High-toughness conjoined rubber tube and production process thereof

Abstract

The invention discloses a high-toughness conjoined rubber tube and a production process thereof, and belongs to the technical field of rubber tubes. The high-toughness connected rubber tube comprises the following raw materials in parts by mass: 100 parts of ethylene propylene diene monomer, 8-15 parts of phenyl silicone rubber, 20-25 parts of filler, 6-10 parts of modified hydroxyl-terminated polysilsesquioxane, 2-5 parts of a vulcanizing agent, 1-3 parts of a vulcanization accelerator, 3-5 parts of a vinyl silane coupling agent and 1.5-3.5 parts of an antioxidant, wherein a polycarbonate chain segment is grafted on a molecular chain of the modified hydroxyl-terminated polysilsesquioxane. Blending of the phenyl silicone rubber and the ethylene propylene diene monomer can help to effectively transfer stress, resist external force, improve the toughness of the connected rubber tube and make up for the problem of poor wear resistance of the ethylene propylene diene monomer. The introduction of the polycarbonate chain segment can improve the compatibility of the components, form an interpenetrating network structure, enhance the toughness and other mechanical properties of the material, and can recover as soon as possible under the action of external force, thereby prolonging the service life of the rubber tube.

Description

Technical Field

[0001] The invention belongs to the technical field of rubber hoses, and in particular relates to a high-toughness one-piece hose and a production process thereof. Background Art

[0002] A one-piece hose is a flexible pipe used to transport liquids or gases in industry, agriculture or home. It has certain elasticity and pressure resistance, can be bent without easily breaking or leaking. In actual application, the one-piece hose can be seamlessly connected with various joints to form a complete transportation system. It is widely used in automobiles, chemicals, construction, gardening, fire protection and other fields to transport water, air, oil, chemicals, etc.

[0003] However, during the material transmission process, the hose itself will be subjected to the pressure brought by the conveying medium. Hoses with poor toughness or poor mechanical properties will be at risk of sudden rupture. At the same time, when the hose is subjected to external forces, such as twisting, pulling or collision, there will also be a risk of leakage. Therefore, in order to extend the service life of the one-piece hose, increase the safety of operators and equipment, and reduce the cost of long-term maintenance and replacement, it is of great significance to prepare a one-piece hose with high toughness and high performance. Summary of the invention

[0004] The purpose of the present invention is to provide a high-toughness one-piece rubber hose and a production process thereof.

[0005] This is to solve the problem of insufficient toughness and poor mechanical properties of the one-piece hose, which may cause hose rupture and leakage, and thus significantly reduce its service life.

[0006] The purpose of the present invention can be achieved through the following technical solutions:

[0007] In a first aspect, the present application provides a high-toughness one-piece rubber hose, which includes the following raw materials in parts by weight:

[0008] 100 parts of EPDM rubber;

[0009] 8-15 parts of phenyl silicone rubber;

[0010] 20-25 parts of filler;

[0011] 6 to 10 parts of modified hydroxyl-terminated polysilsesquioxane;

[0012] 2 to 5 parts of vulcanizing agent;

[0013] 1 to 3 parts of vulcanization accelerator;

[0014] 3-5 parts of vinyl silane coupling agent;

[0015] 1.5-3.5 parts of antioxidant;

[0016] The molecular chain of the modified hydroxyl-terminated polysilsesquioxane is grafted with a polycarbonate segment.

[0017] Preferably, the vulcanizing agent includes one or more combinations of sulfur, thiuram, and disulfide vulcanizing agents.

[0018] Preferably, the vulcanization accelerator includes one or a combination of two of a thiuram vulcanization accelerator and a sulfenamide vulcanization accelerator.

[0019] Preferably, the antioxidant includes one or more combinations of antioxidant 1010, antioxidant 1035, antioxidant 1520, antioxidant 622, and antioxidant B900.

[0020] By adopting the above technical scheme, a blended rubber system of EPDM rubber and phenyl silicone rubber is adopted in the present application. On the one hand, phenyl silicone rubber itself has excellent low temperature resistance and high elastic modulus, can effectively transmit stress, and is not prone to local deformation. After being blended with EPDM rubber, it can be evenly dispersed in the matrix of EPDM rubber in the form of tiny particles, absorb external forces, delay the formation and expansion of cracks, and help the hose to resist greater external forces, thereby improving the overall flexibility and elasticity of the hose; on the other hand, the introduction of phenyl in phenyl silicone rubber can destroy the regularity of the molecular structure of silicone rubber itself, reduce the crystallinity of the polymer, and is more conducive to improving the flexibility of the material. At the same time, phenyl, as a rigid group, can improve the problem of poor wear resistance of EPDM rubber after blending with EPDM rubber, thereby increasing the service life of the hose.

