WO2022011814A1 - 一种双壳层自修复微胶囊及其制备方法和应用 - Google Patents

一种双壳层自修复微胶囊及其制备方法和应用 Download PDF

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WO2022011814A1
WO2022011814A1 PCT/CN2020/114606 CN2020114606W WO2022011814A1 WO 2022011814 A1 WO2022011814 A1 WO 2022011814A1 CN 2020114606 W CN2020114606 W CN 2020114606W WO 2022011814 A1 WO2022011814 A1 WO 2022011814A1
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double
precursor
soluble
shell
water
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French (fr)
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杨晶磊
郭晔
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Hong Kong University of Science and Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02—Making microcapsules or microballoons
    • 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
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • 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
    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/08—Polyesters modified with higher fatty oils or their acids, or with natural resins or resin acids
    • 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
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • 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
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/63—Additives non-macromolecular organic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic

Definitions

  • the invention belongs to the technical field of coatings, and in particular relates to a double-shell layer self-repairing microcapsule and a preparation method and application thereof.
  • Metal corrosion is a long-term problem that has plagued people, often involving very large economic costs and labor costs.
  • the loss caused by corrosion in the United Kingdom in recent years has averaged 10 billion pounds, accounting for 3.5% of GDP; the loss in Germany is about 450 billion euros, accounting for 3.0% of GDP, and the annual corrosion loss in the United States is more than 300 billion US dollars, accounting for 4.2% of GDP.
  • the loss in China is about 3-5% of GDP.
  • the total GDP of the country was 11.94 trillion US dollars.
  • about 358.2-597 billion US dollars of metal was corroded, and about one third of it was corroded. It can be avoided by effective anti-corrosion means, and the market share of anti-corrosion products is huge and has great development prospects.
  • Anti-corrosion and anti-rust coatings are one of the most convenient methods of applying anti-corrosion protection.
  • Anti-corrosion coatings are widely used coatings in modern industry, transportation, energy, marine engineering and other sectors. According to the degree of corrosion resistance of the coating film and the requirements for use, it is usually divided into two types: conventional type and heavy-duty anti-corrosion type.
  • my country's anti-corrosion coatings are mainly used in the chemical and petroleum industries, railways, highways and bridges, metallurgical industries, power and energy industries, machinery and textile industries, industrial products, automobiles, ships and containers, naval equipment and other industries.
  • the painted structure will inevitably suffer from accidents such as collisions, scratches, and even low-speed impact during transportation, assembly, service, or the use of the installed structure after coating, resulting in difficult paint finishes. detected microcracks. During subsequent service, the presence of microcracks can lead to unnoticed corrosion of the underlying structure to very severe rusting or structural failure.
  • some coating materials with self-healing function have appeared on the market, such as intrinsic self-healing materials, PET or PVC-based light-curing and thermal-curing self-healing coating materials. Under the action of its own elastic force or chemical bond, the coating will automatically return to the state before destruction.
  • the intrinsic self-healing material can only repair some very small scratches through the interaction of the material's own elasticity or chemical bonds. For large-area coating damage caused by scratches, it cannot be repaired. To initiate the repair effect, heating or light is often required. It cannot adapt to the complex and diverse use environment without external intervention.
  • the dual-capsule repair system needs to prepare the liquid resin repair base material and the catalyst (curing) agent into microcapsules, respectively. The cost is high, and the particle sizes of the two microcapsules are difficult to achieve uniformity. In addition, it is necessary to ensure that during the actual damage of the two microcapsules, the resin repair substrate and catalyst are released at the damaged place to achieve the best reaction ratio to achieve a good repair effect.
  • the purpose of the present invention is to provide a double-shell layer self-healing microcapsule and its preparation method and application.
  • the double-shell microcapsules When the double-shell microcapsules are damaged and scratches or cracks occur, the microcapsules rupture and release the isocyanate core material, which reacts with the moisture in the air and cures.
  • the self-healing process can be realized without the intervention of external factors, which can effectively prolong the coating process.
  • the service life of the layer and the protected equipment is reduced, and the maintenance cost is reduced, which has good economic benefits.
  • a first aspect of the present invention provides:
  • a double-shell microcapsule comprises a core material, a first wall material layer wrapping the core material, and a second wall material layer wrapping the first wall material.
  • the mass fraction of the core material is 20% to 70%
  • the mass fraction of the first wall material layer is 10% to 30%
  • the mass fraction of the second wall material layer is 10% to 30% in terms of the mass of the double-shell microcapsules. 20% to 50%.
  • the particle size of the above-mentioned double-shell microcapsules is 5 ⁇ m ⁇ 200 ⁇ m.
  • the appearance of the double-shell microcapsules is spherical.
  • the core material is at least one selected from isocyanates containing two or more isocyanate groups
  • the first wall material layer is at least one selected from a polyurethane layer and a polyurea layer
  • the first The second wall material layer is a polyurea formaldehyde resin layer.
  • the above-mentioned core material is at least one selected from isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and lysine diisocyanate.
  • the polyurethane layer includes an oil-soluble polyurethane precursor and a water-soluble polyurethane precursor
  • the polyurea layer includes an oil-soluble polyurea precursor and a water-soluble polyurea precursor.
  • the mass ratio of the oil-soluble polyurethane precursor and the water-soluble polyurethane precursor in the above-mentioned polyurethane layer is 1: (1-2), and the mass ratio of the oil-soluble polyurea precursor and the water-soluble polyurea precursor in the above-mentioned polyurea layer is 1: (1 to 2).
  • the above-mentioned oil-soluble polyurethane precursor is at least one selected from the group consisting of hexamethylene diisocyanate, diphenylmethane diisocyanate, trimer of hexamethylene diisocyanate, and diphenylmethane diisocyanate prepolymer
  • the above-mentioned oil-soluble polyurea precursor is at least one selected from the group consisting of hexamethylene diisocyanate, diphenylmethane diisocyanate, trimer of hexamethylene diisocyanate, and diphenylmethane diisocyanate prepolymer. kind.
