Corrosion-resistant fluoroether rubber polymer material, preparation method thereof and application of corrosion-resistant fluoroether rubber polymer material in airbag pump

Abstract

The invention provides a corrosion-resistant fluoroether rubber polymer material, a preparation method thereof and an application of the corrosion-resistant fluoroether rubber polymer material in an airbag pump. Relates to the technical field of air bag pump component materials. The corrosion-resistant fluoroether rubber polymer material comprises 100-130 parts of a modified perfluoroether rubber polymer, 20-30 parts of a filler, 1-3 parts of a cross-linking agent, 2-5 parts of an accelerant, 3-10 parts of a functional aid and 5-10 parts of an acid acceptor, wherein the modified fluoroether rubber polymer is 6-perfluorobutyl UPy (at) POSS (Polyhedral Oligomeric Silsesquioxane) grafted PPS (Polyphenylene Sulfide) fiber reinforced perfluoroether rubber. The corrosion-resistant fluoroether rubber polymer material disclosed by the invention can be applied to a rubber part of an air bag pump, and the corrosion resistance, the mechanical strength and the wear resistance of the rubber part at high temperature are improved.

Description

Technical Field

[0001] This invention relates to the field of materials technology for airbag pump components, specifically to a corrosion-resistant fluoroether rubber polymer material, its preparation method, and its application in airbag pumps. Background Technology

[0002] In semiconductor wet manufacturing processes, dozens of ultrapure acids, alkalis, and water are often required for etching, grinding, and cleaning. These liquids are typically transported using a pneumatic air pump. The pneumatic air pump adjusts its volume by expanding and contracting its internal pneumatic air chambers to draw in and expel the liquids.

[0003] Rubber components are key parts for the plenum pump to achieve its core functions. The elasticity and sealing properties of rubber ensure that the valve opens and closes sensitively and the seal is reliable, preventing backflow and maintaining pumping efficiency. This requires that the rubber materials (sealing rings, rubber bodies, etc.) in the plenum pump not only have corrosion resistance at room temperature, but also have good corrosion resistance, wear resistance, mechanical strength and toughness at high temperatures. Summary of the Invention

[0004] To address the aforementioned problems, the first aspect of this invention provides a corrosion-resistant fluoroether rubber polymer material, comprising, by weight, 100-130 parts of modified fluoroether rubber polymer, 20-30 parts of filler, 1-3 parts of crosslinking agent, 2-5 parts of accelerator, 3-10 parts of functional additive, and 5-10 parts of acid absorber.

[0005] Among them, the modified fluoroether rubber polymer is 6-perfluorobutylUPy@POSS grafted PPS fiber reinforced fluoroether rubber.

[0006] The corrosion-resistant fluoroether rubber polymer material of this invention uses 6-perfluorobutyl UPy@POSS grafted PPS fiber to reinforce the perfluoroether rubber. The POSS cage in the UPy@POSS core-shell structure can physically block H - / OH - Permeation: The perfluorinated backbone can form a molecular-level barrier layer, inhibiting H2O penetration. - / OH -Penetration enhances acid and alkali resistance. The quadruple hydrogen bonds (bond energy ≈ 100 kJ / mol) of 2-ureido-4[1H]-pyrimidinone (UPy) can dynamically recombine in acid / alkali environments, repairing microcracks and improving mechanical strength and fracture toughness. Polyphenylene sulfide fiber (PPS fiber) forms a "rigid-flexible" gradient transition layer with UPy at high temperatures, which can suppress stress concentration and improve toughness. Furthermore, by modifying UPy with -C4F9 in this invention, high-temperature oxidative decomposition of UPy can be avoided, improving oxidation resistance. High temperatures cause UPy to dissociate, exposing the fluorocarbon chains to oriented arrangement, reducing surface energy and improving the material's wear resistance. When combined with fillers, crosslinking agents, accelerators, functional additives, and acid scavengers, it can improve the corrosion resistance, mechanical properties, and wear resistance of corrosion-resistant fluoroether rubber polymer materials at high temperatures.

[0007] Optionally, the preparation method of 6-perfluorobutylUPy@POSS grafted PPS fiber reinforced perfluoroether rubber includes the following steps:

[0008] S1: Under an inert atmosphere, 2-ureido-4(1H)-pyrimidinone derivative, 1-iodoperfluorobutane, free radical initiator and first solvent are mixed, then the initiator is added, and the mixture is reacted at a first temperature to obtain 6-perfluorobutylUPy;

[0009] Optionally, the synthetic method for 2-ureido-4(1H)-pyrimidinone derivatives is described in reference. Figure 1 As shown, R1 is methyl and R2 is n-butyl.

