Interaction of Anionic Sulfonate Gemini Surfactant with PEO-PPO-PEO Triblock Copolymers

doi:10.6023/A13111118

Abstract

The interaction of anionic sulfonate gemini surfactant 1,3-bis(N-dodecyl-N-propylsulfonate sodium)-propane (12-3-12(SO₃)₂) with two triblock copolymers poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide), F127 (EO₉₇PO₆₉EO₉₇) and P123 (EO₂₀PO₇₀EO₂₀) having the similar hydrophobic PPO central block but with different hydrophilic PEO end block, has been studied in aqueous solution at pH 9 by using differential scanning calorimetry (DSC), isothermal titration calorimetry (ITC), dynamic light scattering (DLS) and NMR techniques. At pH 9, the sulfonate groups of 12-3-12(SO₃)₂are completely deprotonated and each molecule carries two negative charges as an anionic gemini surfactant. DSC measurements have shown that the critical micellar temperature (CMT) of the two copolymers decreases as the 12-3-12(SO₃)₂ concentration increases. Moreover, at intermediate 12-3-12(SO₃)₂ concentrations, there appear two overlapping endothermic peaks, which is related to the aggregate transition between micelles with different sizes and microstructures, which has been substantiated by the DLS and NMR (spin-lattice (T₁) and spin-spin (T₂) relaxation times, and two-dimensional nuclear Overhauser effect spectroscopy (2D NOESY)) measurements. Compared with traditional single-chain ionic surfactants, the anionic gemini surfactant 12-3-12(SO₃)₂has a much stronger ability of lowering the CMT of copolymers, which should be attributed to the stronger aggregation ability and the lower critical micellar concentration of 12-3-12(SO₃)₂. Furthermore, a combination of experiments involving ITC and DLS has shown that 12-3-12(SO₃)₂ binds to the two copolymers at temperatures below and above their CMT. At the temperature below their CMT, the 12-3-12(SO₃)₂micelles form complex with monomeric copolymer, which is similar to that observed in the traditional single-chain ionic surfactant/copolymer systems, but the critical aggregation concentration for the onset of 12-3-12(SO₃)₂binding to the two copolymers is very low. At temperatures above their CMT, the association of 12-3-12(SO₃)₂ with a mixture of monomeric and micellar copolymer or micellar copolymer leads to the formation of mixed copolymer/12-3-12(SO₃)₂ micelles within copolymers and then breakdown of mixed micelles into smaller mixed micelles, but the mixed copolymer/surfactant micelles have not been completely disrupted. Moreover, at high 12-3-12(SO₃)₂concentrations, the hydrodynamic radii (R_h) of F127/12-3-12(SO₃)₂ micelles level off, while the R_h of P123/12-3-12(SO₃)₂ micelles have a gradual increase. The increase of R_hmight be accounted for the increase in micellar weight or aggregation number.

Key words: gemini surfactant, block copolymer, interaction, differential scanning calorimetry, isothermal titration calorimetry

Cite this article

Wang Ruijuan, Wang Yilin. Interaction of Anionic Sulfonate Gemini Surfactant with PEO-PPO-PEO Triblock Copolymers[J]. Acta Chimica Sinica, 2014, 72(1): 41-50.

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阴离子磺酸盐型Gemini表面活性剂与PEO-PPO-PEO嵌段共聚物相互作用的研究