Did you use partially or fully hydrolyzed PVA? At what temperature you stored the samples?
Is there another alcohol in your formulation?
No quantitative method is available for the determination of PVA although, various methods have been
described for the detection of PVA. Filter paper treated with potassium iodide and iodine solutions has
been suggested for measuring Polyvinyl alcohol concentration in wastewater in a concentration range of
1000-20,000 mg/l. the color of polymers, including Polyvinyl alcohol, and their derivatives in various
solvents have been used to identify them. The green complex formed by reaction of polyvinyl alcohol with
boric acid has been used to detect small amounts in polyvinyl chloride resins.
Run a UV spectrum to find the optimum wavelength. Maybe 280nm will be a good one.
Degradation is very much dependent on the temperature. At 20°C for 6 months 50% loss is not unusual.
Wash your column after use with 100% water. In my opinion it is difficult to measure PVA on an SEC column due to its MW distribution.
MAybe a special column for alcohols, an IEX column, will give you better results. Good luck.