聚丁二酸丁二醇酯的合成及其催化剂研究
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摘要
本文通过优化合成工艺条件及选用不同种类的催化剂得到高分子量的PBS。探索PBS合成反应的催化机理及催化剂的活性与其结构的关系。
首先用丁二酸、丁二醇为原料,以钛酸四丁酯为催化剂,采用直接酯化缩聚的方法合成了PBS,考察了醇酸比、催化剂用量、聚合温度、真空度等工艺条件对PBS性能的影响。采用了六种不同的钛系化合物为催化剂合成PBS,考察了不同种类的单一钛系催化剂对得到的PBS的性能的影响及催化活性的差异。本文还研究了选用一种主催化剂与一种助催化剂复合来催化合成PBS,考察了不同种类的助催化剂在PBS合成上的助催化活性及得到的PBS的性能差异。
研究结果表明,1)最佳合成条件为：醇酸比为1.3、单一催化剂浓度为300ppm并在酯化后加入、缩聚温度为230℃、真空度<50Pa、缩聚时间为2.5h；在最佳工艺条件下可得Mn为7.8×104的PBS。2)不同结构的钛络合物或化合物催化合成PBS的催化活性与其分子结构有关,催化剂中心Ti原子上带有较易离去基团和小位阻基团时其活性较高。3)当选用双催化剂来合成PBS时,二(乙酰乙酸乙酯)钛酸二异丙酯(TAIP)/Bi2O3表现出最大的活性,得到了Mn约为1.0×105的PBS；Bi2O3的加入可以显著提高PBS的熔融温度和结晶温度,能加速PBS的结晶,而KH2PO4抑制了PBS的结晶,不同的助催化剂对PBS的分解温度影响不大但使产物的酸值略有增加。
Biodegradable poly(butylenes succinate) (PBS) was prepared by direct esterification and polycondensation route using tetrabutoxytitanium as catalyst. The effects of monomer feed molar ratio, polycondensation temperature and catalyst concentration on molecular weight, acid value and so on were investigated in detail to determine the suitable reaction conditions. Then, six Ti-based compounds with different structure were used as catalysts to synthesize PBS to get insight into the relationships between structure and activity of Ti-based catalysts for PBS synthesis.. Further, a primary catalyst together with different cocatalysts were used to systhesize PBS, catalytic activity of cocatalysts and the effect on properties of products were studied.
The results showed that the optimal synthetic conditions was:monomer feed molar ratio BD/SA 1.3; catalyst concentration 300ppm and catalyst added after esterrification; polycondensation temperature 230℃; the pressure below 50Pa; polycondensation time 2.5h. Under these conditions, PBS with Mn of 7.8 X 104 could be synthesized. The thermal analysis indicated that catalytic activity of different Ti-based compounds was related with its steric hinderance. When Bi2O3 was added into TAIP catalyst as cocatalyst, Mn of the PBS reached to 1×105, which suggested that Bi2O3 was optimal cocatalyst.
首先用丁二酸、丁二醇为原料,以钛酸四丁酯为催化剂,采用直接酯化缩聚的方法合成了PBS,考察了醇酸比、催化剂用量、聚合温度、真空度等工艺条件对PBS性能的影响。采用了六种不同的钛系化合物为催化剂合成PBS,考察了不同种类的单一钛系催化剂对得到的PBS的性能的影响及催化活性的差异。本文还研究了选用一种主催化剂与一种助催化剂复合来催化合成PBS,考察了不同种类的助催化剂在PBS合成上的助催化活性及得到的PBS的性能差异。
研究结果表明,1)最佳合成条件为：醇酸比为1.3、单一催化剂浓度为300ppm并在酯化后加入、缩聚温度为230℃、真空度<50Pa、缩聚时间为2.5h；在最佳工艺条件下可得Mn为7.8×104的PBS。2)不同结构的钛络合物或化合物催化合成PBS的催化活性与其分子结构有关,催化剂中心Ti原子上带有较易离去基团和小位阻基团时其活性较高。3)当选用双催化剂来合成PBS时,二(乙酰乙酸乙酯)钛酸二异丙酯(TAIP)/Bi2O3表现出最大的活性,得到了Mn约为1.0×105的PBS；Bi2O3的加入可以显著提高PBS的熔融温度和结晶温度,能加速PBS的结晶,而KH2PO4抑制了PBS的结晶,不同的助催化剂对PBS的分解温度影响不大但使产物的酸值略有增加。
Biodegradable poly(butylenes succinate) (PBS) was prepared by direct esterification and polycondensation route using tetrabutoxytitanium as catalyst. The effects of monomer feed molar ratio, polycondensation temperature and catalyst concentration on molecular weight, acid value and so on were investigated in detail to determine the suitable reaction conditions. Then, six Ti-based compounds with different structure were used as catalysts to synthesize PBS to get insight into the relationships between structure and activity of Ti-based catalysts for PBS synthesis.. Further, a primary catalyst together with different cocatalysts were used to systhesize PBS, catalytic activity of cocatalysts and the effect on properties of products were studied.
