A perfluoroether rubber, its preparation method and application

Abstract

This invention discloses a perfluoroether rubber, its preparation method, and its applications. The perfluoroether rubber has an A1-B1-A2-B2 block structure, where each of the A1, B1, A2, and B2 blocks is independently polymerized from tetrafluoroethylene and perfluoroalkyl vinyl ethers. The molar percentage of perfluoroalkyl vinyl ether in the B1 or B2 block is higher than that in the A1 block, and also higher than that in the A2 block; the molar percentage of perfluoroalkyl vinyl ether in the B2 block is higher than that in the B1 block. The perfluoroether rubber of this invention has an A1-B1-A2-B2 tetrablock structure, achieving a gradual transition from rigid to flexible to rigid to ultra-flexible, reducing compression set, extending plasma environment life, and exhibiting a high thermal decomposition temperature, allowing for long-term service at temperatures above 300°C.

Description

Technical Field

[0001] This invention relates to the field of rubber, and more specifically, to a perfluoroether rubber, its preparation method, and its application. Background Technology

[0002] Perfluoroelastomer (PFE) rubber, due to its excellent high-temperature resistance, chemical corrosion resistance, and low-temperature flexibility, has become an irreplaceable sealing material for extreme working conditions. High-temperature resistant PFE rubber primarily uses tetrafluoroethylene (TFE) and perfluoroalkyl vinyl ether (PAVE) as the main comonomers, and uses cyano-containing perfluoroolefins, bromine- or iodo-containing olefins, and fluorinated dienes as monomers with high vulcanization points for copolymerization. The TFE / PAVE molar ratio in high-temperature resistant PFE rubber is (55–75):(25–45), and the resulting product can withstand temperatures up to 300°C and is resistant to over 1600 known organic or inorganic solvents. g With a temperature range of approximately -2℃ to 0℃, it is highly favored by industries such as petrochemicals and semiconductors. However, with the development of high-end equipment technology, current perfluoroelastomers face technical bottlenecks when serving for extended periods above 300℃, including increased compression set, insufficient resistance to high-temperature plasma, and accelerated thermal decomposition. Summary of the Invention

[0003] This invention is based on the inventor's discovery and understanding of the following facts and problems: current perfluoroelastomers face technical bottlenecks such as increased compression set, insufficient high-temperature plasma resistance, and accelerated thermal decomposition when serving for extended periods above 300°C.

[0004] This invention aims to at least partially solve one of the technical problems in related technologies. To this end, embodiments of this invention propose a perfluoroether rubber, its preparation method, and its application. The perfluoroether rubber has a four-block structure of A1-B1-A2-B2, achieving a gradual transition from rigid to flexible to rigid to ultra-flexible, reducing compression set, extending plasma environment life, and having a high thermal decomposition temperature, allowing it to serve for extended periods above 300°C.

[0005] This invention provides a perfluoroether rubber having an A1-B1-A2-B2 block structure, including A1 block, B1 block, A2 block and B2 block, wherein each of the A1 block, B1 block, A2 block and B2 block is independently obtained by polymerization of tetrafluoroethylene and perfluoroalkyl vinyl ether.

[0006] The molar percentage content of perfluoroalkyl vinyl ether in the B1 block or B2 block is higher than that in the A1 block, and also higher than that in the A2 block.

[0007] The molar percentage of perfluoroalkyl vinyl ether in the B2 block is higher than that in the B1 block.

[0008] The advantages and technical effects of the perfluoroether rubber in this invention are as follows: The perfluoroether rubber has a tetrablock structure of A1-B1-A2-B2, containing A blocks and B blocks. The molar percentage of perfluoroalkyl vinyl ether in the A blocks is lower than that in the B blocks. The A blocks include A1 blocks and A2 blocks, and the A blocks are high-temperature rigid segments (glass transition temperature T). g ≥0℃); B-blocks include B1 blocks and B2 blocks, and B-blocks are flexible blocks (T g ≤-15℃); tetrablock A1-B1-A2-B2 sequential polymerization achieves a gradual transition from rigid to flexible to rigid to ultra-flexible, breaking through the high-temperature deformation bottleneck of traditional diblock or triblock perfluoroether rubber, reducing compression set due to the high-temperature elastic recovery of the B2 flexible segment, suitable for sealing rings of semiconductor dry etching equipment, can extend life by more than 3 times in a 320℃ plasma environment, providing key material support for chip manufacturing below 5nm, tensile strength retention rate of not less than 80%, thermal decomposition temperature of not less than 455℃, and can serve for a long time above 300℃.

[0009] In some embodiments, the molar ratio of tetrafluoroethylene to perfluoroalkyl vinyl ether in the A1 block is (75-85):(15-25);

[0010] And / or, the glass transition temperature T of the A1 block g ≥0℃;

[0011] And / or, the molar ratio of tetrafluoroethylene to perfluoroalkyl vinyl ether in the B1 block is (45-60):(40-55);

[0012] And / or, the glass transition temperature T of the B1 block g ≤-15℃;

[0013] And / or, the molar ratio of tetrafluoroethylene to perfluoroalkyl vinyl ether in the A2 block is (75-85):(15-25);

[0014] And / or, the glass transition temperature T of the A2 block g ≥0℃;

[0015] And / or, the molar ratio of tetrafluoroethylene to perfluoroalkyl vinyl ether in the B2 block is (40-50):(50-60);

[0016] And / or, the glass transition temperature T of the B2 block g ≤-15℃.

[0017] In some embodiments, the molar percentage of perfluoroalkyl vinyl ether in the B2 block is 5 to 15 mol higher than the molar percentage of perfluoroalkyl vinyl ether in the B1 block.

[0018] In some embodiments, based on the total molar amount of all tetrafluoroethylene and perfluoroalkyl vinyl ether monomers in the perfluoroether rubber, the molar percentage of the total molar amount of tetrafluoroethylene and perfluoroalkyl vinyl ether monomers in each block is as follows: A1 block, 15-25%; B1 block, 25-35%; A2 block, 20-30%; B2 block, 25-35%.

[0019] In some embodiments, the perfluoroalkyl vinyl ether includes at least one of perfluoromethyl vinyl ether, perfluoroethyl vinyl ether, and perfluoropropyl vinyl ether;

[0020] And / or, the A1 block further includes a sulfurization point monomer;

[0021] And / or, the B1 block further includes a sulfurization point monomer;

[0022] And / or, the A2 block further includes a sulfurization point monomer;

[0023] And / or, the B2 block further includes a sulfurization point monomer.

