文章摘要
李海燕,刘仕伟,于世涛.双酸型离子液体催化废PET醇解制备对苯二甲酸二丁酯研究[J].,2018,58(4):342-347
双酸型离子液体催化废PET醇解制备对苯二甲酸二丁酯研究
Study of preparation of dibutyl terephthalate by alcoholysis of waste PET catalyzed by diacid ionic liquid
  
DOI:10.7511/dllgxb201804002
中文关键词: 双酸型离子液体  催化  醇解  聚对苯二甲酸乙二醇酯(PET)
英文关键词: diacid ionic liquid  catalysis  alcoholysis  polyethylene terephthalate (PET)
基金项目:山东省重点研发计划项目(2015GSF1160082016GGX107001);江苏省生物质能源与材料重点实验室开放基金资助项目(JSBEM201802).
作者单位
李海燕,刘仕伟,于世涛  
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中文摘要:
      针对对苯二甲酸直接酯化合成高值增塑剂对苯二甲酸二丁酯(DBTP)存在的原料价高难得,三废排放量大,催化剂用量大、难分离且不可重复利用等问题,以绿色环保、可循环使用的Brnsted-Lewis双酸型离子液体1-(3-磺酸)-丙基-3-甲基咪唑氯铁酸盐\Cl-FeCl3(FeCl3摩尔分数x=0.67)为催化剂,研究了正丁醇醇解廉价易得的废聚对苯二甲酸乙二醇酯(PET)制备增塑剂对苯二甲酸二丁酯的反应.结果表明:在n(PET重复单元)∶n(正丁醇)=1∶3,m(PET)∶m(催化剂)=5∶1,反应温度210 ℃,反应时间8 h的较佳反应条件下,PET醇解率为100%,产物DBTP和乙二醇(EG)收率分别为97.5%和98.2%.同传统催化剂相比,离子液体催化剂的催化性能更高,且重复使用7次其催化性能未见明显降低.傅里叶-红外光谱(FT-IR)分析表明:PET醇解过程由链内酯键断裂和链末端酯键断裂协同完成.
英文摘要:
      The synthesis of high value plasticizer dibutyl terephthalate (DBTP) with terephthalic acid by direct esterification method has some drawbacks, such as high raw material price, large emission of three industrial wastes, large amount and difficulty in separate and no reusable of catalyst. In order to solve such problems, a new type of environment-friendly and reusable catalyst, named Brnsted-Lewis diacid ionic liquid (IL), is proposed to produce DBTP. It is found that diacid IL 1-(3-sulfonic)-propyl-3-methylimidazolium chloroironinate [HO3S-(CH2) 3-mim]Cl-FeCl3 (molar fraction x of FeCl3 is 0.67) is an efficient catalyst for alcoholysis of low-cost waste polyethylene terephthalate (PET), and the optimum reaction conditions are obtained as follows: n(PET repeat units)∶n(n-butanol)=1∶3, m(PET)∶m(catalyst)=5∶1, reaction temperature 210 ℃ and reaction time 8 h. Under the above reaction conditions, the conversion of PET reaches 100%, and the yields of DBTP and ethylene glycol (EG) are 97.5% and 98.2%, respectively. Additionally, compared with traditional catalysts, the IL catalyst has best performance, and the proposed catalyst separated from the product can be reused for seven times without obvious decrease in its catalytic performance. The mechanism of PET chains scission is proved to be a combination of chain end and random chain scission by Fourier transform-infrared spectroscopy (FT-IR) analysis.
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