Abstract: In this paper，a new preparation method of a continuous fixed-bed catalytic system for 6,6'-dihydroxy-3,3,3',3'-tetramethyl-1,1'-spirobiindane was reported with bisphenol A crystalline residue solution as raw material，and sulfonated polyvinyl generation of styrene - divinylbenzene strong acid cation exchange resin as catalyst. Stainless steel reactor with ?30 mm was filled by 50 mL (22g， E = 1.8 mmol H+/mL) dry resin. In the condition of T =150 ℃，WHVS = 0.48h－1，it had reacted continuously for 1000 h，the concentration of 6,6 '-dihydroxy-3,3,3',3'-tetramethyl-1,1'-spirobiindane in reaction solution was stabilized at 43.5%，and the exchange capacity of catalyst remained 3.8 mmol/g. Product was purified by recrystallization，and the melting point was 215—217 ℃，purity was≥ 99.98% (HPLC). By HPLC，IR，NMR and other methods for the analysis of product content and structure，reaction conditions were optimized with a statistical software STATISTIC. The results for the improvement on the production process of bisphenol A residue treatment suggest a brand new method for bisphenol monomer production.

Key words: 6,6'-dihydroxy-3,3,3'-,3'-tetramethyl-1,1'--spirobiindane, bisphenol A, a continuous fixed- bed catalytic system

摘要： 利用双酚A结晶残液为原料，以磺化聚氯代苯乙烯-二乙烯基苯强酸性阳离子交换树脂为催化剂，通过固定床连续催化制备6,6'-二羟基-3,3,3',3'-四甲基-1,1'-螺二氢茚。反应器中装填50mL（22 g，E=1.8 mmol H+/mL）干树脂，在T=150 ℃、WHVS=0.48 h－1条件下，连续反应1000 h，反应液中6,6'-二羟基-3,3,3',3'-四甲基-1,1'-螺二氢茚质量浓度可达43.5%，催化剂交换量保持为3.8 mmol/g。产物经重结晶纯化后熔点215～217 ℃，纯度≥99.98%（HPLC）。通过HPLC、IR、NMR等方法分析产物含量及结构，用STATISTIC统计软件对反应条件进行了优化。研究结果对于改进双酚A生产工艺中的残液处理方式，填补国内在新型双酚类单体生产空白具有重要的意义。

关键词: 6,6'-二羟基-3,3,3',3'-四甲基-1,1'-螺二氢茚, 双酚A, 固定床连续催化