  • the above-mentioned diphenylmethane diisocyanate prepolymer is at least one selected from Huntsman Suprasec2644, Suprasec2244 and Suprasec2344.
  • the trimer of the above-mentioned hexamethylene diisocyanate is at least one selected from Covestro Desmodur N 3390 and Wanhua WANNATE HT-100.
  • the water-soluble polyurethane precursor is at least one selected from water-soluble compounds containing two or more hydroxyl groups, and the water-soluble polyurea precursor is selected from the group consisting of two or more amine groups. At least one of the water-soluble compounds.
  • the above water-soluble polyurethane precursor is at least one selected from the group consisting of 1,4-dibutanol, 1,6-hexanediol, glycerol, 1,3-propanediol, and polypropylene alcohol.
  • the water-soluble polyurea precursor is at least one selected from triethylenetetramine, tetraethylenepentamine, and polyethyleneimine with a molecular weight of 200-2000.
  • the crosslinking degree of the polyurea-formaldehyde resin layer is 5%-20%; the functionality of the polyurea-formaldehyde resin is 2.0-2.5.
  • a second aspect of the present invention provides:
  • a preparation method of double-shell microcapsules comprising the following steps:
  • the oil-soluble precursor in step (1) is an oil-soluble polyurethane precursor
  • the water-soluble precursor in step (2) is a water-soluble polyurethane precursor.
  • the subsequent reactants can be directly added for the reaction without washing.
  • the oil-soluble precursor in step (1) is an oil-soluble polyurea precursor
  • the water-soluble precursor in step (2) is a water-soluble polyurea precursor
  • the stirring in step (2) After the reaction, the step of washing with water is also included.
  • the step of centrifugal water washing the residual water-soluble polyurea precursor in the solution can be washed away, and then the subsequent reactants are added.
  • the emulsifier is selected from gum arabic, polyvinyl alcohol 1788, polyvinyl alcohol 2488, polyvinyl alcohol 124, sodium lauryl sulfate, sodium dodecylbenzenesulfonate, polyvinyl alcohol At least one of oxyethylene octyl phenol ether-10.
  • the modified coupling agent is at least one selected from sorbitol, mannitol and triethanolamine.
  • the dispersant is at least one selected from the group consisting of ethylene-maleic anhydride copolymer, styrene-maleic anhydride copolymer, and polyvinyl alcohol.
  • the urea-formaldehyde resin modifier is selected from the group consisting of bisphenol A, resorcinol, catechol, hydroquinone, phloroglucinol, pyrogallol, and anthracyl at least one of.
  • the urea-formaldehyde resin obtained by direct polymerization of urea and formaldehyde has a low degree of cross-linking, resulting in a soft product, poor solvent resistance and low mechanical strength.
  • adding a urea-formaldehyde resin modifier increases the degree of cross-linking and functionality of the urea-formaldehyde resin, thereby regulating the double shell
  • the surface micro-nano structure of the layered microcapsules enhances the strength of the polyurea-formaldehyde resin layer wall material.
  • the mass ratio of urea to formaldehyde in the urea-formaldehyde prepolymer is (1-10): (1.5-65).
  • the preparation method of the urea-formaldehyde prepolymer in the above step (3) is as follows: mixing urea and formaldehyde, adjusting the pH to 7.5-9.0, stirring at a rotational speed of 100-600 rpm, and reacting at 50 °C to 80 °C for 30 min-90 min to obtain urea - Formaldehyde prepolymer.
  • the mass fraction of the emulsifier is 0.35% to 5.0%.
  • the mass fraction of the modified coupling agent is 0.10% to 1.0% based on the mass of the single-shell microcapsules.
  • the mass fraction of the dispersant is 0.5%-2.0%, and the mass fraction of the urea-formaldehyde resin modifier is 5.0%-30% based on the mass of the double-shell microcapsules.
  • the reaction temperature of the stirring reaction is 30°C to 70°C
  • the stirring speed is 200 rpm to 2000 rpm
  • the stirring time is 5 min to 60 min.
  • the reaction temperature of the stirring reaction is 40°C to 70°C
  • the stirring speed is 200 rpm to 1200 rpm
  • the stirring time is 60 min to 150 min.
  • the reaction temperature of the stirring reaction is 45° C. to 70° C.
  • the stirring speed is 100 rpm to 600 rpm
  • the stirring time is 30 min to 300 min.
  • the pH in the above step (3) is 2.5-3.5.
  • a third aspect of the present invention provides:
  • Double-shell microcapsules in the preparation of coatings and/or adhesives, wherein the double-shell microcapsules are the above-mentioned double-shell microcapsules, or are obtained by the preparation method of the above-mentioned double-shell microcapsules.
  • the double-shell microcapsule of the present invention has two wall material layers, high mechanical strength, and is a one-component repair system. After the coating is damaged, the microcapsule ruptures and releases the isocyanate core material and reacts with the moisture in the air to cure. , intelligently repair damage, and at the same time in a high humidity environment, the isocyanate core material in the microcapsules can absorb the moisture that slowly penetrates into the coating, enhancing the waterproof performance of the coating material.
  • the appearance of the double-shell microcapsules of the present invention is a standard spherical shape, showing a single spherical dispersion, good dispersibility, and good high temperature resistance and solvent resistance stability.
  • the double-shell microcapsules in the present invention have good high temperature resistance and solvent resistance performance.
  • the core material of the microcapsules will volatilize.
  • the core material loss rate of the microcapsule phase change material is only 5% to 10%, which proves that the self-healing microcapsules have good solvent resistance.
  • the microcapsules are not damaged by solvent soaking in the paint.
  • the preparation method of the double-shell microcapsules of the present invention a preparation method belonging to continuous synthesis is disclosed.
