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WO2015109789A1 - 一种含有机硅烷偶联剂及炭黑的橡胶组合物及其制备方法 - Google Patents

一种含有机硅烷偶联剂及炭黑的橡胶组合物及其制备方法 Download PDF

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Publication number
WO2015109789A1
WO2015109789A1 PCT/CN2014/082692 CN2014082692W WO2015109789A1 WO 2015109789 A1 WO2015109789 A1 WO 2015109789A1 CN 2014082692 W CN2014082692 W CN 2014082692W WO 2015109789 A1 WO2015109789 A1 WO 2015109789A1
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Prior art keywords
rubber
weight
parts
seconds
carbon black
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English (en)
French (fr)
Inventor
王梦蛟
周宏斌
石超
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EVE RUBBER INSTITUTE Co Ltd
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EVE RUBBER INSTITUTE Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L7/00Compositions of natural rubber
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/54Silicon-containing compounds
    • C08K5/548Silicon-containing compounds containing sulfur
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29BPREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B7/00Mixing; Kneading
    • B29B7/002Methods
    • B29B7/005Methods for mixing in batches
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • C08K2003/2217Oxides; Hydroxides of metals of magnesium
    • C08K2003/222Magnesia, i.e. magnesium oxide
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20Oxides; Hydroxides
    • C08K3/22Oxides; Hydroxides of metals
    • C08K2003/2296Oxides; Hydroxides of metals of zinc
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/002Physical properties
    • C08K2201/006Additives being defined by their surface area
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/014Additives containing two or more different additives of the same subgroup in C08K
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02TCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00Road transport of goods or passengers
    • Y02T10/80Technologies aiming to reduce greenhouse gasses emissions common to all road transportation technologies
    • Y02T10/86Optimisation of rolling resistance, e.g. weight reduction 

Definitions

  • the invention relates to the field of rubber, in particular to the field of tire manufacture.
  • One of the basic characteristics of rubber is: In the process of use, energy loss occurs due to the hysteresis loss of the rubber compound, and at the same time, it is converted into heat, and heat generation reduces the service life of the tire. Under the premise of not losing the basic properties of the rubber material such as wear resistance and physical properties, reducing the heat generation of the rubber compound will increase the use of the tire.
  • the patent "Rubber Composition” discloses the mixing of natural rubber with silica/organosilane coupling agent to make the composition low in heat generation and wear resistance;
  • Patent “Rubber Composition” (publication number CN1322223A) A diolefin polymer containing white carbon black is disclosed for reducing the rolling resistance of the tire;
  • the patent “rubber composition and the pneumatic tire prepared from the rubber composition” (publication number CN1205016A), the release of natural rubber Or a diene rubber with white carbon black and a specific silane coupling agent to prepare a low heat generating, low rolling resistance tire.
  • the above-mentioned patents all use a polymer mixed with a silica/silane coupling agent, and the rubber composition prepared by the method is inferior in abrasion resistance, particularly in truck tires.
  • the rubber composition of the present invention introduces an organosilane coupling agent to make the carbon black interact more strongly with the diene polymer, the wear resistance is improved, the heat generation is lowered, and the rolling resistance of the tire is lowered.
  • Patent "Use of surface treated carbon black to reduce compound lag and tire rolling resistance in elastomers and to improve wet skid resistance” discloses the interaction between surface treated carbon black and polymer, The carbon black needs to be treated with an oxidizing agent, preferably a diamine compound. Such a treatment method has a residual or unreacted oxidizing agent present in the rubber composition formulation, affecting the vulcanization time of the rubber mixture, especially shortening the scorch time and affecting the processing safety. Sex.
  • organosilane coupling agent of the invention has no effect on the vulcanization characteristics of the formulation, and the surface treatment of the carbon black is directly completed in the process of processing, and it is not necessary to separately treat the carbon black, which is more convenient for processing.
  • the patent "A Process for Increasing the Dispersion of Silica Black” (Application No. CN101786298A) discloses a process for preparing a masterbatch using a polymer and a silica, an organosilane coupling agent, and does not involve how to improve carbon black and polymer. The process of interaction. By using the mixing process of the invention, an organosilane coupling agent is introduced into the rubber composition, thereby enhancing the interaction between the polymer and the carbon black, and improving the performance of the rubber compound. Summary of the invention
  • the present invention is intended to provide a rubber composition reinforced with carbon black and a method for producing the same, which has the advantages of high wear resistance, low heat build-up, and low rolling resistance.
  • the rubber composition contains a diene polymer, carbon black, a certain proportion of an organosilane coupling agent and a corresponding compounding agent, and the polymer is pre-mixed with a carbon black and an organosilane coupling agent to form a masterbatch.
  • the interaction with carbon black, after vulcanization, can improve the wear resistance of the rubber compound, reduce the heat generation performance of the rubber compound, and improve the dynamic performance of the rubber compound.
  • the wear resistance of the tire can be improved and the rolling resistance can be reduced.
  • the process advantages of the invention are as follows: Under the action of the organosilane coupling agent, the effect of the carbon black particles is reduced during the mixing process, the effect between the carbon black and the polymer is increased, and the heat generation of the rubber compound is reduced.
  • the present invention relates to a rubber composition comprising: a diene-based polymer, a carbon black reinforcing agent having a STSA specific surface area of from 0 to 200 m7g, and a til silane coupling agent in an amount depending on the amount of carbon black.
