We demonstrated here novel multistimuli responsive organosilica hybrid nanopaticles (SiO1.5-gPEA NPs) based on graft poly(ether amine)s (gPEAs). Poly(ether amine)s comprised of trimethoxysilyl moieties (TMS-gPEAs) were synthesized via nucleophilic substitution/ring-opening reaction of commercial poly(propylene glycol) diglycidyl ether, Jeffamine L100 and 2-aminoethanolthiol, followed by introducing trimethoxysilyl moieties (TMS) into side-chain via “thiol−ene” reaction. The obtained TMS-gPEAs could be dispersed directly in water to form the core-cross-linked hybrid nanoparticles (SiO1.5-gPEA NPs) with diameter of about 20 nm, which was revealed by TEM and DLS. These obtained SiO1.5-gPEA NPs in aqueous solution were responsive to temperature, pH and ionic strength with tunable cloud point (CP). Simultaneously, SiO1.5-gPEA NPs could encapsulate hydrophobic guest molecule Nile Red in water. It is interesting that SiO1.5-gPEA NPs can sequester the hydrophilic dyes selectively: SiO1.5-gPEA11 NPs could transfer only Rose Bengal (RB) reversibly from the aqueous mixture of RB and Rhodamine 6G (R6G) to toluene, which was controlled by temperature. These characteristics will give SiO1.5-gPEAs potential in smart separation.
We report here a novel amphiphilic PDMS-containing poly(ether amine) (PDMS-gPEA) synthesized through one-pot condensation polymerization of commercial di-epoxy and amine monomers. The obtained PDMS-gPEA could be dispersed directly in aqueous solution to form stable uniform-sized nanoparticles with a diameter of about 16 nm, whose aggregation is responsive to temperature, pH and ionic strength with tunable cloud point (CP). The whole process for the responsive aggregation of PDMS-gPEA nanoparticles was revealed by transmission electron microscope (TEM) and dynamic light scattering (DLS), and was intensively studied by UV-vis spectra. The responsive nanoparticles of PDMS-gPEA possessed the unique selective encapsulation of water-soluble dye, which provides potential applications in smart separations.
We demonstrated here a novel concept of the responsive dispersant based on the amphiphilic zwitterionic poly(ether amine) (Z-SiPEAs), which can control the dispersion of dyes and pigments in water. Z-SiPEAs are composed of short poly (dimethylsiloxane) (PDMS) chain in the backbone and Jeffamine L100 as graft chain. The amino groups in the backbone and carboxyl groups grafted to the backbone make the obtained Z-SiPEAs zwitterionic. Transmission electron microscopy (TEM) and dynamic light scattering (DLS) results revealed that the obtained Z-SiPEAs can self-assemble into nanoparticles in water, which possessed sharp response to temperature, pH, and ionic strength with the tunable clouding point (CP). In the presence of Z-SiPEAs, not only hydrophobic dyes such as Nile Red can be dispersed in water, but the hydrophilic dye Rose Bengal (RB) can be dispersed in unpolar solvents. Further more, Z-SiPEAs can enhance the dispersion of inorganic pigments Titanium White, Iron Red and Chrome Yellow very efficiently in most solvents. It should be noted that the dispersion of organic dyes and inorganic pigments in water can be controlled by temperature in the presence of Z-SiPEAs. ¹H NMR and FT-IR revealed the strong coordination between carboxyl groups in Z-SiPEAs and metal atoms of inorganic pigments. These characteristics will give Z-SiPEAs potential as the novel responsive polymeric dispersant.
A series of well‐defined amphiphilic comb poly (ether amine)s (acPEAs) were successfully synthesized through nucleophilic addition/ring‐opening reaction of commercial available poly(propylene glycol) (PPO) diglycidyl ether and Jeffamine L100, followed by esterification of hydroxyl groups in backbone by alkyl carboxylic acid with different chain length. acPEAs are comprised of hydrophilic short PEO chains and hydrophobic alkyl chains as comb chains, which are grafted on PPO backbone alternately to form well‐defined structure. With the very low critical micelle concentration (CMC) of around 3.0 × 10−3 g/L, the obtained acPEAs can self‐assemble into stable nanomicelles, whose aggregation is responsive to temperature, pH, and ionic strength with tunable cloud point (CP). The CP of acPEAs' aqueous solution increases with the decrease of the length of graft alkyl chains, the decrease of pH value, and the decrease of ionic strength. A transition behavior in the responsive aggregation of micelles formed by acPEA8 and acPEA10 in aqueous solution, especially at low pH value (<7.0), was observed, which was also revealed by DLS results. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 3468–3475, 2010
A series of novel star‐like copolymers H20‐poly(N‐isopropylacrylamide)‐random‐poly(poly(ethylene glycol) methyl ether methacrylate) (H20‐PNIPAm‐r‐PEGMA), which could respond to both temperature and ionic strength stimuli in aqueous solution were synthesized by atom transfer radical polymerization. Stimuli‐response of these copolymers in aqueous solution was characterized by dynamic laser scattering (DLS), 1H‐NMR and turbidity. In aqueous solution, these star‐like copolymers exhibited response to temperature and ionic strength with tunable low‐critical solution temperature (LCST) from 32 to 100°C. The LCST values of copolymers increased with increasing PEGMA contents, while decreased with increasing ionic strength. An interesting phenomenon, which should be a unique character of star‐like copolymer, was observed by the turbidity test of copolymer 1160. The addition of sodium chloride and increase of concentration can let copolymer 1160 behave normally, which was further confirmed by atomic force microscopy and DLS. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010
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