A fluororubber composite material containing fiber and its preparation method and application

Abstract

The present invention relates to the technical field of fiber and rubber composite materials, and belongs to the technical field of CO8L, and specifically relates to a fluororubber composite material containing fiber, and a preparation method and application thereof. A fluororubber composite material containing fiber, the components of which include 80-120 parts of fluororubber raw rubber, 0.1-0.9 parts of fiber, 0.1-2 parts of a crosslinking agent, and 0.5-6 parts of a crosslinking aid, by weight. In the present invention, by limiting the type and amount of raw materials used, the mechanical strength and high temperature resistance of the fluororubber composite material containing fiber can be improved.

Description

Technical Field

[0001] The invention relates to the technical field of fiber and rubber composite materials, belonging to the technical field of CO8L, and specifically to a fluororubber composite material containing fibers and a preparation method thereof. Background Art

[0002] Fluorine-containing rubber has excellent elasticity, thermal stability and chemical stability. The long-term working temperature can be maintained in the range of -39-288℃, and the short-term use temperature limit can reach 315℃. It is generally used in harsh working environments. Fibers containing aromatic ring structures have high heat resistance. The heat resistance temperature of poly(p-phenylene benzobisoxazole) fiber reaches 600℃, the limiting oxygen index is 68, and the heat resistance and flame retardancy are higher than other organic fibers.

[0003] The current Chinese patent application number CN202210539408.0 discloses a PBO composite material, its preparation method and application. Lubricants are used in combination with PBO fibers to improve the interface properties between resin and PBO fibers, and to improve the temperature resistance grade and mechanical properties of the PBO composite material. However, when fibers containing aromatic ring structures are added to fluororubber, the interface bonding between the fibers and fluororubber, high temperature resistance and the stability of mechanical properties at high temperatures must be considered.

[0004] Therefore, providing a fiber-containing fluororubber composite material that has excellent interface bonding performance and stable mechanical properties at high temperatures is the main technical problem that needs to be solved at present. Summary of the invention

[0005] In order to solve the above problems, the first aspect of the present invention provides a fiber-containing fluororubber composite material, which comprises 80-120 parts of fluororubber raw rubber, 0.1-0.9 parts of fiber, 0.1-2 parts of crosslinking agent, and 0.5-6 parts of auxiliary crosslinking agent by weight.

[0006] Preferably, the fluorine-containing rubber raw rubber is selected from one or more of perfluoroether rubber, tetrafluoropropylene rubber, perfluoroether rubber, and fluorinated phosphazene rubber.

[0007] Preferably, the fluorine-containing rubber raw rubber is preferably tetrapropylene fluorine rubber.

[0008] Preferably, the fibers are surface modified fibers.

[0009] Furthermore, the surface modification method of the surface modified fiber comprises the following steps:

[0010] S1. The fiber was reflux extracted with acetone for 10-20 hours, washed with a large amount of deionized water, and dried at 110-130°C for 1-3 hours;

[0011] S2. Soak the fiber in a methanesulfonic acid solution at 55-65°C for 0.5-2h, then wash the fiber with deionized water, and then dry it in a vacuum oven at 110°C for 1-3h to obtain a pretreated fiber;

[0012] S3. The pretreated fiber was added to anhydrous ethanol solvent and ultrasonically dispersed at 25°C for 10-60min using a 300w ultrasonic cleaner to obtain a uniform suspension;

[0013] S4. Add the anti-fatigue additive to the suspension and mix by ultrasonic for 5-20 min;

[0014] S5. Raise the temperature of the ultrasonic cleaner to 80°C and allow the pretreated fiber to react at a constant temperature for 1-3 hours;

[0015] S6. Place the pretreated fiber in a vacuum drying oven at 105-115°C and dry for 1-3 hours to obtain surface-modified fiber.

[0016] In order to overcome the problem of anti-fatigue additives sticking to the roller during the addition process, the inventor accidentally discovered during the experiment that by surface treating the fiber surface, adding the anti-fatigue additive during the treatment process, and introducing the anti-fatigue additive to the surface of the fiber, it is possible to overcome the problem that when the anti-fatigue additive is used alone, it will stick to the roller of the mixing mill during the mixing process, resulting in the problem that the roller of the mixing mill is difficult to clean, reducing production efficiency and increasing equipment maintenance costs; and through the fiber surface modification treatment method defined in the present application, the physical and mechanical properties of the fluororubber composite material containing the fiber can be improved, the problem of anti-fatigue additives sticking to the roller during the addition process can be overcome, and the scope of use of the anti-fatigue additive can be further expanded.

[0017] Furthermore, the surface modification method of the surface modified fiber comprises the following steps:

[0018] S1. By weight, 5 parts of poly(p-phenylene benzobisoxazole) fibers were extracted by reflux with 100 parts of acetone for 12 hours, the poly(p-phenylene benzobisoxazole) fibers were taken out and washed with a large amount of deionized water, and then dried at 120°C for 2 hours;

[0019] S2. 80 parts of a 60 wt % methanesulfonic acid aqueous solution were used to soak the poly(p-phenylene benzobisoxazole) fiber at 60 ° C for 1 h, and then the fiber was fully washed with deionized water, and then dried in a vacuum oven at 110 ° C for 2 h to obtain a pretreated fiber;

[0020] S3. The pretreated fiber was added to anhydrous ethanol solvent and ultrasonically dispersed at 25°C for 30 min using a 300w ultrasonic cleaner to obtain a uniform suspension;

[0021] S4. 0.5 parts of anti-fatigue additive was added to the suspension and ultrasonically mixed for 10 min;

[0022] S5. Raise the temperature of the ultrasonic cleaner to 80°C and allow the pretreated fiber to react at a constant temperature for 2 hours;

[0023] S6. Place the pretreated fiber in a vacuum drying oven at 110°C and dry for 2 hours to obtain surface-modified fiber.

[0024] Preferably, the anti-fatigue aid is a multifunctional maleimide compound.

[0025] Furthermore, the anti-fatigue additive can be purchased from Otsuka Materials Technology (Shanghai) Co., Ltd., model number PAPI.

