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Title: Continuous Flow Fabrication of Block Copolymer-Grafted Silica Micro-Particles in Environmentally Friendly Water/Ethanol Media

Polymer-grafted inorganic particles (PGIPs) are attractive building blocks for numerous chemical and material applications. Surface-initiated controlled radical polymerization (SI-CRP) is the most feasible method to fabricate PGIPs. However, a conventional in-batch reaction still suffers from several disadvantages, including time-consuming purification processes, low grafting efficiency, and possible gelation problems. Herein, a facile method is demonstrated to synthesize block copolymer–grafted inorganic particles, that is, poly(poly(ethylene glycol) methyl ether methacrylate) (PPEGMEMA)-b-poly(N-isopropylacrylamide) (PNIPAM)–grafted silica micro-particles using continuous flow chemistry in an environmentally friendly aqueous media. Immobilizing the chain transfer agent and subsequent SI-CRP can be accomplished sequentially in a continuous flow system, avoiding multi-step purification processes in between. The chain length (MW) of the grafted polymers is tunable by adjusting the flow time or monomer concentration, and the narrower molar mass dispersity (Ð < 1.4) of the grafted polymers reveals the uniform polymer chains on the particles. Moreover, compared with the in-batch reaction at the same condition, the continuous system also suppresses possible gelation problems.
Authors:
 [1] ; ORCiD logo [2] ;  [1] ; ORCiD logo [1]
  1. Case Western Reserve Univ., Cleveland, OH (United States). Dept. of Macromolecular Science and Engineering
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical Sciences Division
Publication Date:
Grant/Contract Number:
AC05-00OR22725; NSF‐1608457; NSF‐1333651
Type:
Accepted Manuscript
Journal Name:
Macromolecular Materials and Engineering
Additional Journal Information:
Journal Name: Macromolecular Materials and Engineering; Journal ID: ISSN 1438-7492
Research Org:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Science Foundation (NSF)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; block copolymers; flow chemistry; graft from reversible addition‐fragmentation chain transfer polymerization
OSTI Identifier:
1484979
Alternate Identifier(s):
OSTI ID: 1479573

Ye, Piaoran, Cao, Peng-Fei, Chen, Qiyi, and Advincula, Rigoberto. Continuous Flow Fabrication of Block Copolymer-Grafted Silica Micro-Particles in Environmentally Friendly Water/Ethanol Media. United States: N. p., Web. doi:10.1002/mame.201800451.
Ye, Piaoran, Cao, Peng-Fei, Chen, Qiyi, & Advincula, Rigoberto. Continuous Flow Fabrication of Block Copolymer-Grafted Silica Micro-Particles in Environmentally Friendly Water/Ethanol Media. United States. doi:10.1002/mame.201800451.
Ye, Piaoran, Cao, Peng-Fei, Chen, Qiyi, and Advincula, Rigoberto. 2018. "Continuous Flow Fabrication of Block Copolymer-Grafted Silica Micro-Particles in Environmentally Friendly Water/Ethanol Media". United States. doi:10.1002/mame.201800451.
@article{osti_1484979,
title = {Continuous Flow Fabrication of Block Copolymer-Grafted Silica Micro-Particles in Environmentally Friendly Water/Ethanol Media},
author = {Ye, Piaoran and Cao, Peng-Fei and Chen, Qiyi and Advincula, Rigoberto},
abstractNote = {Polymer-grafted inorganic particles (PGIPs) are attractive building blocks for numerous chemical and material applications. Surface-initiated controlled radical polymerization (SI-CRP) is the most feasible method to fabricate PGIPs. However, a conventional in-batch reaction still suffers from several disadvantages, including time-consuming purification processes, low grafting efficiency, and possible gelation problems. Herein, a facile method is demonstrated to synthesize block copolymer–grafted inorganic particles, that is, poly(poly(ethylene glycol) methyl ether methacrylate) (PPEGMEMA)-b-poly(N-isopropylacrylamide) (PNIPAM)–grafted silica micro-particles using continuous flow chemistry in an environmentally friendly aqueous media. Immobilizing the chain transfer agent and subsequent SI-CRP can be accomplished sequentially in a continuous flow system, avoiding multi-step purification processes in between. The chain length (MW) of the grafted polymers is tunable by adjusting the flow time or monomer concentration, and the narrower molar mass dispersity (Ð < 1.4) of the grafted polymers reveals the uniform polymer chains on the particles. Moreover, compared with the in-batch reaction at the same condition, the continuous system also suppresses possible gelation problems.},
doi = {10.1002/mame.201800451},
journal = {Macromolecular Materials and Engineering},
number = ,
volume = ,
place = {United States},
year = {2018},
month = {10}
}

Works referenced in this record:

Thiol-Ene Click Chemistry
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  • Hoyle, Charles?E.; Bowman, Christopher?N.
  • Angewandte Chemie International Edition, Vol. 49, Issue 9, p. 1540-1573
  • DOI: 10.1002/anie.200903924