Synthesis and Thermo-Responsive Behavior of Poly(<i>N</i>-isopropylacrylamide)-<i>b</i>-Poly(<i>N</i>-vinylisobutyramide) Diblock Copolymer

Thermo-responsive diblock copolymer, poly(<i>N</i>-isopropylacrylamide)-<i>block</i>-poly(<i>N</i>-vinylisobutyramide) was synthesized via switchable reversible addition–fragmentation chain transfer (RAFT) polymerization and its thermal transition behavior was stu...

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Main Authors: Jun Hyok Yoon, Taehyoung Kim, Myungeun Seo, Sang Youl Kim
Format: Article
Language:English
Published: MDPI AG 2024-03-01
Series:Polymers
Subjects:
Online Access:https://www.mdpi.com/2073-4360/16/6/830
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author Jun Hyok Yoon
Taehyoung Kim
Myungeun Seo
Sang Youl Kim
author_facet Jun Hyok Yoon
Taehyoung Kim
Myungeun Seo
Sang Youl Kim
author_sort Jun Hyok Yoon
collection DOAJ
description Thermo-responsive diblock copolymer, poly(<i>N</i>-isopropylacrylamide)-<i>block</i>-poly(<i>N</i>-vinylisobutyramide) was synthesized via switchable reversible addition–fragmentation chain transfer (RAFT) polymerization and its thermal transition behavior was studied. Poly(<i>N</i>-vinylisobutyramide) (PNVIBA), a structural isomer of poly(<i>N</i>-isopropylacrylamide) (PNIPAM) shows a thermo-response character but with a higher lower critical solution temperature (LCST) than PNIPAM. The chain extension of the PNVIBA block from the PNIPAM block proceeded in a controlled manner with a switchable chain transfer reagent, methyl 2-[methyl(4-pyridinyl)carbamothioylthio]propionate. In an aqueous solution, the diblock copolymer shows a thermo-responsive behavior but with a single LCST close to the LCST of PNVIBA, indicating that the interaction between the PNIPAM segment and the PNVIBA segment leads to cooperative aggregation during the self-assembly induced phase separation of the diblock copolymer in solution. Above the LCST of the PNIPAM block, the polymer chains begin to collapse, forming small aggregates, but further aggregation stumbled due to the PNVIBA segment of the diblock copolymer. However, as the temperature approached the LCST of the PNVIBA block, larger aggregates composed of clusters of small aggregates formed, resulting in an opaque solution.
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spelling doaj.art-e28fce08f09a476197a30f10868cca682024-03-27T14:01:27ZengMDPI AGPolymers2073-43602024-03-0116683010.3390/polym16060830Synthesis and Thermo-Responsive Behavior of Poly(<i>N</i>-isopropylacrylamide)-<i>b</i>-Poly(<i>N</i>-vinylisobutyramide) Diblock CopolymerJun Hyok Yoon0Taehyoung Kim1Myungeun Seo2Sang Youl Kim3Department of Chemistry, Korea Advanced Institute of Science & Technology (KAIST), Daejeon 34141, Republic of KoreaDepartment of Chemistry, Korea Advanced Institute of Science & Technology (KAIST), Daejeon 34141, Republic of KoreaDepartment of Chemistry, Korea Advanced Institute of Science & Technology (KAIST), Daejeon 34141, Republic of KoreaDepartment of Chemistry, Korea Advanced Institute of Science & Technology (KAIST), Daejeon 34141, Republic of KoreaThermo-responsive diblock copolymer, poly(<i>N</i>-isopropylacrylamide)-<i>block</i>-poly(<i>N</i>-vinylisobutyramide) was synthesized via switchable reversible addition–fragmentation chain transfer (RAFT) polymerization and its thermal transition behavior was studied. Poly(<i>N</i>-vinylisobutyramide) (PNVIBA), a structural isomer of poly(<i>N</i>-isopropylacrylamide) (PNIPAM) shows a thermo-response character but with a higher lower critical solution temperature (LCST) than PNIPAM. The chain extension of the PNVIBA block from the PNIPAM block proceeded in a controlled manner with a switchable chain transfer reagent, methyl 2-[methyl(4-pyridinyl)carbamothioylthio]propionate. In an aqueous solution, the diblock copolymer shows a thermo-responsive behavior but with a single LCST close to the LCST of PNVIBA, indicating that the interaction between the PNIPAM segment and the PNVIBA segment leads to cooperative aggregation during the self-assembly induced phase separation of the diblock copolymer in solution. Above the LCST of the PNIPAM block, the polymer chains begin to collapse, forming small aggregates, but further aggregation stumbled due to the PNVIBA segment of the diblock copolymer. However, as the temperature approached the LCST of the PNVIBA block, larger aggregates composed of clusters of small aggregates formed, resulting in an opaque solution.https://www.mdpi.com/2073-4360/16/6/830thermo-responsive polymerlower critical solution temperature (LCST)block copolymercontrolled radical polymerizationreversible addition–fragmentation chain transfer polymerization (RAFT)self-assembly
spellingShingle Jun Hyok Yoon
Taehyoung Kim
Myungeun Seo
Sang Youl Kim
Synthesis and Thermo-Responsive Behavior of Poly(<i>N</i>-isopropylacrylamide)-<i>b</i>-Poly(<i>N</i>-vinylisobutyramide) Diblock Copolymer
Polymers
thermo-responsive polymer
lower critical solution temperature (LCST)
block copolymer
controlled radical polymerization
reversible addition–fragmentation chain transfer polymerization (RAFT)
self-assembly
title Synthesis and Thermo-Responsive Behavior of Poly(<i>N</i>-isopropylacrylamide)-<i>b</i>-Poly(<i>N</i>-vinylisobutyramide) Diblock Copolymer
title_full Synthesis and Thermo-Responsive Behavior of Poly(<i>N</i>-isopropylacrylamide)-<i>b</i>-Poly(<i>N</i>-vinylisobutyramide) Diblock Copolymer
title_fullStr Synthesis and Thermo-Responsive Behavior of Poly(<i>N</i>-isopropylacrylamide)-<i>b</i>-Poly(<i>N</i>-vinylisobutyramide) Diblock Copolymer
title_full_unstemmed Synthesis and Thermo-Responsive Behavior of Poly(<i>N</i>-isopropylacrylamide)-<i>b</i>-Poly(<i>N</i>-vinylisobutyramide) Diblock Copolymer
title_short Synthesis and Thermo-Responsive Behavior of Poly(<i>N</i>-isopropylacrylamide)-<i>b</i>-Poly(<i>N</i>-vinylisobutyramide) Diblock Copolymer
title_sort synthesis and thermo responsive behavior of poly i n i isopropylacrylamide i b i poly i n i vinylisobutyramide diblock copolymer
topic thermo-responsive polymer
lower critical solution temperature (LCST)
block copolymer
controlled radical polymerization
reversible addition–fragmentation chain transfer polymerization (RAFT)
self-assembly
url https://www.mdpi.com/2073-4360/16/6/830
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