硅烷化反应率对白炭黑填充胶料硫化过程中模量持续上升的影响

研究硅烷化反应率对白炭黑填充胶料硫化过程中模量持续上升的影响。结果表明：延长混炼过程中的硅烷化反应恒温时间,可以提高硅烷化反应率,降低白炭黑的絮凝,减缓胶料模量持续上升;硅烷偶联剂种类对胶料模量持续上升有较大影响,在配方中硫原子数相同的前提下,对胶料模量持续上升现象改善效果从优到劣的硅烷偶联剂排列顺序为Si747,TESPT,TESPD,OTES。     

促进剂DPG在白炭黑填充天然橡胶胶料混炼中加料顺序对胶料性能的影响

研究促进剂DPG在白炭黑填充天然橡胶胶料混炼中加料顺序对胶料性能的影响。结果表明：促进剂DPG与NR、白炭黑和硅烷偶联剂同时加入混炼能够参与和促进硅烷化反应,改善白炭黑与NR之间的相容性,减轻白炭黑聚集,因此可降低Payne效应,提高胶料的耐热老化性能,但因其参与硅烷化反应而减小了参与硫化反应的量,导致硫化速率降低,焦烧时间延长,同时由于交联密度下降导致硫化胶的耐磨性能、300%定伸应力和撕裂强度降低及60 ℃时的tanδ增大,因此在配方开发和混炼工艺设计时,应考虑适量补充促进剂DPG在前期混炼阶段加入时的损耗。     

炭黑-白炭黑双相粒子填充天然橡胶的硫化动力学

采用Ghoreisy’s模型和自催化反应模型研究了炭黑-白炭黑双相粒子（CSDPF）的用量及硅烷偶联剂Si 69改性CSDPF对天然橡胶（NR）硫化特性的影响。结果表明,Ghoreisy’s模型能更好地描述CSDPF及改性CSDPF填充NR的硫化过程;随着CSDPF和改性CSDPF用量的增加,NR胶料均出现硫化返原现象,但后者硫化返原现象有所减轻;随着CSDPF和改性CSDPF用量的增加,NR胶料的硫化时间变长,硫化速率下降,硫化反应级数增加;填充硅烷偶联剂Si 69改性CSDPF,胶料的硫化时间变短,硫化速率增加。     

应用橡胶加工分析仪研究白炭黑胶料的硅烷化反应和填料聚集

应用RPA2000橡胶加工分析仪测试白炭黑胶料的弹性模量变化,研究加工过程中白炭黑胶料的硅烷化反应及填料聚集情况。结果表明:白炭黑胶料中形成了一定数量的白炭黑-硅烷偶联剂-橡胶化学键,很大程度上遏制了白炭黑在胶料硫化过程中聚集;较高硫化温度虽然对减少白炭黑的聚集有利,但因为交联密度随之降低,导致白炭黑胶料的损耗因子(tanδ)仍增大;开炼机剪切作用在降低白炭黑胶料的门尼粘度同时打断了橡胶大分子链和破坏了白炭黑-硅烷偶联剂-橡胶交联结构,加剧了白炭黑聚集,使得白炭黑胶料的tanδ明显增大。     

白炭黑填充胶料的焦烧状况研究与改善

研究硅烷偶联剂对白炭黑填充胶料焦烧状况的改善。结果表明:与未添加硅烷偶联剂的胶料相比,添加硅烷偶联剂可显著促进胶料的白炭黑分散并抑制白炭黑在硫化过程中的絮凝,延长焦烧时间;由于形成了白炭黑-硅烷偶联剂TESPT-橡胶网络,硅烷偶联剂TESPT在促进白炭黑分散方面表现出更好的效果,而硅烷偶联剂OTES可以更有效地抑制白炭黑的絮凝,从而延长焦烧时间;两种硅烷偶联剂同时使用可进一步抑制白炭黑的团聚。     

