低聚合度低醇解度聚乙烯醇的制备研究
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摘要
本文主要研究了以下内容：(1)低聚合度聚醋酸乙烯酯的制备；(2)低聚合度聚醋酸乙烯酯溶液醇解和悬浮醇解工艺；(3)醋酸乙烯酯聚合机理和低聚合度聚乙烯醇结构与性能。
首先，探讨了溶液聚合法制备低聚合度聚醋酸乙烯酯过程中各种因素对聚合反应的影响。聚合温度，引发剂浓度，单体：溶剂体积比等因素，均影响低聚合度聚醋酸乙烯酯的生成，同时发现通过改变醋酸乙烯酯浓度来制备低聚合度聚醋酸乙烯酯是一个行之有效的方法。
其次，探讨了低聚合度聚醋酸乙烯酯溶液醇解工艺和悬浮醇解工艺。分析了催化剂、醇解温度、反应物浓度等对醇解度的影响。悬浮醇解法通过调节催化剂浓度、悬浮剂用量等，能有效地控制醇解度的大小，且悬浮醇解得到的聚乙烯醇产品后处理简单，生产成本低。同时，GPC结果表明两种醇解法得到聚乙烯醇的聚合度、分子量分布基本一致。
最后，对低聚合度低醇解度聚乙烯醇的结构进行了表征。FTIR和NMR表明所合成的聚乙烯醇中头-头、头-尾两种连接的方式同时并存，并据此探讨了醋酸乙烯酯的聚合机理。此外，对低聚合度聚乙烯醇的水溶性、表面张力、相变温度、拉伸强度等性能做了初步探讨。
In this paper, the preparation and alcoholysis of polyvinyl acetate of low degree polymerization were studied, and the structures and properties of the resulting polymers were studied.
First, the preparation of polyvinyl acetate of low polymerization through the solution polymerization method was studied. It was found that the temperature, the concentration of initiator and the ratio of vinyl acetate/solvent affect the polymerization seriously.
Next, the solution alcoholysis and suspension alcoholysis process were discussed. The effect of the reaction time, temperature, the concentration of reactant and catalyst on the alcoholysis process were investigated. In the suspension alcoholysis process, the degree of alcoholysis could be efficiently controlled by changing the concentration of catalyst and suspension agent.
Then, the structures of low degree of polymerization polyvinyl acetate and polyvinyl alcohol with FTIR, 1H NMR , 13C NMR and GPC were characterized. The results showed that head-head and head-tail connection coexist in either polyvinyl acetate or polyvinyl alcohol. In view of the results, we investigated the polymerization mechanism of vinyl acetate.
Finally, the properties of the resulting polymers, such as solubility, tensile strength, temperature of transformation, surface tension were investigated.
首先，探讨了溶液聚合法制备低聚合度聚醋酸乙烯酯过程中各种因素对聚合反应的影响。聚合温度，引发剂浓度，单体：溶剂体积比等因素，均影响低聚合度聚醋酸乙烯酯的生成，同时发现通过改变醋酸乙烯酯浓度来制备低聚合度聚醋酸乙烯酯是一个行之有效的方法。
其次，探讨了低聚合度聚醋酸乙烯酯溶液醇解工艺和悬浮醇解工艺。分析了催化剂、醇解温度、反应物浓度等对醇解度的影响。悬浮醇解法通过调节催化剂浓度、悬浮剂用量等，能有效地控制醇解度的大小，且悬浮醇解得到的聚乙烯醇产品后处理简单，生产成本低。同时，GPC结果表明两种醇解法得到聚乙烯醇的聚合度、分子量分布基本一致。
最后，对低聚合度低醇解度聚乙烯醇的结构进行了表征。FTIR和NMR表明所合成的聚乙烯醇中头-头、头-尾两种连接的方式同时并存，并据此探讨了醋酸乙烯酯的聚合机理。此外，对低聚合度聚乙烯醇的水溶性、表面张力、相变温度、拉伸强度等性能做了初步探讨。
In this paper, the preparation and alcoholysis of polyvinyl acetate of low degree polymerization were studied, and the structures and properties of the resulting polymers were studied.
First, the preparation of polyvinyl acetate of low polymerization through the solution polymerization method was studied. It was found that the temperature, the concentration of initiator and the ratio of vinyl acetate/solvent affect the polymerization seriously.
Next, the solution alcoholysis and suspension alcoholysis process were discussed. The effect of the reaction time, temperature, the concentration of reactant and catalyst on the alcoholysis process were investigated. In the suspension alcoholysis process, the degree of alcoholysis could be efficiently controlled by changing the concentration of catalyst and suspension agent.
Then, the structures of low degree of polymerization polyvinyl acetate and polyvinyl alcohol with FTIR, 1H NMR , 13C NMR and GPC were characterized. The results showed that head-head and head-tail connection coexist in either polyvinyl acetate or polyvinyl alcohol. In view of the results, we investigated the polymerization mechanism of vinyl acetate.
Finally, the properties of the resulting polymers, such as solubility, tensile strength, temperature of transformation, surface tension were investigated.
