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WO2019062024A1 - 一种土壤调理剂的制备方法 - Google Patents

一种土壤调理剂的制备方法 Download PDF

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Publication number
WO2019062024A1
WO2019062024A1 PCT/CN2018/077745 CN2018077745W WO2019062024A1 WO 2019062024 A1 WO2019062024 A1 WO 2019062024A1 CN 2018077745 W CN2018077745 W CN 2018077745W WO 2019062024 A1 WO2019062024 A1 WO 2019062024A1
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Prior art keywords
alginate
chitosan
soil
preparing
soil conditioner
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PCT/CN2018/077745
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English (en)
French (fr)
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王锦成
饶品华
陈思浩
王润锴
王学宾
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上海工程技术大学
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Application filed by 上海工程技术大学 filed Critical 上海工程技术大学
Priority to US16/650,008 priority Critical patent/US11390809B2/en
Publication of WO2019062024A1 publication Critical patent/WO2019062024A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K17/00—Soil-conditioning materials or soil-stabilising materials
    • C09K17/14—Soil-conditioning materials or soil-stabilising materials containing organic compounds only
    • C09K17/18—Prepolymers; Macromolecular compounds
    • C09K17/32—Prepolymers; Macromolecular compounds of natural origin, e.g. cellulosic materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K17/00—Soil-conditioning materials or soil-stabilising materials
    • C09K17/40—Soil-conditioning materials or soil-stabilising materials containing mixtures of inorganic and organic compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2101/00—Agricultural use

Definitions

  • the invention relates to the field of soil regulation, and in particular to a method for preparing a soil conditioner.
  • Facility soil refers to the general term for cultivated soil in horticultural facilities such as glass greenhouses, solar greenhouses, and plastic greenhouses. At the end of the last century, China's greenhouse area has leapt to the top in the world. The State clearly stated in the "13th Five-Year Plan” that "accelerating the development of facility agriculture” is an important strategy for developing modern agriculture. As a national economic center, Shanghai's agricultural development has the characteristics of urbanization, and land cultivation resources are highly exploited and utilized. Facility agriculture has become an important part of Shanghai's urban agriculture. However, due to the lack of scientific and rational management and technical measures, the sustainable use cycle of facility soil is not long. After years of frequent cultivation, many production problems such as soil alkalization, nutrient and microbial imbalance will occur, resulting in frequent crop diseases and pests. Production is reduced.
  • Soil conditioner refers to the material added to the soil to improve the physical and chemical properties of the soil and its biological activity. It has extremely significant functions of “water retention, loose soil, fattening, and ventilation”. Although soil conditioners can not replace the use of fertilizers, they can improve soil structure, promote the absorption of nutrients by crops, reduce the amount of fertilizer used, and finally achieve the effect of crop yield increase. Natural soil conditioners, such as gypsum, have a long history in the application of saline soil in China, and have achieved remarkable results, which can reduce the pH and conductivity of saline soil. However, this method has little effect on the regulation of soil organic matter content. Many synthetic soil conditioners have been used in soil improvement practices. For example, the application of polyacrylamide (PAM) in soil can increase rainfall infiltration rate and reduce soil erosion. However, synthetic polymers are difficult to degrade in the environment and are prone to secondary pollution.
  • PAM polyacrylamide
  • the natural polymer material alginate is a natural polysaccharide in brown algae. After being used in the facility soil, no secondary pollution occurs, and the naturally degraded monosaccharide can be directly absorbed by the crop as a carbon source, showing good. Non-toxic degradability, biocompatibility, environmentally friendly materials, alginate also has good thickening, film forming and gelation, which has unique advantages for the improvement of soil physical and chemical properties.
  • Chinese patent CN106588445A discloses a seaweed microbial soil conditioner for salt and alkali.
  • the seaweed microbial soil conditioner for the saline-alkali land is prepared by mixing the following raw materials: acidic raw materials, plant-derived organic matter, animal-derived organic matter, composite probiotics, enzymatic hydrolyzed seaweed extract, medium and trace elements, but the patent only focuses on utilizing each The nutrients are mixed to form a soil conditioner, and the regulation mechanism is single.
  • the invention adopts the core-shell structure to achieve the load conditioning component and is slowly released, and has the intelligences of temperature sensitivity, humidity sensitivity and pH sensitivity, which is beneficial to further improving the conditioning effect and conditioning efficiency of the conditioning agent.