改性煅烧高岭土对EPDM性能的影响

采用硅烷偶联剂对煅烧高岭土进行表面改性，研究硅烷偶联剂品种和用量对煅烧高岭土填充EPDM胶料性能的影响。结果表明。硅烷偶联剂对煅烧高岭土填充EPDM胶料的焦烧时间和正硫化时间影响不大;偶联剂A-17Z的改性作用较为明显，可显著提高EPDM硫化胶的撕裂强度；偶联剂A-172用量过大，对EPDM硫化胶耐溶剂性能不利。     

硅烷偶联剂KH-792对白炭黑／环氧化天然橡胶复合材料性能的影响

研究硅烷偶联剂KH-792对白炭黑/环氧化天然橡胶(ENR)复合材料性能的影响。通过硫化特性测试和红外光谱分析发现,ENR与白炭黑和硅烷偶联剂KH-792之间发生了反应。试验结果表明:硅烷偶联剂KH-792改性白炭黑/ENR胶料的结合胶含量高,硫化胶的抗切割性能和耐磨性能优异;当硅烷偶联剂KH-792用量为白炭黑用量的8%时,其改性效果最佳。     

天然橡胶中蛋白质含量对其白炭黑填充胶料性能的影响

研究天然橡胶（NR）中蛋白质含量对其白炭黑填充胶料性能的影响。结果表明：在未加硅烷偶联剂Si69的胶料中,随着NR中蛋白质含量的增大,胶料的门尼粘度、FL和Fmax增大;与未加硅烷偶联剂Si69的胶料相比,加入硅烷偶联剂Si69的胶料的白炭黑分散性提高,门尼粘度、FL和Fmax减小,t10和t90明显延长;硫化胶的物理性能提高,滚动阻力降低。     

硅烷偶联剂KH550在全钢载重子午线轮胎胎面胶中的应用

研究硅烷偶联剂KH550在全钢载重子午线轮胎胎面胶中的应用。结果表明：在胎面胶中加入硅烷偶联剂KH550,胶料的门尼粘度增大,门尼焦烧时间缩短,硫化速度加快;与未加硅烷偶联剂KH550的硫化胶相比,加入0.75份硅烷偶联剂KH550的硫化胶的定伸应力和撕裂强度略有提高,其他性能相当,同时胶料的损耗因子减小12%,有利于减小轮胎滚动阻力。     

煅烧陶土在三元乙丙橡胶电线电缆胶料中的应用

研究煅烧陶土在三元乙丙橡胶(EPDM)电线电缆胶料中的应用,考察了陶土粒径、陶土用量、硅烷偶联剂用量、填料种类对胶料硫化特性、力学性能、导电和导热性能的影响。结果表明:填充100份粒径为8. 5μm的陶土时胶料的综合性能较好;在陶土填充胶料中配合使用少量硅烷偶联剂A-172(用量为陶土的0. 25%),可以在保证EPDM硫化胶良好的导电和导热性能的前提下进一步提高力学性能。陶土可以取代超细碳酸钙用于EPDM电线电缆料中,具有明显的性能优势。     

Compatibility enhancement of silica and natural rubber compound using UVA-induced silane-grafted saponified skim natural rubber

Silane coupling agents are potential reagents widely used to improve the compatibility between silica and less polar rubber, especially natural rubber (NR). Nevertheless, high temperature is generally required to generate the interaction between the components during the mixing process. Accordingly, an alternative method by grafting the silane coupling agent onto the rubber molecules would be a desirable approach to develop a compatibilizer for the silica-filled NR compound. In this work, skim NR was used as a starting material due to its linear structure. The optimal conditions of the grafting reaction were found to be 1 phr of an alkoxy silane and 5 phr of benzoyl peroxide under 8 min of UVA irradiation time. These conditions were applied for producing the rubber material used in the mixing process of STR 5L and silica. The cure characteristics, silica dispersion and mechanical properties of the rubber compounds were improved, suggesting that the modified rubber was an efficient material for increasing the compatibility between silica and NR.     