  • the first wall material layer can be synthesized and added directly to the reaction solution.
  • the raw material of the second wall material layer is reacted with the outer layer wall material, no intermediate cleaning process is required, the production process is simple, and the product quality and production efficiency are improved.
  • the mechanical strength of the first wall material layer can be enhanced without increasing the thickness of the wall material, and its compactness can be improved to ensure
  • the microcapsules have a high core material ratio, and can increase the functionality of the outer shell surface of the first wall material layer, so as to play a coupling role in the subsequent reaction process of the second wall material layer, and realize the first wall material layer and the second wall material layer. effective and sufficient coupling.
  • FIG. 1 is a schematic structural diagram of a double-shell microcapsule of the present invention.
  • FIG. 2 is a scanning electron microscope view of the double-shelled microcapsules prepared in Example 1.
  • FIG. 2 is a scanning electron microscope view of the double-shelled microcapsules prepared in Example 1.
  • FIG. 3 is a scanning electron microscope view of the double-shelled microcapsules prepared in Example 2.
  • FIG. 3 is a scanning electron microscope view of the double-shelled microcapsules prepared in Example 2.
  • FIG. 4 is a scanning electron microscope view of the double-shell microcapsules prepared in Example 3.
  • FIG. 4 is a scanning electron microscope view of the double-shell microcapsules prepared in Example 3.
  • Figure 5 is a scanning electron microscope image of the double-shelled microcapsules prepared in the comparative example.
  • FIG. 6 is the thermogravimetric analysis curve of the double-shelled microcapsules prepared in Example 1.
  • FIG. 7 is the thermogravimetric analysis curve of the double-shelled microcapsules prepared in Example 2.
  • FIG. 8 is the thermogravimetric analysis curve of the double-shell microcapsules prepared in Example 3.
  • FIG. 8 is the thermogravimetric analysis curve of the double-shell microcapsules prepared in Example 3.
  • FIG. 9 is the thermogravimetric analysis curve of the double-shelled microcapsules prepared in the comparative example.
  • Figure 10 shows the core material loss rate of the double-shell microcapsules prepared in Example 1 after being soaked in different solvents for 20 days.
  • Fig. 11 is the rust-proof performance test diagram of the coating prepared by double-shell microcapsules in Example 1 and the coating of the control group, wherein a is the rust-proof performance test of the coating prepared by double-shell microcapsules in Example 1 Figure, b is the anti-rust performance test chart of the coating of the control group.
  • Fig. 12 is the anti-rust performance test diagram of the coating prepared by double-shell microcapsules in Example 3 and the coating of the control group, wherein a is the anti-rust performance test of the coating prepared by double-shell microcapsules in Example 3 Figure, b is the anti-rust performance test chart of the coating of the control group.
  • FIG. 1 The schematic diagram of the structure of the double-shell microcapsule of the present invention is shown in FIG. 1 .
  • Huntsman Suprasec2644 manufacturer: Huntsman; NCO: 20.1% ⁇ 0.5%; Viscosity (@25°C): 850mPa.s ⁇ 1150mPa.s; Average functionality: 2.0.
  • Embodiment 1 a kind of double shell microcapsule and preparation method thereof:
  • the pH was adjusted to 3.0, the temperature was raised to 52° C., and the reaction was performed for 150 min. After the reaction, the product was washed-filtered-dried to obtain double-shell microcapsules.
  • Embodiment 2 a kind of double shell microcapsule and preparation method thereof:
  • step (4) dissolve 1.5g polyethylene-maleic anhydride copolymer and 1g styrene-maleic anhydride copolymer in 120g water, add 3.5g resorcinol, and add the urea-formaldehyde oligomer obtained in step (4)
  • the product was adjusted to pH 2.9, then the single-shell microcapsules in step (3) were added, the temperature was raised to 58 ° C, and the reaction was performed for 120 min. After the reaction, the product was washed-filtered-dried to obtain double-shelled microcapsules.
  • Embodiment 3 a kind of double shell microcapsule and preparation method thereof:
  • microcapsules prepared in Examples 1 to 3 and the comparative example were scanned by electron microscope, and the corresponding results are shown in Figures 2 to 5 .
  • the double-shell microcapsules prepared in Example 1 are regular spherical, with good dispersibility and no adhesion, and the particle size of the double-shell microcapsules is 10 ⁇ m ⁇ 50 ⁇ m; as shown in Figure 3, the double-shelled microcapsules prepared in Example 2 are spherical, with good dispersibility, and most of them have no adhesion, and the particle size of the double-shelled microcapsules is 5 ⁇ m to 60 ⁇ m; as shown in Figure 4 , the double-shelled microcapsules prepared in Example 3 are in regular spherical shape, with good dispersibility and no adhesion; as shown in Figure 5, the microcapsules prepared in the comparative example have serious adhesions and cannot be obtained and implemented after the reaction for 300 min.
  • Example 3 For products with similar dispersibility, the marked part of the circle in the figure can clearly see the bonding caused by the overflow of the microcapsule core material. It shows that the double-shell microcapsules prepared by the present invention have good spherical shape and dispersibility, no adhesion and uniform particle size.
  • Thermogravimetric analysis was carried out on the microcapsules prepared in Examples 1 to 3 and the comparative example.
  • the test instrument used was a TA-Q50 thermogravimetric analyzer.
  • the test temperature range was 25°C to 800°C, and the heating rate was 10°C/min.
  • the results correspond to As shown in FIGS. 6 to 9 .