[0010] Optionally, the inert atmosphere may be nitrogen or argon.

[0011] Optionally, the molar ratio of 2-ureido-4(1H)-pyrimidinone derivative to 1-iodoperfluorobutane is 1:(1.2-2).

[0012] Optionally, the free radical initiator may be one of azobisisobutyronitrile, benzoyl peroxide, or cyclohexanone peroxide.

[0013] Optionally, the initiator may be one or both of tributyltin hydride or hexamethyldistin.

[0014] Optionally, the first solvent may be anhydrous and oxygen-free toluene or 1,2-dichloroethane.

[0015] Optionally, the first temperature is 70-85℃.

[0016] A perfluorobutyl group was introduced at the 6-position of 2-ureido-4(1H)-pyrimidinone via a free radical addition reaction. The introduction of the perfluorobutyl group reduces the UPy electron cloud density, improves antioxidant and temperature resistance, and enhances resistance to OH radicals. - Nucleophilic attack.

[0017] S2: 6-PerfluorobutylUPy is mixed with 1,3-diaminopropane, a second solvent is added, and the mixture is reacted at a second temperature to obtain 6-perfluorobutylUPy-NH2; then di(trichloromethyl) carbonate and a third solvent are added, and the mixture is reacted at a third temperature to obtain 6-perfluorobutylUPy-NCO.

[0018] Optionally, the molar ratio of 6-perfluorobutylUPy to 1,3-diaminopropane is 1:(1-2).

[0019] Optionally, the second solvent is anhydrous dimethyl sulfoxide.

[0020] Optionally, the second temperature is 0℃-5℃.

[0021] Optionally, the molar ratio of 6-perfluorobutylUPy-NH2 to di(trichloromethyl) carbonate is 1:(0.3-0.6).

[0022] Optionally, the third solvent is anhydrous dichloromethane.

[0023] Optionally, the third temperature is 0℃-25℃.

[0024] S3: Aminopropylheptaisobutylsilsesquioxane (APTES-POSS) and 6-perfluorobutylUPy-NCO were mixed, a fourth solvent was added, and the mixture was reacted at a fourth temperature to obtain 6-perfluorobutylUPy@POSS. The POSS core aggregated in a nonpolar solvent, and the UPy quadruple hydrogen bonds formed the shell.

[0025] Optionally, the molar ratio of aminopropylheptaisobutylsilsesquioxane to 6-perfluorobutylUPy-NCO is 1:(1-2).

[0026] Optionally, the fourth solvent is anhydrous toluene.

[0027] Optionally, the fourth temperature is 20-30℃.

[0028] S4: Fluorocarboxylic acid-modified PPS fibers were immersed in a solution of 6-perfluorobutylUPy@POSS, and then subjected to ultrasonic treatment and hot pressing to obtain a fiber-core-shell structure.

[0029] Optionally, the hot pressing temperature is 110℃-125℃.

[0030] S5: The fiber-core-shell structure is mixed with perfluoroether rubber (FFKM) at the fifth temperature to obtain 6-perfluorobutylUPy@POSS grafted PPS fiber reinforced fluoroether rubber.

[0031] Optionally, the fifth temperature is 60-80℃.

[0032] Optionally, the mass ratio of the fiber-core-shell structure to the perfluoroether rubber is 1:(10-15).

[0033] This invention employs perfluorobutyl modification of UPy, which can reduce the electron cloud density of UPy, improve its antioxidant and temperature resistance, and enhance its resistance to OH radicals. - Nucleophilic attack. Then, using a cage-like silsesquioxane (POSS) core and UPy as a shell, the POSS hydrophobic barrier blocks H. - / OH - penetration.

[0034] Optionally, the preparation method of fluorinated carboxylic acid modified PPS fibers includes the following steps:

[0035] PPS fibers were plasma activated to generate PPS free radicals; then, a mixture of acrylic acid and perfluorooctyl iodine vapor was introduced under vacuum conditions for plasma treatment to obtain PPS fibers modified with fluorinated carboxylic acids.

