芳香族酰胺化合物的合成
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摘要
本文采用S-B技术合成了两种芳香族酰胺化合物。对反应条件进行了探索和优化。着重考察了反应的温度、反应时间、反应的初始温度和升温速度、芳酰氯的滴加速度、溶剂用量、反应物的物料配比等因素对反应的影响,以寻求最佳的反应条件和合成工艺。将合成产物酰胺A和酰胺B用于聚合物的成核剂,并对其成核效果进行了测试。
本文以芳香族酰氯和脂肪族伯胺为原料,来制备芳香族酰胺化合物。产率可达到98%。实验结果表明,适当延长反应时间可提高产率。反应的初始温度愈高,升温速度愈快,产品的收率就愈高。增加任意一种反应物的量都可提高产率,但酰氯过量较胺过量来说,产品收率的增加更为明显。适当提高反应温度,可提高产率。本反应采取将一种反应物酰氯滴加到另一种反应物胺中的实验方法。酰氯的滴加速度愈慢,产品的收率就愈高。溶剂的使用量在不影响反应结果的情况下,应愈少愈好。可用DMSO作为重结晶溶剂对酰胺A进行重结晶。收率在76-78%。溶剂的循环使用不会影响产品的收率。但由于时间关系,对溶剂回收精制和循环使用的次数较少,实验数据还不够充分。
合成产物酰胺A和酰胺B可以用作饱和聚烯烃的成核剂。我们使用差示扫描量热法和偏光显微镜表征成核剂对饱和聚烯烃的成核效果。结果表明:该成核剂的加入均使结晶温度升高,结晶速度加快。并使结晶的尺寸细化,结晶规整均匀,从而使结晶度增大。
In this paper, two triamines were prepared by a Schotten-Bauman reaction. The influence of reaction temperature, reaction time, ratio of reactants and the amount of the solvent were studied in order to find the optimal technological conditions. The procuct was purified by recrystallizition. Synthesize product the triamine A and triamine B can be used as nucleating agent of polyolefin and observe the nucleating effect of the nucleating agent.Trimines were prepared with aromatic acyl chloride and aliphatic amide by a Schotten-Bauman reaction. The product ratio can reach 98%. The result of experiments showed, Propriety extending of reaction time will improve the yield of the product. The beginning temperature of the reaction will lead to high yield. Increasing the amount of any of the two reactants will increase the product ratio. But more acyl chloride makes more product. Relevance increasing of reaction temperature will increase the product ratio. In this reaction, acyl chloride was dropped slowly into amine. The slower acyl chloride dropped, the higher the yield will be. The fewer consumption of the solvent, the higher the production ratio will become. DMSO was used as recrystal solvent to amide A and get a yield of 76-78%. The recycle times of the solvent will not affect the product ratio. As a result of not enough time, the reclaiming, refining and recycling times of the solvent are not enough, and the experiment data are not sufficiency.Synthesize product the triamine A and triamine B can be used as nucleating agent of polyolefin. Differential scanning calorimetry (DSC) and polarized optical microscopy were used to observe the nucleating effect of the nucleating agent. Compared with pure polyolefin, nucleated polyolefin showed a higher crystallization temperature and a faster crystallization rate. With the addition of nucleating agent, the spherulites became so small and even that the crystalline degree of nucleated polyolefin increased, which resulted in higher rigidity.
