A modified ethylene-chlorotrifluoroethylene copolymer material and a method for producing the same

Abstract

The application belongs to the technical field of fluoroplastics, and particularly relates to a modified ethylene-chlorotrifluoroethylene copolymer material and a preparation method thereof. The preparation method of the modified ethylene-chlorotrifluoroethylene copolymer material comprises the following steps: S1, heating reaction of E-MA-GMA and amino polysiloxane under the condition of anhydrous dilution solvent, drying and granulating to obtain a silicone modifier; and S2, uniformly mixing the silicone modifier and ECTFE under a protective atmosphere, and then extruding and granulating to obtain the modified ethylene-chlorotrifluoroethylene copolymer material. The silicone modifier prepared by the reaction of E-MA-GMA and amino polysiloxane is used for blending modification of ECTFE, the adhesion of the ECTFE coating to a smooth metal interface and the cold and hot cycle stability can be significantly improved, and thus the application performance is improved and the application field is widened.

Description

Technical Field

[0001] This invention belongs to the field of fluoroplastics technology, specifically relating to a modified ethylene-chlorotrifluoroethylene copolymer material and its preparation method. Background Technology

[0002] Ethylene-trifluorochloroethylene copolymer (ECTFE), also known as polyethylene trifluorochloroethylene, is an alternating block copolymer composed of ethylene and trifluorochloroethylene. ECTFE possesses excellent properties such as chemical corrosion resistance, low dielectric constant, high temperature resistance, and impermeability, and has good processing performance, making it suitable for manufacturing ECTFE films, ECTFE sheets, ECTFE tubes, and ECTFE fibers. It has wide applications in construction, automotive, microelectronics, aerospace, wire and cable, petrochemical, and photovoltaic industries. However, when used as an anti-corrosion coating or electrode coating, ECTFE still suffers from insufficient adhesion to smooth metal interfaces. To improve adhesion, sandblasting of the uncoated interface or pre-preparation of an interface bonding primer is often required, complicating the construction and molding processes. Furthermore, ECTFE has high hardness and rigidity, and its coefficient of thermal expansion is significantly higher than that of metals, posing a risk of reduced adhesion and delamination under thermal expansion and contraction conditions. Summary of the Invention

[0003] In view of the shortcomings and deficiencies of the existing technology, the primary objective of this invention is to provide a method for preparing modified ethylene-trifluorochloroethylene copolymer materials.

[0004] Another object of the present invention is to provide a modified ethylene-trifluorochloroethylene copolymer material prepared by the above method.

[0005] The objective of this invention is achieved through the following technical solution:

[0006] A method for preparing a modified ethylene-chlorotrifluoroethylene copolymer material includes the following preparation steps:

[0007] S1: The ethylene-acrylate-glycidyl methacrylate terpolymer (E-MA-GMA) and amino polysiloxane are heated and reacted under anhydrous diluent conditions, dried and granulated to obtain an organosilicon modifier.

[0008] S2: The organosilicon modifier and ECTFE are mixed evenly under a protective atmosphere, and then extruded and granulated to obtain the modified ethylene-trifluorochloroethylene copolymer material.

[0009] Furthermore, the E-MA-GMA mentioned in step S1 is selected from Arkema's AX8900.

[0010] Furthermore, the aminopolysiloxane mentioned in step S1 is selected from Dow Corning 8040A amino silicone oil.

[0011] More preferably, the mass ratio of E-MA-GMA to aminopolysiloxane is 100:40~80.

[0012] Further, the anhydrous diluent in step S1 is at least one solvent selected from toluene, xylene, N-methylpyrrolidone, and N,N-dimethylformamide.

[0013] Furthermore, the heating reaction in step S1 is carried out at a temperature of 80~120℃ for 3~6 hours.

[0014] Furthermore, the amount of organosilicon modifier added in step S2 is 4 to 10% of the mass of ECTFE.

[0015] Furthermore, the mixing temperature in step S2 is 240~270℃.

[0016] A modified ethylene-chlorotrifluoroethylene copolymer material was prepared by the above method.

[0017] Compared with the prior art, the beneficial effects of the present invention are:

[0018] (1) The present invention uses the chemical grafting reaction of E-MA-GMA and amino polysiloxane to improve the compatibilization effect of high temperature resistant and flexible polysiloxane in ECTFE, reduce the rigidity of ECTFE coating, and thus improve its adhesion stability in hot and cold environments.

