Ring opening metathesis polymerization of dicyclopentadiene catalyzed by titanium tetrachloride adduct complexes with nitrogen-containing ligands

Abstract

Ring opening metathesis polymerization (ROMP) of dicyclopentadiene (DCPD) catalyzed by titanium tetrachloride adduct complexes such as TiCl4 · 2L [L = pyridine (1), 2‐methylpyridine (2), 2,4,6‐trimethylpyridine (3), 3‐aminopyridine (4), 2‐hyroxypyridine (5)] and CH3Li as cocatalyst was reported. The polymer was characterized by IR and 1H‐NMR methods. Five influencing factors were also discussed. The catalyst systems TiCl4 · 2L/CH3Li (L = 2‐methylpyridine, 2,4,6‐trimethylpyridine) appeared to be very active for the ROMP of DCPD. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 3247–3251, 2000

Synthesis and thermal properties of linear polydicyclopentadiene via ring‐opening metathesis polymerization with a third generation grubbs‐type ruthenium‐alkylidene complex

“…Much less investigated are materials from linear PDCPD, the polymer formed by exclusively ring‐opening the reactive CC double bond of DCPD. Only a handful reports have described the synthesis of linear PDCPD via ROMP using either ill‐defined tungsten and molybdenum initiators, well‐defined, but low reactive titanium catalysts or, as described very recently, using a metal‐free olefin metathesis catalytic system . In these cases, the ROMP reactions were slow and the synthesized linear PDCPD did not exhibit a high degree of molecular weight control.…”

Oxidation and Structuring of Polydicyclopentadiene Thin Layers

“…It is quite a reactive compound. During dicyclopentadiene polymerization, depending on the type of chosen catalytic system [1][2][3][4][5][6] , there are macromolecules formed with olefinic bonds in the main chain or sidechains. The high unsaturation of dicyclopentadiene-based polymers predefines their tendency for oxidative and structural transformations in the thin layer 7 .…”

Metal–Free Ring–Opening Metathesis Polymerization with Hydrazonium Initiators

“…Ring-opening metathesis polymerization (ROMP) is used extensively in both industrial and fine-chemical synthesis to convert feedstock cyclic olefins into high-value polymers. [1][2][3] These unique polymerizations have been enabled by a variety of heterogeneous and homogeneous transition metal catalysts, including those based on tungsten, [4][5][6] titanium, [7][8][9] tantalum, [10,11] niobium, [11] rhenium, [12] iron, [13] and especially ruthenium [14][15][16] and molybdenum [5,6,17] complexes (Figure 1A). While the impact of these reactions on the field of chemistry, and indeed human society, has been profound, there are some wellrecognized drawbacks to the use of transition metal reagents.…”