  • the content of the phase change material core material in the double-shell layer microcapsule prepared in Example 2 is about 39%, and the double-shell layer microcapsule core material does not start to lose until it is heated to about 150 °C , the core material only loses 5% of its mass when the temperature is raised to 219 °C; as shown in Figure 8, the content of the phase change material core material in the double-shell microcapsules prepared in Example 3 is about 64%, and the double-shell microcapsules The core material starts to lose when heated to about 150 °C, and only loses 5% of the mass of the core material when it is heated to 210 °C; %, the core material has lost 5% of its mass when the temperature is raised to 194 °C, and the mass loss has already begun to occur when the temperature is raised to 100 °C. It can be seen that the double-shell microcapsule phase change material obtained by the present invention has a high content of core materials, and the same quality of microcapsules contains more repair core materials, and has good
  • microcapsules prepared in Example 1 were soaked in four different solvents of water, n-hexane, xylene, and ethyl acetate for 20 days at room temperature, and the loss rate of the core material was measured. The results are shown in Figure 10.
  • the double-shell microcapsules in the present invention have good solvent resistance. After being continuously soaked in solvents such as water, n-hexane, xylene and ethyl acetate for 20 days, the core material of the microcapsule phase change material The loss rate is only 5% to 10%, which proves that the self-healing microcapsules have good solvent resistance, and the microcapsules will not be damaged by the solvent soaking in the coating during the process of mixing into the coating and coating.
  • solvents such as water, n-hexane, xylene and ethyl acetate
  • Application example 1 Self-healing anti-rust coating and its preparation method:
  • Application example 2 Self-healing anti-rust coating and its preparation method:
  • the self-healing anti-rust coating prepared by applying the double-shell microcapsules of the present invention has no corrosion and damage after the 1000h neutral salt spray performance test, and can still provide good protection for the equipment, The coating of the control group has been severely blistered and peeled off.

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Abstract

