Ring-opening metathesis polymerization of tetracyclododecene using various catalyst systems

다국어 초록 (Multilingual Abstract)

<P>Ring-opening metathesis polymerization (ROMP) of a polycyclic olefin monomer (tetracyclododecene, TCD) was carried out using various catalyst systems. The catalysts included titanium-based ternary system (titanium tetrachloride, TiCl<SUB>4</SUB>/triethylaluminum, Et<SUB>3</SUB>Al/triethylamine, Et<SUB>3</SUB>N), tungsten-based ternary system (tungsten hexachloride, WCl<SUB>6</SUB>/triisobutyl aluminum, (i-Bu)<SUB>3</SUB>Al/ethanol), and a ruthenium benzylidene catalyst (Grubbs 1st catalyst). The Grubbs 1st catalyst was most active in ROMP of TCD. The tungsten-based catalyst was found to be more active than the titanium-based catalyst. In contrast to the titanium-based and the Grubbs 1st catalysts, ROMP of TCD with the tungsten-based catalyst was very sensitive to gelation in the course of reaction. The effects of ethanol, WCl<SUB>6</SUB> concentration, TCD/WCl<SUB>6</SUB> ratio, and 1-hexane on the polymerization yield and the polymer gel formation were investigated in detail, and optimized ROMP conditions were determined. Chemical structure of synthesized polymer was characterized using one- and two-dimensional 150 MHz <SUP>13</SUP>C and 600 MHz <SUP>1</SUP>H nuclear magnetic resonance spectroscopy, molecular weights were measured using gel-permeation chromatography, and thermal properties were characterized using differential scanning calorimetry. Number-average molecular weights (M<SUB>n</SUB>) of the polymer were in the range of 1.5–4.7 × 10<SUP>4</SUP> g/mol, and glass transition temperatures were in the range of 185–220°C. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010</P>