The results showed that the optimal synthetic conditions was:monomer feed molar ratio BD/SA 1.3; catalyst concentration 300ppm and catalyst added after esterrification; polycondensation temperature 230℃; the pressure below 50Pa; polycondensation time 2.5h. Under these conditions, PBS with Mn of 7.8 X 104 could be synthesized. The thermal analysis indicated that catalytic activity of different Ti-based compounds was related with its steric hinderance. When Bi2O3 was added into TAIP catalyst as cocatalyst, Mn of the PBS reached to 1×105, which suggested that Bi2O3 was optimal cocatalyst.
引文
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[2]Long Yu, Katherine Dean, Lin Li. Polymer Blends and Composites from Renewable Resources[J]. Progress in Polymer Science,2006,31(6):576-602.
[3]王晓青.生物降解塑料PBS聚酯的研究进展[C].中国塑料加工工业协会专家委员会成立大会暨2005年塑料新材料、新技术国际研讨会,宁波：2005.
[4]季君晖.新型全生物降解塑料PBS进展[J].中国科技成果,2008,(8)：7-9.
[5]孙桂香,罗勇,陆平晔.生物降解PBS聚酯的改性研究进展[J].高分子通报,2011,(2)：102-107.
[6]郭宝华,王国利.聚丁二酸丁二酯的合成与改性研究进展[C].全国生物材料开发与应用技术交流大会暨第四届全国化工应用技术开发热点研讨会,杭州：2009.
[7]Li-Min Deng, Yu-Zhong Wang, Ke-Ke Yang, et al. A New Biodegradable Copolyester Poly(butylene succinate-co-ethylene succinate-co-ethylene terephthalate)[J]. Acta Materialia, 2004,52(20):5871-5878.
[8]段久芳.嵌段聚合物聚乳酸-聚丁二酸丁二醇酯-聚乳酸的制备及其性能研究[J].塑料科技,2009,37(3)：33-35.
[9]M. S. Nikolic, J. Djonlagic. Synthesis and Characterization of Biodegradable Poly(butylene succinate-co-butylene adipate)s[J]. Polymer Degradation and Stability, 2001,74(2):263-270.
[10]孙元碧.生物可降解聚丁二酸／苯基丁二酸丁二醇酯系列共聚物的合成及其结晶行为[J].高分子学报,2006,(6)：745-749.
[11]Mitsuhiro Shibata, Yusuke Inoue, Masanao Miyoshi. Mechanical Properties, Morphology, and Crystallization Behavior of Blends of Poly(1-lactide) with Poly(butylene succinate-co-1-lactate) and Poly(butylene succinate)[J]. Polymer,2006,47(10):3557-3564.
[12]宋亮.聚丁二酸丁二醇酯/多壁碳纳米管复合材料的制备和性能[D].北京：北京化工大学,2009.
[13]Darwin P. R. Kint, Abdelilah Alla, Elise Deloret, et al. Synthesis, Characterization, and Properties of Poly(ethylene terephthalate)/Poly(1,4-butylene succinate) Block Copolymers[J]. Polymer,2003,44(5):1321-1330.
[14]高利斌.成核剂对PBS结晶性能及力学性能的影响[J].北京工商大学学报(自然科学版),2006,24(2)：5-8.
[15]高利斌.全生物降解聚丁二酸丁二醇酯(PBS)的加工改性研究[D].北京：北京工商大学,2006.
[16]张新峰.聚丁二酸丁二醇酯(PBS)的合成表征、共混改性及降解性能研究[D].上海：东华大学,2007.
[17]Yeng-Fong Shih, Tzong-Ming Wu. Enzymatic Degradation Kinetics of Poly(butylene succinate) nanocomposites[J]. Journal of Polymer Research,2008,16(2):109-115.
[18]Lifang Liu, Jianyong Yu, Longdi Cheng, et al. Biodegradability of Poly(butylene succinate) (PBS) Composite Reinforced with Jute Fibre [J]. Polymer Degradation and Stability, 2009,94(1):90-94.
[19]张敏.溶剂对脂肪酶降解高分子量PBS及改性共聚物的影响[J].高等学校化学学报,2010,31(3)：612-615.
[20]曾红梅.静电纺聚丁二酸丁二醇酯(PBS)纳米纤维的制备及其性能研究[D].上海：东华大学,2007.
[21]王群旺.丝素蛋白与聚丁二酸丁二醇酯复合超细纤维膜的制备及性能研究[D].浙江：浙江理工大学,2010.
[22]曾军.聚丁二酸丁二醇酯负载荧光颜料微胶囊的制备与表征[J].高分子材料科学与工程,2006,22(6)：217-214.
[23]Amita Bhatia, Rahul K. Gupta, Sati. N. Bhattacharya, et al. Compatibility of Biodegradable Poly(lactic acid)(PLA) and Poly(butylene succinate)(PBS) Blends for Packaging Application [J]. Korea-Australia Rheology Journal,2007,19(3):125-131.
[24]Momoko Ishii, Masaki Okazaki, Yuji Shibasaki, et al. Convenient Synthesis of Aliphatic Polyesters by Distannoxane-Catalyzed Polycondensation[J]. Biomacromolecules,2001,2(4): 1267-1270.
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