A gel permeation chromatography method to determine grafting efficiency during graft copolymerization

A new method of measuring the efficiencies of free radical grafting reactions is presented. This technique utilizes the compositional analysis capability of dual-detector (ultraviolet and refractive index) gel permeation chromatography (g.p.c.) in which the mixture of polymers resulting from the graft copolymerization reaction is also subjected to separation by molecular size. Samples of the reaction mass drawn from a reactor are diluted with g.p.c. eluent and injected directly into the chromatograph without any other preparative step. Grafting efficiency, graft ratio, molecular weight distributions and the frequency of graft chains along the backbone polymer are simultaneously determined. Low molecular weight diluents (residual monomer, solvent, initiator, etc.) are readily separated from the polymer within the chromatograph, allowing for the determination of the fractional conversion of graft monomer (to grafted and ungrafted polymer) from the same analysis. This simple technique overcomes the need to separate or purify the polymer mixture prior to analysis, as required for most other methods. Experimental results are presented for the grafting of styrene onto cis-polybutadiene. Gelled samples cannot be analysed by this new technique.