[0019] (2) The organosilicon modifier obtained by reacting E-MA-GMA with amino polysiloxane can introduce polar groups such as amine, hydroxyl and ester groups, thereby significantly improving the adhesion to smooth metal interfaces. Detailed Implementation

[0020] The present invention will be further described in detail below with reference to embodiments, but the implementation of the present invention is not limited thereto.

[0021] Example 1

[0022] A method for preparing a modified ethylene-chlorotrifluoroethylene copolymer material includes the following preparation steps:

[0023] S1: Add 30 kg of toluene solvent to the reactor and heat it to 100°C with steam. Then add 6 kg of Dow Corning 8040A amino silicone oil and stir to dissolve. Heat 10 kg of ethylene-acrylate-glycidyl methacrylate terpolymer AX8900 to 100°C to melt it. Then add it to the reactor and stir to react for 4 h. The reaction product is dried and granulated by rotary evaporation to obtain the organosilicon modifier.

[0024] S2: The organosilicon modifier obtained in S1 and ECTFE are added to the mixer at a mass ratio of 6:100. The temperature of the feeding section is controlled at 240~250℃, the temperature of the compression section at 250~260℃ and the temperature of the homogenization section at 260~270℃. The mixture is uniformly mixed under N2 protection and a screw speed of 60r / min. Then it is extruded and granulated to obtain the modified ethylene-trifluorochloroethylene copolymer material.

[0025] Performance testing:

[0026] (1) The modified ethylene-chlorotrifluoroethylene copolymer material was hot-melt sprayed onto the surface of a smooth stainless steel sheet. The resulting anti-corrosion coating showed an adhesion of 19 MPa by the pull-off test (GB / T 5210), while the unmodified ECTFE coating showed an adhesion of 11 MPa. This indicates that the modified ethylene-chlorotrifluoroethylene copolymer material obtained in this invention can significantly improve the adhesion to smooth metal interfaces.

[0027] (2) The obtained modified ethylene-trifluorochloroethylene copolymer material was hot-melt sprayed onto the surface of a smooth stainless steel sheet. The resulting anti-corrosion coating was placed in a high and low temperature alternating test chamber, and the coated sample was subjected to the following high and low temperature cycle test:

[0028] High temperature stage: Set to 100℃±2℃ and maintain for 30 minutes; → Normal temperature stage: Return to normal temperature; → Low temperature stage: Set to -40℃±2℃ and maintain for 30 minutes; → Normal temperature recovery stage: Return to normal temperature again, completing one cycle.

[0029] The above cycle was repeated 50 times, and the sample was stabilized at room temperature for 2 hours before adhesion testing. The anti-corrosion coating prepared in this embodiment showed an adhesion of 17 MPa after high and low temperature cycling testing, while the unmodified ECTFE coating showed an adhesion of 7 MPa. This indicates that the modified ethylene-chlorotrifluoroethylene copolymer material obtained in this invention can significantly improve adhesion stability under both hot and cold environments.

[0030] Example 2

[0031] A method for preparing a modified ethylene-chlorotrifluoroethylene copolymer material includes the following preparation steps:

[0032] S1: Add 30 kg of toluene solvent to the reactor and heat it to 80°C with steam. Then add 8 kg of Dow Corning 8040A amino silicone oil and stir to dissolve. Heat 10 kg of ethylene-acrylate-glycidyl methacrylate terpolymer AX8900 to 80°C to melt it. Then add it to the reactor and stir to react for 6 h. The reaction product is dried and granulated by rotary evaporation to obtain the organosilicon modifier.

[0033] S2: The organosilicon modifier obtained in S1 and ECTFE are added to the mixer at a mass ratio of 4:100. The temperature of the feeding section is controlled at 240~250℃, the temperature of the compression section at 250~260℃ and the temperature of the homogenization section at 260~270℃. The mixture is mixed evenly under N2 protection and screw speed of 60r / min. Then it is extruded and granulated to obtain the modified ethylene-trifluorochloroethylene copolymer material.

