分子动力学模拟预测链中改性溶聚丁苯橡胶结构与性能关系及温度依赖性

通过分子动力学模拟方法,从分子水平上预测了3-巯丙基三乙氧基硅烷和3-巯基-1-丙醇改性的溶聚丁苯橡胶(SSBR)结构与性能关系及温度依赖性。结果表明改性后SSBR的玻璃化温度比未改性的SSBR略有减小,介电常数、溶解度参数、导热系数提高。在所有性能中,氧气渗透率变化最大,3-巯基-1-丙醇改性的SSBR的氧气渗透率比纯的SSBR减少了22%。     

一种硅烷偶联剂的合成及其在白炭黑/天然橡胶复合材料中的应用

采用γ-缩水甘油醚氧丙基三甲氧基硅烷(A187)与对氨基二苯胺(PPDA)反应,制备得到一种具有防老化功能的硅烷偶联剂,并通过1H-NMR、IR和MS对其结构进行表征.之后,将不同用量的硅烷偶联剂用于原位改性白炭黑制备防老功能化白炭黑/天然橡胶(NR)复合材料,并与相应的炭黑/NR、未改性白炭黑/NR及双-(γ-三乙氧基硅基丙基)四硫化物(Si69)改性白炭黑/NR在加工性能、增强性能和防老化性能方面进行对比.硫化特性数据表明,防老偶联剂的添加使复合材料的黏度降低,最大转矩增加,正硫化时间缩短.动态黏弹性能显示,改性后白炭黑的分散性得到明显提高.复合材料的力学性能先随防老偶联剂用量的增加而提高,之后到达平台.当防老偶联剂的用量大于或等于白炭黑质量的10.8%时,复合材料的拉伸强度与炭黑/NR、Si69改性白炭黑/NR相当,远大于未改性白炭黑/NR的强度;而其撕裂强度都大于3种对比复合材料.经过100℃下不同天数的热氧老化后,添加防老偶联剂的复合材料表现出良好的性能保持率,优于添加防老剂4020的3种对比材料,表明防老偶联剂具有更好的防护效果.     

橡胶-填料相互作用对丁苯橡胶/白炭黑复合材料性能的影响

本文研究了硅烷偶联剂原位改性白炭黑对溶聚丁苯橡胶(SSBR)性能的影响,结果表明,通过哈克转矩流变仪对含有偶联剂的SSBR/白炭黑混炼胶进行原位热处理后可明显减弱混炼胶的Payne效应,改善白炭黑在橡胶基体中的分散.原位热处理方法能够明显提高硫化胶的300%定伸应力,降低动态压缩温升,同时可使硫化胶在0℃附近具有较高的损耗因子(tanδ),60℃附近具有较低的tanδ.对不同聚合方式得到的丁苯橡胶,即溶聚丁苯橡胶与乳聚丁苯橡胶(ESBR)/白炭黑复合材料的力学性能及动态力学性能进行了研究,结果表明,白炭黑在SSBR2305中分散效果优于在ESBR1502中;采用偶联剂原位改性白炭黑可以使SSBR2305硫化胶获得与ESBR1502硫化胶相当的物理机械性能,更理想的动态力学性能,从而得到力学性能、抗湿滑性、滚动阻力及耐磨性更加均衡的理想轮胎材料.通过对具有不同偶联效率的SSBR/白炭黑体系的微观结构与性能研究发现,随偶联效率的增加,其结合橡胶含量增加,Payne效应减弱;高偶联效率的S-SBR具有较低的动态压缩温升及较好的耐磨性.     

