Preparation method of fluororubber sealing ring for semiconductor resistant to aging and cracking

Abstract

The present invention relates to the field of sealing rings, and specifically to a preparation method of a fluororubber sealing ring for semiconductors that is resistant to aging and cracking. The present invention uses fluororubber, high-temperature-resistant perfluoroether rubber, carbon black N990, carbon black N330, metal oxides, and vulcanizing agents, mixes them, preforms, vulcanizes for the first time, vulcanizes for the second time, trims the edges, polishes, cleans thoroughly, and packages in a dust-free environment to prepare a fluororubber sealing ring for semiconductors that is resistant to aging and cracking. Carbon black N990 and carbon black N330 are used in combination, which can significantly improve the hardness, strength, and brightness processing performance of perfluoroether rubber and enhance the compression set resistance of the fluororubber sealing ring. The fluororubber sealing ring for semiconductors prepared by the present invention has good physical properties, high-temperature resistance, and aging and cracking resistance, and also shows remarkable effects during actual use. The fluororubber sealing ring for semiconductors prepared by the present invention has almost no cracks on the surface and has good comprehensive performance.

Description

Technical Field

[0001] The present invention relates to the field of sealing rings, in particular to a preparation method of a fluororubber sealing ring for semiconductors with resistance to aging and cracking. Background Art

[0002] The semiconductor process flow is long, involving a variety of chemicals and media, and the use environment is complex and changeable, which puts forward new requirements for the performance of seals. For example, the tolerance to plasma is a typical one. At the same time, there is no universal sealing standard for seals in the semiconductor industry because each semiconductor manufacturer adopts different process conditions. Even FFKM seals cannot have a single formula applicable to all working conditions.

[0003] The selection of the sealing ring material is of great significance to its sealing performance and service life, and the performance of the material directly affects the use performance of the sealing ring. The high-temperature resistance of fluororubber is the same as that of silicone rubber, and it can be said to be the best among current elastomers.

[0004] Chinese Patent CN202111131287.8 discloses a high-temperature resistant silicone rubber sealing ring and its preparation method. The high-temperature resistant silicone rubber sealing ring includes the following raw materials in parts by mass: 93-98 parts of boric acid-polydimethylsiloxane rubber particles, 40-45 parts of reinforcing agent, 1.4-1.9 parts of vulcanizing agent, 1-6 parts of PEG-6000, and 3-8 parts of CeO2. In the technical solution of the present invention, first, hydroxyl-terminated polydimethylsiloxane rubber particles react with 3-(mercapto propyl) methyl dimethoxysilane to generate mercapto-polydimethylsiloxane rubber particles, and then the generated mercapto-polydimethylsiloxane rubber particles react with 4-vinylphenylboric acid to prepare boric acid-polydimethylsiloxane rubber particles, realizing a stable combination between polydimethylsiloxane rubber and boric acid. The synergistic effect between CeO2 and PEG-6000 can endow the silicone rubber with good high-temperature resistant friction stability.

[0005] Chinese Patent CN201810680857.0 discloses a preparation formula and process for a rubber sealing ring for a heat pump, relating to the technical field of rubber sealing ring preparation. The present invention includes the following raw materials in parts by weight: 53 parts of nitrile rubber, 10 parts of PVC masterbatch, 19 parts of carbon black 550, 7 parts of light calcium carbonate, 2.8 parts of titanium dioxide, 0.7 part of stearic acid, 2.5 parts of dibutyl phthalate, 1.2 parts of accelerator NS, 0.8 part of sulfur, 1 part of accelerator TMTD, 4 parts of magnesium oxide, 1.7 parts of antioxidant, 2 parts of pine tar, and 1.5 parts of 900-mesh carborundum. Weigh the raw materials according to the weight parts of each component, and carry out mixing, semi-finished product manufacturing, vulcanization, and repair and storage. By controlling the vulcanization temperature and ensuring a moderate temperature rise gradient, the present invention effectively avoids the phenomenon of under-vulcanization, has good sealing performance, allows a certain amount of eccentric load and eccentric movement, adjusts the mixing ratio of each component, effectively delays aging, and effectively improves the service performance of the sealing ring.

[0006] Chinese Patent CN202011117667.1 discloses a rubber sealing ring preparation process, including a housing. An acoustic rebound material is fixedly connected inside the housing. A protective shell is movably connected inside the acoustic rebound material. An oscillating block is fixedly connected to the inner wall of the protective shell. A top member mechanism is movably connected to the lower end of the oscillating block. A fixing ring is sleeved on the outer surface of the top member mechanism. A cam is rotatably connected to the lower end of the top member mechanism. A disc is fixedly connected to the rear end of the cam. A belt is movably connected to the outer surface of the disc. An endothermic ring is movably connected inside the belt. An airbag is movably connected inside the endothermic ring. Through the continuity of collisions, the generated sound waves are transmitted inside the acoustic rebound material, and at the same time, after rebounding from the acoustic rebound material, they are transmitted in another direction, so that the internal bubbles in the rubber ring are destroyed during molding, thus achieving the effect of making the internal structure compact.