本发明提供一种双壳层自修复微胶囊及其制备方法和应用。该双壳层微胶囊包括芯材、包裹芯材的第一壁材层和包裹第一壁材的第二壁材层。本发明的双壳层微胶囊具备两层壁材层，机械强度高，为单组分修复系统，在涂层受损后，微胶囊破裂释放出异氰酸酯芯材同空气中的水分反应固化，智能修复损伤，同时在高湿度环境中，微胶囊中的异氰酸酯芯材可以吸收缓慢渗入涂层中的水分，增强涂层材料中的防水性能。

Description

一种双壳层自修复微胶囊及其制备方法和应用 技术领域
本发明属于涂料技术领域，尤其涉及一种双壳层自修复微胶囊及其制备方法和应用。
背景技术
金属锈蚀是一个长期困扰人们的难题，往往涉及非常大的经济成本及人工成本，据美国金属学会统计英国近年来腐蚀造成损失平均达100亿英镑，占GDP的3.5％；德国的损失约为450亿欧元，占GDP的3.0％，美国年腐蚀损失达3000多亿美元，占GDP的4.2％。而中国的损失约为GDP的3-5％，2018年全国总GDP总量为11.94万亿美元，换句话就是约有3582-5970亿美元金属被腐蚀，而这其中约有三分之一是可以通过有效的防腐手段避免的，防腐蚀产品的市场份额巨大且具有很大的发展前景。
防腐防锈涂料是防腐蚀保护应用的最多最便捷的方法之一。防腐涂料是现代工业、交通、能源、海洋工程等部门应用极为广泛的一种涂料。按其涂料膜层的耐腐蚀程度和使用要求，通常分为常规型和重防腐型两类。目前，我国的防腐涂料主要应用在化工和石油行业、铁路、公路桥梁、冶金行业、电力和能源工业、机械及纺织行业、工业产品领域、汽车、船舶及集装箱、海军装备等行业。
但是涂装好的结构在运输、装配、服务过程中，或者安装好的结构涂覆后的使用过程中，都会不可避免的经受碰撞、刮擦、甚至低速冲击等意外，从而导致漆面产生难以检测的微裂纹。在随后的服役过程中，微裂纹的存在会导致不被察觉的底层结构的腐蚀直至十分严重的锈迹产生或者结构性失效。为解决这一问题，市面上已出现部分具有自修复功能的涂层材料，如本征类自修复材料，PET或PVC基的光固化和热固化自修复涂层材料，在受到外力破坏后，涂层在自身的弹力或化学键作用下，会自动恢复到破坏前状态，另外还有将环氧树脂等高分子材料和催化剂分别制备成微胶囊而形成的的双胶囊修复体系，再受到外力破坏后分别释放出树脂和催化剂，在裂痕处发生交联反应固化，从而达到修复的目的。
但是本征类自修复材料通过材料自身弹性或化学键的相互作用，仅能修复一些非常细微的划痕，对于因为刮蹭一起的大面积涂层损伤无法修复，要引发修复作用往往需要加热或光照等外力干预，无法适应复杂多样化的使用环境。而双胶囊修复体系需要将液体树脂类修复基材和催(固)化剂分别制备成微胶囊，催(固)化剂类材料往往种类繁多，多为固体材料， 制备成微胶囊工艺复杂，成本高昂，两种微胶囊粒径难以达到统一，另外需要保证两种微胶囊实际破损过程中，在破损处释放树脂修复基材和催化剂达到最佳的反应配比才能实现良好的修复效果。
传统聚氨酯/聚脲和聚脲醛为双层壳微胶囊合成过程中，通常需要在形成第一层壳的反应结束后进行清洗，除去反应溶液中的乳化剂及成壳剂，避免与下一层壁材的原料发生副反应，但只有一层聚氨酯/聚脲外壳的微胶囊机械强度往往较弱，很容易在清洗过程中破裂，造成微胶囊粘结成块，影响产率。
发明内容
本发明的目的在于提供一种双壳层自修复微胶囊及其制备方法和应用。当该双壳层微胶囊收到损失产生划痕或裂纹时，微胶囊破裂释放出异氰酸酯类芯材，与空气中的水分反应固化，无需外部因素介入即可实现自修复过程，可以有效延长涂层及被保护设备的使用寿命，减少维护成本，具有良好的经济效益。
本发明所采取的技术方案为：
本发明的第一个方面，提供：
一种双壳层微胶囊，包括芯材、包裹芯材的第一壁材层和包裹第一壁材的第二壁材层。
优选的，以双壳层微胶囊质量计，上述芯材的质量分数为20％～70％，上述第一壁材层的质量分数为10％～30％，上述第二壁材层的质量分数为20％～50％。
优选的，上述双壳层微胶囊的粒径为5μm～200μm。该双壳层微胶囊外观呈现圆球状。
优选的，上述芯材为选自含两个或两个以上异氰酸根的异氰酸酯中的至少一种，上述第一壁材层为选自聚氨酯层、聚脲层中的至少一种，上述第二壁材层为聚脲醛树脂层。
优选的，上述芯材为选自异佛尔酮二异氰酸酯、4,4'-二环己基甲烷二异氰酸酯、赖氨酸二异氰酸酯中的至少一种。
优选的，上述聚氨酯层包括油溶性聚氨酯前驱体和水溶性聚氨酯前驱体，上述聚脲层包括油溶性聚脲前驱体和水溶性聚脲前驱体。
优选的，上述聚氨酯层中油溶性聚氨酯前驱体和水溶性聚氨酯前驱体的质量比为1：(1～2)，上述聚脲层中油溶性聚脲前驱体和水溶性聚脲前驱体的质量比为1：(1～2)。
优选的，上述油溶性聚氨酯前驱体为选自六亚甲基二异氰酸酯、二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯的三聚体、二苯基甲烷二异氰酸酯预聚体中的至少一种；上述油溶性聚脲前驱体为选自六亚甲基二异氰酸酯、二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯的三聚 体、二苯基甲烷二异氰酸酯预聚体中的至少一种。
优选的，上述二苯基甲烷二异氰酸酯预聚体为选自亨斯迈Suprasec2644、Suprasec2244、Suprasec2344中的至少一种。
优选的，上述六亚甲基二异氰酸酯的三聚体为选自科思创Desmodur N 3390、万华WANNATE HT-100中的至少一种。
优选的，上述水溶性聚氨酯前驱体为选自含两个或两个以上羟基的水溶性化合物中的至少一种，上述水溶性聚脲前驱体为选自含两个或两个以上胺基的水溶性化合物中的至少一种。
优选的，上述水溶性聚氨酯前驱体为选自1,4-二丁醇、1,6-己二醇、丙三醇、1,3-丙二醇、聚丙烯醇中的至少一种。
优选的，上述水溶性聚脲前驱体为选自三乙烯四胺、四乙烯五胺、分子量为200-2000的聚乙烯亚胺中的至少一种。
优选的，上述聚脲醛树脂层的交联度为5％～20％；聚脲醛树脂的官能度为2.0～2.5。
