缩水甘油醚基烯丙基聚氧乙烯醚的合成
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摘要
缩水甘油醚基烯丙基聚氧乙烯醚是制备有机硅柔软剂的重要中间体,常用酸、碱催化法生成的副产物较多,产率较低。文中采用NaH催化法,以烯丙基聚氧乙烯醚400和环氧氯丙烷为原料,在NaH催化作用下,通过开环反应生成烯丙基聚氧乙烯氯醇醚中间体,在NaOH作用下发生闭环反应生成缩水甘油醚基烯丙基聚氧乙烯醚,研究了反应条件对产物封端率的影响,优化了合成工艺,测定了合成产物的封端率,并对合成产物进行了红外光谱分析。结果表明,NaH催化法合成产物的红外光谱含有C=C双键和环氧基,确定了合成产物结构为缩水甘油醚基烯丙基聚氧乙烯醚;合成优化工艺为n(烯丙基聚醚)∶n(环氧氯丙烷)∶n(NaOH)=1.00∶1.75∶1.50,开环温度为70℃,闭环温度为35℃,开环时间1.5 h,闭环时间2.0 h,NaH催化剂用量为4.0‰(以反应物总质量计),最终产物封端率为95.18%。
Glycidyl ether allyl polyoxyethylene ether is an important intermediate for the preparation of silicone softener, which commonly uses acid and alkali catalytic methods for production but more by-products and lower yields often resulted. In this paper NaH catalytic method was used, allyl polyoxyethylene ether 400 and epichlorohydrin were used as raw materials to form allyl polyoxyethylene chlorohydrin ether intermediate by ring opening reaction under NaH as catalysis. The ring closure reaction occurs under the action of NaOH to form glycidyl ether allylate polyoxyethylene ether, the effect of reaction conditions on product end-capping rate of products was studied, the synthesis process was optimized, and the end-capping rate of the synthesized product was determined, and the FT-IR analysis of the synthesized product was carried out. The results show that the infrared spectrum of the product synthesized by NaH catalysis contains C = C double bond and epoxy group, the structure of the synthesized product was determined to be glycidyl ether allyl polyoxyethylene ether; The optimized process was: n(allyl polyether)∶n(epichlorohydrin)∶n(NaOH)=1.00∶1.75∶1.50. The open-loop temperature is 70 ℃,the closed-loop temperature is 35 ℃, the ring-opening time is 1.5 h, the ring closure time is 2.0 h, the amount of NaH catalyst is 4‰(based on the total mass of the reactants), and the final product end-capping rate is 95.18%.
Glycidyl ether allyl polyoxyethylene ether is an important intermediate for the preparation of silicone softener, which commonly uses acid and alkali catalytic methods for production but more by-products and lower yields often resulted. In this paper NaH catalytic method was used, allyl polyoxyethylene ether 400 and epichlorohydrin were used as raw materials to form allyl polyoxyethylene chlorohydrin ether intermediate by ring opening reaction under NaH as catalysis. The ring closure reaction occurs under the action of NaOH to form glycidyl ether allylate polyoxyethylene ether, the effect of reaction conditions on product end-capping rate of products was studied, the synthesis process was optimized, and the end-capping rate of the synthesized product was determined, and the FT-IR analysis of the synthesized product was carried out. The results show that the infrared spectrum of the product synthesized by NaH catalysis contains C = C double bond and epoxy group, the structure of the synthesized product was determined to be glycidyl ether allyl polyoxyethylene ether; The optimized process was: n(allyl polyether)∶n(epichlorohydrin)∶n(NaOH)=1.00∶1.75∶1.50. The open-loop temperature is 70 ℃,the closed-loop temperature is 35 ℃, the ring-opening time is 1.5 h, the ring closure time is 2.0 h, the amount of NaH catalyst is 4‰(based on the total mass of the reactants), and the final product end-capping rate is 95.18%.
引文
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[5]朱新宝,程振朔,李大钱.烯丙基缩水甘油醚的合成方法:中国,201310080317.6[P].2013-06-12.
[6]苏玲,张丽华.聚乙二醇/环氧氯丙烷多羟基聚醚的合成及表征[J].化学推进剂与高分子材料,2013,11(5):66-69.
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