Initiation and Growth of Butadiene Resinous Polymers

Abstract

I tie iporitaneous f o r m a t i o n of a n i n s o~i~e , infii-il>lv 1,utacliene popcorn pol?;mer ha$ been encountered i n c o~i i t . o f Lhe commercial clibtillation u n i t s w h i c h are ic-etl t o purify butadiene for the s?;nthetir r u b b e r proprani. On( t' initiated, the p o l > m e r Shows a logarithmic pro\+ t h i t i b u t a d i e n e monomer and has caused fouling and etet] hurstiiig of large scale distillation e q u i p m e n t i n relatit el? short times. h l t h o u g h it can be initiated in n %ariety of w a y s , iron and a c t i t e oxygen play a11 i m p o r t a n t p a r t i r i its formation. Its growth is retarded b u t n o t t e r m i n a t e d by ~ulcanization accelerators, n hereas c.on\eritional ' i n t ioxidants have little effect.

Detailed Multiphase Chemical Kinetic Model for Polymer Fouling in a Distillation Column

“…For example, a styrene self-initiating fouling mechanism was investigated by Mayo et al , and supported by experimental data and later examined with modern quantum chemistry calculations . There are also fouling studies of BD focusing on the initiation mechanism of BD polymer popcorn, typically with Fe catalysts , and also on the impacts of oxygen. , …”

“…For example, a styrene self-initiating fouling mechanism was investigated by Mayo et al 15,16 and supported by experimental data 17 and later examined with modern quantum chemistry calculations. 18 There are also fouling studies of BD focusing on the initiation mechanism of BD polymer popcorn, typically with Fe catalysts 19,20 and also on the impacts of oxygen. 21,22 However, these literature mechanisms mainly focus on a single monomer under very specific reaction conditions, while the distillation column fouling is much more complicated and the modeling of distillation column fouling requires much more than just the initiation mechanism.…”

Relief system's last line of defense, only line of defense?

“…The Contractor engineers did not recognize that butadiene was a reactive chemical and that uninhibited butadiene in particular was more reactive than inhibited butadiene. This information was readily available in an MSDS that could have been easily obtained from the Client or from numerous sources in the literature [5–20].…”

Oxygen Chemistry in Polymer Fouling: Insights from Multiphase Detailed Kinetic Modeling

“…One of the most prevailing impurities is traces of dissolved oxygen in the unit fluid, which can enter the process as an impurity along with the feedstock, water used for quenching, or additives. Literature experimental investigations have shown that dissolved oxygen can affect fouling significantly, 7−12 where dissolved oxygen was measured to accelerate fouling 7,12 even at parts per million (ppm) level concentrations, 10 while the fouling rate becomes independent of oxygen concentration near air saturation. 12 The effects of dissolved oxygen on fouling rates were recently measured using quartz crystal microbalance with dissipation monitoring (QCM-D), similar to the prediction by our detailed fouling model for QCM-D cell fouling.…”