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Light scattering and surface tensiometric studies of tip-modified PEO-PBO diblock copolymers in water

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Abstract

The micellar and associative properties of four diblock copolymers, Me2N(CH2)2OE79B34 (denoted DE80B34), I−Me3N+(CH2)2OE79B34 (denoted TE80B34), I−Me3N+(CH2)2OE48B22 (denoted TE49B22), and HO(CH2)2OE62B22 (denoted E62B22), in aqueous solution and at various concentrations and temperatures, were investigated by surface tensiometry and dynamic and static laser light scattering. Surface tension measurements enabled the critical micelle concentration (CMC) to be determined at different temperatures, and thus the enthalpy of micellization (ΔH o mic), the free energy of micellization (ΔG o mic), and the entropy of micellization (ΔS o mic) to be ascertained. Dynamic and static light-scattering measurements allowed the micellar parameters to be calculated and the extent of hydration of the copolymer micelle to be obtained qualitatively. The experimental results provided by these techniques are discussed in the terms of the variation in the hydrophilic to hydrophobic (E/B) ratio and end-group modification. Micellar parameters such as the weight-average molar mass (M w), the association number (N w), the thermodynamic radius (r t), and the hydrodynamic radius (r h) obtained from light-scattering data show that the micelles formed by the conventional E m B n and dimethylamino-tipped (DE m B n ) copolymers are harder than those of trimethylammonium-tipped (TE m B n ) copolymers. This difference in micellar properties is considered to be due to differences in polarity and charge effect at the hydrophilic ends of the tip-modified copolymers. The high value of r h for DE m B n and TE m B n copolymers as compared to E62B22 is an indication of micellar aggregation.

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Acknowledgments

We are very grateful to Dr. Carin Tattershall (University of Manchester) for the synthesis of the dimethylamino- and trimethylammonium-tipped diblock copolymers. We are also thankful to Professor Peter M. Budd of the University of Manchester for helpful discussions. Dr. Abbas Khan is grateful to the Higher Education Commission (H.E.C.) Pakistan for financial support under the indigenous Ph.D. fellowship scheme. He also wishes to acknowledge the Third World Academy of Sciences for a split Ph.D. research fellowship to work in the Department of Chemical Physics, University of Science and Technology, Hefei, China.

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Authors and Affiliations

  1. Department of Chemistry, Quaid-I-Azam University, Islamabad, 45320, Pakistan

    Abbas Khan & Mohammad Siddiq

  2. Department of Chemistry, Abdul Wali Khan University, Mardan, Pakistan

    Abbas Khan

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  1. Abbas Khan
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  2. Mohammad Siddiq
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Correspondence to Mohammad Siddiq.

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Khan, A., Siddiq, M. Light scattering and surface tensiometric studies of tip-modified PEO-PBO diblock copolymers in water. J Polym Res 20, 160 (2013). https://doi.org/10.1007/s10965-013-0160-2

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