CAREER: Hydrophilic and Hydrophobic Polymers from Boron-Containing Polyolefins

职业：含硼聚烯烃的亲水性和疏水性聚合物

• 批准号: 1752791
• 负责人: Rebekka Klausen
• 金额: $ 67.5万
• 依托单位: Johns Hopkins University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2018
• 资助国家: 美国
• 起止时间: 2018-02-01 至 2023-01-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1752791&HistoricalAwards=false
• 关键词: CAREER; Hydrophilic; Hydrophobic; Polymers; Boron

Professor Rebekka Klausen of Johns Hopkins University is supported by the Macromolecular, Supramolecular, and Nanochemistry (MSN) program of the Division of Chemistry to develop a chemical strategy that can turn a hydrophobic (water-hating) polymer into a hydrophilic (water-loving) polymer. This method enables the preparation of structures that contain both hydrophobic and hydrophilic segments in precisely controlled amounts and sequences. Polymers are versatile commodity chemicals commonly found in plastics. The ability to control and change the solvent compatibility of a given plastic has profound implications for its applications. Fundamental insights arising from this project include novel synthetic methods yielding well-defined functional polymers and insights into the relationship of chemical structure and water solubility. The materials prepared under this project are useful in applications in which hydrophobic and hydrophilic materials are combined, such as the efficient recovery of crude oil from oil spills in marine environments or as durable and solvent-resistant adhesives. This research program provides valuable training to undergraduate and graduate students in the preparation and design of industrially relevant materials and supports the integration of academic and industrial scientific relationships through an educational initiative that brings professional chemists to a university setting to discuss their current research and career trajectories. Additional aspects of the educational initiative focus on the recruitment and retention of talented students from diverse backgrounds into Science, Technology, Engineering and Mathematics (STEM) fields.The goal of this research is to control the hydrophobicity of organic polymers by replacing one or more carbon-carbon (CC) bonds with the isosteric, isoelectronic, and polar boron-nitrogen (BN) bond. A novel azaborine vinyl monomer is prepared and its homo- and copolymerization is studied. Reflecting the central role of organoborane chemistry in organic synthesis, postpolymerization functionalization converts the pendant C-B bond to a C-OH bond. In the course of this work, fundamental research into the reactive intermediate chemistry of unconventional aromatic structures is pursued, novel functional polyolefins are prepared, and structure-dependent properties are elucidated. The methods to be used include organic synthesis, polymerization chemistry, and tools for the characterization of physical properties. The project integrates research and educational endeavors by supporting: (1) a career and professional development seminar series in Baltimore, (2) promoting training and learning in industrially-relevant polymer science, and (3) broadening the participation of underrepresented groups through a summer undergraduate research stipend.

约翰·霍普金斯大学的Rebekka Klausen教授在化学系高分子、超分子和纳米化学(MSN)计划的支持下，开发了一种化学策略，可以将疏水(憎水)聚合物转变为亲水(亲水)聚合物。这种方法能够制备以精确控制的量和序列同时包含疏水和亲水片段的结构。聚合物是一种通用的商品化学品，通常存在于塑料中。控制和改变特定塑料的溶剂相容性的能力对其应用具有深远的影响。该项目产生的基本见解包括产生定义明确的功能聚合物的新合成方法，以及对化学结构和水溶解度关系的见解。根据该项目制备的材料在将疏水和亲水材料结合在一起的应用中很有用，例如从海洋环境中的石油泄漏中有效地回收原油，或者用作耐久和耐溶剂的粘合剂。这一研究计划为本科生和研究生提供有价值的培训，帮助他们准备和设计与工业相关的材料，并通过一项教育倡议，将专业化学家带到大学环境中讨论他们目前的研究和职业轨迹，支持学术和工业科学关系的整合。这项教育计划的其他方面侧重于招募和留住来自不同背景的有才华的学生进入科学、技术、工程和数学(STEM)领域。这项研究的目标是通过将一个或多个碳-碳(CC)键替换为等立构、等电子和极性的硼-氮(BN)键来控制有机聚合物的疏水性。合成了一种新型氮杂环乙烯基单体，并对其均聚和共聚进行了研究。后聚合官能化反应反映了有机硼烷化学在有机合成中的中心作用，将悬垂的C-B键转化为C-OH键。在这项工作中，我们对非常规芳香族结构的反应中间体化学进行了基础研究，合成了新型的官能化聚烯烃，并阐明了与结构有关的性质。使用的方法包括有机合成、聚合化学和表征物理性质的工具。该项目通过支持：(1)巴尔的摩职业和专业发展研讨会系列，(2)促进与工业相关的聚合物科学的培训和学习，以及(3)通过夏季本科生研究津贴扩大代表不足群体的参与，将研究和教育工作结合在一起。

项目成果

Organoborane Strategy for Polymers Bearing Lactone, Ester, and Alcohol Functionality

具有内酯、酯和醇官能团的聚合物的有机硼烷策略

• DOI: 10.1021/acs.macromol.9b02201
• 发表时间: 2019
• 期刊: Macromolecules
• 影响因子: 5.5
• 作者: Ji, Yuyang;Zhou, Tiffany;van de Wouw, Heidi L.;Klausen, Rebekka S.
• 通讯作者: Klausen, Rebekka S.

Azaborine benzylic ion stability and reactivity in ionic polymerization

离子聚合中氮杂硼啉苄基离子的稳定性和反应活性

• DOI: 10.1039/d1ob02467a
• 发表时间: 2022
• 期刊: Organic & Biomolecular Chemistry
• 影响因子: 3.2
• 作者: Wakefield IV, Herbert;Jiang, Qifeng;Klausen, Rebekka S.
• 通讯作者: Klausen, Rebekka S.

Syndioselective Polymerization of a BN Aromatic Vinyl Monomer

• DOI: 10.1021/acs.macromol.8b01707
• 发表时间: 2018-09-11
• 期刊: MACROMOLECULES
• 影响因子: 5.5
• 作者: Mendis, Shehani N.;Zhou, Tiffany;Klausen, Rebekka S.
• 通讯作者: Klausen, Rebekka S.

Characterization of Styrene–Vinyl Alcohol Copolymers by CP-MAS NMR Spectroscopy

• DOI: 10.1021/acs.macromol.2c01009
• 发表时间: 2022-08
• 期刊: Macromolecules
• 影响因子: 5.5
• 作者: Yuyang Ji;Jonathan Catazaro;Qifeng Jiang;Sophia J. Melvin;Jennifer Jiang;R. Klausen

An Organoborane Vinyl Monomer with Styrene-like Radical Reactivity: Reactivity Ratios and Role of Aromaticity

• DOI: 10.1021/acs.macromol.8b01368
• 发表时间: 2018-08
• 期刊: Macromolecules
• 影响因子: 5.5
• 作者: H. L. van de Wouw;Elorm C Awuyah;Jodie I. Baris;R. Klausen