表面改性SiO2对SSBR/BR绿色轮胎胎面胶结构与性能的影响

采用4种含不同官能基团修饰剂改性的二氧化硅SiO₂增强溶聚丁苯橡胶(SSBR)/顺丁橡胶(BR)共混体系, 制备了SSBR/BR/SiO₂橡胶纳米复合材料, 研究了其结构与性能. 结果表明, 在混炼胶体系中, 与未改性SiO₂填充的SSBR/BR相比, 改性SiO₂填充的SSBR/BR门尼黏度及结合橡胶含量显著增大, 表明填料-橡胶相互作用显著提高; 硫化焦烧时间缩短60%, 硫化速度增大了35%~40%. 在硫化胶体系中改性SiO₂填充的SSBR/BR具有更大的交联密度, 填料分散性明显改善, 同时也表现出更为优异的物理机械性能, 100%和300%定伸模量提高47%以上, 旋转滚筒式磨耗机法(DIN)磨耗降低5%~12%, 生热降低了约7%~13%, 热空气老化性能提升4%~22%, 代表滚动阻力的tanδ在60 ℃降低8%~13%. 此外, 与SSBR/BR/1165MP硫化胶相比, 用90 mmol/kg氨基改性SiO₂填充的SSBR/BR硫化胶的抗湿滑性能提高6.9%, 表现出最优的综合性能. 填料的良好分散及填料与聚合物的相互作用增强对于提高SSBR/BR/SiO₂胎面胶综合力学性能具有重要意义.     

稻壳基二氧化硅/碳复合材料的表面改性及对天然橡胶的影响

以稻壳基二氧化硅/碳复合材料(SiCB)作为天然橡胶(NR)的补强填料, 采用表面化学改性的方法将天然乳胶(NRL)接枝到SiCB表面, 改善其与NR基体的相容性. 研究了不同处理方法对接枝NRL效率的影响, 以及填料填入NR后对硫化橡胶力学性能的影响. 结果表明, 经过硝酸和γ-(甲基丙烯酰氧)丙基三甲氧基硅烷(γ-MPTMS)预处理, NRL能高效接枝在SiCB表面, 得到的样品SiCB_MR10比未处理的SiCB_P有更强的补强能力. 硫化胶NR/SiCB_MR10的拉伸强度、 300%定伸和撕裂强度较NR/SiCB_P分别提高了61.06%, 27.15%和15.90%, 与传统炭黑产品N774填充的硫化胶NR/N774的力学性能相近. 经过NRL接枝改性的SiCB_MR10具有替代商业炭黑的应用前景.     

高分散性SiO2/PMMA复合材料的制备与表征——接枝与交联

以硅烷偶联剂3-(甲基丙烯酰氧)丙基三甲氧基硅烷(MPS)改性SiO2/甲基丙烯酸甲酯(MMA)分散液为原料,通过原位本体聚合制得一系列具有不同SiO2含量和PMMA接枝率的高分散性SiO2/PMMA复合材料,索氏抽提分析复合材料的接枝和交联情况.发现抽提后体系中主要存在3部分物质:抽提液中含游离SiO2的PMMA溶液...     

硫化温度对绿色轮胎胎面胶结构与性能的影响

在轮胎的加工和制备过程中,硫化温度是影响橡胶复合材料网络结构和物理机械性能的重要因素之一.本文研究了硫化温度(140、150、160、170和180℃)对溶聚丁苯橡胶(SSBR)/顺丁橡胶(BR)(未填充体系)及SSBR/BR/白炭黑(SiO2)(填充体系)纳米复合材料的结构和物理机械性能的影响.结果表明:随硫化温度的...     

高耐磨低生热NBR/TBIR复合材料的结构与性能

采用高反式-1,4-丁二烯-异戊二烯共聚橡胶(TBIR)对丁腈橡胶(NBR)进行改性, 制备了高耐磨、 低生热输送轮用白炭黑填充的NBR/TBIR橡胶纳米复合材料. 研究了NBR/TBIR橡胶纳米复合材料的交联密度、 物理力学性能及填料分散性, 探讨了材料的结构对性能的影响. 研究结果表明, 与纯NBR相比, NBR/TBIR橡胶纳米复合材料的硫化速率和交联密度随TBIR用量的增加而增大; 在保持NBR硫化胶基本力学性能、 耐老化性能和耐溶剂性能基本不变的前提下, TBIR的加入使NBR/TBIR硫化胶的耐磨性提高15%, 动态压缩生热降低5%, 动态压缩永久变形降低22%, 白炭黑分散水平提高; 与丁腈橡胶/顺丁橡胶[NBR/BR(80/20), 质量份数比]硫化胶相比, NBR/TBIR(80/20, 质量份数比)硫化胶具有更低的动态压缩生热和动态压缩永久变形及更好的填料分散性.     

