WO2021043123A1 - 一种室温下可多次自修复的微胶囊、制备方法及应用 - Google Patents

一种室温下可多次自修复的微胶囊、制备方法及应用 Download PDF

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WO2021043123A1
WO2021043123A1 PCT/CN2020/112811 CN2020112811W WO2021043123A1 WO 2021043123 A1 WO2021043123 A1 WO 2021043123A1 CN 2020112811 W CN2020112811 W CN 2020112811W WO 2021043123 A1 WO2021043123 A1 WO 2021043123A1
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microcapsule
room temperature
self
multiple times
microcapsules
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PCT/CN2020/112811
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English (en)
French (fr)
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许一婷
王宏超
戴李宗
杨杰
曹莹
张丹丹
张加甜
陈国荣
Original Assignee
厦门大学
金旸（厦门）新材料科技有限公司
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Publication of WO2021043123A1 publication Critical patent/WO2021043123A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/10—Encapsulated ingredients
    • 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
    • B01J13/06—Making microcapsules or microballoons by phase separation
    • B01J13/14—Polymerisation; cross-linking
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
    • C07F7/1804—Compounds having Si-O-C linkages
    • C07F7/1872—Preparation; Treatments not provided for in C07F7/20
    • C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/55—Boron-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08L61/22—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
    • C08L61/24—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds with urea or thiourea
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04—Polysiloxanes
    • 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
    • C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
    • C09D161/04—Condensation polymers of aldehydes or ketones with phenols only
    • C09D161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
    • 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
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • 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
    • 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
    • C09D7/65—Additives macromolecular
    • 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
    • C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
    • 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
    • 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
    • C09J11/08—Macromolecular additives

Definitions

  • the invention belongs to the field of room temperature self-repairing materials, and specifically relates to a microcapsule capable of self-repairing multiple times at room temperature, a preparation method and an application.
  • polymer materials Because of its superior properties, polymer materials have now become an indispensable class of materials in the fields of life, industry, military, and so on. However, since the strength of polymer materials is lower than that of cermets and other materials, how to extend the service life of polymer materials has become a problem of concern. The preparation of self-healing materials is a more effective way to extend the service life of materials, which has attracted more and more attention.
  • Adding microcapsules to the material is a relatively common method for preparing self-healing materials, which can produce a repair effect relatively quickly.
  • Wang Wei et al. (Micro-crack self-repairing microcapsules and their preparation method, Chinese patent, publication number CN102702838A) prepared a kind of capsule core with isocyanate derivatives and chain extender-containing urea-formaldehyde The resin is the wall of the capsule, no additional repair catalyst or initiator is required, and the microcapsules that can realize the fully automatic repair function solve the problem of the small probability of contact with the catalyst or initiator after the capsule core material flows into the crack.
  • the purpose of the present invention is to overcome the shortcomings of the prior art, and provide a microcapsule that can self-repair multiple times at room temperature, a preparation method and an application, and solve the above-mentioned problems in the background art.
  • One of the technical solutions adopted by the present invention to solve its technical problems is to provide a microcapsule capable of self-repairing multiple times at room temperature, including a first microcapsule and a second microcapsule;
  • the wall of the first microcapsule is urea-formaldehyde resin, and the core of the capsule is bispropyl thiopropyl ether borate methyl dimethoxy siloxane, a catalyst and an adhesion promoter.
  • the mass ratio of ether borate methyl dimethoxysiloxane, catalyst and adhesion promoter is 1:0.005 ⁇ 0.015:0.002 ⁇ 0.005;
  • the capsule wall of the second microcapsule is urea-formaldehyde resin, and the capsule core is dihydroxy polydimethylsiloxane, catalyst and adhesion promoter, among which dihydroxy polydimethylsiloxane, catalyst and adhesion promoter
  • the mass ratio is 1:0.005 ⁇ 0.015:0.002 ⁇ 0.005;
  • the mass ratio of the capsule wall and the capsule core of the first microcapsule and the second microcapsule is 1:2.5-5.
  • the catalyst includes dibutyltin dilaurate, and the adhesion promoter is methacryloxypropyltriethoxysilane or bis[3-(trimethoxysilyl)propyl]amine.
  • the second technical solution adopted by the present invention to solve its technical problems is to provide a method for preparing microcapsules that can be self-repaired multiple times at room temperature, which includes the following steps:
  • step 2) Take the bis(allyloxy)methyl borate and mercaptopropylmethyldimethoxysilane obtained in step 1) and dissolve it in the second solvent under the protection of nitrogen, and add the photoinitiator 2-hydroxy- 2-Methylpropiophenone is stirred and reacted under 365nm ultraviolet light at room temperature for 0.5-1.5h, and dried under vacuum at room temperature to obtain bispropyl thiopropyl ether borate methyl dimethoxysiloxane.
  • the capsule wall is made of urea-formaldehyde resin by in-situ polymerization of oil-in-water emulsion, and the capsule core is bispropyl thiopropyl ether borate methyl dimethoxysiloxane, catalyst and adhesive.
  • the first microcapsule with the accelerator and the capsule wall are urea-formaldehyde resin, and the capsule core is the second microcapsule with dihydroxy polydimethylsiloxane, catalyst and adhesion promoter.
  • step 2) Replace the bispropyl sulfopropyl ether borate methyl dimethoxysiloxane in step 1) with dihydroxy polydimethylsiloxane to prepare a second microcapsule;
  • the first solvent is deionized water.
  • the second solvent is chloroform or n-hexane.
  • the emulsifier is sodium dodecylbenzene sulfonate, sodium dodecyl sulfate or OP-10.
