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Title: Rational Design of Efficient Amine Reductant Initiators for Amine–Peroxide Redox Polymerization

Abstract

Amine-peroxide redox polymerization (APRP) has been highly prevalent in industrial and medical applications since the 1950s, yet the initiation mechanism of this radical polymerization process is poorly understood so that innovations in the field are largely empirically driven and incremental. Through a combination of computational prediction and experimental analysis, we elucidate the mechanism of this important redox reaction between amines and benzoyl peroxide for the ambient production of initiating radicals. Our calculations show that APRP proceeds through S N 2 attack by the amine on the peroxide but that homolysis of the resulting intermediate is the rate-determining step. We demonstrate a correlation between the computationally predicted initiating rate and the experimentally measured polymerization rate with an R 2 = 0.80. The new mechanistic understanding was then applied to computationally predict amine reductant initiators with faster initiating kinetics. This led to our discovery of N-(4-methoxyphenyl)pyrrolidine (MPP) as amine reductant, which we confirmed significantly outperforms current state-of-the-art tertiary aromatic amines by ~20-fold, making it the most efficient amine-peroxide redox initiator to date. The application of amines with superior kinetics such as MPP in APRP could greatly accelerate existing industrial processes, facilitate new industrial manufacturing methods, and improve biocompatibility in biomedical applications conductedmore » with reduced initiator concentrations yet higher overall efficiency.« less

Authors:
 [1];  [1];  [1];  [1];  [1];  [1];  [2];  [3];  [2]
  1. Univ. of Colorado, Boulder, CO (United States)
  2. Univ. of Colorado, Boulder, CO (United States); National Renewable Energy Lab. (NREL), Golden, CO (United States)
  3. Univ. of Colorado, Boulder, CO (United States); Univ. of Colorado, Denver, CO (United States)
Publication Date:
Research Org.:
National Renewable Energy Lab. (NREL), Golden, CO (United States)
Sponsoring Org.:
National Science Foundation (NSF)
OSTI Identifier:
1508958
Report Number(s):
NREL/JA-5K00-73770
Journal ID: ISSN 0002-7863
Grant/Contract Number:  
AC36-08GO28308
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 141; Journal Issue: 15; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; redox reactions; polymerization; amine-peroxide redox polymerization; APRP

Citation Formats

Kim, Kangmin, Singstock, Nicholas R., Childress, Kimberly K., Sinha, Jasmine, Salazar, Austyn M., Whitfield, Savannah N., Holder, Aaron M., Stansbury, Jeffrey W., and Musgrave, Charles B. Rational Design of Efficient Amine Reductant Initiators for Amine–Peroxide Redox Polymerization. United States: N. p., 2019. Web. doi:10.1021/jacs.8b13679.
Kim, Kangmin, Singstock, Nicholas R., Childress, Kimberly K., Sinha, Jasmine, Salazar, Austyn M., Whitfield, Savannah N., Holder, Aaron M., Stansbury, Jeffrey W., & Musgrave, Charles B. Rational Design of Efficient Amine Reductant Initiators for Amine–Peroxide Redox Polymerization. United States. doi:10.1021/jacs.8b13679.
Kim, Kangmin, Singstock, Nicholas R., Childress, Kimberly K., Sinha, Jasmine, Salazar, Austyn M., Whitfield, Savannah N., Holder, Aaron M., Stansbury, Jeffrey W., and Musgrave, Charles B. Wed . "Rational Design of Efficient Amine Reductant Initiators for Amine–Peroxide Redox Polymerization". United States. doi:10.1021/jacs.8b13679.
@article{osti_1508958,
title = {Rational Design of Efficient Amine Reductant Initiators for Amine–Peroxide Redox Polymerization},
author = {Kim, Kangmin and Singstock, Nicholas R. and Childress, Kimberly K. and Sinha, Jasmine and Salazar, Austyn M. and Whitfield, Savannah N. and Holder, Aaron M. and Stansbury, Jeffrey W. and Musgrave, Charles B.},
abstractNote = {Amine-peroxide redox polymerization (APRP) has been highly prevalent in industrial and medical applications since the 1950s, yet the initiation mechanism of this radical polymerization process is poorly understood so that innovations in the field are largely empirically driven and incremental. Through a combination of computational prediction and experimental analysis, we elucidate the mechanism of this important redox reaction between amines and benzoyl peroxide for the ambient production of initiating radicals. Our calculations show that APRP proceeds through SN2 attack by the amine on the peroxide but that homolysis of the resulting intermediate is the rate-determining step. We demonstrate a correlation between the computationally predicted initiating rate and the experimentally measured polymerization rate with an R2 = 0.80. The new mechanistic understanding was then applied to computationally predict amine reductant initiators with faster initiating kinetics. This led to our discovery of N-(4-methoxyphenyl)pyrrolidine (MPP) as amine reductant, which we confirmed significantly outperforms current state-of-the-art tertiary aromatic amines by ~20-fold, making it the most efficient amine-peroxide redox initiator to date. The application of amines with superior kinetics such as MPP in APRP could greatly accelerate existing industrial processes, facilitate new industrial manufacturing methods, and improve biocompatibility in biomedical applications conducted with reduced initiator concentrations yet higher overall efficiency.},
doi = {10.1021/jacs.8b13679},
journal = {Journal of the American Chemical Society},
number = 15,
volume = 141,
place = {United States},
year = {2019},
month = {3}
}

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This content will become publicly available on March 27, 2020
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