WO2017121369A1 - 缓释防霉型酪素基中空微球涂层材料及其制备方法 - Google Patents

缓释防霉型酪素基中空微球涂层材料及其制备方法 Download PDF

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WO2017121369A1
WO2017121369A1 PCT/CN2017/071068 CN2017071068W WO2017121369A1 WO 2017121369 A1 WO2017121369 A1 WO 2017121369A1 CN 2017071068 W CN2017071068 W CN 2017071068W WO 2017121369 A1 WO2017121369 A1 WO 2017121369A1
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casein
parts
proof
based hollow
weight
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PCT/CN2017/071068
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French (fr)
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马建中
张帆
徐群娜
杨腾飞
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陕西科技大学
马建中
张帆
徐群娜
杨腾飞
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Priority to DE112017000374.1T priority Critical patent/DE112017000374B4/de
Publication of WO2017121369A1 publication Critical patent/WO2017121369A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/04—Acids; Metal salts or ammonium salts thereof
    • C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/14—Methyl esters, e.g. methyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F289/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds not provided for in groups C08F251/00 - C08F287/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08H—DERIVATIVES OF NATURAL MACROMOLECULAR COMPOUNDS
    • C08H1/00—Macromolecular products derived from proteins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
    • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C11/00—Surface finishing of leather
    • C14C11/003—Surface finishing of leather using macromolecular compounds

Definitions

  • the invention relates to a preparation method of a mildewproof coating material, in particular to a sustained release mildew-proof casein-based hollow microsphere coating material and a preparation method thereof.
  • casein is one of the most widely used film-forming agents in leather finishing agents.
  • its film formation has excellent high temperature resistance, resistance to light and breathability.
  • Sexual and permeable to water vapor therefore, is a widely used leather finishing agent in the production of high-grade leather products.
  • a natural protein extracted from milk it is prone to mildew in practical applications, which severely limits further application in the leather industry.
  • the hollow microsphere polymer is a special functional material having a cavity structure, which has the characteristics of light weight, large specific surface area, good stability and deformability, and at the same time, the hollow microsphere polymer is used.
  • the cavity is coated with some functional compounds, which can be applied to the fields of perfumery, cosmetics and pharmaceuticals by controlling the release rate of the coating.
  • the inventors obtained the polyacrylate-modified casein hollow microsphere emulsion which can be used for leather finishing by emulsion polymerization. The results show that the coating has good hygienic performance and the coating on the leather disabled parts. The covering effect is better, but casein is prone to mildew.
  • the invention aims to provide a sustained release mildew-proof casein-based hollow microsphere coating material and a preparation method thereof, and the sustained release mildew-proof casein-based hollow microsphere coating material prepared by the method can be used in casein On the basis of the hollow microsphere coating material, the film-forming hard and brittleness and hiding performance of the casein coating are further improved, and the durable antibacterial and antifungal properties of the coated substrate are improved.
  • the present invention provides a sustained release mildew-proof casein-based hollow microsphere coating material and a preparation method thereof, and the specific implementation process is as follows:
  • the preparation method of the sustained release mildew-proof casein-based hollow microsphere coating material is realized by the following steps:
  • Step 1 Preparation of caprolactam/SiO 2 co-modified casein composite emulsion:
  • Step 2 Preparation of sustained release mildew-resistant casein-based hollow microspheres:
  • the coupling agent is 3-aminopropyltriethoxysilane, ⁇ -(2,3-epoxypropoxy)propyltrimethoxysilane, N-( ⁇ -aminoethyl)- ⁇ .
  • the silica precursor is ethyl orthosilicate, methyl orthosilicate or isopropyl orthosilicate.
  • the acrylate monomer is a mixture of one or more of methyl methacrylate, ethyl acrylate, butyl acrylate, methacrylic acid or acrylic acid.
  • the fungicide is 2-(sulfomethylthio)benzothiazole, 2-octyl-4-isothiazolinone, 1,2-benzisothiazol-3-one or dichloro One or two mixtures of vinyl salicylamide.
  • the pH system ranges from 6 to 10 and the temperature ranges from 30 ° C to 90 ° C.
  • Sustained-release mildew-proof casein-based hollow microsphere coating material prepared by the method for preparing sustained-release mildew-proof casein-based hollow microsphere coating material.