[0036] Further, polyphenylene sulfide (PPS) fibers were ultrasonically cleaned with acetone / ethanol for 30 min and vacuum dried at 110-120℃. The fibers were then evacuated, argon gas was introduced to 40-60 Pa, and radio frequency treatment was performed at 200-300 W to generate PPS free radicals. While maintaining the vacuum, a mixed vapor of acrylic acid and perfluorooctyl iodine was introduced, followed by plasma treatment at 100-150 W. The fibers were then removed under nitrogen protection and aged at 60-70℃ for 24 h to quench the free radicals, yielding modified PPS fibers.

[0037] In this invention, argon ions bombard the PPS surface to generate free radicals, acrylic acid polymerizes on the surface to form a carboxyl base layer, and perfluorooctyl iodine grafts fluorocarbon chains through an iodine transfer reaction. The treated PPS fiber surface forms a nanofiber structure, increasing the specific surface area and improving the interfacial bonding strength between the modified PPS fiber and UPy.

[0038] Optionally, the functional additives are composite functional additives of perfluoroethylene propylene (FEP) micro powder and B4C nanowires.

[0039] Optionally, the mass ratio of B4C nanowires to polytetrafluoroethylene propylene micropowder is 1:(2-4).

[0040] In this invention, by further adding poly(fluoroethylene propylene) (FEP) micro powder and B4C nanowire composite functional additives, and by compounding FEP micro powder with other substances, FEP micro powder can migrate to the surface to form a transfer film, thereby improving wear resistance. B4C nanowires can form covalent bonds (BO-Si) with 6-perfluorobutylUPy@POSS, and by compounding with other materials, the mechanical properties of the polymer material can be further improved.

[0041] Optionally, the preparation method of the composite functional additive of perfluoroethylene propylene (FEP) micro powder and B4C nanowires includes the following steps:

[0042] a1: B4C nanowires were added to an ethanol solution containing a coupling agent and refluxed at a sixth temperature to obtain fluorinated B4C nanowires.

[0043] a2: Fluorinated B4C nanowires were dispersed in a fifth solvent, poly(perfluoroethylene propylene) micro powder was added, ultrasonic treatment was performed, pH was adjusted to 2-4, and an electric field was applied to obtain FEP@B4C composite powder.

[0044] This invention utilizes B4C nanowires with surface fluorination modification, which enhances compatibility with FEP. Electrostatic self-assembly suppresses agglomeration and further improves the compatibility of FEP@B4C composite powder with fluoroether rubber.

[0045] Optionally, the coupling agent is perfluorooctyltriethoxysilane.

[0046] Optionally, the sixth temperature is 70-85℃.

[0047] Optionally, the fifth solvent is an ethanol solution.

[0048] Optionally, the particle size of the perfluoroethylene propylene micro powder is less than 100 μm, the diameter of the B4C nanowires is less than 50 nm, and the length of the B4C nanowires is 1-4 μm.

[0049] Optionally, the filler can be one or both of carbon black or fumed silica. The filler can embed itself in the UPy hydrogen bond network, hindering molecular chain slippage, and the silanol groups on the carbon black surface can synergistically bond with UPy, improving mechanical properties.

[0050] Optionally, the crosslinking agent is one or more of bis-tert-butylperoxyisopropylbenzene, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane or 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane.

[0051] Optionally, the accelerator is triallyl isocyanurate.

[0052] Optionally, the acid absorber is one of zinc oxide, calcium hydroxide, or nano-magnesium oxide. Preferably, the acid absorber is nano-magnesium oxide. Nano-magnesium oxide can doubly neutralize the HF generated by FFKM cracking without dissolving metal ions, protecting UPy from acid-catalyzed hydrolysis.

[0053] Optionally, the particle size of the nano-magnesium oxide is no higher than 50 nm.

[0054] A second aspect of the present invention provides a method for preparing a corrosion-resistant fluoroether rubber polymer material, the method comprising the following steps:

[0055] (1) The modified fluoroether rubber polymer is mixed at a certain temperature, and then acid absorber and filler are added and mixed again.

[0056] (2) Add functional additives and mix at a certain temperature, then add crosslinking agent and accelerator and mix well;

[0057] (3) Then vulcanize at a certain temperature to obtain corrosion-resistant fluoroether rubber polymer material.

[0058] Optionally, the temperature in step (1) is no higher than 80°C, which can protect the UPy hydrogen bonds and prevent hydrogen bond decomposition.

[0059] Optionally, the temperature in step (2) is no higher than 60°C.

