Multifunctional vulcanizing activator for polyester carcass rubber

Abstract

The invention belongs to the technical field of rubber auxiliaries, and particularly relates to a multifunctional vulcanizing activator for polyester carcass rubber. The raw materials comprise the following components in parts by weight: 30-50 parts of nano-modified zinc oxide, 20-30 parts of hydroxylated fatty acid amide, 15-25 parts of amino silane coupling agent modified montmorillonite, 3-8 parts of an anti-hydrolysis agent and 2-5 parts of hydroxyl-terminated polyether modified graphene quantum dots; functional components such as vulcanization activation, interface adhesion enhancement and damp-heat aging resistance improvement are synergistically compounded, a traditional single-function auxiliary agent system is abandoned, and the rubber material has the advantages that the rubber material formula is simplified, the poor synergism or antagonism effect of multiple auxiliary agents is avoided, and meanwhile the multiple performance requirements of vulcanization, adhesion, aging resistance and the like are synchronously guaranteed.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of rubber auxiliaries, in particular to a multifunctional vulcanization activator for polyester carcass rubber. BACKGROUND

[0002] Polyester fiber is widely used as the carcass skeleton material of rubber products, such as the belt layer of all-steel radial tire, the carcass layer of passenger car tire, the core layer of industrial conveyor belt, etc., due to its high strength, high modulus, excellent fatigue resistance and other characteristics. As the key interface material connecting polyester fiber and rubber matrix, the vulcanization performance, interfacial adhesion performance and aging resistance of polyester carcass rubber directly determine the overall service life and safety performance of rubber products.

[0003] Vulcanization activator is one of the core components of rubber vulcanization system, which mainly activates vulcanization accelerators, reduces vulcanization temperature and time, and improves the crosslinking density and mechanical properties of vulcanized rubber. At present, the commonly used vulcanization activator in polyester carcass rubber is mainly a compound system of zinc oxide (ZnO) and stearic acid (SA), in which zinc oxide provides active zinc ions, stearic acid combines with zinc ions to form zinc stearate, and then activates common accelerators such as thiazole and sulfenamide.

[0004] With the development of rubber products towards high performance, long service life and green environmental protection, the traditional vulcanization activator gradually exposes many defects in the application of polyester carcass rubber, which is difficult to meet the actual demand, as follows: 1. Single function, difficult to meet multiple performance requirements: The traditional zinc oxide-stearic acid system can only achieve vulcanization activation function, and cannot solve the problems of insufficient interfacial adhesion between polyester carcass rubber and polyester fiber, poor aging resistance of vulcanized rubber, etc. In order to improve the interfacial adhesion performance, silane coupling agent, cobalt salt adhesion promoter, etc. need to be added; in order to improve the aging resistance, anti-aging agent needs to be added, which leads to complex rubber formula and easy to produce synergistic adverse effects or antagonistic effects between components. For example, in the formula of polyester carcass rubber of the belt layer of all-steel radial tire, although the addition of cobalt salt adhesion promoter can improve the interfacial adhesion strength, it will accelerate the thermal oxidation of rubber, resulting in the vulcanized rubber prone to cracking, hardening and other aging phenomena during use.

[0005] 2. Large amount of zinc oxide, poor environmental protection and affecting the processing performance of rubber: In traditional systems, the addition amount of zinc oxide is typically 5-10 parts (based on 100 parts of rubber). The use of large amounts of zinc oxide not only increases the cost of the rubber compound but also easily generates dust pollution during production and use, endangering the health of operators. Furthermore, excessive zinc oxide leads to increased Mooney viscosity, decreased processing fluidity, and a risk of scorching during mixing and calendering. For example, a rubber products factory used 8 parts of zinc oxide as a vulcanizing activator when producing polyester-based waterproof membranes. After mixing, the Mooney viscosity of the rubber compound reached 95, edge cracking occurred during calendering, and zinc oxide dust caused the dust concentration in the workshop to exceed the standard by 3 times.