[0026] In order to improve the interfacial bonding force between fiber and fluororubber raw rubber, improve the dispersion performance of fiber in fluororubber raw rubber, reduce the compression permanent deformation value of fluororubber composite material containing fiber, and provide sealing effect, the inventor accidentally found in the experiment that by surface modification of fiber, especially surface modification of poly(p-phenylene benzobisoxazole) fiber, adding PAPI during the surface treatment process, not only the interfacial bonding performance of poly(p-phenylene benzobisoxazole) fiber and fluororubber raw rubber can be enhanced, but also the dispersion performance of poly(p-phenylene benzobisoxazole) fiber in fluororubber raw rubber can be improved. The possible reason is that the two end groups of the multifunctional maleimide in PAPI are relatively active. In the fluororubber raw rubber, it can not only participate in cross-linking through the Alder-Ene reaction, but also form a weak fiber-alkyl bond with the surface of the poly(p-phenylene benzobisoxazole) fiber to play a coupling effect, so that the modified poly(p-phenylene benzobisoxazole) fiber has better bonding performance with the fluororubber raw rubber. At the same time, the multiple benzene ring structures contained in PAPI are conducive to the dispersion of the poly(p-phenylene benzobisoxazole) fiber and further improve the physical and mechanical properties of the fluororubber composite material containing the fiber.

[0027] Preferably, the fiber contains an aromatic ring structure.

[0028] Preferably, the fiber containing an aromatic ring structure includes one or both of poly(p-phenylene benzobisoxazole) fiber and aramid fiber.

[0029] Preferably, the fiber is in the form of one or more of long fiber, short fiber, pulp, and powder.

[0030] Preferably, the fibers are in the form of short fibers with a length of 1-4 mm.

[0031] Furthermore, the fiber is preferably in the form of short fibers with a length of 3 mm.

[0032] In order to improve the fiber-containing fluororubber composite materials so that they can be used at high temperatures and be suitable for use in the product technology fields of semiconductors, photovoltaics, and aerospace, the inventors found during the experiment that by using fibers containing aromatic ring structures, especially poly(p-phenylene benzobisoxazole) fibers and aramid fibers with a length of 1-4 mm, the requirements for long-term use of fiber-containing fluororubber composite materials at high temperatures can be improved, but the morphology of the fibers will affect the dispersibility in the fluororubber raw rubber. Fibers that are too short cannot improve the strength of the composite material and are easy to agglomerate in the rubber, which is not conducive to uniform dispersion in the fluororubber raw rubber. When the type of fiber is changed, especially when polytetrafluoroethylene fiber is used, the thermal decomposition temperature of the rubber material is not significantly improved. When carbon fibers are used, the prepared fiber-containing fluororubber composite material has a relatively large change rate in tensile strength after thermal aging, which affects the application of the fluororubber composite material in the product technology fields of semiconductors, photovoltaics, and aerospace.

[0033] Preferably, the mass ratio of the cross-linking agent to the auxiliary cross-linking agent is 1:(2-4).

[0034] Furthermore, the mass ratio of the cross-linking agent to the auxiliary cross-linking agent is 1:3.

[0035] Preferably, the crosslinking agent is selected from one or more of peroxide compounds, fluorinated alkyl compounds, and fluoroaralkyl phosphonates.

[0036] Furthermore, the peroxide compound is 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane.

[0037] Furthermore, the fluorine-containing alkyl compound is 2,2-bis(3-amino-4-hydroxyphenyl)-hexafluoropropane.

[0038] Furthermore, the cross-linking agent is preferably 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane.

[0039] Preferably, the auxiliary cross-linking agent is selected from one or both of triallyl isocyanurate and trimethallyl isocyanate.

[0040] Furthermore, the auxiliary cross-linking agent is preferably triallyl isocyanurate.

[0041] In order to improve the ability of poly(p-phenylene benzobisoxazole) fibers and aramid fibers to produce good interfacial bonding with fluororubber when added to fluororubber raw rubber, and further improve the mechanical strength and high temperature resistance of fluororubber composite materials containing fibers, the inventors found in experiments that when short fibers with a length of 1-4 mm, especially poly(p-phenylene benzobisoxazole) fibers and aramid fibers with a length of 3 mm are dispersed in fluororubber, by using 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane as a cross-linking agent and triallyl isocyanurate as a co-cross-linking agent, especially when the mass ratio of the cross-linking agent to the co-cross-linking agent is 1:(2-4), especially when the mass ratio of the cross-linking agent to the co-cross-linking agent is 1:3, the ability of poly(p-phenylene benzobisoxazole) fibers and aramid fibers to produce good interfacial bonding with fluororubber when added to fluororubber raw rubber can be improved. Good interface bonding force is generated, and the mechanical strength and high temperature resistance of the fluororubber composite materials containing fibers are further improved. The possible reason is that the cross-linking agent and the auxiliary cross-linking agent generate a cross-linked network structure with the molecular chains in the fluororubber raw rubber at high temperature, and the location of the cross-linking point is random. When short fibers with a length of 1-4 mm, especially poly(p-phenylene benzobisoxazole) fibers and aramid fibers with a length of 3 mm are dispersed in the fluororubber, it can have a certain effect on the generated cross-linked network structure. When the fiber content is too much, it will affect the compactness of the generated cross-linked network structure, which will reduce the tensile strength and elongation at break of the fluororubber composite materials containing fibers, as well as the stability of the tensile strength and elongation at break after high temperature aging, and the thermal decomposition problem of the composite materials has not been significantly improved.

[0042] A second aspect of the present invention provides a method for preparing a fluororubber composite material containing fibers, comprising the following steps:

[0043] The fluororubber raw rubber is plasticized on an open mill and rolled, and then the fiber, cross-linking agent and auxiliary cross-linking agent are gradually added to the fluororubber raw rubber wrapped with rollers on the open mill for mixing. After uniform mixing, a fluororubber composite material containing fiber is obtained, and the roll distance of the open mill is adjusted to calender out sheets, and the sheets are parked for more than 16 hours for standby use.