  • the object of the present invention is to provide a method for preparing a soil conditioner which realizes intelligent controlled release of soil conditioning through molecular structure design and composition control in order to overcome the defects of the prior art described above.
  • a method for preparing a soil conditioner comprising the following steps:
  • the alginate is swelled in distilled water, and then heated to 40 to 60 ° C to prepare an alginate gel;
  • the alginate described in the step (1) is potassium alginate or calcium alginate, and the weight ratio of the alginate to the distilled water is 10-20:100-200.
  • the weight ratio of the chitosan to the alginate gel described in the step (2) is from 10 to 20:80 to 100.
  • the weight ratio of the N-isopropylacrylamide to the alginate/chitosan composite described in the step (3) is from 50 to 70:150 to 200.
  • the soil conditioning material described in the step (4) is humic acid, gypsum or carboxymethyl cellulose, the solvent is dichloromethane, acetone or ethanol, and the soil conditioning material in the oil phase.
  • the weight concentration is from 1 to 3%.
  • the alginate/chitosan/polyisopropylacrylamide composite material in the aqueous phase described in the step (5) has a weight concentration of 1 to 3%, and the oil phase to the water phase weight ratio is 1:4 ⁇ 6.
  • the chitosan has an N-deacetylation degree of 85%-95%; a viscosity of 1000 mPa/s, and if the N-deacetylation degree of chitosan is less than 85%-95%, Affecting the condensation reaction with alginate, even leading to the formation of core-shell structure
  • the polyisopropylacrylamide has a number average molecular weight of 40,000 to 50,000, otherwise the intelligent controlled release property may be affected.
  • the alginate of the invention has the advantages of non-toxic and non-irritating, excellent biocompatibility, easy degradation, high strength, strong plasticity, easy processing and rapid release.
  • the chitosan used in the invention has good biofunctionality and compatibility, safety, microbial degradation and the like, and has active hydroxyl groups and amino groups in macromolecules, and has strong chemical reaction ability;
  • the polyisopropylacrylamide used in the present invention has both a hydrophilic amido group and a hydrophobic isopropyl group in a macromolecular chain, so that an aqueous solution of linear polyisopropylacrylamide and a cross-linked polyiso Both propyl acrylamide hydrogels exhibit temperature sensitive properties.
  • a composite capsule prepared by blending alginate having a sustained release property, a certain reactive chitosan, and a temperature-sensitive polyisopropylacrylamide has a sustained release and environmental response property. Therefore, the use of these characteristics to prepare soil conditioners can adjust the physical and chemical properties of the soil, improve soil quality, and have certain application prospects to develop green and environmentally friendly polymer soil conditioners.
  • the prepared alginate intelligent conditioning agent has the characteristics of temperature sensitivity, humidity sensitivity and pH sensitivity, and the formed core-shell structure can achieve the purpose of slow release of the load component, and can effectively solve the improvement of soil quality and the adjustment of soil structure.
  • potassium alginate or calcium alginate may be selected as a capsule according to soil fertilizer efficiency, and at the same time, necessary nutrients such as nitrogen, phosphorus, potassium and the like may be appropriately added to select multiple synergistic effects.
  • the soil conditioner is added to the soil and can be used to improve the physical and chemical properties of the soil and its biological activity. It has extremely significant functions of “water retention, loosening, fattening, and ventilation”.
  • Potassium alginate gel was prepared by dissolving 10 g of potassium alginate or calcium alginate in 100 g of distilled water, swelling for 1 hour, and then raising the temperature to 40 °C. 10 g of chitosan was added to a three-necked flask. The N-deacetylation degree of chitosan was 85%, the viscosity was 1000 mPa/s, stirred at room temperature and with N 2 for 20 min, and then 80 g of potassium alginate gel was added. The temperature was raised to 70 ° C, stirred for 1 h, kept for 2 h, and dried in a vacuum oven for 30 min to prepare a potassium alginate/chitosan composite.
  • N-isopropylacrylamide was added to 150 g of potassium alginate or calcium alginate/chitosan composite, and stirred at 1500 rpm for 50 minutes at 30 ° C to obtain potassium alginate/chitosan.
  • a polyisopropylacrylamide composite in which the polyisopropylacrylamide has a number average molecular weight of 40,000.
  • the humic acid was dissolved in dichloromethane to obtain an oil phase having a weight concentration of 1%; an aqueous solution having a weight concentration of 1% alginate/chitosan/polyisopropylacrylamide composite was used as the aqueous phase; At °C, the oil phase was added to the water phase.