[0006] 3. Insufficient resistance to damp heat aging affects the service life of the product: Polyester fibers are inherently hygroscopic. In humid and hot environments, the interface between the polyester core rubber and the fiber is prone to hydrolysis, leading to a decrease in adhesive strength. Furthermore, the cross-linking bonds formed by traditional vulcanizing activators have poor hydrolysis resistance, further exacerbating the performance degradation of the vulcanized rubber. For example, after six months of use in a humid and hot underground environment (35℃, 90% relative humidity) for a polyester core conveyor belt in a mine, the interfacial peel strength between the polyester core and the rubber decreased from the initial 8.5 kN / m to 3.2 kN / m, far below the safe operating standard (≥5 kN / m), ultimately resulting in the conveyor belt delamination failure.

[0007] 4. Poor compatibility with different polyester fibers: Different types of polyester fibers (such as PET, PBT, and PTT) have varying levels and structures of functional groups on their surfaces. Traditional vulcanizing activators cannot adjust the active centers according to fiber type, necessitating formula readjustments when adapting to different polyester carcasses, increasing production difficulty and costs. For example, in the production of PET polyester carcass tires and PBT polyester carcass conveyor belts, the ratio of zinc oxide and stearic acid must be adjusted separately, and different types of adhesion promoters must be added to ensure interfacial adhesion performance, severely impacting production efficiency. Summary of the Invention

[0008] To address the aforementioned technical problems of limited functionality, high zinc oxide consumption, insufficient resistance to damp heat aging, and poor compatibility with different polyester fibers, this invention provides the following technical solution: A multifunctional vulcanizing activator for polyester carcass rubber comprises raw materials, wherein the raw materials, by weight, include: 30-50 parts of nano-modified zinc oxide, 20-30 parts of hydroxylated fatty acid amide, 15-25 parts of aminosilane coupling agent-modified montmorillonite, 3-8 parts of anti-hydrolysis agent, and 2-5 parts of hydroxyl-terminated polyether-modified graphene quantum dots.

[0009] As a preferred embodiment of the multifunctional vulcanizing activator for polyester carcass rubber described in this invention, the preparation method of the nano-modified zinc oxide is as follows: (1) dissolve terephthalic acid in excess NaOH to obtain a uniform mixture A of sodium terephthalate and NaOH; (2) introduce the mixture A from the top of the jet reactor through a multi-hole nozzle, and introduce zinc chloride with pre-added anionic surfactant from the side of the jet reactor through a high-speed centrifugal atomizer. After the two are fully mixed in the mixing chamber of the jet reactor, they leave the jet reactor through the diffusion chamber and then enter the closed kettle reactor. While stirring, the material is heated to 55°C and the mixing reaction continues for 30 minutes. Finally, after separation, washing, and drying, nano-modified zinc oxide with a particle size of 50-200 nm is obtained. The weight ratio of zinc terephthalate to zinc oxide in the components of nano-modified zinc oxide is (10-15):(90-85).

[0010] As a preferred embodiment of the multifunctional vulcanizing activator for polyester carcass rubber described in this invention, the hydroxylated fatty acid amide is hydroxystearic acid decanediamine amide or hydroxypalmitic acid hexamethylenediamine amide; its molecular structure simultaneously contains hydroxyl groups, amide groups and long-chain alkyl groups. The hydroxyl groups can form hydrogen bonds with the hydroxyl groups on the surface of polyester fibers, the amide groups can interact with the polar groups in the rubber molecules, and the long-chain alkyl groups can improve the compatibility between the activator and the rubber, thereby enhancing the interfacial adhesion performance.

[0011] As a preferred embodiment of the multifunctional vulcanizing activator for polyester carcass rubber described in this invention, wherein: the aminosilane coupling agent modified montmorillonite is sodium-based montmorillonite modified with γ-aminopropyltriethoxysilane (KH550) or N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane (KH792), and the amount of the modifier is 8%-12% of the weight of montmorillonite; the layered structure of the modified montmorillonite can block the penetration of water molecules, improve the resistance of vulcanized rubber to humid heat aging, and at the same time, the amino groups on its surface can form chemical bonds with polyester fibers and rubber molecules, further enhancing interfacial adhesion.

[0012] As a preferred embodiment of the multifunctional vulcanizing activator for polyester carcass rubber described in this invention, the anti-hydrolysis agent is a carbodiimide compound (such as polycarbodiimide); it can react with the carboxyl groups generated by the hydrolysis of polyester fibers and rubber molecules, inhibiting the continued hydrolysis reaction and improving the service life of the product in humid and hot environments.

