Diblock copolymer grafted particles

Estridge CE, Jayaraman A Diblock copolymer grafted particles as compatibilizers for immiscible binary homopolymer blends, CS Macro Lett 4 155—159, 2015. 

The adsorption of block and graft copolymers is more complex, as the intimate structure of the chain will determine the extent of adsorption [37]. Random copolymers adsorb in an intermediate fashion compared to that of the corresponding homopolymers. Block copolymers retain the adsorption preference of the individual blocks. The hydrophilic block (e.g., PEO the buoy) extends away from the particle surface into the bulk solution, while the hydrophobic anchor block (e.g., PS or PPO) provides a firm attachment to the surface. Figure 6.14 shows the theoretical prediction of diblock copolymer adsorption according to SF theory. In this case, the surface density cr was plotted versus the fraction of anchor segments v, and adsorption was shown to depend on the anchor/buoy composition. 

Gitsov et al 10) produced a nanoreactor fi om laccase and linear poly(ethylene oxide)-dendritic poly(benzyl ether) diblock copolymers. A notable feature of this system is the presence of hydrophobic dendritic pockets that increase the local concentration of water-insoluble organic compounds near the active site where they are oxidized. Li and Hsieh (77) employed a hydrogel fiber membrane, with a large surface area and improved organic solvent solubility in order to facilitate lipase reactions. He (72) grafted lipase onto silica particles, which permitted him to carry out synthesis of polyesters, polycarbonates, polyphosphates, and their copolymers at temperatures up to 150°C. 

In many applications, including colloid stabilization, polymers are end-grafted onto large particles which are intermediate between the planar brush and a star. Curved brushes, with either spherical or cyUndrical symmetry, can also be formed by asymmetric diblock copolymers in the strong segregation limit. When the grafting surface curves towards the polymers (concave curvature), the volume available to the polymer chains is lowered compared to a flat surface. In this case, the chains are stretched throughout the brush and the brush is qualitatively unaltered from the flat case. MC simulations on a tetrahedral lattice for chains inside a spherical cavity... 

With chains anchored to the surface, either by a chemical grafting or an insoluble block, good solvent conditions always produce a repulsion. Consequently, copolymers, e.g., diblock, comb, or graft, tend to comprise the most effective stabilizers. Direct grafting to the particle is feasible but requires chemistry specific to the particle (e.g., Green et al., 1987). Advances in synthetic polymer chemistry continue to increase the types of polymers available for this application (e.g., Reiss et al., 1987). 

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