  • the concentration of the emulsifier is 0.3 wt% to 1.0 wt%.
  • the adhesion promoter is methacryloxypropyltriethoxysilane or bis[3-(trimethoxysilyl)propyl]amine.
  • the mass ratio of the boric acid and 3-allyloxy-1,2-propanediol is 2:8-9, and the bis(allyloxy)methyl borate ,
  • the mass ratio of mercaptopropylmethyldimethoxysilane to 2-hydroxy-2-methylpropiophenone is 6:7-8:0.1-0.3.
  • the mass ratio of the capsule wall to the capsule core is 1:2.5-5.
  • the mass ratio of the urea, ammonium chloride, resorcinol and 37wt% formaldehyde solution is 1:0.1:0.1:3-5.
  • the mass ratio of the dihydroxy polydimethylsiloxane, dibutyltin dilaurate and the adhesion promoter is 1:0.005 to 0.015: 0.002 to 0.005.
  • the mass ratio of the first microcapsule and the second microcapsule when they are mixed is 1:10-20.
  • the third technical solution adopted by the present invention to solve its technical problems is: the application of a microcapsule capable of self-repairing multiple times at room temperature in polymer materials, such as being applied to a variety of resin coatings.
  • the microcapsules which can be self-healed multiple times at room temperature, are dispersed and mixed with matrix resin and other components in a disperser for 1 to 4 hours to obtain a self-healing resin coating.
  • the resin coating is selected from epoxy resin coatings, polyurethane resin coatings, phenolic resin coatings and the like.
  • the preparation steps of self-healing epoxy resin coating are as follows:
  • the epoxy resin is a commercial epoxy resin, that is, a compound containing two or more epoxy groups in the molecule, such as glycidyl ether, glycidyl amine, glycidyl ester, etc.; among them, glycidyl ether has a bisphenol A type , Bisphenol F type and bisphenol S type, etc.; glycidylamines include aniline glycidylamine, diaminodiphenylmethane tetraglycidylamine, etc.; glycidyl esters include diglycidyl p-(phthalate).
  • the third solvent is n-butanol and/or butyl acetate.
  • microcapsules that can be self-repaired multiple times at room temperature are the first microcapsule and the second microcapsule, and the mass ratio of the first microcapsule and the second microcapsule when used in combination is 1:10-20.
  • the curing agent is an amine or acid anhydride compound used in conjunction with epoxy resin, such as 4,4'-diaminodiphenylmethane, ethylenediamine, diethylenetriamine, m-phenylenediamine, etc.; acid anhydride Such as phthalic anhydride, pyromellitic anhydride, methylcyclohexene tetracarboxylic anhydride and so on.
  • epoxy resin such as 4,4'-diaminodiphenylmethane, ethylenediamine, diethylenetriamine, m-phenylenediamine, etc.
  • acid anhydride Such as phthalic anhydride, pyromellitic anhydride, methylcyclohexene tetracarboxylic anhydride and so on.
  • the mass ratio of the component A and the component B is 2 ⁇ 4:1.
  • microcapsules capable of self-repairing multiple times at room temperature can also be applied to the fields of automotive topcoats, automotive primers, smart home paints, smart home parts, electrical and electronic sealants, and the like.
  • the present invention proposes to adopt the method of in-situ polymerization of oil-in-water emulsion to prepare microcapsules with a siloxane coupling agent containing a reversible borate bond as the capsule core and a urea-formaldehyde resin as the capsule wall. Silicone, adhesion promoter and catalyst are used as the core of the capsule, and the microcapsules with urea-formaldehyde resin as the wall are used together to obtain a microcapsule that can be repaired multiple times at room temperature. There are no related reports about this kind of work. .
  • the core material of the microcapsules capable of self-repairing multiple times at room temperature includes a siloxane coupling agent containing a reversible borate bond, a dihydroxy polydimethylsiloxane, a catalyst and an adhesion promoter, and
  • the reported microcapsules, siloxane coupling agent and polydimethylsiloxane are different.
  • the present invention is obtained by reacting boric acid with 3-allyloxy-1,2-propanediol and thiol-ene click chemistry reaction
  • the siloxane coupling agent containing reversible borate linkages, and the capsule cores are prepared by in-situ polymerization of oil-in-water emulsions.
  • siloxane coupling agents containing reversible borate linkages and dihydroxy polydimethylsiloxane.
  • the urea-formaldehyde resin capsule wall has high chemical stability, good mechanical properties, and good film-forming properties. It has little effect on the mechanical properties of the self-healing material. When the material is not damaged, the capsule core material can be stored stably in the capsule wall without being affected.
  • polydimethylsiloxane is cross-linked and cured under the action of a siloxane coupling agent containing a reversible borate bond and a catalyst to quickly repair microcracks and/or cracks, prevent further diffusion and cause macroscopic damage to the material, and cure
  • the formed silicone rubber is chemically stable and has good adhesion to the polymer matrix under the action of the adhesion promoter.
  • the microcracks and/or the borate bonds at the ends of the cracks can reversibly form boric acid bonds and glycol bonds under the action of water in the air.
  • the alcohol bond will react again to form a borate bond.
  • the microcracks and/or cracks can be repaired, and so on.
  • microcracks and/or cracks are generated in the silicone rubber area of the self-healing material again under external force, the microcracks and/or cracks can be repaired repeatedly. Microcracks and/or cracks in the non-silicone rubber repair area will be broken through the microcapsules.
  • the core material is mixed and cured into silicone rubber to achieve the self-repairing effect. The two interact with each other to make the material self-repair repeatedly at room temperature, which greatly extends the service life of the material.