[0013] As a preferred embodiment of the multifunctional vulcanizing activator for polyester carcass rubber described in this invention, the terminal hydroxyl polyether modified graphene quantum dots are graphene quantum dots grafted with polyoxyethylene ether monomethyl ether, with a particle size of 2-10 nm and a grafting rate of 15-25 wt%. The terminal hydroxyl groups on their surface can form hydrogen bonds with the hydroxyl groups of hydroxylated fatty acid amides and the amino groups of montmorillonite modified with aminosilane coupling agents. At the same time, the high specific surface area and excellent thermal conductivity of graphene quantum dots can promote uniform heat transfer during vulcanization, avoid local over-vulcanization, and enhance the mechanical strength and high-temperature aging resistance of the vulcanized rubber, forming multiple synergistic effects with other components in the system.

[0014] As a preferred embodiment of the multifunctional vulcanizing activator for polyester carcass rubber described in this invention, it further includes a preparation method, the specific steps of which are as follows: S1, add nano-modified zinc oxide and hydroxylated fatty acid amide into a high-speed mixer to obtain mixture A; S2, add aminosilane coupling agent modified montmorillonite and hydroxyl-terminated polyether modified graphene quantum dots to mixture A, premix for 10-15 min at 100-120℃ and 1200-1500 r / min, then introduce ultrasonic-assisted dispersion treatment with a power of 300-500W for 5-8 min at an ultrasonic frequency of 20-40kHz, and then continue mixing for 10-15 min at the same temperature and speed to obtain mixture B; S3, the anti-hydrolysis agent is added to mixture B and mixed to obtain a preliminary mixture; then the preliminary mixture is placed in a low-temperature plasma treatment device and subjected to plasma surface modification treatment for 3-6 minutes under the conditions of argon / oxygen mixed atmosphere (volume ratio 3:1), treatment power 150-250W, and treatment pressure 50-100Pa. After treatment, it is cooled to room temperature, pulverized and passed through a 200-mesh sieve to obtain the multifunctional vulcanizing activator.

[0015] As a preferred embodiment of the multifunctional vulcanizing activator for polyester carcass rubber described in this invention, in step S1, the rotation speed of the high-speed mixer is set to 800-1000 r / min, the mixing temperature is set to 80-100℃, and the mixing time is set to 15-20 min.

[0016] As a preferred embodiment of the multifunctional vulcanizing activator for polyester carcass rubber described in this invention, wherein in step S3, the mixing temperature is set to 80-90℃ and the mixing time is set to 10-15min during initial mixing.

[0017] Compared with existing technologies: 1. By synergistically compounding functional components such as vulcanization activation, interfacial adhesion enhancement, and moisture heat aging resistance improvement, the traditional single-function additive system is abandoned. It has the advantages of simplifying rubber compound formulation, avoiding poor synergy or antagonistic effects of multiple additives, and simultaneously ensuring multiple performance requirements such as vulcanization, adhesion, and aging resistance. 2. By using stearic acid to coat and modify nano zinc oxide and reducing its dosage, combined with ultrasonic-assisted dispersion to improve dispersion uniformity, this method replaces the traditional high-dosage zinc oxide system. It has the advantages of reducing dust pollution, improving the flowability of rubber processing, avoiding the risk of scorching, and taking into account both environmental protection and processing stability. 3. By combining the layered barrier effect of montmorillonite modified with aminosilane coupling agent, the hydrolysis inhibition effect of anti-hydrolysis agent, and the stabilizing and enhancing effect of graphene quantum dots modified with hydroxyl-terminated polyether, it has the advantages of inhibiting interfacial hydrolysis reaction, delaying the performance degradation of vulcanized rubber, and extending the service life of products in humid and hot environments. 4. By forming multi-functional interactions between the hydroxyl and amide groups of hydroxylated fatty acid amides and the functional groups on the surface of different polyester fibers, and combined with the chemical bonding effect of aminosilane coupling agents, it has the advantage of being able to adapt to a variety of polyester fibers such as PET, PBT, and PTT, and ensuring stable interfacial adhesion performance without adjusting the formula. Detailed Implementation

[0018] To make the objectives, technical solutions, and advantages of the present invention clearer, the embodiments of the present invention will be described in further detail below. Example 1:

[0019] This invention provides a multifunctional vulcanizing activator for polyester carcass rubber, comprising raw materials, wherein the raw materials, by weight, include: 30 parts of nano-modified zinc oxide, 20 parts of hydroxylated fatty acid amide, 15 parts of aminosilane coupling agent modified montmorillonite, 3 parts of anti-hydrolysis agent, and 2 parts of hydroxyl-terminated polyether modified graphene quantum dots.

