Model study by FT-IR and13C NMR of the interaction of poly(norbornene-alt-maleic anhydride) and its derivatives with select cholate dissolution inhibitors or with select iodonium and sulfonium phot

The fundamental nature of the interactions between poly (norbornene-alt-maleic anhydride) based resins and cholate based dissolution inhibitors (DIs) were studied by FT-IR and NMR spectroscopy. We also studied the role that photo-acid generators (PAGs) play in the dissolution of these polymer resins. We attempted to disentangle the hydrophobic effects of the DIs and PAGs from the specific interactions (Van der Waal's, hydrogen bonding or ionic) that these materials have within the polymer system. We employed solubility studies of DIs and PAGs using cloud point determinations and dissolution inhibition experiments on spun films to determine the extent that hydrophobicity and polymer interactions play in development. We found that for simple cholate derivatives the interactions with maleic anhydride repeating units parallel the dissolution inhibition sequence (t-butyllithocholate > t-butyldeoxycholate > t-butylcholate). For a wider range of cholate derivatives, the cloud point in water is a useful predictive tool, in that it takes into account both the hydrophobicity and the propensity to interact with other moieties. Thus for these materials, dissolution inhibition is governed by both interactions between the DI and the polymer, and the hydrophobic nature of the DIs. In contrast, for the PAGs, the cloud point is not a good predictive tool for dissolution inhibition. We found for onium salt materials, that the extent of dissolution inhibition is predicated by the size of the anion. For example, large sterically hindered anions which give rise to PAGs that exhibit poor solubility in water, paradoxically also show poor dissolution inhibition. This may be because the steric hinderance disfavors interactions with the polymer matrix.