[0021] Modified terminal hydroxyl polysilsesquioxane is also added in the present application. Polysilsesquioxane has a unique cage-like nanostructure and has good thermal stability, chemical stability and dimensional stability. After being blended with EPDM rubber, it can significantly improve the mechanical properties and thermal stability of the material. At the same time, the strong interface interaction formed between the polysilsesquioxane particles and the EPDM rubber matrix can effectively transfer stress and improve the tensile strength and toughness of the material.

[0022] At the same time, a polycarbonate segment is grafted onto the molecular chain of the modified terminal hydroxyl polysilsesquioxane. On the one hand, the polycarbonate segment can connect the terminal hydroxyl polysilsesquioxane and the EPDM rubber matrix, improve the compatibility between the polysilsesquioxane and the EPDM rubber, increase the dispersibility of the polysilsesquioxane, and enhance the interfacial adhesion between the polysilsesquioxane and the matrix material, thereby providing an effective energy dissipation path when subjected to external force.

[0023] On the other hand, the hydroxy-terminated polysilsesquioxane modified with polycarbonate segments can form a stronger chemical bond with the EPDM rubber matrix, and the polycarbonate segments can form an interpenetrating network structure with the EPDM rubber through physical crosslinking, thereby increasing the crosslinking density of the material, enhancing the mechanical properties of the material, and improving the overall performance of the material. In addition, the hydroxy-terminated polysilsesquioxane modified with polycarbonate segments can achieve performance complementarity between polycarbonate and polysilsesquioxane, thereby obtaining a composite material with a more stable structure and better mechanical properties, which helps to improve the overall performance of the one-piece hose.

[0024] Finally, the introduction of polycarbonate chain segments can act as stress concentration points when the hose is subjected to external forces, preventing the rapid propagation of cracks, promoting the energy consumption of cracks, increasing the resistance to crack expansion, and improving the overall toughness. The network structure formed between the polycarbonate chain segments and the EPDM rubber can be rearranged and recovered after the material is deformed, thereby improving the recovery ability and fatigue resistance of the hose, thereby increasing the service life of the hose.

[0025] Preferably, the raw materials of the modified hydroxyl-terminated polysilsesquioxane include hydroxyl-terminated polysilsesquioxane and epoxy carbonate monomer in a mass ratio of 1:(0.3-0.5).

[0026] Preferably, the epoxy polycarbonate monomer includes a combination of one or more of propylene carbonate, ethylene carbonate, glycidyl carbonate, and cyclohexyl epoxy carbonate.

[0027] Preferably, the modified hydroxyl-terminated polysilsesquioxane is prepared according to the following method:

[0028] S101. octavinyl cage silsesquioxane is added to anhydrous dichloromethane, and trifluoromethanesulfonic acid is added after stirring to dissolve, and the mixture is stirred at a constant temperature of 25 to 30° C. for 4 to 5 hours. After the reaction is completed, the lower organic phase is collected by rotary evaporation extraction, and then an acetone aqueous solution is added to the organic phase, and the mixture is hydrolyzed at a constant temperature of 25 to 30° C. for 10 to 12 hours. After the hydrolysis reaction, the mixture is allowed to stand for stratification, and the lower organic phase is dried, rotary evaporated, filtered and chromatographically separated to obtain a hydroxy-terminated polysilsesquioxane;

[0029] S102. Add the catalyst and the hydroxy-terminated polysilsesquioxane obtained in S101 to the epoxy carbonate monomer, mix well, raise the temperature to 200-220° C. under a nitrogen atmosphere, stir and react for 12-15 hours, and finally dry and rotary evaporate to obtain the modified hydroxy-terminated polysilsesquioxane.

[0030] Preferably, the catalyst is a metal salt catalyst.

[0031] More preferably, the catalyst comprises a combination of one or more of sodium stannate, zinc chloride, potassium carbonate and ferric chloride.

[0032] Preferably, the mass ratio of the catalyst to the hydroxy-terminated polysilsesquioxane is (0.6-1):100.