[0007] Although the fluororubber sealing rings prepared according to the above patents and the prior art have certain heat aging resistance, their performance in actual use is uneven, and their comprehensive performance and processing performance are also slightly insufficient. Summary of the Invention

[0008] The purpose of the present invention is to overcome the deficiencies of the prior art and provide a preparation method for a fluororubber sealing ring for semiconductors with resistance to aging cracking. The operation steps are as follows:

[0009] S1: Turn on the mixer, set the temperature to 45 - 50 °C, add 70 - 80 parts of perfluoroether rubber into the internal mixer, knead for 1 - 2 min, then successively add 60 - 80 parts of heat-resistant ethylene propylene diene monomer rubber, 15 - 20 parts of carbon black N990, 15 - 20 parts of carbon black N330, 10 - 15 parts of metal oxide, 7 - 13 parts of plasticizer, 2.5 - 4 parts of vulcanizing agent, 8 - 12 parts of synergist, continue to knead for 5 - 6 min and then take out the rubber compound. Pass the compound through the two-roll mill multiple times for thin-sheeting and turning the compound over, make a triangle package, and after kneading evenly, place it at room temperature for 20 - 24 h;

[0010] S2: Conduct the first-stage vulcanization using a flat vulcanizer at a pressure of 120 - 150 Mpa to obtain a semi-finished product;

[0011] S3: After high-temperature secondary vulcanization, trim the edges, polish, clean and wash, and package in a dust-free environment to obtain a fluororubber seal ring for semiconductors with resistance to aging and cracking.

[0012] As a preference, the metal oxide is magnesium oxide or zinc oxide or calcium oxide.

[0013] As a preference, the plasticizer is paraffin oil or fluorinated wax or palm wax.

[0014] As a preference, the vulcanizing agent is one or a mixture of more than one of 2,5-dimethyl-2,5-di-tert-butylperoxyhexane or dicumyl peroxide or vulcanizing agent BOAP.

[0015] As a preference, the temperature of the first-stage vulcanization is 150 - 170 °C and the time is 10 - 15 min.

[0016] As a preference, the second-stage vulcanization is carried out in a vacuum oven, and the high-temperature secondary vulcanization temperature is 270 - 290 °C and the time is 10 - 24 h.

[0017] As a preference, the preparation method of the heat-resistant ethylene propylene diene monomer rubber is:

[0018] S1: Make 80 - 100 parts of ethylene propylene diene monomer rubber wrap around the two-roll mill, leaving a small amount of accumulated rubber;

[0019] S2: Gradually add 0.5 - 2 parts of stearic acid, 10 - 15 parts of white carbon black, and 2 - 5 parts of plasticizer;

[0020] S3: Then add another 10 - 15 parts of white carbon black and 2 - 5 parts of vulcanizing agent, and mix evenly until there is no residual powder;

[0021] S4: Cut the rubber on both sides 4 times each and then take off the sheet;

[0022] S5: Adjust the roll gap to the minimum and conduct thin-sheeting 5 times (3 times with triangle packages);

[0023] S6: Extrude the film, cool it, add 2 - 5 parts of metal oxide, 12 - 20 parts of calcium carbonate, 3 - 6 parts of dicumyl peroxide, 1 - 3 parts of imide - based compound, and 1 - 3 parts of antioxidant, then knead them evenly, and vulcanize on a flat vulcanizer to obtain a high - temperature - resistant ethylene - propylene - diene monomer rubber.

[0024] As a preference, the imide - based compound is m - phenylenebismaleimide or N,N'-m - phenylene bismaleimide.

[0025] As a preference, the antioxidant is antioxidant D or antioxidant RD or antioxidant NBC or antioxidant MB or antioxidant DNP or antioxidant 124.

[0026] As a preference, the preparation method of the synergist is as follows:

[0027] S1: By weight, in a three - necked flask equipped with a thermometer, an electric stirrer, and a spherical condenser, introduce nitrogen, add 4 - 10 parts of allyl - 3 - methylimidazolium bis(trifluoromethanesulfonyl)imide salt CAS: 655249 - 87 - 9, 36 - 50 parts of imide - based compound, 2 - 5 parts of anhydrous aluminum trichloride, and 200 - 300 parts of DMF. Under vigorous stirring, raise the temperature to 120 - 140 °C and react for 30 - 100 minutes.

[0028] S2: Add 0.5 - 5 parts of diallyl isocyanurate, continue to react for 50 - 120 minutes, stop the reaction, remove DMF by vacuum distillation, pour out and cool quickly to obtain the synergist.

[0029] Reaction mechanism:

[0030] The allyl - 3 - methylimidazolium bis(trifluoromethanesulfonyl)imide salt and the imide - based compound undergo an Alder - ene addition reaction, and the diallyl isocyanurate and the excess imide - based compound undergo an Alder - ene addition reaction. The obtained synergist contains bis(trifluoromethanesulfonyl)imide functional groups and cyano groups, as well as a bismaleimide structure, which can improve the high - temperature resistance and aging - cracking resistance performance of the sealing ring.