  • the present invention has the following beneficial effects:
  • microcapsules prepared by the present invention can be uniformly dispersed in polymer materials. Under the premise of ensuring the mechanical properties of the polymer materials, the microcapsule wall and core materials can be self-repaired at room temperature. Chemically stable.
  • the capsule core material can be stored stably under the protection of the capsule wall.
  • the capsule core material will only contact each other when the microcapsules are broken and solidify at room temperature to prevent premature curing or premature curing of the capsule core material. React with resin matrix.
  • microcapsules When the self-healing material receives external force to produce microcracks and/or cracks, the microcapsules are broken, and the dihydroxy polydimethylsiloxane and bispropyl thiopropyl ether borate methyl esters in the microcapsules are broken. Dimethoxysiloxane, catalyst and adhesion promoter are in contact with each other and mixed and cured to form silicone rubber to repair microcracks and/or cracks.
  • Figure 1 shows the proton nuclear magnetic resonance spectrum and the boron nuclear magnetic resonance spectrum of bis(allyloxy) methyl borate, where a is the proton nuclear magnetic resonance spectrum and b is the boron nuclear magnetic resonance spectrum.
  • Figure 2 Optical image and scanning electron microscopic image of microcapsules with dihydroxy polydimethylsiloxane, catalyst and adhesion promoter as the core of the capsule, where a, b, and c are optical images (scale 50 ⁇ m), and d is Scanning electron micrograph (500X, scale 10 ⁇ m).
  • Example 1 the hydrogen nuclear magnetic resonance spectrum and the boron nuclear magnetic resonance spectrum of the synthesized bis(allyloxy) methyl borate are shown in Figure 1.
  • the prepared capsule core is dihydroxy polydimethylsiloxane, catalyst and
  • the optical image and scanning electron microscope image of the second microcapsule of the adhesion promoter are shown in Figure 2.
  • Example 2 The same process as in Example 1, changing the added amount of microcapsules that can be repaired multiple times at room temperature. They are the second microcapsules whose core is dihydroxy polydimethylsiloxane, catalyst and adhesion promoter. 5g, 5.5g, 6g, 6.5g, the first microcapsules 0.5g, 0.55g, 0.6g, 0.65g (according to By mass percentage, the microcapsules that can be self-repaired multiple times at room temperature are 11%, 12%, 13%, and 14% of the epoxy resin respectively) to obtain the self-healing epoxy resin coating.
  • the epoxy resin coating of the experimental group containing microcapsules and the ordinary epoxy resin coating of the control group prepared in Example 1 were respectively coated on Q235 steel plate. After curing, the coating was crossed and placed in an atmospheric environment for three days. Neutral salt spray test. The experimental results show that the epoxy resin coating in the control group is resistant to neutral salt spray for 300 hours, and the microcapsule content in the experimental group is 11%, 12%, 13%, 14% and 15% of the self-healing epoxy resin coating The resistance to neutral salt spray is 650, 660, 680, 700 and 720 hours respectively.
  • a fork was drawn on the self-healing epoxy resin coating of the experimental group. After being placed in an atmospheric environment for three days, another fork was drawn at the coating fork, and placed in an atmospheric environment for three days to conduct a neutral salt spray resistance test.
  • the experimental results show that the microcapsule content in the experimental group is 11%, 12%, 13%, 14% and 15%.
  • the self-healing epoxy resin coating is resistant to neutral salt spray for 630, 640, 660, 680 and 700 hours respectively. .
  • test group By analogy, the test group's self-healing epoxy resin coating was crossed at the same place, placed in an atmospheric environment for three days, and after three cycles, the neutral salt spray resistance test was performed. The experimental results showed that the microcapsule content in the experimental group was 11%, 12%, 13%, 14% and 15%.
  • the self-healing epoxy resin coatings were resistant to neutral salt spray for 620, 630, 650, 670 and 690 hours, respectively. .
  • the invention discloses a microcapsule capable of self-repairing multiple times at room temperature, a preparation method and an application thereof, and an oil-in-water emulsion in-situ polymerization method is adopted to prepare a siloxane coupling agent containing a reversible borate bond as the core of the capsule , Microcapsules with urea-formaldehyde resin as the wall are used together with microcapsules with dihydroxy polydimethylsiloxane, adhesion promoter and catalyst as the core and urea-formaldehyde resin as the wall.
  • the present invention effectively improves the performance of polymer materials to achieve rapid repair and repeated repair of microcracks, prevent microcracks from spreading and cause macroscopic damage to the material, and greatly extend The service life of the material is widely used in the fields of automotive topcoats, automotive primers, smart home paints, smart home parts, electrical and electronic sealants, etc., and has industrial practicability.

