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Manipulating the Phase Transition Behavior of Dual Temperature-Responsive Block Copolymers by Adjusting Composition and Sequence

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Abstract

Temperature-responsive polymers have garnered significant attention due to their ability to respond to external stimuli. In this work, dual temperature-responsive block copolymers are synthesized via reversible addition-fragmentation chain transfer polymerization (RAFT) polymerization utilizing zwitterionic monomer methacryloyl ethyl sulfobetaine (SBMA) and N-isopropyl acrylamide (NIPAAm) as monomers. The thermal responsive behaviors can be easily modulated by incorporating additional hydrophobic monomer benzyl acrylate (BN) or hydrophilic monomer acrylic acid (AA), adjusting concentration or pH, or varying the degree of polymerization of the block chain segments. The cloud points of the copolymers are determined by UV-Vis spectrophotometry, and these copolymers exhibit both controlled upper and lower critical solubility temperatures (LCST and UCST) in aqueous solution. This study analyzes and summarizes the influencing factors of dual temperature responsive block copolymers by exploring the effects of various conditions on the phase transition temperature of temperature-sensitive polymers to explore the relationship between their properties and environment and structure to make them more selective in terms of temperature application range and regulation laws. It is very interesting that the introduction of poly-acrylic acid (PAA) segments in the middle of di-block copolymer PSBMA55-b-PNIPAAm80 to form PSBMA55-b-PAAx-b-PNIPAAm80 results in a reversal of temperature-responsive behaviors from ‘U’ (LCST < UCST) to ‘n’ (LCST > UCST) type, while the copolymer PSBMA55-b-P(NIPAAm80-co-AAx) not. This work provides a clue for tuning the phase transition behavior of polymers for manufacture of extreme smart materials.

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Acknowledgments

This work was financially supported by the National Natural Science Foundation of China (No. 22271207) and the Project Funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD).

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Authors and Affiliations

  1. Suzhou key Laboratory of Macromolecular Design and Precision Synthesis; Jiangsu Key Laboratory of Advanced Functional Polymer Design and Application; State and Local Joint Engineering Laboratory for Novel Functional Polymeric Materials; College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou, 215123, China

    Zhi Zou, Xiang Xu, Hai-Tao Zhao, Jian-Nan Cheng, Li-Fen Zhang & Zhen-Ping Cheng

  2. State Key Laboratory of Radiation Medicine and Protection; School for Radiological and Interdisciplinary Sciences (RAD-X) and Collaborative Innovation Center of Radiation Medicine of Jiangsu, Soochow University, Suzhou, 215123, China

    Wei-Wei He

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  1. Zhi Zou
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  2. Xiang Xu
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  3. Hai-Tao Zhao
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  4. Jian-Nan Cheng
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  5. Wei-Wei He
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  7. Zhen-Ping Cheng
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Correspondence to Wei-Wei He, Li-Fen Zhang or Zhen-Ping Cheng.

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Zou, Z., Xu, X., Zhao, HT. et al. Manipulating the Phase Transition Behavior of Dual Temperature-Responsive Block Copolymers by Adjusting Composition and Sequence. Chin J Polym Sci 42, 176–187 (2024). https://doi.org/10.1007/s10118-023-3041-0

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