CAREER:SusChEM: Design and Discovery of Polymers with Pendant Rings for Membrane Gas Separations

职业：SusChEM：用于膜气体分离的带有悬垂环的聚合物的设计和发现

• 批准号: 1554236
• 负责人: Haiqing Lin
• 金额: $ 50万
• 依托单位: SUNY at Buffalo
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2016
• 资助国家: 美国
• 起止时间: 2016-03-01 至 2022-02-28
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1554236&HistoricalAwards=false
• 关键词: CAREER; SusChEM; Design; Discovery; Polymers

CAREER 1554236-LinMembrane technology has emerged as an important gas separation technology due to simplicity of operation, compactness, modularity, and high energy efficiency. However, the available membranes for important applications such as CO2/CH4 and C3H6/C3H8 separations are restricted by their deteriorated separation performance when made into industrial thin films operating in the presence of strongly plasticizing components of CO2 and heavy hydrocarbons. These polymers may have superior pure-gas separation performance in thick films of 20 µm or more. However, in the thin films of ~100 nm for industrial composite membranes, these polymers show gas permeability rapidly decreasing with time (i.e., aging). The CO2 and hydrocarbons swell the polymer matrix (i.e., plasticization), leading to weaker size sieving ability and reduced gas selectivity. This project will address these issues by developing a molecular-based mechanistic understanding of the relationship between the polymer structure and thin film properties including permeability, selectivity, aging and plasticization. The integrated educational activities are expected to achieve the following benefits: (a) an educational module for teachers and their students in middle school and high school in the Buffalo Public Schools (a district with a large fraction of students whose background is underrepresented in STEM fields) on membrane technology to solve global climate change; (b) an ongoing polymer workshop to promote the interdisciplinary collaboration on the Buffalo campus and in the Western New York area; (c) improvement in the core courses of Heat and Mass Transfer and Materials Characterization to stimulate students? interests in membrane research; and (d) interdisciplinary training opportunities in polymer synthesis, characterization, membrane separation and modeling for students at the undergraduate and graduate level. The research project will elucidate the effect of polymer pendant rings and crosslinking in the advanced polymeric materials on membrane gas separation properties, including gas permeability and selectivity, thin film stability against aging, and stability against hydrocarbon induced plasticization. These bulky pendent rings disrupt the polymer chain packing, leading to high free volume and permeability, and they are also expected to slow the chain motion, reducing densification or physical aging. The size of the rings will be conveniently tuned during the chemical synthesis, and substituents will be introduced to rationally design the structure. A bottom-up design of crosslinking networks will be generated, which are expected to be resistant to plasticization. A modified free volume model will be used to elucidate the effect of aging and plasticization on membrane separation properties. This interdisciplinary research program integrating materials discovery, synthesis, characterization, modeling and applications will enrich the fundamental understanding of polymer structure/property correlation for membrane gas separation. It is anticipated that the technical approach and materials design guidelines derived from this project will be directly applied to the development of industrial membranes for energy-efficient gas separation. This CAREER project is also expected to enhance students? awareness of materials design and discovery to solve important practical problems.