  • the organosilane coupling agent has the following formula:
  • A is -SCN, -SH, -CI, -NH 2 ;
  • R and R' are a branched or linear alkyl or phenol group having from 1 to 4 carbon atoms, and R and R' may be the same or different;
  • n 0, 1 or 2;
  • Alk is a linear or branched hydrocarbon group having 1 to 1 carbon atom
  • Alkenyl is a linear or branched alkenyl group containing from 1 to 1 carbon atom
  • n 0 or 1
  • Ar is an aryl group having 6 to 12 carbon atoms
  • p is 0 or 1, p and n cannot be 0 at the same time;
  • x is 2 to 8;
  • the most commonly used ones are bis(triethoxypropylsilane) tetrasulfide and disulfide, 3-thiocyanopropyl-triethoxysilane, ⁇ -mercapto-trimethoxysilane.
  • the amount of the organosilane is changed according to the amount of the carbon black.
  • the test results show that the amount of the organosilane coupling agent is 0.5% by weight of the amount of the carbon black (the range of kt% is preferred).
  • a rubber composition having low hysteresis loss and high abrasion resistance comprising: (A) 100 parts by weight of rubber;
  • the rubber is mixed with carbon black and an organosilane coupling agent, and the kneading temperature is in the range of 130-16 CTC for at least 1-5 minutes;
  • the carbon black masterbatch, the antioxidant, the active agent, the accelerator, and the chemical agent are kneaded in a ratio of the composition to prepare a rubber composition, and the final rubber mixing process is one or more segments;
  • the rubber comprises one or more of natural rubber, synthetic polyisoprene rubber, cis-butyl rubber, styrene-butadiene rubber, and other diene-containing unit-containing polymers;
  • R and R' are a branched or linear alkyl or phenol group having from 1 to 4 carbon atoms, and R and R' may be the same or different;
  • n 0, 1 or 2;
  • Alk is a linear or branched hydrocarbon group having 1 to 1 carbon atom
  • Alk ⁇ l is a linear or branched alkenyl group having 1 to 1 carbon atom
  • n 0 or 1
  • Ar is an aryl group having 6 to 12 carbon atoms
  • p is 0 or 1, p and n cannot be 0 at the same time;
  • X is 2 to 8;
  • the most commonly used ones are bis(triethoxypropylsilane) tetrasulfide and disulfide, 3-thiocyanopropyl-triethoxysilane, gamma-mercapto-trimethoxysilane;
  • the rubber composition wherein the silicone compound coupling agent is used in an amount of 0.5% by weight to 10% by weight, preferably 1% by weight to 8%, more preferably 2% by weight to 5% by weight based on the amount of the carbon black;
  • the activator is one or more of a metal oxide and a fatty acid combination and a fatty acid metal soap salt, and the metal oxide is one or more of zinc oxide, magnesium oxide, etc., and the fatty acid metal soap salt is One or more of zinc stearate, zinc borate, etc.;
  • the antioxidant includes an amine antioxidant, a quinoline anti-aging agent, a benzimidazole anti-aging agent, a physical protective wax;
  • the accelerator includes, but is not limited to,
  • the method for measuring the binding rubber content of the 3 ⁇ 4 ⁇ 4t adhesive composition of the present invention is as follows: Weighing a certain weight of unvulcanized rubber sample Soak the unvulcanized rubber in the organic solvent (the preferred toluene solution) for 3 days; remove the sample, replace the immersion: permeable, and then immerse the sample in the organic solution for three days; then wash the sample dry and dry the amount. Calculate the bound gum content according to the theoretical calculation formula.
  • Isoprene rubber IR Qingdao Ikos Materials Co., Ltd.;
  • Liquid silicone firing coupling agent SG-SI998 (bis(triethoxypropylsilane) tetrasulfide), Nanjing Shuguang Auxiliary Co., Ltd.;
  • Organosilane coupling agent X50S Contains 50% N330 carbon black, 50% bis(triethoxypropylsilane) tetraide, Evonik Iridium (Rizhao) Chemical Industry Co., Ltd.;
  • Zinc oxide Dalian zinc oxide plant
  • Antioxidant 020 N-(1.3-dimethylbutyl)- ⁇ '-phenyl-p-phenylenediamine, Jiangsu Shengao Chemical Technology Co., Ltd.; Anti-aging agent RD: 2,2,4-trimethyl-1, 2-dihydroquinoline polymer, Tianjin Kemai Auxiliary Co., Ltd.; accelerator NS ( ⁇ -tert-butyl-2-benzothiazole sulfenamide): Shandong Shanghao Chemical Co., Ltd.; sulfur: Linyi Luozhuang Xin'an Chemical plant Manual comparison example 1
  • One part of the mixture was filled into 100 parts by weight of 20# standard rubber in an internal mixer with a rotation speed of 90 rpm. After 60 seconds of mastication, 33 parts by weight of carbon black N234 was added to the top plug; after 90 seconds of mixing, the top plug was cleaned and added. 17 parts by weight of carbon black; after mixing for 30 seconds, adding 5 parts by weight of zinc oxide, 3 parts by weight of stearic acid, 1.5 parts by weight of antioxidant RD, 1.5 parts by weight of 145 antioxidant 4020, 1 part by weight of microcrystalline wax, mixing 30 After the second, the top plug is cleaned, and the masterbatch is discharged for 30 seconds. The mixing time is 240 seconds, and the rubber discharge is 158 °C.
  • the final rubber compound is mixed with 162 parts by weight of a mixed masterbatch in an internal mixer of 60 ⁇ , and after 30 seconds of mixing, the top plug is added with 1 part by weight of 5 yellow, 1.2 parts by weight of ⁇ agent NS, and mixed. After 60 seconds of refining, it is cleaned for 30 seconds and then discharged into the final rubber. The mixing time is 120 seconds. Discharge 3 ⁇ 4t3 ⁇ 4 98°C
  • the basic formula other compounding agent is: SMR20 100; N23450; zinc oxide 5; stearic acid 3; antioxidant 4020 1. 5; antioxidant RD 1. 5, liquid silicon germanium coupling agent SG-SI9884, microcrystalline wax 1; Promoter NS 1. 2; sulfur yellow 1.