本文以芳香族酰氯和脂肪族伯胺为原料,来制备芳香族酰胺化合物。产率可达到98%。实验结果表明,适当延长反应时间可提高产率。反应的初始温度愈高,升温速度愈快,产品的收率就愈高。增加任意一种反应物的量都可提高产率,但酰氯过量较胺过量来说,产品收率的增加更为明显。适当提高反应温度,可提高产率。本反应采取将一种反应物酰氯滴加到另一种反应物胺中的实验方法。酰氯的滴加速度愈慢,产品的收率就愈高。溶剂的使用量在不影响反应结果的情况下,应愈少愈好。可用DMSO作为重结晶溶剂对酰胺A进行重结晶。收率在76-78%。溶剂的循环使用不会影响产品的收率。但由于时间关系,对溶剂回收精制和循环使用的次数较少,实验数据还不够充分。
合成产物酰胺A和酰胺B可以用作饱和聚烯烃的成核剂。我们使用差示扫描量热法和偏光显微镜表征成核剂对饱和聚烯烃的成核效果。结果表明:该成核剂的加入均使结晶温度升高,结晶速度加快。并使结晶的尺寸细化,结晶规整均匀,从而使结晶度增大。
In this paper, two triamines were prepared by a Schotten-Bauman reaction. The influence of reaction temperature, reaction time, ratio of reactants and the amount of the solvent were studied in order to find the optimal technological conditions. The procuct was purified by recrystallizition. Synthesize product the triamine A and triamine B can be used as nucleating agent of polyolefin and observe the nucleating effect of the nucleating agent.Trimines were prepared with aromatic acyl chloride and aliphatic amide by a Schotten-Bauman reaction. The product ratio can reach 98%. The result of experiments showed, Propriety extending of reaction time will improve the yield of the product. The beginning temperature of the reaction will lead to high yield. Increasing the amount of any of the two reactants will increase the product ratio. But more acyl chloride makes more product. Relevance increasing of reaction temperature will increase the product ratio. In this reaction, acyl chloride was dropped slowly into amine. The slower acyl chloride dropped, the higher the yield will be. The fewer consumption of the solvent, the higher the production ratio will become. DMSO was used as recrystal solvent to amide A and get a yield of 76-78%. The recycle times of the solvent will not affect the product ratio. As a result of not enough time, the reclaiming, refining and recycling times of the solvent are not enough, and the experiment data are not sufficiency.Synthesize product the triamine A and triamine B can be used as nucleating agent of polyolefin. Differential scanning calorimetry (DSC) and polarized optical microscopy were used to observe the nucleating effect of the nucleating agent. Compared with pure polyolefin, nucleated polyolefin showed a higher crystallization temperature and a faster crystallization rate. With the addition of nucleating agent, the spherulites became so small and even that the crystalline degree of nucleated polyolefin increased, which resulted in higher rigidity.
引文
[1] 黄宪.有机合成(上册)[M].高等教育出版社1991:15-19
[2] 郭灿成主编.有机化学[M].科学出版社2001:432-434
[3] R.T.莫里森,R.N.博伊德.有机化学(第四版)[M].科学出版社1983:1003-1005
[4] J.马齐著,陶慎熹译.高等有机化学—结构、反应、合成[M].高等教育出版社1991:297-298
[5] R.T.莫里森,R.N.博伊德.有机化学(第二版)[M].世界图文出版公司1991:429-434
[6] 宁永成 编著.有机化合物结构鉴定与有机波谱学[M].清华大学出版社1989:256-258
[7] 李述文 范如霖编译.实用有机化学手册[M].上海科学技术出版社1986:49
[8] 王福来 编著.有机化学实验[M].武汉大学出版社2001:11-12
[9] 王伯英,乌锡康.有机人名反应集第三册[M].北京:化学工业出版社,1984.
[10] 刘心琦主编.实用化学化工辞典[M].宇航出版社1995:533
[11] 王钰潘,谢荣锦.椰子油脂肪酸单乙醇酰胺的合成.[J]精细化工2002,19(11):623-625.
[12] S ean Milmo,Helean Hanilicz.2000全球表面活性剂综述.[J]郑薇译.精细石油化工进展,2000,2(5):52-59.
[13] Mendrala A L, Waechter Jr J M. The pharmacokinetics of diethanolmine in Sprague-Dawley rats following intravenous administration[J]. Food and Chemical Toxicology, 2001, 39(9): 931-939.
[14] 郭祥峰,贾丽华等.单乙醇脂肪酰胺的合成及性能.[J] 日用化学工业2002,32(2):26-29.