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  • Organic Chemistry (AREA)
  • Wood Science & Technology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Dispersion Chemistry (AREA)
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  • Paints Or Removers (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

本发明公开了一种室温下可多次自修复的微胶囊、制备方法及应用，采用水包油乳液原位聚合的方法制备以含有可逆硼酸酯键的硅氧烷偶联剂为囊芯，以脲醛树脂为囊壁的微胶囊，与以二羟基聚二甲基硅氧烷、粘合促进剂和催化剂为囊芯，以脲醛树脂为囊壁的微胶囊共同使用。利用微胶囊的特点和可逆硼酸酯键的性质，本发明有效改善高分子材料性能，达到可快速修复以及可多次重复修复微裂纹，防止微裂纹扩散造成材料宏观损坏的效果，极大延长材料的使用寿命，进而广泛应用于汽车面漆、汽车底漆、智能家居漆、智能家居零件，电子电气密封胶等领域。

Description

一种室温下可多次自修复的微胶囊、制备方法及应用 技术领域
本发明属于室温自修复材料领域，具体涉及室温下可多次自修复的微胶囊、制备方法及应用。
背景技术
高分子材料由于其较为优异的性能，现在已经成为生活工业军事等领域不可或缺的一类材料。然而由于高分子材料的强度相对金属陶瓷等材料较小，如何延长高分子材料的使用寿命成为人们所关注的问题。制备可自修复材料是延长材料使用寿命比较有效的途径，现已受到越来越多的关注。
材料中外加微胶囊是制备可自修复材料比较普遍的方法，可以比较快速产生修复效果。在微胶囊的研究工作中，王巍等(微裂纹自修复微胶囊及其制备方法，中国专利，公开号CN102702838A)制备了一种以异氰酸酯类衍生物为囊芯，以含扩链剂的脲醛树脂为囊壁，不需要添加额外的修复催化剂或引发剂，而能实现完全自动修复功能的微胶囊，解决了囊芯材料流入裂缝后与催化剂或引发剂接触概率小的问题。高宏等(一种基于巯基-烯点击加成反应制备自修复材料的方法，中国专利，公开号CN109081919A)将聚硫橡胶、丙烯酸酯类单体、引发剂或催化剂和自修复促进剂依次混合均匀得到预聚物，再以与引发剂或催化剂相对应的固化方式进行固化得到自修复材料，该方法简单、高效，制得的自修复材料具有较好的柔韧性。然而一般微胶囊只能单次修复，无法达到重复修复材料。
发明内容
本发明的目的在于克服现有技术的不足之处，提供了一种室温下可多次自修复的微胶囊、制备方法及应用，解决了上述背景技术中的问题。
本发明解决其技术问题所采用的技术方案之一是：提供了一种室温下可多次自修复的微胶囊，包括第一微胶囊和第二微胶囊；
所述第一微胶囊的囊壁为脲醛树脂，囊芯为双丙基硫丙基醚硼酸酯甲基二甲氧基 硅氧烷、催化剂和粘合促进剂，其中双丙基硫丙基醚硼酸酯甲基二甲氧基硅氧烷、催化剂和粘合促进剂质量比为1：0.005～0.015：0.002～0.005；
所述第二微胶囊的囊壁为脲醛树脂，囊芯为二羟基聚二甲基硅氧烷、催化剂和粘合促进剂，其中二羟基聚二甲基硅氧烷、催化剂和粘合促进剂质量比为1：0.005～0.015：0.002～0.005；
所述第一微胶囊和第二微胶囊的囊壁和囊芯的质量比为1：2.5～5。
所述催化剂包括二月桂酸二丁基锡，所述粘合促进剂为甲基丙烯酰氧基丙基三乙氧基硅烷或双[3-(三甲氧基甲硅烷基)丙基]胺。
本发明解决其技术问题所采用的技术方案之二是：提供了一种室温下可多次自修复的微胶囊的制备方法，包括如下步骤：
一)可逆硼酸酯键的硅氧烷偶联剂的制备：通过硼酸与3-烯丙氧基-1,2-丙二醇反应和硫醇-烯点击化学反应得到双丙基硫丙基醚硼酸酯甲基二甲氧基硅氧烷；双丙基硫丙基醚硼酸酯甲基二甲氧基硅氧烷具有可逆共价键，其和非共价键在一定的条件下可以进行键交换，利用这一性质制备可多次自修复材料，以达到可快速修复以及可多次重复修复微裂纹，防止微裂纹扩散造成材料宏观损坏，延长材料的使用寿命。
所述双丙基硫丙基醚硼酸酯甲基二甲氧基硅氧烷的合成路线具体如下：
Figure PCTCN2020112811-appb-000001
1)向圆底烧瓶中加入硼酸和第一溶剂，用KOH调pH约为9～11，加入3-烯丙氧 基-1,2-丙二醇，在20～40℃下搅拌反应4～8h，100～140℃下搅拌蒸发除去第一溶剂，最后在100～140℃真空下干燥，即得双(烯丙氧基)甲基硼酸酯。