  • the weight ratio of oil phase to water phase was 1:4, emulsified at 2000 rpm for 60 minutes to obtain an emulsion; the rotation speed was reduced to 400 rpm at 40 °C. Stirring was continued for 3 hours, and the solvent was evaporated to obtain a milky white colloidal solution; the colloidal solution was centrifuged at 12,000 rpm for 3 hours, and the precipitate was repeatedly washed with distilled water and dried to a constant weight at normal pressure to obtain a white powdery solid microsphere, that is, It is a soil conditioner-containing alginate composite intelligent microsphere of the present invention.
  • Potassium alginate gel was prepared by dissolving 15 g of potassium alginate in 150 g of distilled water, swelling for 2 hours, and then raising the temperature to 50 °C. Adding 15 g of chitosan to a three-necked flask, the N-deacetylation degree of chitosan was 90%; the viscosity was 1000 mPa/s, stirring at room temperature and under N 2 for 25 min, and then adding 90 g of potassium alginate gel. The temperature was raised to 80 ° C, stirred for 1.5 h, kept for 3 h, and dried in a vacuum oven for 40 min to prepare a potassium alginate/chitosan composite.
  • N-isopropylacrylamide 60 g was added to 180 g of potassium alginate/chitosan composite, and stirred at 1800 rpm for 40 minutes at 35 ° C to obtain potassium alginate/chitosan/polyisopropylate.
  • the solvent is removed to obtain a milky white colloidal solution; the colloidal solution is centrifuged at 14,000 rpm for 2 hours, the precipitate is repeatedly washed with distilled water, and dried under normal pressure to a constant weight to obtain a white powdery solid microsphere, which is the present invention.
  • 20 g of calcium alginate was dissolved in 200 g of distilled water, swelled for 3 hours, and then heated to 60 ° C to prepare a potassium alginate or a calcium alginate gel.
  • 20 g of chitosan was added to a three-necked flask, the N-deacetylation degree of chitosan was 90%; the viscosity was 1000 mPa/s, stirred at room temperature and under N 2 for 30 min, and then 100 g of calcium alginate gel was added. The temperature was increased to 70 ° C, stirred for 2 h, kept for 4 h, and dried in a vacuum oven for 50 min to prepare a calcium alginate/chitosan composite.
  • N-isopropylacrylamide was added to 200 g of potassium alginate or calcium alginate/chitosan composite, and stirred at 2000 ° C for 30 minutes at 40 ° C to obtain calcium alginate/chitosan.
  • Polyisopropylacrylamide composite in which the polyisopropylacrylamide has a number average molecular weight of 42,000.
  • the carboxymethyl cellulose is dissolved in ethanol to obtain an oil phase having a weight concentration of 3%; an aqueous solution having a weight concentration of 3% alginate/chitosan/polyisopropylacrylamide composite is used as the aqueous phase; At °C, the oil phase was added to the water phase.
  • the weight ratio of the oil phase to the water phase was 1:6, emulsified at 3000 rpm for 40 minutes to obtain an emulsion; the rotation speed was reduced to 600 rpm at 60 °C. Stirring was continued for 1 hour, and the solvent was evaporated to obtain a milky white colloidal solution; the colloidal solution was centrifuged at 16,000 rpm for 1 hour, the precipitate was repeatedly washed with distilled water, and dried under constant pressure to a constant weight to obtain a white powdery solid microsphere, that is, It is a soil conditioner-containing alginate composite intelligent microsphere of the present invention.
  • thermogravimetric center temperature Infrared spectrum, thermogravimetric center temperature and particle size range of alginate composite smart microspheres prepared in Table 1
  • Example 1 Example 2
  • Example 3 Wave number / cm -1 2800-3000 2800-3000 2800-3000 Wave number / cm -1 3300-3600 3350-3550 3400-3650
  • a method for preparing a soil conditioner comprising the following steps:
  • the aqueous solution of alginate/chitosan/polyisopropylacrylamide composite is used as the aqueous phase, and the alginate/chitosan/polyisopropylacrylamide composite has a weight concentration of 1 in the aqueous phase. %, at 50 ° C, the oil phase was added to the aqueous phase, the weight ratio of oil phase to water phase was: 1:4, emulsified at 2000 rpm for 40 minutes to obtain an emulsion;
  • a method for preparing a soil conditioner comprising the following steps:
  • the aqueous solution of alginate/chitosan/polyisopropylacrylamide composite is used as the aqueous phase, and the weight concentration of the alginate/chitosan/polyisopropylacrylamide composite in the aqueous phase is 3%.