[0034] The modified ethylene-trifluorochloroethylene copolymer material obtained in this embodiment has an adhesion of 16 MPa when tested using the same method as in Example 1, and an adhesion of 15 MPa after high and low temperature cycling tests.

[0035] Example 3

[0036] A method for preparing a modified ethylene-chlorotrifluoroethylene copolymer material includes the following preparation steps:

[0037] S1: Add 30 kg of toluene solvent to the reactor and heat it to 90°C with steam. Then add 7 kg of Dow Corning 8040A amino silicone oil and stir to dissolve. Heat 10 kg of ethylene-acrylate-glycidyl methacrylate terpolymer AX8900 to 90°C to melt it. Then add it to the reactor and stir to react for 5 h. The reaction product is dried and granulated by rotary evaporation to obtain the organosilicon modifier.

[0038] S2: The organosilicon modifier obtained in S1 and ECTFE are added to the mixer at a mass ratio of 5:100. The temperature of the feeding section is controlled at 240~250℃, the temperature of the compression section at 250~260℃ and the temperature of the homogenization section at 260~270℃. The mixture is homogenized under N2 protection and screw speed of 60r / min. Then it is extruded and granulated to obtain the modified ethylene-trifluorochloroethylene copolymer material.

[0039] The modified ethylene-trifluorochloroethylene copolymer material obtained in this embodiment has an adhesion of 17 MPa when tested using the same method as in Example 1, and an adhesion of 15 MPa after high and low temperature cycling tests.

[0040] ‌

[0041] Example 4

[0042] A method for preparing a modified ethylene-chlorotrifluoroethylene copolymer material includes the following preparation steps:

[0043] S1: Add 30 kg of toluene solvent to the reactor and heat it to 110°C with steam. Then add 5 kg of Dow Corning 8040A amino silicone oil and stir to dissolve. Heat 10 kg of ethylene-acrylate-glycidyl methacrylate terpolymer AX8900 to 110°C to melt it. Then add it to the reactor and stir to react for 3 h. The reaction product is dried and granulated by rotary evaporation to obtain the organosilicon modifier.

[0044] S2: The organosilicon modifier obtained in S1 and ECTFE are added to the mixer at a mass ratio of 8:100. The temperature of the feeding section is controlled at 240~250℃, the temperature of the compression section at 250~260℃ and the temperature of the homogenization section at 260~270℃. The mixture is mixed evenly under N2 protection and screw speed of 60r / min. Then it is extruded and granulated to obtain the modified ethylene-trifluorochloroethylene copolymer material.

[0045] The modified ethylene-trifluorochloroethylene copolymer material obtained in this embodiment has an adhesion of 21 MPa when tested using the same method as in Example 1, and an adhesion of 18 MPa after high and low temperature cycling tests.

[0046] Example 5

[0047] A method for preparing a modified ethylene-chlorotrifluoroethylene copolymer material includes the following preparation steps:

[0048] S1: Add 30 kg of toluene solvent to the reactor and heat it to 120°C with steam. Then add 4 kg of Dow Corning 8040A amino silicone oil and stir to dissolve. Heat 10 kg of ethylene-acrylate-glycidyl methacrylate terpolymer AX8900 to 120°C to melt it. Then add it to the reactor and stir to react for 3 h. The reaction product is dried and granulated by rotary evaporation to obtain the organosilicon modifier.

[0049] S2: The organosilicon modifier obtained in S1 and ECTFE are added to the mixer at a mass ratio of 10:100. The temperature of the feeding section is controlled at 240~250℃, the temperature of the compression section at 250~260℃ and the temperature of the homogenization section at 260~270℃. The mixture is uniformly mixed under N2 protection and screw speed of 60r / min. Then it is extruded and granulated to obtain the modified ethylene-trifluorochloroethylene copolymer material.

[0050] The modified ethylene-trifluorochloroethylene copolymer material obtained in this embodiment has an adhesion of 22 MPa when tested using the same method as in Example 1, and an adhesion of 18 MPa after high and low temperature cycling tests.

[0051] Comparative Example 1

[0052] A method for preparing a modified ethylene-chlorotrifluoroethylene copolymer material includes the following preparation steps:

[0053] The ethylene-acrylate-glycidyl methacrylate terpolymer AX8900 and ECTFE were added to a mixer at a mass ratio of 6:100. The temperature of the feeding section was controlled at 240~250℃, the temperature of the compression section at 250~260℃, and the temperature of the homogenization section at 260~270℃. The mixture was stirred evenly under N2 protection and a screw speed of 60 r / min. Then it was extruded and granulated to obtain the modified ethylene-chlorotrifluoroethylene copolymer material.

