离子液体催化酯化反应的研究
|
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:[HSO_3-pmim]HSO_4、[HSO_3-pmim]PTSA、[HSO_3-pN(C_2H_5)_3]HSO_4。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、[HSO_3-pN(C_2H_5)_3]HSO_4三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,[HSO_3-pN(C_2H_5)_3]HSO_4和[HSO_3-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,[HSO_3-pN(C_2H_5)_3]HSO_4和[HSO_3-pmim]HSO_4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,[HSO_3-pmim]HSO_4和[HSO_3-pN(C_2H_5)_3]HSO_4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 %。
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, [HSO_3-pN(C_2H_5)_3]HSO_4, [HSO_3-pmim]HSO_4 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 [HSO_3-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 %. [HSO_3-pN(C_2H_5)_3]HSO_4 and [HSO_3-pmim]HSO_4 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 %. [HSO_3-pmim]HSO_4 and [HSO_3-pN(C_2H_5)_3]HSO_4 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 LD_(50) >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.
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:[HSO_3-pmim]HSO_4、[HSO_3-pmim]PTSA、[HSO_3-pN(C_2H_5)_3]HSO_4。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、[HSO_3-pN(C_2H_5)_3]HSO_4三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,[HSO_3-pN(C_2H_5)_3]HSO_4和[HSO_3-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,[HSO_3-pN(C_2H_5)_3]HSO_4和[HSO_3-pmim]HSO_4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,[HSO_3-pmim]HSO_4和[HSO_3-pN(C_2H_5)_3]HSO_4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 %。
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, [HSO_3-pN(C_2H_5)_3]HSO_4, [HSO_3-pmim]HSO_4 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 [HSO_3-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 %. [HSO_3-pN(C_2H_5)_3]HSO_4 and [HSO_3-pmim]HSO_4 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 %. [HSO_3-pmim]HSO_4 and [HSO_3-pN(C_2H_5)_3]HSO_4 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 LD_(50) >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.
引文
1. Walden P.Bull Acad Imper Sci (St.Petersburg)[J],1914:1800
2. Hurley F H,Frank H.Electrodeposition of aluminum[P].US,2446331.1948-03-08
3. Wilkes J S,Zaworotko M J.Air and water stable 1-ethyl-3-methylimidazolium based ionic liquids[J].J Chem Soc Chem Commun,1992,13:965-967
4. Wasserscheid P,Boesmann A,Bolm C.Synthesis and properties of ionic liquids derived from the“chiral pool”[J].Chem Commun,2002,(3):200-201
5. Liu B Y,Xu D Q,Xu Z Y.Electrochemical synthesis of dendriteic nano-polyaniline in Br?nsted acid ionic liquids[J].J Chin Chem,2005,(23):803-805
6. Holbrey J D,Reichert W M, Swatloski R P,et al.Efficient,halide free synthesis of new,low cost ionic liquids:1,3-dialkylim,idazolium salts containing,methyl- and ethyl-sulfate anions[J].Green Chem,2002,4:407-413
7. Dzyuba S V,Bartsch R A.New room temperature ionic liquid with C2-symmetrical imidazolium cation[J].Chem Commun,2001,(16):1466-1467