2)取步骤1)所得的双(烯丙氧基)甲基硼酸酯和巯丙基甲基二甲氧基硅烷在氮气保护下溶于第二溶剂中，加入光引发剂2-羟基-2-甲基苯丙酮，在室温365nm紫外光下搅拌反应0.5～1.5h，室温真空干燥，即得双丙基硫丙基醚硼酸酯甲基二甲氧基硅氧烷。
二)微胶囊的组装与混合：通过水包油乳液原位聚合制备囊壁为脲醛树脂，囊芯为双丙基硫丙基醚硼酸酯甲基二甲氧基硅氧烷、催化剂与粘合促进剂的第一微胶囊，和囊壁为脲醛树脂，囊芯为二羟基聚二甲基硅氧烷、催化剂与粘合促进剂的第二微胶囊。
1)向圆底烧瓶中加入乳化剂和蒸馏水，加入脲、氯化铵和间苯二酚，搅拌均匀，加入步骤1所得的双丙基硫丙基醚硼酸酯甲基二甲氧基硅氧烷或二羟基聚二甲基硅氧烷、催化剂二月桂酸二丁基锡和相应粘合促进剂，用甲酸调节pH约为3～4，同时调节转速为500～2000rpm剪切乳化5～20min以调节微胶囊大小，加入消泡剂正辛醇除去表面气泡，加入37wt％甲醛溶液，以1℃/min的速度升温至60℃，保持转速反应1～3小时，加入5wt％～20wt％脲继续保持转速保温反应2～4h，离心分离，并用蒸馏水洗涤多次，抽滤后在常温空气中干燥24～48h，得到第一微胶囊；
2)将步骤1)中的双丙基硫丙基醚硼酸酯甲基二甲氧基硅氧烷替换为二羟基聚二甲基硅氧烷，制备得到第二微胶囊；
3)将步骤1)得到第一微胶囊与步骤2)得到第二微胶囊物理混合。
在本发明的一个优选实施方案中，所述第一溶剂为去离子水。
在本发明的一个优选实施方案中，所述第二溶剂为三氯甲烷或正己烷。
在本发明的一个优选实施方案中，所述乳化剂为十二烷基苯磺酸钠、十二烷基硫酸钠或OP-10。所述乳化剂的浓度为0.3wt％～1.0wt％。
在本发明的一个优选实施方案中，所述粘合促进剂为甲基丙烯酰氧基丙基三乙氧基硅烷或双[3-(三甲氧基甲硅烷基)丙基]胺。
在本发明的一个优选实施方案中，所述硼酸和3-烯丙氧基-1,2-丙二醇的质量比为2：8～9，所述双(烯丙氧基)甲基硼酸酯、巯丙基甲基二甲氧基硅烷与2-羟基-2-甲基苯丙酮的质量比为6：7～8：0.1～0.3。
在本发明的一个优选实施方案中，所述囊壁和囊芯的质量比为1：2.5～5。
在本发明的一个优选实施方案中，所述脲、氯化铵、间苯二酚和37wt％甲醛溶液的质量比为1：0.1：0.1：3～5。
在本发明的一个优选实施方案中，所述二羟基聚二甲基硅氧烷、二月桂酸二丁基锡和粘合促进剂质量比为1：0.005～0.015：0.002～0.005。
在本发明的一个优选实施方案中，所述第一微胶囊和第二微胶囊混合使用时的质量比为1：10～20。
本发明解决其技术问题所采用的技术方案之三是：一种室温下可多次自修复的微胶囊在高分子材料中的应用，如应用于多种树脂涂料。将室温下可多次自修复的微胶囊与基体树脂及其它组分在分散机中分散混合1～4h，得到自修复树脂涂料。所述树脂涂料选自环氧树脂涂料、聚氨酯树脂涂料、酚醛树脂涂料等。其中自修复环氧树脂涂料的制备步骤具体如下：
称取一定量环氧树脂，加入15wt％～35wt％第三溶剂，搅拌25～50min，加入10～ 20wt％的室温下可多次自修复的微胶囊，搅拌30～90min至均匀得到组分A。称取一定量固化剂，加入15wt％～35wt％第三溶剂，搅拌10～30min，得到组分B。混合组分A和组分B，搅拌20～60min，即得自修复环氧树脂涂料。
所述环氧树脂为商品环氧树脂，即分子中含有两个或多个环氧基团的化合物，如缩水甘油醚，缩水甘油胺，缩水甘油酯等；其中缩水甘油醚有双酚A型、双酚F型及双酚S型等；缩水甘油胺有苯胺缩水甘油胺、二氨基二苯甲烷四缩水甘油胺等；缩水甘油酯有二缩水甘油对(邻)苯二甲酸酯等。
所述第三溶剂为正丁醇和/或乙酸丁酯。
所述室温下可多次自修复的微胶囊为第一微胶囊和第二微胶囊，第一微胶囊和第二微胶囊混合使用时的质量比为1：10～20。
所述固化剂为与环氧树脂配合使用的胺类或酸酐类化合物等，胺类如4,4’-二氨基二苯甲烷、乙二胺、二乙烯三胺、间苯二胺等；酸酐类如邻苯二甲酸酐、均苯四甲酸酐、甲基环己烯四羧酸酐等。
所述组分A和组分B的质量比为2～4：1。
所述室温下可多次自修复的微胶囊还可应用于汽车面漆、汽车底漆、智能家居漆、智能家居零件，电子电气密封胶等领域。