[0060] Optionally, the vulcanization temperature in step (3) is 150-180℃.

[0061] Compared with the prior art, the present invention achieves at least one of the following beneficial effects:

[0062] (1) The corrosion-resistant fluoroether rubber polymer material of the present invention is made by compounding UPy@POSS grafted PPS fiber reinforced perfluoroether rubber with fillers, crosslinking agents, accelerators, functional additives and acid absorbers, which can improve the corrosion resistance, mechanical properties and wear resistance of the corrosion-resistant fluoroether rubber polymer material at high temperature.

[0063] (2) The corrosion-resistant fluoroether rubber polymer material of the present invention uses PPS fibers modified with fluorinated carboxylic acid. The interfacial bonding strength between the modified PPS fibers and UPy is improved, further enhancing the mechanical properties of the material.

[0064] (3) This invention further adds poly(fluoroethylene propylene) (FEP) micro powder and B4C nanowire composite functional additives. The addition of FEP micro powder and other substances can migrate to the surface to form a transfer film, thereby improving wear resistance. B4C nanowires can form covalent bonds (BO-Si) with 6-perfluorobutylUPy@POSS. When combined with other materials, the mechanical properties of polymer materials can be further improved.

[0065] (4) The corrosion-resistant fluoroether rubber polymer material of the present invention can be applied to the rubber parts (such as rubber rings, rubber bodies or sealing parts) of the wind bag pump to improve the corrosion resistance, mechanical strength and wear resistance of the rubber parts at high temperature. Attached Figure Description

[0066] The accompanying drawings, which are included to provide a further understanding of the invention and form part of this invention, illustrate exemplary embodiments of the invention and are used to explain the invention, but do not constitute an undue limitation of the invention. In the drawings:

[0067] Figure 1 An exemplary embodiment of the synthetic route for the 2-ureido-4(1H)-pyrimidinone derivative of the present invention is shown. Detailed Implementation

[0068] To more clearly illustrate the overall concept of the present invention, a detailed description will be provided below with reference to the accompanying drawings and examples.

[0069] Many specific details are set forth in the following description in order to provide a full understanding of the invention. However, the invention may also be practiced in other ways different from those described herein, and therefore the scope of protection of the invention is not limited to the specific embodiments disclosed below.

[0070] Example 1

[0071] In an exemplary embodiment of the present invention, the corrosion-resistant fluoroether rubber polymer material comprises 100 parts of modified perfluoroether rubber polymer, 20 parts of fumed silica, 1 part of crosslinking agent bis-tert-butylperoxyisopropylbenzene, 2 parts of accelerator triallyl isocyanurate, 3 parts of composite functional additives of poly(fluoroethylene propylene) (FEP) micro powder and B4C nanowires, wherein the mass ratio of B4C nanowires to poly(fluoroethylene propylene) micro powder is 1:2, the particle size of poly(fluoroethylene propylene) micro powder is 50 μm, the diameter of B4C nanowires is 30 nm and the length is 1 μm, and 5 parts of acid-absorbing agent nano-magnesium oxide with a particle size of 20 nm.

[0072] The modified perfluoroether rubber polymer is a 6-perfluorobutylUPy@POSS grafted PPS fiber reinforced perfluoroether rubber. The preparation method includes the following steps:

[0073] S1: Under a nitrogen atmosphere, the 2-ureido-4(1H)-pyrimidinone derivative (synthetic reference) was synthesized. Figure 1 R1 is methyl, R2 is n-butyl), 1-iodoperfluorobutane, and azobisisobutyronitrile were mixed in a reaction flask at a molar ratio of 1:1.2:0.2. Anhydrous and oxygen-free toluene was added and stirred to obtain a suspension. Tributyltin hydride was slowly added dropwise under an ice-water bath. The reaction mixture was heated to 70°C and reacted for 10 h. After cooling to room temperature, saturated NH4Cl aqueous solution was added to quench the reaction. The mixture was extracted with dichloromethane, and the organic phases were combined. The mixture was washed successively with water and saturated brine. After drying, concentration, and purification by column chromatography, 6-perfluorobutylUPy was obtained.