[0024] In some embodiments, the sulfidation point monomers of the A1 block, B1 block, A2 block, and B2 block each independently include at least one of iodine-containing fluoroolefins, bromofluoroolefins, phenolic hydroxyl fluoroolefins, and cyanofluoroolefins.

[0025] And / or, based on the total molar amount of tetrafluoroethylene and perfluoroalkyl vinyl ether monomers in the A1 block, the molar percentage of the sulfidation point monomer in the A1 block is 0.5-0.9%;

[0026] And / or, based on the total molar amount of tetrafluoroethylene and perfluoroalkyl vinyl ether monomers in the B1 block, the molar percentage of the sulfidation point monomer in the B1 block is 0.5-0.7%;

[0027] And / or, based on the total molar amount of tetrafluoroethylene and perfluoroalkyl vinyl ether monomers in the A2 block, the molar percentage of the sulfidation point monomer in the A2 block is 0.8-1.3%;

[0028] And / or, based on the total molar amount of tetrafluoroethylene and perfluoroalkyl vinyl ether monomers in the B2 block, the molar percentage of the sulfurization point monomer in the B2 block is 1.5-2%.

[0029] In some embodiments, the tensile strength retention rate of the perfluoroether rubber is not less than 80%;

[0030] And / or, the compression set of the perfluoroether rubber is not higher than 20%;

[0031] And / or, the thermal decomposition temperature of the perfluoroether rubber is not lower than 455°C.

[0032] This invention provides a method for preparing perfluoroether rubber, comprising the following steps:

[0033] (1) A1 block monomers are polymerized to obtain A1 block polymers; the A1 block monomers include tetrafluoroethylene and perfluoroalkyl vinyl ethers.

[0034] (2) Add the B1 block monomer to the reaction system of step (1) to carry out a polymerization reaction to obtain the A1-B1 block polymer; the B1 block monomer includes tetrafluoroethylene and perfluoroalkyl vinyl ether.

[0035] (3) Add the A2 block monomer to the reaction system of step (2) to carry out a polymerization reaction to obtain the A1-B1-A2 block polymer; the A2 block monomer includes tetrafluoroethylene and perfluoroalkyl vinyl ether;

[0036] (4) Add the B2 block monomer to the reaction system of step (3) to carry out the polymerization reaction to obtain the A1-B1-A2-B2 block perfluoroether rubber; the B2 block monomer includes tetrafluoroethylene and perfluoroalkyl vinyl ether.

[0037] In this embodiment of the invention, perfluoroether rubber is obtained by sequential polymerization according to A1-B1-A2-B2, achieving a gradual transition from rigid to flexible to rigid to ultra-flexible, reducing compression set, extending plasma environment life, and having a high thermal decomposition temperature, allowing it to serve for a long time above 300°C.

[0038] In some embodiments, in step (1), the polymerization reaction is carried out in water;

[0039] And / or, the polymerization reaction is carried out under deoxygenation conditions;

[0040] And / or, the polymerization reaction is carried out at a temperature of 60-90°C;

[0041] And / or, the polymerization reaction is carried out at a pressure of 1.4-2.8 MPa;

[0042] And / or, the polymerization reaction takes 2-10 hours;

[0043] And / or, the A1 block monomer further includes a sulfidation point monomer; based on the total molar amount of tetrafluoroethylene and perfluoroalkyl vinyl ether monomers in the A1 block, the molar percentage of the sulfidation point monomer in the A1 block is 0.5-0.9%;

[0044] And / or, an emulsifier is also added to the polymerization reaction; the emulsifier includes at least one of perfluorooctanoates; the perfluorooctanoate includes at least one of ammonium salts, sodium salts, or potassium salts; the mass of the emulsifier is 0.1-5% of the mass of the perfluoroether rubber;

[0045] And / or, an initiator is also added to the polymerization reaction; the initiator includes ammonium persulfate and / or potassium persulfate; the mass of the initiator is 0.01-1% of the mass of the perfluoroether rubber.

[0046] In some embodiments, in step (2), the polymerization reaction is carried out under deoxygenation conditions;

[0047] And / or, in step (2), the polymerization reaction is carried out at a temperature of 60-90°C;

[0048] And / or, in step (2), the pressure of the polymerization reaction is 1.4-2.8 MPa;

[0049] And / or, in step (2), the polymerization reaction takes 2-10 hours;

[0050] And / or, in step (2), the B1 block monomer further includes a sulfidation point monomer; based on the total molar amount of tetrafluoroethylene and perfluoroalkyl vinyl ether monomers in the B1 block, the molar percentage of the sulfidation point monomer in the B1 block is 0.5-0.7%.

[0051] In some embodiments, in step (3), the polymerization reaction is carried out under deoxygenation conditions;

[0052] And / or, in step (3), the polymerization reaction is carried out at a temperature of 60-90°C;

[0053] And / or, in step (3), the pressure of the polymerization reaction is 1.4-2.8 MPa;

[0054] And / or, in step (3), the polymerization reaction takes 2-10 hours;

[0055] And / or, in step (3), the A2 block monomer further includes a sulfidation point monomer; based on the total molar amount of tetrafluoroethylene and perfluoroalkyl vinyl ether monomers in the A2 block, the molar percentage of the sulfidation point monomer in the A2 block is 0.8-1.3%.

[0056] In some embodiments, in step (4), the polymerization reaction is carried out under deoxygenation conditions;

[0057] And / or, in step (4), the polymerization reaction is carried out at a temperature of 60-90°C;

[0058] And / or, in step (4), the pressure of the polymerization reaction is 1.4-2.8 MPa;

[0059] And / or, in step (4), the polymerization reaction takes 2-10 hours;

[0060] And / or, in step (4), the B2 block monomer further includes a sulfidation point monomer; based on the total molar amount of tetrafluoroethylene and perfluoroalkyl vinyl ether monomers in the B2 block, the molar percentage of the sulfidation point monomer in the B2 block is 1.5-2%;

[0061] And / or, in step (4), the emulsion after polymerization is coagulated, washed and dried to obtain perfluoroether rubber.

[0062] This invention provides an application of perfluoroether rubber for sealing;

[0063] And / or, for use in semiconductor manufacturing, integrated circuit manufacturing, aerospace, new energy manufacturing, high-end manufacturing, and biopharmaceuticals;

[0064] And / or, for use in ambient temperatures above 300°C.

