WO2015074342A1 - 一种以聚氨酯为壁材的环氧微胶囊的制备方法 - Google Patents

一种以聚氨酯为壁材的环氧微胶囊的制备方法 Download PDF

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WO2015074342A1
WO2015074342A1 PCT/CN2014/071285 CN2014071285W WO2015074342A1 WO 2015074342 A1 WO2015074342 A1 WO 2015074342A1 CN 2014071285 W CN2014071285 W CN 2014071285W WO 2015074342 A1 WO2015074342 A1 WO 2015074342A1
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isocyanate
epoxy
water
polyurethane
preparation
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PCT/CN2014/071285
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French (fr)
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朱光明
邬治平
汤皎宁
董必钦
王险峰
韩宁旭
邢峰
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深圳大学
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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
    • B01J13/06—Making microcapsules or microballoons by phase separation
    • B01J13/14—Polymerisation; cross-linking
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step

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  • This invention relates to the field of self-healing materials, and more particularly to the field of self-healing concrete. In particular, it relates to the preparation of microcapsule-type epoxy resin repair agents in self-healing materials.
  • Microcapsule-type self-repairing concrete refers to a structural composite material in which a liquid repair agent is microencapsulated and then pre-embedded with a coarse and fine aggregate in a cement matrix. When the concrete member is microcracked, the stress at the crack tip causes the microcapsule to rupture, and the repair agent flows out, causing the crack to autonomously bridge.
  • Epoxy resin is commonly used as a repairing agent in engineering. Therefore, the preparation of epoxy microcapsules is the most important step to achieve the self-repair of micro cracks in concrete.
  • Common epoxy microcapsules are mostly made of urea-formaldehyde resin as a wall material by in-situ polymerization.
  • Polyurethane is a type of polymer commonly used in the industry. It is a macromolecular compound containing a repeating carbamate group in the main chain by addition of a di(or poly)isocyanate and a di(or)hydroxy compound. Isocyanate has a high degree of unsaturation, is a nucleophilic center, is chemically active, and easily reacts with active hydrogen. In addition to alcohol, isocyanate can also react with water, amines, alcohol amines, phenols, thiols, carboxylic acids, urea.
  • a large amount of water is present in the continuous phase of the conventional preparation method of the epoxy microcapsules, and water reacts with the isocyanate to form a polyurea instead of a polyurethane. Further, in the presence of an amine, the isocyanate is also easily reacted with an epoxy group to form an oxazolidinone ring. If the di(or poly) isocyanate is reacted with a di(or poly) epoxy compound, polymerization occurs to form a polyoxazolidinone to cure the epoxy.
  • the technical problem to be solved by the present invention is to provide a method for preparing an epoxy microcapsule using polyurethane as a wall material to overcome the deficiencies of the prior art.
  • the technical solution adopted by the present invention is to provide a method for preparing an epoxy microcapsule using polyurethane as a wall material, comprising the steps of: preparing an isocyanate-terminated polyurethane prepolymer; and the isocyanate-terminated polyurethane prepolymer Mix with epoxy resin, add emulsifier and water, stir and emulsify to make oil-in-water emulsion; heat up, interface reaction to form capsule wall; filter, rinse the filtrate with water, dry, then make polyurethane as wall epoxy
  • the resin is a microcapsule of a core material.
  • the preparation method provided by the invention can produce microcapsules in which polyurethane is a wall material epoxy resin as a core material, and the method overcomes the adverse effect of water in the formation process of polyurethane.
  • the excess isocyanate is first reacted with a hydroxy compound to obtain an isocyanate-terminated polyurethane prepolymer, and the prepolymer is mixed with the core material epoxy to prepare an oil-in-water emulsion, and at an appropriate temperature and in the presence of a catalyst,
  • the prepolymer reacts with water and undergoes chain extension to obtain epoxy microcapsules using polyurethane as a wall material.
  • the technical scheme of the invention ensures the formation of polyurethane, and at the same time, the curing reaction of the isocyanate or the intermediate product to replace the urea and the epoxy does not occur during the preparation process, and the prepared polyurethane/epoxy microcapsule has good sphericity, smooth surface and thick wall. Uniform, can be used to prepare microcapsule self-healing materials.