引文
[1]郑国汉，唐嗣荣，醋酸乙烯与聚乙烯醇产品需求预测，合成纤维工业，1997，20(4)：27-30
[2]孙丽琴，聚乙烯醇的生产及市场前景分析，石油化工技术经济，2002，3：33-36
[3]白泽双，国内外聚乙烯醇工业的进展及市场展望，贵州化工，2002，27(1)：1-4
[4]郑国汉，我国聚乙烯醇产品市场与发展方向，四川化工，1997，3-6
[5]M. L. Pourciel, J. Launay, W. Sant, et al. Development of photo-polymerisable polyvinyl alcohol for biotechnological applications, Sensors and Actuators B 2003, 94: 330-336
[6]M. V. Francesco, M. Cristina, S. Franco, et al. Pegylated enzyme entrapped in poly(vinyl alcohol) hydrogel for biocatalytic application, Ⅱ Farmaco, 2001, 56: 541-547
[7]M. C. Xu,, Z. Q. Shi, L. L. Feng, et al. Synthesis of gelatin-PVA flavonol glycosides and terpene lactones, Reactive & Functional Polymers, 2001, 46:273-282
[8]乌沙科夫，沈阳新生企业公司译(陈汉校)，聚乙烯醇及其衍生物(第二册)，北京：中国工业出版社，1965，35
[9]冯新德，高分子合成化学(上册)，科学出版社，1981年，76-78
[10]潘才元，高分子化学，中国科学技术大学出版社，1997年，147-148
[11]T. Yamamoto, S. Seki, M. Hirota, et. al, Preparation of high molecular weight poly (vinyl alcohol) , Polymer Journal, 1987, 19 (12) : 1417-1418
[12]T. Yamamoto, S. Seki, R. Fukae, et. al, High molecular weight poly (vinyl alcohol) through photo-emulsion polymerization of vinyl acetate, Polymer Journal 1990, 22 (7) : 567-571
[13]王锐，董纪震，高分子量聚乙烯醇的合成及其分子量分布和立构规整性，北京服装学院学报，1996，16(1)：1-5
[14]吴行，高分子量聚乙烯醇的合成，维纶通讯，1997，17(4)：7-12
[15]A. B. Moustafa, Effect of electrolyte on the emulsifier-free emulsion
polymerization of vinyl acetate, J. Apply Polymer Science, 1997, 66(4): 711-715
[16]W. S. Loo, C. J. Lee, Preparation and molecular structure of polyvinyl alcohol by low temperature bulk polymerization of vinyl acetate and saponification, Int. J. Polymer Mater, 2000, 46(1-2): 181-194
[17]章悦庭，胡绍华，虞和倬等，乳液聚合法合成高相对分子质量聚乙烯醇，合成纤维工业，2001，24(5)：19-22
[18]胡金生，乳液聚合，化学工业出版社，1987年，258-267
[19]复旦大学化学系高分子教研组编，高分子实验技术，复旦大学出版社，1983年，248-249
[20]B．B．科尔沙克，高分子化合物化学，科学出版社，1955年，379-381
[21]汪福，苏文瑞，聚乙烯醇及其纤维工业的现状与发展前景，福建轻纺，2001，10：38-45
[22]刘白玲，曾祥成，杨金华等，聚乙烯醇生物降解的影响因素，材料研究学报，2000，14(1)：108-112
[23]N. Tudorachi, C. N. Cascaval, M. Rusu, et al. Testing of polyvinyl alcohol and starch mixtures as biodegradable polymeric materials, Polymer Testing, 2000, 19:785-799
[24]J. L. Wang, X. C. Quan, L. P. Han, et al. Microbial degradation of quinoline by immobilized cells of burkholderia pickettii, Water Research, 2002, 36:2288-2296
[25]P. Alexy, D. Bakos, G. Grkonova, et al. Poly(vinyl alcohol)-collagen hydrolysate thermoplastic blends:Ⅱ water penetration and biodegradability of melt extruded films, Polymer Testing, 2003, 22:811-818
[26]王鸿博，PVA浆料的性能及应用，纺织化学品，2001，2-5
[27]张钦，赵裕蓉，可完全生物降解塑料，化工新型材料，27：3-8
[28]唐龙贵，翁志学，潘祖仁，聚乙烯醇的使用及其改性，1994，27：408-26
[29]高卫东，范雪荣，王鸿博等，经纱上浆浆料及浆纱机的现状与发展，天津纺织工学院学报，1998，17(4)：108-112
[30]中华人民共和国行业标准：OD／GW4．10-002．23-2001
[31]刘振兴，高分子物理实验，中山大学出版社，1991年，20-26
[32]中华人民共和国国家标准：GB7351-89
[33]D Dibbern-Brunelli, TDZ Atvars, I Joekes, et al., Mapping phases of polyvinyl alcohol and polyvinyl acetate blends by FTIR microspectroseopy and optical fluorescence microscopy, J Appl Polym Sci. 1998,69:645-655
[34]李润卿，有机结构波谱分析，天津大学出版社，2002年，210-212