[0065] In this embodiment of the invention, perfluoroether rubber achieves a gradual transition from rigid to flexible to rigid to ultra-flexible, reduces compression set, extends plasma environment life, and has a high thermal decomposition temperature, allowing it to serve for extended periods above 300°C. It is suitable for applications such as sealing and chip manufacturing. Detailed Implementation

[0066] The embodiments of the present invention are described in detail below. These embodiments are exemplary and intended to explain the present invention, and should not be construed as limiting the present invention.

[0067] An embodiment of the present invention provides a perfluoroether rubber having an A1-B1-A2-B2 block structure, including A1 block, B1 block, A2 block and B2 block, wherein each of the A1 block, B1 block, A2 block and B2 block is independently obtained by polymerization of tetrafluoroethylene and perfluoroalkyl vinyl ether.

[0068] The molar percentage content of perfluoroalkyl vinyl ether in the B1 block or B2 block is higher than that in the A1 block, and also higher than that in the A2 block.

[0069] The molar percentage of perfluoroalkyl vinyl ether in the B2 block is higher than that in the B1 block.

[0070] The molar percentage of perfluoroalkyl vinyl ethers in the block refers to the molar percentage of perfluoroalkyl vinyl ether monomers based on the total molar amount of tetrafluoroethylene and perfluoroalkyl vinyl ether monomers in the block.

[0071] The perfluoroether rubber of this invention has a four-block structure of A1-B1-A2-B2, including A-blocks and B-blocks. The molar percentage of perfluoroalkyl vinyl ether in the A-block is lower than that in the B-block. The A-block includes A1 and A2 blocks, which are high-temperature rigid segments (glass transition temperature Tg ≥ 0℃). The B-block includes B1 and B2 blocks, which are flexible segments (Tg ≤ -15℃). The four-block A1-B1-A2-B2 sequential polymerization achieves a gradual transition from rigid to flexible to rigid to ultra-flexible, breaking through the high-temperature deformation bottleneck of traditional two-block or three-block perfluoroether rubbers. The compression set is reduced due to the high-temperature elastic recovery of the B2 flexible segment. It is suitable for sealing rings in semiconductor dry etching equipment, and its lifespan can be extended by more than 3 times in a 320℃ plasma environment. It provides key material support for the manufacturing of chips below 5nm, with a tensile strength retention rate of not less than 80%, a thermal decomposition temperature of not less than 455℃, and can be used for a long time above 300℃.

[0072] In some embodiments, the perfluoroether rubber has an A1-B1-A2-B2 block structure, including A1 block, B1 block, A2 block and B2 block;

[0073] Optionally, the molar ratio of tetrafluoroethylene to perfluoroalkyl vinyl ether in the A1 block is (75–85):(15–25), specifically, 75–85 (e.g., 75, 77, 78, 80, 82, 83, 85):15–25 (e.g., 15, 17, 18, 20, 22, 23, 25); and / or, the glass transition temperature T of the A1 block... g ≥0℃;

[0074] Optionally, the molar ratio of tetrafluoroethylene to perfluoroalkyl vinyl ether in the B1 block is (45–60):(40–55), specifically, 45–60 (e.g., 45, 48, 50, 52, 55, 58, 60):40–55 (e.g., 40, 42, 45, 48, 50, 52, 55); and / or, the glass transition temperature T of the B1 block... g ≤-15℃;

[0075] Optionally, the molar ratio of tetrafluoroethylene to perfluoroalkyl vinyl ether in the A2 block is (75–85):(15–25), specifically, 75–85 (e.g., 75, 77, 78, 80, 82, 83, 85):15–25 (e.g., 15, 17, 18, 20, 22, 23, 25); and / or, the glass transition temperature T of the A2 block... g ≥0℃;

[0076] Optionally, the molar ratio of tetrafluoroethylene to perfluoroalkyl vinyl ether in the B2 block is (40-50):(50-60), specifically, 40-50 (e.g., 40, 41, 42, 45, 46, 48, 49, 50):50-60 (e.g., 50, 51, 52, 54, 55, 58, 59, 60); and / or, the glass transition temperature T of the B2 block... g ≤-15℃;

[0077] Optionally, the molar ratio of tetrafluoroethylene to perfluoroalkyl vinyl ether in block A1 may be the same as or different from the molar ratio of tetrafluoroethylene to perfluoroalkyl vinyl ether in block A2.

[0078] In this embodiment of the invention, block A is a high-temperature rigid block with a TFE / PAVE molar ratio of (75-85):(15-25) (glass transition temperature Tg≥0℃); block B is a flexible block (Tg≤-15℃); sequential polymerization of A1-B1-A2-B2 achieves block distribution, forming a four-block structure of A1-B1-A2-B2, realizing a gradual transition from rigid to flexible to rigid to ultra-flexible, which is beneficial to further improve the compression set, plasma environment life and thermal decomposition temperature of perfluoroether rubber.

[0079] In some embodiments, the molar percentage of perfluoroalkyl vinyl ether in the B2 block is 5-15 mol% higher than that in the B1 block, i.e., 5-15%, specifically, for example, 5 mol%, 6 mol%, 7 mol%, 8 mol%, 9 mol%, 10 mol%, 11 mol%, 12 mol%, 13 mol%, 14 mol%, 15 mol%.

[0080] In this embodiment of the invention, the PAVE content in block B2 is 5-15 mol% higher than that in block B1, further improving the difference between the flexible and ultra-flexible blocks in the A1-B1-A2-B2 four-block rigid-flexible-rigid-ultra-flexible structure. The flexible block B2 exhibits high-temperature elastic recovery, which is beneficial for further improving the compression set, plasma environment life, and thermal decomposition temperature of perfluoroether rubber. When the PAVE content difference between block B2 and block B1 is too small or too large, the difference between the flexible and ultra-flexible blocks is not significant or is too large, both of which are detrimental to further improving the performance of perfluoroether rubber.

[0081] In some embodiments, based on the total molar amount of all tetrafluoroethylene and perfluoroalkyl vinyl ether monomers of the perfluoroether rubber, the molar percentage of the total molar amount of tetrafluoroethylene and perfluoroalkyl vinyl ether monomers in each block is: A1 block, 15-25%, specifically, for example, 15%, 16%, 18%, 20%, 22%, 24%, 25%.

[0082] B1 blocks, 25-35%, specifically, for example, 25%, 26%, 28%, 30%, 32%, 34%, 35%;

[0083] A2 blocks, 20-30%, specifically, for example, 20%, 22%, 24%, 25%, 26%, 28%, 30%;

[0084] B2 blocks, 25-35%, specifically, for example, 25%, 26%, 28%, 30%, 32%, 34%, 35%.