  • One part of the mixture is filled with 100 parts by weight of 20# standard rubber in a mixer with a speed of 9 (3 ⁇ 4 pm), and after 60 seconds of mastication, a top plug is added to add 33 parts by weight of carbon black N234; after 90 seconds of mixing, i ⁇ h Top plug cleaning, adding 17 parts by weight of carbon black; 155 mixing for 30 seconds, adding 4 parts by weight of liquid silicon, 5 parts by weight of zinc oxide, 3 parts by weight of stearic acid, 1.5 parts by weight of antioxidant RD, 1.5 parts by weight of antioxidant 020, 1 part by weight of microcrystalline wax, after mixing for 30 seconds, ⁇ strong top plug is cleaned, and then mixed for 30 seconds to discharge the masterbatch.
  • the mixing time is 240 seconds, and the discharge temperature is 154 °C.
  • the final rubber is filled with 166 parts by weight of a masterbatch in an internal mixer with a key of 60 rpm. After mixing for 30 seconds, i ⁇ h top plug is added with 1 part by weight of sulfur, 1.2 parts by weight of fiber NS, and kneading 60. After the second cleaning, after mixing for 30 seconds, the final 160 rubber is discharged, the mixing time is 120 seconds, and the rubber discharge is 3 ⁇ 43 ⁇ 4 is 102 °C.
  • Example 1 the performance of Example 1 in which a silane coupling agent was added was compared with that of Comparative Example 1, and the content of the bonding gum was increased by 20%; the resilience performance at 23 ° C and 60 ° C was increased by 11% or more. The temperature rise at the bottom of the compressed heat is reduced by 12%. Abrasive performance improvements are particularly noticeable, DIN wear performance is increased by 18%; Akron wear index is increased by 13%. .
  • a mixing process 100 parts by weight of SMR20 is added to an internal mixer at a speed of 90 rpm, and after 60 seconds of mastication, 26 parts by weight of N115 is added to the top plug; after 90 seconds of mixing, the top plug is cleaned, and the remaining 14 parts by weight of no N115 is added.
  • Final rubber mixing process Add 160 weights to the mixer at 60 rpm! ⁇ One-stage mixing of the masterbatch, after 30 seconds of mastication, adding 1 part by weight of sulfur and 1.2 parts by weight of accelerator NS; mixing after 60 seconds of mixing; mixing after 175 minutes of smelting for 30 seconds, the total mixing time is 120 In seconds, the discharge temperature is 95 °C.
  • the load is 149! ⁇ divided into a batch of masterbatch, kneaded for 80 seconds to put on the top plug, force 5 parts by weight of zinc oxide, 3 parts by weight of stearic acid, 1.5 parts by weight of antioxidant RD, 1.5 parts by weight of anti-aging agent bar; mixing 70 seconds cleaning ; further mixing for 30 seconds; the total mixing time is 180 seconds, and the glue is 3 ⁇ 43 ⁇ 4t at 155 °C.
  • Example 2 As can be seen from the comparative data of Table 4, the temperature rise of the compressed heat generating bottom of Example 2 was lower than that of Comparative Example 2.
  • the dynamic viscoelastic spectrometer measures the tendency of the rubber composition to change in loss factor from low temperature to high temperature. It can be seen from Fig. 1 that the loss factor of Example 2 is lower than that of the Comparative Example 2 in the range of 50 ° C to 80 ° C, indicating that the rolling resistance is lower than that of Comparative Example 2, and it is applied to the tire to reduce the rolling resistance.
  • Example 3 As can be seen from the comparative data of Table 5, the compression heat generation of Example 3 was 8% lower than that of Comparative Example 3, the elasticity was improved, and the binder content was increased by 5%, using the rubber composition and process method designed by the present invention. It is indicated that the use of the method of the present invention can improve the combination of carbon black and rubber, thereby improving dynamic performance and reducing wear.
  • a masterbatch 150 parts by weight of a masterbatch is added, and the top plug is kneaded for 80 seconds, and 5 parts by weight of zinc oxide, 3 parts by weight of stearic acid, and 1.5 parts by weight of an antioxidant are applied.
  • RD 1.5 parts by weight of anti-aging agent bar, micro 245 crystal wax 1, mixing for 70 seconds to clean; re-kneading for 30 seconds to discharge; total mixing time is 180 seconds.
  • the glue is 151 °C.
  • the mixer 61 of the car 61 is 60 rpm, 162 parts by weight of the two-stage mixing masterbatch, mixing for 30 seconds to put the top plug plus 1.5 parts by weight of sulfur and 1.8 parts by weight of the fiber NS; mixing 60 seconds cleaning Re-kneading for 30 seconds, the total mixing time is 120 seconds, and the glue is 98 °C.