[0044] Preferably, the method for preparing the fiber-containing fluororubber composite material comprises the following steps:

[0045] S1. The fluorine-containing rubber raw rubber is plasticized on an open mill and wrapped with a roll, and then the fiber, crosslinking agent, and crosslinking agent are gradually added to the roll package on the open mill to mix the fluorine-containing rubber raw rubber to obtain a rubber mixture wrapped with a roll;

[0046] S2. The rubber mixture of the roll is cut on the left and right sides of the open mill roller 3-10 times, and then the roller distance of the two rollers of the open mill is adjusted to 0.1-0.5mm, and then the triangle package is made 10-30 times. The temperature of the open mill roller is controlled within 60°C. After mixing evenly, the fluororubber composite material containing fibers is obtained, and then the roller distance is adjusted to 1.5-2.0mm for calendering.

[0047] S3. Leave the mixed rubber for more than 16 hours, re-refine for 10 minutes and make sheets for use.

[0048] A third aspect of the present invention provides a fluororubber composite material containing fibers for use in the technical fields of semiconductor, photovoltaic, and aerospace products.

[0049] In one embodiment, the fiber-containing fluororubber composite material is prepared by molding, extrusion, and injection molding to obtain a corresponding product. The product can be used in the technical fields of semiconductor, photovoltaic, and aerospace industries with high cleanliness and high temperature resistance requirements.

[0050] Beneficial Effects

[0051] 1. In the present invention, by limiting the type and form of the fiber used, the performance of the fluororubber composite material containing the fiber can be improved at high temperatures and is suitable for use in the technical fields of semiconductor, photovoltaic, and aerospace products.

[0052] 2. In the present invention, the interfacial bonding force between the fiber and the fluororubber can be improved by limiting the types and dosage ratios of the crosslinking agent and the auxiliary crosslinking agent.

[0053] 3. In the present invention, by limiting the type and amount of raw materials used, the physical and mechanical strength of the fiber-containing fluororubber composite material can be improved, the compression permanent deformation value of the fiber-containing fluororubber composite material can be reduced, and a sealing effect can be provided.

[0054] 4. In the present invention, by limiting the type and amount of raw materials used, the high temperature resistance of the fluororubber composite material containing fibers can be improved.

[0055] 5. The present invention adopts poly(p-phenylene benzobisoxazole) fiber and adds it to fluororubber, which further improves the heat resistance and physical and mechanical properties of fluororubber, and makes the fluororubber composite material containing the fiber have good thermal stability and high cleanliness, thereby expanding the application scope of fluororubber to meet the fields of aerospace, semiconductor and other fields with higher temperature requirements. BRIEF DESCRIPTION OF THE DRAWINGS

[0056] Figure 1 This is the infrared spectrum test result of the surface modified fiber prepared in Example 9.

[0057] Figure 2Schematic diagram of the structure of poly(p-phenylene benzobisoxazole) fiber.

[0058] Figure 3 Schematic diagram of the structure of the anti-fatigue additive PAPI. DETAILED DESCRIPTION

[0059] Example 1

[0060] In a first aspect, the present embodiment provides a fiber-containing fluororubber composite material, which comprises, by weight, 100 parts of fluororubber raw rubber, 1 part of a cross-linking agent, and 3 parts of a co-cross-linking agent.

[0061] The fluorine-containing rubber raw rubber is tetrapropylene fluorine rubber.

[0062] The cross-linking agent is 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane.

[0063] The auxiliary cross-linking agent is triallyl isocyanurate.

[0064] The tetrafluoroethylene rubber can be purchased from Japan AGC Company, model number is 200S.

[0065] The CAS number of the 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane is 78-63-7.

[0066] The CAS number of the triallyl isocyanurate is 1025-15-6.

[0067] A second aspect of the present embodiment provides a method for preparing a fluororubber composite material containing fibers, comprising the following steps:

[0068] S1. The fluorine-containing rubber raw rubber is plasticized on an open mill and wrapped with a roll, and then a cross-linking agent and a cross-linking aid are gradually added to the roll wrapped with a fluorine-containing rubber raw rubber on an open mill for mixing to obtain a rubber mixture wrapped with a roll;

[0069] S2. The rubber mixture of the roll was cut on the left and right sides of the open mill roller 10 times each, and then the roll distance of the two rolls of the open mill was adjusted to 0.1mm and then the triangle package was made 20 times. The temperature of the open mill roller was controlled within 60 ° C. After mixing evenly, the fluororubber composite material containing fibers was obtained, and then the roll distance was adjusted to 2.0mm for calendering.

[0070] S3. Leave the mixed rubber for 17 hours, re-refine for 10 minutes and make sheets for later use.

[0071] A third aspect of this embodiment provides a fiber-containing fluororubber composite material for use in the technical fields of semiconductor, photovoltaic, and aerospace products.

[0072] Example 2

[0073] In a first aspect, the present embodiment provides a fiber-containing fluororubber composite material, which comprises, by weight, 100 parts of fluororubber raw rubber, 0.25 parts of fiber, 1 part of a cross-linking agent, and 3 parts of a co-cross-linking agent.

[0074] The fluorine-containing rubber raw rubber is tetrapropylene fluorine rubber.

[0075] The fiber is poly(p-phenylene benzobisoxazole) fiber.

[0076] The length of the poly(p-phenylene benzobisoxazole) fiber is 3 mm.

[0077] The cross-linking agent is 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane.

[0078] The auxiliary cross-linking agent is triallyl isocyanurate.

[0079] The tetrafluoroethylene rubber can be purchased from Japan AGC Company, model number is 200S.

[0080] The poly(p-phenylene benzobisoxazole) fiber can be purchased from Chengdu Xinchen New Materials Co., Ltd., model PBO ultra short chopped fiber.

[0081] The CAS number of the 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane is 78-63-7.

[0082] The CAS number of the triallyl isocyanurate is 1025-15-6.