  • Example 1 is a Fourier infrared analysis diagram of a microcapsule obtained in Example 1 of the present invention.
  • Figure 2 is an SEM image of the microcapsules obtained in Example 1 of the present invention.
  • the invention provides a preparation method of epoxy microcapsules using polyurethane as a wall material, comprising the following steps: S1: preparing an isocyanate terminated polyurethane prepolymer;
  • the process of the step S1 is: mixing a hydroxy compound, an isocyanate, a solvent, and a catalyst, and heating to 50 to 80 ° C to 100 to 500
  • the polyurethane prepolymer is obtained by stirring the reaction at rpm for 2 to 3 hours;
  • the hydroxy compound includes a dihydroxy compound or a polyhydroxy compound;
  • the isocyanate includes a diisocyanate or a polyisocyanate.
  • the dihydroxy compound is a polyether diol, a polyester diol, ethylene glycol (EG), 1,4-butanediol (BDO), 1,2-propanediol (1,2-PG), 1 , 6-hexanediol (HD), neopentyl glycol (NPG), diethylene glycol (DEG), dipropylene glycol (DPG), 1,2,6-hexanediol, methylpropanediol ( Mixture of one or more of MPD), bisphenol A, preferably BDO.
  • EG ethylene glycol
  • BDO 1,4-butanediol
  • 1,2-propanediol 1,2-propanediol
  • HD 6-hexanediol
  • NPG neopentyl glycol
  • DEG diethylene glycol
  • DPG dipropylene glycol
  • 1,2,6-hexanediol 1,2,6-hexanediol
  • the polyether diol refers to polyvinyl alcohol, polyoxypropylene diol (PPG), polybutadiene diol (HTPB), oxytetramethylene glycol (PTMG); polyester diol refers to poly Ethylene glycol adipate diol (PEA), polyethylene adipate glycol propylene glycol diol, polyadipate diethylene glycol diol (PDA), polyethylene adipate -diethylene glycol ester diol, polyadipate-1,4-butylene glycol diol (PBA), polyethylene adipate-1,4-butylene glycol diol, poly Adipic acid neopentyl glycol-1,6-hexanediol diol, poly- ⁇ -caprolactone diol (PCL), poly(dicarbonate 1,6-hexanediol diol (PHC).
  • PPG polyoxypropylene diol
  • HTPB poly
  • the polyhydroxy compound means a trihydric or higher alcohol, and includes a polyether polyol, a polyester polyol, pentaerythritol (PER), glycerin, trimethylolpropane (TMP), and trishydroxyethylpropane.
  • the polyether polyol means propylene oxide triol (PPT);
  • the polyester polyol means poly ⁇ -caprolactone triol.
  • the hydroxy compound is preferably 1,4-butanediol (BDO) or pentaerythritol (PER).
  • the diisocyanate means toluene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), 1,5-naphthalene diisocyanate (NDI), hexamethylene diisocyanate (HDI), B Benzene diisocyanate (EDI), 4,4'-dicyclohexenemethane diisocyanate (H12MDI), 4,6-xylene diisocyanate (XDI), isophorone diisocyanate (IPDI), p-phenylene diisocyanate ( PPDI), cyclohexyl diisocyanate (THDI), 3,3'-dimethylbiphenyl-4,4' diisocyanate (TODI), 3,3'-dimethyl-4,4'-diphenylmethane Mixing one or more of the diisocyanates, preferably IPDI, MDI, TDI.
  • the polyisocyanate means a trivalent or higher isocyanate, including 4,4',4"-triphenylmethane triisocyanate (TTI), tris(4-isocyanatephenyl) thiophosphate (TPTI), tetraisocyanate, a mixture of one or more of polymethylene polyphenyl polyisocyanate (PAPI) wherein the tetraisocyanate is 2,2'-dimethyl-3,3',5,5'-triphenylmethane Tetraisocyanate (DTTI) and triphenylmethane-2,2'-dimethyl-3,3',5,5'-tetraisocyanate (TPMDMTI).
  • TTI 4,4',4"-triphenylmethane triisocyanate
  • TPTI tris(4-isocyanatephenyl) thiophosphate
  • tetraisocyanate a mixture of one or more of polymethylene polyphenyl polyisocyanate
  • the isocyanate is preferably at least one of IDPI, MDI, TDI and DTTI.