8. Namboodiri V V,Varma R S.An improved preparation of 1,3-dialkylimidazolium tetrafluoroborate ionic liquids using microwaves[J].Tetrahedron Lett,2002,43(31):5381-5383
9. Lévêque J M,Luche J L,Petrier C,et al.An improved preparation of ionic liquids using ultra-sound[J].Green Chem,2002,4:357-360
10.刘宝友,韩菊,魏福祥,等.功能化离子液体及在有机合成中的应用[J].河北工业科技,2006,23(2):104-107
11. Li J,Peng Y,Song G.Mannich reaction catalyzed by carboxyl-functionalized ionic liquid in aqueous media[J].Catal Lett,2005,102(3):159-162
12. Zhao Y W,Long J X,Deng F G,et al.Catalytic amounts of Br?nsted acidic ionic liquids promoted esterification:Study of acidity–activity relationship[J].Catal Commun 2009,10:732-736
13. Song C E,Shim W H,Roh E J.Scandium (ш) triflate immobilesed in ionic liquids:a novel and recycleable catalytic system for Friedel-Crafts alkylation of aromatic compounds with alkenes[J].Chem Commun,2000,17:1695-2696
14. Yin D H,Li C Z,Tao L,et al.Synthesis of diphenylmethane deriveatives in Lewisacidic ionic liquids[J].J Mol Catal,2006,245(1):260-265
15. Jaeger D A,Tucker C E.Diels-Alder reactions in ethylammonium nitrate,a low-melting fused salt[J].Tetrahedron Lett,1989,30(14):1785-1788
16. Hagiwara H,Shimizu Y,Hoshi T,et al.Heterogeneous Heck reaction catalyzed by Pd/C in ionic liquid[J].Tetrahedron Lett,2001,42(26):4349-4351
17.岳彩波,魏运洋.功能性离子液体催化Knoevenagel缩合反应[J].精细化工,2007,24(2):166-168
18. Wheeler C,West K N,Liotta C L.Ionic liquids as catalytic green solvents for nucleophilic displacement reactions[J].Chemical Communications,2001,10:887-888
19. Seddon K R,Stark A.Selective catalytic oxidation of benzyl alcohol and alkybenzenes in ionic liquids[J].Green Chem,2002,4(2):199-123
20. Chauvin Y,Mussmann L,Olivier H.A novel class of versatile solvents for two-phase catalysis:hydrogenation,isomerization,and hydroformylation of alkenes catalyzed by rhodium complexes in liquid 1,3-dialkylimidazolium salts[J].Angew Chem Int Ed,1995,34(23):2698-2700
21. Lee J K,Kim D C,Song C E,et al.Thermal behaveors of ionic liquids under microwave irradiation and their application on microwave-assisted catalytic Beckmann rearrangent of ketoximes[J].Synth Commun,2003,33(13):2301-2307
22. Gui J Z,Cong X H,Liu D,et al.Novel Br?nsted acidic ionic liquid as efficient and reusable catalyst system for esterification[J].Catal Commun,2004,5:473-477
23.李红娟,于世涛,刘福胜,等.酸功能化离子液体催化合成三乙酸甘油酯[J].化工进展,2007,26(8):1120-1124
24.方东,刘祖亮,周新利.功能化离子液体室温催化合成乙酸苄酯[J].应用化学,2007,24(1):85-89
25. Pralhad A G,Gigi G,Jagannath D.Br?nsted acidic ionic liquids derived from alkylamines as catalysts and mediums for Fischer esterification : Study of structur-activity relationship[J].J Mol Catal A:Chem.2008,2:18-186
26. Heudorf U,Sundermann V M,Angerer J.Phthalates:Toxicology and exposure[J].Int J Hyg Environ Health,2007,210:623-634
27. Latini G,Felice C D,Verrotti A.Plasticizers,infant nutrition and reproductive health[J].Reprod Toxicol,2004,19:27-33