[0033] Preferably, the mass ratio of octavinyl cage silsesquioxane to trifluoromethanesulfonic acid is 10:(2.5-3).

[0034] By adopting the above technical scheme, octavinyl cage silsesquioxane is subjected to hydroxylation treatment to introduce terminal hydroxyl groups on the molecular chain of polysilsesquioxane. Further, epoxy carbonate monomer is ring-opened under the action of a catalyst, and the terminal hydroxyl groups on the polysilsesquioxane are used as active sites to link and self-polymerize to form polycarbonate segments. The formed polycarbonate segment-modified terminal hydroxyl polysilsesquioxane has good compatibility with an EPDM rubber matrix, forms a strong interface interaction force, and is more conducive to improving the stability, toughness and other mechanical properties of the rubber matrix.

[0035] Preferably, the phenyl silicone rubber is low-phenyl silicone rubber.

[0036] Preferably, the phenyl content in the low-phenyl silicone rubber is 5-10%.

[0037] By adopting the above technical scheme, low-phenyl silicone rubber has better low-temperature resistance than other phenyl silicone rubbers. After blending with EPDM rubber, it can better compensate for the tendency of EPDM rubber to become brittle at low temperatures, so that the obtained one-piece hose also exhibits higher toughness in low-temperature environments, thereby improving the applicability of the one-piece hose.

[0038] Preferably, the filler is amino-modified nano-silica.

[0039] Preferably, the raw materials of amino-modified nano-silica include nano-silica and aminosilane coupling agent in a mass ratio of 1:(0.25-0.4).

[0040] Preferably, the aminosilane coupling agent includes a combination of one or more of γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β (aminoethyl)-γ-aminopropyltrimethoxysilane, N-β (aminoethyl)-γ-aminopropylmethyldimethoxysilane, N-β (aminoethyl)-γ-aminopropyltriethoxysilane, and N-β (aminoethyl)-γ-aminopropylmethyldiethoxysilane.

[0041] By adopting the above technical solution, nano-silicon dioxide is used as a filler for the EPDM rubber matrix. Its large specific surface area can enhance the interface interaction with the matrix and improve the strength of the material. The introduction of nano-ions also limits the free rotation of the EPDM rubber molecular chain, improves the wear resistance of the composite material, and makes up for the poor wear resistance of the EPDM rubber. At the same time, the addition of nano-silicon dioxide can also promote the formation of more effective cross-linking points between the vulcanizer and the EPDM rubber molecular chain, forming a more uniform and dense vulcanization network, improving the vulcanization efficiency while improving the mechanical properties of the hose.

[0042] Moreover, the nano-silica is amino-modified nano-silica, which can improve its compatibility in the matrix rubber, and the nano-silica modified by the aminosilane coupling agent also has good compatibility and affinity with the phenyl silicone rubber in the material, which greatly reduces the phase separation phenomenon and is beneficial to the uniform distribution of the nano-silica; and the amino group in the amino-modified nano-silica can also react and bond with the hydroxyl group in the modified terminal hydroxyl polysilsesquioxane to form intermolecular forces such as hydrogen bonds, thereby increasing the cross-linking density inside the hose material and improving the toughness and other mechanical properties of the material.

[0043] Preferably, the vinyl silane coupling agent includes a combination of one or more of vinyl triethoxy silane, vinyl trimethoxy silane and vinyl methyl diethoxy silane.

[0044] By adopting the above technical scheme, in order to further improve the blending performance between EPDM rubber and phenyl silicone rubber, the addition of vinyl silane coupling agent can effectively improve the compatibility between the two, and serve as a "bridge" between the two rubbers, connecting and linking the two rubbers to each other, which helps to effectively transfer stress and thus helps to improve the toughness of the material.

[0045] In a second aspect, the present application provides a production process for a high-toughness one-piece hose, comprising the following process steps:

[0046] S201. The EPDM rubber and the phenyl silicone rubber are first mixed to obtain a first mixed rubber material; the first mixed rubber material is second mixed with a modified hydroxyl-terminated polysilsesquioxane, a filler, a vinyl silane coupling agent and an antioxidant to obtain a second mixed rubber material; the second mixed rubber material is third mixed with a vulcanizing agent and a vulcanization accelerator to obtain a mixed rubber material; wherein the first mixing temperature is 80 to 100° C., the second mixing temperature is 100 to 140° C., and the third mixing temperature is 60 to 90° C.;

[0047] S202. The obtained mixed rubber material is extruded into a tube, and then vulcanized at 140 to 160°C;

[0048] S203. Cooling and cutting the vulcanized rubber hose to obtain a high-toughness one-piece rubber hose.

