The crosslinking reaction of poly(vinyl alcohol) (PVA) by esterification using poly(acrylic acid) (PAA) as a crosslinking reagent was investigated to obtain highly insoluble PVA materials. Blend films of PVA and PAA (PVA/PAA = 8/2) were prepared to examine the effect of degree of neutralization (DN) in PAA and heat-treatment conditions on the degree of crosslinking reaction. The degree of crosslinking reaction varied significantly when the DN of PAA changed. The optimum DN for the crosslinking reaction was in the range of 5 to 10 mol %. In the case of unneutralized PAA, the degree of crosslinking reaction was at most 15 mol % by heat treatment for 20 min at 200degreesC. Applying partially neutralized PAA (DN = 10 mol %) raised the degree to about 40 mol % under the same heat-treatment conditions. FTIR analysis revealed that the hydroxyl group of PVA in the film blended with unneutralized. PAA was degraded to a greater degree than that with partially neutralized PAA as a result of heat treatment. It was found that heat treatment at a low pH condition enhances the degradation of the hydroxyl group of PVA, resulting in a decrease of the number of crosslinking sites by esterification. (C) 2003 Wiley Periodicals, Inc.