橡胶-填料相互作用对丁苯橡胶/白炭黑复合材料动态力学性能的影响

分别采用γ-胺丙基三乙氧基硅烷(KH550)、γ-甲基丙烯酰氧基丙基三甲氧基硅烷(KH570)及双-[γ-(三乙氧基硅)丙基]-二硫化物(Si75)湿法改性白炭黑,将改性后的白炭黑、丁苯橡胶(SBR)制成母炼胶,制备出白炭黑(SiO_2)/丁苯橡胶(SBR)复合材料。利用结合胶含量、橡胶加工分析仪、扫描电镜等方法研究了白炭黑与橡胶基体间的相互作用效果及填料在橡胶基体中的分散性,用压缩疲劳生热、动态力学性能分析和滞后损耗测试研究了白炭黑与橡胶基体的作用效果对丁苯橡胶/白炭黑复合材料生热的影响。结果表明,改性后白炭黑与橡胶基体间的相互作用力增大,分散性明显提高,随橡胶-填料相互作用增大,SiO_2/SBR生热明显降低,其中KH550在硫化过程产生化学反应接枝于橡胶大分子,其改性后的白炭黑与丁苯橡胶相互作用力最大,KH550-SiO_2/SBR生热最低。     

橡胶-填料相互作用对丁苯橡胶/白炭黑复合材料动态力学性能的影响EI北大核心CSCD

分别采用γ-胺丙基三乙氧基硅烷(KH550)、γ-甲基丙烯酰氧基丙基三甲氧基硅烷(KH570)及双-[γ-(三乙氧基硅)丙基]-二硫化物(Si75)湿法改性白炭黑,将改性后的白炭黑、丁苯橡胶(SBR)制成母炼胶,制备出白炭黑(SiO_2)/丁苯橡胶(SBR)复合材料。利用结合胶含量、橡胶加工分析仪、扫描电镜等方法研究了白炭黑与橡胶基体间的相互作用效果及填料在橡胶基体中的分散性,用压缩疲劳生热、动态力学性能分析和滞后损耗测试研究了白炭黑与橡胶基体的作用效果对丁苯橡胶/白炭黑复合材料生热的影响。结果表明,改性后白炭黑与橡胶基体间的相互作用力增大,分散性明显提高,随橡胶-填料相互作用增大,SiO_2/SBR生热明显降低,其中KH550在硫化过程产生化学反应接枝于橡胶大分子,其改性后的白炭黑与丁苯橡胶相互作用力最大,KH550-SiO_2/SBR生热最低。     

改性白炭黑/天然橡胶复合材料的制备及性能

采用双-[γ-(三乙氧基硅)丙基]四硫化物(Si69)、γ-甲基丙烯酰氧基丙基三甲氧基硅烷(KH570)、乙基三甲氧基硅烷(11-100)对白炭黑进行表面改性,并制备改性白炭黑/天然橡胶复合材料。利用红外光谱(FT-IR)、热重分析(TG)、扫描电镜、橡胶加工分析仪等测试手段对改性白炭黑及改性SiO_2/NR复合材料的结构与性能进行了表征,并研究其硫化性能及力学性能。结果表明,经FT-IR、TG分析,3种硅烷偶联剂已成功接枝到白炭黑表面;改性SiO_2/NR复合材料相对于未改性SiO_2/NR,焦烧时间变长,正硫化时间缩短,结合胶含量增大;改性SiO_2/NR与未改性SiO_2/NR相比其定伸应力、撕裂强度明显提高,但断裂伸长率有所减小;改性白炭黑在天然橡胶基体中的分散性明显提高,其中Si69-SiO_2在天然橡胶基体中的分散性最好;Si69-SiO_2/NR复合材料的滚动阻力与生热最低;改性后的SiO_2/NR复合材料的拉伸断面粗糙程度增加。     

黄原酸酯基硅烷偶联剂的合成及在丁苯橡胶复合材料中的应用

采用相转移催化法制备了不同烷基链长的乙基黄原酸酯基丙基三乙氧基硅烷（EXS）和辛基黄原酸酯基丙基三乙氧基硅烷（OXS），利用2种黄原酸酯基硅烷偶联剂改性白炭黑并补强丁苯橡胶，研究了复合材料的加工性能、硫化性能、力学性能、耐磨性能、压缩生热、动态力学性能等，同时制备了双-[γ-(三乙氧基硅)丙基]四硫化物（Si-69）和封端型巯基硅烷偶联剂（NXT）改性的复合材料作为对比，探究了新型偶联剂取代NXT和Si-69在橡胶工业中应用的可行性。结果表明，长烷基链的OXS改性的复合材料门尼黏度最低，加工安全性高但硫化速度略慢；新型偶联剂改性的复合材料的力学性能、硬度和耐磨性都优于NXT改性的复合材料，同时滚动阻力较低；采用EXS改性的白炭黑在橡胶基体中的分散性较好，填料-橡胶间的相互作用较大。     