[0049] Beneficial effects of the present invention:

[0050] 1. In the present application, EPDM rubber and phenyl silicone rubber are blended. Under the action of a compatibilizer, namely a vinyl silane coupling agent, the compatibility between the two is significantly improved. The phenyl silicone rubber can be evenly distributed in the EPDM rubber matrix. When subjected to external forces, the high elastic modulus of the phenyl silicone rubber can effectively transmit stress and is not prone to local deformation, which helps the hose to resist greater external forces and give the hose better toughness. In addition, the introduction of phenyl as a rigid group into the EPDM rubber can improve its poor wear resistance and increase the service life of the one-piece hose.

[0051] 2. The present application also adds a modified terminal hydroxyl polysilsesquioxane, on the molecular chain of which a polycarbonate segment is grafted. In addition to enhancing the interfacial adhesion between the polysilsesquioxane and the matrix material, the introduction of the polycarbonate segment can provide an effective energy dissipation path when subjected to external force, thereby reducing the risk of sudden rupture of the hose; it can form an interpenetrating network structure with the EPDM rubber through physical crosslinking, thereby increasing the crosslinking density of the material and enhancing the mechanical properties of the material; it can also rearrange and recover the material after deformation, thereby improving the resilience and fatigue resistance of the hose; and the polycarbonate segment, as a stress concentration point, can also effectively prevent the propagation of cracks, thereby increasing the toughness and other mechanical properties of the one-piece hose. DETAILED DESCRIPTION

[0052] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0053] Preparation Example

[0054] Preparation Example 1 Amino-modified nano-silica

[0055] Preparation Example 1-1, an amino-modified nano-silica, is prepared according to the following method:

[0056] Add 10g of nano-silica (average particle size of 100nm) to 500ml of xylene, and after uniform dispersion, add 3.5g of γ-aminopropyltriethoxysilane, raise the temperature to 75°C, stir the reaction for 4h, let it stand for 12h, and then filter, wash, dry and grind to obtain amino-modified nano-silica.

[0057] Preparation Example 1-2, an amino-modified nano-silica, is different from Preparation Example 1-1 only in that the added amount of γ-aminopropyltriethoxysilane is 2.5 g.

[0058] Preparation Example 1-3, an amino-modified nano-silica, is different from Preparation Example 1-1 only in that the added amount of γ-aminopropyltriethoxysilane is 4 g.

[0059] Preparation Example 2: Modified hydroxyl-terminated polysilsesquioxane

[0060] Preparation Example 2-1, a modified hydroxyl-terminated polysilsesquioxane, was prepared according to the following method:

[0061] S101. Add 10 g of octavinyl cage-type silsesquioxane to 150 ml of anhydrous dichloromethane, stir to dissolve, then add 2.8 g of trifluoromethanesulfonic acid, stir at 25°C for 4.5 h, collect the lower organic phase by rotary evaporation after the reaction, then add 25 ml of 80% acetone aqueous solution to the organic phase, and hydrolyze at 25°C for 12 h. After the hydrolysis reaction, stand and separate, and separate the lower organic phase by drying, rotary evaporation, suction filtration and chromatography to obtain terminal hydroxyl polysilsesquioxane;

[0062] S102. Add 0.8 g of sodium stannate and 100 g of the terminal hydroxyl polysilsesquioxane obtained in S101 to 40 g of propylene carbonate, mix well, raise the temperature to 210° C. under a nitrogen atmosphere, stir and react for 14 h, and finally dry and rotary evaporate to obtain the modified terminal hydroxyl polysilsesquioxane.

[0063] Preparation Example 2-2, a modified hydroxy-terminated polysilsesquioxane, is different from Preparation Example 2-1 only in that the added amount of propylene carbonate is 30 g and the added amount of sodium stannate is 0.6 g.

[0064] Preparation Example 2-3, a modified hydroxy-terminated polysilsesquioxane, is different from Preparation Example 2-1 only in that the added amount of propylene carbonate is 50 g and the added amount of sodium stannate is 1 g.