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

Abstract

本发明涉及一种橡胶组合物以及加工这种橡胶组合物的工艺方法。所述的橡胶组合物包括:100重量份橡胶,5-120重量份炭黑,0.5-12重量份有机硅烷偶联剂,一定重量份数的活化剂、防老剂、硫黄及硫化促进剂;所述制造这种橡胶组合物的工艺方法步骤包括:先将橡胶、炭黑、有机硅烷偶联剂在一定的混炼条件下混炼成母胶,再加入一种或多种橡胶助剂制成橡胶组合物。该发明用于轮胎中能够提高耐磨性,降低滚动阻力。

Description

一种含有机硅烷偶联剂及炭黑的橡胶组合物及其制备方法
¾ ^领域
本发明涉及橡胶领域, 特别轮胎制造领域。
背景 έ ^
橡胶的基本特性之一是: 在使用过程中, 由于胶料的滞后损失而产生能量损耗, 同时转换为热量, 而生热会减少轮胎的使用寿命。在不损耗胶料基本性能如耐磨性、物 理性能的前提下, 降低胶料的生热, 将会提高轮胎使用赫。
专利《橡胶组合物》(公开号 CN1199412A)公布了天然胶与白炭黑 /有机硅烷偶联 剂混合, 使组合物生热低和耐磨性好; 专利《橡胶组合物》(公开号为 CN1322223A)公 布了一种含有白炭黑的二烯烃类聚合物用以降低轮胎滚动阻力;专利《橡胶组合物和所 述象胶组合物制备的气胎》(公开号为 CN1205016A), 公布了天然胶或二烯烃类橡胶加 白炭黑及特定硅烷偶联剂, 制备低生热、低滚阻的轮胎。 以上所述的专利都使用聚合物 与白炭黑 /有 硅烷偶联剂混炼, 该方法制备的橡胶组合物不完善方面是耐磨性差, 特 别是使用在卡车轮胎中。本发明的橡胶组合物舰引入有机硅烷偶联剂,使炭黑与二烯 烃类聚合物相互作用更强, 耐磨性提高, 生热降低, 轮胎滚动阻力降低。
专利《经表面处理的炭黑在弹性体中降低化合物滞后和轮胎滚动阻力以及改进抗 湿滑性的用途》(公开号为 CN102575082A)公布经表面处理的炭黑与聚合物之间相互作 用, 因炭黑需使用氧化剂处理,优选二胺化合物, 这样的处理方式将有残留或者未反应 完全的氧化剂存在橡胶组合物配方中,影响橡胶混合物的硫化时间,特别是容易缩短焦 烧时间, 影响加工安全性。本发明使用有机硅烷偶联剂, 对配方的硫化特性无影响, 且 对炭黑的表面处理在加工的过程中直接完成,不需要单独对炭黑进行处理,更便于加工。
专利《一种提高白炭黑分散的混炼工艺》(申请号为 CN101786298A)公布了使用聚 合物与白炭黑、有机硅烷偶联剂制备母胶的工艺,未涉及怎样提高炭黑与聚合物相互作 用的工艺方法。采用本发明混炼工艺,橡胶组合物中引入有机硅烷偶联剂, 提高了聚合 物与炭黑的相互作用, 提高混炼胶的性能。 发明内容
针对现有技术的问题, 本发明意在提供一种使用炭黑补强的橡胶组合物及其制造 方法, 该组合物具有高耐磨性、 低生热性、 低滚动阻力的优点。
该橡胶组合物含有二烯烃类聚合物、 炭黑、 一定比例的有机硅烷偶联剂以及相应 配合剂,聚合物与炭黑以及有机硅烷偶联剂预先混炼成母胶,倉 多提高聚合物与炭黑的 相互作用, 经硫化后, 可提高混炼胶的耐磨性, 降低混炼胶的生热性能, 提高混炼胶的 动态性能。该发明所涉及的橡胶组合物及加工方法应用于轮胎外胎时,可以提高轮胎的 耐磨性、 降低滚动阻力。
本发明工艺优点是: 在有机硅烷偶联剂作用下, 在混炼过程中减少炭黑粒子间作 用, 增加了炭黑与聚合物间的作用, 降低了胶料的生热。 本发明涉及一种橡胶组合物, 其包含: 含二烯烃类聚合物、 STSA 比表面积为0-200m7g的炭黑补强剂以及用量随炭黑用量而定的有 til硅烷偶联剂。
所述有机硅烷偶联剂通式如下:
( n- ( O )3-„Si- (Alk)m- ( Ar)p)q (A) (I )
Rn'( O)3-nSi- (Alk) (Π)
或!^ !^^-^ ^ ) (m)
式中, 当 q=l时, A为 -SCN, -SH, -CI, -NH2;
当 q=2时, A为 -Sx -;
R和 R'为碳原子从 1至 4的支化或直链的烷基或酚基, R和 R'可以相同, 也可以 不同;
n为 0, 1或 2;
Alk是含有 1至 ό个碳原子的直链或支链烃基;
Alkenyl是含有 1至 ό个碳原子的直链或支链烯基;
m为 0或 1;
Ar是含有 6至 12个碳原子的芳基;
p为 0或 1, p和 n不能同时为 0; x为 2至 8;
其中最常用的为双(三乙氧基丙基硅烷) 四硫化物和二硫化物、 3-硫氰基丙基-三 乙氧基硅烷、 γ -巯基-三甲氧基硅烷。
有机硅烷的用量随着炭黑用量而变化, 试验结果显示有机硅烷偶联剂用量为炭黑 用量的 0. 5wt%-l(kt%范围内, 性倉较优。
本发明进一步涉及如下实施方案: 一种低滞后损失高耐磨的橡胶组合物, 包括: (A)100重量份的橡胶;
(B) 5-120重量份的炭黑, 优选 20-90重量份;
(C) 0.5-12重量份的有机硅烷偶联剂, 此重量份以纯有机硅烷偶联剂含量计; 橡胶组合物还包括活化剂、 防老剂、硫黄、硫化促进剂以及任选的其他橡胶助剂, 其所 示工艺如下:
母炼胶工艺:
橡胶与炭黑、 有机硅烷偶联剂混炼, 混炼温度在 130-16CTC范围内至少持续 1-5分 钟;
终炼胶工艺:
将所述炭黑母胶、 防老剂、 活性剂、 促进剂、 化剂按组合物比例混炼制备成橡 胶组合物, 终炼胶混炼工艺为一段或多段;