[0020] The preparation method of the nano-modified zinc oxide is as follows: (1) Dissolve terephthalic acid in excess NaOH to obtain a uniform mixture A of sodium terephthalate and NaOH; (2) Introduce mixture A from the top of the jet reactor through a multi-hole nozzle, and introduce zinc chloride with pre-added anionic surfactant from the side of the jet reactor through a high-speed centrifugal atomizer. After the two are fully mixed in the mixing chamber of the jet reactor, they leave the jet reactor through the diffusion chamber and enter the closed kettle reactor. While stirring, heat the material to 55°C and continue mixing and reacting for 30 minutes. Finally, after separation, washing and drying, nano-modified zinc oxide with a particle size of 50 nm is obtained. The weight ratio of zinc terephthalate to zinc oxide in the nano-modified zinc oxide is 10:90.

[0021] The hydroxylated fatty acid amide is hydroxystearic acid decanediamine amide or hydroxypalmitic acid hexamethylenediamine amide; its molecular structure contains hydroxyl, amide and long-chain alkyl groups. The hydroxyl group can form hydrogen bonds with the hydroxyl groups on the surface of polyester fibers, the amide group can interact with the polar groups in the rubber molecule, and the long-chain alkyl group can improve the compatibility between the activator and the rubber, thereby enhancing the interfacial adhesion performance.

[0022] The aminosilane coupling agent modified montmorillonite is sodium-based montmorillonite modified with γ-aminopropyltriethoxysilane (KH550) or N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane (KH792), and the amount of modifier is 8% of the weight of montmorillonite. The layered structure of the modified montmorillonite can block the penetration of water molecules and improve the resistance of vulcanized rubber to humid heat aging. At the same time, the amino groups on its surface can form chemical bonds with polyester fibers and rubber molecules, further enhancing interfacial adhesion.

[0023] The anti-hydrolysis agent is a carbodiimide compound (such as polycarbodiimide); it can react with the carboxyl groups generated by the hydrolysis of polyester fibers and rubber molecules, inhibiting the continued hydrolysis reaction and improving the service life of the product in humid and hot environments.

[0024] The hydroxyl-terminated polyether-modified graphene quantum dots are graphene quantum dots grafted with polyoxyethylene ether monomethyl ether, with a particle size of 2 nm and a grafting rate of 15 wt%. The hydroxyl-terminated hydroxyl groups on their surface can form hydrogen bonds with the hydroxyl groups of hydroxylated fatty acid amides and the amino groups of montmorillonite modified with aminosilane coupling agent. At the same time, the high specific surface area and excellent thermal conductivity of graphene quantum dots can promote uniform heat transfer during vulcanization, avoid local over-vulcanization, and enhance the mechanical strength and high-temperature aging resistance of vulcanized rubber, forming multiple synergistic effects with other components in the system.

[0025] It also includes a preparation method, the specific steps of which are as follows: S1, nano-modified zinc oxide and hydroxylated fatty acid amide are added to a high-speed mixer to obtain mixture A; wherein, the speed of the high-speed mixer is set to 800 r / min, the mixing temperature is set to 80℃, and the mixing time is set to 15 min; S2, add aminosilane coupling agent modified montmorillonite and hydroxyl-terminated polyether modified graphene quantum dots to mixture A, premix for 10 min at 100℃ and 1200 r / min, then introduce ultrasonic-assisted dispersion treatment with a power of 300W for 5 min at an ultrasonic frequency of 20kHz, and then continue mixing for 10 min at the same temperature and speed to obtain mixture B; S3, the anti-hydrolysis agent is added to mixture B and mixed to obtain a preliminary mixture; then the preliminary mixture is placed in a low-temperature plasma treatment device and subjected to plasma surface modification treatment for 3 minutes under an argon / oxygen mixed atmosphere (volume ratio 3:1), a treatment power of 150W, and a treatment pressure of 50Pa. After treatment, it is cooled to room temperature, pulverized, and passed through a 200-mesh sieve to obtain the multifunctional vulcanizing activator; wherein, during the preliminary mixing, the mixing temperature is set to 80℃ and the mixing time is set to 10 minutes. Implementation: 2:

[0026] This invention provides a multifunctional vulcanizing activator for polyester carcass rubber, comprising raw materials, wherein the raw materials, by weight, include: 40 parts of nano-modified zinc oxide, 25 parts of hydroxylated fatty acid amide, 20 parts of aminosilane coupling agent modified montmorillonite, 5.5 parts of anti-hydrolysis agent, and 3.5 parts of hydroxyl-terminated polyether modified graphene quantum dots.

[0027] The preparation method of the nano-modified zinc oxide is as follows: (1) Dissolve terephthalic acid in excess NaOH to obtain a uniform mixture A of sodium terephthalate and NaOH; (2) Introduce the mixture A from the top of the jet reactor through a multi-hole nozzle, and introduce zinc chloride with pre-added anionic surfactant from the side of the jet reactor through a high-speed centrifugal atomizer. After the two are fully mixed in the mixing chamber of the jet reactor, they leave the jet reactor through the diffusion chamber and enter the closed kettle reactor. While stirring, heat the material to 55°C and continue mixing and reacting for 30 minutes. Finally, after separation, washing and drying, nano-modified zinc oxide with a particle size of 125 nm is obtained. The weight ratio of zinc terephthalate to zinc oxide in the nano-modified zinc oxide is 15:85.

[0028] The hydroxylated fatty acid amide is hydroxystearic acid decanediamine amide or hydroxypalmitic acid hexamethylenediamine amide; its molecular structure contains hydroxyl, amide and long-chain alkyl groups. The hydroxyl group can form hydrogen bonds with the hydroxyl groups on the surface of polyester fibers, the amide group can interact with the polar groups in the rubber molecule, and the long-chain alkyl group can improve the compatibility between the activator and the rubber, thereby enhancing the interfacial adhesion performance.

[0029] The aminosilane coupling agent modified montmorillonite is sodium-based montmorillonite modified with γ-aminopropyltriethoxysilane (KH550) or N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane (KH792), and the amount of modifier is 10% of the weight of montmorillonite. The layered structure of the modified montmorillonite can block the penetration of water molecules and improve the resistance of vulcanized rubber to humid heat aging. At the same time, the amino groups on its surface can form chemical bonds with polyester fibers and rubber molecules, further enhancing interfacial adhesion.

[0030] The anti-hydrolysis agent is a carbodiimide compound (such as polycarbodiimide); it can react with the carboxyl groups generated by the hydrolysis of polyester fibers and rubber molecules, inhibiting the continued hydrolysis reaction and improving the service life of the product in humid and hot environments.

[0031] The hydroxyl-terminated polyether-modified graphene quantum dots are graphene quantum dots grafted with polyoxyethylene ether monomethyl ether, with a particle size of 6 nm and a grafting rate of 20 wt%. The hydroxyl-terminated hydroxyl groups on their surface can form hydrogen bonds with the hydroxyl groups of hydroxylated fatty acid amides and the amino groups of montmorillonite modified with aminosilane coupling agent. At the same time, the high specific surface area and excellent thermal conductivity of graphene quantum dots can promote uniform heat transfer during vulcanization, avoid local over-vulcanization, and enhance the mechanical strength and high-temperature aging resistance of vulcanized rubber, forming multiple synergistic effects with other components in the system.