本发明的第二个方面，提供：
一种双壳层微胶囊的制备方法，包括如下步骤：
(1)乳化剂溶液中加入芯材和油溶性的前驱体混合液，搅拌反应，得到水包油乳液；
(2)水包油乳液中加入水溶性的前驱体和改性偶联剂混合液，搅拌反应，得到单壳层微胶囊；水溶性的前驱体与油溶性的前驱体在芯材的表面发生界面聚合反应，从而形成第一壁材层。
(3)分散剂与脲醛树脂改性剂的混合溶液中加入单壳层微胶囊和尿素-甲醛预聚物，调节pH，搅拌反应，得到上述组成的双壳层微胶囊。
优选的，当步骤(1)中上述油溶性的前驱体为油溶性聚氨酯前驱体时，步骤(2)中上述水溶性的前驱体为水溶性聚氨酯前驱体。无需清洗即可直接加入后续反应物进行反应。
优选的，当步骤(1)中上述油溶性的前驱体为油溶性聚脲前驱体时，步骤(2)中上述水溶性的前驱体为水溶性聚脲前驱体，步骤(2)中上述搅拌反应后还包括水洗的步骤。采用离心水洗的步骤，能洗去溶液中残留的水溶性聚脲前驱体，再加入后续反应物。
优选的，上述步骤(1)中乳化剂为选自阿拉伯胶、聚乙烯醇1788、聚乙烯醇2488、聚乙烯醇124、十二烷基硫酸酸钠、十二烷基苯磺酸钠、聚氧乙烯辛基苯酚醚-10中的至少一种。
优选的，上述步骤(2)中改性偶联剂为选自山梨醇、甘露醇、三乙醇胺中的至少一种。
优选的，上述步骤(3)中分散剂为选自乙烯-马来酸酐共聚物、苯乙烯-马来酸酐共聚物、聚乙烯醇中的至少一种。
优选的，上述步骤(3)中脲醛树脂改性剂为选自双酚A、间苯二酚、邻苯二酚、对苯二酚、间苯三酚、邻苯三酚、蒽三酚中的至少一种。尿素与甲醛直接聚合得到的脲醛树脂交联度较低，导致产品偏软，耐溶性能差，机械强度较低，因此加入脲醛树脂改性剂提升脲醛树脂交联度和官能度，从而调控双壳层微胶囊的表面微纳米结构，增强聚脲醛树脂层壁材的强度。
优选的，上述步骤(3)中尿素-甲醛预聚物中尿素与甲醛的质量比为(1～10)：(1.5～65)。
优选的，上述步骤(3)中尿素-甲醛预聚物的制备方法为：尿素与甲醛混合，pH调节至7.5～9.0，转速100rpm～600rpm搅拌，50℃～80℃反应30min～90min，得到尿素-甲醛预聚物。
优选的，上述步骤(1)中以水包油乳液的质量计，乳化剂的质量分数为0.35％～5.0％。
优选的，上述步骤(2)中以单壳层微胶囊的质量计，改性偶联剂的质量分数为0.10％～1.0％。
优选的，上述步骤(3)中以双壳层微胶囊的质量计，分散剂的质量分数为0.5％～2.0％，脲醛树脂改性剂的质量分数为5.0％～30％。
优选的，上述步骤(1)中搅拌反应的反应温度为30℃～70℃，搅拌的速度为200rpm～2000rpm，搅拌的时间为5min～60min。
优选的，上述步骤(2)中搅拌反应的反应温度为40℃～70℃，搅拌的速度为200rpm～1200rpm，搅拌的时间为60min～150min。
优选的，上述步骤(3)中搅拌反应的反应温度为45℃～70℃，搅拌的速度为100rpm～600rpm，搅拌的时间为30min～300min。
优选的，上述步骤(3)中pH为2.5～3.5。
本发明的第三个方面，提供：
一种双壳层微胶囊在制备涂料和/或粘接剂中的应用，所述双壳层微胶囊为上述双壳层微胶囊，或者为上述双壳层微胶囊的制备方法制得。
本发明的有益效果为：
1.本发明的双壳层微胶囊具备两层壁材层，机械强度高，为单组分修复系统，在涂层受损后，微胶囊破裂释放出异氰酸酯芯材同空气中的水分反应固化，智能修复损伤，同时在高湿度环境中，微胶囊中的异氰酸酯芯材可以吸收缓慢渗入涂层中的水分，增强涂层材料中的防水性能。
2.本发明的双壳层微胶囊外观呈标准圆球状，呈现出单个圆球分散，分散性良好，并且 具有良好的耐高温、耐溶剂稳定性。
3.本发明中的双壳层微胶囊具有良好的耐高温、耐溶剂性能，升温至150℃以上，微胶囊的芯材才出现挥发的情况，在水、正己烷、二甲苯和乙酸乙酯等溶剂中连续浸泡20天后，微胶囊相变材料的芯材损失率仅为5％～10％，证明该自修复微胶囊具有良好的耐溶剂性能，在掺入涂料到涂布的过程中，微胶囊不会因涂料中的溶剂浸泡而损坏。
4.本发明的双壳层微胶囊的制备方法中，公开了一种属于连续合成的制备方法，通过引入一定的改性偶联剂可以实现合成第一壁材层后直接在反应溶液中加入第二壁材层的原料进行外层壁材的反应，无需中间清洗过程，生产工艺简单，提升产品质量和生产效率。
5.本发明的双壳层微胶囊的制备方法中，通过引入改性偶联剂，既能在不增加壁材厚度的前提下增强第一壁材层的机械强度，提高其致密性，保证微胶囊具有较高芯材率，又能增加第一壁材层外壳表面的官能度，从而在后续第二壁材层反应过程中起到偶联作用，实现第一壁材层和第二壁材层的有效充分偶联。
附图说明
图1为本发明双壳层微胶囊的结构示意图。
图2为实施例1制得的双壳层微胶囊电镜扫描图。
图3为实施例2制得的双壳层微胶囊电镜扫描图。
图4为实施例3制得的双壳层微胶囊电镜扫描图。
图5为对比例制得的双壳层微胶囊电镜扫描图。
图6为实施例1制得的双壳层微胶囊的热失重分析曲线。
图7为实施例2制得的双壳层微胶囊的热失重分析曲线。
图8为实施例3制得的双壳层微胶囊的热失重分析曲线。
图9为对比例制得的双壳层微胶囊的热失重分析曲线。
图10为实施例1制得的双壳层微胶囊在不同溶剂中浸泡20天后的芯材损失率。
图11为实施例1中双壳层微胶囊制得的涂层与对照组涂层的防锈性能测试图，其中a为实施例1中双壳层微胶囊制得涂层的防锈性能测试图，b为对照组涂层的防锈性能测试图。
图12为实施例3中双壳层微胶囊制得的涂层与对照组涂层的防锈性能测试图，其中a为实施例3中双壳层微胶囊制得涂层的防锈性能测试图，b为对照组涂层的防锈性能测试图。
具体实施方式
为了使本发明的发明目的、技术方案及其技术效果更加清晰，以下结合具体实施方式，对本发明进行进一步详细说明。应当理解的是，本说明书中描述的具体实施方式仅仅是为了解释本发明，并非为了限定本发明。