[0074] S2: 6-PerfluorobutylUPy and 1,3-diaminopropane are mixed in a molar ratio of 1:1, anhydrous dimethyl sulfoxide is added, and the mixture is reacted at 2°C to obtain 6-perfluorobutylUPy-NH2; then di(trichloromethyl) carbonate is added, wherein the molar ratio of 6-perfluorobutylUPy-NH2 to di(trichloromethyl) carbonate is 1:0.3, anhydrous dichloromethane is added, and the mixture is reacted at 10°C to obtain 6-perfluorobutylUPy-NCO.

[0075] S3: Mix aminopropylheptaisobutylsilsesquioxane and 6-perfluorobutylUPy-NCO in a molar ratio of 1:1, add anhydrous toluene, and react at 25°C to obtain 6-perfluorobutylUPy@POSS.

[0076] S4: PPS fibers were immersed in a tetrahydrofuran solution (15wt%) of 6-perfluorobutylUPy@POSS and subjected to ultrasonic treatment in sequence, followed by hot pressing at 120℃ and 10MPa for 10min to obtain a fiber-core-shell structure.

[0077] S5: The fiber-core-shell structure and perfluoroether rubber are mixed at a mass ratio of 1:10 and then compounded at 60°C to obtain 6-perfluorobutylUPy@POSS grafted PPS fiber reinforced fluoroether rubber.

[0078] The preparation method of corrosion-resistant fluoroether rubber polymer materials includes the following steps:

[0079] (1) The modified fluoroether rubber polymer was mixed at 70°C, and then acid absorber and fumed silica were added and mixed again.

[0080] (2) Add poly(fluoroethylene propylene) (FEP) micro powder and B4C nanowire composite functional additives and mix at 50°C, then add crosslinking agent and accelerator and mix evenly.

[0081] (3) Vulcanization is carried out at 150℃ to obtain a corrosion-resistant fluoroether rubber polymer material.

[0082] Example 2

[0083] In an exemplary embodiment of the present invention, the corrosion-resistant fluoroether rubber polymer material comprises 130 parts of modified perfluoroether rubber polymer, 30 parts of carbon black, 3 parts of crosslinking agent 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 3 parts of accelerator triallyl isocyanurate, 7 parts of composite functional additives of poly(fluoroethylene propylene) (FEP) micro powder and B4C nanowires, wherein the mass ratio of B4C nanowires to poly(fluoroethylene propylene) micro powder is 1:4, the particle size of poly(fluoroethylene propylene) micro powder is 30 μm, the diameter of B4C nanowires is 10 nm and the length is 4 μm, and 8 parts of acid-absorbing agent nano-magnesium oxide with a particle size of 40 nm.

[0084] The modified perfluoroether rubber polymer is a 6-perfluorobutylUPy@POSS grafted PPS fiber reinforced perfluoroether rubber. The preparation method includes the following steps:

[0085] S1: Under a nitrogen atmosphere, the 2-ureido-4(1H)-pyrimidinone derivative (synthetic reference) was synthesized. Figure 1 R1 is methyl, R2 is n-butyl), 1-iodoperfluorobutane, and azobisisobutyronitrile are mixed in a reaction flask at a molar ratio of 1:2:0.5. Anhydrous and oxygen-free 1,2-dichloroethane is added and stirred to obtain a suspension. Hexamethyldistin is slowly added dropwise under an ice-water bath. The reaction mixture is heated to 85°C and reacted for 10 h. After cooling to room temperature, saturated NH4Cl aqueous solution is added for quenching. The mixture is extracted with dichloromethane, and the organic phases are combined. The mixture is washed successively with water and saturated brine. After drying, concentration, and purification by column chromatography, 6-perfluorobutylUPy is obtained.

[0086] S2: 6-PerfluorobutylUPy and 1,3-diaminopropane are mixed in a molar ratio of 1:2, and anhydrous dimethyl sulfoxide is added. The mixture is reacted at 5°C to obtain 6-perfluorobutylUPy-NH2. Then, di(trichloromethyl) carbonate is added, wherein the molar ratio of 6-perfluorobutylUPy-NH2 to di(trichloromethyl) carbonate is 1:0.6. Anhydrous dichloromethane is added, and the mixture is reacted at 20°C to obtain 6-perfluorobutylUPy-NCO.

[0087] S3: Mix aminopropylheptaisobutylsilsesquioxane and 6-perfluorobutylUPy-NCO in a molar ratio of 1:2, add anhydrous toluene, and react at 30°C to obtain 6-perfluorobutylUPy@POSS.