含硫偶联剂对白炭黑-天然橡胶的硫化特性及力学性能的影响

在橡胶加工体系中,采用偶联剂双-[γ-(三乙氧基硅)丙基]四硫化物(Si69)与硫磺(S)进行互配,保持橡胶内部硫含量不变,制备白炭黑(SiO_2)-天然橡胶(NR)复合材料;借助无转子流变仪、万能拉伸试验机、橡胶加工分析仪等对白炭黑-天然橡胶复合材料进行表征,考察不同Si69-S互配对橡胶复合材料的硫化特性及力学性能的影响。结果表明:随着Si69逐渐替代S含量,白炭黑-天然橡胶复合材料的硫化特性得到改善,白炭黑在天然橡胶基体中的团聚程度减弱,分散性逐渐提高;硫化温度越高,反应速率常数越大;随着Si69逐渐减少,S量逐渐增多,断裂伸长率与撕裂强度总体呈增大趋势;当Si69质量为4.2 g、S的质量为1 g时,硫化胶的拉伸强度达到最大值,为33.8 MPa。     

改性白炭黑在天然橡胶中的分散性及防老作用EI北大核心CSCD

采用γ-氨丙基三乙氧基硅烷(KH550)与3,5-二叔丁基-4-羟基苯乙酸为改性剂,通过两步法改性白炭黑(SiO_2),制备得到一种具有防老功能的白炭黑,将防老白炭黑添加到天然橡胶(NR)中,制备防老SiO_2/NR复合材料,并与未改性SiO_2/NR复合材料进行对比。结果表明,防老SiO_2/NR的焦烧时间变化不大,正硫化时间缩短了35.43%;橡胶加工分析仪与扫描电镜测试结果显示,白炭黑经过接枝改性后在天然橡胶中的分散性得到改善。在100℃下,随着老化时间的不同,防老SiO_2/NR的断裂伸长率变化率与拉伸强度变化率降幅小于未改性SiO_2/NR复合材料。最后,采用FlynnWall-Ozawa法考察了防老SiO_2/NR硫化胶的热氧化活化能,发现白炭黑接枝了防老剂后,SiO_2/NR的热氧化活化能有所提高,起始热失重温度提高了13.4℃。     

改性白炭黑在天然橡胶中的分散性及防老作用

采用γ-氨丙基三乙氧基硅烷(KH550)与3,5-二叔丁基-4-羟基苯乙酸为改性剂,通过两步法改性白炭黑(SiO_2),制备得到一种具有防老功能的白炭黑,将防老白炭黑添加到天然橡胶(NR)中,制备防老SiO_2/NR复合材料,并与未改性SiO_2/NR复合材料进行对比。结果表明,防老SiO_2/NR的焦烧时间变化不大,正硫化时间缩短了35.43%;橡胶加工分析仪与扫描电镜测试结果显示,白炭黑经过接枝改性后在天然橡胶中的分散性得到改善。在100℃下,随着老化时间的不同,防老SiO_2/NR的断裂伸长率变化率与拉伸强度变化率降幅小于未改性SiO_2/NR复合材料。最后,采用FlynnWall-Ozawa法考察了防老SiO_2/NR硫化胶的热氧化活化能,发现白炭黑接枝了防老剂后,SiO_2/NR的热氧化活化能有所提高,起始热失重温度提高了13.4℃。     

新型偶联剂改性气相白炭黑对天然橡胶性能的影响

采用了湿法改性的方式分别制备了偶联剂KH560-油胺(KH560-OA)、KH560-十八胺(KH560-ODA)、双-(γ-三乙氧基硅基丙基)四硫化物(Si69)、γ-(甲基丙烯酰氧)丙基三甲氧基硅烷(KH570)改性的气相白炭黑,然后采用机械共混方法制备了不同硅烷偶联剂改性的白炭黑/NR复合材料,并研究各种改性白炭黑对NR多种性能的影响。研究结果表明,4种偶联剂对白炭黑的改性效果明显,硫化性能、力学性能、加工性能均有所提高;综合各项性能,自制偶联剂KH560-OA改性效果最佳,拉伸强度达到最大(33.34 MPa),磨耗体积最小为0.203 cm~3,并且综合动态机械性能最佳。     

