WO2012062057A1 - Method for improving anti-aging performance due to heat or oxygen of natural rubber traditional sulfur vulcanization system - Google Patents

Method for improving anti-aging performance due to heat or oxygen of natural rubber traditional sulfur vulcanization system Download PDF

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WO2012062057A1
WO2012062057A1 PCT/CN2011/070840 CN2011070840W WO2012062057A1 WO 2012062057 A1 WO2012062057 A1 WO 2012062057A1 CN 2011070840 W CN2011070840 W CN 2011070840W WO 2012062057 A1 WO2012062057 A1 WO 2012062057A1
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parts
natural rubber
zinc oxide
vulcanization system
modified nano
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陈月辉
邓力
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上海工程技术大学
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK  ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
    • C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
    • C09C1/04—Compounds of zinc
    • C09C1/043—Zinc oxide
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G9/00—Compounds of zinc
    • C01G9/02—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances

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  • the invention relates to a method for improving the heat aging resistance of natural rubber traditional sulfur vulcanization system. Background technique
  • the complete sulfur vulcanization system of the diene rubber is composed of a vulcanizing agent, a promoter and an active agent.
  • a vulcanizing agent zinc oxide and stearic acid are classic combinations of vulcanization activators, and the dosage is kept at 5 parts. Therefore, depending on the relative ratio of the vulcanizing agent sulfur to the accelerator, the vulcanization system can be divided into: a conventional vulcanization system, an effective vulcanization system, and a semi-effective vulcanization system.
  • the "Practical Rubber Technology” edited by Yang Qingzhi is described in the section "Various sulfur vulcanization systems" in Section VI: Diene rubber
  • the traditional sulfur vulcanization system refers to the vulcanization system in the range of sulfur content.
  • the amount of sulfur used is 2.5 parts, and the amount of accelerator is 0.5 parts. More than 70% of the vulcanized rubber network is a polysulfide bond. Vulcanized rubber has good initial fatigue properties, and has excellent dynamic and static properties at room temperature. The biggest disadvantage is that it does not heat-resistant oxygen aging, and vulcanized rubber cannot be used for a long time at higher temperatures. To this end, an effective vulcanization system and a semi-effective vulcanization system were designed to improve the heat-resistant oxygen aging properties of natural rubber, but these two types of systems were used to compensate for the defects of poor heat-resistant oxygen aging resistance of natural rubber vulcanization systems, without exception. At the expense of the comprehensive physical and mechanical properties of traditional sulfur vulcanization systems.
  • Zinc oxide is the most commonly used activator of natural rubber. It forms zinc stearate with stearic acid, chelate with cross-linking precursors, adds new cross-linking bonds, increases the cross-linking density of natural rubber, and forms with accelerators. The complex makes the accelerator more active. Therefore, zinc oxide can accelerate the vulcanization rate, increase the crosslink density of the vulcanizate and the thermal aging resistance of the vulcanizate, but ordinary zinc oxide has a large particle size and low activity, which limits its activation.
  • the method of the present invention comprises the steps of: adding in situ surface-modified nano zinc oxide to a natural sulfur vulcanization system of natural rubber, and obtaining a natural rubber product after vulcanization.
  • the in-situ surface-modified nano zinc oxide is prepared by using zinc nitrate and sorbitan oleate as raw materials and stearic acid as a dispersing agent;
  • the preparation method comprises the following steps:
  • step (1) (2) calcining the gel of step (1) at a temperature of 550 to 650 ° C for 4 to 6 hours to obtain an in-situ surface-modified nano zinc oxide;
  • the mass parts are: 120 parts of stearic acid, zinc nitrate 15.68 ⁇ 41.83 parts, sorbitan oleate 1.13 ⁇ 3.01 parts;
  • the natural rubber conventional sulfur vulcanization system is conventional, such as the rubber industry.
  • the components and mass parts of the natural rubber conventional sulfur vulcanization system of the present invention are as follows:
  • the components and mass parts of the natural rubber conventional sulfur vulcanization system are as follows:
  • the accelerator is N-oxydiethylene-2-benzothiazolylsulfenamide.
