General Functionalization Method for Synthesis of α‐Functionalized Polymers by Combination of Anionic Polymerization and Hydrosilation Chemistry

Abstract

Summary: A new general functionalization method (GFM) of synthesizing a-functionalized polymers has been developed. a-Vinyl-functionalized polystyrene was obtained by anionic polymerization of styrene using 4-pentenyllithium as an initiator. Chloromethyldimethylsilane-functionalized polystyrene was successfully synthesized from vinyl-functionalized polystyrene by hydrosilation using Karstedt's catalyst. Nucleophilic substitution of this polymer was carried out in presence of pyrrolidine to obtain a-pyrrolidine-functionalized polystyrene. a-Triethoxysilylpolystyrene was obtained by hydrosilation of a-4-pentenylpolystyrene with triethoxysilane using Karstedt's catalyst.

Multidimensional Mass Spectrometry of Synthetic Polymers and Advanced Materials

“… MALDI‐MS 2 (CAD) spectra of the [ M +Ag] + ions from a) the 31‐mer of an in‐chain‐functionalized polystyrene and b) the 32‐mer of a 4‐arm star‐branched polystyrene, acquired on a ToF/ToF mass spectrometer. The polymers were prepared by combining polystyryllithium with (CH 3 ) 2 SiCl 2 and Cl 2 (CH 3 )Si(CH 2 ) 2 Si(CH 3 )Cl 2 , respectively . a) The a n , b n , and b n i fragments carry a s ‐C 4 H 9 group at one chain end; the other chain‐end substituent is CH 2 CH(Ph)=CH 2 for a n , CH=CH(Ph) for b n and Si(CH 3 ) 2 C(Ph)=CH 2 for b n i .…”

Mehrdimensionale Massenspektrometrie von synthetischen Polymeren und modernen Materialien

“…Das Muster der Fragmentintensitäten im MS/MS‐Spektrum von Abbildung b lässt auf eine lineare, an den Kettenenden substituierte Struktur schließen . Ein ganz anderes Fragmentierungsmuster wird bei einem in der Kette substituierten Polystyrol und bei einem vierarmigen Polystyrol‐Sternpolymer gefunden, wie die MS/MS‐Spektren in Abbildung zeigen . Das in der Kette funktionalisierte Polymer (Abbildung a) ergibt etwa drei Gauß‐Verteilungen der Fragmente mit dem verbindenden Substituenten (b n i ) oder ohne ihn (b n und a n ) und ein Maximum bei einem Wert für n von etwa 15–18, was nahe der mittleren Größe der in der Synthese eingesetzten PS‐Ketten liegt.…”

Tapered copolymers of styrene and 4‐vinylbenzocyclobutene via carbanionic polymerization for crosslinkable polymer films

“…Living anionic polymerization affords polymers with precisely controlled molecular weight and architecture . A variety of functional groups can be introduced into these polymers using functional initiators or various termination reagents that quantitatively terminate the living chain end . With both methods, a plethora of functionalities like hydroxyl groups, acidic units or amino functionalities is accessible.…”

“…Alkoxysilanes, acyl clorides, but also catechols may be suitable functionalities depending on the chosen surface. The attachment of surface reactive silyl groups can be achieved by hydrosilylation reactions of double bonds with the appropriate silanes . Theoretical and quantitative descriptions of tethered polymer chains were published by de Gennes .…”

“…The attachment of surface reactive silyl groups can be achieved by hydrosilylation reactions of double bonds with the appropriate silanes. 2,12 Theoretical and quantitative descriptions of tethered polymer chains were published by de Gennes. 36 Generally two different cases can be distinguished.…”