本发明提出采用水包油乳液原位聚合的方法制备以含有可逆硼酸酯键的硅氧烷偶联剂为囊芯，以脲醛树脂为囊壁的微胶囊，与以二羟基聚二甲基硅氧烷、粘合促进剂和催化剂为囊芯，以脲醛树脂为囊壁的微胶囊共同使用，得到一种室温下可多次自修复的微胶囊，目前此类工作还未见有相关报道。所述室温下可多次自修复的微胶囊的囊芯物质包括含有可逆硼酸酯键的硅氧烷偶联剂、二羟基聚二甲基硅氧烷、催化剂和 粘合促进剂，与已报道的微胶囊、硅氧烷偶联剂和聚二甲基硅氧烷有所不同，本发明通过硼酸与3-烯丙氧基-1,2-丙二醇反应和硫醇-烯点击化学反应得到含有可逆硼酸酯键的硅氧烷偶联剂，再通过水包油乳液原位聚合制备囊芯分别为含有可逆硼酸酯键的硅氧烷偶联剂和二羟基聚二甲基硅氧烷、催化剂与粘合促进剂，囊壁为脲醛树脂的两种微胶囊。利用微胶囊的特点和可逆硼酸酯键的性质，制备得到的自修复材料可以多次重复修复，极大延长材料的使用寿命。脲醛树脂囊壁化学稳定性高，力学性能较好，成膜性好，对自修复材料的机械性能影响不大。材料无损伤时囊芯物质可以稳定保存在囊壁中不受影响，当自修复材料受到外力作用产生微裂纹和/或裂缝时，微胶囊破裂，囊芯物质流出相互接触混合，室温下二羟基聚二甲基硅氧烷在含有可逆硼酸酯键的硅氧烷偶联剂以及催化剂的作用下交联固化，快速修复微裂纹和/或裂缝，防止其进一步扩散造成材料宏观损坏，而且固化形成的硅橡胶化学性质稳定，在粘合促进剂的作用下与高分子基质粘附性好。当固化形成的硅橡胶被外界力破坏时，产生的微裂纹和/或裂缝两端的硼酸酯键在空气中水的作用下可逆生成硼酸键和二醇键，室温下两端的硼酸键和二醇键又会重新反应生成硼酸酯键，同时在可逆键硼酸酯键的交换以及分子链段运动的作用下，以达到修复微裂纹和/或裂缝，以此类推，当被修复后的自修复材料的硅橡胶区再次受外界力作用产生微裂纹和/或裂缝时仍可以重复修复微裂纹和/或裂缝，非硅橡胶修复区产生微裂纹和/或裂缝则通过微胶囊破裂，囊芯物质混合固化成硅橡胶来达到自修复效果，两者相互协同作用使材料在室温下可以多次重复自修复，极大延长材料的使用寿命。
本发明与现有技术相比，具有如下有益效果：
(1)本发明制备的微胶囊可在高分子材料中均匀分散，在保证了高分子材料力学性能的前提下，引入室温下可多次自修复的性能，微胶囊的囊壁和囊芯材料化学性质稳定。
(2)双丙基硫丙基醚硼酸酯甲基二甲氧基硅氧烷和二羟基聚二甲基硅氧烷、催化剂与粘合促进剂分别包封在两种微胶囊中，混合加入到树脂基体中，囊芯物质在囊壁的保护下可以稳定保存，材料出现微裂纹和/或裂缝时，微胶囊破裂时囊芯物质才互相接触室温固化，防止囊芯物质过早固化或与树脂基体反应。
(3)在自修复材料收到外力作用产生微裂纹和/或裂缝时，微胶囊破裂，微胶囊里的二羟基聚二甲基硅氧烷、双丙基硫丙基醚硼酸酯甲基二甲氧基硅氧烷、催化剂和粘合促进剂相互接触混合固化形成硅橡胶，修复微裂纹和/或裂缝。当自修复材料再次收到外力作用时，硅橡胶区产生微裂纹和/或裂缝，两端漏出的硼酸酯键在空气中水的作用下可逆变成硼酸键和二醇键，硼酸键和二醇键在室温下反应再次生成硼酸酯键，大量的硼酸酯可逆键交换和可逆平衡转换以及分子链段的不断运动，通过可逆共价键达到修复材料的效果。硅橡胶以外的区域产生微裂纹和/或裂缝时，通过微胶囊机制来进行自修复。两种自修复的方式相互协同使制备的材料达到室温下可多次自修复的效果。
附图说明
图1为双(烯丙氧基)甲基硼酸酯的核磁共振氢谱和核磁共振硼谱，其中a为核磁共振氢谱，b为核磁共振硼谱。
图2囊芯为二羟基聚二甲基硅氧烷、催化剂与粘合促进剂的微胶囊的光学图像和扫描电子显微图像，其中a、b、c为光学图像(标尺50μm)，d为扫描电子显微图像(500X，标尺10μm)。
具体实施方式
实施例1
(1)室温下可多次自修复的微胶囊的制备
向圆底烧瓶中加入2g硼酸和20mL去离子水，用KOH调pH为10，加入8.55g 3-烯丙氧基-1,2-丙二醇，在30℃下搅拌反应6h，110℃下搅拌蒸发除去水分，最后在110℃真空下干燥，得到双(烯丙氧基)甲基硼酸酯。称取6g双(烯丙氧基)甲基硼酸酯和7.98g巯丙基甲基二甲氧基硅烷在氮气保护下溶于100mL中，加入0.2g 2-羟基-2-甲基苯丙酮，在室温365nm紫外光下搅拌反应1h，室温下真空干燥，得到双丙基硫丙基醚硼酸酯甲基二甲氧基硅氧烷。向圆底烧瓶中加入0.625g十二烷基苯磺酸钠和62.5mL蒸馏水，加入1.25g脲、0.125g氯化铵和0.125g间苯二酚，搅拌均匀，加入8g双丙基硫丙基醚硼酸酯甲基二甲氧基硅氧烷或8g二羟基聚二甲基硅氧烷、0.05g二月桂酸二丁基锡和0.024g双[3-(三甲氧基甲硅烷基)丙基]胺，用甲酸调节pH为3.5，同时调节转速为1000rpm剪切乳化15min，加入2滴正辛醇，加入4g 37wt％甲醛溶液，以1℃/min的速度升温至60℃，保持转速反应1小时，再加入0.125g脲继续保持转速保温反应3h，离心分离，并用蒸馏水洗涤多次，抽滤后在常温空气中干燥36h，得到室温下可多次自修复的微胶囊。
(2)环氧树脂涂料的制备