[0085] In this embodiment of the invention, by optimizing the content of each block in the perfluoroether rubber, it is beneficial to further improve the compression set, plasma environment life and thermal decomposition temperature of the perfluoroether rubber.

[0086] In some embodiments, the perfluoroalkyl vinyl ether includes at least one of perfluoromethyl vinyl ether (PMVE), perfluoroethyl vinyl ether (PEVE), and perfluoropropyl vinyl ether, optionally perfluoroethyl vinyl ether.

[0087] In some embodiments, the A1 block further includes a sulfurization point monomer; and / or, the B1 block further includes a sulfurization point monomer; and / or, the A2 block further includes a sulfurization point monomer; and / or, the B2 block further includes a sulfurization point monomer.

[0088] Optionally, the sulfidation point monomers of the A1 block, B1 block, A2 block, and B2 block each independently include at least one of iodine-containing fluoroolefins, bromofluoroolefins, phenolic hydroxyl fluoroolefins, and cyanofluoroolefins; optionally, iodine trifluoroethylene;

[0089] In some embodiments, based on the total molar amount of tetrafluoroethylene and perfluoroalkyl vinyl ether monomers in the A1 block, the molar percentage of the sulfurization point monomer in the A1 block is 0.5-0.9%, specifically, for example, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%; and / or, based on the total molar amount of tetrafluoroethylene and perfluoroalkyl vinyl ether monomers in the B1 block, the molar percentage of the sulfurization point monomer in the B1 block is 0.5-0.7%, specifically, for example, 0.5%, 0.6%, 0.7%; and / or, based on The total molar amount of tetrafluoroethylene and perfluoroalkyl vinyl ether monomers in the A2 block, wherein the molar percentage of the sulfurization point monomer in the A2 block is 0.8-1.3%, specifically, for example, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%; and / or, based on the total molar amount of tetrafluoroethylene and perfluoroalkyl vinyl ether monomers in the B2 block, wherein the molar percentage of the sulfurization point monomer in the B2 block is 1.5-2%, specifically, for example, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%.

[0090] In some embodiments, the tensile strength retention rate of the perfluoroether rubber is not less than 80%, optionally not less than 85%, and not less than 89%; optionally, ASTM D412 is adopted.

[0091] And / or, the compression set of the perfluoroether rubber is not higher than 20%, optionally not higher than 18%; optionally, it conforms to ASTM D395;

[0092] And / or, the thermal decomposition temperature of the perfluoroether rubber is not lower than 455°C, optionally not lower than 485°C; optionally, TGA 5% loss is used.

[0093] A method for preparing perfluoroether rubber according to an embodiment of the present invention includes the following steps:

[0094] (1) A1 block monomers are polymerized to obtain A1 block polymers; the A1 block monomers include tetrafluoroethylene and perfluoroalkyl vinyl ethers.

[0095] (2) Add the B1 block monomer to the reaction system of step (1) to carry out a polymerization reaction to obtain the A1-B1 block polymer; the B1 block monomer includes tetrafluoroethylene and perfluoroalkyl vinyl ether.

[0096] (3) Add the A2 block monomer to the reaction system of step (2) to carry out a polymerization reaction to obtain the A1-B1-A2 block polymer; the A2 block monomer includes tetrafluoroethylene and perfluoroalkyl vinyl ether;

[0097] (4) Add the B2 block monomer to the reaction system of step (3) to carry out the polymerization reaction to obtain the A1-B1-A2-B2 block perfluoroether rubber; the B2 block monomer includes tetrafluoroethylene and perfluoroalkyl vinyl ether.

[0098] In this embodiment of the invention, perfluoroether rubber is obtained by sequential polymerization according to A1-B1-A2-B2, achieving a gradual transition from rigid to flexible to rigid to ultra-flexible, reducing compression set, extending plasma environment life, and having a high thermal decomposition temperature, allowing it to serve for a long time above 300°C.

[0099] In some embodiments, in step (1), the polymerization reaction is carried out in water; the mass of the water is 1.8-2.2 times the mass of the monomer (perfluoroether rubber), specifically, for example, 1.8 times, 1.9 times, 2.0 times, 2.1 times, 2.2 times.

[0100] In some embodiments, in step (1), the polymerization reaction is carried out under deoxygenation conditions; optionally, the deoxygenation includes at least one of atmospheric deoxygenation and water deoxygenation; water is added to the high-pressure reactor to deoxygenate until the oxygen content is ≤20ppm.

[0101] In some embodiments, in step (1), the molar ratio of tetrafluoroethylene to perfluoroalkyl vinyl ether in the A1 block is (75-85):(15-25), specifically, 75-85 (e.g., 75, 77, 78, 80, 82, 83, 85):15-25 (e.g., 15, 17, 18, 20, 22, 23, 25); and / or, the glass transition temperature T of the A1 block... g ≥0℃.

[0102] In some embodiments, in step (1), the temperature of the polymerization reaction is 60-90°C, specifically, for example, 60°C, 70°C, 80°C, 90°C; the pressure of the polymerization reaction is 1.4-2.8 MPa, specifically, for example, 1.4 MPa, 1.5 MPa, 1.8 MPa, 2.0 MPa, 2.2 MPa, 2.5 MPa, 2.6 MPa, 2.7 MPa, 2.8 MPa; the time of the polymerization reaction is 2-10 hours. Specifically, for example, 2h, 4h, 5h, 6h, 8h, 10h; the polymerization reaction continues until the amount of A1 block tetrafluoroethylene and perfluoroalkyl vinyl ether mixed monomers added reaches the target molar percentage of A1 block in the total amount of tetrafluoroethylene and perfluoroalkyl vinyl ether monomers in the perfluoroether rubber; that is, based on the total molar amount of all tetrafluoroethylene and perfluoroalkyl vinyl ether monomers in the perfluoroether rubber, the total molar amount of tetrafluoroethylene and perfluoroalkyl vinyl ether monomers in the A1 block reaches the target molar percentage.

[0103] In some embodiments, in step (1), the A1 block monomer further includes a sulfidation point monomer; the sulfidation point monomer includes at least one of iodofluoroolefins, bromofluoroolefins, phenolic hydroxyl fluoroolefins, and cyanofluoroolefins; based on the total molar amount of tetrafluoroethylene and perfluoroalkyl vinyl ether monomers in the A1 block, the molar percentage of the sulfidation point monomer in the A1 block is 0.5-0.9%, specifically, for example, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%; optionally, the sulfidation point monomer is added after the tetrafluoroethylene and perfluoroalkyl vinyl ether mixed monomers are added to the target pressure.

