High-strength anti-breaking rubber tube material for automobile and preparation method thereof

Abstract

The application relates to the technical field of rubber materials, in particular to a high-strength anti-fracture automobile rubber pipe material and a preparation method thereof; the rubber pipe material comprises the following components in parts by weight: a rubber matrix, an oil-resistant antioxidant and an inorganic filler; wherein the rubber matrix is selected from at least one of nitrile rubber, hydrogenated nitrile rubber, chlorobutyl rubber and ethylene-propylene-diene rubber; the oil-resistant antioxidant is selected from a compound with the structure of formula I-A: The application provides an automobile rubber pipe material with high strength, anti-fracture and high oil resistance.

Description

Technical Field

[0001] This invention relates to the field of rubber materials technology, specifically to a high-strength, fracture-resistant automotive rubber hose material and its preparation method. Background Technology

[0002] As a core component of fuel delivery, lubrication, and cooling systems, automotive rubber hoses must withstand long-term oil corrosion, alternating high and low temperatures, outdoor ozone aging, and dynamic vibration. Their oil resistance, aging resistance, and mechanical strength directly determine the overall vehicle's operational safety and service life. Currently, most mainstream automotive rubber hoses on the market use nitrile rubber and neoprene rubber as the base material, combined with conventional antioxidants and fillers. However, they still exhibit significant performance shortcomings under complex operating conditions.

[0003] Existing rubber hose materials generally face the problem of poor synergy between oil resistance and anti-aging: although conventional anti-aging agents can alleviate thermo-oxidative aging, they are difficult to resist the performance degradation under oil immersion, which makes rubber hoses prone to swelling, cracking and decreased elasticity; some oil resistance modification schemes improve oil resistance by adding fluorine-containing or silicone-based additives, but due to insufficient compatibility between the additives and the rubber matrix, uneven dispersion occurs, which reduces the material's fracture strength and wear resistance.

[0004] Meanwhile, the automotive industry's requirements for environmental protection and long-term performance are constantly increasing, leading to the gradual restriction of the use of traditional halogenated flame retardants and non-environmentally friendly plasticizers. The introduction of environmentally friendly additives further exacerbates the difficulty of achieving performance balance. Furthermore, existing manufacturing processes often suffer from uneven vulcanization and poor dimensional stability of the tube blank, affecting the high-strength, fracture-resistant performance of the rubber hose. Summary of the Invention

[0005] The purpose of this invention is to provide a high-strength, fracture-resistant automotive rubber hose material and its preparation method, so as to overcome the shortcomings of related technologies.

[0006] According to a first aspect of the present disclosure, a high-strength, fracture-resistant automotive rubber hose material is provided, the rubber hose material comprising the following components in parts by weight: 60-90 parts by weight of rubber matrix, 2-5 parts by weight of oil-resistant antioxidant and 5-15 parts by weight of inorganic filler; The rubber matrix is ​​selected from at least one of nitrile rubber, hydrogenated nitrile rubber, chloroprene rubber, and EPDM rubber; the oil-resistant antioxidant is selected from compounds having the following formula IA structure: R1 and R2 are each independently selected from hydrogen, nitro, halogen atom, hydroxyl, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C2-C30 alkynyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C3-30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted 3-30 membered heterocyclic group, and substituted or unsubstituted 5-30 membered heteroaryl. R3, R4, and R5 are each independently selected from direct bonds, substituted or unsubstituted C1-C10 alkyl groups, substituted or unsubstituted C2-C10 alkenyl groups, substituted or unsubstituted C2-C10 alkynyl groups, and substituted or unsubstituted C1-C10 alkoxy groups. Ar1 is selected from substituted or unsubstituted C3-15 cycloalkyl, substituted or unsubstituted C6-C18 aryl, substituted or unsubstituted 3-15 heterocyclic, and substituted or unsubstituted 5-18 heteroaryl.

[0007] In one aspect of this disclosure, the rubber tube material further includes the following components in parts by weight: 0.25-1.5 parts by weight of vulcanizing agent, 0.25-1.5 parts by weight of vulcanizing accelerator, and 0-10 parts by weight of additives; wherein the additives are selected from at least one of antioxidants, ozone deodorizers, plasticizers, flame retardants, and scorch inhibitors.

[0008] In one aspect of the embodiments of this disclosure, the vulcanizing agent is selected from at least one of insoluble sulfur, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxide)hexane, and benzoyl peroxide.

[0009] In one aspect of the embodiments of this disclosure, the vulcanization accelerator is selected from at least one of N-cyclohexyl-2-benzothiazole sulfenamide, tetramethylthiuram disulfide, dibenzothiazole disulfide, 2-mercaptobenzothiazole, tetrasulfide bispentamethylenethiuram, zinc diethyldithiocarbamate, and zinc dibutyldithiocarbamate.

[0010] In one aspect of this disclosure, the antioxidant is selected from pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 4,4'-thiobis(6-tert-butyl-3-methylphenol) or N-phenyl-α-naphthylamine.

[0011] In one aspect of this disclosure, the anti-ozone agent is selected from N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline, or 2,2,4-trimethyl-1,2-dihydroquinoline polymers.

[0012] In one aspect of the embodiments of this disclosure, the plasticizer is selected from epoxidized soybean oil, trioctyl trimellitate, dioctyl phthalate, diisononyl phthalate, dioctyl adipate, dioctyl sebacate, or chlorinated paraffin.

[0013] In one aspect of this disclosure, the flame retardant is selected from at least one of aluminum hydroxide, magnesium hydroxide, decabromodiphenyl ether, tetrabromobisphenol A, antimony trioxide, brominated epoxy resin, and triphenyl phosphate.

[0014] In one aspect of the embodiments of this disclosure, the scorching inhibitor is selected from at least one of N-cyclohexylthiophthalimide, phthalic anhydride, salicylic acid, benzoic acid, nitrosodiphenylamine, and 2-mercaptobenzimidazole.

[0015] In one aspect of the embodiments of this disclosure, the inorganic filler is selected from at least one of precipitated silica, fumed silica, kaolin, talc, wollastonite, attapulgite, mica, montmorillonite, bentonite, titanium dioxide, calcium carbonate, nano-calcium carbonate, barium sulfate, zinc oxide, magnesium oxide, diatomaceous earth, glass fiber powder, and hollow glass microspheres.

