WO2021169602A1 - 高模量低生热的支撑胶橡胶组合物 - Google Patents

高模量低生热的支撑胶橡胶组合物 Download PDF

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WO2021169602A1
WO2021169602A1 PCT/CN2020/142277 CN2020142277W WO2021169602A1 WO 2021169602 A1 WO2021169602 A1 WO 2021169602A1 CN 2020142277 W CN2020142277 W CN 2020142277W WO 2021169602 A1 WO2021169602 A1 WO 2021169602A1
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weight
parts
rubber composition
rubber
carbon black
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PCT/CN2020/142277
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French (fr)
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王�锋
韩绍楠
庄儒彬
李先业
李丹
李洪兰
仇培超
王慧
邢涛
陈雪梅
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山东玲珑轮胎股份有限公司
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/006—Additives being defined by their surface area
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Definitions

  • the invention relates to the field of tire rubber products, in particular to a support rubber composition with high modulus and low heat generation.
  • the current semi-steel sidewall support rubber formula generally uses carbon black reinforcement system and anti-vulcanization reversion agent to increase the modulus of the rubber compound. Although it can meet its performance requirements, the use conditions of the support rubber are more demanding. The requirements for heat and heat generation are very high; when these two materials are used, the amount of carbon black is large, and the rubber material generates high heat, which affects the performance of the finished tire.
  • the present invention provides a support rubber composition with high modulus and low heat build-up.
  • the rubber composition can effectively reduce the heat generation of the rubber compound and increase the modulus of the rubber compound.
  • a supporting rubber composition with high modulus and low heat build-up comprises 1-60 parts by weight of cis-1,4-polyamide with a cis content of more than 97%.
  • the nitrogen adsorption specific surface area of the carbon black is more than 70 m 2 /g, and the DBP oil absorption value is more than 80 cm 3 /100 g.
  • the BET specific surface area of the highly dispersed silica is more than 100 m 2 /g, and the DBP oil absorption value is more than 1.0 cm 3 /g.
  • the multifunctional crosslinking agent is crosslinking agent WY9188.
  • the heat generation of the rubber compound can be effectively reduced and the modulus of the rubber compound can be improved.
  • the mixing of the rubber composition can be accomplished by a method known to those skilled in the rubber mixing field. For example, under normal circumstances, mixing is carried out in at least two stages, namely at least one non-productive mixing stage and one productive mixing stage. Filler and rubber are mixed in one or more non-productive mixing stages.
  • the rubber composition of the composition specified in Table 1 was prepared in a Banbury internal mixer.
  • the preparation process adopted two separate feeding and mixing stages, namely, a non-productive mixing stage and a productive mixing stage.
  • a non-productive mixing stage mixing is carried out for about 2-3 minutes until the rubber temperature reaches 140°C, which is complete.
  • the mixing time in the productive mixing stage is the time for the rubber temperature to reach 115°C.
  • Sample 1 is used as a comparison sample here, that is, the rubber composition is not optimized for the rubber material ratio.
  • Table 2 shows the physical properties of vulcanized sample 1 and sample 2.
  • the rubber composition with the ingredients specified in Table 3 was prepared in a Banbury internal mixer.
  • the preparation process adopted two separate feeding and mixing stages, namely, a non-productive mixing stage and a productive mixing stage.
  • a non-productive mixing stage mixing is carried out for about 2-3 minutes, until the rubber temperature reaches 140°C, which is complete.
  • the mixing time in the productive mixing stage is the time for the rubber temperature to reach 115°C.
  • sample a The rubber composition is referred to as sample a and sample b here.
  • Sample a is used as a comparative sample here, that is, no optimized rubber material ratio is used in the rubber composition.
  • Table 4 shows the apparent and physical properties of vulcanized samples a and b.
  • the hardness and tan ⁇ at 60°C can be tested according to the test method GB/T531.1 accepted by the tire industry, and MH and ML can be tested according to the test method GB/T16584 accepted by the tire industry.
  • high-dispersion white carbon black is considered to be important for reducing the heat generation of the rubber compound.
  • Highly dispersed silica is an acidic oxide, which reacts with rubber ions through a silane coupling agent to form a chemical bond with strong bond energy, and its binding force is strong.
  • the support rubber formula that uses high-dispersion white carbon black generates less heat when the tire is rolling.
  • Multifunctional cross-linking agent the use of this material is considered to be important for improving the modulus of the compound.
  • Multifunctional cross-linking agent which has a promoting effect and excellent anti-reversion performance.
  • One end contains a promoting group, which has a promoting effect. At the same time, it can have a cross-linking reaction with the polymer, and its vulcanizate has a higher modulus.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

