聚丙烯催化剂内给电子体环丁基-1,1-二甲醇二甲醚的合成

以丙二酸二乙酯和1,3-二氯丙烷为起始原料,经烷基化、酯还原和醚化反应合成环丁基-1,1-二甲醇二甲醚,分别考察了关键因素对3步合成反应的影响。适宜的工艺条件为:①烷基化反应时,丙二酸二乙酯0.1 mol,n(丙二酸二乙酯)∶n(CsOH)∶n(1,3-二氯丙烷)=1.0∶2.2∶1.4,DMSO为100 mL,反应温度30℃,反应时间16 h,收率为93.6%;②酯还原反应时,以无水氯化锌为催化剂,环丁基-1,1-二甲酸二乙酯与硼氢化钾的摩尔比为2.0∶1.0,反应温度60℃,反应时间12 h,收率为88.0%;③醚化反应时,以四丁基溴化铵相转移催化剂,甲苯为溶剂,0.1 mol环丁基-1,1-二甲醇,n(环丁基-1,1-二甲醇)∶n(NaOH)∶n(碳酸二甲酯)=1.0∶8.0∶2.4,催化剂四丁基溴化铵1.25 g,反应温度40℃,收率为61.8%。以丙二酸二乙酯为计三步反应的总收率为50.9%。

Synthesis of polypropylen catalyst internal donor 1,1-cyclobutanedimethanoldimethyl ether

1,1-cyclobutanedimethanoldimethyl ether is synthesized from diethyl malonate and 1,3-di chloropropane by alkylation,ester reduction and etherification.The key effects of reaction conditions were studied and the optimal results are as follows:①in alkylation,diethyl malonate 0.1 mol,n(diethyl malonate)∶n(CsOH)∶n(1,3-dichloropropane)=1.0∶2.2∶1.4,DMSO100 mL,reaction temperacture 30℃,reaction time 16.0 h,the yield of Cyclobutane-1,1-dicarboxylic acid diethyl ester is 93.6%;②in ester reduction,with ZnCl2 as catalyst,molar ration of Cyclobutane-1,1-dicarboxylic acid diethyl ester and KBH4 is 2.0∶1.0,reaction temperacture 60℃,reaction time 12.0 h,the yield of 1,1-Cyclobutanedimethanol is 88.0%;③in etherification,1,1-Cyclobutanedimethanol 0.1 mol,n(1,1-Cyclobutanedimethanol)∶n(NaOH)∶n(dimethyl carbonate)=1.0∶8.0∶2.4,TBAB dosage 1.25 g,reaction tempe rature 40℃ and solvent toluene,the yield of 1,1-cyclobutanedimethanoldimethyl ether is 61.8%.The over yield of the desired product is 50.9%.