[0088] S4: PPS fibers were immersed in a tetrahydrofuran solution (25wt%) of 6-perfluorobutylUPy@POSS and subjected to ultrasonic treatment in sequence, followed by hot pressing at 125℃ and 10MPa for 10min to obtain a fiber-core-shell structure.

[0089] S5: The fiber-core-shell structure and perfluoroether rubber are mixed at a mass ratio of 1:15 and then compounded at 80°C to obtain 6-perfluorobutylUPy@POSS grafted PPS fiber reinforced fluoroether rubber.

[0090] The preparation method of corrosion-resistant fluoroether rubber polymer materials includes the following steps:

[0091] (1) The modified fluoroether rubber polymer was mixed at 60°C, and then an acid absorber and fumed silica were added and mixed again.

[0092] (2) Add poly(fluoroethylene propylene) (FEP) micro powder and B4C nanowire composite functional additives and mix at 50°C, then add crosslinking agent and accelerator and mix evenly.

[0093] (3) Vulcanization is carried out at 180℃ to obtain a corrosion-resistant fluoroether rubber polymer material.

[0094] Example 3

[0095] In an exemplary embodiment of the present invention, the corrosion-resistant fluoroether rubber polymer material comprises 120 parts of modified perfluoroether rubber polymer, 25 parts of fumed silica, 2 parts of crosslinking agent bis-tert-butylperoxyisopropylbenzene, 4 parts of accelerator triallyl isocyanurate, 5 parts of composite functional additives of poly(fluoroethylene propylene) (FEP) micro powder and B4C nanowires, wherein the mass ratio of B4C nanowires to poly(fluoroethylene propylene) micro powder is 1:3, the particle size of poly(fluoroethylene propylene) micro powder is 10 μm, the diameter of B4C nanowires is 10 nm and the length is 3 μm, and 6 parts of acid-absorbing agent nano-magnesium oxide with a particle size of 10 nm.

[0096] The modified perfluoroether rubber polymer is a 6-perfluorobutylUPy@POSS grafted PPS fiber reinforced perfluoroether rubber. The preparation method is based on Example 1, with the main difference being: the PPS fibers are modified with a fluorinated carboxylic acid. The preparation method for the fluorinated carboxylic acid-modified PPS fibers includes the following steps:

[0097] Polyphenylene sulfide (PPS) fibers were ultrasonically cleaned with acetone / ethanol (volume ratio 1:1) for 30 min, and then vacuum dried at 110℃ to obtain the final product. The vacuum was then reduced to 10... -2 Argon gas was introduced to 40 Pa, and radio frequency treatment at 200 W was performed for 5 min to generate PPS free radicals. While maintaining a vacuum, a mixture of acrylic acid and perfluorooctyl iodine vapor was introduced, and plasma treatment at 100 W was performed for 15 min. The mixture was then removed under nitrogen protection and aged at 60 °C for 24 h to quench the free radicals, yielding modified PPS fibers. Other steps were the same as in Example 1.

[0098] Example 4

[0099] Based on Example 3, the main difference is that the PPS fibers are modified with fluorinated carboxylic acids. The preparation method of fluorinated carboxylic acid-modified PPS fibers includes the following steps:

[0100] Polyphenylene sulfide (PPS) fibers were ultrasonically cleaned with acetone / ethanol (volume ratio 1:1) for 30 min, and then vacuum dried at 120℃ to obtain the final product. The vacuum was then reduced to 10... -2 The pressure was increased to 60 Pa by argon gas, and the mixture was treated with 300 W radio frequency for 5 min to generate PPS free radicals. While maintaining a vacuum, a mixture of acrylic acid and perfluorooctyl iodine vapor was introduced, and the mixture was treated with 150 W plasma for 15 min. The mixture was then removed under nitrogen protection and aged at 70 °C for 24 h to quench the free radicals, yielding modified PPS fibers. Other steps were the same as in Example 3.

[0101] Example 5

[0102] Based on Example 3, the main difference lies in the preparation method of the composite functional additive of perfluoroethylene propylene (FEP) micro powder and B4C nanowires, which includes the following steps:

[0103] a1: B4C nanowires were added to an ethanol solution (1.5 wt%) containing perfluorooctyltriethoxysilane and refluxed at 70 °C to obtain fluorinated B4C nanowires.