  • the invention adopts a sol-gel method to in-situ surface modification of nano zinc oxide, and the modified nano zinc oxide improves the dispersibility in the rubber substrate, can fully exert its nano effect, and is applied to natural rubber.
  • the thermal aging resistance of the vulcanized rubber after the accelerated aging of hot air is greatly improved.
  • the in-situ surface-modified nano zinc oxide prepared by the invention reduces the agglomeration caused by the high specific surface energy while ensuring the high activity of the nanoparticle, and applies it to the natural sulfur vulcanization system of natural rubber, so that The nano effect has been fully utilized.
  • the process of the invention is simple, the physical and mechanical properties of the vulcanized rubber are excellent, and the aging resistance of the heat-resistant oxygen is remarkably improved.
  • the invention can also be applied to other sulfur vulcanized diene rubber conventional vulcanization systems, so the application prospect is very broad. detailed description
  • the components and mass parts of the natural rubber conventional sulfur vulcanization system are as follows: 100 parts of natural rubber
  • the dispersing agent stearic acid is heated to 80 ° C to melt, and then zinc nitrate and sorbitan oleate are added, and after stirring for 1 hour, a sol is obtained, and cooling is performed to obtain a gel;
  • step (2) (2) calcining the gel of step (1) at a temperature of 550 Torr for 6 hours to obtain an in situ surface-modified nano zinc oxide;
  • step (1) heating the dispersing agent stearic acid to 80 ° C, then adding zinc nitrate and sorbitan oleate, stirring for 3 hours to obtain a sol, cooling to obtain a gel; (2) calcining the gel of step (1) at a temperature of 650 ° C for 4 hours to obtain an in-situ surface-modified nano zinc oxide;
  • the dispersing agent stearic acid is heated to 80 ° C to melt, and then zinc nitrate and sorbitan oleate are added, and after stirring for 2 hours, a sol is obtained, and cooling is performed to obtain a gel;
  • step (2) (2) calcining the gel of step (1) at a temperature of 600 ° C for 5 hours to obtain an in situ surface-modified nano zinc oxide;
  • Example 3 The in situ surface modified nano zinc oxide of Example 3 was used.
  • the components and mass parts of the natural rubber conventional sulfur vulcanization system are as follows:
  • Example 3 The in situ surface modified nano zinc oxide of Example 3 was used.
  • the components and mass parts of the natural rubber conventional sulfur vulcanization system are as follows:
  • the natural rubber traditional sulfur vulcanization system vulcanizate increased tensile strength by 17.58% before aging, elongation elongation increased by 3.72%; tensile strength retention and elongation at break after aging The retention rate increased by 34.27% and 19.17%, respectively.

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  • Organic Chemistry (AREA)
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Abstract

A method for improving the anti-aging performance due to heat or oxygen of natural rubber traditional sulfur vulcanization system, which includes the following steps: adding in-situ surface modified nano-zinc oxide to natural rubber traditional sulfur vulcanization system, and obtaining natural rubber vulcanizate after vulcanization. Therein said in-situ surface modified nano-zinc oxide is prepared by zinc nitrate and sorbitan oleate as raw materials and stearic acid as dispersant. While ensuring high activity of the nanoparticles, the agglomeration brought by high specific surface energy is weakened in the present invention. The in-situ surface modified nano-zinc oxide is applied to the natural rubber traditional sulfur vulcanization system to fully play its nano-effect. The method can also be applied to diene rubber traditional vulcanization system of sulfur vulcanization.