根据上述的橡胶组合物, 其中所述的橡胶包括天然胶、 合成聚异戊二烯橡胶、 顺 丁胶、 丁苯橡胶及其它含二烯烃单元的聚合物的一种或多种;
根据上述的橡胶组合物, 其中所述的炭黑 STSA比表面积为 10-200m2/g; 根据上述的橡胶组合物, 其中所述的有机硅烷偶联剂为具有以下通式中的一种或 多种:
( Rn- ( RO )3-nSi- (Alk)m- (Ar)p)q (A) (I) Rn' (RO)3-nSi- (Alk) (Π)
或^ !^^^- (m) 式中, 当 q=l时, A为 -SCN, -SH, -CI, -NH2;
当 q=2时, A为 -Sx -;
R和 R'为碳原子从 1至 4的支化或直链的烷基或酚基, R和 R'可以相同, 也可以 不同;
n为 0, 1或 2;
Alk是含有 1至 ό个碳原子的直链或支链烃基;
Alk^l是含有 1至 ό个碳原子的直链或支链烯基;
m为 0或 1;
Ar是含有 6至 12个碳原子的芳基;
p为 0或 1, p和 n不能同时为 0;
X为 2至 8;
其中最常用的为双(三乙氧基丙基硅烷) 四硫化物和二硫化物、 3-硫氰基丙基-三 乙氧基硅院、 γ-巯基-三甲氧基硅院; 根据上述的橡胶组合物, 其中有机硅院偶联剂的用量为炭黑用量的 0.5wt%-10wt%, 优选 lwt%-8%, 更优选 2 wt %-5 wt %; 根据上述的棚交组合物, 其中所述的活化剂为金属氧化物和脂肪酸组合以及脂肪酸 金属皂盐一种或多种,所述金属氧化物为氧化锌、氧化镁等一种或多种,所述脂肪酸金 属皂盐为硬脂酸锌、硼酸锌等一种或多种; 其中防老剂包括胺类防老剂、喹啉类防老剂 、苯并咪唑类防老剂、物理防护蜡; 其中促进剂包括但不限于次磺酰胺类促进剂、噻唑 类纖剂、禾烂姆类腿剂、胍类促进剂或它们的组合, 硫化剂包括但不限于硫黄、不 溶性硫黄、 充油硫黄、 硫黄给予体或它们的组合; 一种根据上述的橡胶组合物制备的橡胶制品。
本发明测 ¾¾t胶组合物结合胶含量所使用的方法为: 称量一定重量的未硫化胶样 品, 将未硫化胶方认有机溶剂中(首选甲苯溶液)浸泡 3天; 将样品取出, 更换有 浸: 透液, 再次将样品¾^有机溶液中浸泡三天; 后将样品洗净干燥称量。根据理论计算公 式计算结合胶含量。
105
Figure imgf000007_0001
W—样品重量
Wfg—炭黑和结合胶重量
mf—混炼胶中填料的重量
mp—混炼胶中橡胶的重量
附图说明
图 1实施例 2与对比例 2 DMA ¾S扫描曲线图
具做施力式
下面用实施例进一步描述本发明, 但是本发明的范围不受这些实施例的限制 用于«例中的^ ^准:
棚仪器 表 1橡胶样品制备的仪器设备
Figure imgf000007_0002
120
表 2硫化胶物理性能的测试方法及仪器
Figure imgf000007_0003
硬度 (ShoreA) GB/T 531.1-2008 硬度计(邵 A) LX-A 上海六菱仪器厂
伺月麵拉力实
拉伸搬 (MPa) GB T 528-2009 A1-3000 高铁检测仪器公司
验机
伺月麵拉力实
扯断伸长率 ( ) GB T 528-2009 A1-3000 高铁检测仪器公司
验机
回弹! "生 (%) GB/T 1681-2009 回弹性测试仪 GT-7042-RE 高铁检测仪器公司 压缩生热 GB/T 1687-1993 压缩生热¾¾佥机 RH-2000N 高铁检测仪器公司
DIN磨耗 GB-T9867-1988 DIN磨耗¾¾佥机 GT-7012-D 高铁检测仪器公司
阿克隆磨耗 ¾¾佥
阿克隆磨耗 GB-T1689-1998 GT-7012-A 高铁检测仪器公司
EPLEXOR
动态粘弹性 GB T9870.1-2006 动态粘弹谱仪 德国 GOBA公司
500N 下列化学药品应用于实施例和对比例
2嘛准橡胶: 马来西亚产标准胶;
异戊橡胶 IR: 青岛伊科斯材料有限公司;
液体有机硅烧偶联剂 SG-SI998: (双(三乙氧基丙基硅烷) 四硫化物), 南京曙光 助剂有限公司;
有机硅烷偶联剂 X50S: 含有 50%N330炭黑, 50%双(三乙氧基丙基硅烷) 四 化物, 赢创岚星(日照)化学工业有限公司;
N115, N234, N550, 卡博特(中国)投资有限公司;
氧化锌, 大连氧化锌厂;
硬脂酸, PF1808, 马来西亚立成有限公司;
防老剂 020: N-(1.3-二甲基丁基) -Ν'-苯基对苯二胺,江苏圣奥化学科技有限公司; 防老剂 RD: 2,2,4-三甲基 -1,2-二氢化喹啉聚合物, 天津科迈助剂有限公司; 促进剂 NS (Ν-叔丁基 -2-苯并噻唑次磺酰胺): 山东尚舜化工有限公司; 硫黄: 临沂罗庄新安化工厂; 说 明 书 对比例 1
140 基本配方其他配合剂为: SMR20 100; N23450; 氧化锌 5; 硬脂酸 3; 防老剂 4020
1. 5; 防老剂 RD 1. 5; 微晶蜡 1; «剂 NS 1. 2; 硫黄 1。
一段混炼在转速为 90rpm的密炼机中力口入 100重量份 20#标准橡胶, 塑炼 60秒后 提上顶栓加入 33重量份炭黑 N234; 混炼 90秒后 顶栓清扫, 加入 17重量份炭黑; 混炼 30秒后加入 5重量份氧化锌, 3重量份硬脂酸, 1.5重量份防老剂 RD, 1.5重量份 145 防老剂 4020, 1重量份微晶蜡, 混炼 30秒后提上顶栓清扫, 再混炼 30秒排出母胶.,混 炼时间为 240秒, 排胶 ¾¾t为 158°C