[0104] In some embodiments, in step (1), an emulsifier is also added to the polymerization reaction; the emulsifier includes at least one of perfluorooctanoates, and the perfluorooctanoate includes at least one of ammonium salt, sodium salt or potassium salt; the mass of the emulsifier is 0.1-5% of the mass of the perfluoroether rubber, specifically, for example, 0.5%, 1%, 2%, 3%, 4% or 5%; optionally, the emulsifier is added to water, the temperature is raised, and then the A1 block monomer is added to carry out the polymerization reaction.

[0105] In some embodiments, in step (1), an initiator is also added to the polymerization reaction; the initiator includes ammonium persulfate and / or potassium persulfate; the mass of the initiator is 0.01-1% of the mass of the perfluoroether rubber (the mass of monomers consumed by the perfluoroether rubber), specifically, for example, 0.01%, 0.02%, 0.05%, 0.1%, 0.5%, 1%; the initiator is added after the tetrafluoroethylene and perfluoroalkyl vinyl ether mixed monomers are added.

[0106] In some embodiments, in step (1), an emulsifier is added to water, then a mixture of tetrafluoroethylene and perfluoroalkyl vinyl ether monomers of the A1 block is added to the target pressure, and then an initiator and a sulfurization point monomer are added to carry out a polymerization reaction to obtain the A1 block polymer.

[0107] In some embodiments, in step (2), the molar ratio of tetrafluoroethylene to perfluoroalkyl vinyl ether in the B1 block is (45–60):(40–55), specifically, 45–60 (e.g., 45, 48, 50, 52, 55, 58, 60):40–55 (e.g., 40, 42, 45, 48, 50, 52, 55); and / or, the glass transition temperature T of the B1 block... g ≤-15℃.

[0108] In some embodiments, in step (2), the polymerization reaction is carried out under deoxygenation conditions; the temperature of the polymerization reaction is 60-90°C, specifically, for example, 60°C, 70°C, 80°C, 90°C; the pressure of the polymerization reaction is 1.4-2.8 MPa, specifically, for example, 1.4 MPa, 1.5 MPa, 1.8 MPa, 2.0 MPa, 2.2 MPa, 2.5 MPa, 2.6 MPa, 2.7 MPa, 2.8 MPa; the time of the polymerization reaction is... 2-10h, specifically, for example, 2h, 4h, 5h, 6h, 8h, 10h; the polymerization reaction continues until the amount of B1 block tetrafluoroethylene and perfluoroalkyl vinyl ether mixed monomers added reaches the target molar percentage of B1 block in the total amount of tetrafluoroethylene and perfluoroalkyl vinyl ether monomers in the perfluoroether rubber; that is, based on the total molar amount of all tetrafluoroethylene and perfluoroalkyl vinyl ether monomers in the perfluoroether rubber, the total molar amount of tetrafluoroethylene and perfluoroalkyl vinyl ether monomers in the B1 block reaches the target molar percentage.

[0109] In some embodiments, in step (2), the B1 block monomer further includes a sulfidation point monomer; the sulfidation point monomer includes at least one of iodofluoroolefins, bromofluoroolefins, phenolic hydroxyl fluoroolefins, and cyanofluoroolefins; based on the total molar amount of tetrafluoroethylene and perfluoroalkyl vinyl ether monomers in the B1 block, the molar percentage of the sulfidation point monomer in the B1 block is 0.5-0.7%, specifically, for example, 0.5%, 0.6%, 0.7%; optionally, the sulfidation point monomer is added after the tetrafluoroethylene and perfluoroalkyl vinyl ether mixed monomers have reached the target pressure.

[0110] In some embodiments, in step (3), the molar ratio of tetrafluoroethylene to perfluoroalkyl vinyl ether in the A2 block is (75-85):(15-25), specifically, 75-85 (e.g., 75, 77, 78, 80, 82, 83, 85):15-25 (e.g., 15, 17, 18, 20, 22, 23, 25); and / or, the glass transition temperature T of the A2 block... g ≥0℃.

[0111] In some embodiments, in step (3), the polymerization reaction is carried out under deoxygenation conditions; the temperature of the polymerization reaction is 60-90°C, specifically, for example, 60°C, 70°C, 80°C, 90°C; the pressure of the polymerization reaction is 1.4-2.8 MPa, specifically, for example, 1.4 MPa, 1.5 MPa, 1.8 MPa, 2.0 MPa, 2.2 MPa, 2.5 MPa, 2.6 MPa, 2.7 MPa, 2.8 MPa; the time of the polymerization reaction is... 2-10h, specifically, for example, 2h, 4h, 5h, 6h, 8h, 10h; the polymerization reaction continues until the amount of A2 block tetrafluoroethylene and perfluoroalkyl vinyl ether mixed monomers added reaches the target molar percentage of A2 block in the total amount of tetrafluoroethylene and perfluoroalkyl vinyl ether monomers in the perfluoroether rubber; that is, based on the total molar amount of all tetrafluoroethylene and perfluoroalkyl vinyl ether monomers in the perfluoroether rubber, the total molar amount of tetrafluoroethylene and perfluoroalkyl vinyl ether monomers in the A2 block reaches the target molar percentage.

[0112] In some embodiments, in step (3), the A2 block monomer further includes a sulfidation point monomer; the sulfidation point monomer includes at least one of iodofluoroolefins, bromofluoroolefins, phenolic hydroxyl fluoroolefins, and cyanofluoroolefins; based on the total molar amount of tetrafluoroethylene and perfluoroalkyl vinyl ether monomers in the A2 block, the molar percentage of the sulfidation point monomer in the A2 block is 0.8-1.3%, specifically, for example, 0.8%, 0.9%, 1.0%, 1.1%, 1.2%, 1.3%; optionally, the sulfidation point monomer is added after the tetrafluoroethylene and perfluoroalkyl vinyl ether mixed monomers are added to the target pressure.

[0113] In some embodiments, in step (4), the molar ratio of tetrafluoroethylene to perfluoroalkyl vinyl ether in the B2 block is (40-50):(50-60), specifically, 40-50 (e.g., 40, 41, 42, 45, 46, 48, 49, 50):50-60 (e.g., 50, 51, 52, 54, 55, 58, 59, 60); and / or, the glass transition temperature T of the B2 block... g ≤-15℃.