[0083] A second aspect of the present embodiment provides a method for preparing a fluororubber composite material containing fibers, comprising the following steps:

[0084] S1. The fluorine-containing rubber raw rubber is plasticized on an open mill and wrapped with a roll, and then the fiber, crosslinking agent, and crosslinking agent are gradually added to the roll package on the open mill to mix the fluorine-containing rubber raw rubber to obtain a rubber mixture wrapped with a roll;

[0085] S2. The rubber mixture of the roll was cut on the left and right sides of the open mill roller 10 times each, and then the roll distance of the two rolls of the open mill was adjusted to 0.1mm and then the triangle package was made 20 times. The temperature of the open mill roller was controlled within 60 ° C. After mixing evenly, the fluororubber composite material containing fibers was obtained, and then the roll distance was adjusted to 2.0mm for calendering.

[0086] S3. Leave the mixed rubber for 17 hours, re-refine for 10 minutes and make sheets for later use.

[0087] A third aspect of this embodiment provides a fiber-containing fluororubber composite material for use in the technical fields of semiconductor, photovoltaic, and aerospace products.

[0088] Example 3

[0089] In a first aspect, the present embodiment provides a fiber-containing fluororubber composite material, which comprises, by weight, 100 parts of fluororubber raw rubber, 0.5 parts of fiber, 1 part of a cross-linking agent, and 3 parts of a cross-linking aid.

[0090] The fluorine-containing rubber raw rubber is tetrapropylene fluorine rubber.

[0091] The fiber is poly(p-phenylene benzobisoxazole) fiber.

[0092] The length of the poly(p-phenylene benzobisoxazole) fiber is 3 mm.

[0093] The cross-linking agent is 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane.

[0094] The auxiliary cross-linking agent is triallyl isocyanurate.

[0095] The tetrafluoroethylene rubber can be purchased from Japan AGC Company, model number is 200S.

[0096] The poly(p-phenylene benzobisoxazole) fiber can be purchased from Chengdu Xinchen New Materials Co., Ltd., model PBO ultra short chopped fiber.

[0097] The CAS number of the 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane is 78-63-7.

[0098] The CAS number of the triallyl isocyanurate is 1025-15-6.

[0099] A second aspect of the present embodiment provides a method for preparing a fluororubber composite material containing fibers, comprising the following steps:

[0100] S1. The fluorine-containing rubber raw rubber is plasticized on an open mill and wrapped with a roll, and then the fiber, crosslinking agent, and crosslinking agent are gradually added to the roll package on the open mill to mix the fluorine-containing rubber raw rubber to obtain a rubber mixture wrapped with a roll;

[0101] S2. The rubber mixture of the roll was cut on the left and right sides of the open mill roller 10 times each, and then the roll distance of the two rolls of the open mill was adjusted to 0.1mm and then the triangle package was made 20 times. The temperature of the open mill roller was controlled within 60 ° C. After mixing evenly, the fluororubber composite material containing fibers was obtained, and then the roll distance was adjusted to 2.0mm for calendering.

[0102] S3. Leave the mixed rubber for 17 hours, re-refine for 10 minutes and make sheets for later use.

[0103] A third aspect of this embodiment provides a fiber-containing fluororubber composite material for use in the technical fields of semiconductor, photovoltaic, and aerospace products.

[0104] Example 4

[0105] In a first aspect, the present embodiment provides a fiber-containing fluororubber composite material, which comprises, by weight, 100 parts of fluororubber raw rubber, 0.75 parts of fiber, 1 part of a cross-linking agent, and 3 parts of a co-cross-linking agent.

[0106] The fluorine-containing rubber raw rubber is tetrapropylene fluorine rubber.

[0107] The fiber is poly(p-phenylene benzobisoxazole) fiber.

[0108] The length of the poly(p-phenylene benzobisoxazole) fiber is 3 mm.

[0109] The cross-linking agent is 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane.

[0110] The auxiliary cross-linking agent is triallyl isocyanurate.

[0111] The tetrafluoroethylene rubber can be purchased from Japan AGC Company, model number is 200S.

[0112] The poly(p-phenylene benzobisoxazole) fiber can be purchased from Chengdu Xinchen New Materials Co., Ltd., model PBO ultra short chopped fiber.

[0113] The CAS number of the 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane is 78-63-7.

[0114] The CAS number of the triallyl isocyanurate is 1025-15-6.

[0115] A second aspect of the present embodiment provides a method for preparing a fluororubber composite material containing fibers, comprising the following steps:

[0116] S1. The fluorine-containing rubber raw rubber is plasticized on an open mill and wrapped with a roll, and then the fiber, crosslinking agent, and crosslinking agent are gradually added to the roll package on the open mill to mix the fluorine-containing rubber raw rubber to obtain a rubber mixture wrapped with a roll;

[0117] S2. The rubber mixture of the roll was cut on the left and right sides of the open mill roller 10 times each, and then the roll distance of the two rolls of the open mill was adjusted to 0.1mm and then the triangle package was made 20 times. The temperature of the open mill roller was controlled within 60 ° C. After mixing evenly, the fluororubber composite material containing fibers was obtained, and then the roll distance was adjusted to 2.0mm for calendering.

[0118] S3. Leave the mixed rubber for 17 hours, re-refine for 10 minutes and make sheets for later use.

[0119] A third aspect of this embodiment provides a fiber-containing fluororubber composite material for use in the technical fields of semiconductor, photovoltaic, and aerospace products.

[0120] Example 5

[0121] In a first aspect, the present embodiment provides a fiber-containing fluororubber composite material, which comprises, by weight, 100 parts of fluororubber raw rubber, 1 part of fiber, 1 part of cross-linking agent, and 3 parts of auxiliary cross-linking agent.

[0122] The fluorine-containing rubber raw rubber is tetrapropylene fluorine rubber.

[0123] The fiber is poly(p-phenylene benzobisoxazole) fiber.

[0124] The length of the poly(p-phenylene benzobisoxazole) fiber is 3 mm.

[0125] The cross-linking agent is 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane.

[0126] The auxiliary cross-linking agent is triallyl isocyanurate.

[0127] The tetrafluoroethylene rubber can be purchased from Japan AGC Company, model number is 200S.

[0128] The poly(p-phenylene benzobisoxazole) fiber can be purchased from Chengdu Xinchen New Materials Co., Ltd., model PBO ultra short chopped fiber.

