Tailored Chain Sequences of Pendant Functional Groups and Resulting Phase Behavior of Gel-State Functionalized Blocky Copolymers

侧链官能团的定制链序列和凝胶态官能化嵌段共聚物的相行为

• 批准号: 1809291
• 负责人: Robert Moore
• 金额: $ 45.01万
• 依托单位: Virginia Polytechnic Institute and State University
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2018
• 资助国家: 美国
• 起止时间: 2018-06-01 至 2021-12-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1809291&HistoricalAwards=false
• 关键词: Tailored; Chain; Sequences; Pendant; Functional

PART 1: NON-TECHNICAL SUMMARYBlock copolymers are a unique class of long chain molecules (polymers) that are made up of two different chains (blocks) attached together at one of their ends. If the blocks possess distinctly different chemical properties, then they may be capable of self-assembling into well-ordered physical structures that impart material properties that are very different, and often better, than the properties of the individual blocks alone. Unfortunately, the chemical synthesis of block copolymers is generally much more complicated, energy intensive, and expensive compared to that employed in synthesizing a typical commodity polymer of just one block. While polymer chemists have made remarkable progress in developing new ways to synthesize block copolymers, commercial success has been limited and often relegated to applications in high-cost fields such as advanced medical devices or semiconductor manufacture. In this project, a new physical approach will be used to create blocky copolymers in a straightforward, economically-attractive fashion by selectively modifying specific sequences of units along the chains of commercially available polymers. The breakthrough approach here involves performing chemistry in the gel state, whereby specific portions of the chains are essentially hidden from the modifying chemistry. This research will provide significant advancements in accelerating the creation of tailored block copolymer assemblies and enhance fundamental insight toward next-generation membrane technologies. With respect to the grand challenges facing our society, this project will provide cost-effective, readily available alternative materials needed to meet critical demands for water purification membranes, fuel cell membranes for clean energy conversion, and environmentally-friendly materials for the medical and healthcare industries. The interdisciplinary nature of research activities in this project, ranging from pure chemistry to materials structure and properties, will provide a plethora of educational opportunities to a diverse community of students and researchers eager to contribute to our nation's leadership in a scientifically and technologically advanced society.PART 2: TECHNICAL SUMMARYThis project will focus on a new way to create blocky copolymers using straightforward, post polymerization chemistries on semi-crystalline homopolymers in the gel state. With reactions upon only the accessible amorphous chain segments within the semi-crystalline network, this new physical process yields a non-random, blocky incorporation of functionality, and is a simple alternative to the complex polymerization mechanisms that are conventionally employed in the synthesis of block copolymers. Building upon recent discoveries that semi-crystalline polymers, such as syndiotactic polystyrene and poly(ether ether ketone), can be brominated in the heterogeneous gel-state as a simple way to create blocky copolymers with tailored sequence distributions, this project aims to engage a wealth of substitution chemistries available with brominated aromatic templates to create a wide variety of new blocky copolymers as a means to systematically manipulate phase behavior and thus the formation of ordered morphologies with tailored properties. In addition to the substitution chemistries, the morphological parameters of the semi-crystalline gel will be altered by controlled temperature, concentration, and solvent to precisely affect the sequences of functionalized and non-functionalized chain segments. The grand challenge to be addressed in this project will be: Can we now direct the formation of ordered phase-separated domains, similar to that observed with conventional block copolymers, by tailoring the chemical composition of these new, gel-state functionalized, blocky copolymer systems? Membranes of the blocky copolymers will be architecturally tailored for energy conversion and water purification applications. The interdisciplinary nature of research activities in this project, ranging from pure chemistry to materials structure and properties, will help to educate a diverse community of researchers, including underrepresented groups. Educational outreach activities will engage citizens of all ages through the focus on cutting-edge research aimed at ensuring a healthier, more energy-efficient global society.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

