fiber 20%~40%, toughening agent 3%~10%, polytetrafluoroethylene 10%~20%, antioxidant 0.2%~1%, lubricant 0.2%~0.7%, colorant 1%~3%, heat stabilizer 0.1%~0.5%, balance polyamide resin; The alkali-free glass fiber contains less than 0.5% alkali metal oxides, has a diameter of 10~16μm, and a length of 3~5mm.

2. The composite material resistant to tetrachloromethane corrosion as described in claim 1, characterized in that: The polyamide resin is PA612 with a relative viscosity of 2.2~2.

5.

3. The composite material resistant to tetrachloromethane corrosion as described in claim 1, characterized in that: The polytetrafluoroethylene has a diameter of 12~18μm and a molecular weight of 4×10⁻⁶. 4 ~6×10 4 .

4. The composite material resistant to tetrachloromethane corrosion as described in claim 1, characterized in that: The lubricant includes at least one of PETS, OP wax, silicone masterbatch, and mesoamide.

5. The composite material resistant to tetrachloromethane corrosion as described in claim 1, characterized in that: The colorant includes at least one of nylon-carrier aniline black masterbatch and PE-carrier black masterbatch.

6. The composite material resistant to tetrachloromethane corrosion as described in claim 1, characterized in that: The heat stabilizer includes at least one of the following: inorganic copper salt nylon heat stabilizer, organic copper salt nylon heat stabilizer, inorganic phosphate nylon heat stabilizer, and a compound heat stabilizer of aluminum silicate treated with titanate and dipentaerythritol propionate.

7. The composite material resistant to tetrachloromethane corrosion as described in claim 1, characterized in that: The antioxidants include primary antioxidants and secondary antioxidants; The primary antioxidant includes at least one of antioxidant 245, antioxidant 1010, and antioxidant 1098. The auxiliary antioxidant includes at least one of antioxidant 168, antioxidant 626, and antioxidant 9228.

8. The composite material resistant to tetrachloromethane corrosion as described in claim 7, characterized in that: The toughening agent includes at least one of grafted POE, grafted LLDPE, grafted PP and grafted EPDM.

9. The method for preparing the tetrachloromethane-resistant composite material according to any one of claims 1 to 8, characterized in that, Includes the following steps: S1: After mixing polyamide resin, toughening agent, and colorant evenly, add lubricant, polytetrafluoroethylene, heat stabilizer, primary antioxidant, and secondary antioxidant and mix evenly to obtain a mixture; S2: The mixture is added to the main feed port of the twin-screw extruder. Alkali-free glass fiber is added via a side feeder after loss of weight. After melting, extrusion, cooling, air drying, and pelletizing, a composite material resistant to tetrachloromethane corrosion is obtained. The temperature of the twin-screw extruder from the first zone to the die head is 180℃, 225℃, 230℃, 230℃, 230℃, 230℃, 230℃, 230℃, 230℃, 230℃, 230℃, 240℃; the screw speed is 280 rpm, and the feeding speed is 10-20 rpm.

10. The application of the tetrachloromethane-resistant composite material as described in claim 1 in a conveying system.

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