[0054] The modified ethylene-trifluorochloroethylene copolymer material obtained in this comparative example had an adhesion of 20 MPa when tested using the same method as in Example 1, and an adhesion of 13 MPa after high and low temperature cycling tests.

[0055] The performance comparison between Comparative Example 1 and Example 1 shows that without the addition of high-temperature resistant and flexible polysiloxane for modification, the thermal cycling stability of the resulting coating is reduced.

[0056] Comparative Example 2

[0057] A method for preparing a modified ethylene-chlorotrifluoroethylene copolymer material includes the following preparation steps:

[0058] Ethylene-acrylate-glycidyl methacrylate terpolymer AX8900, Dow Corning 8040A amino silicone oil, and ECTFE were added to a mixer. The mass ratio of AX8900+8040A to ECTFE was controlled at 6:100, and the mass ratio of AX8900 to 8040A was controlled at 10:6. The temperature of the feed section of the mixer was controlled at 240~250℃, the temperature of the compression section at 250~260℃, and the temperature of the homogenization section at 260~270℃. The mixture was uniformly mixed under N2 protection and a screw speed of 60 r / min, and then extruded and granulated to obtain the modified ethylene-chlorotrifluoroethylene copolymer material.

[0059] The modified ethylene-trifluorochloroethylene copolymer material obtained in this comparative example had an adhesion of 15 MPa when tested using the same method as in Example 1, and an adhesion of 9 MPa after high and low temperature cycling tests.

[0060] The performance comparison between Comparative Example 2 and Example 1 shows that directly using E-MA-GMA and amino polysiloxane for blending modification results in a poorer compatibilizing effect of polysiloxane in ECTFE, leading to a significant reduction in the modification effect.

[0061] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any changes, modifications, substitutions, combinations, or simplifications made without departing from the spirit and principle of the present invention shall be considered equivalent substitutions and shall be included within the protection scope of the present invention.

Claims

1. A method for preparing a modified ethylene-chlorotrifluoroethylene copolymer material, characterized in that: The preparation steps include the following: S1: E-MA-GMA and aminopolysiloxane are heated and reacted under anhydrous diluent conditions, dried and granulated to obtain an organosilicon modifier; S2: The organosilicon modifier and ECTFE are mixed evenly under a protective atmosphere, and then extruded and granulated to obtain the modified ethylene-trifluorochloroethylene copolymer material.

2. The method for preparing a modified ethylene-chlorotrifluoroethylene copolymer material according to claim 1, characterized in that: The E-MA-GMA mentioned in step S1 is selected from Arkema AX8900.

3. The method for preparing a modified ethylene-chlorotrifluoroethylene copolymer material according to claim 1, characterized in that: The amino polysiloxane mentioned in step S1 is selected from Dow Corning 8040A amino silicone oil.

4. The method for preparing a modified ethylene-chlorotrifluoroethylene copolymer material according to claim 1, characterized in that: The mass ratio of E-MA-GMA to aminopolysiloxane is 100:40~80.

5. The method for preparing a modified ethylene-trifluorochloroethylene copolymer material according to claim 1, characterized in that: The anhydrous diluent in step S1 is at least one of toluene, xylene, N-methylpyrrolidone, and N,N-dimethylformamide.

6. The method for preparing a modified ethylene-chlorotrifluoroethylene copolymer material according to claim 1, characterized in that: The heating reaction in step S1 is carried out at a temperature of 80~120℃ for 3~6 hours.

7. The method for preparing a modified ethylene-chlorotrifluoroethylene copolymer material according to claim 1, characterized in that: The amount of organosilicon modifier added in step S2 is 4 to 10% of the mass of ECTFE.

8. The method for preparing a modified ethylene-chlorotrifluoroethylene copolymer material according to claim 1, characterized in that: The mixing temperature in step S2 is 240~270℃.

9. A modified ethylene-chlorotrifluoroethylene copolymer material, characterized in that: It is prepared by the method described in any one of claims 1 to 9.