  • the invention Compared with the prior art, the invention has the following advantages: the invention adopts the emulsification and biodegradability of casein as a matrix to prepare a hollow microsphere polymer film-forming material, which not only improves the defect of the mildew of the casein coating. Moreover, it can impart good hygienic properties, hiding performance and long-term release mildew resistance to the coating, and greatly increase the added value of the coated substrate.
  • Figure 1 is a transmission electron microscope (TEM) photograph of a sustained release mildew-proof casein-based hollow microsphere coating material prepared in accordance with the above-described steps.
  • Fig. 2 is a photograph showing the antifungal effect of the sustained-release mold-proof casein-based hollow microspheres formed in accordance with the above-described steps.
  • Fig. 3 is a graph showing the sustained release of the antifungal agent after the sustained release mildew-proof casein-based hollow microspheres prepared in accordance with the above-described steps.
  • Step 1) Preparation of caprolactam/SiO 2 co-modified casein emulsion.
  • the mass of the caprolactam emulsion co-modified with caprolactam/SiO 2 was 100 parts, and in a 100 mL three-necked flask equipped with a stirrer and a condensing device, 2.6 parts of casein, 1.4 parts of triethanolamine and 57.9 parts of deionized water were added in parts by mass. The temperature was raised to 50 ° C.
  • Step 2) Preparation of sustained-release mildew-proof casein-based hollow microspheres.
  • the mass of the sustained-release mildew-type casein-based hollow microsphere emulsion was 100 parts, and the temperature was raised to 60 ° C in a mass fraction, and 4.4 parts of caprolactam/SiO 2 was added to a 250 mL three-necked flask equipped with a stirrer and a condensing device.
  • Step 1) Preparation of caprolactam/SiO 2 co-modified casein emulsion.
  • the mass of the caprolactam emulsion was 100 parts by weight of caprolactam/SiO 2 , and 5.6 parts of casein, 3.4 parts of triethanolamine and 50.9 parts of deionized water were added in parts by mass in a 100 mL three-necked flask equipped with a stirrer and a condensing device. The temperature was raised to 55 ° C.
  • Step 2) Preparation of sustained-release mildew-proof casein-based hollow microspheres.
  • the mass of the sustained-release mildew-type casein-based hollow microsphere emulsion was 100 parts, and the temperature was raised to 65 ° C by mass, and 5.4 parts of caprolactam/SiO 2 was added to a 250 mL three-necked flask equipped with a stirrer and a condensing device.
  • Step 1) Preparation of caprolactam/SiO 2 co-modified casein emulsion.
  • the mass of the caprolactam emulsion with caprolactam/SiO 2 was 100 parts, and in a 100 mL three-necked flask equipped with a stirrer and a condensing device, 8.6 parts of casein, 5.4 parts of triethanolamine and 43.9 parts of deionized water were added in parts by mass. The temperature was raised to 60 ° C.
  • Step 2) Preparation of sustained-release mildew-proof casein-based hollow microspheres.
  • the mass of the sustained-release mildew-type casein-based hollow microsphere emulsion was 100 parts, and the temperature was raised to 70 ° C in a mass fraction, and 6.4 parts of caprolactam/SiO 2 was added to a 250 mL three-necked flask equipped with a stirrer and a condensing device.
  • Step 1) Preparation of caprolactam/SiO 2 co-modified casein emulsion.
  • the mass of the caprolactam emulsion modified with caprolactam/SiO 2 was 100 parts, and 11.6 parts of casein, 7.4 parts of triethanolamine and 36.9 parts of deionized water were added in parts by mass in a 100 mL three-necked flask equipped with a stirrer and a condensing device. The temperature was raised to 65 ° C.
  • Step 2) Preparation of sustained-release mildew-proof casein-based hollow microspheres.
  • the mass of the sustained-release mildew-type casein-based hollow microsphere emulsion was 100 parts, and the temperature was raised to 75 ° C.
  • 7.4 parts of caprolactam/SiO 2 was added.
  • Casein emulsion 60.8 parts of deionized water, 11.8 parts of acrylate monomer and 15.7 parts of ammonium persulfate aqueous solution, after the addition is completed, stir for 2.5 hours; then add 4.3 parts of antifungal agent to adjust the pH of the emulsion to 9, temperature After stirring at 75 ° C for 7 h, then cooling to room temperature and discharging, a slow release mold-proof casein-based hollow microsphere was obtained.