一种高模量低生热的支撑胶橡胶组合物。所述橡胶组合物的原料按照重量份数计，包括1～60重量份顺式含量在97％以上的顺式-1，4-聚异戊二烯橡胶、1～80重量份顺式含量在95％以上的顺式-1，4-聚丁二烯橡胶、50～120重量份炭黑、1～30重量份高分散白炭黑、1～30重量份多功能交联剂。有益效果：通过在配方中应用多功能交联剂、并配合高分散白炭黑的使用，可有效降低胶料的生热、提高胶料的模量。

Description

[根据细则37.2由ISA制定的发明名称]　高模量低生热的支撑胶橡胶组合物 技术领域
本发明涉及轮胎橡胶制品领域，尤其涉及一种高模量低生热的支撑胶橡胶组合物。
 背景技术
现行半钢胎侧支撑胶配方中一般采用炭黑补强体系和抗硫化返原剂来提高胶料的模量，虽然可以满足其性能要求，但由于支撑胶使用条件较为苛刻，对其模量和生热的要求非常高；使用这两种材料时炭黑用量较大，胶料生热高，影响成品轮胎的性能。
 技术问题
现行半钢胎侧支撑胶配方炭黑用量较大，胶料生热高，影响成品轮胎的性能。
 技术解决方案
针对上述现有技术的不足，本发明提供给一种高模量低生热的支撑胶橡胶组合物。该橡胶组合物可有效降低胶料的生热、提高胶料的模量。
一种高模量低生热的支撑胶橡胶组合物，所述橡胶组合物的原料按照重量份数计，包括1～60重量份顺式含量在97%以上的顺式-1,4-聚异戊二烯橡胶、1～80重量份顺式含量在95%以上的顺式-1,4-聚丁二烯橡胶、50～120重量份炭黑、1～30重量份高分散白炭黑、1～30重量份多功能交联剂。
进一步的，所述炭黑的氮吸附比表面积在70m 2/g以上、DBP吸油值在80cm 3/100g以上。
进一步的，所述高分散白炭黑的BET比表面积在100m 2/g以上、DBP吸油值在1.0cm 3/g以上。
进一步的，所述多功能交联剂为交联剂WY9188。
 有益效果
通过在配方中应用多功能交联剂、并配合高分散白炭黑的使用，可有效降低胶料的生热、提高胶料的模量。
 本发明的实施方式
橡胶组合物的混炼可以采用橡胶混炼领域技术人员已知的方法完成。例如在通常情况下，在至少两个阶段中进行混炼，即至少一个非生产性混炼阶段，和一个生产性混炼阶段。填充材料与橡胶在一个或多个非生产性混炼阶段进行混炼。
实例1
在Banbury密炼机中制备如表1中所规定成分的橡胶组合物，制备过程采取两个分开的加料混炼阶段，即一个非生产性混炼阶段和一个生产性混炼阶段。非生产性阶段进行约2-3min的混炼，直至橡胶温度达到140℃，即完成。生产性混炼阶段的混炼时间是使橡胶温度达到115℃的时间。
该橡胶组合物在这里被称之为样品1、样品2。样品1在这里被当做对比样，即在橡胶组合物中未使用最优化的橡胶材料配比。
所有的样品在约151℃硫化约30min。表2给出了硫化样品1与样品2的物理性能。
表1  实例1所规定成分的橡胶组合物原料表
Figure dest_path_image002
表2  实例1橡胶组合物性能表
Figure dest_path_image004
实例2