  • the molar ratio of the -OH/-NCO group of the dihydroxy compound or polyhydroxy compound to the diisocyanate or polyisocyanate used in the present method is 1:1.8 to 2.2;
  • the solvent is preferably a mixture of one or more of acetone, methyl ethyl ketone, cyclohexanone, toluene, xylene, ethyl acetate, butyl acetate, tetrahydrofuran, dioxane, dimethylformamide;
  • the catalyst is added in an amount of 0.2 to 0.4% by weight based on the total mass of the diisocyanate or polyisocyanate, and the catalyst refers to an organometallic catalyst including: stannous octoate, dibutyltin dilaurate (DBTDL), lead isooctanoate And a mixture of one or more of lead octoate, zinc isooctanoate, zinc octoate, iron acetylacetonate, zinc naphthenate, cobalt naphthenate, and potassium oleate, preferably DBTDL.
  • DBTDL dibutyltin dilaurate
  • lead isooctanoate And a mixture of one or more of lead octoate, zinc isooctanoate, zinc octoate, iron acetylacetonate, zinc naphthenate, cobalt naphthenate, and potassium oleate, preferably DBTDL.
  • the mass ratio of the isocyanate-terminated polyurethane prepolymer, epoxy, emulsifier (dry weight) and water is 1:1 ⁇ 2:0.05 ⁇ 0.15:4 ⁇ 20, stirring rate
  • the temperature is from 600 to 1200 rpm
  • the emulsification reaction temperature is from 3 to 30 ° C
  • the emulsification reaction time is from 5 to 10 minutes.
  • the emulsifier is styrene-maleic anhydride block copolymer (SMA), polyoxyethylene polyoxypropylene, ethylenediamine polyoxyethylene-polyoxypropylene block polyether, heteroblock polyether, Tween (tween), span, polyvinyl alcohol (PVA), alkylphenol ethoxylates, fatty alcohol polyoxyethylene ethers, alkyl glycosides (alkyl A mixture of one or more of polyglycoside, APG), preferably SMA, PVA.
  • SMA styrene-maleic anhydride block copolymer
  • PVA polyoxyethylene polyoxypropylene
  • ethylenediamine polyoxyethylene-polyoxypropylene block polyether heteroblock polyether
  • Tween tween
  • span polyvinyl alcohol
  • PVA polyvinyl alcohol
  • alkylphenol ethoxylates alkylphenol ethoxylates
  • fatty alcohol polyoxyethylene ethers alkyl
  • the reaction temperature is 50 to 75 ° C
  • the reaction time is 1 to 3 hours.
  • the polyurethane/epoxy microcapsules prepared by the invention have good sphericity, smooth surface and uniform wall thickness, and can be used for preparing microcapsule self-repairing materials. The following is further described in conjunction with specific embodiments.
  • the reaction solution was filtered, and the filter cake was washed with distilled water, filtered, and repeated three times, and then dried at 45 ° C for 12 h to obtain a polyurethane-coated epoxy microcapsule.
  • Fourier infrared analysis was performed on the microcapsules. The experimental results are shown in Fig. 1.