  • Step 1) Preparation of caprolactam/SiO 2 co-modified casein emulsion.
  • the mass of the caprolactam emulsion modified with caprolactam/SiO 2 was 100 parts, and in a 100 mL three-necked flask equipped with a stirrer and a condensing device, 14.6 parts of casein, 9.4 parts of triethanolamine and 29.9 parts of deionized water were added in parts by mass.
  • the temperature was raised to 70 ° C, after the casein was fully dissolved, the temperature was raised to 85 ° C, 42.1 parts of caprolactam aqueous solution and 2.5 parts of coupling agent were added dropwise to the system, and then 1.5 parts of silica precursor was added dropwise, and the heat retention reaction was continued for 3 hours. After the reaction is stopped, the mixture is cooled to room temperature to obtain a caprolactam/SiO 2 co-modified casein emulsion composite emulsion;
  • Step 2) Preparation of sustained-release mildew-proof casein-based hollow microspheres.
  • the mass of the sustained-release mildew-type casein-based hollow microsphere emulsion was 100 parts, and the temperature was raised to 80 ° C in a mass fraction, and 8.4 parts of caprolactam/SiO 2 was added to a 250 mL three-necked flask equipped with a stirrer and a condensing device.

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Abstract

一种缓释防霉型酪素基中空微球涂层材料及其制备方法。以酪素为基材，引入甲基丙烯酸甲酯、丙烯酸丁酯、甲基丙烯酸等单体，采用种子乳液聚合法和碱溶胀法制备了具有特殊中空结构的酪素基聚合物乳液。同时，利用中空微球的特殊结构，在其内部包覆防霉剂，通过改变外界的释放条件，有望赋予皮革缓释防霉的作用。将该材料应用在皮革涂饰剂中，对提升苯胺革和全粒面革制品质量和档次具有重要的意义。

Description

缓释防霉型酪素基中空微球涂层材料及其制备方法 技术领域
本发明涉及防霉涂层材料的制备方法，具体涉及一种缓释防霉型酪素基中空微球涂层材料及其制备方法。
背景技术
皮革是皮胶原蛋白质的加工产品，是霉菌生长的良好营养源，因此皮革在加工、贮存，使用过程中易生长繁殖细菌和霉菌，导致皮革制品上产生霉斑，不仅影响皮革的外观，而且会显著降低皮革的物理机械性能，严重影响皮革的销售和使用性能随着皮革制品使用范围的日益广泛，我国皮革出口量的逐年增加，消除皮革霉变的问题就越显突出。为了防止皮革及制品长霉，最有效的办法是加入防霉剂。直接使用防霉剂时，防霉效果持续时间短，产生局部毒性大。因此，如何在不造成污染和毒副作用的情况下，使防霉剂持久保持其抗菌防霉效果，成为亟待解决的重点和难点。