[0114] In some embodiments, in step (4), the polymerization reaction is carried out under deoxygenation conditions; the temperature of the polymerization reaction is 60-90°C, specifically, for example, 60°C, 70°C, 80°C, 90°C; the pressure of the polymerization reaction is 1.4-2.8 MPa, specifically, for example, 1.4 MPa, 1.5 MPa, 1.6 MPa, 1.7 MPa, 1.8 MPa, 2.0 MPa, 2.2 MPa, 2.5 MPa, 2.6 MPa, 2.7 MPa, 2.8 MPa; ... The reaction time is 2-10 hours, specifically, for example, 2 hours, 4 hours, 5 hours, 6 hours, 8 hours, and 10 hours; the polymerization reaction continues until the amount of B2 block tetrafluoroethylene and perfluoroalkyl vinyl ether mixed monomers added reaches the target molar percentage of B2 block tetrafluoroethylene and perfluoroalkyl vinyl ether monomers in the perfluoroether rubber; that is, based on the total molar amount of all tetrafluoroethylene and perfluoroalkyl vinyl ether monomers in the perfluoroether rubber, the total molar amount of B2 block tetrafluoroethylene and perfluoroalkyl vinyl ether monomers reaches the target molar percentage.

[0115] In this embodiment of the invention, the B2 segment in gradient polymerization uses low-pressure polymerization (e.g., 1.8 MPa) to promote the PAVE insertion rate, which improves the block regularity compared with the traditional high-pressure method (e.g., 2.0-3.0 MPa), which is beneficial to provide block compliance and reduce the rigid structure of the block.

[0116] In some embodiments, in step (4), the B2 block monomer further includes a sulfidation point monomer; the sulfidation point monomer includes at least one of iodofluoroolefins, bromofluoroolefins, phenolic hydroxyl fluoroolefins, and cyanofluoroolefins; based on the total molar amount of tetrafluoroethylene and perfluoroalkyl vinyl ether monomers in the B2 block, the molar percentage of the sulfidation point monomer in the B2 block is 1.5-2%, specifically, for example, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%; optionally, the sulfidation point monomer is added after the tetrafluoroethylene and perfluoroalkyl vinyl ether mixed monomers are added to the target pressure.

[0117] In some embodiments, unreacted monomers are recovered, and then block monomers (a mixture of tetrafluoroethylene and perfluoroalkyl vinyl ether monomers) are added for polymerization. For example, optionally, in steps (2), (3), or (4), unreacted monomers are recovered first, and then block monomers are added to the reaction system for polymerization. Optionally, unreacted monomers are discharged to a monomer recovery tank and then pumped into a monomer tank via a recovery membrane press. The monomer recovery tank also needs to treat the recovered monomers, for example, by removing moisture or other impurities, before pumping them into the monomer tank for storage.

[0118] In some embodiments, in steps (1), (2), (3) or (4), a mixture of tetrafluoroethylene and perfluoroalkyl vinyl ether monomers is continuously introduced during the reaction to maintain the target pressure.

[0119] In some embodiments, in step (4), the emulsion after polymerization is coagulated, washed, and dried to obtain perfluoroether rubber; optionally, the washing is done with water.

[0120] An application of a perfluoroether rubber according to an embodiment of the present invention is for sealing;

[0121] And / or, for use in semiconductor manufacturing, integrated circuit manufacturing, aerospace, new energy manufacturing, high-end manufacturing, and biopharmaceuticals; optionally, semiconductor manufacturing and integrated circuit manufacturing include chip manufacturing; new energy manufacturing and high-end manufacturing include new energy and high-end manufacturing components; semiconductor manufacturing includes sealing rings for semiconductor dry etching equipment;

[0122] And / or, used at an ambient temperature above 300°C, preferably above 310°C, above 320°C, above 330°C, above 340°C, or above 350°C.

[0123] In this embodiment of the invention, perfluoroether rubber achieves a gradual transition from rigid to flexible to rigid to ultra-flexible, reduces compression set, extends plasma environment life, and has a high thermal decomposition temperature, allowing it to serve for extended periods above 300°C. It is suitable for applications such as sealing and chip manufacturing.

[0124] The present invention will now be described with reference to specific embodiments. It should be noted that these embodiments are merely descriptive and do not limit the present invention in any way.

[0125] Example 1

[0126] A perfluoroether rubber and its preparation method:

[0127] Raw rubber synthesis: In a reactor, A1 block: TFE / PMVE = 80 / 20 (molar ratio), 2.5 MPa × 80 °C;

[0128] B1 block: TFE / PMVE = 55 / 45, 2.0MPa × 80℃;

[0129] A2 block is the same as A1: TFE / PMVE = 80 / 20, 2.5MPa × 80℃;

[0130] B2 block: TFE / PMVE = 45 / 55, 1.8MPa × 80℃;

[0131] Based on the total molar amount of all tetrafluoroethylene and perfluoroalkyl vinyl ether monomers in the perfluoroether rubber, the molar ratio of the total molar amount of tetrafluoroethylene and perfluoroalkyl vinyl ether monomers in each block of A1-B1-A2-B2 is 20:30:25:25.

[0132] The preparation method of perfluoroether rubber includes the following steps:

[0133] 1) Add deionized water to the high-pressure reactor and deoxygenate until the oxygen content is ≤20ppm; add ammonium perfluorooctanoate emulsifier (0.5% of the mass of perfluoroether rubber) and heat to 80℃;

[0134] 2) A1 block polymerization: TFE / PMVE = 80 / 20 mixed monomers are pressed into the pressure to 2.5MPa, 15g of initiator ammonium persulfate and 70g of vulcanization point monomer iodine trifluoroethylene are added, and the reaction is carried out until the molar amount of TFE / PMVE mixed monomers reaches 20% of the total molar amount of tetrafluoroethylene and perfluoroalkyl vinyl ether monomers in the perfluoroether rubber;

[0135] 3) B1 block polymerization: Unreacted monomers are recovered, and a TFE / PMVE = 55 / 45 mixed monomer mixture is injected to a pressure of 2.0 MPa. 70 g of vulcanizing point monomer iodine trifluoroethylene is added using an additive pump. The reaction continues until the molar amount of TFE / PMVE mixed monomers added reaches 30% of the total molar amount of tetrafluoroethylene and perfluoroalkyl vinyl ether monomers in the perfluoroether rubber.