  • the oil phase was added to the water phase at 70 ° C, and the weight ratio of the oil phase to the water phase was 1:6, and the emulsion was emulsified at 3000 rpm for 60 minutes to obtain an emulsion;

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Soil Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Soil Conditioners And Soil-Stabilizing Materials (AREA)

Abstract

本发明涉及一种土壤调理剂的制备方法，将海藻酸盐在蒸馏水中润胀得到海藻酸盐凝胶，加入壳聚糖制备得到海藻酸盐/壳聚糖复合材料，再与N-异丙基丙烯酰胺反应，并溶于水得到水相，土壤调理材料溶于溶剂中，获得油相，将油相与水相混合再进过搅拌反应及离心分离，制备得到产品。与现有技术相比，本发明通过分子层面的结构设计和组成调控，实现土壤调理智能控释。

Description

一种土壤调理剂的制备方法 技术领域
本发明涉及土壤调节领域，尤其是涉及一种土壤调理剂的制备方法。
背景技术
设施土壤是指玻璃温室、日光温室、塑料大棚等园艺设施栽培土壤的总称。上世纪末，我国大棚面积已跃居世界第一，国家在《“十三五”规划纲要》中明确将“加快发展设施农业”作为发展现代农业的重要战略。上海作为全国经济中心，其农业发展具有都市化特点，土地耕作资源得到高度开发利用，设施农业已成为上海都市农业的重要组成部分。然而，因为缺乏科学合理的管理和技术措施，设施土壤的可持续利用周期不长，经过多年的频繁耕种，也会产生土壤碱化、养分和微生物失衡等诸多生产问题，致使作物病害虫害频发、产量降低。
基于此，人们提出了许多土壤问题解决策略，如使用土壤调理剂。土壤调理剂是指加入土壤中，用于改善土壤的物理和化学性质及其生物活性的材料，有极其显著的“保水、松土、增肥、透气”等功能。土壤调理剂，虽无法代替肥料的使用，但却可以改良土壤结构，促进作物对营养元素的吸收，减少化肥使用量，最后达到作物增产的效果。天然土壤调理剂，如石膏等在我国盐渍土的应用上历史悠久，并取得过很显著的效果，可以降低盐渍土壤的pH和电导率。然而，该方法对于土壤的有机质含量调节作用很小。许多人工合成土壤调理剂已用于土壤改良实践中，如土壤中施用聚丙烯酰胺(PAM)可以提高降雨入渗率，减少土壤侵蚀量。然而，人工合成高分子在环境中难以降解，易产生二次污染。
长期的土壤调理实践表明，现有土壤调理剂很难满足环境友好、智能响应、可控释放与高效率的要求，也不符合土壤调理剂的未来发展趋势。天然高分子材料海藻酸盐是褐藻类中的天然多糖类，在设施土壤中使用后，无二次污染产生，且其经自然降解后的单糖可作为碳源直接被农作物吸收，显示良好的无毒可降解性、生物相容性，是环境友好型材料外，海藻酸盐还具有良好的增稠性、成膜性和凝胶性，这对于土壤理化性质的改良具有独特的优势。
目前，海藻酸盐作为土壤调理剂的研究很少，大部分研究集中在生物医药等方面。杨军星等(杨军星，王琦，王媛媛，韩舒，姚佳伟，邵思奇，王敬龙，刘志辉，郭玉鹏.双重载药多层海藻酸盐-壳聚糖缓释微球的制备及体外释放.高等学校化学学报,2015,36: 1025-1032)采用滴注法将海藻酸钠与钙离子交联，制成负载血管内皮生长因子(VEGF)的海藻酸钙核壳球，利用层层自组装技术形成了多组分药物的载药缓释体系。赵萌等(赵萌，蔡沙，屈方宁，方亚鹏.内源乳化法制备海藻酸盐微胶囊的研究进展.食品工业科技,2013,22:392-396)采用内源乳化法选择与改变内部包埋成分，在不同实验条件下，成功将乳酸菌、DNA、蛋白质等包埋进海藻酸盐微胶囊。然而，作为真正实用并符合农作物生长规律的土壤调理剂还必须解决如何通过核壳微球的结构设计，实现其对土壤理化性质调节成分的智能控释。