[0032] It also includes a preparation method, the specific steps of which are as follows: S1, nano-modified zinc oxide and hydroxylated fatty acid amide are added to a high-speed mixer to obtain mixture A; wherein, the speed of the high-speed mixer is set to 900 r / min, the mixing temperature is set to 90℃, and the mixing time is set to 17.5 min; S2, add aminosilane coupling agent modified montmorillonite and hydroxyl-terminated polyether modified graphene quantum dots to mixture A, premix at 110℃ and 1350 r / min for 12.5 min, then introduce ultrasonic-assisted dispersion treatment with a power of 400W and an ultrasonic frequency of 30kHz for 6.5 min, and then continue to mix at the same temperature and speed for 12.5 min to obtain mixture B; S3, the anti-hydrolysis agent is added to mixture B and mixed to obtain a preliminary mixture; then the preliminary mixture is placed in a low-temperature plasma treatment device and subjected to plasma surface modification treatment for 4.5 min under an argon / oxygen mixed atmosphere (volume ratio 3:1), a treatment power of 200 W, and a treatment pressure of 75 Pa. After treatment, it is cooled to room temperature, pulverized, and passed through a 200-mesh sieve to obtain the multifunctional vulcanizing activator; wherein, during the preliminary mixing, the mixing temperature is set to 85 °C and the mixing time is set to 12.5 min. Implementation: 3:

[0033] This invention provides a multifunctional vulcanizing activator for polyester carcass rubber, comprising raw materials, wherein the raw materials, by weight, include: 50 parts of nano-modified zinc oxide, 30 parts of hydroxylated fatty acid amide, 25 parts of aminosilane coupling agent modified montmorillonite, 8 parts of anti-hydrolysis agent, and 5 parts of hydroxyl-terminated polyether modified graphene quantum dots.

[0034] The preparation method of the nano-modified zinc oxide is as follows: (1) Dissolve terephthalic acid in excess NaOH to obtain a uniform mixture A of sodium terephthalate and NaOH; (2) Introduce mixture A from the top of the jet reactor through a multi-hole nozzle, and introduce zinc chloride with pre-added anionic surfactant from the side of the jet reactor through a high-speed centrifugal atomizer. After the two are fully mixed in the mixing chamber of the jet reactor, they leave the jet reactor through the diffusion chamber and enter the closed kettle reactor. While stirring, heat the material to 55°C and continue mixing and reacting for 30 minutes. Finally, after separation, washing and drying, nano-modified zinc oxide with a particle size of 200 nm is obtained. The weight ratio of zinc terephthalate to zinc oxide in the nano-modified zinc oxide is 12:88.

[0035] The hydroxylated fatty acid amide is hydroxystearic acid decanediamine amide or hydroxypalmitic acid hexamethylenediamine amide; its molecular structure contains hydroxyl, amide and long-chain alkyl groups. The hydroxyl group can form hydrogen bonds with the hydroxyl groups on the surface of polyester fibers, the amide group can interact with the polar groups in the rubber molecule, and the long-chain alkyl group can improve the compatibility between the activator and the rubber, thereby enhancing the interfacial adhesion performance.

[0036] The aminosilane coupling agent modified montmorillonite is sodium-based montmorillonite modified with γ-aminopropyltriethoxysilane (KH550) or N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane (KH792), and the amount of modifier is 12% of the weight of montmorillonite. The layered structure of the modified montmorillonite can block the penetration of water molecules and improve the resistance of vulcanized rubber to humid heat aging. At the same time, the amino groups on its surface can form chemical bonds with polyester fibers and rubber molecules, further enhancing interfacial adhesion.

[0037] The anti-hydrolysis agent is a carbodiimide compound (such as polycarbodiimide); it can react with the carboxyl groups generated by the hydrolysis of polyester fibers and rubber molecules, inhibiting the continued hydrolysis reaction and improving the service life of the product in humid and hot environments.

[0038] The hydroxyl-terminated polyether-modified graphene quantum dots are graphene quantum dots grafted with polyoxyethylene ether monomethyl ether, with a particle size of 10 nm and a grafting rate of 25 wt%. The hydroxyl-terminated hydroxyl groups on their surface can form hydrogen bonds with the hydroxyl groups of hydroxylated fatty acid amides and the amino groups of montmorillonite modified with aminosilane coupling agent. At the same time, the high specific surface area and excellent thermal conductivity of graphene quantum dots can promote uniform heat transfer during vulcanization, avoid local over-vulcanization, and enhance the mechanical strength and high-temperature aging resistance of vulcanized rubber, forming multiple synergistic effects with other components in the system.