[0136] 4) A2 block polymerization: Unreacted monomers are recovered, and TFE / PMVE = 80 / 20 mixed monomers are injected to a pressure of 2.5 MPa. 90g of vulcanizing point monomer iodine trifluoroethylene is added using an additive pump. The reaction continues until the molar amount of TFE / PMVE mixed monomers added reaches 25% of the total molar amount of tetrafluoroethylene and perfluoroalkyl vinyl ether monomers in the perfluoroether rubber.

[0137] 5) B2 block polymerization: Unreacted monomers are recovered, and TFE / PMVE = 45 / 55 monomers are injected to a pressure of 1.8 MPa. 110 g of vulcanizing point monomer iodine trifluoroethylene is added using an additive pump. The reaction continues until the molar amount of TFE / PMVE mixed monomers reaches 25% of the total molar amount of tetrafluoroethylene and perfluoroalkyl vinyl ether monomers in the perfluoroether rubber.

[0138] 6) The emulsion is coagulated, washed with water, and dried to obtain raw gum.

[0139] Example 2

[0140] The preparation method is the same as that of the perfluoroether rubber in Example 1, except that the content of PMVE in the B2 block in the block structure is adjusted to 60%, that is, in step 5), TFE / PMVE = 40 / 60.

[0141] Comparative Example 1

[0142] A perfluoroether rubber and its preparation method:

[0143] Raw rubber synthesis: Traditional AB block structure: A block: TFE / PMVE = 80 / 20, 2.5MPa × 80℃ (molar ratio);

[0144] B-block: TFE / PMVE = 50 / 50, 2.0MPa × 80℃;

[0145] Based on the total molar amount of all tetrafluoroethylene and perfluoroalkyl vinyl ether monomers in the perfluoroether rubber, the ratio of the total molar amount of tetrafluoroethylene and perfluoroalkyl vinyl ether monomers in each block of AB is 60:40.

[0146] The preparation method of perfluoroether rubber includes the following steps:

[0147] 1) Add deionized water to the high-pressure reactor and deoxygenate until the oxygen content is ≤20ppm; add ammonium perfluorooctanoate emulsifier (0.5% of the mass of perfluoroether rubber) and heat to 80℃;

[0148] 2) Block polymerization: TFE / PMVE = 80 / 20 mixed monomers are pressed into the pressure to 2.5 MPa, 15 g of initiator ammonium persulfate and 70 g of vulcanization point monomer iodine trifluoroethylene are added, and the reaction is carried out until the molar amount of TFE / PMVE mixed monomers reaches 60% of the total molar amount of tetrafluoroethylene and perfluoroalkyl vinyl ether monomers in the perfluoroether rubber;

[0149] 3) B-block polymerization: Unreacted monomers are recovered, and a 50 / 50 TFE / PMVE mixed monomer mixture is injected to a pressure of 2.0 MPa. 70 g of vulcanizing point monomer iodine trifluoroethylene is added using an additive pump. The reaction continues until the molar amount of the TFE / PMVE mixed monomer mixture reaches 40% of the total molar amount of tetrafluoroethylene and perfluoroalkyl vinyl ether monomers in the perfluoroether rubber.

[0150] 4) The emulsion is coagulated, washed with water, and dried to obtain raw gum.

[0151] Table 1 Comparison of performance tests of perfluoroether rubber (after aging at 300℃ for 72 hours)

[0152]

[0153] As can be seen from Examples 1 and 2, the perfluoroether rubber of the present invention has a four-block structure of A1-B1-A2-B2, realizing a gradual transition from rigid to flexible to rigid to ultra-flexible. The compression set is reduced to ≤20%, which is due to the high-temperature elastic recovery of the B2 flexible segment. The lifespan is extended by more than 3 times in a plasma environment at 320°C, the tensile strength retention rate is not less than 80%, the thermal decomposition temperature is not less than 455°C, and it can be used for a long time at temperatures above 300°C. It is suitable for multiple fields such as sealing and chip manufacturing.

[0154] Compared with Example 1, Example 2 has a higher B2 block PMVE content, a tensile strength retention rate of up to 92%, a lower compression set, and a thermal decomposition temperature of up to 492°C.

[0155] Comparing Example 1 and Comparative Example 1, Comparative Example 1 uses a traditional AB block structure, with a tensile strength retention rate as low as 68%, a compression set as high as about 40%, and a thermal decomposition temperature of 455°C. When it is in long-term service at temperatures above 300°C, it faces technical bottlenecks such as increased compression set, insufficient resistance to high-temperature plasma, and accelerated thermal decomposition.

[0156] In this invention, the terms "one embodiment," "some embodiments," "example," "specific example," or "some examples," etc., refer to a specific feature, structure, material, or characteristic described in connection with that embodiment or example, which is included in at least one embodiment or example of the invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples. Moreover, without contradiction, those skilled in the art can combine and integrate the different embodiments or examples described in this specification, as well as the features of different embodiments or examples.

[0157] Although the above embodiments have been shown and described, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention. Any changes, modifications, substitutions and variations made to the above embodiments by those skilled in the art are within the protection scope of the present invention.

Claims

1. A perfluoroether rubber, characterized in that, The perfluoroether rubber has an A1-B1-A2-B2 block structure, including A1 block, B1 block, A2 block and B2 block, wherein each of the A1 block, B1 block, A2 block and B2 block is independently obtained by polymerization of tetrafluoroethylene and perfluoroalkyl vinyl ether. The molar ratio of tetrafluoroethylene to perfluoroalkyl vinyl ether in the A1 block is (75~85):(15~25); The molar ratio of tetrafluoroethylene to perfluoroalkyl vinyl ether in the B1 block is (45~60):(40~55); The molar ratio of tetrafluoroethylene to perfluoroalkyl vinyl ether in the A2 block is (75~85):(15~25); The molar ratio of tetrafluoroethylene to perfluoroalkyl vinyl ether in the B2 block is (40~50):(50~60); Based on the total molar amount of all tetrafluoroethylene and perfluoroalkyl vinyl ether monomers in the perfluoroether rubber, the molar percentage of the total molar amount of tetrafluoroethylene and perfluoroalkyl vinyl ether monomers in each block is as follows: A1 block, 15~25%; B1 block, 25~35%; A2 block, 20~30%; B2 block, 25~35%. The molar percentage of perfluoroalkyl vinyl ether in the B2 block is 5-15 mol higher than that in the B1 block.

2. The perfluoroether rubber according to claim 1, characterized in that, The glass transition temperature T of the A1 block g ≥0℃; And / or, the glass transition temperature T of the B1 block g ≤-15℃; And / or, the glass transition temperature T of the A2 block g ≥0℃; And / or, the glass transition temperature T of the B2 block g ≤-15℃.