28. Li Y F,Zhuang M Z,Li T,et al.Neurobehavioral toxicity study of dibutyl phthalateon rats following in utero and lactational exposure[J]．J Appl Toxicol，2009，29：603-611
29. Kovacic P，Jacintho J D．Reproductive toxins: pervasive theme of Oxidative Stress andelectron transfer [J]．Curr Med Chem，2001，8：863-892
30. Pereira C，Mapuskar K，Rao C V．Chronic toxicity of diethyl phthalate in male Wistarrats-A dose-response study[J]．Regul Toxicol Pharm，2006，45：169-177
31.胡雄星，韩中豪，刘必寅，等．邻苯二甲酸酯的毒性及其在环境中的分布[J]．环境科学与管理，2007，32，（1）：37-40
32. Rahman M，Brazel C S．The plasticizer market：an assessment of traditionalplasticizers and research trends to meet new challenges[J]．Prog Polym Sci，2004，29：1223-1248
33.任仁．警惕邻苯二甲酸酯污染[J]．大学化学，2003，18（6）：33-36
34.王琦，贾润礼．聚氯乙烯增塑剂的研究[J]．绝缘材料，2007，40（5）：38-41
35.雍奎刚，刘忠科，刘宝钊．PVC无毒增塑剂的应用和发展[J]．2007，35（6）：88-91
36. BASF．BASF increases production of speciality plasticizer[N]．Plastics Additives &Compounding，2006-11-12（8）
37. BASF．BASF ponders restructure of US plasticizers operations[N]．Additives forPolymers，2003-9（8）
38. BASF．BASF plasticizer ahead in eco-efficiency rating[N]．Additives for Polymers，2008-9（3）
39. Brunner M，B ttcher A，Breitscheidel B，et al．Method for hydrogenating benzenepolycarboxylic acids or derivatives thereof by using a catalyst containing macropores[P]．US，6284917 B1，2001-9-4
40.丁云杰，刁成际，马立新．一种制备1,2-环己烷二甲酸二元酯的方法[P]．中国，101417950A．2009-4-29
41. Grass M，Kaizik A，Bueschken W，et al．Catalyst and method for hydrogenatingaromatic compounds[P]．US，7361714 B2，2008-4-22
42.石万聪．新型增塑剂环己烷二羧酸二烷基酯[J]．塑料助剂，2010，（1）：17-22
43.商集平，周少杰，方猷泉．一种环保增塑剂－1,2-环己烷二羧酸二异辛酯的制备方法[P]．中国，101613282 A．2009-12-30
44. Wadey B L．An innovative plasticizer for sensitive applications[J]．J Vinyl & AdditTechn，2003，9：172-176
45. Kim J，Shin S C．Controlled release of atenolol from the ethylene-vinyl acetatematrix[J]．Int J Pharm，2004，273：23-27
46.蒋平平，崇明本，张典鹏，等．加快我国新型环境友好增塑剂柠檬酸酯研究与应用[J]．塑料助剂，2003，（5）：1-8
47. Ljungberg N，Wesslen B．Tributyl citrate oligomers as plasticizers for poly (lacticacid)：thermo-mechanical film properties and aging[J]．Polymer，2003，44：7679-7688．
48.张丽．柠檬酸酯类增塑剂的市场现状及前景[J]．塑料助剂，2008，（1）：10-11
49.徐群，邢凤兰，薛红艳，等．柠檬酸酯的合成与应用评述[J]．化工进展，2002，21（8）：576-578
50.李丹娜，张慧俐，张普玉．合成柠檬酸三丁酯的催化体系的研究进展[J]．中州大学学报，2005，22（2）：119-121
51.岑兰，孙鸣剑，王雪晶．环境友好无毒柠檬酸酯增塑剂的应用研究进展[J]．弹性体，2007，17（6）：69-73
52.乔艳辉，滕俊江，黄小梅．氨基磺酸催化合成柠檬酸三戊酯的工艺研究[J]．应用化工，2009，38（8）：1139-1141
53.李继忠．邻苯二甲酸二异辛酯和邻苯二甲酸二正辛酯的合成[J]．兰州理工大学学报，2006，32（1）：73-75
54.谭强，万辉，管国锋．SO42-/TiO2-Al2O3固体酸催化剂催化合成均苯四甲酸四异辛酯[J]．石油化工，2005，34（4）：372-375
55.李秀瑜.氯化铁催化合成柠檬酸三丁酯[J].化学世界，1999，（8）：400-402
56. Okuhara，Toshio．New catalytic functions of heteropoly compounds as solidacids[J]．Catal Today，2002，73(1-2)：167-176
57.栾向海，孙晓波，石晓华，等．己二酸二正辛酯的催化合成及反应动力学[J]．精细化工，2008，25（12）：1232-1235
58.资炎，郭红云．功能化离子液体催化邻苯二甲酸二辛酯的合成及其工艺[J]．工业催化，2008，16（5）：53-57
59. Xie C X，Li H L，Li L，et al．Synthesis of plasticizer ester using acid-functionalizedionic liquid as catalyst[J]. J Hazard Mater，2008，151：847-850