Description

提高天然橡胶传统硫黄硫化体系耐热氧老化性能的方法 技术领域  Method for improving heat-resistant oxygen aging performance of natural rubber traditional sulfur yellow vulcanization system
本发明涉及一种提高天然橡胶传统硫黄硫化体系耐热氧老化性能 的方法。 背景技术  The invention relates to a method for improving the heat aging resistance of natural rubber traditional sulfur vulcanization system. Background technique
二烯类橡胶完整的硫黄硫化体系是由硫化剂、 促进剂和活性剂三 部分组成。 其中氧化锌与硬脂酸是硫化活性剂的经典组合， 用量一直 保持 5 份不变。 因此， 根据硫化剂硫黄与促进剂的相对比例不同， 硫 化体系可分为： 传统硫化体系、 有效硫化体系和半有效硫化体系。 杨清芝主编的《实用橡胶工艺学》在第六节 "各种硫黄硫化体系" 章节中叙述道： 二烯类橡胶传统硫黄硫化体系是指通常硫黄用量范围 的硫化体系。 对天然橡胶而言， 硫黄的用量为常用的 2.5份， 促进剂的 用量为 0.5份。硫化胶网络中 70%以上是多硫键。硫化胶具有良好的初 始疲劳性能， 室温条件下具有优良的动静态性能， 最大的缺点是不耐 热氧老化， 硫化胶不能在较高温度下长期使用。 为此设计了有效硫化体系和半有效硫化体系来提高天然橡胶的耐 热氧老化性能， 但是用这两类体系来弥补天然橡胶传统硫黄硫化体系 耐热氧老化性能差的缺陷， 无一例外都是以牺牲传统硫黄硫化体系的 综合物理机械性能为代价的。 氧化锌是天然橡胶最常用的活化剂， 它与硬脂酸生成硬脂酸锌， 与交联先驱体螯合， 增加新的交联键， 提高天然橡胶的交联密度， 并 与促进剂形成络合物， 使促进剂更加活泼。 因此， 氧化锌可以加快硫 化速度， 提高硫化胶的交联密度和耐热氧老化性能， 但是普通氧化锌 的粒径大， 活性低而限制其活化作用的发挥。 纳米科技改变了氧化锌 的活性， 纳米氧化锌带来的纳米效应， 使其硫化活性有了质的提高， 可是材料的粒径越小， 其聚集结团的倾向越大， 纳米效应也越难体现。 发明内容 The complete sulfur vulcanization system of the diene rubber is composed of a vulcanizing agent, a promoter and an active agent. Among them, zinc oxide and stearic acid are classic combinations of vulcanization activators, and the dosage is kept at 5 parts. Therefore, depending on the relative ratio of the vulcanizing agent sulfur to the accelerator, the vulcanization system can be divided into: a conventional vulcanization system, an effective vulcanization system, and a semi-effective vulcanization system. The "Practical Rubber Technology" edited by Yang Qingzhi is described in the section "Various sulfur vulcanization systems" in Section VI: Diene rubber The traditional sulfur vulcanization system refers to the vulcanization system in the range of sulfur content. For natural rubber, the amount of sulfur used is 2.5 parts, and the amount of accelerator is 0.5 parts. More than 70% of the vulcanized rubber network is a polysulfide bond. Vulcanized rubber has good initial fatigue properties, and has excellent dynamic and static properties at room temperature. The biggest disadvantage is that it does not heat-resistant oxygen aging, and vulcanized rubber cannot be used for a long time at higher temperatures. To this end, an effective vulcanization system and a semi-effective vulcanization system were designed to improve the heat-resistant oxygen aging properties of natural rubber, but these two types of systems were used to compensate for the defects of poor heat-resistant oxygen aging resistance of natural rubber vulcanization systems, without exception. At the expense of the comprehensive physical and mechanical properties of traditional sulfur vulcanization systems. Zinc oxide is the most commonly used activator of natural rubber. It forms zinc stearate with stearic acid, chelate with cross-linking precursors, adds new cross-linking bonds, increases the cross-linking density of natural rubber, and forms with accelerators. The complex makes the accelerator more active. Therefore, zinc