Addition polymerization of 5-ethylidene-2-norbornene by cationic palladium cationic complex and subsequent derivatization

Abstract

Poly(5-ethylidene-2-norbornene) (PENB) was synthesized via a vinylic pathway using a cationic palladium-based catalyst, displaying high activity up to 1.06×10 6 g-PENB/mol Pd. The effects of the monomer to catalyst ratio, temperature, reaction time, and concentration on the polymerization were investigated systematically. The control tests and spectroscopic analyses of the PENB indicate that 5-ethylidene-2-norbornene is polymerized via an addition polymerization using endocyclic double bonds. The post-modification was also performed using a free radical graft polymerization. The resulting PENB copolymers were characterized by IR, 1 H NMR, and GPC analyses.

5‐Ethylidene‐2‐norbornene Polymerization by α‐Diimine Nickel Catalyst: A Revealing Insight into the Pivotal Function of Binuclear and Mononuclear Catalyst Structure in Tailoring Polymer Architecture

“…Besides, the previous studies (nickel-and palladium-based catalysts) clarified that irrespective of MAO/Ni molar ratio, the elevation of polymerization temperature can be regarded as a potential contributing factor that enhances the productivity. [18,29,30] As demonstrated, the programmed rise in the reaction temperature leads to a similar trend in ENB homopolymerization mono and binuclear catalysts (Table 2). Remarkably, in the case of binuclear catalysts, the increase in efficiency was most prominent after the increase in temperature (from 0 to 25 °C).…”

“…[ 17 ] Concerning ENB polymerization, high activity (1.06 × 10 6 g‐PENB/mol Pd) was recorded for palladium‐based catalyst. [ 18 ] Concerning the ethylene copolymerization with 5‐ethylidene‐2‐norbornene, the vanadium catalyst has been demonstrated to be highly active, enjoying the capacity to yield a polymer with a high molecular weight and a higher degree of comonomer insertion. [ 19 ] It was particularly understood that the application of Pd N ‐heterocyclic carbene complexes as a catalyst has been adjusted to provide a soluble high molecular weight poly 5‐ethylidene‐2‐norbornene (PENB).…”

“…[ 21 ] The functionalization of 5‐ethylidene‐2‐norbornene with methyl methacrylate functional group has been also investigated. [ 18 ] Taking into account the fact that the C═C ethylidene bond associated with 5‐ethylidene‐2‐norbornene (classified as one of the norbornene derivatives) remains unchanged. This C═C ethylidene can be modified so as to produce polymers with a varying degree of functionalization.…”

Polymerization of 5-Alkylidene-2-norbornenes with Highly Active Pd–N-Heterocyclic Carbene Complex Catalysts: Catalyst Structure–Activity Relationships

“…To the best of our knowledge, the addition polymerization of MNB was reported only once by Hennis et al ENB is a large-scale industrial product widely used in the synthesis of vinyl (addition) terpolymers from ethylene, propylene, and dienes; , however, the behavior of this bifunctional monomer in the presence of catalytic systems for addition polymerization is poorly understood. Titanium-, nickel-, and palladium-containing systems were used as catalysts for its homopolymerization. ,,, Recently, it was found from an analysis of NMR spectra, that in some cases, the cationic polymerization of ENB can occur along with its addition polymerization (Scheme ). , Therefore, it seems reasonable to search for selective, highly active, and stable catalyst systems for the addition polymerization of 5-alkylidene-2-norbornenes.…”

“…Titanium-, nickel-, and palladium-containing systems were used as catalysts for its homopolymerization. 39,58,61,62 Recently, it was found from an analysis of NMR spectra, that in some cases, the cationic polymerization of ENB can occur along with its addition polymerization (Scheme 1). 39,40 Therefore, it seems reasonable to search for selective, highly active, and stable catalyst systems for the addition polymerization of 5-alkylidene-2-norbornenes.…”