[0129] The CAS number of the 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane is 78-63-7.

[0130] The CAS number of the triallyl isocyanurate is 1025-15-6.

[0131] A second aspect of the present embodiment provides a method for preparing a fluororubber composite material containing fibers, comprising the following steps:

[0132] S1. The fluorine-containing rubber raw rubber is plasticized on an open mill and wrapped with a roll, and then the fiber, crosslinking agent, and crosslinking agent are gradually added to the roll package on the open mill to mix the fluorine-containing rubber raw rubber to obtain a rubber mixture wrapped with a roll;

[0133] S2. The rubber mixture of the roll was cut on the left and right sides of the open mill roller 10 times each, and then the roll distance of the two rolls of the open mill was adjusted to 0.1mm and then the triangle package was made 20 times. The temperature of the open mill roller was controlled within 60 ° C. After mixing evenly, the fluororubber composite material containing fibers was obtained, and then the roll distance was adjusted to 2.0mm for calendering.

[0134] S3. Leave the mixed rubber for 17 hours, re-refine for 10 minutes and make sheets for later use.

[0135] A third aspect of this embodiment provides a fiber-containing fluororubber composite material for use in the technical fields of semiconductor, photovoltaic, and aerospace products.

[0136] Example 6

[0137] In a first aspect, the present embodiment provides a fiber-containing fluororubber composite material, which comprises, by weight, 100 parts of fluororubber raw rubber, 0.5 parts of fiber, 1 part of a cross-linking agent, and 3 parts of a cross-linking aid.

[0138] The fluorine-containing rubber raw rubber is tetrapropylene fluorine rubber.

[0139] The fiber is aramid fiber.

[0140] The length of the aramid fiber is 3 mm.

[0141] The cross-linking agent is 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane.

[0142] The auxiliary cross-linking agent is triallyl isocyanurate.

[0143] The tetrafluoroethylene rubber can be purchased from Japan AGC Company, model number is 200S.

[0144] The aramid fiber can be purchased from Yantai Taihe New Materials Co., Ltd., model Para-aramid.

[0145] The CAS number of the 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane is 78-63-7.

[0146] The CAS number of the triallyl isocyanurate is 1025-15-6.

[0147] A second aspect of the present embodiment provides a method for preparing a fluororubber composite material containing fibers, comprising the following steps:

[0148] S1. The fluorine-containing rubber raw rubber is plasticized on an open mill and wrapped with a roll, and then the fiber, crosslinking agent, and crosslinking agent are gradually added to the roll package on the open mill to mix the fluorine-containing rubber raw rubber to obtain a rubber mixture wrapped with a roll;

[0149] S2. The rubber mixture of the roll was cut on the left and right sides of the open mill roller 10 times each, and then the roll distance of the two rolls of the open mill was adjusted to 0.1mm and then the triangle package was made 20 times. The temperature of the open mill roller was controlled within 60 ° C. After mixing evenly, the fluororubber composite material containing fibers was obtained, and then the roll distance was adjusted to 2.0mm for calendering.

[0150] S3. Leave the mixed rubber for 17 hours, re-refine for 10 minutes and make sheets for later use.

[0151] A third aspect of this embodiment provides a fiber-containing fluororubber composite material for use in the technical fields of semiconductor, photovoltaic, and aerospace products.

[0152] Example 7

[0153] In a first aspect, the present embodiment provides a fiber-containing fluororubber composite material, which comprises, by weight, 100 parts of fluororubber raw rubber, 0.25 parts of fiber, 1 part of a cross-linking agent, and 3 parts of a co-cross-linking agent.

[0154] The fluorine-containing rubber raw rubber is tetrapropylene fluorine rubber.

[0155] The fiber is polytetrafluoroethylene fiber.

[0156] The length of the polytetrafluoroethylene fiber is 3 mm.

[0157] The cross-linking agent is 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane.

[0158] The auxiliary cross-linking agent is triallyl isocyanurate.

[0159] The tetrafluoroethylene rubber can be purchased from Japan AGC Company, model number is 200S.

[0160] The polytetrafluoroethylene fiber can be purchased from Shanghai Jinyou Fluoride Materials Co., Ltd., model number JUSF-WN-S1.

[0161] The CAS number of the 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane is 78-63-7.

[0162] The CAS number of the triallyl isocyanurate is 1025-15-6.

[0163] A second aspect of the present embodiment provides a method for preparing a fluororubber composite material containing fibers, comprising the following steps:

[0164] S1. The fluorine-containing rubber raw rubber is plasticized on an open mill and wrapped with a roll, and then the fiber, crosslinking agent, and crosslinking agent are gradually added to the roll package on the open mill to mix the fluorine-containing rubber raw rubber to obtain a rubber mixture wrapped with a roll;

[0165] S2. The rubber mixture of the roll was cut on the left and right sides of the open mill roller 10 times each, and then the roll distance of the two rolls of the open mill was adjusted to 0.1mm and then the triangle package was made 20 times. The temperature of the open mill roller was controlled within 60 ° C. After mixing evenly, the fluororubber composite material containing fibers was obtained, and then the roll distance was adjusted to 2.0mm for calendering.

[0166] S3. Leave the mixed rubber for 17 hours, re-refine for 10 minutes and make sheets for later use.

[0167] A third aspect of this embodiment provides a fiber-containing fluororubber composite material for use in the technical fields of semiconductor, photovoltaic, and aerospace products.

[0168] Example 8

[0169] In a first aspect, the present embodiment provides a fiber-containing fluororubber composite material, which comprises, by weight, 100 parts of fluororubber raw rubber, 0.25 parts of fiber, 1 part of a cross-linking agent, and 3 parts of a co-cross-linking agent.

[0170] The fluorine-containing rubber raw rubber is tetrapropylene fluorine rubber.

[0171] The fibers are carbon fibers.

[0172] The length of the carbon fiber is 3 mm.

[0173] The cross-linking agent is 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane.

[0174] The auxiliary cross-linking agent is triallyl isocyanurate.

[0175] The tetrafluoroethylene rubber can be purchased from Japan AGC Company, model number is 200S.