中国专利CN106588445A公开了盐碱地专用的海藻微生物土壤调理剂。该盐碱地专用海藻微生物土壤调理剂由以下原料混合配制而成：酸性原料，植物源有机质，动物源有机质，复合益生菌剂，酶解海藻提取物，中微量元素，但是该专利仅侧重于利用各种具有营养成分混合起来构成土壤调理剂，调节机制单一。而本发明采用核壳结构达到负载调理成分且缓慢释放，并具有温敏、湿敏和pH敏感等智能性，有利于进一步提升调理剂的调理效果和调理效率。
发明内容
本发明的目的就是为了克服上述现有技术存在的缺陷而提供一种通过分子层面的结构设计和组成调控，实现土壤调理智能控释的土壤调理剂的制备方法。
本发明的目的可以通过以下技术方案来实现：
一种土壤调理剂的制备方法，采用以下步骤：
(1)将海藻酸盐溶于蒸馏水中润胀，然后升温至40～60℃，制备得到海藻酸盐凝胶；
(2)在室温和通N 2情况下向壳聚糖中加入海藻酸盐凝胶，升温至70～90℃，搅拌1～2h，保持2～4h，干燥得到海藻酸盐/壳聚糖复合材料；
(3)将N-异丙基丙烯酰胺加入到海藻酸盐/壳聚糖复合材料中，在30～40℃下，以1500～2000转/min的转速搅拌30～50min，获得海藻酸盐/壳聚糖/聚异丙基丙烯酰胺复合材料；
(4)将土壤调理材料溶于溶剂中，获得油相；
(5)将海藻酸盐/壳聚糖/聚异丙基丙烯酰胺复合材料水溶液作为水相，在50～70℃下，将油相加到水相中，以2000～3000转/min的转速乳化40～60min，获得乳液；
(6)降低转速至400～600转/min，于40～60℃持续搅拌1～3h，挥去溶剂，获得乳白色的胶体溶液；将胶体溶液在12,000～16,000转/min下离心分离1～3h，蒸馏水反复洗涤沉淀， 常压干燥至恒重，得到白色粉末状固体微球，即为本发明的含土壤调理剂的海藻酸盐复合智能微球。
作为优选的实施方式，步骤(1)中所述的海藻酸盐为海藻酸钾或海藻酸钙，海藻酸盐与蒸馏水的重量比为10-20：100-200。
作为优选的实施方式，步骤(2)中所述的壳聚糖与海藻酸盐凝胶的重量比为10-20：80-100。
作为优选的实施方式，步骤(3)中所述的N-异丙基丙烯酰胺与海藻酸盐/壳聚糖复合材料的重量比为50-70：150-200。
作为优选的实施方式，步骤(4)中所述的土壤调理材料为腐殖酸、石膏或羧甲基纤维素，所述的溶剂为二氯甲烷、丙酮或乙醇，油相中土壤调理材料的重量浓度为1～3％。
作为优选的实施方式，步骤(5)中所述的水相中海藻酸盐/壳聚糖/聚异丙基丙烯酰胺复合材料的重量浓度为1～3％，油相与水相重量比为1∶4～6。
作为优选的实施方式，所述的壳聚糖的N-脱乙酰度为85％-95％；粘度为1000mPa/s，如果壳聚糖的N-脱乙酰度低于85％-95％，会影响和海藻酸盐的缩合反应，甚至会导致核壳结构无法形成
作为优选的实施方式，所述的聚异丙基丙烯酰胺的数均分子量为40000-50000，否则智能控释性能会受到影响。
与现有技术相比，本发明海藻酸盐具有无毒无刺激性、优良的生物相容性，易降解、强度高，可塑性强，易加工成型而且具有缓释性等优点。本发明所使用的壳聚糖具有较好的生物官能性和相容性、安全性、微生物降解性等优良性能，而且大分子中有活泼的羟基和氨基，具有较强的化学反应能力；另外，本发明使用的聚异丙基丙烯酰胺的大分子链上同时具有亲水性的酰氨基和疏水性的异丙基，使得线型聚异丙基丙烯酰胺的水溶液以及交联后的聚异丙基丙烯酰胺水凝胶都呈现出温度敏感特性。因此，将具有缓释性能的海藻酸盐、一定反应活性的壳聚糖以及具有温度敏感特性的聚异丙基丙烯酰胺共混制备的复合胶囊具有缓释与环境响应性质。