3. The perfluoroether rubber according to claim 1, characterized in that, The perfluoroalkyl vinyl ether includes at least one of perfluoromethyl vinyl ether, perfluoroethyl vinyl ether, and perfluoropropyl vinyl ether; And / or, the A1 block further includes a sulfurization point monomer; And / or, the B1 block further includes a sulfurization point monomer; And / or, the A2 block further includes a sulfurization point monomer; And / or, the B2 block further includes a sulfurization point monomer.

4. The perfluoroether rubber according to claim 3, characterized in that, The sulfidation point monomers of the A1 block, B1 block, A2 block, and B2 block each independently include at least one of iodine-containing fluoroolefins, bromofluoroolefins, phenolic hydroxyl fluoroolefins, and cyanofluoroolefins. And / or, based on the total molar amount of tetrafluoroethylene and perfluoroalkyl vinyl ether monomers in the A1 block, the molar percentage of the sulfidation point monomer in the A1 block is 0.5-0.9%; And / or, based on the total molar amount of tetrafluoroethylene and perfluoroalkyl vinyl ether monomers in the B1 block, the molar percentage of the sulfidation point monomer in the B1 block is 0.5-0.7%; And / or, based on the total molar amount of tetrafluoroethylene and perfluoroalkyl vinyl ether monomers in the A2 block, the molar percentage of the sulfidation point monomer in the A2 block is 0.8-1.3%; And / or, based on the total molar amount of tetrafluoroethylene and perfluoroalkyl vinyl ether monomers in the B2 block, the molar percentage of the sulfur point monomer in the B2 block is 1.5-2%.

5. The perfluoroether rubber according to claim 1, characterized in that, The tensile strength retention rate of the perfluoroether rubber is not less than 80%; And / or, the compression set of the perfluoroether rubber is not higher than 20%; And / or, the thermal decomposition temperature of the perfluoroether rubber is not lower than 455°C.

6. A method for preparing a perfluoroether rubber according to any one of claims 1-5, characterized in that, Includes the following steps: (1) The A1 block monomer is subjected to a polymerization reaction to obtain the A1 block polymer; the A1 block monomer includes tetrafluoroethylene and perfluoroalkyl vinyl ether; (2) Add the B1 block monomer to the reaction system of step (1) to carry out the polymerization reaction to obtain the A1-B1 block polymer; the B1 block monomer includes tetrafluoroethylene and perfluoroalkyl vinyl ether; (3) Add the A2 block monomer to the reaction system of step (2) to carry out the polymerization reaction to obtain the A1-B1-A2 block polymer; the A2 block monomer includes tetrafluoroethylene and perfluoroalkyl vinyl ether; (4) Add the B2 block monomer to the reaction system of step (3) to carry out the polymerization reaction to obtain the A1-B1-A2-B2 block perfluoroether rubber; the B2 block monomer includes tetrafluoroethylene and perfluoroalkyl vinyl ether.

7. The method for preparing perfluoroether rubber according to claim 6, characterized in that, In step (1), the polymerization reaction is carried out in water; And / or, the polymerization reaction is carried out under deoxygenation conditions; And / or, the polymerization reaction is carried out at a temperature of 60-90 °C; And / or, the polymerization reaction is carried out at a pressure of 1.4-2.8 MPa; And / or, the polymerization reaction takes 2-10 h; And / or, the A1 block monomer further includes a sulfurization point monomer; based on the total molar amount of tetrafluoroethylene and perfluoroalkyl vinyl ether monomers in the A1 block, the molar percentage of the sulfurization point monomer in the A1 block is 0.5-0.9%; And / or, an emulsifier is also added to the polymerization reaction; the emulsifier includes at least one of perfluorooctanoates; the perfluorooctanoate includes at least one of ammonium salts, sodium salts, or potassium salts; the mass of the emulsifier is 0.1-5% of the mass of the perfluoroether rubber; And / or, an initiator is also added to the polymerization reaction; the initiator includes ammonium persulfate and / or potassium persulfate; the mass of the initiator is 0.01-1% of the mass of the perfluoroether rubber.

8. The method for preparing perfluoroether rubber according to claim 6, characterized in that, In step (2), the polymerization reaction is carried out under deoxygenation conditions; And / or, in step (2), the polymerization reaction is carried out at a temperature of 60-90°C; And / or, in step (2), the pressure of the polymerization reaction is 1.4-2.8 MPa; And / or, in step (2), the polymerization reaction takes 2-10 h; And / or, in step (2), the B1 block monomer further includes a sulfidation point monomer; based on the total molar amount of tetrafluoroethylene and perfluoroalkyl vinyl ether monomers in the B1 block, the molar percentage of the sulfidation point monomer in the B1 block is 0.5-0.7%; And / or, in step (3), the polymerization reaction is carried out under deoxygenation conditions; And / or, in step (3), the polymerization reaction temperature is 60-90°C; And / or, in step (3), the pressure of the polymerization reaction is 1.4-2.8 MPa; And / or, in step (3), the polymerization reaction takes 2-10 h; And / or, in step (3), the A2 block monomer further includes a sulfurization point monomer; based on the total molar amount of tetrafluoroethylene and perfluoroalkyl vinyl ether monomers in the A2 block, the molar percentage of the sulfurization point monomer in the A2 block is 0.8-1.3%; And / or, in step (4), the polymerization reaction is carried out under deoxygenation conditions; And / or, in step (4), the polymerization reaction is carried out at a temperature of 60-90°C; And / or, in step (4), the pressure of the polymerization reaction is 1.4-2.8 MPa; And / or, in step (4), the polymerization reaction takes 2-10 h; And / or, in step (4), the B2 block monomer further includes a sulfidation point monomer; based on the total molar amount of tetrafluoroethylene and perfluoroalkyl vinyl ether monomers in the B2 block, the molar percentage of the sulfidation point monomer in the B2 block is 1.5-2%; And / or, in step (4), the emulsion after polymerization is coagulated, washed and dried to obtain perfluoroether rubber.

9. The application of a perfluoroether rubber according to any one of claims 1-5 or a perfluoroether rubber prepared by the preparation method according to any one of claims 6-8, characterized in that, Used for sealing; Alternatively, it can be used in semiconductor manufacturing, integrated circuit manufacturing, aerospace, new energy manufacturing, and biopharmaceuticals.

10. The application according to claim 9, characterized in that, Use in ambient temperatures above 300℃.

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