[0065] Preparation Example 2-4, a modified hydroxy-terminated polysilsesquioxane, is different from Preparation Example 2-1 only in that propylene carbonate is replaced by an equal amount of glycidyl carbonate.

[0066] Preparation Example 2-5, a modified hydroxy-terminated polysilsesquioxane, is different from Preparation Example 2-1 only in that the amount of propylene carbonate added is 20 g.

[0067] Preparation Example 2-6, a modified hydroxy-terminated polysilsesquioxane, is different from Preparation Example 2-1 only in that the amount of propylene carbonate added is 60 g.

[0068] Preparation Example 2-7, a modified hydroxyl-terminated polysilsesquioxane, was prepared according to the following method:

[0069] Add 10 g of octavinyl cage-type silsesquioxane to 150 ml of anhydrous dichloromethane, stir to dissolve, then add 2.8 g of trifluoromethanesulfonic acid, and stir at a constant temperature of 25°C for 4.5 hours. After the reaction is completed, collect the lower organic phase by rotary evaporation extraction, and then add 25 ml of 80% acetone aqueous solution to the organic phase, and hydrolyze at a constant temperature of 25°C for 12 hours. After the hydrolysis reaction, let it stand and separate the layers. The lower organic phase is obtained by drying, rotary evaporation, suction filtration and chromatography separation.

[0070] Example

[0071] Embodiment 1, a high-toughness one-piece hose, comprises the following process steps:

[0072] S201. 1 kg of ethylene propylene diene monomer rubber (Mooney viscosity of 70 MU) and 120 g of low phenyl silicone rubber (phenyl content of 5-10%) are first mixed to obtain a first mixed rubber material; the first mixed rubber material is second mixed with 80 g of the modified terminal hydroxyl polysilsesquioxane prepared in Preparation Example 2-1, 230 g of the amino-modified nano-silica prepared in Preparation Example 1-1, 40 g of vinyl trimethoxy silane and 25 g of antioxidant B900 to obtain a second mixed rubber material; the second mixed rubber material is third mixed with 40 g of sulfur and 20 g of sulfonamide vulcanization accelerator to obtain a mixed rubber material; wherein the first mixing temperature is 85° C., the second mixing temperature is 130° C., and the third mixing temperature is 80° C.;

[0073] S202. The obtained mixed rubber material is extruded into a tube, and then vulcanized at 150°C;

[0074] S203. Cool the vulcanized rubber hose and cut it to obtain a high-toughness one-piece rubber hose.

[0075] Embodiments 2 to 5 are high-toughness one-piece hoses, which differ from Embodiment 1 only in that the raw materials and their proportions are adjusted, as shown in Table 1:

[0076] Table 1 Formula table of Example 1 to Example 5

[0077] Example 1 Example 2 Example 3 Example 4 Example 5 EPDM 100 100 100 100 100 Low phenyl silicone rubber 120 80 150 120 120 Amino modified nano silica 230 230 230 200 250 Modified hydroxyl-terminated polysilsesquioxane 80 80 80 60 100 Vinyltrimethoxysilane 40 30 50 40 40 Antioxidant B900 25 15 35 25 25 sulfur 40 40 40 20 50 Sulfenamide vulcanization accelerator 20 20 20 10 30

[0078] Among them, Example 2 uses the amino-modified nano-silica prepared in Preparation Example 1-2; Example 3 uses the amino-modified nano-silica prepared in Preparation Example 1-3; Example 4 uses the modified terminal hydroxyl polysilsesquioxane prepared in Preparation Example 2-3; Example 5 uses the modified terminal hydroxyl polysilsesquioxane prepared in Preparation Example 2-2.

[0079] Example 6 is a high-toughness one-piece hose, which is different from Example 1 only in that the modified hydroxyl-terminated polysilsesquioxane prepared in Preparation Example 2-1 is replaced by an equal amount of the modified hydroxyl-terminated polysilsesquioxane prepared in Preparation Example 2-4.

[0080] Example 7 is a high-toughness one-piece hose, which is different from Example 1 only in that the modified hydroxyl-terminated polysilsesquioxane prepared in Preparation Example 2-1 is replaced by an equal amount of the modified hydroxyl-terminated polysilsesquioxane prepared in Preparation Example 2-5.

[0081] Example 8 is a high-toughness one-piece hose, which is different from Example 1 only in that the modified hydroxyl-terminated polysilsesquioxane prepared in Preparation Example 2-1 is replaced by an equal amount of the modified hydroxyl-terminated polysilsesquioxane prepared in Preparation Example 2-6.

