新型二元醇（2-甲基-1，3-丙二醇）合成研究
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摘要
二元醇类作为医药、涂料工业的重要中间体应用非常广泛，传统的二元醇有1，4-丁二醇(1，4BDO)、二甘醇、新戊二醇(NPG)、1，3-丙二醇(1，3PDO)、己二醇(HDO)等。2-甲基-1，3-丙二醇(MPO)是一种新型二元醇，由于其独特的分子结构使其在很多方面正逐渐取代传统二元醇，有很大的市场前景，但国内尚无完整地生产工艺。
本文提出了一种新的合成MPO的工艺路线，即采用以异丁烯为原料经氯化、水解、加氢等过程合成得到该产品。该工艺过程具有设备简单、工艺先进、便于操作、投入较少、易于实现等特点，同时又为异丁烯的应用开辟了一条新路，弥补了国内合成空白。
本文在氯化反应过程中，自行设计制作出了氯化管式反应器，在该反应器中异丁烯和氯气迅速混合反应生成二氯异丁烯，根据该氯化反应特征利用正交试验和单因素试验考察了有关因素的影响并优化得到了最佳工艺条件，二氯异丁烯的总收率达65％以上，选择性达80％；接着，对二氯异丁烯进行水解反应制得了2-甲烯-1，3-丙二醇，讨论了相关因素对水解反应的影响，并通过正交试验和单因素试验得到了较佳工艺条件，二氯异丁烯的转化率达100％；同时还对制备的2-甲烯-1，3-丙二醇在常压下采用三氧化二铝负载钯催化剂催化加氢得目的产物MPO，并对产品进行了鉴定，从而打通了整个工艺路线。
本文根据工程设计以及应用方面的需要还对MPO及其水溶液的表面性质进行了研究，为此新型二元醇的应用提供了一定量的基础数据。
As important industrial chemicals, dihydroxy alcohols are applied for many fields, classical dihydroxy alcohols include l,4BD0, diglycol, NPG, 1,3PDO, HDO and so on. MPO is a kind of new dihydroxy alcohols. Because of its unique molecular structure, 2-methyl-1,3-propanediol(MPO) is instead of classical dihydroxy alcohols gradually. So MPO has huge market foreground. But MPO has not been had a integrated production technology in China.
A new synthesis route: the preparation of MPO, which 2-methyl-1-propene reacted with chlorine, alkali and hydrogen was discussed. This process have a lot of excellences, such as simple equipments, advanced process, being convenient of manipulation, less devotion, being prone to come true and so on, at the same time, the route inaugurated another application for 2-methyl-1-propene, making up synthesis blank in China and abroad.
First, a chlorinator was self-designed in this paper, and dichloride of 2-methyl-1-propene was synthesized by 2-methyl-1-propene reacted with chlorine fast in this reactor. By means of the Orthogonal Experiments design and single factor experiments, the influence of several reaction variables on the yield were examined and the optimum reaction conditions under the intervallic operation were obtained, the yield and selectivity of dichloride of 2-methyl-1-prop-ene were more than 65% and 80% respectively. Second, the preparation of 2-methylene-1, 3-propanediol, which dichloride of 2-methyl-1-propene reacted with alkali was investigated. By means of the Orthogonal Experiments design and single factor experiments, the influence of several reaction variables on the yield were examined and the optimum reaction conditions under the intervallic operation were obtained, the conversion of dichloride of 2-methyl-1-propene was 100%. Moreover the preparation of MPO, which 2-methylene-1, 3-propanediol reacted with hydrogen, in presence of Al_2O_3-Pd catalyst, was gotten, and the product was appraised. So the route was opened up.
In addition, in order to cater for engineering design and application, interfacial forces of pure product and MPO+H_2O were studied in this paper. A mass of base data were provided for application of this new dihydroxy alcohols.