终炼胶混炼在? t I为 60φπι的密炼机中力口入 162重量份一段混炼母胶,混炼 30秒 后 顶栓加入 1重量份 5黄, 1.2重量份 β剂 NS,混炼 60秒后清扫,混炼 30秒后 排出终炼胶, 混炼时间为 120秒, 排胶 ¾t¾ 98°C
150 例 1
基本配方其他配合剂为: SMR20 100; N23450; 氧化锌 5; 硬脂酸 3; 防老剂 4020 1. 5; 防老剂 RD 1. 5 ,液体硅垸偶联剂 SG- SI9884, 微晶蜡 1; 促进剂 NS 1. 2; 硫黄 1。
一段混炼在转速为 9(¾pm的密炼机中力口入 100重量份 20#标准橡胶, 塑炼 60秒后 提上顶栓加入 33重量份炭黑 N234; 混炼 90秒后 i^h顶栓清扫, 加入 17重量份炭黑; 155 混炼 30秒后加入 4重量份液体硅院, 5重量份氧化锌, 3重量份硬脂酸, 1.5重量份防 老剂 RD, 1.5重量份防老剂 020, 1重量份微晶蜡,混炼 30秒后 ί壯顶栓清扫,再混 炼 30秒排出母胶, 混炼时间为 240秒, 排胶温度为 154°C。
.终炼胶在$键为 60rpm的密炼机中力口入 166重量份一段母胶,混炼 30秒后 i^h顶 栓加入 1重量份硫黄, 1.2重量份纖剂 NS,混炼 60秒后清扫,混炼 30秒后排出终炼 160 胶, 混炼时间为 120秒, 排胶 ¾¾ 为 102°C。
表 3实施例 1和对比例 1性能对比表
橡胶组合物配方名称 对比例 1 实施例 1
结合胶含量% 41 49.2
回弹性能 回弹性, 23°C , %, 42 47 回弹性, 60eC, %, 48 56
底部温升' c 21.4 18.7
压缩生热
压缩变形% 4.2 3.8
DIN磨耗指数 117 138.1
磨耗指标
阿克隆磨耗指数 109 123.7
从表 3中可以看出,添加硅烷偶联剂的实施例 1性能与对比例 1比,结合胶含量提 高 20%; 23°C及 60°C回弹性能均提高 11%以上。 压缩生热底部温升下降 12%。 磨耗性能 改善尤为明显, DIN磨耗性能提高 18%; 阿克隆磨耗指数提高 13%。。
165 对比例 2
基本配方: SMR20 100; N115 40; 硅烷偶联剂 X50S 8; 氧化锌 5; 硬脂酸 3; 防 老剂 4020 1. 5; 防老剂 RD 1. 5; 微晶蜡 1; 促进剂 NS 1. 2; 硫黄 1。
一段混炼工艺:在转速为 90rpm的密炼机中加入 100重量份 SMR20, 塑炼 60秒 后 顶栓加入 26重量份 N115; 混炼 90秒后 顶栓清扫, 并加入剩余 14重量份 no N115; 混炼 30秒后加入 8重量份硅烷偶联剂 X50S, 1.5重量份防老剂 4020,1.5重量份 防老剂 RD、 5重量份氧化锌、 3重量份硬脂酸、 1重量份微晶蜡; 混炼 30秒提上顶栓 清扫; 混炼 30秒排胶, 总混时间为 240秒, 排胶 ¾¾t为 161°C
终炼胶混炼工艺: 在转速为 60rpm的密炼机中加入 160重!^分一段混炼母胶, 塑 炼 30秒后 顶栓加入 1重量份硫黄及 1.2重量份促进剂 NS; 混炼 60秒后清扫; 混 175 炼 30秒后排胶, 总混炼时间为 120秒, 排胶温度为 95°C。
例 2
基本配方: SMR20 100; N115 40; 硅烷偶联剂 X50S 8; 氧化锌 5; 硬脂酸 3; 防 老剂 4020 1. 5; 防老剂 RD 1. 5; 微晶蜡 1; 促进剂 NS 1. 2; 硫黄 1。 一段混炼工艺:
180 在车键为 90rpm的密炼机中力口入 100重量份 SMR20塑炼 50秒后 顶栓, 力口入
26重量份 N115以及 5.3重量份硅烷 X50S, 混炼 90秒后 ί壯顶栓清扫, 力口入 14重量 份 N115以及 2.7重量份硅烷 TESPT, 混炼 30秒 顶栓清扫, 混炼 30秒排胶; 总混 炼时间为 200秒, 排胶 ¾¾t为 160°C。 二段混炼工艺:
在车 为 90rpm的密炼机中力口入 149重!^分一段母胶, 混炼 80秒提上顶栓, 力口入 5重量份氧化锌、 3重量份硬脂酸、 1.5重量份防老剂 RD,1.5重量份防老剂欄; 混炼 70秒清扫; 再混炼 30秒排胶; 总混炼时间为 180秒, 排胶 ¾¾t为 155°C。
终炼胶混炼工艺:
在车 为 60rpm的密炼机中加入 160重!^分二段混炼母胶,混炼 30秒提上顶栓加 1重量份硫黄及 1.2重量份 剂 NS; 混炼 60秒清扫; 再混炼 30秒排胶, 总混炼时间 为 120秒, 排胶 ¾¾t为 104°C。
表 4实施例 2与对比例 2方案性能指数对比表
Figure imgf000011_0001
从表 4对比数据可以看出, 实施例 2的压缩生热底部温升低于对比例 2约 17%。 动态粘弹谱仪测试橡胶组合物在从低温到高温的损耗因子变化趋势。 从图 1中可 以看出在 50°C至 80°C范围内, 实施例 2的损耗因子低于对比例 2方案, 说明滚动阻力 低于对比例 2, 应用于轮胎中, 可降低滚动阻力。
对比例 3
IR 100; N550 80; 氧化锌 5; 硬脂酸 3; 防老剂 RD 1. 5; 防老剂 4020 1. 5; 微晶 蜡 1; 硫黄 2; 促进剂 NS 1. 8.
