淀粉基生物降解塑料的研究
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摘要
淀粉基生物降解塑料是一种重要的可降解高分子材料。本论文致力于在保证材料生物可降解性的同时，改善材料的力学性能和耐水性，并对其熔体流动性的变化进行了分析。最后，粗测了生物降解性并进行了吹膜的尝试。
首先，本论文比较了食用淀粉、工业淀粉和木薯淀粉三种热塑性淀粉塑料的力学性能并分析了甘油含量的影响。其次，以水和甘油作为增塑剂，利用单螺杆挤出机制备了淀粉与聚乙烯醇的共混物，并就聚乙烯醇和甘油含量对体系力学性能和耐水性的影响作了分析。第三，以水和甘油作为增塑剂，利用单螺杆挤出机制备热塑性淀粉(TPS)，然后再用单螺杆挤出机将TPS与分子量为5万的聚己内酯共混挤出。之后，分析了各组分的含量对体系力学性能、耐水性及熔体流动性的影响。第四，在平衡湿含量为12％的淀粉中加入增塑剂甘油，利用双螺杆挤出机制造热塑性淀粉，然后利用单螺杆挤出机将TPS分别与不同分子量的聚己内酯以及乙烯-乙烯醇共聚物(EVOH)共混挤出，并对共混物性能的影响因素进行了类似的分析。此外，还对TPS/EVOH共混体系的润滑和母料制备法进行了分析研究。最后，利用室内土埋法粗测了TPS/PCL和TPS/EVOH共混物部分试样的生物降解性并尝试用配比为60:40和50:50的共混物吹膜。
Starch-based biodegradable plastics is a kind of important degradable polymer material. In this paper, improving the mechanical properties and water-resistance of the material was focused on, ensuring its biodegradability at the same time. And the change of melt flow index was analyzed. In the end, biodegradability was measured roughly and film was blowed.
Firstly, the mechanical properties of three different thermoplastic starches made from edible starch, industrial starch and cassava starch were compared and the influence of the glycerol content on the properties of each system was analyzed. Secondly, starch was blended with polyvinyl alcohol by single screw extruder with water and glycerol as plasticizers. The influence of the contents of PVA and glycerol on the mechanical property and water-resistance of the material was also analyzed. Thirdly, thermoplastic starch was prepared through single screw extruder with water and glycerol as plasticizers, which was then blended with polycaprolactone with the molecular weight of 50 000 by single screw extruder. Then the influence of the contents of different constituents on the mechanical properties, water-resistance and melt flow index was studied. Finally, glycerol as a plasticizer was added into starch with equilibrium moisture content of 12%. And thermoplastic starch was prepared by double screw extruder. Then
it was blended with polycaprolactone with different molecular weight and ethylene-vinyl alcohol copolymer by single screw extruder. Then similar studies on the factors of the properties of the blends were conducted. In addition, the lubrication and method of making TPS/EVOH blends from master batch were studied. Finally, the biodegradability of some samples of TPS/EVOH and TPS/PCL blends were measured roughly by indoor soil burial method and film was tried to blow with TPS/PCL blends in the ratio 60:40 and 50:50.
首先，本论文比较了食用淀粉、工业淀粉和木薯淀粉三种热塑性淀粉塑料的力学性能并分析了甘油含量的影响。其次，以水和甘油作为增塑剂，利用单螺杆挤出机制备了淀粉与聚乙烯醇的共混物，并就聚乙烯醇和甘油含量对体系力学性能和耐水性的影响作了分析。第三，以水和甘油作为增塑剂，利用单螺杆挤出机制备热塑性淀粉(TPS)，然后再用单螺杆挤出机将TPS与分子量为5万的聚己内酯共混挤出。之后，分析了各组分的含量对体系力学性能、耐水性及熔体流动性的影响。第四，在平衡湿含量为12％的淀粉中加入增塑剂甘油，利用双螺杆挤出机制造热塑性淀粉，然后利用单螺杆挤出机将TPS分别与不同分子量的聚己内酯以及乙烯-乙烯醇共聚物(EVOH)共混挤出，并对共混物性能的影响因素进行了类似的分析。此外，还对TPS/EVOH共混体系的润滑和母料制备法进行了分析研究。最后，利用室内土埋法粗测了TPS/PCL和TPS/EVOH共混物部分试样的生物降解性并尝试用配比为60:40和50:50的共混物吹膜。
Starch-based biodegradable plastics is a kind of important degradable polymer material. In this paper, improving the mechanical properties and water-resistance of the material was focused on, ensuring its biodegradability at the same time. And the change of melt flow index was analyzed. In the end, biodegradability was measured roughly and film was blowed.