[0031] Technical effects:

[0032] The preparation method of an aging - cracking - resistant fluororubber sealing ring for semiconductors of the present invention, compared with the prior art, has the following remarkable effects:

[0033] 1. Using carbon black N990 and carbon black N330 together can significantly improve the hardness, strength, and brightness processing performance of perfluoroether rubber, and improve the compression set of the aging - cracking - resistant fluororubber sealing ring for semiconductors.

[0034] 2. The fluororubber sealing ring for semiconductor with anti-aging and cracking prepared by the present invention has good physical properties, high temperature resistance, anti-aging and cracking resistance, and also has remarkable effects in actual use;

[0035] 3. The fluororubber sealing ring for semiconductor with anti-aging and cracking prepared by the present invention has almost no cracks on the surface and has good comprehensive properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] Figure 1 It is a fluororubber sealing ring for semiconductor with anti-aging and cracking. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0037] The present invention will be further described below through specific embodiments:

[0038] The exemplary embodiments disclosed by the present invention will be described in more detail below with reference to the drawings. These embodiments are for a more thorough understanding of the present invention and for completely communicating the scope of the present invention to those skilled in the art. Although the exemplary embodiments disclosed by the present invention are shown in the drawings, it should be understood that the present invention should not be limited by the embodiments described herein.

[0039] The Shore A hardness is tested according to GB / T 531.1-2008 "Rubber, vulcanized or thermoplastic - Determination of indentation hardness - Part 1: Durometer method (Shore hardness)". The tensile properties are tested according to GB / T 528-2009 "Rubber, vulcanized or thermoplastic - Determination of tensile stress-strain properties". The heat aging resistance in air is tested according to GB / T 3512-2001 "Rubber, vulcanized or thermoplastic - Accelerated aging and heat resistance tests in air". The test method for anti-aging and cracking resistance is as follows: The vulcanized rubber specimen (5 cm × 1 cm × 2 mm) is aged in a high-temperature aging oven. After aging, the specimen is placed at room temperature for more than 2 h, and then pasted on a cylinder with the same diameter and bent into the same arc, and the number and size of cracks on the surface of the specimen are observed and compared.

[0040] Example 1

[0041] A preparation method of a fluororubber sealing ring for semiconductor with anti-aging and cracking, and its operation steps are as follows:

[0042] S1: Turn on the mixer, set the temperature to 45 °C, add 70 g of perfluoroether rubber into the internal mixer, mix for 1 min, and then add 60 g of high-temperature resistant ethylene propylene diene monomer rubber, 15 g of carbon black N990, 15 g of carbon black N330, 10 g of metal oxide, 7 g of plasticizer, 2.5 g of vulcanizing agent, and 8 g of synergist in sequence. Continue to mix for 5 min and then take out the rubber compound. Pass the rubber compound through the two-roll mill for multiple thin passes and turn it over, make a triangular package, and after mixing evenly, place it at room temperature for 20 h;

[0043] S2: Perform the first-stage vulcanization using a flat vulcanizer at a pressure of 120 Mpa to obtain semi-finished products;

[0044] S3: After high-temperature secondary vulcanization, trim the edges, polish, clean and wash, and package in a dust-free environment to obtain a fluororubber seal ring for semiconductors that resists aging and cracking.

[0045] The metal oxide mentioned above is magnesium oxide.

[0046] The plasticizer mentioned above is paraffin oil.

[0047] The vulcanizing agent mentioned above is 2,5-dimethyl-2,5-di-tert-butylperoxyhexane.

[0048] The temperature of the first-stage vulcanization is 150 °C and the time is 10 min.

[0049] The second-stage vulcanization is carried out in a vacuum oven. The high-temperature secondary vulcanization temperature is 270 °C and the time is 10 h.

[0050] The preparation method of the high-temperature resistant ethylene propylene diene monomer rubber is as follows:

[0051] S1: On an open mill, make 80 g of ethylene propylene diene monomer rubber wrap around the roll, leaving a small amount of accumulated rubber;

[0052] S2: Gradually add 0.5 g of stearic acid, 10 g of white carbon black, and 2 g of plasticizer;

[0053] S3: Then add another 10 g of white carbon black and 2 g of vulcanizing agent, and mix them evenly until there is no residual powder;

[0054] S4: Cut left and right 4 times each and then take off the sheet;

[0055] S5: Adjust the roll gap to the minimum and thin-pass 5 times (3 times with triangular wrapping);

[0056] S6: Take out the sheet, cool it, add 2 g of metal oxide, 12 g of calcium carbonate, 3 g of diisopropylbenzene peroxide, 1 g of imide-based compound, and 1 g of antioxidant, and mix them evenly. Vulcanize on a flat vulcanizer to obtain high-temperature resistant ethylene propylene diene monomer rubber.