  • the wall material of the capsule is polyurethane. SEM observation As shown in Fig. 2, the epoxy microcapsules made of polyurethane as the wall material have good sphericity, smooth surface and uniform wall thickness, and the particle size is 20-70 ⁇ m.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Dispersion Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

一种以聚氨酯为壁材的环氧微胶囊的制备方法，包括以下步骤：制备以异氰酸酯封端的聚氨酯预聚体；将以异氰酸酯封端的聚氨酯预聚体与环氧树脂混合，加入乳化剂和水，搅拌，乳化反应制成水包油乳液；升温，界面反应形成囊壁；过滤，将沉淀物用水漂洗，干燥，即得以聚氨酯为壁材环氧树脂为芯材的微胶囊。

Description

一种以聚氨酯为壁材的环氧微胶囊的制备方法 技术领域
本发明涉及自修复材料领域，尤其是涉及自修复混凝土领域。具体地说，涉及到自修复材料中微胶囊型环氧树脂修复剂的制备。
 背景技术
自修复材料是智能材料中的一种，当其遭受破坏时，能自主修复其中的裂纹、空洞等缺陷。微胶囊型自修复混凝土是指将液态修复剂微胶囊化，然后与粗细骨料一起预先包埋水泥基体中的一种结构性复合材料。当混凝土构件产生微裂纹时，裂纹尖端的应力使微胶囊破裂，修复剂流出，使裂纹自主弥合。工程上常用环氧树脂作为修复剂，因此制备环氧微胶囊是实现混凝土对微裂纹自主修复的最重要一步。常见的环氧微胶囊多以脲醛树脂作为壁材，通过原位聚合法制得。
聚氨酯是工业上常用的一类聚合物，它是由二（或多）异氰酸酯与二（或多）羟基化合物加聚而成，在主链上含有重复氨基甲酸酯基团的大分子化合物。异氰酸酯具有高度的不饱和性，是个亲核中心，化学性质活泼，易与活泼氢反应，除醇以外，异氰酸酯还能与水、胺、醇胺、酚、硫醇、羧酸、脲反应。环氧微胶囊常用制备方法的连续相中存在大量的水，水与异氰酸酯反应生成聚脲，而不是聚氨酯。此外，在胺存在的情况下，异氰酸酯还易与环氧基团反应，生成恶唑烷酮环。如是二（或多）异氰酸酯与二（或多）环氧化合物反应，则发生聚合，生成聚恶唑烷酮，使环氧固化。这两点给制备聚氨酯/环氧微胶囊带来了技术上的障碍。
有文献 [异氰酸酯与醇、水反应规律的研究，顾继友，高振华，科学技术与工程，3（5），2003，462-463] 进一步表明，异氰酸酯与水的反应速率比醇快，在醇与水都存在的情况下，醇的浓度要远高于水的浓度（10倍以上）才能使主产物为聚氨酯，显然，这个条件在水包油乳液体系中是难以达到的。
 技术问题
本发明所要解决的技术问题在于提供一种以聚氨酯为壁材的环氧微胶囊的制备方法，以克服现有技术的不足。
技术解决方案
本发明所采用的技术方案是提供一种以聚氨酯为壁材的环氧微胶囊的制备方法，包括以下步骤：制备以异氰酸酯封端的聚氨酯预聚体；将所述以异氰酸酯封端的聚氨酯预聚体与环氧树脂混合，加入乳化剂和水，搅拌，乳化，制成水包油乳液；升温，界面反应形成囊壁；过滤，将滤出物用水漂洗，干燥，即得以聚氨酯为壁材环氧树脂为芯材的微胶囊。
有益效果
本发明所提供制备方法可制得聚氨酯为壁材环氧树脂为芯材的微胶囊，该方法克服了在聚氨酯形成过程中水的不利影响。先将过量的异氰酸酯与羟基化合物反应，得到以异氰酸酯封端的聚氨酯预聚体，再将预聚体与芯材环氧混合，制成水包油乳液，在适当温度和催化剂存在的条件下，使预聚体与水发生界面反应，进行扩链，得到以聚氨酯为壁材的环氧微胶囊。本发明技术方案保证了聚氨酯的形成，同时在制备过程中不会发生异氰酸酯或中间产物取代脲与环氧的固化反应，所制得的聚氨酯/环氧微胶囊球形度好、表面光滑、壁厚均匀，可用于制备微胶囊型自修复材料。