因此，利用这些特点制备土壤调理剂，可调节土壤理化性质，改良土壤品质，具备一定的应用前景研制绿色环保的高分子土壤调理剂。所制备的海藻酸盐智能调理剂具有温敏、湿敏和pH敏感的特性，而且所形成的核壳结构可以达到负载成分缓慢释放的目的，可有效解决改善土壤质量，调节土壤结构。另外，也可根据土壤肥效选择海藻酸钾或海藻酸钙作为囊壳，同时适当添加所需营养物质，如：氮、磷、钾等肥料以及选择达到多重增效的作用。该土壤调理剂加入土壤中，可用于改善土壤的物理和化学性 质及其生物活性的材料，有极其显著的“保水、松土、增肥、透气”等功能。
具体实施方式
下面结合具体实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人员进一步理解本发明，但不以任何形式限制本发明。应当指出的是，对本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进。这些都属于本发明的保护范围。
实施例1
将10g海藻酸钾或海藻酸钙溶于100g蒸馏水中，润胀1h，然后升温至40℃，制备海藻酸钾凝胶。在三颈烧瓶中加入10g壳聚糖，壳聚糖的N-脱乙酰度为85％，粘度为1000mPa/s，在室温和通N 2情况下搅拌20min，再加入海藻酸钾凝胶80g，升温至70℃，搅拌1h，保持2h,在真空烘箱中干燥30min，制备海藻酸钾/壳聚糖复合材料。将50g N-异丙基丙烯酰胺加入150g海藻酸钾或海藻酸钙/壳聚糖复合材料中，在30℃下、以1500转/分钟的转速搅拌50分钟，获得海藻酸钾/壳聚糖/聚异丙基丙烯酰胺复合材料，其中聚异丙基丙烯酰胺的数均分子量为40000。将腐殖酸溶于二氯甲烷中，获得重量浓度为1％的油相；将重量浓度为1％海藻酸盐/壳聚糖/聚异丙基丙烯酰胺复合材料水溶液作为水相；在50℃下，将油相加到水相中，油相与水相重量比为：1∶4，以2000转/分钟的转速乳化60分钟，获得乳液；降低转速至400转/分钟，于40℃持续搅拌3小时，挥去溶剂，获得乳白色的胶体溶液；将胶体溶液在12,000转/分钟下离心分离3小时，蒸馏水反复洗涤沉淀，常压干燥至恒重，得到白色粉末状固体微球，即为本发明的含土壤调理剂的海藻酸盐复合智能微球。
本实施例所制得的海藻酸盐复合智能微球的红外光谱、粒径、热稳定性能和智能控释性能见表1和表2所示。
实施例2
将15g海藻酸钾溶于150g蒸馏水中，润胀2h，然后升温至50℃，制备海藻酸钾凝胶。在三颈烧瓶中加入15g壳聚糖，壳聚糖的N-脱乙酰度为90％；粘度为1000mPa/s，在室温和通N 2情况下搅拌25min，再加入海藻酸钾凝胶90g，升温至80℃，搅拌1.5h，保持3h,在真空烘箱中干燥40min，制备海藻酸钾/壳聚糖复合材料。将60g N-异丙基丙烯酰胺加入180g海藻酸钾/壳聚糖复合材料中，在35℃下、以1800转/分钟的转速搅拌40分钟，获得海藻酸钾/壳聚糖/聚异丙基丙烯酰胺复合材料，其中聚异丙基丙烯酰胺的数均分子量为45000。将石膏溶于丙酮中，获得重量浓度为2％的油相；将重量浓度为2％海藻酸盐/壳聚糖/聚异丙基 丙烯酰胺复合材料水溶液作为水相；在60℃下，将油相加到水相中，油相与水相重量比为：1∶5，以2500转/分钟的转速乳化50分钟，获得乳液；降低转速至500转/分钟，于50℃持续搅拌2小时，挥去溶剂，获得乳白色的胶体溶液；将胶体溶液在14,000转/分钟下离心分离2小时，蒸馏水反复洗涤沉淀，常压干燥至恒重，得到白色粉末状固体微球，即为本发明的含土壤调理剂的海藻酸盐复合智能微球。
本实施例所制得的海藻酸盐复合智能微球的红外光谱、粒径、热稳定性能和智能控释性能见表1和表2所示。
实施例3