[0057] The imide-based compound mentioned above is m-phenylene bismaleimide.

[0058] The antioxidant mentioned above is antioxidant D.

[0059] The preparation method of the synergist is as follows:

[0060] S1: In a three-necked flask equipped with a thermometer, an electric stirrer, and a spherical condenser, nitrogen is introduced, and 4 g of allyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide salt CAS: 655249-87-9, 36 g of imide-based compound, 2 g of anhydrous aluminum trichloride, and 200 g of DMF are added. Under vigorous stirring, the temperature is raised to 120 °C and the reaction is carried out for 30 minutes;

[0061] S2: Add 0.5 g of diallyl isocyanurate, continue the reaction for 50 minutes, stop the reaction, distill off DMF under reduced pressure, pour out and quickly cool to obtain a synergist.

[0062] Example 2

[0063] A preparation method of a fluororubber sealing ring for semiconductor resistant to aging and cracking, the operation steps are as follows:

[0064] S1: Turn on the mixer, set the temperature to 45 °C, add 74 g of perfluoroether rubber to the internal mixer, mix for 1 min, and then sequentially add 65 g of high-temperature ethylene propylene diene monomer rubber, 16 g of carbon black N990, 16 g of carbon black N330, 12 g of metal oxide, 9 g of plasticizer, 3 g of vulcanizing agent, 9 g of synergist, continue mixing until 5 min, then take out the rubber compound, pass it through the open mill multiple times for thin passing and turning the rubber, make a triangular package, and after mixing evenly, place it at room temperature for 21 h;

[0065] S2: Carry out primary vulcanization using a flat vulcanizer, with a pressure of 130 Mpa, to obtain a semi-finished product;

[0066] S3: After high-temperature secondary vulcanization, trim, polish, clean and wash, and package in a dust-free environment to obtain a fluororubber sealing ring for semiconductor resistant to aging and cracking.

[0067] The metal oxide described is zinc oxide.

[0068] The plasticizer described is fluorinated wax.

[0069] The vulcanizing agent described is dicumyl peroxide.

[0070] The temperature of the primary vulcanization described is 155 °C and the time is 12 min.

[0071] The secondary vulcanization is carried out in a vacuum oven, and the high-temperature secondary vulcanization temperature is 275 °C and the time is 15 h.

[0072] The preparation method of the high-temperature ethylene propylene diene monomer rubber is as follows:

[0073] S1: On the open mill, make 85 g of ethylene propylene diene monomer rubber wrap the roll, leaving a small amount of accumulated rubber;

[0074] S2: Gradually add 1 g of stearic acid, 12 g of white carbon black, and 3 g of plasticizer;

[0075] S3: Then add 12 g of silica and 3 g of vulcanizing agent, and mix them evenly until there is no residual powder.

[0076] S4: Cut the sheet 4 times on each side and then take off the sheet.

[0077] S5: Adjust the roll gap to the minimum and thin pass 5 times (3 times with triangular wrapping).

[0078] S6: Take out the sheet, cool it, add 3 g of metal oxide, 14 g of calcium carbonate, 4 g of dicumyl peroxide, 2 g of imide-based compound, and 2 g of antioxidant, and knead them evenly. Vulcanize on a flat vulcanizer to obtain heat-resistant ethylene propylene diene monomer rubber.

[0079] The imide-based compound is m-phenylene bismaleimide.

[0080] The antioxidant is antioxidant RD.

[0081] The preparation method of the synergist is as follows:

[0082] S1: In a three-necked flask equipped with a thermometer, an electric stirrer, and a spherical condenser, introduce nitrogen, add 6 g of allyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide salt CAS: 655249-87-9, 40 g of imide-based compound, 3 g of anhydrous aluminum trichloride, and 240 g of DMF. Under vigorous stirring, raise the temperature to 125 °C and react for 60 minutes.

[0083] S2: Add 2 g of diallyl isocyanurate, continue to react for 70 minutes, stop the reaction, remove DMF by vacuum distillation, pour out and cool quickly to obtain the synergist.

[0084] Example 3

[0085] A preparation method of an aging-resistant and crack-resistant fluororubber seal ring for semiconductors, the operation steps of which are as follows:

[0086] S1: Turn on the mixer, set the temperature to 50 °C, add 78 g of perfluoroether rubber to the internal mixer, knead for 2 min, then sequentially add 75 g of heat-resistant ethylene propylene diene monomer rubber, 18 g of carbon black N990, 18 g of carbon black N330, 14 g of metal oxide, 11 g of plasticizer, 3.5 g of vulcanizing agent, and 11 g of synergist, continue to knead for 6 min and then take out the rubber compound. Thin pass and turn the rubber on the open mill multiple times, make triangular wrapping, knead evenly, and place it at room temperature for 23 h.

[0087] S2: Conduct first-stage vulcanization using a flat vulcanizer at a pressure of 140 Mpa to obtain a semi-finished product.