本发明双壳层微胶囊的结构示意图如图1所示。
试剂说明：
亨斯迈Suprasec2644，生产厂家：亨斯迈；NCO：20.1％±0.5％；粘度(@25℃)：850mPa.s～1150mPa.s；平均官能度：2.0。
实施例1：一种双壳层微胶囊及其制备方法：
(1)在烧杯中加入100g水，3g阿拉伯胶，40℃恒温，500rpm搅拌10min，得到乳化剂溶液；
(2)在烧杯中加入14g的4,4'-二环己基甲烷二异氰酸酯和1g亨斯迈Suprasec2644，室温500rpm搅拌均匀，得到油相；
(3)将上述的油相加入乳化剂溶液中，40℃下，1200rpm搅拌20min后，加入3g 1,4-丁二醇，1g丙三醇和0.5g山梨醇，调节搅拌速度至500rpm，升温到60℃反应100min后得到单壳层的微胶囊，将反应体系降温至30℃以下；
(4)将3g间苯二酚和3g聚乙烯-马来酸酐共聚物溶于100g水中混合均匀，加入到上述单壳层微胶囊中；
(5)将8g尿素同20g的质量分数为37％甲醛溶液混合，400rpm搅拌，并调节pH＝8.5，65℃反应50min形成尿素-甲醛预聚物后加入到步骤(4)的单壳层微胶囊中，将pH调节到3.0，升温到52℃，反应150min，反应结束后对产物进行洗涤-过滤-干燥，得到双壳层微胶囊。
实施例2：一种双壳层微胶囊及其制备方法：
(1)在烧杯中加入100g水，2g聚乙烯醇1788，45℃恒温，500rpm搅拌10min，得到乳化剂溶液；
(2)在烧杯中加入13g 4,4'-二环己基甲烷二异氰酸酯，40℃加热，加入2g六亚甲基二异氰酸酯,500rpm搅拌均匀，得到油相；
(3)将上述的油相加入乳化剂溶液中，45℃下，1000rpm搅拌15min后，加入6g四乙烯五胺，1g分子量1800的聚乙烯亚胺，调节搅拌速度至400rpm，升温到65℃反应70min，得到的产物离心并用水清洗5次除去溶液中的胺类和乳化剂备用，得到单壳层微胶囊；
(4)将5g尿素同13g质量分数为37％甲醛溶液混合，500rpm搅拌，并调节pH＝8.2，75℃反应45min，得到尿素-甲醛低聚物；
(5)将1.5g聚乙烯-马来酸酐共聚物和1g苯乙烯-马来酸酐共聚物溶于120g水中，加入3.5g间苯二酚，并加入步骤(4)得到的尿素-甲醛低聚物，将pH调节到2.9，随后加入步骤(3)中的单壳层微胶囊，升温到58℃，反应120min，反应结束后对产物进行洗涤-过滤-干燥，得到双壳层微胶囊。
实施例3：一种双壳层微胶囊及其制备方法：
(1)在烧杯中加入200g水，1.5g聚乙烯醇1788，0.5g聚氧乙烯辛基苯酚醚-10，40℃恒温，500rpm搅拌60min，得到乳化剂溶液；
(2)在烧杯中加入26g的4,4'-二环己基甲烷二异氰酸酯，2g亨斯迈Suprasec2644，2g的万华HT-10，室温下500rpm搅拌均匀，得到油相；
(3)将上述油相加入乳化剂溶液中，40℃下，1200rpm搅拌20min后，加入4g的1,3-丙二醇，1g三乙醇胺和0.6g山梨醇，调节搅拌速度至500rpm，升温到60℃反应100min后得到单壳层微胶囊，将反应体系降温至30℃以下；
(4)将4g间苯二酚和2.5g聚乙烯-马来酸酐共聚物溶于200g水中混合均匀，加入到步骤(3)的溶液中；
(5)将7.5g尿素同19g质量分数为37％甲醛溶液混合，400rpm搅拌，并调节pH＝8.5，65℃反应50min形成尿素-甲醛预聚物后加入到步骤(4)的溶液中，将pH调节到3.2，升温到56℃，反应150min，反应结束后对产物进行洗涤-过滤-干燥，得到双壳层微胶囊。
对比例：一种微胶囊及其制备方法：
(1)在烧杯中加入200g水，1.5g聚乙烯醇1788，0.5g聚氧乙烯辛基苯酚醚-10，40℃恒温，500rpm搅拌60min，得到乳化剂溶液；
(2)在烧杯中加入26g的4,4'-二环己基甲烷二异氰酸酯，2g亨斯迈Suprasec2644，2g万华HT-10，室温500rpm搅拌均匀，得到油相；
(3)将上述的油相加入乳化剂溶液中，40℃下，1200rpm搅拌20min后，加入6g的1,3-丙二醇，调节搅拌速度至500rpm，升温到60℃反应100min后得到单壳层微胶囊，将反应体系降温至30℃以下；
(4)将4g间苯二酚和2.5g聚乙烯-马来酸酐共聚物溶于200g水中混合均匀，加入到步 骤(3)的溶液中；
(5)将7.5g尿素同19g的质量分数为37％甲醛溶液混合，400rpm搅拌，并调节pH＝8.5，65℃反应50min形成尿素-甲醛预聚物后加入到步骤(4)的溶液中，将pH调节到3.2，升温到56℃，反应300min，反应结束后对产物进行洗涤-过滤-干燥，得到微胶囊。
测试例：
对实施例1～3和对比例制得的微胶囊进行电镜扫描，结果对应如图2～图5所示。
由图2～图5可得，如图2所示，实施例1制得的双壳层微胶囊呈规则的圆球状，分散性良好，无粘连，双壳层微胶囊的粒径为10μm～50μm；如图3所示，实施例2制得的双壳层微胶囊呈圆球状，分散性良好，绝大部分无粘连，双壳层微胶囊粒径为5μm～60μm；如图4所示，实施例3制得的双壳层微胶囊呈规则的圆球状，分散性良好，无粘连；如图5所示，对比例制得的微胶囊粘连严重，在反应300min后仍无法得到与实施例3分散性相近的产品，图中圈圈标记部分可以明显看出微胶囊芯材溢出导致的粘结。表明本发明制得的双壳层微胶囊具有良好的圆球状和分散性，无粘连，粒径均匀。
对实施例1～3和对比例制得的微胶囊进行热失重分析，所用测试仪器为TA-Q50热重分析仪，测试温度区间为25℃～800℃，升温速率10℃/min，结果对应如图6～图9所示。