60. Li H L，Yu S T，Liu F S，et al．Synthesis of dioctyl phthalate using acidfunctionalized ionic liquid as catalyst[J]. Catal Commun，2007，8：1759-1762
61.李红娟，于世涛，刘福胜，等．酸功能化离子液体催化合成三乙酸甘油酯[J]．化工进展，2007，26（8）：1120-1124
62. Gui J Z，Cong X H，Liu D，et al．Novel Br?nsted acidic ionic liquid as e cient andreusable catalyst system for esterification[J].Catal Commun，2004，5：473-477
63. Xu J M，Jiang J C，Zuo Z Y，et al．Synthesis of tributyl citrate using acid ionic liquidas catalyst[J].Process Saf Environ，2010，88：28-30
64.王有菲，龚国珍，高珊，等．磺酸基功能化的离子液体催化合成柠檬酸三丁酯[J]．应用化工，2008，37（10）：1125-1128
65.蒋平平，费柳月，蒋春林．聚己二酸二元醇酯合成研究与表征[J]．高校化学工程学报，2008，22（4）：714-719
66.夏明珠，雷武，王风云，等．钛酸四丁酯催化合成邻苯二甲酸双十八酯[J]．精细化工，2008，25（1）：87-89
67.杨辉琼，易翔．[bmim]BF4离子液体的制备及其催化酯化反应研究[J]．湖南工程学院学报，2008，18（1）：80-83
68. Fang D，Zhou X L，Ye Z W，et al．Br?nsted Acidic Ionic Liquids and Their Use asDual Solvent Catalysts forFischer Esterifications[J]．Ind Eng Chem Res，2006，45，7982-7984
69.王晓化，陶国宏，寇元，等．离子液体酸性的红外光谱探针法研究[J]．物理化学学报，2005，25（1）：528-533
70.全国橡胶与橡胶制品标准化技术委员会化学助剂分技术委员会．GB/T 1668-2008增塑剂酸值及酸度的测定[S]．北京：中国标准出版社，2008
2. Hurley F H,Frank H.Electrodeposition of aluminum[P].US,2446331.1948-03-08
3. Wilkes J S,Zaworotko M J.Air and water stable 1-ethyl-3-methylimidazolium based ionic liquids[J].J Chem Soc Chem Commun,1992,13:965-967
4. Wasserscheid P,Boesmann A,Bolm C.Synthesis and properties of ionic liquids derived from the“chiral pool”[J].Chem Commun,2002,(3):200-201
5. Liu B Y,Xu D Q,Xu Z Y.Electrochemical synthesis of dendriteic nano-polyaniline in Br?nsted acid ionic liquids[J].J Chin Chem,2005,(23):803-805
6. Holbrey J D,Reichert W M, Swatloski R P,et al.Efficient,halide free synthesis of new,low cost ionic liquids:1,3-dialkylim,idazolium salts containing,methyl- and ethyl-sulfate anions[J].Green Chem,2002,4:407-413
7. Dzyuba S V,Bartsch R A.New room temperature ionic liquid with C2-symmetrical imidazolium cation[J].Chem Commun,2001,(16):1466-1467
8. Namboodiri V V,Varma R S.An improved preparation of 1,3-dialkylimidazolium tetrafluoroborate ionic liquids using microwaves[J].Tetrahedron Lett,2002,43(31):5381-5383
9. Lévêque J M,Luche J L,Petrier C,et al.An improved preparation of ionic liquids using ultra-sound[J].Green Chem,2002,4:357-360
10.刘宝友,韩菊,魏福祥,等.功能化离子液体及在有机合成中的应用[J].河北工业科技,2006,23(2):104-107
11. Li J,Peng Y,Song G.Mannich reaction catalyzed by carboxyl-functionalized ionic liquid in aqueous media[J].Catal Lett,2005,102(3):159-162
12. Zhao Y W,Long J X,Deng F G,et al.Catalytic amounts of Br?nsted acidic ionic liquids promoted esterification:Study of acidity–activity relationship[J].Catal Commun 2009,10:732-736
13. Song C E,Shim W H,Roh E J.Scandium (ш) triflate immobilesed in ionic liquids:a novel and recycleable catalytic system for Friedel-Crafts alkylation of aromatic compounds with alkenes[J].Chem Commun,2000,17:1695-2696
14. Yin D H,Li C Z,Tao L,et al.Synthesis of diphenylmethane deriveatives in Lewisacidic ionic liquids[J].J Mol Catal,2006,245(1):260-265