[0088] S3: After secondary vulcanization at high temperature, trim the edges, polish, clean and wash, and package in a dust-free environment to obtain a fluororubber seal ring for semiconductors that is resistant to aging and cracking.

[0089] The metal oxide mentioned above is zinc oxide.

[0090] The plasticizer mentioned above is fluorowax.

[0091] The vulcanizing agent mentioned above is dicumyl peroxide.

[0092] The temperature for the first-stage vulcanization is 165 °C and the time is 14 min.

[0093] The second-stage vulcanization is carried out in a vacuum oven. The high-temperature secondary vulcanization temperature is 285 °C and the time is 20 h.

[0094] The preparation method of the high-temperature resistant ethylene propylene diene monomer rubber is as follows:

[0095] S1: On an open mill, make 95 g of ethylene propylene diene monomer rubber wrap around the roll, leaving a small amount of accumulated rubber.

[0096] S2: Gradually add 1.5 g of stearic acid, 14 g of white carbon black, and 4 g of plasticizer.

[0097] S3: Add another 14 g of white carbon black and 4 g of vulcanizing agent, and mix them evenly until there is no residual powder.

[0098] S4: Cut left and right 4 times each and then take off the sheet.

[0099] S5: Adjust the roll gap to the minimum and thin pass 5 times (3 times with triangular wrapping).

[0100] S6: Take out the sheet, cool it, add 4 g of metal oxide, 18 g of calcium carbonate, 5 g of dicumyl peroxide, 2 g of imide-based compound, and 2 g of antioxidant, and mix them evenly by remilling. Vulcanize on a flat vulcanizer to obtain high-temperature resistant ethylene propylene diene monomer rubber.

[0101] The imide-based compound mentioned above is N, N'-m-phenylene bismaleimide.

[0102] The antioxidant mentioned above is antioxidant NBC.

[0103] The preparation method of the synergist is as follows:

[0104] S1: In a three-necked flask equipped with a thermometer, an electric stirrer, and a spherical condenser, introduce nitrogen, add 8 g of allyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide CAS: 655249-87-9, 45 g of imide-based compound, 4 g of anhydrous aluminum trichloride, and 280 g of DMF. Under vigorous stirring, raise the temperature to 135 °C and react for 90 minutes.

[0105] S2: Add 4 g of diallyl isocyanurate, continue the reaction for 90 minutes, stop the reaction, remove DMF by vacuum distillation, pour out and quickly cool to obtain the synergist.

[0106] Example 4

[0107] A preparation method of a fluororubber sealing ring for semiconductors resistant to aging and cracking, the operation steps of which are as follows:

[0108] S1: Turn on the mixer, set the temperature to 50 °C, add 80 g of perfluoroether rubber to the internal mixer, knead for 2 min, then sequentially add 80 g of high-temperature ethylene propylene diene monomer rubber, 20 g of carbon black N990, 20 g of carbon black N330, 15 g of metal oxide, 13 g of plasticizer, 4 g of vulcanizing agent, and 12 g of synergist, continue kneading until 6 min, then take out the rubber compound, pass it through the open mill multiple times for thin passing and turning the rubber, make a triangle package, after kneading evenly, place it at room temperature for 24 h;

[0109] S2: Conduct first-stage vulcanization using a flat vulcanizer under a pressure of 150 Mpa to obtain a semi-finished product;

[0110] S3: After high-temperature secondary vulcanization, trim the edges, polish, clean and wash, and package in a dust-free environment to obtain a fluororubber sealing ring for semiconductors resistant to aging and cracking.

[0111] The metal oxide described is calcium oxide.

[0112] The plasticizer described is palm wax.

[0113] The vulcanizing agent described is vulcanizing agent BOAP.

[0114] The temperature of the first-stage vulcanization is 170 °C and the time is 15 min.

[0115] The second-stage vulcanization is carried out in a vacuum oven, the high-temperature secondary vulcanization temperature is 290 °C and the time is 24 h.

[0116] The preparation method of the high-temperature ethylene propylene diene monomer rubber is as follows:

[0117] S1: Make 100 g of ethylene propylene diene monomer rubber wrap the roll on the open mill, leaving a small amount of accumulated rubber;

[0118] S2: Gradually add 2 g of stearic acid, 15 g of white carbon black, and 5 g of plasticizer;

[0119] S3: Add another 15 g of white carbon black and 5 g of vulcanizing agent, and mix them evenly until there is no remaining powder;

[0120] S4: Cut the knife left and right 4 times each and then take off the sheet;

[0121] S5: Adjust the roll gap to the minimum and conduct thin passing 5 times (including 3 times of making a triangle package);

[0122] S6: Sheet out, cool down, add 5 g of metal oxide, 20 g of calcium carbonate, 6 g of dicumyl peroxide, 3 g of imide-based compound, and 3 g of antioxidant, and knead them evenly. Vulcanize on a flat vulcanizer to obtain high-temperature resistant ethylene propylene diene monomer rubber.

[0123] The imide-based compound is N,N'-m-phenylene bismaleimide.

