Adsorption of PEO–PPO–PEO Triblock Copolymers with End-Capped Cationic Chains of Poly(2-dimethylaminoethyl methacrylate)

Abstract

We study the adsorption of a symmetric triblock copolymer of ethylene oxide, EO, and propylene oxide, PO, end-capped with quarternized poly(2-dimethylaminoethyl methacrylate), DMAEMA (DMAEMA(24)-EO(132)PO(50)EO(132)-DMAEMA(24)). Light scattering and tensiometry are used to measure the relative size of the associated structures and surface excess at the air-liquid interface. The adsorbed amount, the amount of coupled water, and the viscoelasticity of the adsorbed polymer layer are measured on hydrophobic and hydrophilic surfaces (polypropylene, cellulose, and silica) by using quartz crystal microgravimetry (QCM) and surface plasmon resonance (SPR) at different ionic strengths and temperatures. The results of the experiments are compared with those obtained after adsorption of the uncharged precursor copolymer, without the cationic end-caps (EO(132)PO(50)EO(132)). DMAEMA(24)-EO(132)PO(50)EO(132)-DMAEMA(24) possesses higher affinity with the negatively charged silica and cellulose surfaces while the uncharged copolymer adsorbs to a larger extent on polypropylene surfaces. In this latter case, adsorption increases with increasing solution ionic strength and temperature. Adsorption of EO(132)PO(50)EO(132) on silica surfaces has little effect on the water contact angle (WCA), while adsorption of DMAEMA(24)-EO(132)PO(50)EO(132)-DMAEMA(24) increases the WCA of silica to 32°, indicating a large density of exposed PPO blocks upon adsorption. After adsorption of EO(132)PO(50)EO(132) and DMAEMA(24)-EO(132)PO(50)EO(132)-DMAEMA(24) on PP, the WCA is reduced by ≈14° and ≈28°, respectively, due to the exposed hydrophilic EO and highly water-soluble DMAEMA segments on the surfaces. The extent of surface coverage at saturation at the polypropylene/liquid interfaces (≈31 and 40 nm(2)/molecule obtained by QCM and SPR, respectively) is much lower, as expected, when compared with results obtained at the air/liquid interface, where a tighter packing is observed. The percentage of water coupled to the adsorbed cationic polymer decreases with solution ionic strength. Overall, these observations are ascribed to the effects of electrostatic screening, polymer hydrodynamic size, and solvency.