[0176] The carbon fiber can be purchased from Shanghai Huazheng Composite Materials Co., Ltd., and the model number is PTCCF-PV-6.

[0177] The CAS number of the 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane is 78-63-7.

[0178] The CAS number of the triallyl isocyanurate is 1025-15-6.

[0179] A second aspect of the present embodiment provides a method for preparing a fluororubber composite material containing fibers, comprising the following steps:

[0180] S1. The fluorine-containing rubber raw rubber is plasticized on an open mill and wrapped with a roll, and then the fiber, crosslinking agent, and crosslinking agent are gradually added to the roll package on the open mill to mix the fluorine-containing rubber raw rubber to obtain a rubber mixture wrapped with a roll;

[0181] S2. The rubber mixture of the roll was cut on the left and right sides of the open mill roller 10 times each, and then the roll distance of the two rolls of the open mill was adjusted to 0.1mm and then the triangle package was made 20 times. The temperature of the open mill roller was controlled within 60 ° C. After mixing evenly, the fluororubber composite material containing fibers was obtained, and then the roll distance was adjusted to 2.0mm for calendering.

[0182] S3. Leave the mixed rubber for 17 hours, re-refine for 10 minutes and make sheets for later use.

[0183] A third aspect of this embodiment provides a fiber-containing fluororubber composite material for use in the technical fields of semiconductor, photovoltaic, and aerospace products.

[0184] Example 9

[0185] In a first aspect, the present embodiment provides a fiber-containing fluororubber composite material, which comprises, by weight, 100 parts of fluororubber raw rubber, 0.25 parts of fiber, 1 part of a cross-linking agent, and 3 parts of a co-cross-linking agent.

[0186] The fluorine-containing rubber raw rubber is tetrapropylene fluorine rubber.

[0187] The fiber is poly(p-phenylene benzobisoxazole) fiber.

[0188] The length of the poly(p-phenylene benzobisoxazole) fiber is 3 mm.

[0189] The fiber is a surface-modified fiber.

[0190] The surface modification method of the surface modified fiber comprises the following steps:

[0191] S1. By weight, 5 parts of poly(p-phenylene benzobisoxazole) fibers were extracted by reflux with 100 parts of acetone for 12 hours, the poly(p-phenylene benzobisoxazole) fibers were taken out and washed with a large amount of deionized water, and then dried at 120°C for 2 hours;

[0192] S2. 80 parts of a 60 wt % methanesulfonic acid aqueous solution were used to soak the poly(p-phenylene benzobisoxazole) fiber at 60 ° C for 1 h, and then the fiber was fully washed with deionized water, and then dried in a vacuum oven at 110 ° C for 2 h to obtain a pretreated fiber;

[0193] S3. The pretreated fiber was added to anhydrous ethanol solvent and ultrasonically dispersed at 25°C for 30 min using a 300w ultrasonic cleaner to obtain a uniform suspension;

[0194] S4. 0.5 parts of anti-fatigue additive was added to the suspension and ultrasonically mixed for 10 min;

[0195] S5. Raise the temperature of the ultrasonic cleaner to 80°C and allow the pretreated fiber to react at a constant temperature for 2 hours;

[0196] S6. Place the pretreated fiber in a vacuum drying oven at 110°C and dry for 2 hours to obtain surface-modified fiber.

[0197] The anti-fatigue auxiliary agent is a multifunctional maleimide compound.

[0198] The anti-fatigue additive can be purchased from Otsuka Materials Technology (Shanghai) Co., Ltd., model number PAPI.

[0199] The cross-linking agent is 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane.

[0200] The auxiliary cross-linking agent is triallyl isocyanurate.

[0201] The tetrafluoroethylene rubber can be purchased from Japan AGC Company, model number is 200S.

[0202] The poly(p-phenylene benzobisoxazole) fiber can be purchased from Chengdu Xinchen New Materials Co., Ltd., model PBO ultra short chopped fiber.

[0203] The CAS number of the 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane is 78-63-7.

[0204] The CAS number of the triallyl isocyanurate is 1025-15-6.

[0205] A second aspect of the present embodiment provides a method for preparing a fluororubber composite material containing fibers, comprising the following steps:

[0206] S1. The fluorine-containing rubber raw rubber is plasticized on an open mill and wrapped with a roll, and then the fiber, crosslinking agent, and crosslinking agent are gradually added to the roll package on the open mill to mix the fluorine-containing rubber raw rubber to obtain a rubber mixture wrapped with a roll;

[0207] S2. The rubber mixture of the roll was cut on the left and right sides of the open mill roller 10 times each, and then the roll distance of the two rolls of the open mill was adjusted to 0.1mm and then the triangle package was made 20 times. The temperature of the open mill roller was controlled within 60 ° C. After mixing evenly, the fluororubber composite material containing fibers was obtained, and then the roll distance was adjusted to 2.0mm for calendering.

[0208] S3. Leave the mixed rubber for 17 hours, re-refine for 10 minutes and make sheets for later use.

[0209] A third aspect of this embodiment provides a fiber-containing fluororubber composite material for use in the technical fields of semiconductor, photovoltaic, and aerospace products.

[0210] Example 10

[0211] In a first aspect, the present embodiment provides a fiber-containing fluororubber composite material, which comprises, by weight, 100 parts of fluororubber raw rubber, 0.5 parts of fiber, 1 part of a cross-linking agent, and 3 parts of a cross-linking aid.

[0212] The fluorine-containing rubber raw rubber is tetrapropylene fluorine rubber.

[0213] The fiber is poly(p-phenylene benzobisoxazole) fiber.

[0214] The length of the poly(p-phenylene benzobisoxazole) fiber is 3 mm.

[0215] The fiber is a surface-modified fiber, and the surface modification method of the surface-modified fiber is the same as that in Example 9.

[0216] The cross-linking agent is 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane.

[0217] The auxiliary cross-linking agent is triallyl isocyanurate.

[0218] The tetrafluoroethylene rubber can be purchased from Japan AGC Company, model number is 200S.

