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Title: Synthetic strategy for preparing chiral double-semicrystalline polyether block copolymers

Here, we report an effective strategy for the synthesis of semi-crystalline block copolyethers with well-defined architecture and stereochemistry. As an exemplary system, triblock copolymers containing either atactic (racemic) or isotactic ( R or S) poly(propylene oxide) end blocks with a central poly(ethylene oxide) mid-block were prepared by anionic ring-opening procedures. Stereochemical control was achieved by an initial hydrolytic kinetic resolution of racemic terminal epoxides followed by anionic ring-opening polymerization of the enantiopure monomer feedstock. The resultant triblock copolymers were highly isotactic (meso triads [ mm]% ~ 90%) with optical microscopy, differential scanning calorimetry, wide angle x-ray scattering and small angle x-ray scattering being used to probe the impact of the isotacticity on the resultant polymer and hydrogel properties.
Authors:
 [1] ;  [1] ;  [1] ;  [1] ;  [1] ;  [1]
  1. Univ. of California, Santa Barbara, CA (United States)
Publication Date:
Grant/Contract Number:
AC02-05CH11231
Type:
Accepted Manuscript
Journal Name:
Polymer Chemistry
Additional Journal Information:
Journal Volume: 6; Journal Issue: 9; Journal ID: ISSN 1759-9954
Publisher:
Royal Society of Chemistry
Research Org:
Univ. of California, Santa Barbara, CA (United States)
Sponsoring Org:
USDOE Advanced Research Projects Agency - Energy (ARPA-E)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE
OSTI Identifier:
1346162

McGrath, Alaina J., Shi, Weichao, Rodriguez, Christina G., Kramer, Edward J., Hawker, Craig J., and Lynd, Nathaniel A.. Synthetic strategy for preparing chiral double-semicrystalline polyether block copolymers. United States: N. p., Web. doi:10.1039/c4py01503g.
McGrath, Alaina J., Shi, Weichao, Rodriguez, Christina G., Kramer, Edward J., Hawker, Craig J., & Lynd, Nathaniel A.. Synthetic strategy for preparing chiral double-semicrystalline polyether block copolymers. United States. doi:10.1039/c4py01503g.
McGrath, Alaina J., Shi, Weichao, Rodriguez, Christina G., Kramer, Edward J., Hawker, Craig J., and Lynd, Nathaniel A.. 2014. "Synthetic strategy for preparing chiral double-semicrystalline polyether block copolymers". United States. doi:10.1039/c4py01503g. https://www.osti.gov/servlets/purl/1346162.
@article{osti_1346162,
title = {Synthetic strategy for preparing chiral double-semicrystalline polyether block copolymers},
author = {McGrath, Alaina J. and Shi, Weichao and Rodriguez, Christina G. and Kramer, Edward J. and Hawker, Craig J. and Lynd, Nathaniel A.},
abstractNote = {Here, we report an effective strategy for the synthesis of semi-crystalline block copolyethers with well-defined architecture and stereochemistry. As an exemplary system, triblock copolymers containing either atactic (racemic) or isotactic (R or S) poly(propylene oxide) end blocks with a central poly(ethylene oxide) mid-block were prepared by anionic ring-opening procedures. Stereochemical control was achieved by an initial hydrolytic kinetic resolution of racemic terminal epoxides followed by anionic ring-opening polymerization of the enantiopure monomer feedstock. The resultant triblock copolymers were highly isotactic (meso triads [mm]% ~ 90%) with optical microscopy, differential scanning calorimetry, wide angle x-ray scattering and small angle x-ray scattering being used to probe the impact of the isotacticity on the resultant polymer and hydrogel properties.},
doi = {10.1039/c4py01503g},
journal = {Polymer Chemistry},
number = 9,
volume = 6,
place = {United States},
year = {2014},
month = {12}
}