Hydrolysis of Poly(fluoroacrylate) Thin Films Synthesized from the Vapor Phase

The post-synthesis surface reaction of vapor-deposited polymer thin films is a promising technique in engineering heterogeneous surface chemistry. Because the existing research has neglected marginally reactive precursor films in preference of their highly reactive counterparts, our knowledge of kinetics and loss of film integrity during the reaction are limited. To address these limitations, we characterize hydrolysis of two fluoroacrylates, poly(1H,1H,2H,2H-perfluorooctyl acrylate) (pPFOA) and poly(2,2,3,4,4,4-hexafluorobutyl acrylate) (pHFBA), with sodium hydroxide using X-ray photoelectron spectroscopy. Without crosslinking with di (ethylene glycol)divinyl ether (DEGDVE) and grafting with trichlorovinyl silane, the films degrade rapidly during hydrolysis. An SN2 mechanism describes hydrolysis well, with rate constants of 0.0029 +/- 0.0004 and 0.011 +/- 0.001 L mol-1s-1 at 30 degrees C for p(PFOA-coDEGDVE) and p(HFBA-co-DEGDVE), respectively. Our detailed study of hydrolysis kinetics of marginally reactive fluoroacrylates demonstrates the full capability and limitations of the post-synthesis reaction. Importantly, copolymers are characterized using a density correction new to polymer chemical vapor deposition.

Automated summary

The detailed study of hydrolysis kinetics of marginally reactive fluoroacrylates demonstrates the full capability and limitations of the post-synthesis reaction. The hydrolysis of two fluoroacrylates, poly(1H,1H,2H,2H-perfluorooctyl acrylate) (pPFOA) and poly(2,2,3,4,4,4-hexafluorobutyl acrylate) (pHFBA), is characterized using X-ray photoelectron spectroscopy. The films degrade rapidly during hydrolysis without crosslinking or grafting, and an SN2 mechanism well describes the hydrolysis process.