众所周知，酪素是皮革涂饰剂中应用较为广泛的成膜剂之一，除了具有良好的生物相容性、生物降解性之外，其成膜具有较优的耐高温性、耐打光、透气性和透水汽性，因此，是生产高档皮革制品中应用广泛的皮革涂饰剂。然而，作为一种从牛奶中提取出来的天然蛋白质，在实际应用时，其易发生霉变，严重限制了在皮革工业中的进一步应用。
目前，中空微球聚合物是一种具有空腔结构的特殊功能材料，该类聚合物具有质轻、比表面积大、稳定性好和可形变等特性，同时，利用中空微球聚合物的空腔包覆一些功能性化合物，通过控制包覆物的释放速率，可将其应用在香料、化妆品及药物领域。在前期研究中，发明人采用乳液聚合法获得了可用于皮革涂饰的聚丙烯酸酯改性酪素中空微球乳液，结果显示，涂层的卫生性能较好，且涂层对皮革伤残部位的遮盖作用较好，但酪素易发霉。
发明内容
本发明目的在于提供一种缓释防霉型酪素基中空微球涂层材料及其制备方法，采用该方法制备的缓释防霉型酪素基中空微球涂层材料，能够在酪素中空微球涂层材料的基础上，进一步改善酪素涂层的成膜硬脆和遮盖性能，并且提高涂饰基材的持久抗菌防霉的特性。
为实现上述目的，本发明提供了一种缓释防霉型酪素基中空微球涂层材料及其制备方法，具体实现过程如下：
缓释防霉型酪素基中空微球涂层材料的制备方法，由以下步骤实现：
步骤一：己内酰胺/SiO2共改性酪素复合乳液的制备：
取2.6～14.6重量份的酪素，1.4～9.4重量份的三乙醇胺和29.9～57.9重量份的去离子水，置于三口烧瓶中，50℃～70℃温度下充分溶解；
然后滴速加入34.1～42.1重量份的己内酰胺水溶液和0.5～1.5重量份的偶联剂；
最后，滴加1.5～3.5重量份的二氧化硅前驱体，保温反应1～3h，室温冷却，即得己内酰胺/SiO2共改性酪素复合乳液；
步骤二：缓释防霉性酪素基中空微球的制备：
取4.4～8.4重量份的步骤一中所述己内酰胺/SiO2共改性酪素复合乳液、57.8～69.8重量份的去离子水、5.8～13.8重量份的丙烯酸酯类单体和9.7～17.7重量份的过硫酸铵水溶液，置于三口烧瓶中，60℃～80℃温度下搅拌1～3h；
然后加入2.3～10.3重量份的防霉剂，调节pH体系，升温保温反应，搅拌1-9h，冷却，即得缓释防霉型的酪素基中空微球。
步骤一中，偶联剂为3-氨丙基三乙氧基硅烷、γ-(2,3-环氧丙氧基)丙基三甲氧基硅烷、N-(β-氨乙基)-γ-氨丙基三甲氧基硅烷或3-(甲基丙烯酰氧)丙基三甲氧基硅烷中的一种或两种混合物。
步骤一中，二氧化硅前驱体为正硅酸乙酯、正硅酸甲酯或正硅酸异丙酯。
步骤二中，丙烯酸酯类单体为甲基丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、甲基丙烯酸或丙烯酸中的一种或多种混合物。
步骤二中，防霉剂为2-(硫氢基甲硫基)苯并噻唑，2-辛基-4-异噻唑啉-酮，1,2-苯并异噻唑-3-酮或者二氯乙烯基水杨酰胺中的一种或者两种混合物。
步骤二中，pH体系范围为6-10，温度为30℃-90℃。
缓释防霉型酪素基中空微球涂层材料的制备方法制得的缓释防霉型酪素基中空微球涂层材料。
有益效果
本发明相对于现有技术，其优点如下：本发明采用具有乳化性和生物降解性的酪素为基体，制备成中空微球聚合物成膜材料，不仅改善酪素涂层易霉变的缺陷，而且可赋予涂层良好的卫生性能、遮盖性能和长久缓释防霉性能，大幅度提高涂膜基材的附加值。
附图说明
图1为依照此说明的上述步骤制得的缓释防霉型酪素基中空微球涂层材料的透射电镜(TEM)照片。
图2为依照此说明的上述步骤制得的缓释防霉型酪素基中空微球成膜的防霉效果照片。
图3为依照此说明的上述步骤制得的缓释防霉型酪素基中空微球涂饰后革样的防霉剂缓释结果。
具体实施方式
下面结合具体的实施方式对本发明进行详细的说明。