本文提出了一种新的合成MPO的工艺路线，即采用以异丁烯为原料经氯化、水解、加氢等过程合成得到该产品。该工艺过程具有设备简单、工艺先进、便于操作、投入较少、易于实现等特点，同时又为异丁烯的应用开辟了一条新路，弥补了国内合成空白。
本文在氯化反应过程中，自行设计制作出了氯化管式反应器，在该反应器中异丁烯和氯气迅速混合反应生成二氯异丁烯，根据该氯化反应特征利用正交试验和单因素试验考察了有关因素的影响并优化得到了最佳工艺条件，二氯异丁烯的总收率达65％以上，选择性达80％；接着，对二氯异丁烯进行水解反应制得了2-甲烯-1，3-丙二醇，讨论了相关因素对水解反应的影响，并通过正交试验和单因素试验得到了较佳工艺条件，二氯异丁烯的转化率达100％；同时还对制备的2-甲烯-1，3-丙二醇在常压下采用三氧化二铝负载钯催化剂催化加氢得目的产物MPO，并对产品进行了鉴定，从而打通了整个工艺路线。
本文根据工程设计以及应用方面的需要还对MPO及其水溶液的表面性质进行了研究，为此新型二元醇的应用提供了一定量的基础数据。
As important industrial chemicals, dihydroxy alcohols are applied for many fields, classical dihydroxy alcohols include l,4BD0, diglycol, NPG, 1,3PDO, HDO and so on. MPO is a kind of new dihydroxy alcohols. Because of its unique molecular structure, 2-methyl-1,3-propanediol(MPO) is instead of classical dihydroxy alcohols gradually. So MPO has huge market foreground. But MPO has not been had a integrated production technology in China.
A new synthesis route: the preparation of MPO, which 2-methyl-1-propene reacted with chlorine, alkali and hydrogen was discussed. This process have a lot of excellences, such as simple equipments, advanced process, being convenient of manipulation, less devotion, being prone to come true and so on, at the same time, the route inaugurated another application for 2-methyl-1-propene, making up synthesis blank in China and abroad.
First, a chlorinator was self-designed in this paper, and dichloride of 2-methyl-1-propene was synthesized by 2-methyl-1-propene reacted with chlorine fast in this reactor. By means of the Orthogonal Experiments design and single factor experiments, the influence of several reaction variables on the yield were examined and the optimum reaction conditions under the intervallic operation were obtained, the yield and selectivity of dichloride of 2-methyl-1-prop-ene were more than 65% and 80% respectively. Second, the preparation of 2-methylene-1, 3-propanediol, which dichloride of 2-methyl-1-propene reacted with alkali was investigated. By means of the Orthogonal Experiments design and single factor experiments, the influence of several reaction variables on the yield were examined and the optimum reaction conditions under the intervallic operation were obtained, the conversion of dichloride of 2-methyl-1-propene was 100%. Moreover the preparation of MPO, which 2-methylene-1, 3-propanediol reacted with hydrogen, in presence of Al_2O_3-Pd catalyst, was gotten, and the product was appraised. So the route was opened up.
In addition, in order to cater for engineering design and application, interfacial forces of pure product and MPO+H_2O were studied in this paper. A mass of base data were provided for application of this new dihydroxy alcohols.
引文
[1] J. Julia, D. Salvatella, J. Lope. Aqueous polyurethane dispersions for adhesive applications[J]. Adhe-sives Age, 1994, 37(5): 26-29.
[2] C. J. Sullivan. High Performance Polyester Coating Systems Introduction of 2-Methyl-1, 3-Propanediol[C]. ⅩⅫ FATIPEC Congress. 1994(5): 15-19.
[3] 程能林．溶剂手册[M]．化学工业出版社．1995(2)：366-369．
[4] 朱东，赵训香．2-甲基．1，3-丙二醇在涂料用聚酯树脂合成中的应用研究[J]．涂料技术．1998(4)：29-31．
[5] 方冉，陈延辉，高敬民．MPD在高固体聚酯氨基烘干磁漆中的应用研究[J]．现代涂料与涂装．2003(3)：3-9．
[6] 孙先良．绿色涂料与新型粉末涂料和涂装技术的发展[J]．现代化化工．2003，23(6)：6-9；
[7] S. H. Harris. New Intermediates for the Performance Polyesters: 2-Methyl-1, 3-Propane-diol[C]. 45th Annual Conference. 1990(4): 56-61.
[8] C. J. Sullivan. Designing Polyester Resin Performance With2-Methyl-1, 3-Propanedio[J] the Society of the Plastics Industry. 1993(2): 8-11.
