Herein are disclosed modified vinyl alcohol polymers (mPVOH), wherein the mPVOH can comprise structure VII: ##STR1##

and at least one structure comprising structure IX: ##STR2##

or structure X: ##STR3##

wherein —R can independently comprise an unsubstituted hydrocarbon moiety comprising at least one alpha hydrogen or a substituted hydrocarbon moiety comprising at least one alpha hydrogen. The mPVOH can be useful in oxygen barrier applications, such as a forming an oxygen barrier layer of a packaging article. Also disclosed are methods of forming mPVOH and methods of using mPVOH to make packaging articles with a superior barrier to entry by atmospheric oxygen.