Initiators for atom transfer radical polymerization (ATRP) bearing different functional groups (aldehyde, aromatic hydroxyl, dimethyl amino) were synthesized and characterized. Monotelechelics with low molecular weight were obtained by ATRP of styrene using these initiators in the presence of the CuBr/bpy catalytic complex. α,ω‐Telechelic polymers with double molecular weights with respect to the starting materials were prepared by coupling of monotelechelics under atom transfer radical generation conditions, in the absence of monomer, using CuBr as catalyst, tris[2‐(dimethylamino)ethyl]amine (Me6TREN) as a ligand, under Cu0 mediated reductive conditions and with toluene as solvent. Terminal Br atoms present in monotelechelic polystyrenes (PS) as a consequence of the ATRP mechanism also offer other routes for preparing telechelic polymers. Aldehyde functionalized polymer was etherified with hydroquinone furnishing telechelic PS with a molecular weight that was two times higher. All polymers were characterized by spectral methods (NMR, IR spectroscopy) as well as by GPC.Synthesis of initiators for atom transfer radical polymerization bearing different functional groups, for example, aldehyde, aromatic hydroxyl, dimethyl amino.magnified imageSynthesis of initiators for atom transfer radical polymerization bearing different functional groups, for example, aldehyde, aromatic hydroxyl, dimethyl amino.
Abstract1,4‐Dibromo‐2‐(bromomethyl)benzene and 1,3‐dibromo‐5‐(bromomethyl)benzene were used as initiators in the atom transfer radical polymerization of styrene in conjunction with CuBr/2,2′‐bipyridine as a catalyst. The resulting polystyrene (PSt)‐based macromonomers, possessing at one end a 2,5‐dibromophenylene or 3,5‐dibromophenylene moiety, were used in combination with 2,5‐dihexylbenzene‐1,4‐diboronic acid for Suzuki coupling in the presence of Pd(PPh3)4 as a catalyst or with the system NiCl2/2,2′‐bipyridine/triphenylphosphine/Zn for Yamamoto polymerization. Polyphenylenes (PPs) with PSt chains as substitution groups were obtained. The same macromonomers were used in Yamamoto copolycondensation reactions, in combination with a poly(ε‐caprolactone) (PCL) macromonomer, and this resulted in PPs with PSt/PCL side chains. The obtained PPs had good solubility properties in common organic solvents at room temperature similar to those of the starting macromonomers. The new polymers were characterized with 1H (13C) NMR, IR, and gel permeation chromatography. The optical properties of the polymers were monitored with UV and fluorescence spectroscopy. The thermal behaviors of the macromonomers and final PPs were investigated with differential scanning calorimetry and compared. The morphology of PPs containing PSt and PCL blocks was characterized with atomic force microscopy, and a microphase‐separated layered morphology was observed. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 879–896, 2005
2,5‐Dibromo‐1,4‐(dihydroxymethyl)benzene was used as initiator in ring‐opening polymerization of ε‐caprolactone in the presence of stannous octoate (Sn(Oct)2) catalyst. The resulting poly(ε‐caprolactone) (PCL) macromonomer, with a central 2,5‐dibromo‐1,4‐diphenylene group, was used in combination with 1,4‐dibromo‐2,5‐dimethylbenzene for a Suzuki coupling in the presence of Pd(PPh3)4 as catalyst or using the system NiCl2/bpy/PPh3/Zn for a Yamamoto‐type polymerization. The poly(p‐phenylenes) (PPP) obtained, with PCL side chains, have solubility properties similar to those of the starting macromonomer, ie soluble in common organic solvents at room temperature. The new polymers were characterized by 1H and 13C NMR and UV spectroscopy and also by GPC measurements. The thermal behaviour of the precursor PCL macromonomer and the final poly(p‐phenylene)‐graft‐poly(ε‐caprolactone) copolymers were investigated by thermogravimetric analysis and differential scanning calorimetry analyses and compared. Copyright © 2004 Society of Chemical Industry
Poly(ε-caprolactone) (PCL)-based macromonomers and the corresponding substituted polyphenylene polymers have been synthesized in various chemical structures. The effect of chemical structure and the crystallization of PCL on the resulting morphology in thin films have been investigated. PCL macromonomers containing the central 2,5-dibromo-1,4-phenylene moiety were synthesized by ring-opening polymerization (ROP). Poly(phenylene) polymers were then synthesized by cross-coupling of the PCL macromonomers in Yamamato polycondensation reactions. Thin films of macromonomers and polymers were prepared by spin-coating on silicon substrates, and the resulting morphology in thin films was characterized by atomic force microscopy (AFM). Substitution of semicrystalline PCL side chains to the rigid poly(phenylene) backbone induced layered morphology in thin films. Our results indicate that increasing backbone rigidity causes grafted PCL side blocks to crystallize in better-defined layered structures parallel to the underlying substrate. Such layering was not observed when polystyrene (PSt) or poly(2-methyloxazoline) (POx) polymers were grafted to the rigid poly(phenylene) backbone. Hindering PCL crystallization by attaching PSt or POx to the end of PCL also prevented the formation of layered structures.
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