oxide can accelerate the vulcanization rate, increase the crosslink density of the vulcanizate and the thermal aging resistance of the vulcanizate, but ordinary zinc oxide has a large particle size and low activity, which limits its activation. Nanotechnology changed zinc oxide The activity, the nano-effect of nano-zinc oxide, has a qualitative improvement in its vulcanization activity, but the smaller the particle size of the material, the greater the tendency of aggregation and agglomeration, and the more difficult the nano-effect is. Summary of the invention
本发明的目的是公开一种提高天然橡胶传统硫黄硫化体系耐热氧 老化性能的方法， 以克服现有技术存在的上述缺陷。 本发明的方法， 包括如下步骤： 将原位表面改性纳米氧化锌加入 到天然橡胶传统硫黄硫化体系中， 硫化后获得天然橡胶制品。 原位表面改性纳米氧化锌与天然橡胶的质量份比为： 原位表面改 性纳米氧化锌： 天然橡胶 = 1〜5份： 100份；  SUMMARY OF THE INVENTION It is an object of the present invention to disclose a method for improving the heat-resistant oxygen aging properties of natural rubber conventional sulfur vulcanization systems to overcome the above-mentioned drawbacks of the prior art. The method of the present invention comprises the steps of: adding in situ surface-modified nano zinc oxide to a natural sulfur vulcanization system of natural rubber, and obtaining a natural rubber product after vulcanization. The mass ratio of in-situ surface modified nano zinc oxide to natural rubber is: in situ surface modification nano zinc oxide: natural rubber = 1~5 parts: 100 parts;
所述原位表面改性纳米氧化锌是以硝酸锌和失水山梨醇油酸酯为 原料， 以硬脂酸为分散剂制备的；  The in-situ surface-modified nano zinc oxide is prepared by using zinc nitrate and sorbitan oleate as raw materials and stearic acid as a dispersing agent;
制备方法， 包括如下步骤：  The preparation method comprises the following steps:
( 1 )将分散剂硬脂酸加热至 80°C熔融， 然后加入硝酸锌和失水山 梨醇油酸酯， 搅拌 1〜3小时后得到溶胶， 冷却获得凝胶；  (1) heating the dispersing agent stearic acid to 80 ° C, then adding zinc nitrate and sorbitan oleate, stirring for 1 to 3 hours to obtain a sol, and cooling to obtain a gel;
( 2 ) 将步骤 （1 ) 的凝胶在 550〜650°C的温度下煅烧 4〜6小时， 得到原位表面改性的纳米氧化锌；  (2) calcining the gel of step (1) at a temperature of 550 to 650 ° C for 4 to 6 hours to obtain an in-situ surface-modified nano zinc oxide;
质量份为： 硬脂酸 120份， 硝酸锌 15.68〜41.83份， 失水山梨醇油 酸酯 1.13〜3.01份；  The mass parts are: 120 parts of stearic acid, zinc nitrate 15.68~41.83 parts, sorbitan oleate 1.13~3.01 parts;
所述天然橡胶传统硫黄硫化体系为常规的， 如可采用 《橡胶工业 本发明的天然橡胶传统硫黄硫化体系的组份和质量份如下:  The natural rubber conventional sulfur vulcanization system is conventional, such as the rubber industry. The components and mass parts of the natural rubber conventional sulfur vulcanization system of the present invention are as follows:
天然橡胶 100份  Natural rubber 100 parts
硫黄 2〜3份  Sulfur 2~3 parts
促进剂 NOBS 0.5〜0.7份  Promoter NOBS 0.5~0.7 parts
硬脂酸 1〜2份  Stearic acid 1~2 parts
优选的， 天然橡胶传统硫黄硫化体系的组份和质量份如下:  Preferably, the components and mass parts of the natural rubber conventional sulfur vulcanization system are as follows:
天然橡胶 100份 硫黄 2.5份 100 parts of natural rubber 2.5 parts of sulfur
促进剂 NOBS 0.7份  Promoter NOBS 0.7 parts
