PP成核剂中间体二环[2.2.1]庚-5-烯-2,3-二酸酐的合成
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摘要
以环戊二烯与顺丁烯二酸酐为原料,通过Diels-Alder反应合成了聚丙烯成核剂中间体二环[2.2.1]庚-5-烯-2,3-二酸酐。通过实验确定了合成二环[2.2.1]庚-5-烯-2,3-二酸酐的优化条件为:顺丁烯二酸酐与环戊二烯摩尔比1.000∶1.050;溶剂石油醚与乙酸乙酯等体积混合,溶剂用量占进料总质量的46%;环戊二烯滴加温度控制在10～15℃,滴加30 min;升至60℃,继续反应20 min。在优化条件下,二环[2.2.1]庚-5-烯-2,3-二酸酐的收率大于95%。熔点、元素分析、红外光谱及X射线衍射分析均表明合成产物为目标产物。
Cyclopentadiene and maleic anhydride were used as raw materials to prepare biocyclo[2.2.1]hept-5-ene-2,3-dianhydride via Diels-Alder reaction,which was the intermediate of nucleating agent for propylene polymerization. The experimental results indicate that the optimized conditions for biocyclo[2.2.1]hept-5-ene-2,3-dianhydride synthesis are as follows:the molar ratio of maleic anhydride and cyclopentadiene is 1.000∶1.050. Petroleum ether and ethyl acetate are mixed isovolumically as solvent whose mass fraction in feedstock is 46%. Cyclopentadiene is controlled to drop at the temperature between 10 and 15 ℃ for 30 min and continues to react at 60 ℃ for 20 min. The yield of biocyclo[2.2.1]hept-5-ene-2,3-dianhydride is beyond95%. The results of elemental analysis,Fourier transform infrared spectroscope and X-ray diffractometer show the synthesized product is the target one.
Cyclopentadiene and maleic anhydride were used as raw materials to prepare biocyclo[2.2.1]hept-5-ene-2,3-dianhydride via Diels-Alder reaction,which was the intermediate of nucleating agent for propylene polymerization. The experimental results indicate that the optimized conditions for biocyclo[2.2.1]hept-5-ene-2,3-dianhydride synthesis are as follows:the molar ratio of maleic anhydride and cyclopentadiene is 1.000∶1.050. Petroleum ether and ethyl acetate are mixed isovolumically as solvent whose mass fraction in feedstock is 46%. Cyclopentadiene is controlled to drop at the temperature between 10 and 15 ℃ for 30 min and continues to react at 60 ℃ for 20 min. The yield of biocyclo[2.2.1]hept-5-ene-2,3-dianhydride is beyond95%. The results of elemental analysis,Fourier transform infrared spectroscope and X-ray diffractometer show the synthesized product is the target one.
引文
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[3]赵世成,辛忠,盛波扬.降冰片烯二羧酸盐类成核剂在等规聚丙烯中的成核效应[J].高分子材料科学与工程,2009,25(3):46-49.
[4]吴浩,徐日炜,曹宏伟,等.二环[2.2.1]庚烷二羧酸盐对聚丙烯的成核效果[J].北京化工大学学报,2008,35(1):62-65.
[5]张跃飞,罗贤祖,常瑶,等.环[2.2.1]庚烷二羧酸盐成核剂对聚丙烯结晶行为和力学性能的影响[J].塑料工业,2013,41(3):76-78.
[6]美利肯公司.饱和[2.2.2]二羧酸盐热塑性塑料成核剂及其热塑性塑料组合物:中国,100365046C[P].2008-01-30.
[7]Milliken&Company.Highly nucleated syndiotactic polypropylene:US,6887963B2[P].2005-05-03.
[8]Milliken&Company.Bimolecular nucleation methods for thermoplastics:US,7129323B2[P].2006-10-31.
[9]Milliken&Company.Clarifying agent formulations for thermoplastics exhibiting very high nucleation efficacy:US,6521685B1[P].2003-02-18.
[10]Milliken&Company.Concentrates of saturated bicyclic dicarboxylate salts to facilitate use thereof as polymer nucleation additives:US,7078450B2[P].2006-07-18.
[11]Milliken&Company.Polymer additive compositions comprising highly versatile thermoplastic nucleators:US,7094820B2[P].2006-08-22.
[12]中国石油化工股份有限公司,中国石油化工股份有限公司催化剂北京燕山分公司.一种二环[2.2.1]庚-5-烯-2,3-二羧酸二钠的制备方法:中国,201210428987.8[P].2012-10-31.
[13]袁耀锋,王文峰.从轨道对称守恒原理看Diels-Alder反应区域选择性[J].大学化学,2016,31(1):68-74.
[14]马黎明,杨正银.双环戊二烯的新型分解法[J].化学世界,1992,33(10):471-474.
[15]李兴存,单敏.双环戊二烯气相解聚工艺的改进[J].石油化工,2008,37(11):1152-1154.
[16]邱慎海,包宗宏.共沸进料裂解双环戊二烯实验研究[J].石油学报(石油加工),2006,22(4):25-29.
[17]王亚红,曲晓姝,祝波,等.连续反应-精馏法制备环戊二烯(CPD)[J].吉林化工学院学报,2003,20(4):62-64
[18]Milliken&Company.Polymer additive compositions comprising highly versatile thermoplastic nucleators:US,0096895A1[P].2004-05-22.
[19]Milliken&Company.Nucleating additive formulations of bicycle[2.2.1]heptane dicarboxylate salts:US,0075434A1[P].2005-04-07.