[0082] Example 9 is a high-toughness one-piece rubber hose, which is different from Example 1 only in that an equal amount of high-phenyl silicone rubber (phenyl content is 30-50%) is used to replace the low-phenyl silicone rubber.

[0083] Example 10 is a high-toughness one-piece rubber hose, which is different from Example 1 only in that an equal amount of nano-silicon dioxide (average particle size of 100 nm) is used to replace the amino-modified nano-silicon dioxide prepared in Preparation Example 1-1.

[0084] Comparative Example

[0085] Comparative Example 1 is a high-toughness one-piece hose, which is different from Example 1 only in that the added amount of low-phenyl silicone rubber is 50 g.

[0086] Comparative Example 2 is a high-toughness one-piece hose, which is different from Example 1 only in that the added amount of low-phenyl silicone rubber is 200 g.

[0087] Comparative Example 3 is a high-toughness one-piece hose, which is different from Example 1 only in that no low-phenyl silicone rubber is added.

[0088] Comparative Example 4 is a high-toughness one-piece hose, which is different from Example 1 only in that the amount of modified terminal hydroxyl polysilsesquioxane prepared in Preparation Example 2-1 added is 40 g.

[0089] Comparative Example 5 is a high-toughness one-piece rubber hose, which is different from Example 1 only in that the amount of modified terminal hydroxyl polysilsesquioxane prepared in Preparation Example 2-1 added is 120 g.

[0090] Comparative Example 6 is a high-toughness one-piece rubber hose, which is different from Example 1 only in that the modified hydroxyl-terminated polysilsesquioxane prepared in Preparation Example 2-1 is not added.

[0091] Comparative Example 7 is a high-toughness one-piece rubber hose, which is different from Example 1 only in that the modified hydroxyl-terminated polysilsesquioxane prepared in Preparation Example 2-1 is replaced by an equal amount of the modified hydroxyl-terminated polysilsesquioxane prepared in Preparation Example 2-7.

[0092] Performance testing

[0093] 1. Mechanical properties test: According to the relevant records in GB / T 528-2009 "Determination of tensile stress-strain properties of vulcanized rubber or thermoplastic rubber", the tensile strength test of the vulcanized rubber obtained in the embodiment and the comparative example was carried out at room temperature (25°C) and -20°C.

[0094] 2. Wear resistance test: According to the relevant records in GB / T 1689-2014 "Determination of wear resistance of vulcanized rubber (using Akron abrasion tester)", the wear resistance test of the one-piece hose in the embodiment and the comparative example was carried out.

[0095] The above test results are shown in Table 2:

[0096] Table 2 Performance test results

[0097]

[0098] From Table 2, combined with Example 1 and Example 2 to Example 6, it can be seen that the tensile strength, elongation at break and wear volume of Example 2 to Example 6 under different conditions do not change significantly compared with Example 1, indicating that the toughness and wear resistance of Example 2 to Example 6 are not significantly different from Example 1. The difference between Example 2 to Example 6 and Example 1 is only that the raw materials and the ratio of the raw materials are adjusted within the required range, indicating that changing the raw materials and the ratio of the raw materials within the required range has little effect on the performance of the obtained one-piece hose.

[0099] Combining Example 1, Example 7, Example 8 and Comparative Example 7, it can be seen that the tensile strength and elongation at break of Example 7, Example 8 and Comparative Example 7 under different conditions are lower than those of Example 1, among which the tensile strength of Comparative Example 7 under low temperature environment is more obviously reduced, and the wear volume is increased compared with Example 1. It is shown that the toughness and wear resistance of Example 7, Example 8 and Comparative Example 7 are lower than those of Example 1. The modified hydroxyl-terminated polysilsesquioxane used in Example 7, Example 8 and Comparative Example 7 reduces or increases the amount of epoxy carbonate monomer added during the preparation process. Specifically, the amount of monomer is reduced in Example 7, resulting in a decrease in the number of polycarbonate segments grafted on the modified hydroxyl-terminated polysilsesquioxane, a decrease in the molecular weight of the polycarbonate segment, a decrease in the crosslinking density between the polycarbonate segment and the EPDM rubber, a decrease in the stress transmission effect, and a decrease in the toughness and wear resistance of the material. The modified hydroxyl-terminated polysilsesquioxane in Comparative Example 7 has no grafted polycarbonate segment, and the effect of improving the material performance is also significantly reduced. In Example 8, the amount of monomer added was increased, resulting in the formation of polycarbonate segments with excessively large molecular weights. The excessive rigidity of the material was not conducive to the improvement of toughness.

