仿生改性水基共聚物包膜氮肥的制备及其性能研究

doi:10.3864/j.issn.0578-1752.2022.20.009

摘要/Abstract

摘要：

【目的】为了提高水基共聚物膜材料的耐水性,依据仿生学原理,采用疏水效果好的纳米二氧化硅和1H,1H,2H,2H-全氟癸基三甲氧基硅烷对其进行疏水改性,明确最佳改性配比及机理,进而制备出缓释效果好的环境友好型包膜氮肥。【方法】采用三因素三水平L₉(3³)正交试验设计,探究添加不同比例的壳聚糖（0.5%、1.0%、1.5%）、淀粉（0.5%、1.0%、1.5%）和聚乙烯醇（PVA）（2%、3%、4%）对水基共聚物膜材料性能的影响,通过水基共聚物膜材料的吸水率及极差分析筛选出疏水效果好的最优配比。在优选的水基共聚物包膜材料中分别加入0.5%、1.0%、1.5%、2.0%、2.5%、3.0%、3.5%和4.0%的纳米二氧化硅进行疏水改性,通过测定纳米改性水基共聚物膜材料的吸水率和渗透率明确最佳纳米二氧化硅用量。随后,将优选的纳米改性水基共聚物膜材料分别置于含0.5%、1.0%、1.5%和2.0%的1H,1H,2H,2H-全氟癸基三甲氧基硅烷（FAS）的正己烷溶液中进行自组装改性,探究组装浓度对膜材料性能的影响。通过对改性前后水基共聚物膜材料疏水性及透性等变化明确其改性效果,通过改性前后膜材料红外光谱特征、表面微观结构变化探讨其疏水改性机理。并通过土壤培养试验探究所制备的仿生改性水基共聚物包膜尿素的养分释放特性。【结果】当壳聚糖含量为0.5%、淀粉含量为1.5%、PVA含量为4.0%时所制备的水基共聚物膜材料吸水率最低,为42.50%。与水基共聚物膜材料相比,纳米二氧化硅改性水基共聚物膜材料、纳米二氧化硅和FAS双重改性水基共聚物膜材料的吸水率分别降低了38.54%和55.98%,铵离子的渗透率分别降低了24.14%和44.58%,水分子渗透率分别降低了36.14%和60.98%。红外光谱结果表明,纳米二氧化硅改性水基共聚物膜材料的-OH数量减少,并且观察到了Si-O-Si摇摆振动和反对称伸缩振动,纳米二氧化硅和FAS双重改性后水基共聚物材料表面观察到了C-F键。扫描电镜和能谱分析结果表明,在纳米二氧化硅改性水基共聚物膜材料表面发现Si元素,纳米二氧化硅和FAS双重改性水基共聚物膜材料表面发现F元素,并且观察到粗糙的表面结构,其水接触角由62.5°提升到118.6°,表现出良好的疏水效果。此外,土壤培养试验结果表明,纳米二氧化硅改性水基共聚物包膜尿素（NWCU）、纳米二氧化硅和FAS双重改性水基共聚物包膜尿素（SNWCU）的养分缓释期明显延长,SNWCU养分累积释放80%所需时间由改性前的10 d左右提升了28 d左右。【结论】采用纳米二氧化硅和FAS对水基共聚物膜材料进行联合改性可以显著改善水基共聚物膜材料的耐水性及透性,所制备的仿生改性水基共聚物包膜氮肥具有良好的缓释效果。

关键词: 水基共聚物, 疏水改性, 微观结构特征, 红外光谱特征, 养分释放特征

Abstract:

【Objective】The water-based polymer material is widely used in slow-release fertilizers due to its degradability, non-toxicity and good film-forming properties, but due to its poor water resistance, resulting in poor slow-release effect of the prepared coated fertilizer. In order to improve its water resistance ability, according to the principle of bionics, the nano silica and 1H,1H,2H,2H-perfluorodecyltrimethoxysilane were used for hydrophobic modification, the optimal modification ratio and mechanism were determined, and then the environmentally friendly coated urea with better slow-release effect was prepared. 【Method】 This experiment used a three-factor three-level L₉ (3³) orthogonal design to explore the content of chitosan (0.5%, 1.0%, and 1.5%), starch content (0.5%, 1.0%, and 1.5%) and polyvinyl alcohol (PVA) content ( 2%, 3%, and 4%) on the performance of water-based polymer films, the optimal ratio with better hydrophobic effect was screened through water absorption and range analysis. Furthermore, 0.5%, 1.0%, 1.5%, 2.0%, 2.5%, and 3.0% of nano silica was add to the preferred coating materials for hydrophobic modification, respectively. The optimal amount of nano silica was confirmed by measuring the water absorption and permeability of the nano-modified water-based polymer films. Subsequently, the preferred nano-modified water-based polymer film was placed in the nhexane solution containing 0.5%, 1.0%, 1.5%, and 2.0% 1H,1H,2H,2H-perfluorodecyltrimethoxysilane for self-assembly modification, and then the effect of assembly concentration on the properties of films was explored. The modification effect was clarified by the changes of the film's hydrophobicity and permeability, and the hydrophobic modification mechanism was explored through the infrared spectrum characteristics and surface microstructure changes of the films before and after modification. The nutrient release experiments in soil were conducted to explore the nutrient release characters of the biomimetic modified water-based copolymer coated urea. The results of the nutrient release experiments in soil were used to investigate the sustained nutrient release period of nano-modified and biomimetic modified water-based copolymer-coated urea.【Result】 When the content of chitosan was 0.5%, the content of starch was 1.5%, and the content of PVA was 4.0%, the water absorption of the prepared water-based polymer film was the lowest, which was 42.50%. Compared with water-based polymers, the water absorption rates of nano-silica modified water-based copolymer, nano-silica and FAS dual-modified water-based copolymer membrane materials were reduced by 38.54% and 55.98%, respectively, the water permeability were reduced by 36.14% and 60.98%, respectively, and the NH₄⁺ permeability were reduced by 24.14% and 44.58%, respectively. Infrared spectroscopy results showed that the amount of -OH in the nano-silica modified water-based copolymer membrane material was reduced, and Si-O-Si swing vibration and anti-symmetric stretching vibration were observed. The water after the double modification of nano-silica and FAS C-F bonds were observed on the surface of the base copolymer material. The scanning electron microscopy and energy spectrum analysis results showed that Si element appeared on the surface of nano-silica modified water-based copolymer membrane material, and F element appeared on the surface of nano-silica and FAS dual-modified water-based copolymer membrane material and observed a rough surface structure, the water contact angles were increased from 62.5º to 118.6º, and then the coating material could slow down the release effect. In addition, the results of soil culture experiments showed that the control release period of nutrients for nano-silica modified water-based copolymer-coated urea (NWCU), nano-silica and FAS dual-modified water-based copolymer-coated urea (SNWCU) was significantly prolonged. The control release period of nano-silica and FAS dual-modified water-based copolymer-coated urea was increased to about 28 days compared with those of WCU about 10 days. 【Conclusion】 According to the principle of biomimetics, the combined modification with nano-silica and FAS could significantly improve the water resistance and permeability of water-based polymer films, which the prepared biomimetic modified water-based copolymer coated nitrogen fertilizer had a good slow-release effect.

Key words: water-based copolymer, hydrophobic modification, microstructure characteristics, infrared spectroscopy characteristics, nutrient release characteristics

陈春羽,陈松岭,韩艳玉,任立军,邹洪涛,张玉龙. 仿生改性水基共聚物包膜氮肥的制备及其性能研究[J]. 中国农业科学, 2022, 55(20): 3970-3982.

CHEN ChunYu,CHEN SongLing,HAN YanYu,REN LiJun,ZOU HongTao,ZHANG YunLong. Preparation and Properties of Bionic Modified Water-Based Polymer Coated Urea[J]. Scientia Agricultura Sinica, 2022, 55(20): 3970-3982.

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项目Item	A	B	C
k1	56.59	85.70	72.43
k2	73.67	70.48	85.07
k3	95.40	69.49	68.16
R	38.81	15.21	12.64