Two-Way CO2-Responsive Polymer Particles with Controllable Amphiphilic Properties.

Multiple stimuli-responsive amphiphilic block copolymers of poly(methacrylic acid) (PMAA) and poly(2-dimethylaminoethyl methacrylate) (PDMAEMA) were used as emulsifiers to prepare two-way CO2 stimuli-responsive poly(methyl methacrylate) (PMMA) latex particles via aqueous emulsion polymerization. The polymerization at pH 2 and 50 °C produced mainly PDMAEMA-surfaced PMMA latex particles, whereas the polymerization at pH 12 and 50 °C produced mainly PMAA-surfaced particles. Both types of latex particles appeared to precipitate at higher pH values from the emulsifier of a longer PDMAEMA block length. The direction from precipitation to dispersion for PDMAEMA-surfaced particles or from dispersion to precipitation for PMAA-surfaced particles in response to CO2 bubbling of the pH 12 dispersion of particles depended on the PDMAEMA block length. Together, this study reveals that-by tuning the PDMAEMA block length in PMAA-b-PDMAEMA used as an emulsifier and polymerization at pH 2 or 12-PMMA latex particles can exhibit two-way CO2 responsiveness between dispersion and precipitation. Thus, due to their simple preparation and unique dual pH and CO2 responsiveness, these newly developed PMAA-b-PDMAEMA emulsifiers provide a highly efficient approach for the development of smart PMMA latex nanoparticles with desirable multifunctional properties.

Multistimuli-Responsive Emulsifiers Based on Two-Way Amphiphilic Diblock Polymers.

Diblock copolymers of poly(tert-butyl methacrylate) (PtBuMA) and poly(2-dimethylaminoethyl methacrylate) (PDMAEMA) of four different block lengths were prepared by sequential two-step reversible addition-fragmentation chain transfer radical polymerization, followed by hydrolysis of the PtBuMA blocks to obtain poly(methacrylic acid)-b-PDMAEMA (PMAA-b-PDMAEMA). The effect of the PDMAEMA block length on the multistimuli-responsive amphiphilic features of both types of diblock copolymers was investigated as CO2-switchable emulsifiers for emulsification/demulsification of n-octane (an oil) in water in response to CO2/N2 bubbling. The amphiphilicity of PtBuMA-b-PDMAEMA was switched on, and the amphiphilicity of PMAA-b-PDMAEMA was switched off by CO2 bubbling at pH 12 and 25 °C to achieve emulsification/demulsification. A longer PDMAEMA block length in PMAA-b-PDMAEMA conferred more sensitive CO2-responsive amphiphilicity but reduced the extent of recovery of emulsification ability on N2 bubbling. This newly developed diblock copolymer system could potentially serve as a "multifunctional surfactant" for CO2-switchable emulsification/demulsification of oil-in-water and water-in-oil mixtures.