[0100] Combining Example 1 and Example 9, it can be seen that the tensile strength of Example 9 at room temperature is lower than that of Example 1, and in a low temperature environment, the tensile strength decreases significantly, and the wear volume does not change much compared with Example 1. Example 9 uses high-phenyl silicone rubber, in which the phenyl content is much higher than the low-phenyl silicone rubber in Example 1. The introduction of a large amount of phenyl will increase the rigidity of the material and improve the wear resistance of the material, but excessive rigidity will make the material brittle, especially in a low temperature environment, the tendency to become brittle is more obvious.

[0101] Combining Example 1 and Example 10, it can be seen that the tensile strength and elongation at break of Example 10 under different conditions are lower than those of Example 1, and the wear volume is increased, indicating that the toughness and wear resistance of Example 10 are lower than those of Example 1. The filler used in Example 10 is nano-silicon dioxide that has not been modified by amino groups, and its compatibility with the EPDM rubber matrix is ​​reduced. During the production process, nano-silicon dioxide is easy to agglomerate, and the reinforcing effect on the material is reduced. The toughness and wear resistance of the one-piece hose are reduced. At the same time, without the effect of amino groups, the chemical bonding between nano-silicon dioxide and each component is reduced, resulting in a decrease in the interface bonding force between the material components, and the performance and wear resistance are also reduced.

[0102] Combining Example 1 and Comparative Examples 1 to 3, it can be seen that the tensile strength and elongation at break of Comparative Examples 1 to 3 under different conditions are reduced compared with Example 1, and the wear volume is significantly increased, among which the tensile strength of Comparative Example 3 is most significantly reduced, and it is significantly reduced under low temperature conditions, and the wear volume is also significantly increased, indicating that the toughness and wear resistance of Comparative Examples 1 to 3 are significantly reduced compared with Example 1. Comparative Examples 1 to 3 change the amount of low phenyl silicone rubber added compared with Example 1. Specifically, in Comparative Example 1, the amount of low-phenyl silicone rubber added was reduced, and the decrease in elastic modulus resulted in a decrease in the stress transfer effect of the material, a decrease in the ability to resist deformation, and a decrease in the low-temperature resistance of the material. At the same time, the reduction in the phenyl content also resulted in a decrease in the wear resistance of the material. In Comparative Example 3, no low-phenyl silicone rubber was added, and the performance degradation was more obvious. The low-temperature resistance of the one-piece hose was significantly reduced, and the wear resistance of the material was also significantly reduced due to the lack of phenyl effect. In Comparative Example 2, the amount of low-phenyl silicone rubber added was increased, which would hinder the internal molecular movement of the material, which would be unfavorable for delaying the formation and expansion of cracks in the material, resulting in a decrease in the toughness of the material.

[0103] Combining Example 1 and Comparative Examples 4 to 6, it can be seen that the tensile strength and elongation at break of Comparative Examples 4 to 6 under different conditions are significantly reduced compared with Example 1, and the wear volume is significantly increased, among which the tensile strength of Comparative Example 6 decreases most significantly, indicating that the toughness and wear resistance of Comparative Examples 4 to 6 are significantly reduced compared with Example 1. Comparative Examples 4 to 6 vary the amount of modified terminal hydroxyl polysilsesquioxane added compared to Example 1. Specifically, in Comparative Example 4, the amount of modified terminal hydroxyl polysilsesquioxane added is reduced, the interface interaction with the EPDM rubber matrix is ​​reduced, the stress transfer effect is reduced, the ability to resist deformation is reduced, the toughness of the one-piece hose is reduced, and the content of polycarbonate segments is also reduced, the density of the interpenetrating network structure formed is reduced, the overall performance of the material is reduced, and the crack propagation speed is not well suppressed; in Comparative Example 6, no modified terminal hydroxyl polysilsesquioxane is added, and the performance is more significantly reduced compared to Comparative Example 4, and a cross-linked structure cannot be formed by connecting EPDM rubber and phenyl silicone rubber, and the performance of the material is significantly reduced; in Comparative Example 5, the amount added is increased, resulting in excessive cross-linking inside the formed one-piece hose material, which is not conducive to improving the toughness of the material.