将20g海藻酸钙溶于200g蒸馏水中，润胀3h，然后升温至60℃，制备海藻酸钾或海藻酸钙凝胶。在三颈烧瓶中加入20g壳聚糖，壳聚糖的N-脱乙酰度为90％；粘度为1000mPa/s，在室温和通N 2情况下搅拌30min，再加入海藻酸钙凝胶100g，升温至70℃，搅拌2h，保持4h,在真空烘箱中干燥50min，制备海藻酸钙/壳聚糖复合材料。将70g N-异丙基丙烯酰胺加入200g海藻酸钾或海藻酸钙/壳聚糖复合材料中，在40℃下，以2000转/分钟的转速搅拌30分钟，获得海藻酸钙/壳聚糖/聚异丙基丙烯酰胺复合材料，其中聚异丙基丙烯酰胺的数均分子量为42000。将羧甲基纤维素溶于乙醇中，获得重量浓度为3％的油相；将重量浓度为3％海藻酸盐/壳聚糖/聚异丙基丙烯酰胺复合材料水溶液作为水相；在70℃下，将油相加到水相中，油相与水相重量比为：1∶6，以3000转/分钟的转速乳化40分钟，获得乳液；降低转速至600转/分钟，于60℃持续搅拌1小时，挥去溶剂，获得乳白色的胶体溶液；将胶体溶液在16,000转/分钟下离心分离1小时，蒸馏水反复洗涤沉淀，常压干燥至恒重，得到白色粉末状固体微球，即为本发明的含土壤调理剂的海藻酸盐复合智能微球。
本实施例所制得的海藻酸盐复合智能微球的红外光谱、粒径、热稳定性能和智能控释性能见表1和表2所示。
表1制备的海藻酸盐复合智能微球的红外光谱、热失重中心温度及粒径范围
  实施例1 实施例2 实施例3
波数/cm -1 2800-3000 2800-3000 2800-3000
波数/cm -1 3300-3600 3350-3550 3400-3650
热失重中心温度/℃ 450-550 470-580 490-590
粒径范围/μm 10-20 20-30 30-40
表2海藻酸盐复合智能微球的智能控释性能
实施例 0℃ 5℃ 15℃ 25℃ 35℃
实施例1 0 2％ 15％ 35％ 60％
实施例2 0 4％ 20％ 40％ 70％
实施例3 0 6％ 25％ 45％ 80％
实施例4
一种土壤调理剂的制备方法，采用以下步骤：
(1)将10g海藻酸钾溶于200g蒸馏水中，润胀1h，然后升温至40℃，制备海藻酸盐凝胶；
(2)在三颈烧瓶中加入10g壳聚糖，壳聚糖的N-脱乙酰度为95％；粘度为1000mPa/s，在室温和通N 2情况下搅拌20min，再加入海藻酸盐凝胶80g，升温至70℃，搅拌1h，保持2h,在真空烘箱中干燥30min，制备海藻酸盐/壳聚糖复合材料；
(3)将50g N-异丙基丙烯酰胺加入150g海藻酸盐/壳聚糖复合材料中，在30℃下、以1500转/分钟的转速搅拌30分钟，获得海藻酸盐/壳聚糖/聚异丙基丙烯酰胺复合材料，其中聚异丙基丙烯酰胺的数均分子量为50000。
(4)将土壤调理材料腐殖酸溶于二氯甲烷溶剂中，获得油相，在油相中土壤调理材料的重量浓度为1％；
(5)将海藻酸盐/壳聚糖/聚异丙基丙烯酰胺复合材料水溶液作为水相，水相中，海藻酸盐/壳聚糖/聚异丙基丙烯酰胺复合材料的重量浓度为1％，在50℃下，将油相加到水相中，油相与水相重量比为：1∶4，以2000转/分钟的转速乳化40分钟，获得乳液；
(6)降低转速至400转/分钟，于40℃持续搅拌1小时，挥去溶剂，获得乳白色的胶体溶液；将胶体溶液在12,000转/分钟下离心分离1小时，蒸馏水反复洗涤沉淀，常压干燥至恒重，得到白色粉末状固体微球，即为本发明的含土壤调理剂的海藻酸盐复合智能微球。
实施例5
一种土壤调理剂的制备方法，采用以下步骤：
(1)将20g海藻酸钙溶于100g蒸馏水中，润胀3h，然后升温至60℃，制备海藻酸盐凝胶；
(2)在三颈烧瓶中加入20g壳聚糖，壳聚糖的N-脱乙酰度为92％；粘度为1000mPa/s，在室温和通N 2情况下搅拌30min，再加入海藻酸盐凝胶100g，升温至90℃，搅拌2h，保持4h,在真空烘箱中干燥50min，制备海藻酸盐/壳聚糖复合材料；
(3)将70g N-异丙基丙烯酰胺加入200g海藻酸盐/壳聚糖复合材料中，40℃下，以2000转/分钟的转速搅拌50分钟，获得海藻酸盐/壳聚糖/聚异丙基丙烯酰胺复合材料，其中聚异丙基丙烯酰胺的数均分子量为48000；