[0124] The antioxidant is antioxidant 124.

[0125] The preparation method of the synergist is as follows:

[0126] S1: In a three-necked flask equipped with a thermometer, an electric stirrer, and a spherical condenser, introduce nitrogen, add 10 g of allyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide salt CAS: 655249-87-9, 50 g of imide-based compound, 5 g of anhydrous aluminum trichloride, and 300 g of DMF. Under vigorous stirring, raise the temperature to 140 °C and react for 100 minutes;

[0127] S2: Add 5 g of diallyl isocyanurate, continue to react for 120 minutes, stop the reaction, distill off DMF under reduced pressure, pour out and quickly cool to obtain the synergist.

[0128] Comparative Example 1

[0129] A preparation method of an aging-resistant and crack-resistant fluororubber sealing ring for semiconductors, the operating steps are as follows:

[0130] S1: Turn on the mixer, set the temperature to 45 °C, add 70 g of perfluoroether rubber to the internal mixer, knead for 1 min, then sequentially add 60 g of high-temperature resistant ethylene propylene diene monomer rubber, 15 g of carbon black N990, 15 g of carbon black N330, 10 g of metal oxide, 7 g of plasticizer, and 2.5 g of vulcanizing agent, continue to knead for 5 min and then take out the rubber compound, pass and turn the rubber compound thinly on the open mill for multiple times, make a triangle package, knead evenly, and place it at room temperature for 20 h;

[0131] S2: Conduct first-stage vulcanization using a flat vulcanizer at a pressure of 120 Mpa to obtain a semi-finished product;

[0132] S3: After high-temperature secondary vulcanization, trim the edges, polish, clean and wash, and package in a dust-free environment to obtain an aging-resistant and crack-resistant fluororubber sealing ring for semiconductors.

[0133] The metal oxide is magnesium oxide.

[0134] The plasticizer is paraffin oil.

[0135] The vulcanizing agent is 2,5-dimethyl-2,5-di-tert-butylperoxyhexane.

[0136] The vulcanization temperature for the first stage is 150 °C and the time is 10 min.

[0137] The second-stage vulcanization is carried out in a vacuum oven. The high-temperature secondary vulcanization temperature is 270 °C and the time is 10 h.

[0138] The preparation method of the high-temperature resistant ethylene propylene diene monomer rubber is as follows:

[0139] S1: Make 80 g of ethylene propylene diene monomer rubber wrap around the rolls on the open mill, leaving a small amount of accumulated rubber.

[0140] S2: Gradually add 0.5 g of stearic acid, 10 g of white carbon black, and 2 g of plasticizer.

[0141] S3: Add another 10 g of white carbon black and 2 g of vulcanizing agent, and mix them evenly until there is no residual powder.

[0142] S4: Cut the rubber on both sides 4 times each and then take off the sheet.

[0143] S5: Adjust the roll gap to the minimum and thin pass 5 times (3 times with triangular wrapping).

[0144] S6: Take out the sheet, cool it, add 2 g of metal oxide, 12 g of calcium carbonate, 3 g of dicumyl peroxide, 1 g of imide-based compound, and 1 g of antioxidant, and knead them evenly. Vulcanize on a flat vulcanizer to obtain the high-temperature resistant ethylene propylene diene monomer rubber.

[0145] The imide-based compound is m-phenylene bismaleimide.

[0146] The antioxidant is antioxidant D.

[0147] Comparative Example 2

[0148] A preparation method of a fluororubber sealing ring for semiconductor with anti-aging and anti-cracking properties, and its operation steps are as follows:

[0149] S1: Turn on the internal mixer, set the temperature to 45 °C, add 70 g of perfluoroether rubber into the internal mixer, knead for 1 min, and then sequentially add 60 g of high-temperature resistant ethylene propylene diene monomer rubber, 15 g of carbon black N990, 15 g of carbon black N330, 10 g of metal oxide, 7 g of plasticizer, 2.5 g of vulcanizing agent, and 8 g of synergist. Continue to knead for 5 min and then take out the rubber compound. Conduct multiple thin passes and turn the rubber on the open mill, make triangular wrapping, and knead evenly. Then place it at room temperature for 20 h.

[0150] S2: Conduct the first-stage vulcanization using a flat vulcanizer with a pressure of 120 Mpa to obtain a semi-finished product.

[0151] S3: After secondary vulcanization at high temperature, trim the edges, polish, clean and wash, and package in a dust-free environment to obtain a fluororubber seal ring for semiconductors that is resistant to aging and cracking.

[0152] The metal oxide described above is magnesium oxide.

[0153] The plasticizer described above is paraffin oil.

[0154] The vulcanizing agent described above is 2,5-dimethyl-2,5-di-tert-butylperoxyhexane.

[0155] The temperature for the first-stage vulcanization is 150 °C and the time is 10 min.

[0156] The second-stage vulcanization is carried out in a vacuum oven. The high-temperature secondary vulcanization temperature is 270 °C and the time is 10 h.