[0039] It also includes a preparation method, the specific steps of which are as follows: S1, nano-modified zinc oxide and hydroxylated fatty acid amide are added to a high-speed mixer to obtain mixture A; wherein, the speed of the high-speed mixer is set to 1000 r / min, the mixing temperature is set to 100℃, and the mixing time is set to 20 min; S2, add aminosilane coupling agent modified montmorillonite and hydroxyl-terminated polyether modified graphene quantum dots to mixture A, premix at 120℃ and 1500 r / min for 15 min, then introduce ultrasonic-assisted dispersion treatment with a power of 500W for 8 min at an ultrasonic frequency of 40kHz, and then continue mixing at the same temperature and speed for 15 min to obtain mixture B; S3, the anti-hydrolysis agent is added to mixture B and mixed to obtain a preliminary mixture; then the preliminary mixture is placed in a low-temperature plasma treatment device and subjected to plasma surface modification treatment for 6 minutes under an argon / oxygen mixed atmosphere (volume ratio 3:1), a treatment power of 250W, and a treatment pressure of 100Pa. After treatment, it is cooled to room temperature, pulverized, and passed through a 200-mesh sieve to obtain the multifunctional vulcanizing activator; wherein, during the preliminary mixing, the mixing temperature is set to 90℃ and the mixing time is set to 15 minutes.

[0040] Comparative Example 1: The difference between Comparative Example 1 and Example 1 is as follows: The modified zinc oxide is prepared by adding zinc terephthalate and nano zinc oxide in a weight ratio of 10:90 to a high-speed mixer, and introducing the same type and amount of anionic surfactant as in Example 1. The mixture is then dry-modified by high-speed mixing to finally obtain modified zinc oxide.

[0041] Comparative Example 2: The difference between Comparative Example 2 and Example 1 is as follows: A method for preparing a multifunctional vulcanizing activator for polyester carcass rubber, the specific steps of which are as follows: S1, nano-modified zinc oxide and hydroxylated fatty acid amide are added to a high-speed mixer to obtain mixture A; wherein, the speed of the high-speed mixer is set to 800 r / min, the mixing temperature is set to 80℃, and the mixing time is set to 15 min; S2, add hydroxyl-terminated polyether modified graphene quantum dots to mixture A, premix for 10 min at 100℃ and 1200 r / min, then introduce ultrasonic-assisted dispersion treatment with a power of 300W for 5 min at an ultrasonic frequency of 20kHz, and then continue mixing for 10 min at the same temperature and speed to obtain the finished product.

[0042] When the multifunctional vulcanizing activators prepared in Examples 1, 1, and 2 above are applied to polyester carcass rubber, they replace the traditional indirect ZnO. The formulations used are shown in Table 1 below:

[0043] The product was manufactured according to the above formula, and its performance was tested. The following data were obtained, as detailed in Table 2: Table 2: Physical Property Data Table

[0044] Analysis of the data in the table above: (1) The performance comparison of the two rubber compounds in Example 1 and the indirect method ZnO shows that the multifunctional vulcanizing activator prepared in Example 1 has a slightly better vulcanization activation efficiency than the indirect method ZnO, and the adhesion performance before and after hot air aging has a more obvious advantage, especially the anti-hydrolysis performance is outstanding. It can be seen that although the zinc content of the multifunctional vulcanizing activator in Example 1 is much lower than that of the indirect method ZnO, it does not affect the performance. (2) The performance comparison of the two rubber compounds in Example 1 and Comparative Example 1 shows that the product prepared in Example 1 has a greater advantage in vulcanization activity. It can be seen that the introduction of the jet reactor plays a crucial role in improving the activity of zinc. (3) The performance comparison of the two rubber compounds in Example 1 and Comparative Example 2 shows that the ultrasonic and low-temperature plasma treatment technology plays a crucial role in further improving the adhesion performance and anti-hydrolysis performance.

[0045] Although the present invention has been described above with reference to embodiments, various modifications can be made and components can be replaced with equivalents without departing from the scope of the invention. In particular, as long as there is no structural conflict, the features in the disclosed embodiments can be combined with each other in any manner. The lack of an exhaustive description of these combinations in this specification is merely for the sake of brevity and resource conservation. Therefore, the present invention is not limited to the specific embodiments disclosed herein, but includes all technical solutions falling within the scope of the claims.