[0219] The poly(p-phenylene benzobisoxazole) fiber can be purchased from Chengdu Xinchen New Materials Co., Ltd., model PBO ultra short chopped fiber.

[0220] The CAS number of the 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane is 78-63-7.

[0221] The CAS number of the triallyl isocyanurate is 1025-15-6.

[0222] A second aspect of the present embodiment provides a method for preparing a fluororubber composite material containing fibers, comprising the following steps:

[0223] S1. The fluorine-containing rubber raw rubber is plasticized on an open mill and wrapped with a roll, and then the fiber, crosslinking agent, and crosslinking agent are gradually added to the roll package on the open mill to mix the fluorine-containing rubber raw rubber to obtain a rubber mixture wrapped with a roll;

[0224] S2. The rubber mixture of the roll was cut on the left and right sides of the open mill roller 10 times each, and then the roll distance of the two rolls of the open mill was adjusted to 0.1mm and then the triangle package was made 20 times. The temperature of the open mill roller was controlled within 60 ° C. After mixing evenly, the fluororubber composite material containing fibers was obtained, and then the roll distance was adjusted to 2.0mm for calendering.

[0225] S3. Leave the mixed rubber for 17 hours, re-refine for 10 minutes and make sheets for later use.

[0226] A third aspect of this embodiment provides a fiber-containing fluororubber composite material for use in the technical fields of semiconductor, photovoltaic, and aerospace products.

[0227] Embodiment 11

[0228] In a first aspect, the present embodiment provides a fiber-containing fluororubber composite material, which comprises, by weight, 100 parts of fluororubber raw rubber, 0.75 parts of fiber, 1 part of a cross-linking agent, and 3 parts of a co-cross-linking agent.

[0229] The fluorine-containing rubber raw rubber is tetrapropylene fluorine rubber.

[0230] The fiber is poly(p-phenylene benzobisoxazole) fiber.

[0231] The length of the poly(p-phenylene benzobisoxazole) fiber is 3 mm.

[0232] The fiber is a surface-modified fiber, and the surface modification method of the surface-modified fiber is the same as that in Example 9.

[0233] The cross-linking agent is 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane.

[0234] The auxiliary cross-linking agent is triallyl isocyanurate.

[0235] The tetrafluoroethylene rubber can be purchased from Japan AGC Company, model number is 200S.

[0236] The poly(p-phenylene benzobisoxazole) fiber can be purchased from Chengdu Xinchen New Materials Co., Ltd., model PBO ultra short chopped fiber.

[0237] The CAS number of the 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane is 78-63-7.

[0238] The CAS number of the triallyl isocyanurate is 1025-15-6.

[0239] A second aspect of the present embodiment provides a method for preparing a fluororubber composite material containing fibers, comprising the following steps:

[0240] S1. The fluorine-containing rubber raw rubber is plasticized on an open mill and wrapped with a roll, and then the fiber, crosslinking agent, and crosslinking agent are gradually added to the roll package on the open mill to mix the fluorine-containing rubber raw rubber to obtain a rubber mixture wrapped with a roll;

[0241] S2. The rubber mixture of the roll was cut on the left and right sides of the open mill roller 10 times each, and then the roll distance of the two rolls of the open mill was adjusted to 0.1mm and then the triangle package was made 20 times. The temperature of the open mill roller was controlled within 60 ° C. After mixing evenly, the fluororubber composite material containing fibers was obtained, and then the roll distance was adjusted to 2.0mm for calendering.

[0242] S3. Leave the mixed rubber for 17 hours, re-refine for 10 minutes and make sheets for later use.

[0243] A third aspect of this embodiment provides a fiber-containing fluororubber composite material for use in the technical fields of semiconductor, photovoltaic, and aerospace products.

[0244] Example 12

[0245] In a first aspect, the present embodiment provides a fiber-containing fluororubber composite material, which comprises, by weight, 100 parts of fluororubber raw rubber, 1 part of fiber, 1 part of cross-linking agent, and 3 parts of auxiliary cross-linking agent.

[0246] The fluorine-containing rubber raw rubber is tetrapropylene fluorine rubber.

[0247] The fiber is poly(p-phenylene benzobisoxazole) fiber.

[0248] The length of the poly(p-phenylene benzobisoxazole) fiber is 3 mm.

[0249] The fiber is a surface-modified fiber, and the surface modification method of the surface-modified fiber is the same as that in Example 9.

[0250] The cross-linking agent is 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane.

[0251] The auxiliary cross-linking agent is triallyl isocyanurate.

[0252] The tetrafluoroethylene rubber can be purchased from Japan AGC Company, model number is 200S.

[0253] The poly(p-phenylene benzobisoxazole) fiber can be purchased from Chengdu Xinchen New Materials Co., Ltd., model PBO ultra short chopped fiber.

[0254] The CAS number of the 2,5-dimethyl-2,5-bis(tert-butylperoxy)hexane is 78-63-7.

[0255] The CAS number of the triallyl isocyanurate is 1025-15-6.

[0256] A second aspect of the present embodiment provides a method for preparing a fluororubber composite material containing fibers, comprising the following steps:

[0257] S1. The fluorine-containing rubber raw rubber is plasticized on an open mill and wrapped with a roll, and then the fiber, crosslinking agent, and crosslinking agent are gradually added to the roll package on the open mill to mix the fluorine-containing rubber raw rubber to obtain a rubber mixture wrapped with a roll;

[0258] S2. The rubber mixture of the roll was cut on the left and right sides of the open mill roller 10 times each, and then the roll distance of the two rolls of the open mill was adjusted to 0.1mm and then the triangle package was made 20 times. The temperature of the open mill roller was controlled within 60 ° C. After mixing evenly, the fluororubber composite material containing fibers was obtained, and then the roll distance was adjusted to 2.0mm for calendering.

[0259] S3. Leave the mixed rubber for 17 hours, re-refine for 10 minutes and make sheets for later use.

[0260] A third aspect of this embodiment provides a fiber-containing fluororubber composite material for use in the technical fields of semiconductor, photovoltaic, and aerospace products.