[0157] The preparation method of the high-temperature resistant ethylene propylene diene monomer rubber is as follows:

[0158] S1: On an open mill, make 80 g of ethylene propylene diene monomer rubber wrap around the roll, leaving a small amount of accumulated rubber.

[0159] S2: Gradually add 0.5 g of stearic acid, 10 g of white carbon black, and 2 g of plasticizer.

[0160] S3: Add another 10 g of white carbon black and 2 g of vulcanizing agent, and mix them evenly until there is no remaining powder.

[0161] S4: Cut the rubber sheet 4 times on each side and then take off the sheet.

[0162] S5: Adjust the roll gap to the minimum and thin-pass 5 times (3 times with triangular wrapping).

[0163] S6: Take out the sheet, cool it, add 2 g of metal oxide, 12 g of calcium carbonate, 3 g of diisopropylbenzene peroxide, 1 g of imide-based compound, and 1 g of antioxidant, and knead them evenly. Vulcanize on a flat vulcanizer to obtain high-temperature resistant ethylene propylene diene monomer rubber.

[0164] The imide-based compound described above is m-phenylene bismaleimide.

[0165] The antioxidant described above is antioxidant D.

[0166] The preparation method of the synergist is as follows:

[0167] S1: In a three-necked flask equipped with a thermometer, an electric stirrer, and a spherical condenser, introduce nitrogen, add 36 g of imide-based compound, 2 g of anhydrous aluminum trichloride, and 200 g of DMF. Under vigorous stirring, raise the temperature to 120 °C and react for 30 minutes.

[0168] S2: Add 0.5 g of diallyl isocyanurate, continue the reaction for 50 minutes, stop the reaction, remove DMF by vacuum distillation, pour out and quickly cool to obtain the synergist.

[0169] Comparative Example 3

[0170] A preparation method of a fluororubber sealing ring for semiconductor with aging and cracking resistance, the operation steps are as follows:

[0171] S1: Turn on the mixer, set the temperature to 45 °C, add 70 g of perfluoroether rubber into the internal mixer, mix for 1 min, then sequentially add 60 g of high-temperature ethylene propylene diene monomer rubber, 15 g of carbon black N990, 15 g of carbon black N330, 10 g of metal oxide, 7 g of plasticizer, 2.5 g of vulcanizing agent, 8 g of synergist, continue to mix for 5 min and then take out the rubber compound, pass and turn the rubber compound thinly on the open mill for multiple times, make a triangle package, after mixing evenly, place it at room temperature for 20 h;

[0172] S2: Conduct first-stage vulcanization using a flat vulcanizer, with a pressure of 120 Mpa, to obtain a semi-finished product;

[0173] S3: After high-temperature secondary vulcanization, trim, polish, clean and wash, and package in a dust-free environment to obtain a fluororubber sealing ring for semiconductor with aging and cracking resistance. The metal oxide is magnesium oxide.

[0174] The plasticizer is paraffin oil.

[0175] The vulcanizing agent is 2,5-dimethyl-2,5-di-tert-butylperoxyhexane.

[0176] The temperature of the first-stage vulcanization is 150 °C and the time is 10 min.

[0177] The second-stage vulcanization is carried out in a vacuum oven, and the high-temperature secondary vulcanization temperature is 270 °C and the time is 10 h.

[0178] The preparation method of the high-temperature ethylene propylene diene monomer rubber is as follows:

[0179] S1: Make 80 g of ethylene propylene diene monomer rubber wrap the roll on the open mill, leaving a small amount of accumulated rubber;

[0180] S2: Gradually add 0.5 g of stearic acid, 10 g of white carbon black, and 2 g of plasticizer;

[0181] S3: Add another 10 g of white carbon black and 2 g of vulcanizing agent, and mix evenly until there is no residual powder;

[0182] S4: Cut the knife left and right 4 times each and then take off the sheet;

[0183] S5: Adjust the roll gap to the minimum and pass thinly 5 times (3 times with a triangle package);

[0184] S6: Sheet out, cool down, add 2 g of metal oxide, 12 g of calcium carbonate, 3 g of dicumyl peroxide, 1 g of imide-based compound, and 1 g of antioxidant, and knead evenly. Vulcanize on a flat vulcanizer to obtain high-temperature resistant ethylene-propylene-diene monomer (EPDM) rubber.

[0185] The imide-based compound is m-phenylene bismaleimide.

[0186] The antioxidant is antioxidant D.

[0187] The preparation method of the synergist is as follows:

[0188] S1: In a three-necked flask equipped with a thermometer, an electric stirrer, and a spherical condenser, introduce nitrogen, add 4 g of allyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide salt CAS: 655249-87-9, 36 g of imide-based compound, 2 g of anhydrous aluminum trichloride, and 200 g of DMF. Under vigorous stirring, raise the temperature to 120 °C and react for 30 minutes.

[0189] S2: Stop the reaction, remove DMF by vacuum distillation, pour out and cool quickly to obtain the synergist.