[0104] It should be noted that, in this article, relational terms such as first and second, etc. are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Moreover, the terms "include", "comprise" or any other variants thereof are intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements includes not only those elements, but also other elements not explicitly listed, or also includes elements inherent to such process, method, article or device.

[0105] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A high-toughness one-piece hose, characterized in that: The high-toughness one-piece hose comprises the following raw materials in parts by mass: 100 parts of EPDM rubber; 8-15 parts of phenyl silicone rubber; 20-25 parts of filler; 6 to 10 parts of modified hydroxyl-terminated polysilsesquioxane; 2 to 5 parts of vulcanizing agent; 1 to 3 parts of vulcanization accelerator; 3-5 parts of vinyl silane coupling agent; 1.5-3.5 parts of antioxidant; The molecular chain of the modified hydroxyl-terminated polysilsesquioxane is grafted with a polycarbonate segment.

2. The high-toughness one-piece hose according to claim 1, characterized in that: The raw materials of the modified terminal hydroxyl polysilsesquioxane include terminal hydroxyl polysilsesquioxane and epoxy carbonate monomer in a mass ratio of 1: (0.3-0.5).

3. The high-toughness one-piece hose according to claim 2, characterized in that: The epoxy polycarbonate monomer includes one or more combinations of propylene carbonate, ethylene carbonate, glycidyl carbonate, and cyclohexyl epoxy carbonate.

4. The high-toughness one-piece hose according to claim 2, characterized in that: The modified hydroxyl-terminated polysilsesquioxane is prepared according to the following method: S101. octavinyl cage silsesquioxane is added to anhydrous dichloromethane, and trifluoromethanesulfonic acid is added after stirring to dissolve, and the mixture is stirred at a constant temperature of 25 to 30° C. for 4 to 5 hours. After the reaction is completed, the lower organic phase is collected by rotary evaporation extraction, and then an acetone aqueous solution is added to the organic phase, and the mixture is hydrolyzed at a constant temperature of 25 to 30° C. for 10 to 12 hours. After the hydrolysis reaction, the mixture is allowed to stand for stratification, and the lower organic phase is dried, rotary evaporated, filtered and chromatographically separated to obtain a hydroxy-terminated polysilsesquioxane; S102. Add the catalyst and the hydroxy-terminated polysilsesquioxane obtained in S101 to the epoxy carbonate monomer, mix well, raise the temperature to 200-220° C. under a nitrogen atmosphere, stir and react for 12-15 hours, and finally dry and rotary evaporate to obtain the modified hydroxy-terminated polysilsesquioxane.

5. The high-toughness one-piece hose according to claim 4, characterized in that: The catalyst is a metal salt catalyst.

6. The high-toughness one-piece hose according to claim 1, characterized in that: The phenyl silicone rubber is low-phenyl silicone rubber.

7. The high-toughness one-piece hose according to claim 1, characterized in that: The filler is amino-modified nano-silicon dioxide.

8. The high-toughness one-piece hose according to claim 7, characterized in that: The raw materials of the amino-modified nano-silica include nano-silica and aminosilane coupling agent in a mass ratio of 1:(0.25-0.4).

9. The high-toughness one-piece hose according to claim 1, characterized in that: The vinyl silane coupling agent includes one or more of vinyl triethoxy silane, vinyl trimethoxy silane and vinyl methyl diethoxy silane.

10. A production process for a high-toughness one-piece hose according to any one of claims 1 to 9, characterized in that: The process steps include: S201. The EPDM rubber and the phenyl silicone rubber are first mixed to obtain a first mixed rubber material; the first mixed rubber material is second mixed with a modified hydroxyl-terminated polysilsesquioxane, a filler, a vinyl silane coupling agent and an antioxidant to obtain a second mixed rubber material; the second mixed rubber material is third mixed with a vulcanizing agent and a vulcanization accelerator to obtain a mixed rubber material; wherein the first mixing temperature is 80 to 100° C., the second mixing temperature is 100 to 140° C., and the third mixing temperature is 60 to 90° C.; S202. The obtained mixed rubber material is extruded into a tube, and then vulcanized at 140 to 160°C; S203. Cooling and cutting the vulcanized rubber hose to obtain a high-toughness one-piece rubber hose.

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