[0104] a2: Fluorinated B4C nanowires were dispersed in an ethanol solution, poly(perfluoroethylene propylene) micropowder was added, and the mixture was subjected to ultrasonic treatment. The pH was adjusted to 2, and a 15kV high-voltage electric field was applied for 20 minutes to allow the positively charged B4C to directionally combine with the negatively charged FEP. The mixture was then freeze-dried at -40℃ to obtain FEP@B4C composite powder. Other steps were the same as in Example 3.

[0105] Example 6

[0106] Based on Example 3, the main difference lies in the preparation method of the composite functional additive of perfluoroethylene propylene (FEP) micro powder and B4C nanowires, which includes the following steps:

[0107] a1: Add B4C nanowires to an ethanol solution containing perfluorooctyltriethoxysilane (perfluorooctyltriethoxysilane accounts for 2 wt%) and reflux at 80 °C to obtain fluorinated B4C nanowires.

[0108] a2: Fluorinated B4C nanowires were dispersed in an ethanol solution, poly(perfluoroethylene propylene) micropowder was added, and the mixture was subjected to ultrasonic treatment. The pH was adjusted to 3, and a 15kV high-voltage electric field was applied for 20 minutes to allow the positively charged B4C to directionally combine with the negatively charged FEP. The mixture was then freeze-dried at -40℃ to obtain FEP@B4C composite powder. Other steps were the same as in Example 3.

[0109] Example 7

[0110] The main difference from Example 1 is that the functional additive is only poly(fluoroethylene propylene) (FEP) micro powder.

[0111] Example 8

[0112] The main difference from Example 1 is that the functional additive is only B4C nanowires.

[0113] Comparative Example 1

[0114] Based on Example 1, the main difference lies in the preparation method of the corrosion-resistant fluoroether rubber polymer material, which includes the following steps:

[0115] (1) Mix perfluoroether rubber and PPS fiber at 70°C, then add acid absorber and fumed silica and continue mixing.

[0116] (2) Add poly(fluoroethylene propylene) (FEP) micro powder and B4C nanowire composite functional additives and mix at 50°C, then add crosslinking agent and accelerator and mix evenly.

[0117] (3) Vulcanization is carried out at 150℃ to obtain a corrosion-resistant fluoroether rubber polymer material.

[0118] Comparative Example 2

[0119] The main difference from Example 1 is that no functional additives were added.

[0120] Test case

[0121] The corrosion-resistant fluoroether rubber polymer materials prepared in the examples and comparative examples were subjected to performance tests, and the test results are shown in Table 1.

[0122] Temperature resistance test: After aging the corrosion-resistant fluoropolymer material at 200℃ for 168 hours, the tensile strength retention rate is tested.

[0123] Acid resistance test: The corrosion-resistant fluoroether rubber polymer material was immersed in 98% concentrated sulfuric acid at 100°C for 70 hours, and the change rate of tensile strength was measured.

[0124] Alkali resistance test: The corrosion-resistant fluoroether rubber polymer material was immersed in a 70% sodium hydroxide solution at 100°C for 70 hours, and the change rate of tensile strength was measured.

[0125] Abrasion resistance: Abrasion resistance was tested according to GB / T 1689-2014, Akron abrasion (cm). 3 / 1.61km.

[0126] Table 1

[0127]

[0128]

[0129] Referring to Table 1, the corrosion-resistant fluoropolymer rubber material exhibits good temperature resistance, with a tensile strength retention rate of not less than 80% at temperatures not lower than 200℃. It also demonstrates good high-temperature corrosion resistance, with a tensile strength change rate not exceeding 2.5% under acidic conditions and not exceeding 5% under alkaline conditions. Furthermore, it exhibits good abrasion resistance, with an Akron abrasion wear not exceeding 25 × 10⁻⁶. -3 cm 3 / 1.61km.

[0130] In summary, the corrosion-resistant fluoroether rubber polymer material of the present invention can be applied to the rubber components of windshield pumps, which can improve the corrosion resistance, mechanical strength and wear resistance of the rubber components at high temperatures.

[0131] The above description is merely an embodiment of the present invention and is not intended to limit the invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principle of the present invention should be included within the scope of the claims of the present invention.

Claims

1. A corrosion-resistant fluoropolymer rubber material, characterized in that, By weight, the corrosion-resistant fluoroether rubber polymer material includes 100-130 parts of modified perfluoroether rubber polymer, 20-30 parts of filler, 1-3 parts of crosslinking agent, 2-5 parts of accelerator, 3-10 parts of functional additives, and 5-10 parts of acid absorber. Among them, the modified fluoroether rubber polymer is 6-perfluorobutylUPy@POSS grafted PPS fiber reinforced perfluoroether rubber.