硬脂酸 1.2份 所述的促进剂 NOBS的化学名称是 N-氧联二亚乙基 -2-苯并噻唑基 次磺酰胺。 本发明采用溶胶-凝胶法对纳米氧化锌进行原位表面改性， 改性后 的纳米氧化锌提高了在橡胶基材中的分散性， 能充分发挥其纳米效应， 将其应用于天然橡胶传统硫黄硫化体系， 热空气加速老化后硫化胶的 耐热氧老化性能有大幅度地提高。 本发明制备的原位表面改性纳米氧化锌， 在保证纳米颗粒高活性 的同时减弱了其由于高的比表面能而带来的团聚现象， 将其应用于天 然橡胶传统硫黄硫化体系， 使其纳米效应得到了充分地发挥。 本发明 工艺简单， 硫化胶的物理机械性能优良， 耐热氧老化性能显著提高。 本发明也可应用于其它的硫黄硫化的二烯类橡胶传统硫化体系， 因此 应用前景非常广阔。 具体实施方式  Stearic acid 1.2 parts The accelerator The chemical name of NOBS is N-oxydiethylene-2-benzothiazolylsulfenamide. The invention adopts a sol-gel method to in-situ surface modification of nano zinc oxide, and the modified nano zinc oxide improves the dispersibility in the rubber substrate, can fully exert its nano effect, and is applied to natural rubber. In the traditional sulfur vulcanization system, the thermal aging resistance of the vulcanized rubber after the accelerated aging of hot air is greatly improved. The in-situ surface-modified nano zinc oxide prepared by the invention reduces the agglomeration caused by the high specific surface energy while ensuring the high activity of the nanoparticle, and applies it to the natural sulfur vulcanization system of natural rubber, so that The nano effect has been fully utilized. The process of the invention is simple, the physical and mechanical properties of the vulcanized rubber are excellent, and the aging resistance of the heat-resistant oxygen is remarkably improved. The invention can also be applied to other sulfur vulcanized diene rubber conventional vulcanization systems, so the application prospect is very broad. detailed description
实施例中， 按 GB/T 528-1998国家标准测试天然橡胶硫化胶的拉伸 强度和拉断伸长率。 天然橡胶硫化胶的热空气加速老化在 401A型热老化试验箱内进 行， 老化条件为 100°C x72h， 按照 GB/T 3512-2001国家标准执行。 以下结合实施例对本发明作进一步具体描述， 但并不局限于此。 对比例  In the examples, the tensile strength and elongation at break of the natural rubber vulcanizate were tested in accordance with GB/T 528-1998 national standard. The hot air accelerated aging of natural rubber vulcanizates is carried out in a 401A heat aging test chamber with an aging condition of 100 ° C x 72 h, in accordance with GB/T 3512-2001 national standards. The present invention will be further specifically described below with reference to the embodiments, but is not limited thereto. Comparative example
所述天然橡胶传统硫黄硫化体系的组份和质量份如下: 天然橡胶 100份 The components and mass parts of the natural rubber conventional sulfur vulcanization system are as follows: 100 parts of natural rubber
硫黄 2.5份  Sulphur 2.5 parts
促进剂 NOBS 0.7份  Promoter NOBS 0.7 parts
硬脂酸 1.2份  Stearic acid 1.2 parts
普通氧化锌 5份。 测得的天然橡胶热空气加速老化前后硫化胶的拉伸强度、 拉断伸 长率以及拉伸强度保持率、 拉断伸长率保持率见表 1。 实施例 1  Ordinary zinc oxide 5 parts. The measured tensile strength, tensile elongation and tensile strength retention, and elongation at break of the vulcanized rubber before and after accelerated natural rubber hot air accelerated aging are shown in Table 1. Example 1
( 1 )将分散剂硬脂酸加热至 80°C熔融， 然后加入硝酸锌和失水山 梨醇油酸酯， 搅拌 1小时后得到溶胶， 冷却获得凝胶；  (1) The dispersing agent stearic acid is heated to 80 ° C to melt, and then zinc nitrate and sorbitan oleate are added, and after stirring for 1 hour, a sol is obtained, and cooling is performed to obtain a gel;
