Synthesis of well‐defined hairy polymer microspheres by precipitation polymerization and surface‐initiated atom transfer radical polymerization

Abstract

A variety of polymer microspheres were successfully synthesized by the surface-initiated atom transfer radical polymerization (SI-ATRP) of monomers by using monodisperse polymer microsphere having benzyl halide moiety as a multifunctional polymeric initiator. First, a series of monodisperse polymer microsphere having benzyl chloride with variable monomer ratio (P(St-DVB-VBC)) were synthesized by the precipitation polymerization of styrene (St), divinylbenzene (DVB), and 4-vinylbenzyl chloride (VBC). Next, hairy polymer microspheres were synthesized by the surface-initiated ATRP of various monomers with P(St-DVB-VBC) microsphere as a multifunctional polymeric initiator. The hair length determined by the SEC analysis of free polymer was increased with the increase of M/I. These hairy polymer microspheres were characterized by SEM, FT-IR, and Cl content measurements.Among many controlled "grafting from" polymerizations, controlled/"living" radical polymerization techniques (CRPs) (e.g., nitroxide-mediated radical polymerization, 34 atom transfer radical polymerization (ATRP), [35][36][37] and RAFT polymerization [38][39][40] are widely used because of their good control over the polymer chain length, grafting densities, broad applicability to a wide range of monomers, and mild reaction conditions. These living techniques are able to generate grafted homopolymers, copolymers and block copolymers.Additional supporting information may be found in the online version of this article.

Development of Thermally Responsive PolyNIPAm Microcarrier for Application of Cell Culturing—Part I: A Feasibility Study

“…Subsequently, oligoradical and precursor particles were generated, and the polymer chains continue to grow until a critical chain length was reached, where the particles became insoluble in the solvent [ 24 ]. Indeed, the resultant size of the polyNIPAm microspheres, of between 0.6 and 1.5 µm ( Figure 3 ), synthesized from the AIBN thermal initiator, is typical for the products of a precipitation polymerization reaction [ 25 ].…”

Atom Transfer Radical Polymerization of Styrene and Acrylates: Effects of Catalyst, Ligand, Solvent, and Initiator

“…The polymerization system could be changed according to the monomer type of ATRP and SI-ATRP [52,53]. PMDETA as a ligand and anisole as a solvent was chosen for the ATRP of acrylate monomers (nBA, nBMA, and tBMA) (Scheme 2).…”

Ionic, Core-Corona Polymer Microsphere-Immobilized MacMillan Catalyst for Asymmetric Diels-Alder Reaction

“…The D n of 1d 10 B was 1.08 µm with narrow size distribution (U = 1.13). The core-corona polymer microsphere functionalized with phenylsulfonate (CCM-SO3Ph) 2 was synthesized by the surface-initiated atom transfer radical polymerization (SI-ATRP) of styrene (70 mol %) and phenyl p-styrenesulfonate (S) (30 mol %) by using 1d20C or 1d10B as a macroinitiator [55]. In the polymerization, benzyl chloride (BnCl) was simultaneously added as a sacrificial initiator.…”

“…By the SEC analysis of the resultant free polymer initiated with BnCl, both Mn and Mw/Mn of the grafted polymers onto the surface of 1 were estimated. In FT-IR of 2, two characteristic absorption peaks at 1376 and 1175 cm −1 were observed for the stretching vibration of the S = O bond The core-corona polymer microsphere functionalized with phenylsulfonate (CCM-SO 3 Ph) 2 was synthesized by the surface-initiated atom transfer radical polymerization (SI-ATRP) of styrene (70 mol %) and phenyl p-styrenesulfonate (S) (30 mol %) by using 1d 20 C or 1d 10 B as a macroinitiator [55]. In the polymerization, benzyl chloride (BnCl) was simultaneously added as a sacrificial initiator.…”