反式-1,4-丁二烯-异戊二烯共聚橡胶改性的高性能轿车轮胎胎面胶的结构与性能

研究了新一代合成橡胶-反式-1,4-丁二烯-异戊二烯共聚橡胶(TBIR)在高性能轿车轮胎胎面胶(溶聚丁苯橡胶/顺丁橡胶(SSBR/BR))中的应用及SSBR/BR/TBIR共混胶的结构与性能.结果表明,相对于无定型的SSBR和BR,TBIR由于具有一定的结晶性而呈现出较高的生胶强度、模量和韧性.但相比反式聚异戊二烯(TPI),由于丁二烯单体单元的引入降低了聚合物链的结构规整性,TBIR的结晶熔融焓、熔点和玻璃化转变温度均明显降低.采用10~20份TBIR与SSBR/BR并用改性,同时加入30份炭黑和45份白炭黑,SSBR/BR/TBIR混炼胶的格林强度和定伸应力提高,焦烧时间(tc10)和工艺正硫化时间(tc90)基本保持不变.SSBR/BR/TBIR混炼胶经过150oC硫化反应,制备的硫化胶物理机械性能优异,抗拉伸疲劳性能提高4.6~6.3倍,压缩强度提高21.4%~23.1%,耐磨耗性能提高10.8%~15.1%,耐湿滑性能提高13.6%~40.4%,滚动阻力维持不变.填料分散仪和透射电镜(TEM)结果表明,相比SSBR/BR硫化胶,SSBR/BR/TBIR硫化胶填料分散度提高7.3%~14.9%,填料聚集体平均尺寸降低1.4~2.7μm.可结晶的TBIR的高生胶强度及模量可显著抑制混炼胶中填料的聚集,改善硫化胶中填料的分散性,最终贡献于SSBR/BR/TBIR硫化胶优异的抗拉伸疲劳性、高的耐磨性、抗湿滑性、压缩强度、定伸模量等性能,TBIR是应用于高性能轿车轮胎胎面胶的一种理想新合成橡胶.     

秸秆预处理工艺对秸秆基人造板性能的影响

随着木材工业的快速发展,以及木材原料的日益减少,利用农作物秸秆代替木材生产复合材料十分必要。 本文以水稻秸秆为原料,以脲醛树脂为粘合剂,通过湿热法、偶联剂表面化学改性的方法,对秸秆表面进行改性,从而提高了树脂和秸秆之间的结合力,探索了水稻秸秆板的制作工艺。 实验表明较好的制备工艺为:温度150 ℃,压强15 MPa,热压时间8 min,树脂胶粉和水的质量比为1:1,脲醛树脂胶含量为15%(质量分数),发现秸秆表面预处理采用γ-缩水甘油醚氧丙基三甲氧基硅烷(KH560)偶联剂后,所制得的秸秆板的诸多性能优于未经预处理及采用γ-氨丙基三乙氧基硅烷(KH550)进行改性后所制的秸秆板。     

Silica dispersion and properties of silica filled ESBR/BR/NR ternary blend composites by applying wet masterbatch technology

Silica is used as a reinforcing filler in the rubber product such as a tire. When silica contents increased in the composite, deterioration of the processability and silica dispersion in silica-rubber composites cannot be overcome only by adding a silane coupling agent. Therefore, silica wet-masterbatch (WMB) technology is considered for manufacturing highly silica filled composites. Herein, we investigated silica dispersion, cure behavior, mechanical properties, abrasion characteristics, and viscoelastic properties of 3 types of WMB blend composites. Up to 82% improvement in silica dispersion was determined by the Payne effect and confirmed by atomic-force microscopy. The tensile strength and elongation at break increased and tan δ at 60 °C decreased by improving silica dispersion. The silica WMB is suitable for manufacturing highly silica filled composites.     