附图说明
图1是本发明实施例1所制得微胶囊的傅里叶红外分析图；
图2是本发明实施例1所制得微胶囊的SEM图。
 本发明的实施方式
为了使本发明所要解决的技术问题、技术方案及有益效果更加清楚明白，以下结合附图及实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
本发明提供一种以聚氨酯为壁材的环氧微胶囊的制备方法，包括以下步骤：S1：制备以异氰酸酯封端的聚氨酯预聚体；
S2： 将所述以异氰酸酯封端的聚氨酯预聚体与环氧树脂混合，加入乳化剂和水，搅拌，乳化，制成水包油乳液；
S3：升温，界面反应形成囊壁；
S4：过滤，将沉淀物用水漂洗，干燥，即得以聚氨酯为壁材环氧树脂为芯材的微胶囊。
具体地，所述步骤S1的过程为：将羟基化合物、异氰酸酯、溶剂、催化剂混合，升温至50~80℃，以100~500 rpm转速搅拌反应2~3小时得到聚氨酯预聚体；所述羟基化合物包括二羟基化合物或多羟基化合物；所述异氰酸酯包括二异氰酸酯或多异氰酸酯。
其中，二羟基化合物为聚醚二元醇、聚酯二元醇、乙二醇（EG）、1,4-丁二醇（BDO）、1,2-丙二醇（1,2-PG）、1,6-己二醇（HD）、新戊二醇（NPG）、一缩二乙二醇（DEG）、一缩二丙二醇（DPG）、1,2,6-己二醇、甲基丙二醇（MPD）、双酚A中的一种或几种的混合，优选BDO。其中，聚醚二元醇是指聚乙烯醇、聚氧化丙烯二醇（PPG）、聚丁二烯二醇（HTPB）、氧四甲撑二醇（PTMG）；聚酯二元醇是指聚己二酸乙二醇酯二醇（PEA）、聚己二酸乙二醇-丙二醇酯二醇、聚己二酸一缩二乙二醇酯二醇（PDA）、聚己二酸乙二醇-一缩二乙二醇酯二醇、聚己二酸-1,4-丁二醇酯二醇（PBA）、聚己二酸乙二醇-1,4-丁二醇酯二醇、聚己二酸新戊二醇-1,6-己二醇酯二醇、聚ε-己内酯二醇（PCL）、聚碳酸1,6-己二醇酯二醇（PHC）。
其中，多羟基化合物是指三元以上的醇，包括聚醚多元醇、聚酯多元醇、季戊四醇（PER）、丙三醇、三羟甲基丙烷（TMP）、三羟乙基丙烷。其中，聚醚多元醇是指氧化丙烯三醇（PPT）；聚酯多元醇是指聚ε-己内酯三醇。
作为本发明的进一步改进，羟基化合物优选1,4-丁二醇（BDO）或季戊四醇（PER）。
其中，二异氰酸酯是指甲苯二异氰酸酯（TDI）、4,4′-二苯基甲烷二异氰酸酯（MDI）、1,5-萘二异氰酸酯（NDI）、六亚甲基二异氰酸酯（HDI）、乙苯二异氰酸酯（EDI）、4,4′-二环己烯甲烷二异氰酸酯（H12MDI）、4,6-二甲苯二异氰酸酯（XDI）、异佛尔酮二异氰酸酯（IPDI）、对苯二异氰酸酯（PPDI）、环己基二异氰酸酯（THDI）、3,3′-二甲基联苯-4,4′二异氰酸酯（TODI）、3,3′-二甲基-4,4′-二苯基甲烷二异氰酸酯中的一种或几种的混合，优选IPDI、MDI、TDI。
其中，多异氰酸酯是指三元以上的异氰酸酯，包括4,4′,4″-三苯基甲烷三异氰酸酯（TTI）、硫代磷酸三（4-异氰酸酯基苯基）（TPTI）、四异氰酸酯、多亚甲基多苯基多异氰酸酯（PAPI）中的一种或几种的混合，其中，四异氰酸酯为2,2′-二甲基-3,3′,5,5′-三苯基甲烷四异氰酸酯（DTTI）和三苯基甲烷-2,2′-二甲基-3,3′,5,5′-四异氰酸酯（TPMDMTI）。
作为本发明的进一步改进，异氰酸酯优选IDPI、MDI、TDI及DTTI中的至少一种。
进一步地，本法所采用二羟基化合物或多羟基化合物与二异氰酸酯或多异氰酸酯的-OH/-NCO基团摩尔比为1:1.8~2.2；
