• ISSN 1008-505X
  • CN 11-3996/S
王倩, 熊玉竹, 罗惠元, 江猛, 张清坡, 谢兰. 改性再生油合成可降解材料制备缓释肥的技术参数研究[J]. 植物营养与肥料学报, 2019, 25(7): 1257-1264. DOI: 10.11674/zwyf.18303
引用本文: 王倩, 熊玉竹, 罗惠元, 江猛, 张清坡, 谢兰. 改性再生油合成可降解材料制备缓释肥的技术参数研究[J]. 植物营养与肥料学报, 2019, 25(7): 1257-1264. DOI: 10.11674/zwyf.18303
WANG Qian, XIONG Yu-zhu, LUO Hui-yuan, JIANG Meng, ZHANG Qing-po, XIE Lan. Optimization of parameters using modified recycling oil for preparation of degradable polyurethane coating material of slow-release fertilizer[J]. Journal of Plant Nutrition and Fertilizers, 2019, 25(7): 1257-1264. DOI: 10.11674/zwyf.18303
Citation: WANG Qian, XIONG Yu-zhu, LUO Hui-yuan, JIANG Meng, ZHANG Qing-po, XIE Lan. Optimization of parameters using modified recycling oil for preparation of degradable polyurethane coating material of slow-release fertilizer[J]. Journal of Plant Nutrition and Fertilizers, 2019, 25(7): 1257-1264. DOI: 10.11674/zwyf.18303

改性再生油合成可降解材料制备缓释肥的技术参数研究

Optimization of parameters using modified recycling oil for preparation of degradable polyurethane coating material of slow-release fertilizer

  • 摘要:
    目的 回收油提纯后直接合成的生物基聚氨酯 (PUs),耐湿耐热性能较差,不适宜于用作肥料缓释包膜材料。本文在聚氨酯合成过程中引入能提高产品的机械、耐水、抗老化等性能的γ―氨丙基三乙氧基硅烷 (KH550) 对PUs进行改性,并初步测定了该包膜肥料养分的释放特征。
    方法 回收的食用油和反复使用的炸油来自贵州省毕节市的餐馆。依次用磷酸、蒸馏水、NaOH、NaCl清洗提纯后得到再生油。将制得的再生油与过氧乙酸按质量比1∶0.3混合,经过中和、洗涤、蒸馏,与乙二醇反应生成醇化再生油。将醇化再生油与KH550在80℃下按一定比例混合搅拌2 h,制成含KH550分别为0、10%、20%和30%的醇化再生油混合物。在BYC-300型包衣机中加入150 g尿素 (包衣温度为60℃,转速为1300 r/min),按尿素重量的3%加入上述混合物,再滴加MDI-50进行包衣,即制备得KH550改性聚氨酯 (K-PUs) 包膜尿素 (PCUs-0、PCUs-1、PCUs-2、PCUs-3)。参考Oertli等方法测定了该包膜肥料的缓释性能。
    结果 1) 回收油经过多步提纯后得到的再生油仍保持原油的分子结构,含有官能团碳碳双键。2) 再生油经过预改性后明显增加活性基团羟基,为聚氨酯的合成提供反应基团。3) 通过化学反应将再生油合成为新型生物基聚氨酯,并在聚氨酯合成过程中成功引入硅烷偶联剂KH550,从而得到改性PUs包膜材料。4) KH550的存在使得改性后PUs的疏水性相比于未改性的提高了48%~74%;孔隙率相比于未改性前降低了31%~54%;热稳定性相比于未改性的PUs在T5%提高了3%~11%、T50%提高了6%~32%、T80%提高了4%~11%。氮素模拟试验表明PCUs氮的累积释放速率明显降低。改性后的PCUs氮素在第30天累积释放不超过70%,未改性PCUs氮素在第30天累积释放超过90%。5) 当KH550含量为20%时,改性PUs具有最大的接触角和最低的孔隙率,其值分别为113.31°和10.91%,该条件下制备的PCUs综合性能最佳。
    结论 以回收油为原料合成新型生物基聚氨酯,需进行醇化后,再与硅烷偶联剂混合,并加入MDI-50进行反应,形成KH550含量为20%的改性生物基聚氨酯。以该材料包膜的尿素30天氮素累积释放量不超过70%,可以满足可降解缓释肥的要求。

     

    Abstract:
    Objectives The polyurethane, synthesized directly from the purified recycled cooking oils, is weak in hot and humid resistance, and not qualified for fertilizers coating materials. In this paper, a silane coupling agent γ-aminopropyl triethoxy silane (KH550) was introduced in the process of polyurethane synthesis, and the availability of the modified coating materials for making coated fertilizer was tested.
    Methods The oil used was collected from the restaurants in Guiyang. The oil was firstly purified with phosphorous acid, distilled water, NaOH and NaCl in turn. Then the oil was pre-modified by peracetic acid and ethylene glycol. The pre-modified oil was mixed in different ratios with KH550 to form mixtures containing KH550 of 0, 10%, 20% and 30%. Urea was coated with the above PUs in rate of 3% of urea weight to make slow-release fertilizers. The nitrogen release period of the coated fertilizers was determined using modified Oertli method.
    Results  1) The recycled oil was achieved when the recovered oil was treated with multi-step purification, and it maintained the molecular structure of carbon-carbon double bonds groups. 2) After pre-modification of recycled oil, it supplied the hydroxyl groups for the synthesis of polyurethane. 3) The experimental results showed that KH550 was successfully introduced and amended PUs coating material was synthesized. 4) Compared with the unmodified PUs, the hydrophobicity of modified PUs was increased by 48%–74%; the coating porosity was reduced by 31%–54%; the thermal stability was increased by 3%–11% at T5%, 6%–32% at T50%, and 4%–11% at T80%. As a result, the N cumulative release rate of modified PCUs was significantly reduced. The N cumulative release of modified PCUs was less than 70% on the 30 th day, which was considerably lower than the rate of unmodified PCUs (90%). 5) When the content of KH550 was 20%, the water contact angle was the biggest (113.31o), and the porosity was the lowest (10.91%). The comprehensive performance of PCUs was the best.
    Conclusions A novel bio-based polyurethanes has been synthesized by pre-modified recycled oil and the introduce of silane coupling agent in the process of polyurethane synthesis. Using the modified polyurethanes containing 20% of KH550 as coating material, cumulative N release is less than 70% on the 30 th day, proving the prospect of the practical use of the modified polyurethanes.

     

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