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.

由于操作简单，紧凑，模块化和高能源效率，职业1554236-Linmmbrane技术已成为重要的气体分离技术。但是，重要应用的可用机制，例如CO2/CH4和C3H6/C3H8的分离受到限制，由于其在具有强烈塑化二氧化碳和重型碳氢化合物的强化成分的情况下，其分离性能恶化的分离性能恶化。这些聚合物在20 µm或更多的厚膜中可能具有优质的纯气体分离性能。然而，在工业复合膜的薄膜中，这些聚合物显示出随时间的时间（即衰老）迅速降低的气体通透性。二氧化碳和碳氢化合物膨胀聚合物基质（即增塑），导致尺寸较弱的筛分能力和降低的气体选择性。该项目将通过对聚合物结构与薄膜特性之间的关系（包括渗透率，选择性，衰老和塑性）之间的关系发展基于分子的机械理解来解决这些问题。预计综合的教育活动将获得以下好处：（a）在水牛公立学校中的中学和高中的教师及其学生的教育模块（在STEM领域的背景不足的学生中有很大一部分的学生）在膜技术上的代表性不足，以解决全球气候变化； （b）正在进行的聚合物研讨会，以促进布法罗校园和纽约西部地区的跨学科合作； （c）改进热，传质和材料表征以刺激学生的核心课程？在本科和研究生水平的学生中，在聚合物合成，表征，膜分离和建模的跨学科培训机会中。该研究项目将阐明高级聚合物材料中聚合物吊带环的影响，并在膜气体分离特性中进行交联，包括气体渗透性和选择性，对衰老的薄膜稳定性以及抗碳氢化合物诱导的增塑的稳定性。这些笨重的吊环破坏了聚合物链的堆积，导致了很高的游离体积和渗透性，并且预计它们也会减慢链运动的速度，从而减少致密性或物理衰老。在化学合成过程中，将方便地调整环的尺寸，并将引入子接头以合理设计结构。将产生交联网络的自下而上设计，预计将对增塑具有抵抗力。修改的自由体积模型将用于阐明衰老和增塑对膜分离特性的影响。该跨学科研究计划整合了材料发现，综合，表征，建模和应用，将丰富对聚合物结构/特性相关性的基本理解，用于膜气体分离。预计从该项目得出的技术方法和材料设计指南将直接应用于工业膜的开发，以进行节能气体分离。这个职业项目也有望增强学生？意识到材料设计和发现以解决重要的实际问题。

项目成果

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

• DOI: 10.1016/j.memsci.2021.120140
• 发表时间: 2022-02-15
• 期刊: JOURNAL OF MEMBRANE SCIENCE
• 影响因子: 9.5
• 作者: Hu, Leiqing;Clark, Krysta;Lin, Haiqing
• 通讯作者: Lin, Haiqing

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

• DOI: 10.1016/j.memsci.2021.120184
• 发表时间: 2021-12
• 期刊: Journal of Membrane Science
• 影响因子: 9.5
• 作者: Gengyi Zhang;Thien N. Tran;Liang Huang;E. Deng;Adrienne K. Blevins;Wenji Guo;Yifu Ding;Haiqing Lin

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

• DOI: 10.1016/j.memsci.2021.120063
• 发表时间: 2022-02-15
• 期刊: JOURNAL OF MEMBRANE SCIENCE
• 影响因子: 9.5
• 作者: Alebrahim, Taliehsadat;Chakraborty, Alisa;Lin, Haiqing
• 通讯作者: Lin, Haiqing