[15] 梁勤学,曾广溯.N-硬脂基芥酸酰胺的合成与应用.[J]精细化工2000,17(9):547-548
[12] 吴文娟,徐冬梅等.乙撑双硬脂酰胺的合成.[J]石油化工2003,32(12):1055-1057
[13] 范瑞兰,胡瑞钰等.N-烷基二茂铁丙稀酰胺的合成与表征.[J]内蒙古大学学报(自然科学版)2003,34(1):33-36
[14] 霍永恩,程玉芳.取代芳酰胺丙基杂氮硅三环化合物的合成.[J]有机硅材料2002,16(2):1—3
[15] Minoru Tsuda. S—B esterification of poly(vinyl alcohol). Ⅱ. Die Makromolokulare Chomie. 1964, 72(3): 188-190
[16] Stacy B. Evans, J. E. Mulvaney, H. K. Hall Jr. On the synthesis of pure (meth) acrylate esters and their corresponding homopolymers, Journal of Polymer Science Part A: Polymer Chemistry. 1990, 28(5): 1073-1078
[17] Ro96,953 EP409,684 JP59,227,930 US4904,804
[18] 汪多仁主编.溶剂与专用化学品生产配方和合成工艺—精细化工品实用生产技术手册[M].科学技术文献出版社 2001:262-267
[19] 司航主编.有机化工原料(第二版)[M].化学工业出版社 1996:943
[20] 刘光启等.化学化工物性手册(有机卷)[M].化学工业出版社2001:498
[21] 程能林.溶剂手册(第二版)[M].化学工业出版社 材料科学与工程出版中心2002:831-832
[22] Concise International Chemical Assessment Document 35 N-METHYL-2-PYRROLIDONE Bengt Akesson, Department of Occupational Environment Health, University Hospital, Lund, Sweden. The UN Environment Programme, WHO
[22] Natta, D: Corradini, P. Nuovo Cimento, Su饱和聚烯烃1,1960,15,40.
[23] Ranby, B; Rabek, J. F. Photodegradation Photo-oxidation and Photo stabilization of Polymers, John Wiley & Sons, 1975.
[24] Salovey, R; Dammont, F. J Polym Sci, Part A. 1963, 1, 2155.
[25] Aglietto, M; Bertani, R. Makromol Chem 1992, 193, 179.
[26] Shamshad, A; Basfar, A. A. Rad Phys Chem 2000, 57, 447.
[27] Wong, A. C. Y.; Leung, W. W. M. J Vinyl Addit Techo 1997, 3, 64
[28] MaCauley, N. J.; Harkin-Jones E. M. A.; Murphy, W. R. Polym Eng Sci 1998, 38, 516.
[29] Murarova, A.; Marcincin, A; Jambrich, M. Chemicke Listy 1997, 91, 751.
[30] Yuksekkalayci, C.; Yilmazer, U.; Orbey, N. Polym Eng Sci 1999, 39, 1216.
[31] Crarnez, M. C.; Oliveira, M. J.; Crawford, R. J. J Mater Sci 2001, 36, 2151.
[32] Xiang, C.; Sue, H. J.; Chu, J.; Masuda, K. Polym Eng Sci 2001, 41, 23
[33] 最新工业助剂大全(上卷)[M].化学工业出版社 1997:1056
[34] Beil21,237;21,6(5)321 Fery, L,P,A, et al. Bull. soc. chim. Belg. 1960
[35] 实用精细化学品手册有机卷下册[M].化学工业出版社1996:1736
[36] Hatada K, Shimada M, Fujita K et al. Chem Lett, 1974; 26(2): 439
[37] Hatada K, Shimada M, Ono Y et al. J Catal, 1975; 37(1): 166
[38] Liu Kouchang, Wayne, Taylor PD et al. lnt C1: C07D201/08, US Pat 4824967, 1989-04-25
[39] 余仲建等.现代有机分析[M].天津科学技术出版社 1994:268
[40] 苟梁武.含盐N-烷酮水溶液分离回收工艺及设备研究.[J]四川轻化工学院学报2003,(16)3:60-63
[41] 蒋登高等.精细有机合成单元反应及工艺[M].化学工业出版社2001:139-143
[41] 王克智.聚烯烃成核剂的开发与进展.[J]塑料科技1994,101(3):50-54