第一部分：非技术概述嵌段共聚物是一类独特的长链分子（聚合物），其由两个不同的链（嵌段）在其一端连接在一起构成。 如果嵌段具有明显不同的化学性质，那么它们可能能够自组装成有序的物理结构，赋予材料性质，这些性质与单独的单个嵌段的性质非常不同，并且通常更好。 不幸的是，嵌段共聚物的化学合成与合成仅一个嵌段的典型商品聚合物中所采用的化学合成相比通常复杂得多、能量密集且昂贵得多。 虽然聚合物化学家在开发合成嵌段共聚物的新方法方面取得了显着进展，但商业上的成功有限，并且通常被降级为高成本领域的应用，如先进的医疗设备或半导体制造。 在这个项目中，一种新的物理方法将被用来创造嵌段共聚物在一个简单的，经济上有吸引力的方式，通过选择性地修改特定序列的单元沿着链的商业聚合物。 这里的突破性方法涉及在凝胶状态下进行化学反应，由此链的特定部分基本上隐藏在改性化学物质之外。 这项研究将在加速定制嵌段共聚物组件的创建方面提供重大进展，并增强对下一代膜技术的基本见解。 对于我们社会面临的巨大挑战，该项目将提供具有成本效益的，现成的替代材料，以满足水净化膜，清洁能源转换燃料电池膜以及医疗和保健行业的环保材料的关键需求。 该项目的研究活动具有跨学科性质，从纯化学到材料结构和性质，将为渴望为我国在科学和技术先进社会中的领导地位做出贡献的多样化的学生和研究人员提供大量的教育机会。技术总结该项目将集中在一种新的方法来创建嵌段共聚物使用简单的，后聚合化学的半结晶均聚物在凝胶状态。通过仅在半结晶网络内的可接近的无定形链段上进行反应，这种新的物理过程产生非随机的嵌段官能团并入，并且是常规用于合成嵌段共聚物的复杂聚合机理的简单替代。基于最近的发现，半结晶聚合物，如间规聚苯乙烯和聚（醚醚酮），可以以非均相凝胶状态溴化，作为产生具有定制序列分布的嵌段共聚物的简单方法，该项目旨在利用溴化芳香族模板的大量替代化学物质来创建各种各样的新嵌段共聚物，作为系统地操纵相的手段。行为，从而形成具有定制性质的有序形态。 除了取代化学之外，半结晶凝胶的形态参数将通过控制温度、浓度和溶剂来改变，以精确地影响官能化和非官能化链段的序列。 在这个项目中要解决的重大挑战将是：我们现在可以直接形成有序的相分离域，与传统的嵌段共聚物观察到的类似，通过定制这些新的，凝胶状态官能化，嵌段共聚物系统的化学组成？嵌段共聚物的膜将在结构上适合于能量转换和水净化应用。 该项目研究活动的跨学科性质，从纯化学到材料结构和性质，将有助于教育多样化的研究人员社区，包括代表性不足的群体。 教育推广活动将通过关注旨在确保更健康，更节能的全球社会的尖端研究来吸引所有年龄段的公民。该奖项反映了NSF的法定使命，并通过使用基金会的知识价值和更广泛的影响审查标准进行评估而被认为值得支持。

项目成果

Phosphonium-Based Polyzwitterions: Influence of Ionic Structure and Association on Mechanical Properties

• DOI: 10.1021/acs.macromol.0c02166
• 发表时间: 2020-12
• 期刊: Macromolecules
• 影响因子: 5.5
• 作者: Philip J. Scott;G. Spiering;Yangyang Wang;Z. Seibers;R. Moore;R. Kumar;B. Lokitz;T. Long

Blocky bromination of syndiotactic polystyrene via post-polymerization functionalization in the heterogeneous gel state

• DOI: 10.1039/c8py01008k
• 发表时间: 2018-10
• 期刊: Polymer Chemistry
• 影响因子: 4.6
• 作者: Kristen F. Noble;A. M. Noble;S. Talley;R. Moore

Compatibilization of Polyester/Polyamide Blends with a Phosphonated Poly(ethylene terephthalate) Ionomer: Comparison of Monovalent and Divalent Pendant Ions

聚酯/聚酰胺共混物与膦酸化聚对苯二甲酸乙二醇酯离聚物的相容性：一价和二价悬垂离子的比较

• DOI: 10.1021/acsapm.9b00097
• 发表时间: 2019
• 期刊: ACS Applied Polymer Materials
• 影响因子: 5
• 作者: Ju, Lin;Dennis, Joseph M.;Heifferon, Katherine V.;Long, Timothy E.;Moore, Robert B.
• 通讯作者: Moore, Robert B.

Sulfonation of blocky brominated PEEK to prepare hydrophilic-hydrophobic blocky copolymers for efficient proton conduction

• DOI: 10.1016/j.ssi.2019.03.006
• 发表时间: 2019-08-01
• 期刊: SOLID STATE IONICS
• 影响因子: 3.2
• 作者: Anderson, Lindsey J.;Moore, Robert B.
• 通讯作者: Moore, Robert B.

Synthesis and characterization of a nematic fully aromatic polyester based on biphenyl 3,4′-dicarboxylic acid

• DOI: 10.1039/c9py00683d
• 发表时间: 2019-08-21
• 期刊: POLYMER CHEMISTRY
• 影响因子: 4.6
• 作者: Heifferon, Katherine, V;Spiering, Glenn A.;Long, Timothy E.
• 通讯作者: Long, Timothy E.