2. The corrosion-resistant fluoroether rubber polymer material according to claim 1, characterized in that, The preparation method of 6-perfluorobutylUPy@POSS grafted PPS fiber reinforced perfluoroether rubber includes the following steps: S1: Under an inert atmosphere, 2-ureido-4(1H)-pyrimidinone derivative, 1-iodoperfluorobutane, free radical initiator and first solvent are mixed, then the initiator is added, and the mixture is reacted at a first temperature to obtain 6-perfluorobutylUPy; S2: 6-PerfluorobutylUPy is mixed with 1,3-diaminopropane, a second solvent is added, and the mixture is reacted at a second temperature to obtain 6-perfluorobutylUPy-NH2; then bis(trichloromethyl) carbonate and a third solvent are added, and the mixture is reacted at a third temperature to obtain 6-perfluorobutylUPy-NCO; S3: Mix aminopropylheptaisobutylsilsesquioxane and 6-perfluorobutylUPy-NCO, add a fourth solvent, and react at a fourth temperature to obtain 6-perfluorobutylUPy@POSS; S4: Fluorocarboxylic acid-modified PPS fibers were immersed in a solution of 6-perfluorobutylUPy@POSS, and then subjected to ultrasonic treatment and hot pressing to obtain a fiber-core-shell structure. S5: The fiber-core-shell structure is mixed with perfluoroether rubber at the fifth temperature to obtain 6-perfluorobutylUPy@POSS grafted PPS fiber reinforced fluoroether rubber.

3. The corrosion-resistant fluoroether rubber polymer material according to claim 2, characterized in that, The preparation method of fluorinated carboxylic acid modified PPS fibers includes the following steps: PPS fibers were plasma activated to generate PPS free radicals; then, a mixture of acrylic acid and perfluorooctyl iodine vapor was introduced under vacuum conditions for plasma treatment to obtain PPS fibers modified with fluorinated carboxylic acids.

4. The corrosion-resistant fluoropolymer rubber material according to claim 1, characterized in that, The functional additives are composite functional additives of perfluoroethylene propylene micro powder and B4C nanowires.

5. The corrosion-resistant fluoroether rubber polymer material according to claim 4, characterized in that, The preparation method of the composite functional additive of poly(perfluoroethylene propylene) micro powder and B4C nanowires includes the following steps: a1: B4C nanowires were added to an ethanol solution containing a coupling agent and refluxed at a sixth temperature to obtain fluorinated B4C nanowires. a2: Fluorinated B4C nanowires were dispersed in a fifth solvent, poly(perfluoroethylene propylene) micro powder was added, ultrasonic treatment was performed, pH was adjusted to 2-4, and an electric field was applied to obtain FEP@B4C composite powder.

6. The corrosion-resistant fluoroether rubber polymer material according to claim 5, characterized in that, The particle size of the polytetrafluoroethylene propylene micro powder is less than 100 μm, the diameter of the B4C nanowires is less than 50 nm, and the length of the B4C nanowires is 1-4 μm.

7. The corrosion-resistant fluoroether rubber polymer material according to claim 1, characterized in that, The filler is one or both of carbon black or fumed silica. And / or the crosslinking agent is one or more of bis-tert-butylperoxyisopropylbenzene, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane or 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane; And / or the accelerator is triallyl isocyanurate; And / or the acid absorbent is one of zinc oxide, calcium hydroxide or nano magnesium oxide.

8. A method for preparing a corrosion-resistant fluoroether rubber polymer material as claimed in any one of claims 1-7, characterized in that, The preparation method includes the following steps: (1) The modified fluoroether rubber polymer is mixed at a certain temperature, and then acid absorber and filler are added and mixed again. (2) Add functional additives and continue mixing at a certain temperature, then add crosslinking agent and accelerator and mix well; (3) Then vulcanize at a certain temperature to obtain corrosion-resistant fluoroether rubber polymer material.

9. The preparation method according to claim 8, characterized in that, In step (1), the temperature must not exceed 80℃; And / or the temperature in step (2) is not higher than 60°C; And / or the vulcanization temperature in step (3) is 150-180℃.

10. The application of a corrosion-resistant fluoroether rubber polymer material as described in any one of claims 1-7 in a wind pump.

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