[0016] In one aspect of this disclosure, the rubber matrix is ​​selected from any combination of the following: a) A combination of nitrile rubber and chloroprene rubber; wherein the mass ratio of the nitrile rubber to the chloroprene rubber is selected from (6-8):(2-4); b) A combination of hydrogenated nitrile butadiene rubber and chloroprene rubber; wherein the mass ratio of the hydrogenated nitrile butadiene rubber to the chloroprene rubber is selected from (7-9):(1-3); c) A combination of nitrile rubber and ethylene propylene diene monomer (EPDM) rubber; wherein the mass ratio of the nitrile rubber to the EPDM rubber is selected from (5-7):(3-5); d) A combination of hydrogenated nitrile butadiene rubber, nitrile butadiene rubber and chloroprene rubber; wherein the mass ratio of the hydrogenated nitrile butadiene rubber, nitrile butadiene rubber and chloroprene rubber is selected from (4-6):(2-3):(2-3). In one aspect of this disclosure, the oil-resistant antioxidant is selected from compounds having the following formula IB structure: R1 and R2 are each independently selected from substituted or unsubstituted C1-C10 alkyl or substituted or unsubstituted C1-C10 alkoxy groups; the substituted C1-C10 alkyl and substituted C1-C10 alkoxy groups are substituted by one or more amino groups; R3 and R4 are each independently selected from C1-C5 alkyl or C1-C5 alkoxy; R5 is selected from direct bond, substituted or unsubstituted C1-C5 alkyl or substituted or unsubstituted C1-C5 alkoxy; the substituted C1-C5 alkyl and substituted C1-C5 alkoxy are substituted by one or more amino groups; R6 is selected from hydrogen, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C1-C10 alkoxy, substituted or unsubstituted C6-C12 aryl or 5-12 heteroaryl.

[0017] In one aspect of this disclosure, the oil-resistant antioxidant is selected from compounds having the following formula IC structure: R1 and R2 are each independently selected from substituted or unsubstituted C1-C10 alkyl or substituted or unsubstituted C1-C10 alkoxy groups; the substituted C1-C10 alkyl and substituted C1-C10 alkoxy groups are substituted by one or more amino groups; R7 is selected from hydrogen, substituted or unsubstituted C1-C10 alkyl groups; the substituted C1-C10 alkyl group is substituted by one or more halogen atoms.

[0018] In one aspect of this disclosure, the oil-resistant antioxidant is selected from compound 1 or compound 2: In one aspect of this disclosure, compound 1 or compound 2 is prepared by the following steps: Step 1-a: Take bis(3-aminopropyl)-terminated polydimethylsiloxane, dehydrate it for 1-1.5 h at 80 °C and under vacuum conditions of -0.08 to -0.1 MPa to remove moisture, and then cool it to room temperature for later use; take 4-methoxyphenyl isocyanate or p-trifluoromethoxyphenyl isocyanate; dry it with 4 Å molecular sieve for later use. The number-average molecular weight Mn of the bis(3-aminopropyl)-terminated polydimethylsiloxane is selected from 2000-4500; Step 2-a: In a dry reaction vessel under nitrogen protection, add anhydrous toluene or ethyl acetate as a solvent, the amount of solvent being 3-5 times the mass of bis(3-aminopropyl)-terminated polydimethylsiloxane; then add bis(3-aminopropyl)-terminated polydimethylsiloxane and stir until completely dissolved, the stirring speed being selected from 200-300 r / min; Step 3-a: Weigh 4-methoxyphenyl isocyanate or p-trifluoromethoxyphenyl isocyanate at 2.2-2.4 times the molar amount of bis(3-aminopropyl)-terminated polydimethylsiloxane added in step 2-a, and then slowly add it dropwise to the reaction vessel at a rate of 3-10 mL / min. During the dropwise addition, control the temperature of the reaction system to not exceed 40℃. After the dropwise addition is complete, add the catalyst dibutyltin dilaurate, raise the temperature to 90℃-100℃, and maintain the temperature for 2-4 hours. Step 4-a: After the reaction is complete, the reaction system is heated to 100℃-110℃ and distilled under a vacuum of -0.08 to -0.1MPa for 0.5-1.5h to remove the solvent and unreacted isocyanate raw materials; then it is cooled to room temperature to obtain compound 1 or compound 2. When 4-methoxyphenyl isocyanate is selected as the starting material, compound 1 is obtained; when p-trifluoromethoxyphenyl isocyanate is selected as the starting material, compound 2 is obtained.

[0019] In one aspect of this disclosure, the rubber tube material comprises the following components in parts by weight: 56 parts by weight of nitrile rubber, 24 parts by weight of chloroprene rubber, 5 parts by weight of compound 2, 3 parts by weight of calcium carbonate, 4 parts by weight of fumed silica, 1.2 parts by weight of insoluble sulfur, 0.8 parts by weight of N-cyclohexyl-2-benzothiazole sulfenamide, 0.5 parts by weight of N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, 2 parts by weight of epoxidized soybean oil, 3 parts by weight of magnesium hydroxide, and 0.5 parts by weight of N-cyclohexylthiophthalimide.

[0020] According to a second aspect of the present disclosure, a method for preparing the aforementioned high-strength, fracture-resistant automotive rubber hose material is provided, the method comprising the following steps: Preparation of oil-resistant antioxidant: Preparation of compound 2; Pretreatment: Nitrile rubber and chloroprene rubber were plasticized separately in a two-roll mill to obtain a plasticized rubber matrix; the prepared compound 2 was vacuum dried to remove moisture; Mixing: Add the plasticized nitrile rubber and chloroprene rubber to a mixer and mix at a low speed of 30-40 r / min for 2-3 min. Then add calcium carbonate, fumed silica, epoxidized soybean oil and magnesium hydroxide in sequence. Adjust the speed to 60-80 r / min and mix for 5-7 min. Then add N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, N-cyclohexylthiophthalimide and compound 2. Adjust the speed to 40-50 r / min and mix for 3-4 min. Finally, add insoluble sulfur and N-cyclohexyl-2-benzothiazole sulfenamide, adjust the speed to 30-40 r / min and mix for 2-3 min to obtain the compound. Slicing: The compound rubber is sliced ​​and left to stand to obtain the rested compound rubber; Extrusion molding: Add the rested compound rubber to the rubber extruder, set the temperature of each section of the extruder: feeding section 60-70℃, plasticizing section 80-90℃, die head section 90-95℃, and screw speed 20-30r / min; extrude through the rubber tube die to obtain a continuous unvulcanized rubber tube blank; Vulcanization and shaping: The unvulcanized rubber tube blank is fed into the vulcanizing tank and vulcanized using a two-stage vulcanization process. After vulcanization, it is cooled to room temperature to obtain the high-strength, anti-breakage automotive rubber tube material.