(4)将土壤调理材料石膏溶于丙酮溶剂中，获得油相，在油相中土壤调理材料的重量浓度为3％；
(5)将海藻酸盐/壳聚糖/聚异丙基丙烯酰胺复合材料水溶液作为水相，水相中海藻酸盐/壳聚糖/聚异丙基丙烯酰胺复合材料的重量浓度为3％，在70℃下，将油相加到水相中，油相与水相重量比为：1∶6，以3000转/分钟的转速乳化60分钟，获得乳液；
(6)降低转速至600转/分钟，于60℃持续搅拌3小时，挥去溶剂，获得乳白色的胶体溶液；将胶体溶液在16,000转/分钟下离心分离3小时，蒸馏水反复洗涤沉淀，常压干燥至恒重，得到白色粉末状固体微球，即为本发明的含土壤调理剂的海藻酸盐复合智能微球。
以上对本发明的具体实施例进行了描述。需要理解的是，本发明并不局限于上述特定实施方式，本领域技术人员可以在权利要求的范围内做出各种变形或修改，这并不影响本发明的实质内容。

Claims (10)

  1. 一种土壤调理剂的制备方法，其特征在于，该方法采用以下步骤：
    (1)将海藻酸盐溶于蒸馏水中润胀，然后升温至40～60℃，制备得到海藻酸盐凝胶；
    (2)在室温和通N 2情况下向壳聚糖中加入海藻酸盐凝胶，升温至70～90℃，搅拌1～2h，保持2～4h，干燥得到海藻酸盐/壳聚糖复合材料；
    (3)将N-异丙基丙烯酰胺加入到海藻酸盐/壳聚糖复合材料中，在30～40℃下，以1500～2000转/min的转速搅拌30～50min，获得海藻酸盐/壳聚糖/聚异丙基丙烯酰胺复合材料；
    (4)将土壤调理材料溶于溶剂中，获得油相；
    (5)将海藻酸盐/壳聚糖/聚异丙基丙烯酰胺复合材料水溶液作为水相，在50～70℃下，将油相加到水相中，以2000～3000转/min的转速乳化40～60min，获得乳液；
    (6)降低转速至400～600转/min，于40～60℃持续搅拌1～3h，挥去溶剂，获得乳白色的胶体溶液；将胶体溶液在12,000～16,000转/min下离心分离1～3h，蒸馏水反复洗涤沉淀，常压干燥至恒重即可。
  2. 根据权利要求1所述的一种土壤调理剂的制备方法，其特征在于，步骤(1)中所述的海藻酸盐为海藻酸钾或海藻酸钙。
  3. 根据权利要求1所述的一种土壤调理剂的制备方法，其特征在于，步骤(1)中所述的海藻酸盐与蒸馏水的重量比为10-20：100-200。
  4. 根据权利要求1所述的一种土壤调理剂的制备方法，其特征在于，步骤(2)中所述的壳聚糖与海藻酸盐凝胶的重量比为10-20：80-100。
  5. 根据权利要求1所述的一种土壤调理剂的制备方法，其特征在于，步骤(3)中所述的N-异丙基丙烯酰胺与海藻酸盐/壳聚糖复合材料的重量比为50-70：150-200。
  6. 根据权利要求1所述的一种土壤调理剂的制备方法，其特征在于，步骤(4)中所述的土壤调理材料为腐殖酸、石膏或羧甲基纤维素，所述的溶剂为二氯甲烷、丙酮或乙醇。
  7. 根据权利要求1所述的一种土壤调理剂的制备方法，其特征在于，步骤(4)中所述的油相中土壤调理材料的重量浓度为1～3％。
  8. 根据权利要求1所述的一种土壤调理剂的制备方法，其特征在于，步骤(5)中所述的水相中海藻酸盐/壳聚糖/聚异丙基丙烯酰胺复合材料的重量浓度为1～3％。
  9. 根据权利要求1所述的一种土壤调理剂的制备方法，其特征在于，步骤(5)中所述的油相与水相重量比为1∶4～6。
  10. 根据权利要求1-9中任一项所述的一种土壤调理剂的制备方法，其特征在于，所述的壳聚糖的N-脱乙酰度为85％-95％；粘度为1000mPa/s，所述的聚异丙基丙烯酰胺的数均分子量为40000-50000。
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