由图6～图9可得，如图6所示，实施例1制得的双壳层微胶囊中相变材料芯材含量约为47.8％，双壳层微胶囊芯材在加热到150℃左右才开始损失；如图7所示，实施例2制得的双壳层微胶囊中相变材料芯材含量约为39％，双壳层微胶囊芯材在加热到150℃左右才开始损失，升温至219℃时芯材也仅损失5％的质量；如图8所示，实施例3制得的双壳层微胶囊中相变材料芯材含量约为64％，双壳层微胶囊芯材在加热到150℃左右才开始损失，升温至210℃时芯材也仅损失5％的质量；如图9所示，对比例制得的微胶囊中相变材料芯材含量约为28％，升温至194℃时芯材已经损失5％的质量，升温至100℃时已经开始出现质量损失。可见，本发明制得的双壳层微胶囊相变材料芯材含量高，相同质量的微胶囊中含有更多的修复型芯材，具有良好的耐高温性能，升温至150℃以上，微胶囊的芯材才出现挥发的情况。
对实施例1制得的微胶囊在室温下水、正己烷、二甲苯、乙酸乙酯4种不同溶剂中浸泡20天，测定其芯材损失率，结果如图10所示。
由图10可得，本发明中的双壳层微胶囊具有良好的耐溶剂性能，在水、正己烷、二甲苯和乙酸乙酯等溶剂中连续浸泡20天后，微胶囊相变材料的芯材损失率仅为5％～10％，证明该自修复微胶囊具有良好的耐溶剂性能，在掺入涂料到涂布的过程中，微胶囊不会因涂料中的 溶剂浸泡而损坏。
应用例1：自修复防锈涂层及其制备方法：
将10g实施例1制得的双壳层微胶囊同90g市售水性醇酸树脂面漆加入到塑料杯中，500rpm机械搅拌10min，装入喷枪中喷涂到铁板表面，室温放置6h涂层表干后再次进行喷涂，共进行3-4次喷涂，涂层厚度100μm-150μm，待涂层完全固化后，用刀片在表面划刻“十”字划痕，浸入10％氯化钠溶液中浸泡35天，结果如图11(a)所示。取市售水性醇酸树脂面漆，不添加微胶囊进行相同的喷涂和浸泡操作，作为对照组，结果如图11(b)所示。
由图11可看出，应用本发明双壳层微胶囊制得的自修复防锈涂层在10％氯化钠溶液中浸泡35天后，未发生锈蚀和损伤，仍能为设备提供良好的保护作用，而对照组涂层划痕严重锈蚀，涂层表面起泡破裂。
应用例2：自修复防锈涂层及其制备方法：
将市售环氧树脂漆A组分和B组分按产品说明混合得到90g环氧漆，加入10g实施例3制得的双壳层微胶囊，600rpm机械搅拌10min，刷涂到铁板表面，涂层厚度100μm±20μm，待涂层完全固化后，用刀片在表面划刻“一”字划痕，按照GBT 1771-2007进行中性盐雾测试，经过1000h盐雾性能测试，结果如图12(a)所示。取市售环氧树脂漆A组分和B组分按产品说明混合得到90g环氧漆，进行相同的刷涂和盐雾测试操作，作为对照组，结果如图12(b)所示。
由图12可看出，应用本发明双壳层微胶囊制得的自修复防锈涂层经1000h中性盐雾性能测试后，未发生锈蚀和损伤，仍能为设备提供良好的保护作用，而对照组涂层已经严重起泡，并发生脱落。
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其他的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。

Claims (10)

  1. 一种双壳层微胶囊，其特征在于：包括芯材、包裹所述芯材的第一壁材层和包裹所述第一壁材的第二壁材层。
  2. 根据权利要求1所述的双壳层微胶囊，其特征在于：以双壳层微胶囊质量计，所述芯材的质量分数为20％～70％，所述第一壁材层的质量分数为10％～30％，所述第二壁材层的质量分数为20％～50％。
  3. 根据权利要求1或2所述的双壳层微胶囊，其特征在于：所述芯材为选自含两个或两个以上异氰酸根的异氰酸酯中的至少一种，所述第一壁材层为选自聚氨酯层、聚脲层中的至少一种，所述第二壁材层为聚脲醛树脂层。
  4. 根据权利要求3所述的双壳层微胶囊，其特征在于：所述聚氨酯层包括油溶性聚氨酯前驱体和水溶性聚氨酯前驱体，所述聚脲层包括油溶性聚脲前驱体和水溶性聚脲前驱体。
  5. 根据权利要求4所述的双壳层微胶囊，其特征在于：所述油溶性聚氨酯前驱体为选自六亚甲基二异氰酸酯、二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯的三聚体、二苯基甲烷二异氰酸酯预聚体中的至少一种；所述油溶性聚脲前驱体为选自六亚甲基二异氰酸酯、二苯基甲烷二异氰酸酯、六亚甲基二异氰酸酯的三聚体、二苯基甲烷二异氰酸酯预聚体中的至少一种。
  6. 根据权利要求4所述的双壳层微胶囊，其特征在于：所述水溶性聚氨酯前驱体为选自含两个或两个以上羟基的水溶性化合物中的至少一种，所述水溶性聚脲前驱体为选自含两个或两个以上胺基的水溶性化合物中的至少一种。
  7. 一种双壳层微胶囊的制备方法，其特征在于：包括如下步骤：
    (1)乳化剂溶液中加入芯材和油溶性的前驱体混合液，搅拌反应，得到水包油乳液；
    (2)水包油乳液中加入水溶性的前驱体和改性偶联剂混合液，搅拌反应，得到单壳层微胶囊；
    (3)分散剂与脲醛树脂改性剂的混合溶液中加入单壳层微胶囊和尿素-甲醛预聚物，调节pH，搅拌反应，得到如权利要求1～6任一项组成的双壳层微胶囊。
  8. 根据权利要求7所述的双壳层微胶囊的制备方法，其特征在于：当步骤(1)中所述油溶性的前驱体为油溶性聚氨酯前驱体时，步骤(2)中所述水溶性的前驱体为水溶性聚氨酯前驱体；优选的，当步骤(1)中所述油溶性的前驱体为油溶性聚脲前驱体时，步骤(2)中所述水溶性的前驱体为水溶性聚脲前驱体，步骤(2)中所述搅拌反应后还包括水洗的步骤。
  9. 根据权利要求7所述的双壳层微胶囊的制备方法，其特征在于：步骤(2)中所述改性偶联剂为选自山梨醇、甘露醇、三乙醇胺中的至少一种。
  10. 一种双壳层微胶囊在制备涂料和/或粘接剂中的应用，其特征在于：所述双壳层微胶囊为权利要求1～6任一项所述双壳层微胶囊，或者为权利要求7～9任一项所述双壳层微胶囊的制备方法制得。
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