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Title: Phase separation during bulk polymerization of methyl methacrylate

Abstract

We report on the phase separation of methyl methacrylate (MMA) and poly(methyl methacrylate) (PMMA) during bulk free-radical polymerization. The phase separation is induced when the reaction is initiated at room temperature by the redox reaction of benzoyl peroxide in the presence of an amine. During the reaction, the ratio of MMA and PMMA changes continuously. Separation into MMA-rich and PMMA-rich phases coincides with the onset of the Trommsdorff effect. At room temperature, the interface between the two phases remains, even after drying the remaining monomer. When the sample is annealed above the glass transition temperature Tg, the interface disappears. Due to the frozen dynamics of the polymer chains, subsequent cooling below Tg does not result in further phase separation. This result provides evidence for the existence of rich, thermodynamically stable states, which are typically suppressed due to the frozen dynamics of polymers at temperatures below the Tg, after thermal processing above the Tg.

Authors:
ORCiD logo [1];  [2];  [3];  [4];  [3];  [2]
  1. Colorado School of Mines, Golden, CO (United States); Osaka Prefecture Univ. (Japan)
  2. Colorado School of Mines, Golden, CO (United States)
  3. Osaka Prefecture Univ. (Japan)
  4. National Renewable Energy Lab. (NREL), Golden, CO (United States)
Publication Date:
Research Org.:
National Renewable Energy Lab. (NREL), Golden, CO (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Fuel Cell Technologies Office (EE-3F)
OSTI Identifier:
1484435
Report Number(s):
NREL/JA-5K00-72873
Journal ID: ISSN 0032-3896
Grant/Contract Number:  
AC36-08GO28308
Resource Type:
Accepted Manuscript
Journal Name:
Polymer Journal
Additional Journal Information:
Journal Volume: 51; Journal ID: ISSN 0032-3896
Publisher:
Society of Polymer Science
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; acrylic monomers; benzoyl peroxide; esters; free radical polymerization; free radicals; glass transition; redox reactions

Citation Formats

Suzuki, Yasuhito, Cousins, Dylan S., Shinagawa, Yuya, Bell, Robert T., Matsumoto, Akikazu, and Stebner, Aaron P. Phase separation during bulk polymerization of methyl methacrylate. United States: N. p., 2018. Web. doi:10.1038/s41428-018-0142-7.
Suzuki, Yasuhito, Cousins, Dylan S., Shinagawa, Yuya, Bell, Robert T., Matsumoto, Akikazu, & Stebner, Aaron P. Phase separation during bulk polymerization of methyl methacrylate. United States. doi:10.1038/s41428-018-0142-7.
Suzuki, Yasuhito, Cousins, Dylan S., Shinagawa, Yuya, Bell, Robert T., Matsumoto, Akikazu, and Stebner, Aaron P. Fri . "Phase separation during bulk polymerization of methyl methacrylate". United States. doi:10.1038/s41428-018-0142-7.
@article{osti_1484435,
title = {Phase separation during bulk polymerization of methyl methacrylate},
author = {Suzuki, Yasuhito and Cousins, Dylan S. and Shinagawa, Yuya and Bell, Robert T. and Matsumoto, Akikazu and Stebner, Aaron P.},
abstractNote = {We report on the phase separation of methyl methacrylate (MMA) and poly(methyl methacrylate) (PMMA) during bulk free-radical polymerization. The phase separation is induced when the reaction is initiated at room temperature by the redox reaction of benzoyl peroxide in the presence of an amine. During the reaction, the ratio of MMA and PMMA changes continuously. Separation into MMA-rich and PMMA-rich phases coincides with the onset of the Trommsdorff effect. At room temperature, the interface between the two phases remains, even after drying the remaining monomer. When the sample is annealed above the glass transition temperature Tg, the interface disappears. Due to the frozen dynamics of the polymer chains, subsequent cooling below Tg does not result in further phase separation. This result provides evidence for the existence of rich, thermodynamically stable states, which are typically suppressed due to the frozen dynamics of polymers at temperatures below the Tg, after thermal processing above the Tg.},
doi = {10.1038/s41428-018-0142-7},
journal = {Polymer Journal},
number = ,
volume = 51,
place = {United States},
year = {2018},
month = {11}
}

Journal Article:
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Works referenced in this record:

A review of polymer dissolution
journal, August 2003