End‐Functionalized Chains via Anionic Polymerization: Can the Problems with Using Diphenylethylene Derivatives be Solved by using Bisphenol F?

Abstract

The controlled functionalization of polymers via anionic polymerization draws great attention not only because of the importance of introducing functionality into otherwise unfunctionalized polymers, but also because of the possibility to use the resulting macromonomers to make a variety of complex architectures. The versatile family of 1,1‐diphenylethylene (DPE) derivatives is widely used to produce many different functionalized (co)polymers. DPE can be added either as an end‐capping agent or be activated by butyllithium to initiate the polymerization. However, each approach faces potential problems in gaining precise control over the number of DPE moieties per chain. In this work, for the first time, the effectiveness of each approach is compared by the characterization of 1,1‐bis(4‐tert‐butyldimethylsiloxyphenyl)ethylene functionalized polystyrene, synthesized via both the procedures. A combination of NMR, size exclusion chromatography, matrix‐assisted laser desorption ionization‐time of flight (MALDI‐ToF) mass spectrometry, and interaction chromatography is used. To overcome the limitations of DPE derivatives, the use of a novel (protected) bisphenol F potassium initiator is proposed.

Synthesis of a Hierarchically Branched Dendritic Polymer Possessing Multiple Dendrons on a Dendrimer-like Backbone

“…For BSt, the styrenic double bond was selectively polymerized while butenyl remained unreacted, yielding a living oligomer, sec -Bu-(BSt) m Li ( m = 1–4). DPE-OSiBuMe 2 underwent one-step efficient addition to the living oligomer due to the easy formation of the resulting carbanion that is stabilized by conjugation of the two phenyl rings. , Nonetheless, DPE derivatives usually cannot dimerize or homopolymerize due to steric hindrance, , unless pairs of DPE derivatives with, respectively, electron-pulling and pushing substituents were used . Arm-1 and Arm-2 were prepared under identical conditions but different batches with a feed molar ratio of sec -BuLi:BSt:DPE-OSiBuMe 2 :St ≈ 1:2:1:75.…”

Quo Vadis Carbanionic Polymerization?

“…Toward this direction, many reports were documented by employing anionic polymerization and postpolymerization reactions for synthezing noncovalent bonded block polymers (hydrogen bonding, stereocomplexation, etc. ). − Our group reported the synthesis of supramolecular block copolymers (PS-DAT- sb -PI-Thy) via anionic polymerization and hydrogen bonding. Well-defined thymine end-functionalized PI (PI-Thy) and diaminotriazine (DAT) end-functionalized PS were synthesized by employing the EO end-capping method of the corresponding carbanionic living chains followed by suitable transformation reactions.…”

Temperature Gradient Interaction Chromatography: A Perspective

“…The NP-TGIC separation of homopolymers with different functional groups has been successfully achieved by our group [38,39], showing that it is possible to follow chain end functional group transformations and to obtain successful separation of chains with a molar mass of up to 200,000 g mol −1 which differ only by the presence of a single primary alcohol functionality at the chainend [39]. At such molar masses, any attempt to identify the presence of, or to attempt to quantify the extent of end-functionalization by NMR or MALDI-ToF MS would be an act of futility.…”