Claims

1. A multifunctional vulcanizing activator for polyester carcass rubber, comprising raw materials, characterized in that, The raw materials, by weight, include: 30-50 parts of nano-modified zinc oxide, 20-30 parts of hydroxylated fatty acid amide, 15-25 parts of aminosilane coupling agent-modified montmorillonite, 3-8 parts of anti-hydrolysis agent, and 2-5 parts of hydroxyl-terminated polyether-modified graphene quantum dots.

2. The multifunctional vulcanizing activator for polyester carcass rubber according to claim 1, characterized in that, The preparation method of the nano-modified zinc oxide is as follows: (1) Dissolve terephthalic acid in excess NaOH to obtain a homogeneous mixture A of sodium terephthalate and NaOH; (2) Mixture A is introduced from the top of the jet reactor through a multi-hole nozzle, and zinc chloride with pre-added anionic surfactant is introduced from the side of the jet reactor through a high-speed centrifugal atomizer. After the two are fully mixed in the mixing chamber of the jet reactor, they leave the jet reactor through the diffusion chamber and then enter the closed kettle reactor. The material is heated to 55°C while stirring, and the mixing reaction continues for 30 minutes. Finally, after separation, washing and drying, nano-modified zinc oxide with a particle size of 50-200 nm is obtained. The weight ratio of zinc terephthalate to zinc oxide in the nano-modified zinc oxide composition is (10-15):(90-85).

3. The multifunctional vulcanizing activator for polyester carcass rubber according to claim 1, characterized in that, The hydroxylated fatty acid amide is hydroxystearic acid decanediamine amide or hydroxypalmitic acid hexamethylenediamine amide.

4. The multifunctional vulcanizing activator for polyester carcass rubber according to claim 1, characterized in that, The aminosilane coupling agent modified montmorillonite is sodium-based montmorillonite modified with γ-aminopropyltriethoxysilane or N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, and the amount of modifier is 8%-12% of the weight of montmorillonite.

5. The multifunctional vulcanizing activator for polyester carcass rubber according to claim 1, characterized in that, The anti-hydrolysis agent is a carbodiimide compound.

6. The multifunctional vulcanizing activator for polyester carcass rubber according to claim 1, characterized in that, The hydroxyl-terminated polyether-modified graphene quantum dots are graphene quantum dots grafted with polyoxyethylene ether monomethyl ether, with a particle size of 2-10 nm and a grafting rate of 15-25 wt%.

7. The multifunctional vulcanizing activator for polyester carcass rubber according to claim 1, characterized in that, It also includes a preparation method, the specific steps of which are as follows: S1, add nano-modified zinc oxide and hydroxylated fatty acid amide into a high-speed mixer to obtain mixture A; S2, add aminosilane coupling agent modified montmorillonite and hydroxyl-terminated polyether modified graphene quantum dots to mixture A, premix for 10-15 min at 100-120℃ and 1200-1500 r / min, then introduce ultrasonic-assisted dispersion treatment with a power of 300-500W for 5-8 min at an ultrasonic frequency of 20-40kHz, and then continue mixing for 10-15 min at the same temperature and speed to obtain mixture B; S3, add the anti-hydrolysis agent to mixture B and mix to obtain a preliminary mixture; then place the preliminary mixture in a low-temperature plasma treatment device and perform plasma surface modification treatment for 3-6 minutes under the conditions of argon / oxygen mixed atmosphere, treatment power of 150-250W and treatment pressure of 50-100Pa. After treatment, cool to room temperature, crush and pass through a 200-mesh sieve to obtain the multifunctional vulcanizing activator.

8. The multifunctional vulcanizing activator for polyester carcass rubber according to claim 7, characterized in that, In S1, the speed of the high-speed mixer is set to 800-1000 r / min, the mixing temperature is set to 80-100℃, and the mixing time is set to 15-20 min.

9. A multifunctional vulcanizing activator for polyester carcass rubber according to claim 7, characterized in that, In step S3, during the initial mixing, the mixing temperature is set to 80-90℃ and the mixing time is set to 10-15min.

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