实施案例一：
步骤1)：制备己内酰胺/SiO2共改性酪素乳液。以己内酰胺/SiO2共改性酪素乳液的质量为100份，按质量份数，在装有搅拌器和冷凝装置的100mL三口烧瓶加入2.6份酪素、1.4份三乙醇胺和57.9份去离子水，升温至50℃，待酪素充分溶解后，升温至65℃，向体系中滴加34.1份己内酰胺水溶液和0.5份偶联剂，之后，滴加3.5份二氧化硅前驱体，继续保温反应1h，停止反应后，冷却至室温出料，即获得己内酰胺/SiO2共改性酪素乳液复合乳液；
步骤2)：制备缓释防霉型的酪素基中空微球。以缓释防霉型酪素基中空微球乳液的质量为100份，按质量份数，升温至60℃，在装有搅拌器和冷凝装置的250mL三口烧瓶加入4.4份己内酰胺/SiO2共改性酪素乳液、69.8份去离子水、5.8份丙烯酸酯类单体以及9.7份过硫酸铵水溶液，滴加完毕后，搅拌1h；再加入10.3份防霉剂，调节乳液pH为6，温度为30℃，继续搅拌1h，之后冷却至室温，出料，即可获得缓释防霉型的酪素基中空微球。
实施案例二：
步骤1)：制备己内酰胺/SiO2共改性酪素乳液。以己内酰胺/SiO2共改性酪素乳液的质量为100份，按质量份数，在装有搅拌器和冷凝装置的100mL三口烧瓶加入5.6份酪素、3.4份三乙醇胺和50.9份去离子水，升温至55℃，待酪素充分溶解后，升温至70℃，向体系中滴加36.1份己内酰胺水溶液和1.0份偶联剂，之后，滴加3.0份二氧化硅前驱体，继续保温反应1.5h，停止反应后，冷却至室温出料，即获得己内酰胺/SiO2共改性酪素乳液复合乳液；
步骤2)：制备缓释防霉型的酪素基中空微球。以缓释防霉型酪素基中空微球乳液的质量为100份，按质量份数，升温至65℃，在装有搅拌器和冷凝装置的250mL三口烧瓶加入5.4份己内酰胺/SiO2共改性酪素乳液、66.8份去离子水、7.8份丙烯酸酯类单体以及11.7份过硫酸铵水溶液，滴加完毕后，搅拌1.5h；再加入8.3份防霉剂，调节乳液pH为7，温度为45℃，继续搅拌3h，之后冷却至室温，出料，即可获得缓释防霉型的酪素基中空微球。
实施案例三：
步骤1)：制备己内酰胺/SiO2共改性酪素乳液。以己内酰胺/SiO2共改性酪素乳液的质量为100份，按质量份数，在装有搅拌器和冷凝装置的100mL三口烧瓶加入8.6份酪素、5.4份三乙醇胺和43.9份去离子水，升温至60℃，待酪素充分溶解后，升温至75℃，向体系中滴加38.1份己内酰胺水溶液和1.5份偶联剂，之后，滴加2.5份二氧化硅前驱体，继续保温反应2.0h，停止反应后，冷却至室温出料，即获得己内酰胺/SiO2共改性酪素乳液复合乳液；
步骤2)：制备缓释防霉型的酪素基中空微球。以缓释防霉型酪素基中空微球乳液的质量为100份，按质量份数，升温至70℃，在装有搅拌器和冷凝装置的250mL三口烧瓶加入6.4份己内酰胺/SiO2共改性酪素乳液、63.8份去离子水、9.8份丙烯酸酯类单体以及13.7份过硫酸铵水溶液，滴加完毕后，搅拌2h；再加入6.3份防霉剂，调节乳液pH为8，温度为60℃，继续搅拌5h，之后冷却至室温，出料，即可获得缓释防霉型的酪素基中空微球。
实施案例四：
步骤1)：制备己内酰胺/SiO2共改性酪素乳液。以己内酰胺/SiO2共改性酪素乳液的质量为100份，按质量份数，在装有搅拌器和冷凝装置的100mL三口烧瓶加入11.6份酪素、7.4份三乙醇胺和36.9份去离子水，升温至65℃，待酪素充分溶解后，升温至80℃，向体系中滴加40.1份己内酰胺水溶液和2.0份偶联剂，之后，滴加2.0份二氧化硅前驱体，继续保温反应2.5h，停止反应后，冷却至室温出料，即获得己内酰胺/SiO2共改性酪素乳液复合乳液；
步骤2)：制备缓释防霉型的酪素基中空微球。以缓释防霉型酪素基中空微球乳液的质量为100份，按质量份数，升温至75℃，在装有搅拌器和冷凝装置的250mL三口烧瓶加入7.4份己内酰胺/SiO2共改性酪素乳液、60.8份去离子水、11.8份丙烯酸酯类单体以及15.7份过硫酸铵水溶液，滴加完毕后，搅拌2.5h；再加入4.3份防霉剂，调节乳液pH为9，温度为75℃，继续搅拌7h，之后冷却至室温，出料，即可获得缓释防霉型的酪素基中空微球。