Filler-elastomer interactions: influence of silane coupling agent on crosslink density and thermal stability of silica/rubber composites

In this work, the crosslink density and thermal stability of the silica/rubber composites treated by silane coupling agents, i.e., gamma-aminopropyl triethoxysilane (APS), gamma-chloropropyl trimethoxysilane (CPS), and gamma-methacryloxypropyl trimethoxysilane (MPS), were investigated. The chemical structures of modified silicas were studied in term of solid-state 29Si NMR spectroscopy. The crosslink density of the composites was determined by swelling measurement. The development of organic functional groups on silica surfaces treated by coupling agents led to an increase in the crosslink density of the composites, resulting in increasing final thermal stability of the composites. The composites treated by MPS showed the superior crosslink density and thermal stability in these systems. The results could be explained by the fact that the organic functional groups of silica surfaces by silane surface treatments led to an increase of the adhesion at interfaces between silicas and the rubber matrix.     

Surface modification of silica nanoparticles by a polyoxyethylene sorbitan and silane coupling agent to prepare high-performance rubber composites

The interfacial interaction between nano-silica and rubber matrix is very important for the preparation of high-performance rubber composites. In this paper, we first proposed the use of TWEEN-20 as a new silica modifier, it has four long arms consisting of three polyether chains with terminal hydroxyl group and a fatty chain. The oxygen on the polyether can form a hydrogen bond with the silanol groups on silica surface, and the terminal hydroxyl groups can chemically react with the silanol groups without any VOCs. Moreover, the long fatty chain can weaken silica polarity to obtain a better compatibility with rubber, so that silica modified by TWEEN-20 with chemical reaction and physical absorption can homogeneously disperses in rubber matrix. Nextly, we prepared high-performance natural rubber (NR) composites by adjusting the ratio of TWEEN-20 to TESPT to adjust the physical and chemical interaction between nano-silica and rubber molecular chains. The results indicated that the performances, including the filler dispersion, static mechanical properties, and dynamic heating (viscoelastic self-heating), were optimal when the ratio of TESPT to TWEEN-20 was 2:1. In addition, one-third of TESPT was replaced by TWEEN-20 to prepare silica/rubber composites, which can reduce one-third of VOCs, improve “scorchy”, and achieve high dispersion of silica.     

Effect of sol–gel derived in situ silica on the morphology and mechanical behavior of natural rubber and acrylonitrile butadiene rubber blends

Silica particles were generated and grown in situ by sol–gel method into rubber blends comprised of natural rubber (NR) and acrylonitrile butadiene rubber (NBR) at various blend ratios. Silica formed into rubber matrix was amorphous in nature. Amount of in situ silica increased with increase in natural rubber proportion in the blends during the sol–gel process. Morphology studies showed that the generated in situ silica were nanoparticles of different shapes and sizes mostly grown into the NR phase of the blends. In situ silica filled NR/NBR blend composites showed improvement in the mechanical and dynamic mechanical behaviors in comparison to those of the unfilled and externally filled NR/NBR blend composites. For the NR/NBR blend at 40/60 composition, in particular, the improvement was appreciable where size and dispersion of the silica particles into the rubber matrix were found to be more uniform. Dynamic mechanical analysis revealed a strong rubber–in situ silica interaction as indicated by a positive shift of the glass transition temperature of both the rubber phases in the blends.     

Plasma polymerization of acetylene onto silica: an approach to control the distribution of silica in single elastomers and immiscible blends