[9] C. J. Sullivan, C. G. angfeng. Diol Building Block Offers Options For Performance Properties[J]. Adhensive Age. 1994, 37(3): 20-24.
[10] M. Doolhausen, W. Warrach. Polyurethane adhesives technology[J]. Adhesives Age. 1982, 25(6): 28-32.
[11 ] C. J. Sullivan, M. E. Dillon. Novel Terephthalate-based Polyesters Resins[J]. J. Amer. Paint and Coatings. 1991. 76(27): 36-39.
[12] V. C. Malshe, M. V. K. Mandlecha. Production of Butane 1, 3-Diol, Propane 1, 3-Diol and Other Diols and Polyols[P]. WO: 0056688. 2000-09-28.
[13] C. J. Sullivan, D. C. Dehm, E. E. Reich and M. E. Dillon. Polyester Resins Based Upon 2-methyl-1, 3-Propanediol[J]. J. Coat. Technology. 1990, 62(791): 37-41.
[14] F. N. Jones, Lu, D. D-L. Properties of Higher-Solids Polyester/Melamine Enamels Made from Monodisperse Oligoesters[J]. J. Coat. Technology. 1987, 59(751): 73-76.
[15] P. M. Duncan, M. R. Van De Mark and C. J. Sullivan. New Monomer Offers Advantages For High-Solids Polyesters Evaluating 2-methyl-1, 3-Propanediol as a Direct Substitute for Neopentyl Glycol In Polyesters Resins[J]. Modem Paint and Coatings. 1990, 80(6): 51-54.
[16] C. J. Sullivan, W. P. Becker, W. J. Cleland. Polyesters Plasticizers Made With 2-methyl[57] Piotr Cysewski, Alicja Gackowska, Jerzy Gaca. Experimental and theoretical studies on formation and degradation of chloro organic compounds[J]. Chemosphere. 2006(63): 165-170.
[58] 宋立旺．烯烃气体混合物氯化反应研究．大连理工大学硕士研究生论文[D]．2000(8)．
[59] 胡性之．甲代烯丙基氯．精细与专用化学品[J]．1999(1)：18-20．
[60] 国内发展动态．精细与专用化学品[J]．2005(5)：6．
[61] 王福安．化工数据导引．化学工业出版社[M]．1995(10)．
[62] 杨基和，赵世勇，季建银．石蜡氧化制蜂蜡管式反应器设计[J]．天然气与石油．2004，22(1)：42-46．
[63] 金属管浮子流量计．选型资料．开封仪表有线公司[J]．2003(3)：15-20．
[64] Schulze, K.; Hartmann, S.; Krueger, H.; Muehlstaedt, M.; Richter, C.; Richter, H. Synthesis and characterization of polychlorinated isobutenes[J]. Journal fuer Praktische Chemie. 1984, 326(3): 433-442.
[65] 陈敏恒，丛德滋，方图南，齐鸣斋．化工原理[M]．化学工业出版社．2003(5)．
[66] 蒋登高，章亚东，周彩荣．精细有机合成反应及工艺[M]．化学工艺出版社．2003(1)．
[67] 齐江，戴献元．醇类稀溶液的溶剂萃取研究[J]．现代化工．1999，19(10)：9-12．
[68] 程世绪．铜液表面张力的测定[J]．中氮肥．2002(6)，50-51．
[69] 天津大学物理化学教研室．物理化学[M]．高等教育出版社．2003(4)．
[70] 刘光启，马连湘，刘杰．化学化工物性数据手册[D]．化学工业出版社．2005(5)．
[2] C. J. Sullivan. High Performance Polyester Coating Systems Introduction of 2-Methyl-1, 3-Propanediol[C]. ⅩⅫ FATIPEC Congress. 1994(5): 15-19.