称取50g环氧树脂，加入7g正丁醇和3g乙酸丁酯，搅拌30min，加入7g囊芯为二羟基聚二甲基硅氧烷、催化剂与粘合促进剂的第二微胶囊和0.7g囊芯为双丙基硫丙基醚硼酸酯甲基二甲氧基硅氧烷的第一微胶囊，搅拌30min至均匀得到组分A。称取15g固化剂，加入2.1g正丁醇和0.9g乙酸丁酯，搅拌30min，得到组分B。混合组分A和组分B，搅拌30min，即得自修复环氧树脂涂料。
实施例1中，合成的双(烯丙氧基)甲基硼酸酯的核磁共振氢谱和核磁共振硼谱 见图1，制备的囊芯为二羟基聚二甲基硅氧烷、催化剂与粘合促进剂的第二微胶囊的光学图像和扫描电子显微镜图像见图2。
实施例2～5
(1)同实施例1。
(2)同实施例1工艺，改变室温下可多次自修复的微胶囊的添加量，分别为囊芯为二羟基聚二甲基硅氧烷、催化剂与粘合促进剂的第二微胶囊5g，5.5g，6g，6.5g，囊芯为双丙基硫丙基醚硼酸酯甲基二甲氧基硅氧烷的第一微胶囊0.5g，0.55g，0.6g，0.65g(按质量百分比，室温下可多次自修复的微胶囊分别为环氧树脂的11％，12％，13％，14％)，得到自修复环氧树脂涂料。
称取50g环氧树脂，加入7g正丁醇和3g乙酸丁酯，搅拌30min，得到组分A。称取15g固化剂，加入2.1g正丁醇和0.9g乙酸丁酯，搅拌30min，得到组分B。混合组分A和组分B，搅拌30min，即得对照组环氧树脂涂料。
实施例6
(1)同实施例1。
(2)称取50g聚氨酯树脂，加入20g乙酸丁酯，6.5g囊芯为二羟基聚二甲基硅氧烷、催化剂与粘合促进剂的第二微胶囊，0.65g囊芯为双丙基硫丙基醚硼酸酯甲基二甲氧基硅氧烷的第一微胶囊，搅拌1h，加入25g多异氰酸酯类固化剂，搅拌1h，得到自修复聚氨酯树脂涂料。
实施例7
(1)同实施例1。
(2)称取50g酚醛树脂，5.5g囊芯为二羟基聚二甲基硅氧烷、催化剂与粘合促进剂的第二微胶囊，0.55g囊芯为双丙基硫丙基醚硼酸酯甲基二甲氧基硅氧烷的第一微胶囊，10g丁醇和15g二甲苯，搅拌1h，加入5g聚酰胺固化剂，搅拌30min，得到自修复酚醛树脂涂料。
实施例8
(1)同实施例1。
(2)称取50g水性聚氨酯树脂类商用汽车面漆、6g囊芯为二羟基聚二甲基硅氧烷、催化剂与粘合促进剂的第二微胶囊、0.6g囊芯为双丙基硫丙基醚硼酸酯甲基二甲氧基硅氧烷的第一微胶囊，加入15g去离子水、5g交联剂，在分散机中分散混合3h，得到自修复汽车面漆。
双(烯丙氧基)甲基硼酸酯的核磁共振氢谱和核磁共振硼谱见图1。
囊芯为二羟基聚二甲基硅氧烷、催化剂与粘合促进剂的第二微胶囊的光学图像和扫描电子显微图像见图2。
自修复性能试验：
实施例1制备的含有微胶囊的实验组环氧树脂涂料与对照组普通环氧树脂涂料分别涂布在Q235钢板上，固化完全后在涂层上划叉，大气环境下放置三天，进行耐中性盐雾测试。实验结果表明对照组环氧树脂涂层耐中性盐雾时间为300小时，实验组中 微胶囊含量分别为11％，12％，13％，14％和15％的自修复环氧树脂涂层耐中性盐雾分别为650，660，680，700和720小时。
在实验组自修复环氧树脂涂层上划叉，大气环境下放置三天后，在涂层划叉处再次划叉，大气环境下放置三天，进行耐中性盐雾测试。实验结果表明实验组中微胶囊含量分别为11％，12％，13％，14％和15％的自修复环氧树脂涂层耐中性盐雾分别为630，640，660，680和700小时。
以此类推，在实验组自修复环氧树脂涂层上同一个地方划叉，大气环境下放置三天，循环三次后，进行耐中性盐雾测试。实验结果表明实验组中微胶囊含量分别为11％，12％，13％，14％和15％的自修复环氧树脂涂层耐中性盐雾分别为620，630，650，670和690小时。
以上所述，仅为本发明较佳实施例而已，故不能依此限定本发明实施的范围，即依本发明专利范围及说明书内容所作的等效变化与修饰，皆应仍属本发明涵盖的范围内。
工业实用性
本发明公开了一种室温下可多次自修复的微胶囊、制备方法及应用，采用水包油乳液原位聚合的方法制备以含有可逆硼酸酯键的硅氧烷偶联剂为囊芯，以脲醛树脂为囊壁的微胶囊，与以二羟基聚二甲基硅氧烷、粘合促进剂和催化剂为囊芯，以脲醛树脂为囊壁的微胶囊共同使用。利用微胶囊的特点和可逆硼酸酯键的性质，本发明有效改善高分子材料性能，达到可快速修复以及可多次重复修复微裂纹，防止微裂纹扩散造成材料宏观损坏的效果，极大延长材料的使用寿命，进而广泛应用于汽车面漆、汽车底漆、智能家居漆、智能家居零件，电子电气密封胶等领域,具有工业实用性。

Claims (12)

  1. 一种室温下可多次自修复的微胶囊，其特征在于：包括第一微胶囊和第二微胶囊；