在Banbury密炼机中制备如表3中所规定成分的橡胶组合物，制备过程采取两个分开的加料混炼阶段，即一个非生产性混炼阶段和一个生产性混炼阶段。非生产性阶段分别进行约2-3min的混炼，直至橡胶温度达到140℃，即完成。生产性混炼阶段的混炼时间是使橡胶温度达到115℃的时间。
该橡胶组合物在这里被称之为样品a、样品b。样品a在这里被当做对比样，即在橡胶组合物中未使用最优化的橡胶材料配比。
所有的样品在约151℃硫化约30min。表4给出了硫化样品a、b的表观和物理性能。
表3  实例2所规定成分的橡胶组合物原料表
Figure dest_path_image006
表4  实例2橡胶组合物性能表
Figure dest_path_image008
这些结果表明，在支撑胶配方中使用了高分散白炭黑和多功能交联剂后，能够使胶料的生热明显降低，模量得到明显提升。
硬度、60℃tanδ可根据轮胎工业可接受的测试方法GB/T531.1进行，MH、ML可根据轮胎工业可接受的测试方法GB/T16584进行。60℃tanδ值越低，意味着胶料的生热越低；硬度、MH、MH-ML值越高，意味着胶料的模量越高。
本发明中，高分散白炭黑，此材料的使用被认为对降低胶料的生热是重要的。高分散白炭黑是一种酸性氧化物，其与橡胶离子通过硅烷偶联剂反应形成具有较强键能的化学键，其结合力强。在轮胎滚动时使用高分散白炭黑的支撑胶配方生热较低。
多功能交联剂，此材料的使用被认为对提升胶料的模量是重要的。多功能交联剂，其具有促进作用和优良的抗硫化返原性能，一端含有促进基团，具有促进作用，同时可与聚合物发生交联反应，其硫化胶具有较高的模量。
 工业实用性
本发明可用其他的不违背本发明的精神或主要特征的具体形式来概述。因此，无论从哪一点来看，本发明的上述实施方案都只能认为是对本发明的说明而不能限制本发明，权利要求书指出了本发明的范围，而上述的说明并未指出本发明的范围，因此，在与本发明的权利要求书相当的含义和范围内的任何改变，都应认为是包括在本发明的权利要求书的范围内。

Claims (4)

  1. 一种高模量低生热的支撑胶橡胶组合物，其特征在于，所述橡胶组合物的原料按照重量份数计，包括1～60重量份顺式含量在97%以上的顺式-1,4-聚异戊二烯橡胶、1～80重量份顺式含量在95%以上的顺式-1,4-聚丁二烯橡胶、50～120重量份炭黑、1～30重量份高分散白炭黑、1～30重量份多功能交联剂。
  2. 如权利要求1所述的高模量低生热的支撑胶橡胶组合物，其特征在于，所述炭黑的氮吸附比表面积在70m 2/g以上、DBP吸油值在80cm 3/100g以上。
  3. 如权利要求1所述的高模量低生热的支撑胶橡胶组合物，其特征在于，所述高分散白炭黑的BET比表面积在100m 2/g以上、DBP吸油值在1.0cm 3/g以上。一种具有促进作用，同时具有抗硫化返原性能的多功能交联剂。
  4. 如权利要求1所述的高模量低生热的支撑胶橡胶组合物，其特征在于，所述多功能交联剂为交联剂WY9188。
PCT/CN2020/142277 2020-02-26 2020-12-31 高模量低生热的支撑胶橡胶组合物 WO2021169602A1 (zh)

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