Poly(phthalidylidene arylene)s: Synthesis of poly(3,3‐phthalidylidene‐4,4′‐biphenylylene) by precipitative homopolycondensation of 3‐(4‐biphenylyl)‐3‐chlorophthalide

Abstract

The synthesis of poly(3,3-phthalidylidene-4,4' -biphenylylene) (PPB) by precipitative Friedel-Crafts homopolycondensation of 3-(4-biphenylyl)-3-chlorophthalide was studied. The polymer-catalyst complex precipitated from the initially homogeneous reaction mixture was shown to be active and providing the growth of macromolecular chains. The polymer obtained in the form of smooth, transparent glass-like particles, depending on the reaction parameters, may have either uni-or bimodal molecular weight distribution. Molecular characteristics were not found to depend on the size of the polymer particles. "Precipitative" PPB shows improved properties and higher crystallinity in comparison with "solution" PPB. ZUSAMMENFASSUNG: Die Synthese von Poly(3,3-phthalidyliden-4,4'-biphenylylen) (PPB) durch eine Friedel-Crafts-Fallungspolykondensation von 3-(Biphenyl-4-yl)-3-chlorphthalid wurdeuntersucht. Der aus der urspriinglich homogenen Reaktionsmischung ausgefallte Polymer-Katalysator-Komplex erwies sich als aktiv und forderte das Wachstum der Polymerketten. Die in Form von glatten, tranparenten, glasartigen Partikeln erhaltenen Polymeren zeigen, abhangig von den Reaktionsparametern, entweder uni-oder bimodale Molekulargewichtsverteilung. Die Polymereigenschaften sind unabhangig von der PartikelgroDe. Verglichen mit aus der Liisungspolymerisation erhaltenem PPB zeigt das mittels Fallungspolykondensation hergestellte PPB verbesserte Eigenschaften und hdhere Kristallinitat.

Aromatic polymers obtained by precipitation polycondensation: 4. Synthesis of poly(ether ketone ketone)s

“…after phase separation. Recently we have [6][7][8][9][10] shown that precipitation electrophilic Friedel Crafts polycondensation can be performed in such a way that the polymer precipitate presents quite uniform small particles. This process has unquestionable technological advantages, since pure polymer can be recovered just by filtration followed by washing with organic solvents and drying.…”

Photo-induced synthesis of polymeric nanoparticles and chemiluminescent degradable materials via flow chemistry

“…Furthermore, Br-TEG presents no acute toxicity compared to methyl iodide, which we previously used in the nucleophilic substitution reaction with the alcohol group. 25 1 H, 13 C NMR, and LC-MS confirmed the successful formation of the AA monomer (Fig. 2B and Table S1, Fig.…”

“…S1, ESI †). 13 63 mmol, 1 eq.,) was dissolved in anhydrous DMF (120 mL) under an inert atmosphere. 2-[2-(2-methoxyethoxy)ethoxy]ethyl bromide (Br-TEG) (7.92 mL, 31.99 mmol, 1.63 eq.)…”

“…12 Other examples of particle synthesis by precipitation polymerisation are the formation of particles following polycondensation reactions. 13,14 Photoinduced precipitation polymerisation is of particular interest since the reaction is carried out at room temperature with all the advantages of photochemistry such as spatiotemporal control. Photoinitiators of type I [15][16][17] or II 18,19 are generally employed, therefore producing particles via free or controlled radical chain growth polymerisation.…”

Novel rearrangement in the synthesis of poly(phthalidylidenearylene)s by self-condensation of 3-aryl-3-chlorophthalides. 2. Effect of monomer structure and reaction conditions

“…It seems very likely that the rearrangement proposed represents a consequence of cation transformations resulting in formation of more stable ions (e.g. 8). From this point of view, analysis of the results of polymer preparations using different monomers and different reaction conditions may contribute to clarify the rearrangement mechanism.…”