Fundamental Study on Organoclay Nanocomposites Based on Functionalized Block Copolymer, Functionalized Liquid-Crystalline Polymer, and Functionalized Polynorbornene

摘要：张东。韩家机构：阿克伦大学提案编号：0406752研究：将研究与实现高度剥离的有机粘土纳米复合材料相关的原理和机制的基本问题。 通过阴离子聚合、羟基化/氧化反应合成端嵌段C带有官能团的二烯类ABC型三嵌段共聚物，通过缩聚反应合成功能化的热致液晶聚合物（TLCP），通过开环易位聚合合成带有羟基、乙酸基或胺基的功能化聚异戊二烯（PNB）。 然后，通过使用微型双螺杆混炼机熔融共混，将每种聚合物与化学改性的有机粘土或有机碳纳米颗粒混合，以产生具有高度剥离的纳米复合材料。 基于二烯的、末端嵌段官能化的ABC型三嵌段弹性体具有优于常规苯乙烯-嵌段-丁二烯共聚物（SB橡胶）的优点，因为可以通过明智地控制ABC型三嵌段共聚物中二烯嵌段的微观结构来获得纳米复合材料的经由非常高程度的剥离而大大改善的机械性能。 基本前提是在有机粘土或有机碳纳米颗粒与聚合物基质之间提供有吸引力的相互作用：官能化ABC型三嵌段共聚物、官能化TLCP或官能化PNB。 将使用原位傅里叶变换红外光谱法测试吸引相互作用的存在。 剥离的程度将使用X-射线衍射，透射电子显微镜，和振荡剪切流变仪进行测试，和纳米复合材料的机械性能（拉伸强度，撕裂强度，动态模量，和冲击强度）将进行研究。 对这些纳米复合材料的形成、结构和动力学的研究可以更好地理解与实现高度剥离的有机粘土纳米复合材料相关的原理和机制，本研究项目的基本概念将有助于其他研究人员通过设计和合成新的聚合物体系或合成可用于改性层状硅酸盐或石墨表面的新型表面活性剂。更广泛的影响：这些活动产生的更广泛影响体现在两个方面：（i）它将激励其他研究人员在坚实的科学基础上开发新一代纳米复合材料，（ii）它将有助于为美国聚合物制造业开辟道路，以生产新的有吸引力和成本效益的新型纳米复合材料，以及（iii）它将帮助价值400亿美元的美国轮胎制造业创新/改变现有的制造工艺，以提高轮胎的撕裂强度和滚动阻力。

ABSTRACTPI: Chang D. Han Institution: University of AkronProposal Number: 0406752Research: Fundamental issues concerning the principles and mechanisms associated with achieving a highly-exfoliated organoclay nanocomposite will be investigated. Diene-based ABC-type triblock copolymers with a functional group in the endblock C will be synthesized via anionic polymerization followed by hydroxylation/oxidation reactions, a functionalized thermotropic liquid-crystalline polymer (TLCP) will be synthesized via condensation polymerization, and functionalized polynorbornenes (PNB) with hydroxyl, acetic, or amine groups will be synthesized via ring opening metathesis polymerization. Then each of the polymers will be mixed, via melt blending using a micro twin-screw compounder, with chemically-modified organoclay or oganocardbon nanoparticles to produce nanocomposites with a high degree of exfoliation. Diene-based, endblock-functionalized ABC-type triblock elastomers have advantages over the conventional styrene-ran-butadiene copolymers (SB rubber) in that greatly improved mechanical properties, via a very high degree of exfoliation, of the nanocomposites can be obtained by judiciously controlling the microstructure of the diene block in an ABC-typle triblock copolymer. The basic premise is to provide attractive interactions between the organoclay or organocarbon nanoparticles and the polymer matrix: functionalized ABC-type triblock copolymer, functionalized TLCP, or functionalized PNB. The presence of attractive interactions will be tested using in-situ Fourier transform infrared spectroscopy. The degree of exfoliation will be tested using X-ray diffraction, transmission electron microscopy, and oscillatory shear rheometry, and the mechanical properties (tensile strength, tear strength, dynamic modulus, and impact strength) of the nanocomposites will be investigated. Investigation of the formation, structure, and dynamics of these nanocomposites can lead to a better understanding of the principles and mechanisms associated with achieving highly-exfoliated organoclay nanocomposites, and potentially to the development of novel nanocomposite materials.The fundamental concepts that will be developed from this research project should help other researchers to develop new nanocomposites either by designing and synthesizing new polymer systems or synthesizing new surfactants that can be used to modify the surfaces of layered silicates or graphite. Broader Impacts: The broader impacts resulting from these activities lie in two areas: (i) it will stimulate other researchers to develop new generations of nanocomposites on the basis of sound scientific foundations, (ii) it will help open avenues for the U.S. polymer fabrication industry to produce new attractive and cost-effective novel nanocomposites, and (iii) it will help the $40 billion U.S. tire manufacturing industry to innovate/alter the existing manufacturing processes for improved tear strength and rolling resistance of tires.