[42] 马承银等.饱和聚烯烃成核剂研究的进展.[J]现代塑料加工应用2002,14(1):41-44
[43] 井手文雄.聚合物的结晶与成核剂.[J]塑料世界(日),1997,(4):164
[44] J.M.史密斯.化工动力学[M].化学工业出版社1988:27-31
[45] 朱文涛.物理化学(上册)[M].清华大学出版社1995:298-299
[46] 朱文涛.物理化学(下册)[M].清华大学出版社1995:209—210
[47] Binsbergen, F. L. [J] Polym Sci, Part B 1973, 11, 117
[48] Banks, W.; Sharpies, A. Makromol Chem 1963, 67, 42
[49] Lotz, B.; Fillon, B.; Thierry, A.; Wittmann, J. C. J Polym Bulletin 1991, 25, 101
[50] Kumaraswamy, G.; Verma, R. K.; Issaian, A. M.; Wang, P. Polymer 2000, 41, 8931
[51] Masubuchi, Y.; Watanabe, K.; Nagatake, W.; Takimoto, J. I.; Koyama, K. Polymer
[2] 郭灿成主编.有机化学[M].科学出版社2001:432-434
[3] R.T.莫里森,R.N.博伊德.有机化学(第四版)[M].科学出版社1983:1003-1005
[4] J.马齐著,陶慎熹译.高等有机化学—结构、反应、合成[M].高等教育出版社1991:297-298
[5] R.T.莫里森,R.N.博伊德.有机化学(第二版)[M].世界图文出版公司1991:429-434
[6] 宁永成 编著.有机化合物结构鉴定与有机波谱学[M].清华大学出版社1989:256-258
[7] 李述文 范如霖编译.实用有机化学手册[M].上海科学技术出版社1986:49
[8] 王福来 编著.有机化学实验[M].武汉大学出版社2001:11-12
[9] 王伯英,乌锡康.有机人名反应集第三册[M].北京:化学工业出版社,1984.
[10] 刘心琦主编.实用化学化工辞典[M].宇航出版社1995:533
[11] 王钰潘,谢荣锦.椰子油脂肪酸单乙醇酰胺的合成.[J]精细化工2002,19(11):623-625.
[12] S ean Milmo,Helean Hanilicz.2000全球表面活性剂综述.[J]郑薇译.精细石油化工进展,2000,2(5):52-59.
[13] Mendrala A L, Waechter Jr J M. The pharmacokinetics of diethanolmine in Sprague-Dawley rats following intravenous administration[J]. Food and Chemical Toxicology, 2001, 39(9): 931-939.
[14] 郭祥峰,贾丽华等.单乙醇脂肪酰胺的合成及性能.[J] 日用化学工业2002,32(2):26-29.
[15] 梁勤学,曾广溯.N-硬脂基芥酸酰胺的合成与应用.[J]精细化工2000,17(9):547-548
[12] 吴文娟,徐冬梅等.乙撑双硬脂酰胺的合成.[J]石油化工2003,32(12):1055-1057
[13] 范瑞兰,胡瑞钰等.N-烷基二茂铁丙稀酰胺的合成与表征.[J]内蒙古大学学报(自然科学版)2003,34(1):33-36
[14] 霍永恩,程玉芳.取代芳酰胺丙基杂氮硅三环化合物的合成.[J]有机硅材料2002,16(2):1—3
[15] Minoru Tsuda. S—B esterification of poly(vinyl alcohol). Ⅱ. Die Makromolokulare Chomie. 1964, 72(3): 188-190
[16] Stacy B. Evans, J. E. Mulvaney, H. K. Hall Jr. On the synthesis of pure (meth) acrylate esters and their corresponding homopolymers, Journal of Polymer Science Part A: Polymer Chemistry. 1990, 28(5): 1073-1078
[17] Ro96,953 EP409,684 JP59,227,930 US4904,804
[18] 汪多仁主编.溶剂与专用化学品生产配方和合成工艺—精细化工品实用生产技术手册[M].科学技术文献出版社 2001:262-267
[19] 司航主编.有机化工原料(第二版)[M].化学工业出版社 1996:943
[20] 刘光启等.化学化工物性手册(有机卷)[M].化学工业出版社2001:498
[21] 程能林.溶剂手册(第二版)[M].化学工业出版社 材料科学与工程出版中心2002:831-832
[22] Concise International Chemical Assessment Document 35 N-METHYL-2-PYRROLIDONE Bengt Akesson, Department of Occupational Environment Health, University Hospital, Lund, Sweden. The UN Environment Programme, WHO
[22] Natta, D: Corradini, P. Nuovo Cimento, Su饱和聚烯烃1,1960,15,40.
