Grafting-To and From for Multiplexed Chemical-Warfare-Agent Responsive Polymer Brushes

He, Qilin; Luo, Shao-Xiong Lennon; Jin, Tianyi; Liu, Mingyu; Park, Sohyun; Alexander-Katz, Alfredo; McDonald, Benjamin R.; Fornasiero, Francesco; Swager, Timothy M.

doi:10.1021/acs.chemmater.2c03405

Title: Grafting-To and From for Multiplexed Chemical-Warfare-Agent Responsive Polymer Brushes

Journal Article · Thu Feb 16 00:00:00 EST 2023 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.2c03405· OSTI ID:2005083

^[1];

^[1]; Park, Sohyun ^[1]; Alexander-Katz, Alfredo ^[1]; McDonald, Benjamin R. ^[1];

^[2];

^[1]

Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)

Surface-tethered polymers have important applications in functional polymer coatings, particularly for the development of chemically responsive surfaces. Here, we combined the traditional grafting-to and grafting-from methods to create a new surface grafting strategy, termed grafting-to and from, using surface-initiated ring-opening metathesis polymerization (SI-ROMP). In this method, poly(pentafluorophenyl methacrylate) is grafted to an amine terminated surface. Surplus reactive esters after reaction with surface amines render this polymer a connecting or tie layer that can be further reacted to provide dense ROMP initiation sites. This amplification of grafting sites results in thick and environmentally stable polymer brushes upon SI-ROMP. With the goal of developing polymer-grafted breathable membranes that autonomously react to multiple chemical warfare agents (CWAs), we demonstrate the benefit of this method by employing amine reactive monomers in the grafting-from step. This enables diverse postsynthetic functionalization for the facile screening of chemical motifs to enhance response capabilities to mustard blister agents. Surface-tethered triarylmethanol-containing polymers with four distinct functional groups are prepared and challenged with the vapor of 2-chloroethyl ethyl sulfide (CEES), a simulant of mustard agent, in humid air. Importantly, hydroxyl groups effectively improve CWA response and the resulting polymer brushes show chain collapse after both CEES and diethylchlorophosphate (DCP) treatment. Our results illustrate that the grafting-to and from method can be used to grow functional and robust polymer coatings for various applications.

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Research Organization:: Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA); Defense Threat Reduction Agency Contract; National Institutes of Health (NIH)

Grant/Contract Number:: AC52-07NA27344; HDTRA1-22-1-0005; P30-ES002109

OSTI ID:: 2005083

Report Number(s):: LLNL-JRNL-842920; 1064831

Journal Information:: Chemistry of Materials, Vol. 35, Issue 4; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Title: Grafting-To and From for Multiplexed Chemical-Warfare-Agent Responsive Polymer Brushes

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