实施案例五：
步骤1)：制备己内酰胺/SiO2共改性酪素乳液。以己内酰胺/SiO2共改性酪素乳液的质量为100份，按质量份数，在装有搅拌器和冷凝装置的100mL三口烧瓶加入14.6份酪素、9.4份三乙醇胺和29.9份去离子水，升温至70℃，待酪素充分溶解后，升温至85℃，向体系中滴加42.1份己内酰胺水溶液和2.5份偶联剂，之后，滴加1.5份二氧化硅前驱体，继续保温反应3h，停止反应后，冷却至室温出料，即获得己内酰胺/SiO2共改性酪素乳液复合乳液；
步骤2)：制备缓释防霉型的酪素基中空微球。以缓释防霉型酪素基中空微球乳液的质量为100份，按质量份数，升温至80℃，在装有搅拌器和冷凝装置的250mL三口烧瓶加入8.4份 己内酰胺/SiO2共改性酪素乳液、57.8份去离子水、13.8份丙烯酸酯类单体以及17.7份过硫酸铵水溶液，滴加完毕后，搅拌3h；再加入2.3份防霉剂，调节乳液pH为10，温度为90℃，继续搅拌9h，之后冷却至室温，出料，即可获得缓释防霉型的酪素基中空微球。
本发明的内容不限于实施例所列举，本领域普通技术人员通过阅读本发明说明书而对本发明专利中技术方案采取的任何等效的变换，均为本发明的权利要求所涵盖。

Claims (7)

  1. 缓释防霉型酪素基中空微球涂层材料的制备方法，其特征在于：
    由以下步骤实现：
    步骤一：己内酰胺/SiO2共改性酪素复合乳液的制备：
    取2.6～14.6重量份的酪素，1.4～9.4重量份的三乙醇胺和29.9～57.9重量份的去离子水，置于三口烧瓶中，50℃～70℃温度下充分溶解；
    然后匀速滴加34.1～42.1重量份的己内酰胺水溶液和0.5～1.5重量份的偶联剂；
    最后，滴加1.5～3.5重量份的二氧化硅前驱体，保温反应1～3h，室温冷却，即得己内酰胺/SiO2共改性酪素复合乳液；
    步骤二：缓释防霉型酪素基中空微球的制备：
    取4.4～8.4重量份的步骤一中所述己内酰胺/SiO2共改性酪素复合乳液、57.8～69.8重量份的去离子水、5.8～13.8重量份的丙烯酸酯类单体和9.7～17.7重量份的过硫酸铵水溶液，置于三口烧瓶中，60℃～80℃温度下搅拌1～3h；
    然后加入2.3～10.3重量份的防霉剂，调节pH体系，升温保温反应，搅拌1-9h，冷却至室温，即得缓释防霉型酪素基中空微球。
  2. 根据权利要求1所述的缓释防霉型酪素基中空微球涂层材料的制备方法，其特征在于：步骤一中，偶联剂为3-氨丙基三乙氧基硅烷、γ-(2,3-环氧丙氧基)丙基三甲氧基硅烷、N-(β-氨乙基)-γ-氨丙基三甲氧基硅烷或3-(甲基丙烯酰氧)丙基三甲氧基硅烷中的一种或两种混合物。
  3. 根据权利要求1所述的缓释防霉型酪素基中空微球涂层材料的制备方法，其特征在于：步骤一中，二氧化硅前驱体为正硅酸乙酯、正硅酸甲酯或正硅酸异丙酯。
  4. 根据权利要求1所述的缓释防霉型酪素基中空微球涂层材料的制备方法，其特征在于：步骤二中，丙烯酸酯类单体为甲基丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、甲基丙烯酸或丙烯酸中的一种或多种混合物。
  5. 根据权利要求1所述的缓释防霉型酪素基中空微球涂层材料的制备方法，其特征在于：步骤二中，防霉剂为2-(硫氢基甲硫基)苯并噻唑，2-辛基-4-异噻唑啉-酮，1,2-苯并异噻唑-3-酮或者二氯乙烯基水杨酰胺中的一种或者两种混合物。
  6. 根据权利要求1所述的缓释防霉型酪素基中空微球涂层材料的制备方法，其特征在于：步骤二中，所述pH体系范围为6-10，温度为30℃-90℃。
  7. 如权利要求1所述的缓释防霉型酪素基中空微球涂层材料的制备方法制得的缓释防霉型酪素基中空微球涂层材料。
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