[0021] Compared with the prior art, the beneficial effects of the present invention are: it provides an oil-resistant antioxidant that can simultaneously improve the oil resistance and fracture resistance of rubber, and uses it to prepare a rubber pipe material that has both high strength and fracture resistance and high oil resistance. Detailed Implementation

[0022] To make the objectives, technical solutions, and advantages of this application clearer, the technical solutions of this application will be clearly and completely described below in conjunction with embodiments. Obviously, the described embodiments are only some embodiments of this application, not all embodiments. The embodiments described herein are illustrative in nature and are used to provide a basic understanding of this application. The embodiments of this application should not be construed as limiting this application.

[0023] For the sake of brevity, this article only discloses a few specific numerical ranges. However, any lower limit can be combined with any upper limit to form an unspecified range; and any lower limit can be combined with other lower limits to form an unspecified range, just as any upper limit can be combined with any other upper limit to form an unspecified range. Furthermore, each individually disclosed point or single value can itself serve as a lower or upper limit and be combined with any other point or single value or with other lower or upper limits to form an unspecified range.

[0024] In this disclosure, the term "alkyl" refers to an aliphatic hydrocarbon group, which can be straight-chain or branched. Branched refers to one or more lower alkyl groups, such as methyl, ethyl, or propyl, that link a linear alkyl chain. "Lower alkyl" refers to a group containing about 1 to about 6 carbon atoms in the chain, which can be straight-chain or branched.

[0025] In this disclosure, the term "alkenyl" refers to an aliphatic hydrocarbon group containing at least one carbon-carbon double bond, which can be straight-chain or branched. Branched refers to one or more lower alkyl groups, such as methyl, ethyl, or propyl, attached to a linear alkenyl chain. "Lower alkenyl" refers to a group containing about 2 to about 6 carbon atoms in the chain, which can be straight-chain or branched.

[0026] In this disclosure, the term "alkynyl" refers to an aliphatic hydrocarbon group containing at least one carbon-carbon triple bond, which can be straight-chain or branched. Branching refers to one or more lower alkyl groups, such as methyl, ethyl, or propyl, attached to a linear alkynyl chain. "Lower alkynyl" refers to a chain containing about 2 to about 6 carbon atoms, which can be straight-chain or branched. Non-limiting examples of alkynyl groups include ethynyl, propynyl, 2-butynyl, 3-methylbutynyl, n-pentynyl, and decynyl.

[0027] In this disclosure, the term "aryl" refers to an aromatic monocyclic or polycyclic ring system. An aryl group may optionally be substituted with one or more "cyclic substituents," which may be the same or different, as defined herein. Non-limiting examples of suitable aryl groups include phenyl and naphthyl.

[0028] In this disclosure, the term "heteroaryl" refers to an aromatic monocyclic or polycyclic ring system, wherein one or more ring atoms are elements other than carbon, such as nitrogen, oxygen, or sulfur, either individually or in combination, and preferably a heteroaryl contains about 5 to about 6 ring atoms. A "heteroaryl" may optionally be substituted by one or more "cyclic substituents," which may be the same or different, as defined herein. The prefixes azido, oxa, or thiado preceding the name of a heteroaryl root indicate that at least one nitrogen, oxygen, or sulfur atom is present as a ring atom, respectively. The nitrogen atom of a heteroaryl may optionally be oxidized to the corresponding N-oxide. Suitable, non-limiting examples of heteroaryl groups include pyridyl, pyrazinyl, furanyl, phenylthio, pyrimidinyl, isoxazolyl, isothiazolyl, oxazolyl, thiazolyl, pyrazolyl, furazanyl, pyrroleyl, pyrazolyl, triazolyl, 1,2,4-thiadiazolyl, pyrazinyl, pyridazinyl, quinoxalinyl, 2,3-diazanaphthyl, imidazo[1,2-a]pyridyl, imidazo[2,1-b]thiazolyl, benzofurazanyl, indoleyl, azaindoleyl, benzimidazolyl, benzothiopheneyl, quinolinyl, imidazolyl, thiophenepyridyl, quinazolinyl, thiophenepyrimidinyl, pyrrolopyridyl, imidazopyridyl, isoquinolinyl, benzoazaindoleyl, 1,2,4-triazinyl, benzothiazolyl, etc.

[0029] In this disclosure, the term "amino" refers to the -NR′R′′ group. The amino group may optionally be substituted. In an unsubstituted amino group, R′ and R′′ are hydrogen. In a substituted amino group, R′ and R′′ may each independently be, but not limited to, hydrogen, alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, alkylcycloalkyl, alkylheterocycloalkyl, alkoxy, sulfonyl, alkenyl, alkanoyl, aryl, arylalkyl, or heteroaryl, provided that R′ and R′′ are not both hydrogen. In a substituted amino group, R′ and R′′ may cyclize to form a cyclic amino group, such as pyrrolidinyl or piperidinyl. Such cyclic amino groups may incorporate other heteroatoms, for example, to form piperazine or morpholine groups. Such cyclic amino groups may optionally be substituted, for example, by an amino, hydroxyl, or oxo group.

[0030] In this disclosure, the term "alkoxy" refers to -O-alkyl. Alkoxy can refer to a straight-chain, branched, or cyclic, saturated or unsaturated oxy-hydrocarbon chain, including, for example, methoxy, ethoxy, propoxy, isopropoxy, butoxy, tert-butoxy, and pentoxy. Alkoxy may optionally be substituted by one or more alkoxy substituents ("substituted alkoxy").

[0031] In this disclosure, the term "cycloalkyl" refers to a non-aromatic mono- or polycyclic ring system, preferably containing about 5 to about 7 ring atoms. The cycloalkyl group may optionally be substituted with one or more "cyclic substituents," which may be the same or different, as defined above. Suitable monocyclic cycloalkyl groups, without limitation, include cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, etc. Suitable polycyclic cycloalkyl groups, without limitation, include 1-decahydronaphthyl, norcamphenyl, adamantyl, etc. In this disclosure, the term "cycloalkoxy" refers to a group in which one or more carbon atoms in the mono- or polycyclic ring system of the "cycloalkyl" group are substituted with oxygen atoms.