一段混炼工艺:
在车键为 90rpm的密炼机中力口入 100重量份合成异戊橡胶 IR塑炼 50秒后 f^i:顶 栓, 力口入 23重!^分炭黑 N550, 混炼 90秒后 f^i:顶栓清扫, 力口入 27重量份炭黑 N550, 混炼 30秒 顶栓清扫, 混炼 30秒排胶; 总混炼时间为 200秒, 排胶 ¾¾t为 159°C。 205 二段混炼工艺:
在车 为 90rpm的密炼机中力口入 180重!^分一段母胶, 混炼 80秒提上顶栓, 力口入 5重量份氧化锌、 3重量份硬脂酸、 1.5重量份防老剂 RD, 1.5重量份防老剂棚 ,1重 量份微晶蜡; 混炼 70秒清扫; 再混炼 30秒排胶; 总混炼时间为 180秒, 排挤 ¾¾t为 149 °C。
210 终炼胶混炼工艺:
在车 为 60rpm的密炼机中加入 192重!^分二段混炼母胶,混炼 30秒提上顶栓加 2重量份硫黄及 1.8重量份 剂 NS; 混炼 60秒清扫; 再混炼 30秒排胶, 总混炼时间 为 120秒, 排胶 ¾¾t为 98°C。
实施例 3
215 IR 100; N550 80; X50S 8; 氧化锌 5; 硬脂酸 3; 防老剂 RD 1. 5; 防老剂 4020 1. 5; 微晶蜡 1; 硫黄 2; 促进剂 NS 1. 8.
一段混炼工艺:
在车键为 90rpm的密炼机中力口入 100重量份合成异戊橡胶 IR塑炼 50秒后 f^i:顶 栓, 力口入 50重量份炭黑 N550以及 5重量份硅烷偶联剂 X50S, 混炼 90秒后 ί壯顶栓 220 清扫, 力口入 30重量份炭黑 Ν550以及 3重量份偶 «lj X50S, 混炼 30秒提上顶栓清扫, 混炼 60秒排胶; 总混炼时间为 230秒, 排胶温度为 162°C。
二段混炼工艺:
在车 为 90rpm的密炼机中力口入 188重!^分一段母胶, 混炼 80秒提上顶栓, 力口入 5重量份氧化锌、 3重量份硬脂酸、 1.5重量份防老剂 RD, 1.5重量份防老剂欄。 1 225 重量份微晶蜡; 混炼 70秒清扫; 再混炼 30秒排胶; 总混炼时间为 180秒, 胶胶温度为 152°C。
三段混炼工艺:
在车 为 60rpm的密炼机中加入 200重!^分二段混炼母胶,混炼 30秒提上顶栓加 2重量份硫黄及 1.8重量份 剂 NS; 混炼 60秒清扫; 再混炼 30秒排胶, 总混炼时间 230 为 120秒, 排胶 ¾¾t为 103°C。 10 表 5实施例 3与对比例 3方案性能指数对比表
Figure imgf000013_0001
从表 5对比数据可以看出, 使用本发明所设计的橡胶组合物及工艺方法, 实施例 3 的压缩生热比对比例 3低 8%, 弹性提高, 结合胶含量提高 5%。 说明使用本发明方法能 够提高炭黑与橡胶的结合, 从而提升动态性能和降低磨耗。
235 对比例 4
I 100; N375 50; 氧化锌 5; 硬脂酸 3; 防老剂 RD 1. 5; 防老剂 4020 1. 5; 微晶 蜡 1; 硫黄 1. 5; 纖剂 NS 1. 8.