不同偶联剂对白炭黑表面的改性及其表征

采用3种硅烷偶联剂双-[γ-(三乙氧基硅)丙基]四硫化物(Si69)、γ-甲基丙烯酰氧基丙基三甲氧基硅烷(KH570)、乙基三甲氧基硅烷(11-100)对沉淀法白炭黑粉体进行有机湿法改性。借助傅里叶红外光谱、接触角仪、纳米粒度及Zeta电位仪、扫描电镜等检测手段对白炭黑改性前后的结构及性能进行表征,研究考察3种不同偶联剂对沉淀法白炭黑的疏水性及分散性的影响。结果表明:3种不同硅烷偶联剂都已成功接枝到白炭黑表面,其中Si69改性的白炭黑剩余羟基数与未改性白炭黑表面羟基数的比值最小,为34.23%;经偶联剂改性后的白炭黑,团聚现象减弱,粒径分布变窄,分散性得到改善,疏水性大小依次为Si69-Si O_2KH570-Si O_211-100-Si O_2;综合对比3种偶联剂的改性效果,Si69的改性效果最好。     

离子液体改性白炭黑/天然橡胶复合材料的制备及性能EI北大核心CSCD

用离子液体1-烯丙基-3-甲基氯化咪唑(AMI)改性白炭黑(SiO_2),制备改性白炭黑/天然橡胶(NR)复合材料。采用红外光谱、X射线光电子能谱、扫描电镜等方法分析了改性前后白炭黑的微观结构,研究了AMI对SiO_2/NR复合材料结构与性能的影响。结果表明,AMI改性白炭黑可明显提高白炭黑的分散性,减小白炭黑在橡胶基体中的实际分布粒径,提高白炭黑与橡胶基体的界面相互作用,增加橡胶复合材料的结合胶含量,提高复合材料的综合力学性能。当AMI用量为2 phr时,白炭黑在橡胶基体中的分散性最好,分布粒径最小,结合胶含量最高,综合力学性能最好。与未改性的SiO_2/NR复合材料相比,AMI-SiO_2/NR复合材料拉伸强度提高了18%,撕裂强度提高了41.4%,300%定伸应力提高了39.2%,100%定伸应力提高了25%。     

Effect of the temperature on surface modification of silica and properties of modified silica filled rubber composites

The modified silica at different temperature (MSaDT) with bis(3-triethoxysilylpropyl)tetrasulfide (TESPT), and MSaDT filled solution styrene butadiene rubber (SSBR) composites were prepared to investigate the effect of temperature on surface modification of silica. The results showed that TESPT was successfully bonded on the surface of silica by chemical bonds. The grafting degree (K) of MSaDT of 50 °C was 62.2% and higher than that at the other temperatures. The thermal weight loss and the size distribution of MSaDT showed that the silanol of TESPT hydrolysates reacted with the surface hydroxyl groups of silica, decreasing the average size and agglomeration of modified silica. For 50 °C modified silica/SSBR composite, the static mechanical properties and rubber–filler interaction of the composite were better than those of the others. As far as dynamic mechanical properties are concerned, the 50 °C modified silica/SSBR composite owned a best combination of low rolling resistance and high wet skid resistance.     

Reinforcement and antioxidation effects of antioxidant functionalized silica in styrene–butadiene rubber

In order to improve the dispersion of silica in rubber matrix and to avoid volatility and extractability of the antioxidants, antioxidant functionalized silica is synthesized through reaction of precipitated silica and antioxidant coupling agent which is synthesized by (3-glycidyloxypropyl)trimethoxysilane (A-187) and N-phenyl-1,4-phenylenediamine (PPDA). This antioxidant functionalized silica with different antioxidant content is then incorporated into styrene–butadiene rubber (SBR) to study their reinforcement and antioxidation effects. The tensile strength of these composites is much higher than that of neat silica/SBR, and increases with increasing antioxidant content. It is close to that of bis(triethoxysilylpropyl)tetrasulfane (TESPT) modified silica/SBR when the antioxidant content exceeds 3.9% (by weight to silica). Furthermore, SBR filled with antioxidant functionalized silica has greatly improved stability in thermal oxidative ageing and damp heat ageing.     