[0032] In this disclosure, the term "heterocyclic group" refers to a non-aromatic saturated monocyclic or polycyclic ring system, wherein one or more ring atoms in the ring system are elements other than carbon, such as nitrogen, oxygen, or sulfur, either individually or in combination. Adjacent oxygen and / or sulfur atoms are absent in the ring system, and preferred heterocycles contain about 5 to about 6 ring atoms. The prefixes aza, oxa, or thioa preceding the name of the heterocyclic group indicate that at least one nitrogen, oxygen, or sulfur atom is present as a ring atom, respectively. The heterocyclic group may optionally be substituted with one or more "cyclic substituents," which may be the same or different, as defined herein. The nitrogen or sulfur atom of the heterocyclic group may optionally be oxidized to the corresponding N-oxide, S-oxide, or S,S-dioxide. Non-limiting examples of suitable monocyclic heterocyclic rings include piperidinyl, pyrrolyl, piperazine, morpholinyl, thiomorpholinyl, thiazolyl, 1,3-dioxolanecycloyl, 1,4-dioxacyclohexyl, tetrahydrofuranyl, tetrahydrophenylthio, tetrahydrothiopyranyl, etc.

[0033] The present disclosure will be further described below by way of specific embodiments. Unless otherwise specified, all chemical reagents used in the embodiments of the present disclosure are obtained through conventional commercial means. Unless otherwise specified, all contents mentioned below are mass contents. Unless otherwise specified, it is understood that the process is carried out at room temperature.

[0034] Example Example 1 Example 1 includes the following steps: 1. Preparation of Compound 1: Bis(3-aminopropyl)-terminated polydimethylsiloxane (Mn~3000) was dehydrated for 1 h at 80 °C under vacuum conditions of -0.08 to -0.1 MPa to remove moisture, and then cooled to room temperature for later use. 4-Methoxyphenyl isocyanate was dried using a 4 Å molecular sieve for later use. Anhydrous toluene was added as a solvent to a nitrogen-protected dry reaction vessel, with the solvent volume being three times the mass of the bis(3-aminopropyl)-terminated polydimethylsiloxane. Then, the bis(3-aminopropyl)-terminated polydimethylsiloxane was added and stirred until completely dissolved at a stirring rate of 200 r / min. 4-Methoxyphenyl isocyanate was then added according to the bis(3-aminopropyl)-terminated polydimethylsiloxane... Weigh out 2.2 times the molar amount of the bis(3-aminopropyl)-terminated polydimethylsiloxane and slowly add it dropwise to the reaction vessel at a rate of 5 mL / min. During the addition, control the temperature of the reaction system to not exceed 40 °C. After the addition is complete, add the catalyst dibutyltin dilaurate (the mass of the catalyst added is 1% of the mass of the bis(3-aminopropyl)-terminated polydimethylsiloxane), raise the temperature to 95 °C, and maintain the temperature for 3 h. After the reaction is complete, raise the temperature of the reaction system to 105 °C and distill it under a vacuum of -0.08 to -0.1 MPa for 1 h to remove the solvent and unreacted 4-methoxyphenyl isocyanate. Then cool to room temperature to obtain compound 1. The reaction process is shown below: 2. Preparation of the rubber tube in this embodiment: 56 parts by weight of nitrile rubber and 24 parts by weight of chloroprene rubber were respectively plasticized in a two-roll mill. The plasticizing temperature was controlled at about 45°C and the plasticizing time was 8 min to obtain a uniformly plasticized rubber matrix. The prepared compound 1 was dried at 60°C and under vacuum conditions of -0.08 to -0.1 MPa for 45 min to remove trace moisture and volatile impurities, and then cooled to room temperature for later use. Add the plasticized nitrile rubber and chloroprene rubber to a mixer and mix at a low speed of 30 r / min for 3 min, controlling the mixing temperature at approximately 70°C. Then, add 3 parts by weight of calcium carbonate, 4 parts by weight of fumed silica, 2 parts by weight of epoxidized soybean oil, and 3 parts by weight of magnesium hydroxide in sequence. Adjust the speed to 80 r / min, raise the temperature to 90°C, and mix for 7 min. Finally, add 0.5 parts by weight of N-(1,3-dimethylbutyl)-N'- Phenyl p-phenylenediamine, 0.5 parts by weight of N-cyclohexylthiophthalimide, and 5 parts by weight of compound 1; adjust the speed to 50 r / min, lower the temperature to 70℃, and mix for 4 min; finally, add 1.2 parts by weight of insoluble sulfur and 0.8 parts by weight of N-cyclohexyl-2-benzothiazole sulfenamide, adjust the speed to 30 r / min, and mix for 3 min. The mixing temperature is strictly controlled below 95℃ to avoid premature vulcanization, and the compound is obtained.

[0035] Transfer the mixed rubber to a two-roll mill and pass it through a thin mill 5 times to produce sheets with a sheet thickness of about 4-6 mm. Then, let it stand for 8 hours in an environment with room temperature and relative humidity of 40%-60% to eliminate the internal stress generated during the mixing process.

[0036] After the rubber compound has been left to stand, it is added to a rubber extruder. The temperature is 60-70°C in the feeding section, 80-90°C in the plasticizing section, and 90-95°C in the die head section. The screw speed is 20-30 r / min. The extrusion is carried out through a rubber tube die to obtain a continuous unvulcanized rubber tube blank with a wall thickness uniformity error of ≤±0.1mm. The extruded uncured rubber tube blank is fed into a vulcanizing tank and subjected to a two-stage vulcanization process: the first stage vulcanization temperature is 155℃-160℃, the vulcanization pressure is 12-15MPa, and the vulcanization time is 15min, to ensure complete cross-linking of the tube blank; the second stage vulcanization temperature is 120-125℃, and the vulcanization time is 3-4h, to further improve the cross-linking density and performance stability; after vulcanization, it is naturally cooled to room temperature to obtain the automotive rubber tube material (outer diameter 12mm, inner diameter 8mm) of this embodiment.