一段混炼工艺:
在 为 90rpm的密炼 中力口入 100重量份合成异戊橡胶 IR塑炼 50秒后 顶 240 栓,力口入 33重量份炭黑 N375,混炼 60秒后 顶栓清扫,力口入 17重量份炭黑 N375, 混炼 30秒 顶栓清扫, 混炼 60秒排胶; 总混炼时间为 200秒, 排胶 为 161°C。
二段混炼工艺:
在车 1为 90rpm的密炼机中力口入 150重量分一段母胶, 混炼 80秒提上顶栓,力口入 5重量份氧化锌、 3重量份硬脂酸、 1.5重量份防老剂 RD, 1.5重量份防老剂欄, 微 245 晶蜡 1, 混炼 70秒清扫; 再混炼 30秒排胶; 总混炼时间为 180秒。排胶 为 151 °C。
终炼胶混炼工艺:
在车 61为 60rpm的密炼机中力口入,162重量份二段混炼母胶,混炼 30秒提上顶栓加 1.5重量份硫黄及 1.8重量份纖剂 NS; 混炼 60秒清扫; 再混炼 30秒排胶, 总混炼时 间为 120秒,排胶 为 98°C。
250 实施例 4
IR 100; N375 50; 液体硅烷偶联剂 2; 氧化锌 5; 硬脂酸 3; 防老剂 RD 1. 5; 防 老剂 4020 1. 5; 微晶蜡 1; 硫黄 2; 促进剂 NS 1. 8. 一段混炼工艺:
在车键为 90rpm的密炼机中力口入 100重量份合成异戊橡胶 IR塑炼 50秒后 f^i:顶 255 栓, 加入 30重量份炭黑 N375以及 1.2重量份液体硅烷偶联剂, 混炼 60秒后 f^i:顶栓 清扫, 力口入 20重量份炭黑 N375以及 0.8重量份液体硅烷偶联剂, 混炼 30秒 顶栓 清扫, 混炼 60秒排胶; 总混炼时间为 200秒, 排胶 ¾¾t为 159°C。
二段混炼工艺:
在车 为 90rpm的密炼机中力口入 152重!^分一段母胶, 混炼 80秒提上顶栓, 力口入 260 5重量份氧化锌、 3重量份硬脂酸、 1.5重量份防老剂 RD, 1.5重量份防老剂棚, 微 晶蜡 1; 混炼 70秒清扫; 再混炼 30秒排胶; 总混炼时间为 180秒, 排胶 ¾¾t为 154°C。
三段混炼工艺:
在车 为 60rpm的密炼机中加入 164重!^分二段混炼母胶,混炼 30秒提上顶栓加 1.5重量分 黄及 1.8重量伤腿剂 NS; 混炼 60秒清扫; 再混炼 30秒排胶, 总混炼时 265 间为 120秒, 排胶 ¾¾t l02°C
表 6实施例 4与对比例 4方案性能指数对比表
Figure imgf000014_0001
从表 6对比数据可以看出,使用本发明所设计的橡胶组合物及工艺方法,实施例 6 的压缩生热底部温升值比对比例 6低 11%, 弹性提高, 结合胶含量提高 11%。 说明使用 本发明方法能够提高炭黑与橡胶的结合, 从而提升动态性能。

Claims

权 利 要 求 书
1、 一种低滞后损失高耐磨的橡胶组^勿, 包括:
(A) 100重量份的橡胶;
(B) 5-120重量份的炭黒, 优选 20-90重量份;
(Q0.5-12重!^分的有机硅焼偶联剂, 此重量份以纯有机硅院偶联剂含量计; 橡胶组 勿还包括活化剂、 防老剂、硫黄、硫化観剂以及任选的其他橡胶助剂,其所 示工艺如下:
母炼胶工艺:
橡胶与炭黑、 有机硅烷偶联剂混炼, 混炼温度在 130-16CTC范围内至少持续 1-5分 钟;
终炼胶工艺:
将所述炭黑母胶、 防老剂、 活性剂、 促进剂、 硫化剂按组合物比例混炼制备成橡 胶组合物, 终炼胶混炼工艺为一段或多段。
2、根据权利要求 1所述的橡胶组合物, 其中所述的橡胶包括天然胶、合成聚异戊 二烯橡胶、 顺丁胶、 丁苯橡 3«其它含二烯烃单元的聚合物的一种或多种。
3、 根据权利要求 1 所述的橡胶组合物, 其中所述的炭黑 STSA 比表面积为
Figure imgf000015_0001
4、根据权利要求 1 的橡胶组合物, 其中 的有机硅垸偶联剂为具有以下通 式中的一种或多种:
( Rn- ( RO )3-nSi- (Alk)m- ( Ar)p)q (A) (I )
Rn' (RO )3-nSi- (Alk) (Π) 或^ !^ ^^- (m) 式中, 当 q=l时, A为 -SCN, -SH, -CI, -NH2;
当 q=2时, A为 -Sx -;
R和 R'为碳原子从 1至 4的支化或直链的烷基或酚基, R和 R'可以相同, 也可以 不同;
n为 0, 1或 2;
Alk是含有 1至 ό个碳原子的直链或支链烃基;
Alkenyl是含有 1至 ό个碳原子的直链或支链烯基;
m为 0或 1 ;
Ar是含有 6至 12个碳原子的芳基;
p为 0或 1, p和 n不能同时为 0;
X为 2至 8;
其中最常用的为双(三乙氧基丙基硅烷) 四硫化物和二硫化物、 3-硫氰基丙基-三 乙氧基硅烷、 γ -巯基-三甲氧基硅烷。
5、 根据权利要求 1所述的橡胶组合物, 其中有机硅烷偶联剂的用量为炭黑用量的 0.5wt%-10wt%, 优选 lwt%-8%, ;¾¾t 2 wt %-5 wt %。
6、 根据权利要求 1戶; M的橡胶组合物, 其中戶 的活化剂为金属氧化物和脂肪酸组 合以及脂肪酸金属皂盐一种或多种, 所述金属氧化物为氧化锌、 氧化镁等一种或多种, 所述脂肪酸金属皂盐为硬脂酸锌、 硼酸锌等一种或多种; 其中防老剂包括胺类防老剂、 喹啉类防老剂、苯并咪唑类防老剂、物理防护蜡; 其中^ ί剂包括但不限于次磺酰胺类 促进剂、 噻唑类促进剂、禾烂姆类促进剂、胍类碰剂或它们的组合, 硫化剂包括但不 限于硫黄、 不溶性硫黄、 充油硫黄、 硫黄给予体或它们的组合。
7、 一种根据权利要求 1-6中腿的橡胶组合物制备的橡胶制品。
PCT/CN2014/082692 2014-01-23 2014-07-22 一种含有机硅烷偶联剂及炭黑的橡胶组合物及其制备方法 Ceased WO2015109789A1 (zh)

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