[3] 程能林．溶剂手册[M]．化学工业出版社．1995(2)：366-369．
[4] 朱东，赵训香．2-甲基．1，3-丙二醇在涂料用聚酯树脂合成中的应用研究[J]．涂料技术．1998(4)：29-31．
[5] 方冉，陈延辉，高敬民．MPD在高固体聚酯氨基烘干磁漆中的应用研究[J]．现代涂料与涂装．2003(3)：3-9．
[6] 孙先良．绿色涂料与新型粉末涂料和涂装技术的发展[J]．现代化化工．2003，23(6)：6-9；
[7] S. H. Harris. New Intermediates for the Performance Polyesters: 2-Methyl-1, 3-Propane-diol[C]. 45th Annual Conference. 1990(4): 56-61.
[8] C. J. Sullivan. Designing Polyester Resin Performance With2-Methyl-1, 3-Propanedio[J] the Society of the Plastics Industry. 1993(2): 8-11.
[9] C. J. Sullivan, C. G. angfeng. Diol Building Block Offers Options For Performance Properties[J]. Adhensive Age. 1994, 37(3): 20-24.
[10] M. Doolhausen, W. Warrach. Polyurethane adhesives technology[J]. Adhesives Age. 1982, 25(6): 28-32.
[11 ] C. J. Sullivan, M. E. Dillon. Novel Terephthalate-based Polyesters Resins[J]. J. Amer. Paint and Coatings. 1991. 76(27): 36-39.
[12] V. C. Malshe, M. V. K. Mandlecha. Production of Butane 1, 3-Diol, Propane 1, 3-Diol and Other Diols and Polyols[P]. WO: 0056688. 2000-09-28.
[13] C. J. Sullivan, D. C. Dehm, E. E. Reich and M. E. Dillon. Polyester Resins Based Upon 2-methyl-1, 3-Propanediol[J]. J. Coat. Technology. 1990, 62(791): 37-41.
[14] F. N. Jones, Lu, D. D-L. Properties of Higher-Solids Polyester/Melamine Enamels Made from Monodisperse Oligoesters[J]. J. Coat. Technology. 1987, 59(751): 73-76.
[15] P. M. Duncan, M. R. Van De Mark and C. J. Sullivan. New Monomer Offers Advantages For High-Solids Polyesters Evaluating 2-methyl-1, 3-Propanediol as a Direct Substitute for Neopentyl Glycol In Polyesters Resins[J]. Modem Paint and Coatings. 1990, 80(6): 51-54.
[16] C. J. Sullivan, W. P. Becker, W. J. Cleland. Polyesters Plasticizers Made With 2-methyl[57] Piotr Cysewski, Alicja Gackowska, Jerzy Gaca. Experimental and theoretical studies on formation and degradation of chloro organic compounds[J]. Chemosphere. 2006(63): 165-170.
[58] 宋立旺．烯烃气体混合物氯化反应研究．大连理工大学硕士研究生论文[D]．2000(8)．
[59] 胡性之．甲代烯丙基氯．精细与专用化学品[J]．1999(1)：18-20．
[60] 国内发展动态．精细与专用化学品[J]．2005(5)：6．
[61] 王福安．化工数据导引．化学工业出版社[M]．1995(10)．
[62] 杨基和，赵世勇，季建银．石蜡氧化制蜂蜡管式反应器设计[J]．天然气与石油．2004，22(1)：42-46．
[63] 金属管浮子流量计．选型资料．开封仪表有线公司[J]．2003(3)：15-20．
[64] Schulze, K.; Hartmann, S.; Krueger, H.; Muehlstaedt, M.; Richter, C.; Richter, H. Synthesis and characterization of polychlorinated isobutenes[J]. Journal fuer Praktische Chemie. 1984, 326(3): 433-442.
[65] 陈敏恒，丛德滋，方图南，齐鸣斋．化工原理[M]．化学工业出版社．2003(5)．
[66] 蒋登高，章亚东，周彩荣．精细有机合成反应及工艺[M]．化学工艺出版社．2003(1)．
[67] 齐江，戴献元．醇类稀溶液的溶剂萃取研究[J]．现代化工．1999，19(10)：9-12．
[68] 程世绪．铜液表面张力的测定[J]．中氮肥．2002(6)，50-51．
[69] 天津大学物理化学教研室．物理化学[M]．高等教育出版社．2003(4)．
[70] 刘光启，马连湘，刘杰．化学化工物性数据手册[D]．化学工业出版社．2005(5)．