• ISSN 1008-505X
  • CN 11-3996/S
张坤, 徐静, 张民. PPC/PBS包膜尿素膜材料降解特征[J]. 植物营养与肥料学报, 2015, 21(3): 624-631. DOI: 10.11674/zwyf.2015.0309
引用本文: 张坤, 徐静, 张民. PPC/PBS包膜尿素膜材料降解特征[J]. 植物营养与肥料学报, 2015, 21(3): 624-631. DOI: 10.11674/zwyf.2015.0309
ZHANG Kun, XU Jing, ZHANG Min. Degradation behavior of PPC/PBS as urea coating in soil[J]. Journal of Plant Nutrition and Fertilizers, 2015, 21(3): 624-631. DOI: 10.11674/zwyf.2015.0309
Citation: ZHANG Kun, XU Jing, ZHANG Min. Degradation behavior of PPC/PBS as urea coating in soil[J]. Journal of Plant Nutrition and Fertilizers, 2015, 21(3): 624-631. DOI: 10.11674/zwyf.2015.0309

PPC/PBS包膜尿素膜材料降解特征

Degradation behavior of PPC/PBS as urea coating in soil

  • 摘要: 【目的】 生物可降解树脂包膜材料用于生产控释肥,以防止传统聚烯烃类树脂包膜材料对土壤造成的潜在危害。研究不同膜材、在不同类型土壤中的降解速度,可以为提高包膜肥料的施用效果和土壤生态环境效应提供技术支持。【方法】 本文以聚碳酸亚丙酯(PPC)与聚丁二酸丁二醇酯(PBS)两种可生物降解树脂(质量比7:5)作为尿素包膜材料进行田间土埋试验。用红外光谱、热失重和扫描电镜测定方法测定PPC/PBS包膜尿素膜材料试样在降解过程中质量损失百分率,对样品降解前后的结构和表面形貌变化进行表征,分析膜材料在土壤中的降解特征。【结果】 1)红外光谱分析表明,随着土埋时间的延长,在3480 cm-1处的-OH单峰吸收强度先增加后消失,1849~1543 cm-1处羰基吸收峰强度明显增加,在2363 cm-1和2331 cm-1处出现-C=C=C和-C=C=O等累积双键的不对称伸缩振动吸收峰,说明膜材料链结构经历了先断链、后氧化的过程,且膜材料在降解过程中形成了新物质,降解方式是以树脂结构中任意酯键部位切断的方式为主; 2)热失重分析表明,膜材料中PPC树脂在土壤中先行降解,膜材料中随着PPC结构含量的减少,PBS越来越多的发挥其抑制PPC分解的热稳定作用,表现为膜材料的热分解温度移向高温; 3)扫描电镜观察发现,初始状态下的包膜尿素的表面致密均一,没有孔洞,随着埋土时间延长,膜材料表面先行降解,膜的表面为由光滑变粗糙,出现孔洞,随时间延长降解程度增加,表面和内部都变得疏松,孔洞逐渐长大并且同时向周围延伸并与其它孔洞贯穿,孔洞增大到20 m左右,膜的厚度变薄,仅为40~50 m,但包膜仍然保持原有的轮廓,说明膜材料在土壤中可以降解,但会延续一定的时间; 4)膜材料的土埋降解试验表明,初期降解速度较慢,随着时间的延长, 试样生物降解度逐渐增加,在第五个月达到5%失重,之后失重速率明显增快,显示出良好的降解性,到10月份已达到78%的失重率。土壤中的膜材料在12个月内可以被完全降解, 对环境友好。【结论】 PPC/PBS包膜尿素膜材料降解特征为:包膜表面先行降解;膜材料中PPC树脂在土壤中先行降解;降解方式以树脂结构中任意酯键部位切断的方式为主;膜材料降解速度以1~5月份较慢,6~10月份迅速增快,10月份后减慢,一年之内能够完全降解。

     

    Abstract: 【Objective】 Biodegradable resin has been used as coating materials in manufacture of controlled/slow-released fertilizers in order to prevent the persistent polyolefin resin from potential damage to soil. Different coating materials have different degradation behavior in soils, which influence the final application effects of coated fertilizers. Therefore, the study of the degradation characteristics of the coating materials will provide directly support for the correct application of coated fertilizers and the safety of soil ecological environment. 【Methods】 Two kinds of biodegradable polymers, poly(propylene carbonate)(PPC) and poly(butylenes succinate)(PBS)(mass ratio, PPC:PBS=7:5) were used as coating materials for urea in a burial soil experiment. Infrared spectroscopy(FTIR), scanning electron microscopy(SEM), and thermo-gravimetric analyses(TGA) were used to investigate the degradation characteristics of the PPC/PBS film. The degradation behavior of the coating material in soil including the weight loss, structure change, thermal properties and the surface morphology of polymer films was simulated. 【Results】 1) The FTIR analysis shows that the absorption strength of -OH around 3480 cm-1 increases firstly and then decreases, and the carbonyl absorption peaks are strengthen at 1849-1543 cm-1 significantly. The asymmetry stretching vibration absorption peaks of the cumulative double bonds, -C=C=C and -C=C=O, appear at 2363 and 2331 cm-1, respectively, indicating that the molecular chain of the coating materials is broken up firstly and then oxidized, forming new compounds. The random cleavage of the ester bonds are initiated in the biodegradable resin structure. 2) The thermo-gravimetric analysis shows that the thermal decomposition temperature of the degraded membrane moves to higher temperature compared to the initial, which demonstrates that the PPC resin in the membrane is degraded firstly in the soil and then the PBS section with larger proportion plays more inhibitory effect to reduce the further decomposition of PPC. 3) The SEM analysis shows that the PPC/PBS film is found suitable to the rugged surface of urea and combined tightly on the surface of urea. The initial surface is smooth with uniform density and no holes on it. As the buried time elongated, the membrane surface becomes rough and a few of micropores of 3-5 m appears. With the degree of degradation increasing, the membrane structure becomes loose, and the micropores gradually grow up in the internal surface and then extend into the surrounding structure. The pore size increases to about 20 m and the thickness of the film is thinned to 40-50 m. However, the PPC/PBS coating still keeps the original frame, which shows that the degradation process of the membrane material needs a certain time. 4) The tested degradable films have good biological degradabilities with a low initial degradation rate. As the buried time extension, the sample biodegradation degrees increase gradually, about 5% of weight loss is found within five months, after that, the weight loss rate is significantly accelerated and reaches to 78% in October, decomposed completely within 12 months. 【Conclusions】 The degradation behavior of PPC/PBS as urea coating material in soil is initiated on the coating surface caused by the cleavage of chemical structure of film, then followed by biodegradation of the ester bonds at random. The degradation rates of the coating materials are slow within the first five months, then increased dramatically within the following five months, and biodegraded completely in 12 months.

     

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