    所述第一微胶囊的囊壁为脲醛树脂，囊芯为双丙基硫丙基醚硼酸酯甲基二甲氧基硅氧烷、催化剂和粘合促进剂，其中双丙基硫丙基醚硼酸酯甲基二甲氧基硅氧烷、催化剂和粘合促进剂质量比为1：0.005～0.015：0.002～0.005；
    所述第二微胶囊的囊壁为脲醛树脂，囊芯为二羟基聚二甲基硅氧烷、催化剂和粘合促进剂，其中二羟基聚二甲基硅氧烷、催化剂和粘合促进剂质量比为1：0.005～0.015：0.002～0.005；
    所述第一微胶囊和第二微胶囊的囊壁和囊芯的质量比为1：2.5～5。
  2. 根据权利要求1所述的一种室温下可多次自修复的微胶囊，其特征在于：所述催化剂包括二月桂酸二丁基锡，所述粘合促进剂为甲基丙烯酰氧基丙基三乙氧基硅烷或双[3-(三甲氧基甲硅烷基)丙基]胺。
  3. 一种室温下可多次自修复的微胶囊的制备方法，其特征在于，包括如下步骤：
    一)可逆硼酸酯键的硅氧烷偶联剂的制备：通过硼酸与3-烯丙氧基-1,2-丙二醇反应和硫醇-烯点击化学反应得到双丙基硫丙基醚硼酸酯甲基二甲氧基硅氧烷；
    二)微胶囊的组装与混合：通过水包油乳液原位聚合制备囊壁为脲醛树脂，囊芯为双丙基硫丙基醚硼酸酯甲基二甲氧基硅氧烷、催化剂与粘合促进剂的第一微胶囊，和囊壁为脲醛树脂，囊芯为二羟基聚二甲基硅氧烷、催化剂与粘合促进剂的第二微胶囊。
  4. 根据权利要求3所述的一种室温下可多次自修复的微胶囊的制备方法，其特征 在于，所述步骤一)可逆硼酸酯键的硅氧烷偶联剂的制备的合成路线为：
    Figure PCTCN2020112811-appb-100001
  5. 根据权利要求3所述的一种室温下可多次自修复的微胶囊的制备方法，其特征在于，所述步骤一)可逆硼酸酯键的硅氧烷偶联剂的制备包括如下步骤：
    1)将硼酸和第一溶剂混合，用KOH调pH约为9～11，加入3-烯丙氧基-1,2-丙二醇，在20～40℃下搅拌反应4～8h，100～140℃下搅拌蒸发除去第一溶剂，最后在100～140℃真空下干燥，即得双(烯丙氧基)甲基硼酸酯；
    2)取步骤1)所得的双(烯丙氧基)甲基硼酸酯和巯丙基甲基二甲氧基硅烷在氮气保护下溶于第二溶剂中，加入光引发剂2-羟基-2-甲基苯丙酮，在室温365nm紫外光下搅拌反应0.5～1.5h，室温真空干燥，即得双丙基硫丙基醚硼酸酯甲基二甲氧基硅氧烷；
  6. 根据权利要求5所述的一种室温下可多次自修复的微胶囊的制备方法，其特征在于：所述第一溶剂为去离子水，第二溶剂为三氯甲烷或正己烷。
  7. 根据权利要求5所述的一种室温下可多次自修复的微胶囊的制备方法，其特征在于：所述硼酸和3-烯丙氧基-1,2-丙二醇的质量比为2：8～9，所述双(烯丙氧基)甲基硼酸酯、巯丙基甲基二甲氧基硅烷与2-羟基-2-甲基苯丙酮的质量比为6：7～8：0.1～0.3。
  8. 根据权利要求3所述的一种室温下可多次自修复的微胶囊的制备方法，其特征 在于，所述步骤二)微胶囊的组装与混合包括如下步骤：
    1)将乳化剂、蒸馏水、脲、氯化铵和间苯二酚混合，搅拌均匀，加入步骤一)制备的双丙基硫丙基醚硼酸酯甲基二甲氧基硅氧烷、催化剂二月桂酸二丁基锡和相应粘合促进剂，用甲酸调节pH为3～4，同时调节转速为500～2000rpm剪切乳化5～20min以调节微胶囊大小，加入消泡剂正辛醇除去表面气泡，加入37wt％甲醛溶液，以1℃/min的速度升温至60℃，保持转速反应1～3小时，加入5wt％～20wt％脲继续保持转速保温反应2～4h，离心分离，并用蒸馏水洗涤多次，抽滤后在常温空气中干燥24～48h，得到第一微胶囊；
    2)将步骤1)中的双丙基硫丙基醚硼酸酯甲基二甲氧基硅氧烷替换为二羟基聚二甲基硅氧烷，制备得到第二微胶囊；
    3)将步骤1)得到第一微胶囊与步骤2)得到第二微胶囊物理混合。
  9. 根据权利要求8所述的一种室温下可多次自修复的微胶囊的制备方法，其特征在于：所述乳化剂为十二烷基苯磺酸钠、十二烷基硫酸钠或OP-10，乳化剂的浓度为0.3wt％～1.0wt％。
  10. 根据权利要求8所述的一种室温下可多次自修复的微胶囊的制备方法，其特征在于：所述脲、氯化铵、间苯二酚和37wt％甲醛溶液的质量比为1：0.1：0.1：3～5。
  11. 一种室温下可多次自修复的微胶囊在高分子材料中的应用。
  12. 根据权利要求11所述的一种室温下可多次自修复的微胶囊在高分子材料中的应用，其特征在于：将第一微胶囊、第二微胶囊以1:10～20的质量比混合，并均匀分散于高分子树脂涂料中，所述高分子树脂涂料包括环氧树脂涂料、聚氨酯树脂涂料、酚醛树脂涂料。
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