Journal article
Oxygen-Initiated Free-Radical Polymerization of Alkyl Acrylates at High Temperatures
Macromolecules, v 54(17), pp 7925-7930
14 Sep 2021
Abstract
Molecular oxygen has been reported to be a strong inhibitor at low temperatures. Here, it is shown that the introduction of oxygen gas into the free-radical polymerization of n-butyl acrylate (nBA) results in high conversion of the monomer in a very short time at temperatures above 140 degrees C without the use of any conventional initiators. By conducting first-principles calculations based on density functional theory, this work for the first time identifies and kinetically studies the most-likely reactions via which molecular oxygen contributes to polymer chain initiation. It provides theoretical and experimental evidence that molecular oxygen acts as a catalyst in alkyl acrylate free-radical polymerization at high temperatures. A triplet diradical intermediate is generated from solvated oxygen reacting with an alkyl acrylate monomer. The intermediate then reacts with another monomer and thermally dissociates from molecular oxygen to proceed toward polymerization. This theoretical finding is supported by laboratory experiments showing that in the presence of a very small amount of molecular oxygen and in the absence of any thermal initiators, free-radical polymerization of nBA occurs sustainably and proceeds to a very high monomer conversion. This work opens a new path for a more economic and sustainable production of higher-quality acrylic polymers using molecular oxygen as an initiator catalyst.
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Details
- Title
- Oxygen-Initiated Free-Radical Polymerization of Alkyl Acrylates at High Temperatures
- Creators
- Shi Liu - University of PennsylvaniaLauren Chua - University of PennsylvaniaAhmad Arabi Shamsabadi - Drexel UniversityPatrick Corcoran - Drexel UniversityAbhirup Patra - Univ Penn, Dept Chem, Philadelphia, PA 19104 USAMichael C. Grady - Axa (United Kingdom)Masoud Soroush - Drexel UniversityAndrew M. Rappe - University of Pennsylvania
- Publication Details
- Macromolecules, v 54(17), pp 7925-7930
- Publisher
- American Chemical Society; Washington, DC
- Number of pages
- 6
- Grant note
- CBET-1803215; CBET-1804285 / U.S. National Science Foundation; National Science Foundation (NSF)
- Resource Type
- Journal article
- Language
- English
- Academic Unit
- Chemical and Biological Engineering
- Web of Science ID
- WOS:000697107700025
- Scopus ID
- 2-s2.0-85114138225
- Other Identifier
- 991019168644804721
InCites Highlights
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- Collaboration types
- Domestic collaboration
- International collaboration
- Web of Science research areas
- Polymer Science