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本文研究了聚环氧氯丙烷在环已酮及α-氯萘中测定其特性粘度[η]时的降解问题。得知该聚合物在加热溶解和粘度测定时会发生降解反应。但是,在溶剂中加入0.5%(重量百分数)的抗氧剂2,6-二特丁基对甲酚后,降解反应基本上可以被防止。以甲苯为溶剂,乙醇为沉淀剂,在50℃,对聚环氧氯丙烷进行三次重复沉淀分级,测定各级份的[η],并且用渗透压法订定,得到二个Houwink方程: [η]_(CH)=2.51×10~(-5)M_η~(0.87) dl/g (环己酮、50℃) [η]_(CN)=2.23×10~(-5)M_η~(0.33) dl/g (α-氯萘、100℃) 并得到Huggins公式和Kraemer公式中的参数k’和β的平均值: k’_(CH)=0.358 β_(CH)=0.144 k’_(CN)=0.365 β_(CN)=0.138 聚环氧氯丙在烷环己酮中,50℃时的比浓粘度(η_(SP)/c)_(CH)值以及在α-氯萘中,100℃时的比浓粘度(η_(SP)/c)_(CN)值,当两者浓度相同时,符合下式: lg(η_(SP)/c)_(CN)=0.956lg(η_(SP)/c)_(CH)-0.251(浓度在0～2×10~(-3) g/ml 范围内)。
This article studies the degradation of polyepichlorohydrin when its intrinsic viscosity [η] is measured in cyclohexanone and α-chloronaphthalene. The polymer was found to undergo a degradation reaction upon dissolution under heat and viscosity measurements. However, the degradation reaction can be substantially prevented by adding 0.5% by weight of the antioxidant 2,6-di-tert-butyl-p-cresol to the solvent. Using toluene as the solvent and ethanol as the precipitating agent, the polyepichlorohydrin was repeatedly subjected to repeated precipitation and classification at 50 ° C. The [η] of each fraction was determined and determined by the osmotic pressure method to obtain two Houwink equations: [ η] _ (CH) = 2.51 × 10-5 M_η ~ (0.87) dl / g (cyclohexanone at 50 ℃) [η] _ (CN) = 2.23 × 10 -5 M_η ~ 0.33) dl / g (α-chloronaphthalene at 100 ° C) and the average of the parameters k ’and β in the Huggins and Kraemer equations is obtained: k’ = (CH) = 0.358 β CH = 0.144 k ’ CN) = 0.365 β_ (CN) = 0.138 Polyepichlorohydrin In alkancyclohexanone, the reduced viscosity (η SP / c) _ (CH) The reduced viscosity (η SP / c) _ (CN) at 100 ° C corresponds to the following formula when both concentrations are the same: lg (η SP / c) _ (CN) = 0.956 lg (SP) / c) _ (CH) -0.251 (concentration in the range of 0 ~ 2 × 10 -3 g / ml).