( 2) 将步骤 （1 ) 的凝胶在 550Ό的温度下煅烧 6小时， 得到原位 表面改性的纳米氧化锌；  (2) calcining the gel of step (1) at a temperature of 550 Torr for 6 hours to obtain an in situ surface-modified nano zinc oxide;
硬脂酸 120克  Stearic acid 120g
硝酸锌 41.83克  Zinc nitrate 41.83 g
失水山梨醇油酸酯 3.01克  Loss of sorbitol oleate 3.01 g
所述天然橡胶传统硫黄硫化体系的组份和质量份如下:  The components and mass parts of the natural rubber conventional sulfur vulcanization system are as follows:
天然橡胶 100份  Natural rubber 100 parts
硫黄 2.5份  Sulphur 2.5 parts
促进剂 NOBS 0.7份  Promoter NOBS 0.7 parts
硬脂酸 1.2份  Stearic acid 1.2 parts
原位表面改性纳米氧化锌 1份。 测得的天然橡胶热空气加速老化前后硫化胶的拉伸强度、 拉断伸 长率以及拉伸强度保持率、 拉断伸长率保持率见表 1。 实施例 2  In situ surface modification of 1 part of nano zinc oxide. The measured tensile strength, tensile elongation and tensile strength retention, and elongation at break of the vulcanized rubber before and after accelerated natural rubber hot air accelerated aging are shown in Table 1. Example 2
( 1 )将分散剂硬脂酸加热至 80°C熔融， 然后加入硝酸锌和失水山 梨醇油酸酯， 搅拌 3小时后得到溶胶， 冷却获得凝胶； ( 2 ) 将步骤 （1 ) 的凝胶在 650°C的温度下煅烧 4小时， 得到原位 表面改性的纳米氧化锌； (1) heating the dispersing agent stearic acid to 80 ° C, then adding zinc nitrate and sorbitan oleate, stirring for 3 hours to obtain a sol, cooling to obtain a gel; (2) calcining the gel of step (1) at a temperature of 650 ° C for 4 hours to obtain an in-situ surface-modified nano zinc oxide;
硬脂酸 120克  Stearic acid 120g
硝酸锌 15.68克  Zinc nitrate 15.68 g
失水山梨醇油酸酯 1.13克  Sorbitan oleate 1.13 g
所述天然橡胶传统硫黄硫化体系的组份和质量份如下:  The components and mass parts of the natural rubber conventional sulfur vulcanization system are as follows:
天然橡胶 100份  Natural rubber 100 parts
硫黄 2.5份  Sulphur 2.5 parts
促进剂 NOBS 0.7份  Promoter NOBS 0.7 parts
硬脂酸 1.2份  Stearic acid 1.2 parts
原位表面改性纳米氧化锌 2份。 测得的天然橡胶热空气加速老化前后硫化胶的拉伸强度、 拉断伸 长率以及拉伸强度保持率、 拉断伸长率保持率见表 1。 实施例 3  In situ surface modification of nano zinc oxide 2 parts. The measured tensile strength, tensile elongation and tensile strength retention, and elongation at break of the vulcanized rubber before and after accelerated natural rubber hot air accelerated aging are shown in Table 1. Example 3
( 1 )将分散剂硬脂酸加热至 80°C熔融， 然后加入硝酸锌和失水山 梨醇油酸酯， 搅拌 2小时后得到溶胶， 冷却获得凝胶；  (1) The dispersing agent stearic acid is heated to 80 ° C to melt, and then zinc nitrate and sorbitan oleate are added, and after stirring for 2 hours, a sol is obtained, and cooling is performed to obtain a gel;
( 2 ) 将步骤 （1 ) 的凝胶在 600°C的温度下煅烧 5小时， 得到原位 表面改性的纳米氧化锌；  (2) calcining the gel of step (1) at a temperature of 600 ° C for 5 hours to obtain an in situ surface-modified nano zinc oxide;
硬脂酸 120克  Stearic acid 120g
硝酸锌 20.91克  Zinc nitrate 20.91 g
失水山梨醇油酸酯 2.01克  Sorbitan oleate 2.01 g
所述天然橡胶传统硫黄硫化体系的组份和质量份如下:  The components and mass parts of the natural rubber conventional sulfur vulcanization system are as follows:
天然橡胶 100份  Natural rubber 100 parts
硫黄 2.5份  Sulphur 2.5 parts
促进剂 NOBS 0.7份  Promoter NOBS 0.7 parts
硬脂酸 1.2份  Stearic acid 1.2 parts