Incorporation of nano-sized mesoporous MCM-41 material used as fillers in natural rubber composite

The nano-sized mesoporous MCM-41 (without template), and the modification of MCM-41 (without template) were used to prepare natural rubber (NR) composites. The effects of coupling agents γ-aminopropyltriethoxysilane (KH-550), γ-methacryloxypropyltrimethoxysilane (KH-570), bis-(γ-triethoxysilylpropyl)-tetrasulfide (Si-69), isopropyl tri-(dioctylpyrophosphate)titanate (NDZ-201) on the mechanical properties of the composites were also investigated. The results showed that the tensile properties of Natural rubber/mesoporous MCM-41 nanocomposite were improved as compared with those of NR compound. KH-570 had good effect on enhancing the overall properties of the composites. Scanning electron microscopy (SEM) observations revealed that the modified nano-sized MCM-41 material was well dispersed in the polymer matrix and the enhancement of the interface between the matrix and fillers was obtained.     

The effect of silane coupling agent on iron sand for use in magnetorheological elastomers Part 1: Surface chemical modification and characterization

Bis-(3-triethoxysilylpropyl) tetrasulphane (TESPT) was employed for surface modification of iron sand for use in magnetorheological elastomers (MREs). The amount of TESPT was varied at five levels (2, 4, 6, 8 and 10 wt%) relative to iron sand content to assess the optimum amount of coupling agent for interfacial bonding and damping performance. Evidence that coupling had occurred between iron sand and TESPT was identified by Raman Spectroscopy and the grafting percentage was determined by thermogravimetric analysis. Subsequently, isotropic MREs containing unmodified and modified iron sand particles and natural rubber were prepared. Crosslink density assessment by swelling testing provided evidence that the tetrasulphane group of TESPT formed crosslinks with the rubber chains. The results exhibited the advantages of TESPT as a coupling agent between iron sand particles and rubber and also revealed that 6% TESPT content produced the highest crosslink density. The effects of the amount of TESPT on dynamic mechanical properties the morphological characteristics of the MREs were also investigated.     

ESBR/SiO2胶乳的破乳动力学及复合材料性能

系统探究了NaCl和CaCl2溶液絮凝乳聚丁苯橡胶/白炭黑(ESBR/SiO2)胶乳的行为及破乳动力学,考察了硅烷偶联剂TESPT和NXT对复合材料力学性能、动态黏弹性能和流变性能的影响。研究发现,NaCl溶液破乳呈现匀速破乳、加速破乳的过程,而CaCl2溶液破乳则呈现匀速破乳、加速破乳和减速破乳3个阶段。白炭黑粒子对体系破乳效应的影响存在差异,这主要是因为二价Ca^2+对电荷中和能力比一价Na^+高,导致白炭黑的成核中心作用不同。此外,发现硅烷偶联剂NXT使白炭黑在橡胶基体中的分散性显著提高,使其复合材料的硫化性能得到优化,力学性能明显提高,在保持抗湿滑性能时滚动阻力明显降低。     

Incorporation of modified soy protein isolate as filier in BR/SBR blends

The surface modification of soy protein isolate (SPI) and the use of modified SPI as reinforcing filler replaced carbon black in BR/SBR composites were studied. The effects of coupling agents γ-aminopropyltriethoxysilane (KH-550), γ-methacryloxypropyltrimethoxysilane (KH-570), bis-(γ-triethoxysilylpropyl)-tetrasulfide (Si-69), isopropyl tri-(dioctylpyrophosphate) titanate (NDZ-201) on the physical and mechanical properties of the composites were also investigated. Modified SPI was analyzed by Infrared spectra, scanning electron microscopy, and X-ray diffraction. The results showed that the optimal reaction conditions were determined, that is, the optimal reactions were 4 g SPI, 50% Glycidyl methacrylate (by SPI weight), 3 h of reaction time and 80 °C reaction temperature. Through the physical and mechanical properties of composite, the results showed that when a small number of modified SPI (3–5 phr) as reinforcement agent was used, the mechanical properties were improved. KH-550 had good effect on enhancing the overall properties of the composites.     

