Novel organotin‐containing shell‐cross‐linked knedel and core‐cross‐linked knedel: Synthesis and application in catalysis

A series of novel organotin‐containing core‐cross‐linked knedels and shell‐cross‐linked knedels were first synthesized facilely from poly(styrene)‐b‐poly(acrylate acid) nanoparticles in different selective solvents Tetrahydrofuran (THF)/H₂O or THF/n‐octane] by using organotin compound 1,3‐dichloro‐tetra‐n‐butyl‐distannoxane as a new cross‐linker. The formation of the 1‐chloro‐3‐carboxylato‐tetra‐n‐butyl‐distannoxane layer in our cross‐linking reaction was supported by Fourier transform infrared (FT‐IR) and inductive coupled plasma emission spectrometer (ICP) analysis of the resulting shell‐cross‐linked knedels and core‐cross‐linked knedels. Transmission electron microscopy (TEM) study showed the spherical morphology and the size of the core‐cross‐linked knedels and shell‐cross‐linked knedel. Especially, the layer structure of the core‐cross‐linked knedels was clearly displayed in TEM image. The increase of extent of cross‐linking lead to the increasing of diameter for the shell‐cross‐linked knedels, whereas there was no significant effect on the core‐cross‐linked knedels. Dynamic light scattering (DLS) measurements gave hydrodynamic diameters of the core‐cross‐linked knedels that were in agreement with the TEM diameters. Moreover, the wall thickness of the shell layer of the core‐cross‐linked knedels could be easily modified by varying the block copolymer composition. Notably, the organotin‐containing core‐cross‐linked knedel exhibited highly efficient catalytic activity for the aqueous esterification reaction under nearly neutral conditions. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010