[0037] Example 2 Example 2 includes the following steps: 1. Preparation of Compound 2: Bis(3-aminopropyl)-terminated polydimethylsiloxane (Mn~3000) was dehydrated for 1 h at 80 °C under vacuum conditions of -0.08 to -0.1 MPa to remove moisture, and then cooled to room temperature for later use. p-Trifluoromethoxyphenyl isocyanate was dried using a 4 Å molecular sieve for later use. Anhydrous toluene was added as a solvent to a nitrogen-protected dry reaction vessel, with the solvent volume being three times the mass of the bis(3-aminopropyl)-terminated polydimethylsiloxane. Then, bis(3-aminopropyl)-terminated polydimethylsiloxane was added and stirred until completely dissolved at a stirring rate of 200 r / min. p-Trifluoromethoxyphenyl isocyanate was then dissolved in the bis(3-aminopropyl)-terminated polydimethylsiloxane... Weigh out 2.2 times the molar amount of the bis(3-aminopropyl)-terminated polydimethylsiloxane and slowly add it dropwise to the reaction vessel at a rate of 5 mL / min. During the addition, control the temperature of the reaction system to not exceed 40 °C. After the addition is complete, add the catalyst dibutyltin dilaurate (the mass of the catalyst added is 1% of the mass of the bis(3-aminopropyl)-terminated polydimethylsiloxane), raise the temperature to 95 °C, and maintain the temperature for 3 h. After the reaction is complete, raise the temperature of the reaction system to 105 °C and distill it under a vacuum of -0.08 to -0.1 MPa for 1 h to remove the solvent and unreacted p-trifluoromethoxyphenyl isocyanate. Then cool to room temperature to obtain compound 2. The reaction process is shown below: 2. Preparation of the rubber tube in this embodiment: 56 parts by weight of nitrile rubber and 24 parts by weight of chloroprene rubber were respectively plasticized in a two-roll mill. The plasticizing temperature was controlled at about 45°C and the plasticizing time was 8 min to obtain a uniformly plasticized rubber matrix. The prepared compound 2 was dried at 60°C and under vacuum conditions of -0.08 to -0.1 MPa for 45 min to remove trace moisture and volatile impurities, and then cooled to room temperature for later use. Add the plasticized nitrile rubber and chloroprene rubber to a mixer and mix at a low speed of 30 r / min for 3 min, controlling the mixing temperature at approximately 70°C. Then, add 3 parts by weight of calcium carbonate, 4 parts by weight of fumed silica, 2 parts by weight of epoxidized soybean oil, and 3 parts by weight of magnesium hydroxide in sequence. Adjust the speed to 80 r / min, raise the temperature to 90°C, and mix for 7 min. Finally, add 0.5 parts by weight of N-(1,3-dimethylbutyl)-N'- Phenyl p-phenylenediamine, 0.5 parts by weight of N-cyclohexylthiophthalimide, and 5 parts by weight of compound 2; adjust the speed to 50 r / min, lower the temperature to 70℃, and mix for 4 min; finally, add 1.2 parts by weight of insoluble sulfur and 0.8 parts by weight of N-cyclohexyl-2-benzothiazole sulfenamide, adjust the speed to 30 r / min, and mix for 3 min. The mixing temperature is strictly controlled below 95℃ to avoid premature vulcanization, and the compound is obtained.

[0038] Transfer the mixed rubber to a two-roll mill and pass it through a thin mill 5 times to produce sheets with a sheet thickness of about 4-6 mm. Then, let it stand for 8 hours in an environment with room temperature and relative humidity of 40%-60% to eliminate the internal stress generated during the mixing process.

[0039] After the rubber compound has been left to stand, it is added to a rubber extruder. The temperature is 60-70°C in the feeding section, 80-90°C in the plasticizing section, and 90-95°C in the die head section. The screw speed is 20-30 r / min. The extrusion is carried out through a rubber tube die to obtain a continuous unvulcanized rubber tube blank with a wall thickness uniformity error of ≤±0.1mm. The extruded uncured rubber tube blank is fed into a vulcanizing tank and subjected to a two-stage vulcanization process: the first stage vulcanization temperature is 155℃-160℃, the vulcanization pressure is 12-15MPa, and the vulcanization time is 15min, to ensure complete cross-linking of the tube blank; the second stage vulcanization temperature is 120-125℃, and the vulcanization time is 3-4h, to further improve the cross-linking density and performance stability; after vulcanization, it is naturally cooled to room temperature to obtain the automotive rubber tube material (outer diameter 12mm, inner diameter 8mm) of this embodiment.

[0040] Comparative Example 1 59.5 parts by weight of nitrile rubber and 25.5 parts by weight of chloroprene rubber were respectively plasticized in an open mill. The plasticizing temperature was controlled at about 45°C and the plasticizing time was 8 minutes to obtain a uniformly plasticized rubber matrix. Add the plasticized nitrile rubber and chloroprene rubber to a mixer and mix at a low speed of 30 r / min for 3 min, with the mixing temperature controlled at about 70℃. Then, add 3 parts by weight of calcium carbonate, 4 parts by weight of fumed silica, 2 parts by weight of epoxidized soybean oil, and 3 parts by weight of magnesium hydroxide in sequence. Adjust the speed to 80 r / min, raise the temperature to 90℃, and mix for 7 min. Then, add 0.5 parts by weight of N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine and 0.5 parts by weight of N-cyclohexylthiophthalimide. Adjust the speed to 50 r / min, lower the temperature to 70℃, and mix for 4 min. Finally, add 1.2 parts by weight of insoluble sulfur and 0.8 parts by weight of N-cyclohexyl-2-benzothiazole sulfenamide, adjust the speed to 30 r / min, and mix for 3 min, strictly controlling the mixing temperature below 95℃ to avoid premature vulcanization, to obtain the compound rubber.

[0041] Transfer the mixed rubber to a two-roll mill and pass it through a thin mill 5 times to produce sheets with a sheet thickness of about 4-6 mm. Then, let it stand for 8 hours in an environment with room temperature and relative humidity of 40%-60% to eliminate the internal stress generated during the mixing process.

[0042] After the rubber compound has been left to stand, it is added to a rubber extruder. The temperature is 60-70°C in the feeding section, 80-90°C in the plasticizing section, and 90-95°C in the die head section. The screw speed is 20-30 r / min. The extrusion is carried out through a rubber tube die to obtain a continuous unvulcanized rubber tube blank with a wall thickness uniformity error of ≤±0.1mm. The extruded uncured rubber tube blank is fed into a vulcanizing tank and subjected to a two-stage vulcanization process: the first stage vulcanization temperature is 155℃-160℃, the vulcanization pressure is 12-15MPa, and the vulcanization time is 15min, to ensure complete cross-linking of the tube blank; the second stage vulcanization temperature is 120-125℃ and the vulcanization time is 3-4h, to further improve the cross-linking density and performance stability; after vulcanization, it is naturally cooled to room temperature to obtain the automotive rubber tube material of this comparative example (outer diameter 12mm, inner diameter 8mm).

