Monomer sequencing and microstructural analysis on polymers of dimethyl norbornene dicarboxylate and 7‐oxanorbornene dicarboxylic derivatives employing ruthenium catalysts by ring‐opening metathesis polymerization

Abstract

The physiochemical properties, comonomer sequencing, and regiospecificity of the linkages between monomeric units within homo/copolymers based on 5,6‐di‐substituted norbornene and 7‐oxanorbornene type monomers by ring‐opening metathesis polymerization are reported and correlated to their primary and secondary structural elements. In general, first‐generation Grubbs‐I1 ruthenium catalyst generates polymers with high trans content that exhibits an extended secondary structure with exo,exo substituents, whereas second‐generation Grubbs‐I2 catalyst produces polymers with high cis content that forms tight turns, resulting in a compact structure. Furthermore, I2‐produced polymers exhibit a high level of alternating cis–trans double bonds along their polymeric backbone. In stark contrast, both first‐ and second‐generation Grubbs catalysts display complete reversal in cis/trans selectivity when an oxygen atom is in position‐7 of the norbornene‐ring along with mono‐endo‐substitution in position‐5 or 6, and hence highlighting the importance of stereoelectronic complexation by the catalyst with the next incoming monomer for cis/trans selectivity. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014, 52, 2477–2501

The chemistry of the carbon-transition metal double and triple bond: Annual survey covering the year 2014

“…77) [363], fluorescent groups and PEG groups (copolymer) [364]; polyoxometallates [365], dendriditically connected to a polylactate and a polystyrene system [366], and dendritic connection to anthraquinone moieties [367]; (19) bis(norbornenesuccinimide)s connected through a perylene ring [368]; (20) aza-Diels-Alder derived azanorbornenes (e.g. 80) [369]; (21) oxanorbornenes connected to azide groups [370]; (22) oxanorbornenecuccinic anhydride (81) [371]; (23) oxanorbornenesuccinimides, including those connected to alkyne groups [372], and to dendrimeric systems [373,374]; and (24) oxanorbornenedicarboxylate esters connected to guanidine groups [375]. The kinetic resolution of a racemic oxanorbornene (e.g.…”

Poly(alkylidene chlorophosphate)s via Acyclic Diene Metathesis Polymerization: A General Platform for the Postpolymerization Modification of Poly(phosphoester)s

“…20−23 Troev and co-workers used in a series of papers reactive poly(H-phosphonate)s for the introduction of various pendant groups. 24,25 The metathesis platform already tolerates many reactive groups, such as anhydrides; 26,27 however, highly nucleophilic groups, acrylates, and others are either difficult to introduce or hamper the removal of the catalyst. 28 With the approaches presented herein, potentially biocompatible materials will be accessible and may find applications in polymer therapeutics or adhesives.…”

“…This work helps to fill the gap by the presentation of an approach for the synthesis of diverse functional and degradable polyesters: The approach uses metathesis polymerization to generate reactive and degradable poly(phosphoester)s (PPEs) that can be modified to create highly functional materials which are only accessible via postmodification. PPEs have found increasing attention during the past years due to different synthetic methods via ring-opening polymerization and polycondensation or polytransesterification methods and the straightforward preparation of water-soluble or temperature-responsive polymers. − Recently, the Wooley lab used anionic ring-opening polymerization to synthesize reactive PPEs carrying reactive olefins or alkynes in the side chain with subsequent postmodification and assembly to degradable drug carriers, for example. − Troev and co-workers used in a series of papers reactive poly(H-phosphonate)s for the introduction of various pendant groups. , The metathesis platform already tolerates many reactive groups, such as anhydrides; , however, highly nucleophilic groups, acrylates, and others are either difficult to introduce or hamper the removal of the catalyst . With the approaches presented herein, potentially biocompatible materials will be accessible and may find applications in polymer therapeutics or adhesives.…”