Synthesis of novel thiol-functionalized mesoporous silica nanorods and their sorbent properties on heavy metals

Novel thiol-functionalized mesoporous silica nanorods (MSNRs) were synthesized through a base co-condensation method, in which two organoalkoxysilanes, tetraethoxylsilane (TEOS) and bis[3-(triethoxysilyl)propyl]tetrasulfide (TESPT), were used as silica precursors simultaneously. TESPT was firstly used for both morphology control and inner surface functionalization of mesoporous silica hybrid materials. The microstructures as well as porous character of the MSNRs were characterized by means of SEM, XRD, TEM and N₂ sorption measurements. Infrared spectrum analysis and heavy metal ions (Ag⁺ and Cd²⁺) adsorption measurements were carried out to confirm the functionalized framework of MSNRs.     

表面接枝防老剂的白炭黑在天然橡胶中的应用

为了提高白炭黑与橡胶的相容性,同时防止防老剂的挥发,采用γ-缩水甘油醚氧丙基三甲氧基硅烷与对氨基二苯胺(PPDA)的反应物对白炭黑进行表面改性,得到表面接枝防老剂的白炭黑。将改性白炭黑应用于天然橡胶(NR)中考察其增强与防老性能,并与炭黑/NR、未改性白炭黑/NR和Si69改性白炭黑/NR复合材料相比较(均添加防老剂4020)。结果表明,改性白炭黑/NR复合材料的焦烧时间延长,硫化时间缩短,白炭黑在橡胶中的分散性提高,同时具备更出色的力学性能。随着表面接枝防老剂含量的增加,改性白炭黑/NR复合材料的拉伸强度和撕裂强度比未改性白炭黑和Si69改性白炭黑/NR均有大幅提高。当接枝的PPDA含量达到5.27%(与白炭黑的质量比)时,其拉伸强度比未改性白炭黑/NR提高了90%,比Si69改性白炭黑/NR提高了73%,并接近炭黑/NR; 其撕裂强度是未改性白炭黑/NR的5倍,Si69改性白炭黑/NR的2.5倍,炭黑/NR的2倍。另外,表面接枝防老剂的白炭黑/NR复合材料具有优异的抗热氧、抗臭氧和湿热老化性能;其抗臭氧老化性能优于添加通用防老剂4020的对比复合材料。     

聚酰亚胺表面处理玻璃纤维/环氧树脂复合材料力学性能

采用浇铸成型工艺制备含0.5wt%、长度分别为1 mm、3 mm、5 mm的短切玻璃纤维/环氧树脂（GF/EP）复合材料,研究含活性酚羟基和不含酚羟基的两种聚酰亚胺（PI）处理GF表面对纤维束拉伸强度及GF/EP复合材料力学性能的影响,并进一步研究PI处理GF对复合材料热性能的影响。研究结果表明,经过PI处理的GF,集束性和拉伸强度得到提高。含活性酚羟基聚酰亚胺（PI1）处理的GF拉伸强度由原丝束的517 MPa提高到1 032 MPa,不含酚羟基聚酰亚胺（PI2）处理的GF提高到986 MPa。当PI1处理的GF长度为3 mm时,GF/EP复合材料的力学性能最好,拉伸强度比未处理的提高23.62%,拉伸模量提高34.03%,弯曲强度提高28.74%,断裂韧性提高13.04%;PI2处理的GF,GF/EP复合材料拉伸强度提高15.87%,拉伸模量提高23.70%,弯曲强度提高14.11%,断裂韧性提高4.05%。此外,PI处理GF对GF/EP复合材料热性能也有一定程度的提高。     

EPDM-g-MAH/CaCO3复合材料力学及热老化性能的表征

以二甲苯为溶剂,溶液法制备马来酸酐(MAH)接枝EPDM,并向溶液中加入适量碳酸钙(C aCO3),与已接枝的马来酸酐(MAH)反应。待反应完全后,以丙酮为沉淀剂,得到EPDM-g-MAH/C a-CO3弹性体复合材料。溶胀及拉伸性能测试结果表明,复合材料形成有效交联,且材料的拉伸强度、断裂伸长率和模量均得到大幅提高,且在C aCO3含量达到体系总质量的20%时,复合材料呈现最佳力学性能。认为,上述实验结果是因为碱性的C aCO3的C a2 可以与接枝在EPDM上的MAH发生配合反应,进而成为EPDM的交联中心,形成有效交联,从而促进了EPDM力学性能的提高,ATR-FT-IR的测试结果被用于证实上述观点。文中还对复合材料的热氧老化性能进行了测试。