[35]李润卿，有机结构波谱分析，天津大学出版社，2002年，285-288
[2]孙丽琴，聚乙烯醇的生产及市场前景分析，石油化工技术经济，2002，3：33-36
[3]白泽双，国内外聚乙烯醇工业的进展及市场展望，贵州化工，2002，27(1)：1-4
[4]郑国汉，我国聚乙烯醇产品市场与发展方向，四川化工，1997，3-6
[5]M. L. Pourciel, J. Launay, W. Sant, et al. Development of photo-polymerisable polyvinyl alcohol for biotechnological applications, Sensors and Actuators B 2003, 94: 330-336
[6]M. V. Francesco, M. Cristina, S. Franco, et al. Pegylated enzyme entrapped in poly(vinyl alcohol) hydrogel for biocatalytic application, Ⅱ Farmaco, 2001, 56: 541-547
[7]M. C. Xu,, Z. Q. Shi, L. L. Feng, et al. Synthesis of gelatin-PVA flavonol glycosides and terpene lactones, Reactive & Functional Polymers, 2001, 46:273-282
[8]乌沙科夫，沈阳新生企业公司译(陈汉校)，聚乙烯醇及其衍生物(第二册)，北京：中国工业出版社，1965，35
[9]冯新德，高分子合成化学(上册)，科学出版社，1981年，76-78
[10]潘才元，高分子化学，中国科学技术大学出版社，1997年，147-148
[11]T. Yamamoto, S. Seki, M. Hirota, et. al, Preparation of high molecular weight poly (vinyl alcohol) , Polymer Journal, 1987, 19 (12) : 1417-1418
[12]T. Yamamoto, S. Seki, R. Fukae, et. al, High molecular weight poly (vinyl alcohol) through photo-emulsion polymerization of vinyl acetate, Polymer Journal 1990, 22 (7) : 567-571
[13]王锐，董纪震，高分子量聚乙烯醇的合成及其分子量分布和立构规整性，北京服装学院学报，1996，16(1)：1-5
[14]吴行，高分子量聚乙烯醇的合成，维纶通讯，1997，17(4)：7-12
[15]A. B. Moustafa, Effect of electrolyte on the emulsifier-free emulsion
polymerization of vinyl acetate, J. Apply Polymer Science, 1997, 66(4): 711-715
[16]W. S. Loo, C. J. Lee, Preparation and molecular structure of polyvinyl alcohol by low temperature bulk polymerization of vinyl acetate and saponification, Int. J. Polymer Mater, 2000, 46(1-2): 181-194
[17]章悦庭，胡绍华，虞和倬等，乳液聚合法合成高相对分子质量聚乙烯醇，合成纤维工业，2001，24(5)：19-22
[18]胡金生，乳液聚合，化学工业出版社，1987年，258-267
[19]复旦大学化学系高分子教研组编，高分子实验技术，复旦大学出版社，1983年，248-249
[20]B．B．科尔沙克，高分子化合物化学，科学出版社，1955年，379-381
[21]汪福，苏文瑞，聚乙烯醇及其纤维工业的现状与发展前景，福建轻纺，2001，10：38-45
[22]刘白玲，曾祥成，杨金华等，聚乙烯醇生物降解的影响因素，材料研究学报，2000，14(1)：108-112
[23]N. Tudorachi, C. N. Cascaval, M. Rusu, et al. Testing of polyvinyl alcohol and starch mixtures as biodegradable polymeric materials, Polymer Testing, 2000, 19:785-799
[24]J. L. Wang, X. C. Quan, L. P. Han, et al. Microbial degradation of quinoline by immobilized cells of burkholderia pickettii, Water Research, 2002, 36:2288-2296
[25]P. Alexy, D. Bakos, G. Grkonova, et al. Poly(vinyl alcohol)-collagen hydrolysate thermoplastic blends:Ⅱ water penetration and biodegradability of melt extruded films, Polymer Testing, 2003, 22:811-818
[26]王鸿博，PVA浆料的性能及应用，纺织化学品，2001，2-5
[27]张钦，赵裕蓉，可完全生物降解塑料，化工新型材料，27：3-8
[28]唐龙贵，翁志学，潘祖仁，聚乙烯醇的使用及其改性，1994，27：408-26
[29]高卫东，范雪荣，王鸿博等，经纱上浆浆料及浆纱机的现状与发展，天津纺织工学院学报，1998，17(4)：108-112
[30]中华人民共和国行业标准：OD／GW4．10-002．23-2001
[31]刘振兴，高分子物理实验，中山大学出版社，1991年，20-26
[32]中华人民共和国国家标准：GB7351-89
[33]D Dibbern-Brunelli, TDZ Atvars, I Joekes, et al., Mapping phases of polyvinyl alcohol and polyvinyl acetate blends by FTIR microspectroseopy and optical fluorescence microscopy, J Appl Polym Sci. 1998,69:645-655
[34]李润卿，有机结构波谱分析，天津大学出版社，2002年，210-212
[35]李润卿，有机结构波谱分析，天津大学出版社，2002年，285-288