[0190]

[0191] Although the above embodiments have been described, once those skilled in the art learn the basic creative concept, they can make additional changes and modifications to these embodiments. Therefore, the above are only the embodiments of the present invention, and do not limit the patent protection scope of the present invention. Any equivalent structural or equivalent process transformation made by using the content of the specification and drawings of the present invention, or directly or indirectly applied in other related technical fields, shall be equally included in the patent protection scope of the present invention.

Claims

1. Preparation method of fluororubber sealing ring for semiconductor resistant to aging and cracking, and its operation steps are as follows: S1: Turn on the mixer, set the temperature to 45 - 50 °C, add 70 - 80 parts of perfluoroether rubber into the internal mixer, mix for 1 - 2 min, then successively add 60 - 80 parts of high-temperature ethylene propylene diene monomer rubber, 15 - 20 parts of carbon black N990, 15 - 20 parts of carbon black N330, 10 - 15 parts of metal oxide, 7 - 13 parts of plasticizer, 2.5 - 4 parts of vulcanizing agent, 8 - 12 parts of synergist, continue to mix for 5 - 6 min and then take out the rubber compound. Perform multiple thin passes and turnovers on the open mill, make a triangle wrap, and after mixing evenly, place it at room temperature for 20 - 24 h; S2: Conduct first-stage vulcanization using a flat vulcanizer, with a pressure of 120 - 150 Mpa, to obtain a semi-finished product; S3: After high-temperature secondary vulcanization, trim the edges, polish, clean and wash, and package in a dust-free environment to obtain a fluororubber sealing ring for semiconductor resistant to aging and cracking; The preparation method of the synergist is as follows: S1: By weight, in a three-necked flask equipped with a thermometer, an electric stirrer, and a spherical condenser, introduce nitrogen, add 4 - 10 parts of allyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide CAS: 655249-87-9 and 36 - 50 parts of imide-based compound, 2 - 5 parts of anhydrous aluminum trichloride, 200 - 300 parts of DMF. Under vigorous stirring, raise the temperature to 120 - 140 °C and react for 30 - 100 minutes; S2: Add 0.5 - 5 parts of diallyl isocyanurate, continue to react for 50 - 120 minutes, stop the reaction, distill off DMF under reduced pressure, pour out and quickly cool to obtain the synergist.

2. The preparation method of a fluororubber sealing ring for semiconductor with anti-aging cracking according to claim 1, characterized in that: The metal oxide is magnesium oxide or zinc oxide or calcium oxide.

3. The preparation method of a fluororubber sealing ring for semiconductor with aging and cracking resistance according to claim 1, characterized in that: The vulcanizing agent is one or more of 2,5-dimethyl-2,5-di-tert-butylperoxyhexane or dicumyl peroxide or vulcanizing agent BOAP.

4. The preparation method of a fluororubber sealing ring for semiconductor with anti-aging cracking according to claim 1, characterized in that:

5. The preparation method of a fluororubber sealing ring for semiconductor with aging and cracking resistance according to claim 1, characterized in that: The temperature of the first-stage vulcanization is 150 - 170 °C and the time is 10 - 15 min.

6. The preparation method of a fluororubber sealing ring for semiconductor resistant to aging and cracking according to claim 1, characterized in that: The second-stage vulcanization is carried out in a vacuum oven, and the high-temperature secondary vulcanization temperature is 270 - 290 °C and the time is 10 - 24 h. The preparation method of the high-temperature ethylene propylene diene monomer rubber is as follows: S1: On the open mill, make 80 - 100 parts of ethylene propylene diene monomer rubber wrap the roll, leaving a small amount of accumulated rubber; 7. The preparation method of a fluororubber sealing ring for semiconductor with anti-aging and cracking resistance according to claim 6, characterized in that: S2: Gradually add 0.5 - 2 parts of stearic acid, 10 - 15 parts of white carbon black, and 2 - 5 parts of plasticizer; S3: Then add another 10 - 15 parts of white carbon black and 2 - 5 parts of vulcanizing agent, and mix evenly until there is no residual powder; S4: Cut the knife left and right 4 times each and then take off the sheet; S5: Adjust the roll gap to the minimum and perform 5 thin passes (3 times with a triangle wrap); S6: Take out the sheet, cool it, add 2 - 5 parts of metal oxide, 12 - 20 parts of calcium carbonate, 3 - 6 parts of dicumyl peroxide, 1 - 3 parts of imide-based compound, and 1 - 3 parts of antioxidant, and mix and knead evenly. Vulcanize on a flat vulcanizer to obtain high-temperature ethylene propylene diene monomer rubber. The imide-based compound is m-phenylene bismaleimide or N,N''-m-phenylene bismaleimide.

8. The preparation method of a fluororubber sealing ring for semiconductor resistant to aging and cracking according to claim 7, characterized in that: The antioxidant mentioned above is antioxidant D, antioxidant RD, antioxidant NBC, antioxidant MB, antioxidant DNP or antioxidant 124.

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