Surface modification of silica by acetylene plasma polymerization is applied in order to improve the dispersion in and compatibility with single rubbers and their blends. Silica, used as a reinforcing filler for elastomers, is coated with a polyacetylene (PA) film under vacuum conditions. Water penetration measurements show a change in surface energy due to the PA‐film deposition. The weight loss measured by thermo‐gravimetric analysis (TGA) is higher for the PA‐coated silica compared to the untreated filler, confirming the deposition of the PA film on the silica surface. Time of flight‐secondary ion mass spectrometry (ToF‐SIMS) shows the well‐defined PA cluster peaks in the high mass region. Scanning electron microscopy (SEM) measurements show silica aggregates, coalesced by the coating with smooth and uniform surfaces, but without significant change in specific surface area. Elemental analysis by energy dispersive X‐ray spectroscopy (EDX) measurements also confirms the deposition of the polymeric film on the silica surface, as the carbon content is increased. The performance of single polymers and their incompatible blends based on S‐SBR and EPDM, filled with untreated, PA‐ and silane‐treated silica, is investigated by measurements of the bound rubber content, weight loss related to bound rubber, cure kinetics, reinforcement parameter, Payne effect, and mechanical properties. The PA‐ and silane‐modified silica‐filled pure S‐SBR and EPDM samples show a lower filler–filler networking compared to the unmodified silica‐filled elastomers. Decrease in the reinforcement parameter (α_F) for the plasma‐polymerized silica‐filled samples also proves a better dispersion compared to silane‐modified and untreated silica‐filled samples. On the other hand, the PA‐silica‐filled samples show a higher bound rubber content due to stronger filler–polymer interactions. Finally, the PA‐silica‐filled pure EPDM and S‐SBR/EPDM blends show high tensile strength and elongation at break values, considered to be the result of best dispersion and compatibilization with EPDM. Copyright © 2008 John Wiley & Sons, Ltd.     

Structure and properties of star‐shaped solution‐polymerized styrene‐butadiene rubber and its co‐coagulated rubber filled with silica/carbon black‐I: morphological structure and mechanical properties

The morphological structure and mechanical properties of the star‐shaped solution‐polymerized styrene‐butadiene rubber (SSBR) and organically modified nanosilica powder/star‐shaped SSBR co‐coagulated rubber (N‐SSBR) both filled with silica/carbon black (CB) were studied. The results showed that, compared with SSBR, silica powder could be mixed into N‐SSBR much more rapidly, and N‐SSBR/SiO₂ nanocomposite had better filler‐dispersion and processability. N‐SSBR/SiO₂/CB vulcanizates displayed higher glass‐transition temperature and lower peak value of internal friction loss than SSBR/SiO₂/CB vulcanizates. In the N‐SSBR/SiO₂/CB vulcanizates, filler was dispersed in nano‐scale resulting in good mechanical properties. Composites filled with silica/CB doped filler exhibited more excellent mechanical properties than those filled with a single filler because of the better filler‐dispersion and stronger interfacial interaction with macromolecular chains. N‐SSBR/SiO₂/CB vulcanizates exhibited preferable performance in abrasion resistance and higher bound rubber content as the blending ratio of silica to CB was 20:30. Copyright © 2008 John Wiley & Sons, Ltd.     

Development of Natural Rubber-Fibrous Nano Clay Attapulgite Composites: The Effect of Chemical Treatment of Filler on Mechanical and Dynamic Mechanical Properties of Composites

Common nano clay fillers have layered structure. Some nano clays like Attapulgite (AT), Sepiolite have rod like fibrous structure. Compared to layered structured clay fibrous clay AT can undergo better dispersion in polymer matrix leading to better improvement in composite properties. Chemical modifications of AT are done through amine treatment as well as by amine+silane treatment to get chemically modified fillers AAT and SAT respectively. In the present investigation, nano composites are prepared using natural rubber (NR) filled with AT, AAT and SAT. Three different loadings of each filler are used namely 2.5, 5, and 10 phr (parts per hundred of rubber). Mechanical properties like tensile strength, elongation at break increase with the increase in filler loading up to 5 phr there after these properties marginally fall when loading is increased to 10 phr due to problem of filler dispersion at higher loading. However, modulus at 300% elongation and tear strength increases with the increase in filler loading up to 10 phr. Very similar trend can also be observed for composites with chemically modified fillers, AAT and SAT. But the degree of reinforcement is higher in the case of AAT and SAT compared to that of unmodified filler AT for the same filler loading. This difference is mainly due to better polymer-filler interaction and filler dispersion in the case of chemically modified clays AAT and SAT compared to unmodified AT. Tear strength of composites increases remarkably with the addition of AT and which is further enhanced when chemically modified clays AAT and SAT are added. Dynamic-mechanical analyses of different clay composites give idea about the difference in the degree of polymer–filler interaction due to chemical treatment of filler.