[0261] Performance Testing

[0262] 1. Tensile performance test

[0263] The fiber-containing fluororubber composite materials prepared in Examples 1-12 were vulcanized to obtain standard test specimens, and the tensile strength, elongation at break, and 100% modulus of the standard test specimens were measured in accordance with "GB / T 528-2009 Determination of tensile stress-strain properties of vulcanized rubber or thermoplastic rubber". In each example, 10 test specimens were provided for testing, the maximum and minimum values ​​were removed, and the average value was taken. The test results are shown in Table 1.

[0264] 2. Decomposition temperature test

[0265] The fiber-containing fluororubber composite material prepared in Examples 1-12 was vulcanized to obtain standard test specimens. Part of the standard test specimens was placed in a thermogravimetric analysis test equipment under a N2 atmosphere. The heating rate was 10°C / min. The test temperature range was 50-750°C. The decomposition temperature was tested, the maximum and minimum values ​​were removed, and the average value was taken. The test results are shown in Table 1.

[0266] From the test results in Table 1, it can be seen that when the anti-fatigue additive PAPI is used to modify the surface of the poly(p-phenylene benzobisoxazole) fiber, the thermal decomposition problem of the fluororubber composite material can be improved, and the heat resistance of the fluororubber composite material during application can be further improved.

[0267] 3. Compression set test

[0268] The fiber-containing fluororubber composite materials prepared in Examples 1-12 were vulcanized to obtain standard test specimens, which were placed in an aging box at 200° C. for 72 hours and tested in accordance with “ASTM D395-03 Standard test methods for rubber property-Compression Set”. In each example, 10 test specimens were provided for testing, the maximum and minimum values ​​were removed, and the average value was taken. The test results are shown in Table 1.

[0269] The test results in Table 1 show that the compression set test value of the fluororubber composite material can be reduced by surface modification of the poly(p-phenylene benzobisoxazole) fiber with the anti-fatigue additive PAPI, and the sealing performance of the fluororubber composite material during application can be further improved.

[0270] 4. Hot air aging test

[0271] The fiber-containing fluororubber composite materials prepared in Examples 1-12 were vulcanized to obtain standard test specimens, which were placed in an aging box at 200°C for 72 hours. The change rate of tensile strength, the change rate of elongation at break, and the change rate of 100% modulus were measured in accordance with "GB / T3512-2014 Hot air aging and heat resistance test for vulcanized rubber or thermoplastic rubber". In each example, 10 test specimens were provided for testing, the maximum and minimum values ​​were removed, and the average value was taken. The test results are shown in Table 2.

[0272] 5. Infrared test

[0273] The surface modified fiber prepared in Example 9 was tested by infrared spectrometer. The test results are shown in Figure 1 .

[0274] pass Figure 1 It can be seen that the surface modified fiber is at 1625cm -1 and 918cm -1 and 1713cm -1 Characteristic peaks appeared at 1625cm -1 and 918cm -1 It is the C=N and COC stretching vibration peak of the oxazole ring on the poly(p-phenylene benzobisoxazole) molecular chain, 1713 cm -1 It is the C=O stretching vibration peak on the maleimide of the anti-fatigue additive PAPI molecular chain.

[0275] Table 1

[0276]

[0277] Table 2

[0278]

Claims

1. A fluororubber composite material containing fibers, characterized in that: By weight, the components include 80-120 parts of fluorine-containing rubber, 0.1-0.9 parts of fiber, 0.1-2 parts of cross-linking agent, and 0.5-6 parts of auxiliary cross-linking agent; The fluorine-containing rubber raw rubber is tetrapropylene fluorine rubber; The fiber contains an aromatic ring structure, and the fiber containing the aromatic ring structure is a poly(p-phenylene benzobisoxazole) fiber; The fiber is in the form of short fibers with a length of 1-4 mm, and the fiber is a surface-modified fiber; The surface modification method of the surface modified fiber comprises the following steps: S1. The fiber was reflux extracted with acetone for 10-20 hours, washed with a large amount of deionized water, and dried at 110-130°C for 1-3 hours; S2. Soak the fiber in a methanesulfonic acid solution at 55-65°C for 0.5-2h, then wash the fiber with deionized water, and dry it in a vacuum oven at 110°C for 1-3h to obtain a pretreated fiber; S3. The pretreated fiber was added to anhydrous ethanol solvent and ultrasonically dispersed at 25°C for 10-60min using a 300w ultrasonic cleaner to obtain a uniform suspension; S4. Add the anti-fatigue additive to the suspension and mix by ultrasonic for 5-20 min; S5. Raise the temperature of the ultrasonic cleaner to 80°C and allow the pretreated fiber to react at a constant temperature for 1-3 hours; S6. The pretreated fiber is placed in a vacuum drying oven at 105-115°C and dried for 1-3 hours to obtain a surface-modified fiber; The anti-fatigue auxiliary agent is a multifunctional maleimide compound.

2. The fiber-containing fluororubber composite material according to claim 1, characterized in that: The mass ratio of the cross-linking agent to the auxiliary cross-linking agent is 1:(2-4).

3. The fiber-containing fluororubber composite material according to claim 1, characterized in that: The crosslinking agent is selected from one or more of peroxide compounds, fluorinated alkyl compounds, and fluoroaralkyl phosphonates.

4. The fiber-containing fluororubber composite material according to claim 1, characterized in that: The auxiliary cross-linking agent is selected from one or both of triallyl isocyanurate and trimethallyl isocyanate.

5. A method for preparing a fiber-containing fluororubber composite material according to any one of claims 1 to 4, characterized in that: The following steps are involved: The fluororubber raw rubber is plasticized on an open mill and rolled, and then the fiber, cross-linking agent and auxiliary cross-linking agent are gradually added to the fluororubber raw rubber wrapped with rollers on the open mill for mixing. After uniform mixing, a fluororubber composite material containing fiber is obtained, and the roll distance of the open mill is adjusted to calender out sheets, and the sheets are parked for more than 16 hours for standby use.

6. A fiber-containing fluororubber composite material as claimed in any one of claims 1 to 4, which is used in the technical fields of semiconductor, photovoltaic and aerospace products.

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