CAREER 1554236-Lin膜技术由于操作简单、紧凑、模块化和高能效而成为一种重要的气体分离技术，但是，用于 CO2/CH4 和 C3H6/C3H8 分离等重要应用的可用膜受到其自身性能的限制。当制成工业强薄膜时，在二氧化碳和重质烃的增塑成分存在下，分离性能会降低。这些聚合物在厚膜中可能具有优异的纯气体分离性能。然而，在工业复合膜的约 100 nm 薄膜中，这些聚合物的透气性随着时间的推移而迅速降低（即老化），二氧化碳和碳氢化合物会使聚合物基质膨胀（即塑化）。导致尺寸筛分能力变弱和气体选择性降低，该项目将通过对聚合物结构和薄膜特性之间的关系进行基于分子的机理理解来解决这些问题。综合教育活动预计将实现以下效益：(a) 为布法罗公立学校（该地区大部分地区的初中和高中教师及其学生）提供教育模块。 (b) 正在进行的聚合物研讨会，以促进布法罗校区和纽约西部地区的跨学科合作； (c) 改进传热传质和材料核心课程；激发学生对膜研究的兴趣；以及（d）为本科生和研究生提供聚合物合成、表征、膜分离和建模的跨学科培训机会。先进的聚合物材料对膜气体分离性能的影响，包括气体渗透性和选择性、薄膜的抗老化稳定性以及对烃诱导塑化的稳定性。这些庞大的悬环会破坏聚合物链的堆积，从而导致高自由体积和渗透性。它们还有望减缓链运动，减少致密化或物理老化，在化学合成过程中可以方便地调整环的大小，并引入取代基来合理设计交联网络的结构。改进的自由体积模型将用于阐明老化和塑化对膜分离性能的影响，这一集材料发现、合成、表征、建模和应用于一体的跨学科研究项目将丰富这一项目。对膜气体分离聚合物结构/性能相关性的基本了解预计该项目得出的技术方法和材料设计指南将直接应用于节能气体分离工业膜的开发。还期望增强学生的材料设计和发现能力以解决重要的实际问题。

项目成果

Gas transport characteristics of supramolecular networks of metal-coordinated highly branched Poly(ethylene oxide)

金属配位高支化聚环氧乙烷超分子网络的气体传输特性

• DOI: 10.1016/j.memsci.2021.120063
• 发表时间: 2021-11-01
• 期刊: Journal of Membrane Science
• 影响因子: 9.5
• 作者: Taliehsadat Alebrahim;A. Chakraborty;Leiqing Hu;Shalini Patil;Shiwang Cheng;Durga P. Acharya;C. Doherty;A. Hill;Timothy R. Cook;Haiqing Lin
• 通讯作者: Haiqing Lin

Effect of Branch Length on the Structural and Separation Properties of Hyperbranched Poly(1,3-dioxolane)

支链长度对超支化聚(1,3-二氧戊环)结构和分离性能的影响

• DOI: 10.1021/acs.macromol.1c02045.s001
• 发表时间: 2021-12-21
• 期刊: Macromolecules
• 影响因子: 5.5
• 作者: Liang Huang;Wenji Guo;H. Mondal;Skye Schaefer;Thien N. Tran;Shouhong Fan;Yifu Ding;Haiqing Lin
• 通讯作者: Haiqing Lin

Thin-film composite membranes based on hyperbranched poly(ethylene oxide) for CO2/N2 separation

基于超支化聚环氧乙烷的薄膜复合膜用于 CO2/N2 分离

• DOI: 10.1016/j.memsci.2021.120184
• 发表时间: 2022-02
• 期刊: Journal of Membrane Science
• 影响因子: 9.5
• 作者: Zhang, Gengyi;Tran, Thien N.;Huang, Liang;Deng, Erda;Blevins, Adrienne;Guo, Wenji;Ding, Yifu;Lin, Haiqing
• 通讯作者: Lin, Haiqing

Superior CO2/N2 separation performance of highly branched Poly(1,3 dioxolane) plasticized by polyethylene glycol

聚乙二醇增塑的高支化聚(1,3二氧戊环)优异的CO2/N2分离性能

• DOI: 10.1016/j.memsci.2022.120352
• 发表时间: 2022-04
• 期刊: Journal of Membrane Science
• 影响因子: 9.5
• 作者: Guo, Wenji;Tran, Thien N.;Mondal, Himangshu;Schaefer, Skye;Huang, Liang;Lin, Haiqing
• 通讯作者: Lin, Haiqing

Mixed matrix membranes for post-combustion carbon capture: From materials design to membrane engineering

用于燃烧后碳捕获的混合基质膜：从材料设计到膜工程

• DOI: 10.1016/j.memsci.2021.120140
• 发表时间: 2022-02
• 期刊: Journal of Membrane Science
• 影响因子: 9.5
• 作者: Hu, Leiqing;Clark, Krysta;Alebrahim, Taliehsadat;Lin, Haiqing
• 通讯作者: Lin, Haiqing