15. Jaeger D A,Tucker C E.Diels-Alder reactions in ethylammonium nitrate,a low-melting fused salt[J].Tetrahedron Lett,1989,30(14):1785-1788
16. Hagiwara H,Shimizu Y,Hoshi T,et al.Heterogeneous Heck reaction catalyzed by Pd/C in ionic liquid[J].Tetrahedron Lett,2001,42(26):4349-4351
17.岳彩波,魏运洋.功能性离子液体催化Knoevenagel缩合反应[J].精细化工,2007,24(2):166-168
18. Wheeler C,West K N,Liotta C L.Ionic liquids as catalytic green solvents for nucleophilic displacement reactions[J].Chemical Communications,2001,10:887-888
19. Seddon K R,Stark A.Selective catalytic oxidation of benzyl alcohol and alkybenzenes in ionic liquids[J].Green Chem,2002,4(2):199-123
20. Chauvin Y,Mussmann L,Olivier H.A novel class of versatile solvents for two-phase catalysis:hydrogenation,isomerization,and hydroformylation of alkenes catalyzed by rhodium complexes in liquid 1,3-dialkylimidazolium salts[J].Angew Chem Int Ed,1995,34(23):2698-2700
21. Lee J K,Kim D C,Song C E,et al.Thermal behaveors of ionic liquids under microwave irradiation and their application on microwave-assisted catalytic Beckmann rearrangent of ketoximes[J].Synth Commun,2003,33(13):2301-2307
22. Gui J Z,Cong X H,Liu D,et al.Novel Br?nsted acidic ionic liquid as efficient and reusable catalyst system for esterification[J].Catal Commun,2004,5:473-477
23.李红娟,于世涛,刘福胜,等.酸功能化离子液体催化合成三乙酸甘油酯[J].化工进展,2007,26(8):1120-1124
24.方东,刘祖亮,周新利.功能化离子液体室温催化合成乙酸苄酯[J].应用化学,2007,24(1):85-89
25. Pralhad A G,Gigi G,Jagannath D.Br?nsted acidic ionic liquids derived from alkylamines as catalysts and mediums for Fischer esterification : Study of structur-activity relationship[J].J Mol Catal A:Chem.2008,2:18-186
26. Heudorf U,Sundermann V M,Angerer J.Phthalates:Toxicology and exposure[J].Int J Hyg Environ Health,2007,210:623-634
27. Latini G,Felice C D,Verrotti A.Plasticizers,infant nutrition and reproductive health[J].Reprod Toxicol,2004,19:27-33
28. Li Y F,Zhuang M Z,Li T,et al.Neurobehavioral toxicity study of dibutyl phthalateon rats following in utero and lactational exposure[J]．J Appl Toxicol，2009，29：603-611
29. Kovacic P，Jacintho J D．Reproductive toxins: pervasive theme of Oxidative Stress andelectron transfer [J]．Curr Med Chem，2001，8：863-892
30. Pereira C，Mapuskar K，Rao C V．Chronic toxicity of diethyl phthalate in male Wistarrats-A dose-response study[J]．Regul Toxicol Pharm，2006，45：169-177
31.胡雄星，韩中豪，刘必寅，等．邻苯二甲酸酯的毒性及其在环境中的分布[J]．环境科学与管理，2007，32，（1）：37-40
32. Rahman M，Brazel C S．The plasticizer market：an assessment of traditionalplasticizers and research trends to meet new challenges[J]．Prog Polym Sci，2004，29：1223-1248
33.任仁．警惕邻苯二甲酸酯污染[J]．大学化学，2003，18（6）：33-36
34.王琦，贾润礼．聚氯乙烯增塑剂的研究[J]．绝缘材料，2007，40（5）：38-41
35.雍奎刚，刘忠科，刘宝钊．PVC无毒增塑剂的应用和发展[J]．2007，35（6）：88-91
36. BASF．BASF increases production of speciality plasticizer[N]．Plastics Additives &Compounding，2006-11-12（8）
37. BASF．BASF ponders restructure of US plasticizers operations[N]．Additives forPolymers，2003-9（8）