[0043] Comparative Example 2 56 parts by weight of nitrile rubber and 24 parts by weight of chloroprene rubber were respectively plasticized in a two-roll mill at a plasticizing temperature of about 45°C for 8 minutes to obtain a uniformly plasticized rubber matrix. Bis(3-aminopropyl)-terminated polydimethylsiloxane was dried at 60°C under a vacuum of -0.08 to -0.1 MPa for 45 minutes to remove trace amounts of moisture and volatile impurities, and then cooled to room temperature for later use. Add the plasticized nitrile rubber and chloroprene rubber to a mixer and mix at a low speed of 30 r / min for 3 min, controlling the mixing temperature at approximately 70°C. Then, add 3 parts by weight of calcium carbonate, 4 parts by weight of fumed silica, 2 parts by weight of epoxidized soybean oil, and 3 parts by weight of magnesium hydroxide in sequence. Adjust the speed to 80 r / min, raise the temperature to 90°C, and mix for 7 min. Then, add 0.5 parts by weight of N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine. 0.5 parts by weight of N-cyclohexylthiophthalimide and 5 parts by weight of bis(3-aminopropyl)-terminated polydimethylsiloxane; adjust the speed to 50 r / min, lower the temperature to 70℃, and mix for 4 min; finally, add 1.2 parts by weight of insoluble sulfur and 0.8 parts by weight of N-cyclohexyl-2-benzothiazole sulfenamide, adjust the speed to 30 r / min, and mix for 3 min. The mixing temperature should be strictly controlled below 95℃ to avoid premature vulcanization, and the mixed rubber is obtained.

[0044] Transfer the mixed rubber to a two-roll mill and pass it through a thin mill 5 times to produce sheets with a sheet thickness of about 4-6 mm. Then, let it stand for 8 hours in an environment with room temperature and relative humidity of 40%-60% to eliminate the internal stress generated during the mixing process.

[0045] After the rubber compound has been left to stand, it is added to a rubber extruder. The temperature is 60-70°C in the feeding section, 80-90°C in the plasticizing section, and 90-95°C in the die head section. The screw speed is 20-30 r / min. The extrusion is carried out through a rubber tube die to obtain a continuous unvulcanized rubber tube blank with a wall thickness uniformity error of ≤±0.1mm. The extruded uncured rubber tube blank is fed into a vulcanizing tank and subjected to a two-stage vulcanization process: the first stage vulcanization temperature is 155℃-160℃, the vulcanization pressure is 12-15MPa, and the vulcanization time is 15min, to ensure complete cross-linking of the tube blank; the second stage vulcanization temperature is 120-125℃ and the vulcanization time is 3-4h, to further improve the cross-linking density and performance stability; after vulcanization, it is naturally cooled to room temperature to obtain the automotive rubber tube material of this comparative example (outer diameter 12mm, inner diameter 8mm).

[0046] The difference between Comparative Example 2 and Example 1 is that Comparative Example 2 directly uses bis(3-aminopropyl)-terminated polydimethylsiloxane as an oil-resistant antioxidant.

[0047] Comparative Example 3 56 parts by weight of nitrile rubber and 24 parts by weight of chloroprene rubber were respectively plasticized in a two-roll mill at a plasticizing temperature of about 45°C for 8 minutes to obtain a uniformly plasticized rubber matrix. Bis(3-aminopropyl)-terminated polydimethylsiloxane was dried at 60°C under a vacuum of -0.08 to -0.1 MPa for 45 minutes to remove trace amounts of moisture and volatile impurities, and then cooled to room temperature for later use. Add the plasticized nitrile rubber and chloroprene rubber to a mixer and mix at a low speed of 30 r / min for 3 min, controlling the mixing temperature at approximately 70°C. Then, add 3 parts by weight of calcium carbonate, 4 parts by weight of fumed silica, 2 parts by weight of epoxidized soybean oil, and 3 parts by weight of magnesium hydroxide in sequence. Adjust the speed to 80 r / min, raise the temperature to 90°C, and mix for 7 min. Finally, add 0.5 parts by weight of N-(1,3-dimethylbutyl)-N'- Phenyl p-phenylenediamine, 0.5 parts by weight of N-cyclohexylthiophthalimide, and 5 parts by weight of montmorillonite; adjust the speed to 50 r / min, lower the temperature to 70℃, and mix for 4 min; finally, add 1.2 parts by weight of insoluble sulfur and 0.8 parts by weight of N-cyclohexyl-2-benzothiazole sulfenamide, adjust the speed to 30 r / min, and mix for 3 min. The mixing temperature is strictly controlled below 95℃ to avoid premature vulcanization, and the compound is obtained.

[0048] Transfer the mixed rubber to a two-roll mill and pass it through a thin mill 5 times to produce sheets with a sheet thickness of about 4-6 mm. Then, let it stand for 8 hours in an environment with room temperature and relative humidity of 40%-60% to eliminate the internal stress generated during the mixing process.

[0049] After the rubber compound has been left to stand, it is added to a rubber extruder. The temperature is 60-70°C in the feeding section, 80-90°C in the plasticizing section, and 90-95°C in the die head section. The screw speed is 20-30 r / min. The extrusion is carried out through a rubber tube die to obtain a continuous unvulcanized rubber tube blank with a wall thickness uniformity error of ≤±0.1mm. The extruded uncured rubber tube blank is fed into a vulcanizing tank and subjected to a two-stage vulcanization process: the first stage vulcanization temperature is 155℃-160℃, the vulcanization pressure is 12-15MPa, and the vulcanization time is 15min, to ensure complete cross-linking of the tube blank; the second stage vulcanization temperature is 120-125℃ and the vulcanization time is 3-4h, to further improve the cross-linking density and performance stability; after vulcanization, it is naturally cooled to room temperature to obtain the automotive rubber tube material of this comparative example (outer diameter 12mm, inner diameter 8mm).

[0050] The difference between Comparative Example 3 and Example 1 is that Comparative Example 3 uses montmorillonite as an oil-resistant antioxidant.

[0051] Oil resistance test and fracture resistance test: Oil resistance testing was conducted according to GB / T1690-2010. Rubber tubing samples with a length of 100 mm were cut from the examples and comparative samples, and the inner and outer diameters and mass of each sample were recorded. ASTM No. 1 standard oil was selected as the test liquid and poured into the liquid resistance testing apparatus, ensuring sufficient oil to cover all rubber tubing samples. The temperature of the test liquid was controlled at 25°C using a constant temperature bath, and the samples were immersed for 144 hours. After immersion, the rubber tubing samples were removed, the surface was cleaned with anhydrous ethanol, and allowed to air dry. The dimensions of the dried rubber tubing samples were measured, and the dimensional change rate was calculated as: Dimensional change rate = (Δd / d0) × 100%, where Δd is the diameter difference before and after immersion, and d0 is the diameter of the sample before immersion (diameter = outer diameter - inner diameter). The results are shown in Table 1 below.