[23] Ranby, B; Rabek, J. F. Photodegradation Photo-oxidation and Photo stabilization of Polymers, John Wiley & Sons, 1975.
[24] Salovey, R; Dammont, F. J Polym Sci, Part A. 1963, 1, 2155.
[25] Aglietto, M; Bertani, R. Makromol Chem 1992, 193, 179.
[26] Shamshad, A; Basfar, A. A. Rad Phys Chem 2000, 57, 447.
[27] Wong, A. C. Y.; Leung, W. W. M. J Vinyl Addit Techo 1997, 3, 64
[28] MaCauley, N. J.; Harkin-Jones E. M. A.; Murphy, W. R. Polym Eng Sci 1998, 38, 516.
[29] Murarova, A.; Marcincin, A; Jambrich, M. Chemicke Listy 1997, 91, 751.
[30] Yuksekkalayci, C.; Yilmazer, U.; Orbey, N. Polym Eng Sci 1999, 39, 1216.
[31] Crarnez, M. C.; Oliveira, M. J.; Crawford, R. J. J Mater Sci 2001, 36, 2151.
[32] Xiang, C.; Sue, H. J.; Chu, J.; Masuda, K. Polym Eng Sci 2001, 41, 23
[33] 最新工业助剂大全(上卷)[M].化学工业出版社 1997:1056
[34] Beil21,237;21,6(5)321 Fery, L,P,A, et al. Bull. soc. chim. Belg. 1960
[35] 实用精细化学品手册有机卷下册[M].化学工业出版社1996:1736
[36] Hatada K, Shimada M, Fujita K et al. Chem Lett, 1974; 26(2): 439
[37] Hatada K, Shimada M, Ono Y et al. J Catal, 1975; 37(1): 166
[38] Liu Kouchang, Wayne, Taylor PD et al. lnt C1: C07D201/08, US Pat 4824967, 1989-04-25
[39] 余仲建等.现代有机分析[M].天津科学技术出版社 1994:268
[40] 苟梁武.含盐N-烷酮水溶液分离回收工艺及设备研究.[J]四川轻化工学院学报2003,(16)3:60-63
[41] 蒋登高等.精细有机合成单元反应及工艺[M].化学工业出版社2001:139-143
[41] 王克智.聚烯烃成核剂的开发与进展.[J]塑料科技1994,101(3):50-54
[42] 马承银等.饱和聚烯烃成核剂研究的进展.[J]现代塑料加工应用2002,14(1):41-44
[43] 井手文雄.聚合物的结晶与成核剂.[J]塑料世界(日),1997,(4):164
[44] J.M.史密斯.化工动力学[M].化学工业出版社1988:27-31
[45] 朱文涛.物理化学(上册)[M].清华大学出版社1995:298-299
[46] 朱文涛.物理化学(下册)[M].清华大学出版社1995:209—210
[47] Binsbergen, F. L. [J] Polym Sci, Part B 1973, 11, 117
[48] Banks, W.; Sharpies, A. Makromol Chem 1963, 67, 42
[49] Lotz, B.; Fillon, B.; Thierry, A.; Wittmann, J. C. J Polym Bulletin 1991, 25, 101
[50] Kumaraswamy, G.; Verma, R. K.; Issaian, A. M.; Wang, P. Polymer 2000, 41, 8931
[51] Masubuchi, Y.; Watanabe, K.; Nagatake, W.; Takimoto, J. I.; Koyama, K. Polymer