Long linear 1,4-polybutadienes end-functionalized with associative groups were studied as additives to hydrocarbon fluids to mitigate the fire hazard of their mist in crash scenarios. These polymers were molecularly designed to overcome both the shear-degradation of long polymer chains in turbulent flows, and the chain collapse induced by the random placement of associative groups along polymer backbones.Linear polymers with discrete numbers of carboxyl groups on chain ends were investigated first: an innovative synthetic strategy was devised to achieve unprecedented backbone lengths and precise control of the number of carboxyl groups on chain ends (N). A very narrow range of N was found to allow both sufficient end-association strength and polymer solubility in apolar media. Shear rheology revealed the end-association of very long chains in apolar media leads to the formation of flower-like micelles interconnected by bridging chains. The polymer with N = 4 and Mw= 430 kg/mol was found shear-resistant, effective in providing fire protection to jet fuel at concentrations as low as 0.3wt%, well-soluble in jet fuel ranging from -30 to +70�C, and showing little interference with dewatering.Four pairs of complementary associative end-groups of varying strengths were also investigated, in the hope of achieving supramolecules with both mist-control ability and better utilization of polymer building blocks. Shear rheology revealed the strength of complementary end-association required to achieve supramolecules capable of modulating solution rheological properties.

Synthesis and potency of long end-associative polymers for mist control

248th National Meeting (2014)

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