[0052] Fracture resistance testing was conducted according to GB / T528-2009. Three sets of tensile specimens were uniformly cut circumferentially from the samples in the examples and comparative examples, with three parallel specimens in each set, ensuring the absence of defects such as bubbles and cracks. The specimens were cut from the pipe wall while retaining the original wall thickness. A 0-50kN range, 0.5-grade precision electronic universal testing machine was used. After calibration and adjustment, the clamping distance was adjusted to 50mm, and the specimens were uniformly clamped and aligned with the gauge length. The testing speed was set to 500mm / min, and the specimens were stretched uniformly until fracture. The gauge length at fracture was recorded. Outliers exceeding 20% ​​deviation were removed from each set, and the average value was taken to obtain the elongation at break = (L... b -L0) / L0×100%; where L0 is the initial gauge length; L b This is the gauge length at the time of fracture.

[0053] Table 1 As can be seen, Examples 1 and 2 exhibit both fracture resistance and high oil resistance. This is because compounds 1 and 2 possess a polysiloxane backbone, which can prevent oil molecules from penetrating, thus achieving oil resistance. Furthermore, compounds 1 and 2 contain urea bonds, which form hydrogen bonds with the rubber molecular chain, effectively fixing the compounds and reducing migration and loss under oil immersion, thereby improving long-term oil resistance. Moreover, compound 2 demonstrates even better oil resistance because it further contains an -O-CF3 group. As a superoleophobic group, this group not only further prevents oil molecule penetration but also has a high CF bond energy, preventing product degradation or performance degradation due to oil chemical erosion, thus enhancing long-term oil resistance. Additionally, the polydimethylsiloxane Si-O bonds in the backbones of compounds 1 and 2 possess large bond angles and long bond lengths, facilitating internal rotation and endowing the molecular chain with flexibility and deformability, thereby increasing elongation at break.

[0054] Other embodiments of this disclosure will readily occur to those skilled in the art upon consideration of the specification and practice of the disclosure herein. This disclosure is intended to cover any variations, uses, or adaptations of this disclosure that follow the general principles of this disclosure and include common knowledge or customary techniques in the art not disclosed herein.

Claims

1. A high-strength, fracture-resistant automotive rubber hose material, characterized in that, The rubber hose material comprises the following components in parts by weight: 60-90 parts by weight of rubber matrix, 2-5 parts by weight of oil-resistant antioxidant and 5-15 parts by weight of inorganic filler; The rubber matrix is ​​selected from at least one of nitrile rubber, hydrogenated nitrile rubber, chloroprene rubber, and EPDM rubber; the oil-resistant antioxidant is selected from compounds having the following formula IA structure: R1 and R2 are each independently selected from hydrogen, nitro, halogen atom, hydroxyl, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C2-C30 alkynyl, substituted or unsubstituted C1-C30 alkoxy, substituted or unsubstituted C3-30 cycloalkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted 3-30 membered heterocyclic group, and substituted or unsubstituted 5-30 membered heteroaryl. R3, R4, and R5 are each independently selected from direct bonds, substituted or unsubstituted C1-C10 alkyl groups, substituted or unsubstituted C2-C10 alkenyl groups, substituted or unsubstituted C2-C10 alkynyl groups, and substituted or unsubstituted C1-C10 alkoxy groups. Ar1 is selected from substituted or unsubstituted C3-15 cycloalkyl, substituted or unsubstituted C6-C18 aryl, substituted or unsubstituted 3-15 heterocyclic, and substituted or unsubstituted 5-18 heteroaryl.

2. The high-strength, fracture-resistant automotive rubber hose material according to claim 1, characterized in that, The rubber hose material also includes the following components in parts by weight: 0.25-1.5 parts by weight of vulcanizing agent, 0.25-1.5 parts by weight of vulcanizing accelerator, and 0-10 parts by weight of additives; wherein the additives are selected from at least one of antioxidants, ozone deodorizers, plasticizers, flame retardants, and scorch inhibitors.

3. The high-strength, fracture-resistant automotive rubber hose material according to claim 2, characterized in that, The rubber tubing material satisfies at least one of the following conditions: (1) The vulcanizing agent is selected from at least one of insoluble sulfur, dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di(tert-butylperoxide)hexane, and benzoyl peroxide; (2) The vulcanization accelerator is selected from at least one of N-cyclohexyl-2-benzothiazole sulfenamide, tetramethylthiuram disulfide, dibenzothiazole disulfide, 2-mercaptobenzothiazole, tetrasulfide bispentamethylenethiuram, zinc diethyldithiocarbamate, and zinc dibutyldithiocarbamate. (3) The antioxidant is selected from pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], octadecyl β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 4,4'-thiobis(6-tert-butyl-3-methylphenol) or N-phenyl-α-naphthylamine; (4) The ozone-resistant agent is selected from N-isopropyl-N'-phenyl-p-phenylenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, 6-ethoxy-2,2,4-trimethyl-1,2-dihydroquinoline or 2,2,4-trimethyl-1,2-dihydroquinoline polymer; (5) The plasticizer is selected from epoxidized soybean oil, trioctyl trimellitate, dioctyl phthalate, diisononyl phthalate, dioctyl adipate, dioctyl sebacate or chlorinated paraffin. (6) The flame retardant is selected from at least one of aluminum hydroxide, magnesium hydroxide, decabromodiphenyl ether, tetrabromobisphenol A, antimony trioxide, brominated epoxy resin, and triphenyl phosphate; (7) The scorching inhibitor is selected from at least one of N-cyclohexylthiophthalimide, phthalic anhydride, salicylic acid, benzoic acid, nitrosodiphenylamine, and 2-mercaptobenzimidazole; (8) The inorganic filler is selected from at least one of precipitated silica, fumed silica, kaolin, talc, wollastonite, attapulgite, mica, montmorillonite, bentonite, titanium dioxide, calcium carbonate, nano calcium carbonate, barium sulfate, zinc oxide, magnesium oxide, diatomaceous earth, glass fiber powder, and hollow glass microspheres.

4. The high-strength, fracture-resistant automotive rubber hose material according to claim 1, characterized in that, The rubber matrix is ​​selected from any of the following combinations: a) A combination of nitrile rubber and chloroprene rubber; wherein the mass ratio of the nitrile rubber to the chloroprene rubber is selected from (6-8):(2-4); b) A combination of hydrogenated nitrile butadiene rubber and chloroprene rubber; wherein the mass ratio of the hydrogenated nitrile butadiene rubber to the chloroprene rubber is selected from (7-9):(1-3); c) A combination of nitrile rubber and ethylene propylene diene monomer (EPDM) rubber; wherein the mass ratio of the nitrile rubber to the EPDM rubber is selected from (5-7):(3-5); d) A combination of hydrogenated nitrile butadiene rubber, nitrile butadiene rubber and chloroprene rubber; wherein the mass ratio of the hydrogenated nitrile butadiene rubber, nitrile butadiene rubber and chloroprene rubber is selected from (4-6):(2-3):(2-3).