原位表面改性纳米氧化锌 3份。 测得的天然橡胶热空气加速老化前后硫化胶的拉伸强度、 拉断伸 长率以及拉伸强度保持率、 拉断伸长率保持率见表 1。 实施例 4 In situ surface modification of 3 parts of nano zinc oxide. The tensile strength, elongation at break, tensile strength retention and elongation at break of the vulcanized rubber before and after accelerated natural rubber hot air accelerated aging are shown in Table 1. Example 4
采用实施例 3的原位表面改性纳米氧化锌。 所述天然橡胶传统硫黄硫化体系的组份和质量份如下:  The in situ surface modified nano zinc oxide of Example 3 was used. The components and mass parts of the natural rubber conventional sulfur vulcanization system are as follows:
天然橡胶 100份  Natural rubber 100 parts
硫黄 2.5份  Sulphur 2.5 parts
促进剂 NOBS 0.7份  Promoter NOBS 0.7 parts
硬脂酸 1.2份  Stearic acid 1.2 parts
原位表面改性纳米氧化锌 4份。 测得的天然橡胶热空气加速老化前后硫化胶的拉伸强度、 拉断伸 长率以及拉伸强度保持率、 拉断伸长率保持率见表 1。 实施例 5  In situ surface modification of 4 parts of nano zinc oxide. The measured tensile strength, tensile elongation and tensile strength retention, and elongation at break of the vulcanized rubber before and after accelerated natural rubber hot air accelerated aging are shown in Table 1. Example 5
采用实施例 3的原位表面改性纳米氧化锌。 所述天然橡胶传统硫黄硫化体系的组份和质量份如下:  The in situ surface modified nano zinc oxide of Example 3 was used. The components and mass parts of the natural rubber conventional sulfur vulcanization system are as follows:
天然橡胶 100份  Natural rubber 100 parts
硫黄 2.5份  Sulphur 2.5 parts
促进剂 NOBS 0.7份  Promoter NOBS 0.7 parts
硬脂酸 1.2份  Stearic acid 1.2 parts
原位表面改性纳米氧化锌 5份。 测得的天然橡胶热空气加速老化前后硫化胶的拉伸强度、 拉断伸 长率以及拉伸强度保持率、 拉断伸长率保持率见表 1。 拉伸强度/ MPa 拉伸强度 MPa 拉伸强度 拉断伸长率拉断伸长率 拉断伸长率 实 例 In situ surface modification of 5 parts of nano zinc oxide. The tensile strength, elongation at break, tensile strength retention and elongation at break of the vulcanized rubber before and after accelerated natural rubber hot air accelerated aging are shown in Table 1. Tensile strength / MPa tensile strength MPa tensile strength tensile elongation elongation elongation elongation elongation example
老化前 老化后 保持率 /% /%老化前 /%老化后 保持率 /% 对比例 18.2 7.2 39.56 619 375 60.58 实施例 1 14.8 7.7 52.03 783 365 46.62 实施例 2 18.3 13.8 75.41 683 546 79.94 实施例 3 19.0 13.8 72.63 670 504 75.22 实施例 4 19.7 12.3 72.59 660 531 80.45 实施例 5 21.4 15.8 73.83 642 512 79.75 与加入 5份普通氧化锌 （对比例） 相比， 在加入同量的原位表面 改性纳米氧化锌后 （实施例 5 ) ， 天然橡胶传统硫黄硫化体系硫化胶老 化前的拉伸强度提高了 17.58%， 拉断伸长率提高了 3.72%; 老化后的 拉伸强度保持率和拉断伸长率保持率则分别提高了 34.27%和 19.17%。  Pre-aging aging retention rate /% /% pre-aging /% post-aging retention rate /% Comparative Example 18.2 7.2 39.56 619 375 60.58 Example 1 14.8 7.7 52.03 783 365 46.62 Example 2 18.3 13.8 75.41 683 546 79.94 Example 3 19.0 13.8 72.63 670 504 75.22 Example 4 19.7 12.3 72.59 660 531 80.45 Example 5 21.4 15.8 73.83 642 512 79.75 Compared with the addition of 5 parts of ordinary zinc oxide (comparative), the same amount of in-situ surface-modified nano zinc oxide was added. After (Example 5), the natural rubber traditional sulfur vulcanization system vulcanizate increased tensile strength by 17.58% before aging, elongation elongation increased by 3.72%; tensile strength retention and elongation at break after aging The retention rate increased by 34.27% and 19.17%, respectively.

