Novel organosoluble polynorbornene bearing a polar, pendant, ester-bridged epoxy group via living ring-opening metathesis polymerization

摘要

A novel organosoluble polynorbornene bearing a polar, pendant, ester-bridged epoxy group [poly(oxiran-2-ylmethyl 2-methylbicyclo[2.2.1]hept-5-ene-2-carboxylate) (polyOMMC)] was prepared via the living ring-opening metathesis polymerization (ROMP) of active norbornenes with a Ru catalyst. PolyOMMC exhibited excellent solubility in a variety of solvents. The number-average molecular weight of polyOMMC linearly increased with the [M]/[I] ratio (where [M] is the monomer concentration and [I] is the initiator concentration), and a narrow polydispersity of 1.09-1.19 was observed; this was considered a living polymerization. When ROMP of oxiran-2-ylmethyl 2-methylbicyclo[2.2.1]hept-5-ene-2-carboxylate with [M]/[I] = 350 was carried out at 30 degrees C in CH2Cl2, the number-average molecular weight (7.01 x 10(4); polydispersity index = 1.07) was close to the calculated molecular weight (7.28 x 10(4)), and a diblock copolymer was observed after the addition of another monomer ([M]/[I] = 350) with an increase in the number-average molecular weight (1.60 x 10(5); polydispersity index = 1.11), which was close to the calculated molecular weight (1.61 x 10(5)). The modified polynorbornenes retained good solubility in methylene chloride, tetrahydrofuran, dimethyl sulfoxide, dimethylformamide, NN-dimethylacetamide, and N-methyl-2-pyrrdione. High-performance polynorbornenes with active epoxy groups could be designed with great potential for applications in photoresists, UV curing, and elastomers. (c) 2006 Wiley Periodicals, Inc.