5. The high-strength, fracture-resistant automotive rubber hose material according to claim 1, characterized in that, The oil-resistant antioxidant is selected from compounds having the following formula IB structure: R1 and R2 are each independently selected from substituted or unsubstituted C1-C10 alkyl or substituted or unsubstituted C1-C10 alkoxy groups; the substituted C1-C10 alkyl and substituted C1-C10 alkoxy groups are substituted by one or more amino groups; R3 and R4 are each independently selected from C1-C5 alkyl or C1-C5 alkoxy; R5 is selected from direct bond, substituted or unsubstituted C1-C5 alkyl or substituted or unsubstituted C1-C5 alkoxy; the substituted C1-C5 alkyl and substituted C1-C5 alkoxy are substituted by one or more amino groups; R6 is selected from hydrogen, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C1-C10 alkoxy, substituted or unsubstituted C6-C12 aryl or 5-12 heteroaryl.

6. The high-strength, fracture-resistant automotive rubber hose material according to claim 5, characterized in that, The oil-resistant antioxidant is selected from compounds having the following formula IC structure: R1 and R2 are each independently selected from substituted or unsubstituted C1-C10 alkyl or substituted or unsubstituted C1-C10 alkoxy groups; the substituted C1-C10 alkyl and substituted C1-C10 alkoxy groups are substituted by one or more amino groups; R7 is selected from hydrogen, substituted or unsubstituted C1-C10 alkyl groups; the substituted C1-C10 alkyl group is substituted by one or more halogen atoms.

7. The high-strength, fracture-resistant automotive rubber hose material according to claim 6, characterized in that, The oil-resistant antioxidant is selected from either compound 1 or compound 2: 。 8. The high-strength, fracture-resistant automotive rubber hose material according to claim 7, characterized in that, Compound 1 or compound 2 is prepared by the following steps: Step 1-a: Take bis(3-aminopropyl)-terminated polydimethylsiloxane, dehydrate it for 1-1.5 h at 80 °C and under vacuum conditions of -0.08 to -0.1 MPa to remove moisture, and then cool it to room temperature for later use; take 4-methoxyphenyl isocyanate or p-trifluoromethoxyphenyl isocyanate; dry it with 4 Å molecular sieve for later use. The number-average molecular weight Mn of the bis(3-aminopropyl)-terminated polydimethylsiloxane is selected from 2000-4500; Step 2-a: In a dry reaction vessel under nitrogen protection, add anhydrous toluene or ethyl acetate as a solvent, the amount of solvent being 3-5 times the mass of bis(3-aminopropyl)-terminated polydimethylsiloxane; then add bis(3-aminopropyl)-terminated polydimethylsiloxane and stir until completely dissolved, the stirring speed being selected from 200-300 r / min; Step 3-a: Weigh 4-methoxyphenyl isocyanate or p-trifluoromethoxyphenyl isocyanate at 2.2-2.4 times the molar amount of bis(3-aminopropyl)-terminated polydimethylsiloxane added in step 2-a, and then slowly add it dropwise to the reaction vessel at a rate of 3-10 mL / min. During the dropwise addition, control the temperature of the reaction system to not exceed 40℃. After the dropwise addition is complete, add the catalyst dibutyltin dilaurate, raise the temperature to 90℃-100℃, and maintain the temperature for 2-4 hours. Step 4-a: After the reaction is complete, the reaction system is heated to 100℃-110℃ and distilled under a vacuum of -0.08 to -0.1MPa for 0.5-1.5h to remove the solvent and unreacted isocyanate raw materials; then it is cooled to room temperature to obtain compound 1 or compound 2. When 4-methoxyphenyl isocyanate is selected as the starting material, compound 1 is obtained; when p-trifluoromethoxyphenyl isocyanate is selected as the starting material, compound 2 is obtained.

9. The high-strength, fracture-resistant automotive rubber hose material according to any one of claims 1-8, characterized in that, The rubber hose material comprises the following components in parts by weight: 56 parts by weight of nitrile rubber, 24 parts by weight of chloroprene rubber, 5 parts by weight of compound 2, 3 parts by weight of calcium carbonate, 4 parts by weight of fumed silica, 1.2 parts by weight of insoluble sulfur, 0.8 parts by weight of N-cyclohexyl-2-benzothiazole sulfenamide, 0.5 parts by weight of N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, 2 parts by weight of epoxidized soybean oil, 3 parts by weight of magnesium hydroxide, and 0.5 parts by weight of N-cyclohexylthiophthalimide.

10. A method for preparing the high-strength, fracture-resistant automotive rubber hose material as described in claim 8 or 9, characterized in that, The method includes the following steps: Preparation of oil-resistant antioxidant: Preparation of compound 2; Pretreatment: Nitrile rubber and chloroprene rubber were plasticized separately in a two-roll mill to obtain a plasticized rubber matrix; the prepared compound 2 was vacuum dried to remove moisture; Mixing: Add the plasticized nitrile rubber and chloroprene rubber to a mixer and mix at a low speed of 30-40 r / min for 2-3 min. Then add calcium carbonate, fumed silica, epoxidized soybean oil and magnesium hydroxide in sequence. Adjust the speed to 60-80 r / min and mix for 5-7 min. Then add N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine, N-cyclohexylthiophthalimide and compound 2. Adjust the speed to 40-50 r / min and mix for 3-4 min. Finally, add insoluble sulfur and N-cyclohexyl-2-benzothiazole sulfenamide, adjust the speed to 30-40 r / min and mix for 2-3 min to obtain the compound. Slicing: The compound rubber is sliced ​​and left to stand to obtain the rested compound rubber; Extrusion molding: The stored rubber compound is added to a rubber extruder, and the temperatures of each section of the extruder are set as follows: feeding section 60-70℃, plasticizing section 80-90℃, and die head section 90-95℃. The screw speed is 20-30 r / min. The extrusion is carried out through a rubber tube die to obtain a continuous unvulcanized rubber tube blank. Vulcanization and shaping: The unvulcanized rubber tube blank is fed into a vulcanizing tank and vulcanized using a two-stage vulcanization process. After vulcanization, it is cooled to room temperature to obtain the high-strength, fracture-resistant automotive rubber tube material.

Images