【作者】 黄淑娟；

【导师】 蒋平平；

【作者基本信息】 江南大学 ， 化学工艺， 2011， 硕士

【摘要】 本文研究了以多种离子液体为催化剂合成新型环保无毒增塑剂酯的方法。考察了不同离子液体催化合成DBCH、DIOCH及TBC的效果,筛选出催化效果较好且能重复利用的几种离子液体后,考察了离子液体催化合成增塑剂酯的最佳工艺条件,同时研究其重复利用性能。合成制备了十种离子液体,并由红外、核磁对其结构进行了表征。通过吡啶探针红外确定了九种酸性离子液体的Br?nsted酸性,并以pH值来表征离子液体的酸性大小,最后通过TG分析研究了离子液体的热分解温度,表明所合成的酸性离子液体均有较强酸性和热稳定性。考察了不同种类离子液体催化合成环己烷1,2-二甲酸二酯和TBC的效果,筛选出了三种催化活性较高且可以重复利用的磺酸功能化的Bronsted酸性离子液体:[HSO₃-pmim]HSO₄、[HSO₃-pmim]PTSA、[HSO₃-pN（C₂H₅）₃]HSO₄。通过单因素实验法分别考察了酸性离子液体催化合成环己烷1,2-二甲酸二酯和TBC的最佳工艺条件。合成DBCH的最佳工艺条件:n（正丁醇）:n（HHPA）为2.5:1;离子液体用量为1%（以HHPA质量计）;反应温度为130-150 oC;反应时间8 h。合成DIOCH的最佳工艺条件:n（异辛醇）:n（HHPA）为2.5:1;离子液体用量为1 %;反应温度为170-190 oC;反应时间4 h。合成TBC的最佳工艺条件:n（正丁醇）:n（柠檬酸）为4.5:1;离子液体用量为1 %（以柠檬酸质量计）;反应温度为130-150 oC;反应时间8 h。而后在确定的工艺条件下,考察[HSO3-pmim]HSO4、[HSO3-pmim]PTSA、[HSO₃-pN（C₂H₅）₃]HSO₄三种离子液体在催化合成环己烷1,2-二甲酸二酯和TBC的重复利用性能。对于DBCH来说,[HSO₃-pN（C₂H₅）₃]HSO₄和[HSO₃-pmim]PTSA重复利用性能较好,均能重复4次以上并保持酯化率大于90 %;而对于DIOCH,[HSO₃-pN（C₂H₅）₃]HSO₄和[HSO₃-pmim]HSO₄重复利用性能较好,能重复利用6次以上并保持酯化率在93 %以上;对于合成TBC来说,[HSO₃-pmim]HSO₄和[HSO₃-pN（C₂H₅）₃]HSO₄重复利用性能较好,均能重复5次以上并保持酯化率大于96%。通过红外、质谱、核磁等手段确定了所合成的环己烷1,2-二甲酸二酯的结构;由气相色谱分析得到DBCH的纯度为99.30 %,DIOCH的纯度为98.86 %;而DBCH的热分解温度为218 oC,DIOCH的热分解温度为280 oC。同时测得DBCH与DIOCH的急性经口毒性LD50 >10 000 mg·kg-1,均属实际无毒。并对产品外观、色号、酸值、气味、黏度、折光率进行了表征。通过红外确定了合成的TBC的结构,同时确定其纯度为99.76 %。更多还原

【Abstract】 Three kinds of novel environmental-friendly plasticizers have been successfully synthesized by esterification using a series of acidic ionic liquids as catalysts. The catalytic activity of different ionic liquids have been examined and compared. Then we have selected several kinds of ionic liquids which are of excellent catalytic activities and can be reused after the esterification. We have also studied the optimum reaction conditions of synthesizing the novel plasticizers, including the reuse performances of the ionic liquids.Ten kinds of ionic liquids were synthesized and their structures were examined by IR and NMR. And the Br?nsted acidic and acidity of the ionic liquids have been researched through IR, the thermal stabilities of the ionic liquids have been examined by TG. The results showed that the ionic liquids are of strong acidic and good thermal abilities.For the synthesis of 1,2-cyclohexane dicarboxylates and TBC, three kinds of HSO3-functionalized ionic liquids, [HSO₃-pN（C₂H₅）₃]HSO₄, [HSO₃-pmim]HSO₄ and [HSO3-pmim]PTSA, showed better catalytic activity compared to the other acidic ionic liquids. They also showed good reuse performances since they could be easily separated from the products after reaction. The reaction conditions of using these Br?nsted acidic and HSO3-functionalized ionic liquids were determined by single factor experiments.The optimum reaction conditions of synthesizing dibutyl 1,2-cyclohexane dicarboxylates（DBCH） using ionic liquids as catalysts was studied. And the results were determined as follows: molar ratio of butanol to hexahydrophthalic anhydride（HHPA） was 2.5:1, amount of catalyst was 1 % （based on the mass of HHPA）, reaction temperature was 130-150 oC, reaction time was 8 h.The condition of synthesizing dioctyl 1,2-cyclohexane dicarboxylate （DIOCH） using ionic liquids as catalysts was studied. The optimum reaction conditions of esterification were determined as follows: molar ratio of isooctanol to HHPA was 2.5:1, amount of catalyst was 1 % （based on the mass of HHPA）, reaction temperature was 170-190 oC, reaction time was 4 h.The condition of synthesizing tributyl citrate （TBC） using ionic liquids as catalysts was studied. The optimal reaction conditions of esterification were determined as follows: molar ratio of butanol to citric acid（CA） was 4.5:1, amount of catalyst was 1 % （based on the mass of CA）, reaction temperature was 130-150 oC, reaction time was 8 h.Under the optimal reaction conditions, [HSO3-pN（C2H5）3]HSO4 and [HSO₃-pmim]PTSA were more suitable for the synthesis of DBCH and they could both be reused at least 4 times with the conversion not less than 90 %. [HSO₃-pN（C₂H₅）₃]HSO₄ and [HSO₃-pmim]HSO₄ were more applicable for the synthesis of dioctyl 1,2-cyclohexane dicarboxylate and could be reused at least 6 times with the conversion around 93 %. [HSO₃-pmim]HSO₄ and [HSO₃-pN（C₂H₅）₃]HSO₄ could be reused 5 times with the conversion above 96 % for the synthesis of TBC.The environmental-friendly plasticizers synthesized were characterized by IR, MS, NMR and GC. The purity of DBCH was 99.30 %, while DIOCH was 98.86 % and TBC was 99.76 %. Thermal decomposition temperature was determined by TG analysis. DIOCH began to decompose at 280 oC, and DBCH started to decompose at 218 oC. The acute mice oral toxicity results of both DBCH and DIOCH were LD₅₀ >10,000mg/kg, indicating that DBCH and DIOCH were actual non-toxic. Thus DBCH and DIOCH could be used as environmental-friendly plasticizers. And the appearance, color, acid value, odor, viscosity and refractive index of the products were also studied.更多还原