Tailored and Functionalized Polyolefin Structures via Metathesis Polycondensation Chemistry

通过复分解缩聚化学定制和功能化聚烯烃结构

• 批准号: 0314110
• 负责人: K. Wagener
• 金额: --
• 依托单位: University of Florida
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2003
• 资助国家: 美国
• 起止时间: 2003-07-01 至 2007-12-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0314110&HistoricalAwards=false
• 关键词: Tailored; Functionalized; Polyolefin; Structures; via

Acyclic diene metathesis polymerization will be employed in the pursuit of 4 research objectives: to define structure property relationships in branched polyethylene and related (functionalized) materials, to create a set of "Bio-Olefins" for tissue engineering and other bioapplications, to explore solid state metathesis chemistry, and to continue to expand the catalyst base for this metathesis oriented polycondensation chemistry. Precision synthesis techniques based on ADMET chemistry will be used to create branched polyethylene, where the branch identity and frequency can be controlled in an exact manner. Completely new functionalized versions of polyethylene will be made, and the structure/property relationships of these model ADMET polymers will be examined. Doing so will set clear goals for the generation of useful functionalized polyethylene structures. Collaborations on this aspect of the research are established with two industrial research laboratories in the USA in addition to the University of Pennsylvania and the Max Planck Institute for Polymer Research in Germany. Polyolefins containing amino acid and dipeptide branches have been made via this condensation chemistry, polymers which readily crystallize thus rendering them as durable materials for biomedical applications. Attaching known biologically active peptide sequences to the polyolefin backbone will advance this research. The biological activity of these materials will be examined in collaboration with two separate research groups, one at the University of Florida and the other at MIT; higher order structures within these polymers will be accessed via collaboration with Kyoto University in Japan. Solid-state metathesis polymerization thus far has produced the first known metathesis polycondensation chemistry occurring at room temperature. This facile method of polymer synthesis may prove useful in generating otherwise intractable polymer structures, some of which are conjugated in nature. Collaborations regarding this aspect of the work are in place with the research group at the University of Florida that investigates conjugated polymer systems. The catalyst base for ADMET chemistry will continue at a low level. Metathesis catalyst research, which is being done in several organometallic laboratories around the world, benefits ADMET chemistry; the metathesis catalyst work done within this project is being tailored especially for metathesis polycondensation.Polyethylene is the largest volume plastic made in the world, with a demand for more than 110 billion pounds produced in the year 2000 alone. Its impact on society is obvious and important, and so conducting research on polyethylene and related materials can influence a large number of people. This research is designed to strengthen the utility of polyethylene further by understanding fundamental issues associated with crystallization of this material, by synthesizing functionalized versions, and by expanding into tissue engineering, drug delivery, and other biomedical applications. Amino acids and peptides are being attached to the backbone of the plastic to create this new class of biomaterials. The research provides an intensive educational and training basis for undergraduate, Masters, and PhD students in chemistry and materials science. Included in the plan are several collaborations with other research groups in the USA, Germany, and Japan. These interactions will broaden the student's exposure beyond the University of Florida and our nation.

无环二烯复分解聚合将在追求4个研究目标：确定支链聚乙烯和相关（功能化）材料的结构性质关系，创建一套用于组织工程和其他生物应用的“生物烯烃”，探索固态复分解化学，并继续扩大这种面向复分解的缩聚化学的催化剂基础。基于ADMET化学的精密合成技术将用于制造支链聚乙烯，其中分支的身份和频率可以以精确的方式控制。全新的聚乙烯功能化版本将被制造出来，这些模型ADMET聚合物的结构/性质关系将被检查。这样做将为产生有用的功能化聚乙烯结构设定明确的目标。除了宾夕法尼亚大学和德国马克斯普朗克聚合物研究所外，还与美国的两个工业研究实验室建立了这方面的研究合作。含有氨基酸和二肽分支的聚烯烃已经通过这种缩合化学制成，这种聚合物易于结晶，从而使它们成为生物医学应用的耐用材料。将已知的具有生物活性的肽序列连接到聚烯烃主链上将会推进这一研究。这些材料的生物活性将与两个独立的研究小组合作进行研究，一个在佛罗里达大学，另一个在麻省理工学院；这些聚合物中的高阶结构将通过与日本京都大学的合作获得。固态复分解聚合迄今为止已经产生了已知的第一个在室温下发生的复分解缩聚化学。这种简单的聚合物合成方法可能被证明可用于生成其他难以处理的聚合物结构，其中一些本质上是共轭的。关于这方面工作的合作是与佛罗里达大学研究共轭聚合物系统的研究小组进行的。ADMET化学的催化剂碱将继续保持在低水平。世界上几个有机金属实验室正在进行的复分解催化剂研究使ADMET化学受益；在这个项目中所做的分解催化剂工作是专门为分解缩聚而定制的。聚乙烯是世界上产量最大的塑料，仅2000年一年的需求量就超过1100亿磅。它对社会的影响是明显而重要的，因此对聚乙烯及其相关材料的研究可以影响到很多人。本研究旨在通过了解与该材料结晶相关的基本问题，通过合成功能化版本，并通过扩展到组织工程，药物输送和其他生物医学应用，进一步加强聚乙烯的实用性。氨基酸和多肽被附着在塑料的主干上，从而创造了这种新型的生物材料。本研究为化学与材料科学专业的本科生、硕士生和博士生提供了密集的教育和培训基础。该计划包括与美国、德国和日本的其他研究小组的几项合作。这些互动将扩大学生在佛罗里达大学和我们国家之外的曝光。