38. BASF．BASF plasticizer ahead in eco-efficiency rating[N]．Additives for Polymers，2008-9（3）
39. Brunner M，B ttcher A，Breitscheidel B，et al．Method for hydrogenating benzenepolycarboxylic acids or derivatives thereof by using a catalyst containing macropores[P]．US，6284917 B1，2001-9-4
40.丁云杰，刁成际，马立新．一种制备1,2-环己烷二甲酸二元酯的方法[P]．中国，101417950A．2009-4-29
41. Grass M，Kaizik A，Bueschken W，et al．Catalyst and method for hydrogenatingaromatic compounds[P]．US，7361714 B2，2008-4-22
42.石万聪．新型增塑剂环己烷二羧酸二烷基酯[J]．塑料助剂，2010，（1）：17-22
43.商集平，周少杰，方猷泉．一种环保增塑剂－1,2-环己烷二羧酸二异辛酯的制备方法[P]．中国，101613282 A．2009-12-30
44. Wadey B L．An innovative plasticizer for sensitive applications[J]．J Vinyl & AdditTechn，2003，9：172-176
45. Kim J，Shin S C．Controlled release of atenolol from the ethylene-vinyl acetatematrix[J]．Int J Pharm，2004，273：23-27
46.蒋平平，崇明本，张典鹏，等．加快我国新型环境友好增塑剂柠檬酸酯研究与应用[J]．塑料助剂，2003，（5）：1-8
47. Ljungberg N，Wesslen B．Tributyl citrate oligomers as plasticizers for poly (lacticacid)：thermo-mechanical film properties and aging[J]．Polymer，2003，44：7679-7688．
48.张丽．柠檬酸酯类增塑剂的市场现状及前景[J]．塑料助剂，2008，（1）：10-11
49.徐群，邢凤兰，薛红艳，等．柠檬酸酯的合成与应用评述[J]．化工进展，2002，21（8）：576-578
50.李丹娜，张慧俐，张普玉．合成柠檬酸三丁酯的催化体系的研究进展[J]．中州大学学报，2005，22（2）：119-121
51.岑兰，孙鸣剑，王雪晶．环境友好无毒柠檬酸酯增塑剂的应用研究进展[J]．弹性体，2007，17（6）：69-73
52.乔艳辉，滕俊江，黄小梅．氨基磺酸催化合成柠檬酸三戊酯的工艺研究[J]．应用化工，2009，38（8）：1139-1141
53.李继忠．邻苯二甲酸二异辛酯和邻苯二甲酸二正辛酯的合成[J]．兰州理工大学学报，2006，32（1）：73-75
54.谭强，万辉，管国锋．SO42-/TiO2-Al2O3固体酸催化剂催化合成均苯四甲酸四异辛酯[J]．石油化工，2005，34（4）：372-375
55.李秀瑜.氯化铁催化合成柠檬酸三丁酯[J].化学世界，1999，（8）：400-402
56. Okuhara，Toshio．New catalytic functions of heteropoly compounds as solidacids[J]．Catal Today，2002，73(1-2)：167-176
57.栾向海，孙晓波，石晓华，等．己二酸二正辛酯的催化合成及反应动力学[J]．精细化工，2008，25（12）：1232-1235
58.资炎，郭红云．功能化离子液体催化邻苯二甲酸二辛酯的合成及其工艺[J]．工业催化，2008，16（5）：53-57
59. Xie C X，Li H L，Li L，et al．Synthesis of plasticizer ester using acid-functionalizedionic liquid as catalyst[J]. J Hazard Mater，2008，151：847-850
60. Li H L，Yu S T，Liu F S，et al．Synthesis of dioctyl phthalate using acidfunctionalized ionic liquid as catalyst[J]. Catal Commun，2007，8：1759-1762
61.李红娟，于世涛，刘福胜，等．酸功能化离子液体催化合成三乙酸甘油酯[J]．化工进展，2007，26（8）：1120-1124
62. Gui J Z，Cong X H，Liu D，et al．Novel Br?nsted acidic ionic liquid as e cient andreusable catalyst system for esterification[J].Catal Commun，2004，5：473-477
63. Xu J M，Jiang J C，Zuo Z Y，et al．Synthesis of tributyl citrate using acid ionic liquidas catalyst[J].Process Saf Environ，2010，88：28-30
64.王有菲，龚国珍，高珊，等．磺酸基功能化的离子液体催化合成柠檬酸三丁酯[J]．应用化工，2008，37（10）：1125-1128
65.蒋平平，费柳月，蒋春林．聚己二酸二元醇酯合成研究与表征[J]．高校化学工程学报，2008，22（4）：714-719
66.夏明珠，雷武，王风云，等．钛酸四丁酯催化合成邻苯二甲酸双十八酯[J]．精细化工，2008，25（1）：87-89
67.杨辉琼，易翔．[bmim]BF4离子液体的制备及其催化酯化反应研究[J]．湖南工程学院学报，2008，18（1）：80-83
68. Fang D，Zhou X L，Ye Z W，et al．Br?nsted Acidic Ionic Liquids and Their Use asDual Solvent Catalysts forFischer Esterifications[J]．Ind Eng Chem Res，2006，45，7982-7984
69.王晓化，陶国宏，寇元，等．离子液体酸性的红外光谱探针法研究[J]．物理化学学报，2005，25（1）：528-533
70.全国橡胶与橡胶制品标准化技术委员会化学助剂分技术委员会．GB/T 1668-2008增塑剂酸值及酸度的测定[S]．北京：中国标准出版社，2008