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Self-associations and temperature dependence of aqueous solutions of zwitterionically modified N-isopropylacrylamide copolymers

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Abstract

Thermosensitive copolymer solutions are prepared from various molar ratios of N-isopropylacrylamide (NIPAM) and the zwitterionic monomer N-(methacryloxypropyl)-N,N-dimethyl-N-(3-sulfopropyl) ammonium betaine (Zw) by free radical polymerization. In the current study, we examined the rheological properties of poly (NIPAM/sulfobetaine) copolymer solutions. We found that the rheological properties are conceptually linked with the copolymer chemical structure and chain topology. We also report the effects of bulk molar mass and zwitterions on flow curve ɳ (\( \overset{\cdot }{\upgamma} \)). With the introduction of the charged group in the PNIPAM-chain, its viscoelastic phase behavior and lower critical solution temperature (LCST) are affected. At varying concentrations of zwitterionic copolymer, they showed a shear thinning behavior with two relaxation regimes for entanglement relaxation and zwitterionic interaction. Interestingly, the zwitterionic interactions are related to the molar concentration of zwitterionic monomer. This is eventually associated with the topology of the copolymer chain. Our results also showed that there was a linear increase in the LCST of these solutions as a function of zwitterionic moieties.

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Notes

  1. A critical gel has δ = 45°, which corresponds to dG′/dω = dG″/dω = d|G*|/dω = 0.7 according to the Kramers-Kronig relations (Kramers (1927), Kronig (1926)), which were verified to be true for δ ~ d|η*|/dω for single phase systems (Stadler and Münstedt (2008a,b)). Due to the validity of the Cox-Merz rule (η (\( \overset{\cdot }{\upgamma} \)) ≡ |η*|(ω)) for single phase samples, we can conclude that d|η*|/dω ≡ dη/d\( \overset{\cdot }{\upgamma} \) and, thus, that dη/d\( \overset{\cdot }{\upgamma} \) = − 0.3 corresponds to δ ≈ 45°, which means that a sample with dη/d\( \overset{\cdot }{\upgamma} \) = − 0.3 is a critical gel, as long as both rules are valid, which is the case in general for single phase systems, as are under investigation here (except pure polyzwitterion).

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Acknowledgments

The authors acknowledge financial aid from the National Research Foundation of Korea (110100713), Nanshan District Key Lab for Biopolymers and Safety Evaluation (No.KC2014ZDZJ0001A). The authors would also like to thank the staffs of the CBNU central lab for helping with the FESEM images.

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    Authors and Affiliations

    1. College of Materials Science and Engineering, Shenzhen University, Shenzhen, 518060, People’s Republic of China

      Saud Hashmi, Amin GhavamiNejad, Bing Du & Florian J. Stadler

    2. School of Semiconductor and Chemical Engineering, Chonbuk National University, Baekjero 567, Deokjin-gu, Jeonju, Jeonbuk, 561-756, Republic of Korea

      Saud Hashmi, Amin GhavamiNejad, Francis O. Obiweluozor & Florian J. Stadler

    3. Department of Chemical Engineering, NED University of Engineering and Technology, University Road, Karachi, 75270, Pakistan

      Saud Hashmi

    4. Department of Polymer, Omidiyeh Branch, Islamic Azad University, 63731-93719, Omidiyeh, Iran

      Mohammad Vatankhah-Varnoosfaderani

    5. Nanshan District Key Lab for Biopolymers and Safety Evaluation, Shenzhen, 518060, China

      Bing Du & Florian J. Stadler

    6. Shenzhen Key Laboratory of Special Functional Materials, Shenzhen, 518060, People’s Republic of China

      Bing Du & Florian J. Stadler

    7. Shenzhen Engineering Laboratory for Advanced Technology of Ceramics, Shenzhen, 518060, People’s Republic of China

      Bing Du & Florian J. Stadler

    8. Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, NC, 27599-3290, USA

      Mohammad Vatankhah-Varnoosfaderani

    9. Department of Bionanosystem Engineering, Graduate School, Chonbuk National University, Jeonju, 561-756, Republic of Korea

      Amin GhavamiNejad

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    1. Saud Hashmi
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    Correspondence to Amin GhavamiNejad, Bing Du or Florian J. Stadler.

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    Saud Hashmi and Mohammad Vatankhah-Varnoosfaderani contributed equally to this work.

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    Hashmi, S., Vatankhah-Varnoosfaderani, M., GhavamiNejad, A. et al. Self-associations and temperature dependence of aqueous solutions of zwitterionically modified N-isopropylacrylamide copolymers. Rheol Acta 54, 501–516 (2015). https://doi.org/10.1007/s00397-015-0837-z

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