The Effects of a “Palm Oil” Faiiy Acid Additive and a Silane Coupling Agent on the Curing Characteristics and Vulcanizate Properties of Silica-Filled Natural Rubber Compounds

Comparison study on effects of a “palm oil” fatty acid additive (POFA) and a silane coupling agent on the curing characteristics and vulcan-izates properties of silica-filled natural rubber were studied. Compared to the control compound, the incorporation of both ingredients enhances the cure rate and cure state of the rubber compounds. Both ingredients were found to be effective in reducing the viscosity of the rubber compounds. Swelling measurement and scanning electron microscopy studies indicate that both ingredients increase the cross-link density, improve filler dispersion, and, consequently, enhance the vulcanizate properties.     

硅烷偶联剂在填充白炭黑斜交轮胎胎面胶中的应用

研究了硅烷偶联剂在填充白炭黑斜交轮胎胎面胶中的应用,试验结果表明,在填充白炭黑的胎面胶中加入偶联剂Si69,可以降低胶料的粘度,缩短焦烧时间和正硫化时间,增大硫化胶的邵尔A型硬度和300%定伸应力;采用三段混炼可以改善胶料的挤出工艺性能和胎面挤出尺寸稳定性。     

Effect of adding different silane coupling agents on metal friction and wear in mixing process

The function of silane coupling agent in rubber mixing field is to combine inorganic matrix with rubber organic matrix. Silica is commonly used in the rubber mixing field to strengthen rubber. The size and amount of silica aggregates in the mixing process are important factors affecting the wear of the mixing chamber. The wear of the mixing chamber would lead to a increasing gap between the mixer chamber and the rotor, which caused the mixing efficiency reducing. It also affected the dispersion effect, then affected the mechanical and physical properties of the vulcanized rubber. In this paper, the effects of rubber compound on metal friction and wear were studied by using four silane coupling agents commonly used in rubber mixing field. The experiment was carried out at 15°C, and the attention should be paid to drying during sample preparation to avoid the deviation of the experiment caused by hydrolysis of silane coupling agent. The results showed that silanization reaction occured between silica and silane coupling agent in the mixing process. The mixing temperature was usually maintained at 145 to 155°C for 1 min in the mixer, and the silanization reaction rate was the fastest during this time. We took this rubber compound as the research object and studied the friction and wear of the rubber compound on the mixing chamber in the mixing process. The products of the silylation reaction are alcohol and water. This paper studies the corrosion and abrasion of the mixing chamber by water at high temperatures. In the mixing process, abrasive wear was the main wear form, but the corrosion wear caused by high temperature steam still occupied a large proportion.     

Preparation of Silica‐Based Rubber Compounds without the Use of a Silane Coupling Agent through the Use of Epoxidized Natural Rubber

The present study represents a new concept: the possibility of preparing a rubber compound filled with silica without the use of a silane coupling agent. For this purpose two different types of silica have been compounded with two different grades of epoxidized natural rubber (ENR) without the use of a silane coupling agent. The mechanical and other properties of the resulting compounds have been compared with two reference compounds prepared from natural rubber (NR) and silica with and without the addition of a silane coupling agent bis‐(triethoxysilylpropyl)tetrasulfane (TESPT). It is shown that by using ENR as rubber component together with silica, it is possible without the use of coupling agents to achieve significantly improved mechanical properties with respect to similar NR compounds without coupling agents. The reason for these improvements lies in the polar nature of ENR which interacts strongly with the silica surface by hydrogen bonding mechanism. This does not happen when NR or another non‐polar rubber component is used. Thus, in this latter case the use of silane coupling agents to make the silica surface more non‐polar and hydrophobic is needed to have a good reinforcing effect and overall performances from the composite studied.     