Firstly, the mechanical properties of three different thermoplastic starches made from edible starch, industrial starch and cassava starch were compared and the influence of the glycerol content on the properties of each system was analyzed. Secondly, starch was blended with polyvinyl alcohol by single screw extruder with water and glycerol as plasticizers. The influence of the contents of PVA and glycerol on the mechanical property and water-resistance of the material was also analyzed. Thirdly, thermoplastic starch was prepared through single screw extruder with water and glycerol as plasticizers, which was then blended with polycaprolactone with the molecular weight of 50 000 by single screw extruder. Then the influence of the contents of different constituents on the mechanical properties, water-resistance and melt flow index was studied. Finally, glycerol as a plasticizer was added into starch with equilibrium moisture content of 12%. And thermoplastic starch was prepared by double screw extruder. Then
it was blended with polycaprolactone with different molecular weight and ethylene-vinyl alcohol copolymer by single screw extruder. Then similar studies on the factors of the properties of the blends were conducted. In addition, the lubrication and method of making TPS/EVOH blends from master batch were studied. Finally, the biodegradability of some samples of TPS/EVOH and TPS/PCL blends were measured roughly by indoor soil burial method and film was tried to blow with TPS/PCL blends in the ratio 60:40 and 50:50.
引文
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[3]康情．内江科技，1996，17(3)：31～33
[4]陈和生，孙振业．塑料科技，2000，(4)：36～38
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[8]王天民．生态环境材料．天津大学出版社，2000
[9]益小苏等．材料导报，1994，(4)：49
[10]刘永禄等．现代塑料加工应用，1994，(6)：23
[11]鲁江等．塑料科技，2000，(6)：47～49
[12]赵科．化工进展，2001，(11)：46～47
[13]邱清华．现代化工，1999，(2)：19
[14]邱威扬等，塑料工业，1998，26(4)：106～108
[15]高建平等．高分子材料科学与工程，1999，15(3)：93～95
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[20]KRISHNA. J Appl Polym Sci, 1998, 70: 2252～2257
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[25]D.Bikiaris, E. Pavlidou, J.Prinos. Polym Degrad Stab, 1998, 60:437～447
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[30]赵建青．塑料工业，1992，(5)：16～19
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[32]张一烽．高分子材料科学与工程，2000，16(2)：47～50
[33]高建平．高分子材料科学与工程，2000，16(1)：63～66
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[35]丁浩．塑料应用技术．化学工业出版社，1999
[36]王琳霞．塑料科技，2002，(1)：37～40
[37]李云政，蔡博伟．塑料，1997，26(3)：30～32
[38]李晓等．塑料工业，1999，27(6)：28～30
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[40]吴强．甘肃科技，2000，(4)：53
[41]何光波，黄世强．化工新型材料，1995，(2)：27～29
[42]Robson F. Storey, Amelia E.Taylor. J Mcromol Sci Pure Appl Chem, 1998, A35(5): 723～750
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[47]AKIRA IWAWOTO, YUTAKA TOKIWA. J Appl Polym Sci, 1994, 52: 1357～1360
[48]CHRISTINE V.BENEDICT. J Appl Polym Sci., 1983, 28:327～334
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[52]LUC AVEROUS, CHRISTOPHE FRINGANT. Polym Eng Sci, 2001, 41(5): 727～734
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[57]Akahori, Shin-ichi; Osawa, Zenjiro. Polym Degrad Stab, 1994, 45(3): 261～265
[58]L.WANG, R.L.SHOGREN, C.CARRIERE. Polym Eng Sci., 2000, 40(2):499
[59]鲁江等．塑料科技，2000，(4)：47～49
[60]O.S.ODUSANYA, U.S.ISHIAKU, B.M.N.AZEMI. Polym Eng Sci., 2000, 40(6): 998～1305
[61]DONG-KEON KWEON, DONG-SOOCHA, HYUN-JINPARK, SEUNG-TAIK LIM. J Appl Polym Sci, 2000, 78(5): 986～993
[62]EUI-JUN CHOI, CHANG-HYEON KIM, JUNG-KI PARK. Macromolecules, 1999, 32:7402～7408
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