Claims

权 利 要 求 Rights request
1. 提高天然橡胶传统硫黄硫化体系耐热氧老化性能的方法， 其特 征在于， 包括如下步骤： 将原位表面改性纳米氧化锌加入到天然橡胶 传统硫黄硫化体系中， 硫化后获得天然橡胶硫化胶； 1. A method for improving the heat-resistant oxygen aging property of a natural sulfur yellow vulcanization system, characterized in that the method comprises the steps of: adding an in-situ surface-modified nano zinc oxide to a natural sulfur vulcanization system, and vulcanizing a natural rubber vulcanization system. Glue
所述原位表面改性纳米氧化锌是以硝酸锌和失水山梨醇油酸酯为 原料， 以硬脂酸为分散剂制备的。  The in-situ surface-modified nano zinc oxide is prepared by using zinc nitrate and sorbitan oleate as raw materials and stearic acid as a dispersing agent.
2. 根据权利要求 1所述的方法， 其特征在于， 所述原位表面改性 纳米氧化锌的制备方法， 包括如下步骤： 2. The method according to claim 1, wherein the method for preparing the in-situ surface-modified nano zinc oxide comprises the following steps:
( 1 )将分散剂硬脂酸加热至 80°C熔融， 然后加入硝酸锌和失水山 梨醇油酸酯， 搅拌得到溶胶， 冷却获得凝胶；  (1) heating the dispersing agent stearic acid to 80 ° C, then adding zinc nitrate and sorbitan oleate, stirring to obtain a sol, and cooling to obtain a gel;
( 2 ) 将步骤 （1 ) 的凝胶在 550〜650°C的温度下煅烧 4〜6小时， 得到原位表面改性的纳米氧化锌。  (2) The gel of the step (1) is calcined at a temperature of 550 to 650 ° C for 4 to 6 hours to obtain an in-situ surface-modified nano zinc oxide.
3. 根据权利要求 2所述的方法， 其特征在于， 质量份为： 硬脂酸 120份， 硝酸锌 15.68〜41.83份， 失水山梨醇油酸酯 1.13〜3.01份。 3. The method according to claim 2, wherein the parts by mass are: 120 parts of stearic acid, 15.68 to 41.83 parts of zinc nitrate, and 1.13 to 3.01 parts of sorbitan oleate.
4. 根据权利要求 1、 2或 3所述的方法， 其特征在于， 原位表面改 性纳米氧化锌与天然橡胶的质量份比为： 原位表面改性纳米氧化锌： 天然橡胶 = 1〜5份： 100份。 The method according to claim 1, 2 or 3, wherein the mass ratio of the in-situ surface-modified nano zinc oxide to the natural rubber is: in-situ surface-modified nano zinc oxide: natural rubber = 1~ 5 servings: 100 servings.
5. 根据权利要求 4所述的方法， 其特征在于， 所述天然橡胶传统 硫黄硫化体系的组份和质量份如下： 天然橡胶 100份， 硫黄 2〜3份， 促进剂 NOBS 0.5〜0.7份， 硬脂酸 1〜2份。 The method according to claim 4, wherein the natural rubber conventional sulfur vulcanization system has the following components and mass parts: 100 parts of natural rubber, 2 to 3 parts of sulfur, and 0.5 to 0.7 parts of accelerator NOBS. 1 to 2 parts of stearic acid.
PCT/CN2011/070840 2010-11-11 2011-01-31 Method for improving anti-aging performance due to heat or oxygen of natural rubber traditional sulfur vulcanization system WO2012062057A1 (en)

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