Properties of natural rubber composites reinforced with silica or carbon black: influence of cure accelerator content and filler dispersion

Filler dispersion is a critical factor in determining the properties of filled rubber composites. Silica has a high density of silanol groups on the surface, which lead to strong filler–filler interactions and a poor filler dispersions. A cure accelerator, N‐tert‐butyl‐2‐benzothiazole sulfenamide (TBBS), was found to improve filler dispersion in silica‐filled natural rubber (NR) compounds. For the silica‐filled NR compounds without the silane coupling agent, the reversion ratio generally increased with increase in TBBS content, whereas those of the silica‐filled NR compounds containing the silane coupling agent and carbon black‐filled NR compounds decreased linearly. The tensile strength of the silica‐filled NR vulcanizate without the silane coupling agent increased as the TBBS content increased, whereas carbon black‐filled samples did not show a specific trend. The experimental results were explained by TBBS adsorption on the silica surface and the improvement of silica dispersion with the aid of TBBS. Copyright © 2003 Society of Chemical Industry     

Reinforcement of maleated natural rubber by precipitated silica

Graft copolymers of maleic anhydride and natural rubber or so‐called maleated natural rubbers (MNRs) were prepared in a molten state with varying maleic anhydride contents from 4 to 10 phr. In this work, the filler–filler and filler–rubber interactions of the MNR and precipitated silica were investigated. The MNR compounds containing 40 phr of silica both with and without 9 wt % of silane coupling agent were prepared. By increasing the maleic anhydride contents, the Mooney viscosity and cure times were increased, but the torque differences and cure rate indices were decreased. Bound rubber was increased with increasing maleic anhydride content, indicating an increase of filler–rubber interaction. In case of the compounds without silane, the MNR with 6 phr of maleic anhydride showed the lowest filler–filler interaction as indicated by a decrease of storage modulus upon an increase of strain in the filled compound i.e., Payne effect. This MNR compound also yielded the optimum mechanical properties. It has been demonstrated that a use of MNR with appropriate maleic anhydride content can reduce filler–filler interaction dramatically and hence improve a silica dispersion, as confirmed by SEM micrographs, resulting in an enhancement of the mechanical and dynamical properties. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

硅烷偶联剂的应用进展

简要介绍了硅烷偶联剂的偶联机理、选用原则及其在复合材料中的应用，包括用作玻璃纤维的处理剂、无机粉末填料的处理剂和胶粘剂、密封剂的增粘剂；另外，还介绍了硅烷偶联剂对橡胶性能的影响。     

Influence of polymer–filler interactions on retraction behaviors of natural rubber vulcanizates reinforced with silica and carbon black

In general, silica‐filled rubber compounds contain a silane coupling agent to improve the filler dispersion and polymer–filler interactions. The silane coupling agent modifies the silica surface and makes crosslinks between the rubber and the silica. Influence of the modification of silica on the retraction behaviors of natural rubber (NR) vulcanizates reinforced with silica and carbon black was studied. Variation of the retraction behaviors of NR vulcanizates with filler composition was also investigated. The vulcanizates containing the silane coupling agent were recovered faster than those without the silane coupling agent. The recovery difference between the vulcanizates without and with the silane coupling agent increased with increased silica content. For the vulcanizates containing the silane coupling agent, the retraction behaviors were nearly the same, irrespective of filler composition. But, for the vulcanizates without the silane coupling agent, the vulcanizate was recovered more and more slowly as the silica content increased. The experimental results are explained with the polymer–filler interactions, modification of silica surface, and formation of crosslinks between silica and rubber. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 691–696, 2006     

低滚动阻力轿车轮胎胎面配方的材料选择

研究溶聚丁苯橡胶(SSBR)、白炭黑、硅烷偶联剂和特殊弹性体Nanoprene BM75对低滚动阻力轮胎胎面胶性能的影响。结果表明:采用合适结构的SSBR替代乳聚丁苯橡胶或采用白炭黑替代炭黑都可以在提高轮胎抗湿滑性能的同时降低滚动阻力,改性SSBR的动态性能优于相同微观结构的未改性SSBR;新型硅烷偶联剂胶料比传统硅烷偶联剂胶料动态性能更好;特殊弹性体Nanoprene BM75也可有效降低滚动阻力。