进一步地，溶剂优选丙酮、甲乙酮、环己酮、甲苯、二甲苯、醋酸乙酯、醋酸丁酯、四氢呋喃、二氧六环、二甲基甲酰胺中的一种或几种的混合；
进一步地，催化剂的加入量为二异氰酸酯或多异氰酸酯总质量的0.2~0.4%，所述催化剂是指有机金属类催化剂，包括：辛酸亚锡、二丁基锡二月桂酸酯（DBTDL）、异辛酸铅、辛酸铅、异辛酸锌、辛酸锌、乙酰丙酮铁、环烷酸锌、环烷酸钴、油酸钾中的一种或几种的混合，优选DBTDL。
具体地，在所述步骤b中，以异氰酸酯封端的聚氨酯预聚体、环氧、乳化剂（干重）和水的质量比为1:1~2:0.05~0.15:4~20，搅拌速率为600~1200rpm，乳化反应温度为3~30℃，乳化反应时间为5~10分钟。其中，乳化剂为苯乙烯-马来酸酐嵌段共聚物（SMA）、聚氧乙烯聚氧丙烯、乙二胺聚氧乙烯-聚氧丙烯嵌段聚醚、杂嵌段型聚醚、吐温（tween）、司班（span）、聚乙烯醇（PVA）、烷基酚聚氧乙烯醚、脂肪醇聚氧乙烯醚、烷基糖苷（alkyl polyglycoside，APG）中的一种或几种的混合，优选SMA、PVA。
具体地，在所述步骤c中，反应温度为50 ~ 75℃，反应时间为1 ~ 3小时。
本发明所制得的聚氨酯/环氧微胶囊球形度好、表面光滑、壁厚均匀，可用于制备微胶囊型自修复材料。以下结合具体实施例进一步说明。
实施例1
取1.38 g丙三醇、10 g IPDI、5 g丙酮、0.03 g催化剂DBTDL，混合均匀，加入到三口烧瓶中，在60℃、300 rpm转速下搅拌反应2~3 h，得到以异氰酸酯封端的聚氨酯预聚体；将预聚体与18 g环氧E-51混合均匀后，加入到装有100 g 浓度为1wt%的PVA水溶液的三口烧瓶中，在20℃、1000 rpm转速下乳化10 min， 60℃保温反应1~2 h。冷却后将反应液过滤，滤饼用蒸馏水清洗，再过滤，反复3次，然后45℃干燥12 h，得到聚氨酯包覆的环氧微胶囊。对微胶囊进行傅里叶红外分析，实验结果如图1所示，在1720、1650和773 cm-1处存在聚氨酯中酯键（O=C-O）的特征吸收峰，证实本法所制得微胶囊的壁材为聚氨酯。SEM观察如图2所示，所制得以聚氨酯为壁材的环氧微胶囊球形度好、表面光滑、壁厚均匀，粒径20~70 μm。
实施例2
取3 g 聚乙二醇、6 g IPDI、5 g 丙酮、0.03 g催化剂DBTDL，混合均匀，加入到三口烧瓶中，在60℃、300 rpm转速下搅拌反应2~3 h，得到以异氰酸酯封端的聚氨酯预聚体；将预聚体与10 g环氧E-51混合均匀后，加入到装有100 g 浓度为1 wt%的PVA水溶液的三口烧瓶中，在20℃、1000 rpm转速下乳化10 min， 60℃保温反应1~2 h。冷却后将反应液过滤，滤饼用蒸馏水清洗，再过滤，反复3次，然后45℃干燥12 h，得到聚氨酯包覆的环氧微胶囊。
实施例3
取1.38 g 丙三醇、10 g IPDI、5 g甲苯、0.03 g催化剂DBTDL，混合均匀，加入到三口烧瓶中，在60℃、300 rpm转速下搅拌反应2~3h，得到以异氰酸酯封端的聚氨酯预聚体；将预聚体与18 g环氧E-51混合均匀后，加入到含100 g浓度为1 wt%的SMA（Scripset 520）水溶液的三口烧瓶中，在20℃、1000 rpm转速下乳化10 min，60℃保温反应1~2 h，将反应液过滤，滤饼用蒸馏水清洗，再过滤，反复3次，然后45℃干燥12 h，得到聚氨酯包覆环氧微胶囊。
以上所述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的精神和原则之内所作的任何修改、等同替换和改进等，均应包含在本发明的保护范围之内。

Claims (10)

  1. 一种以聚氨酯为壁材的环氧微胶囊的制备方法，其特征在于，包括以下步骤：
    S1：制备以异氰酸酯封端的聚氨酯预聚体；
    S2： 将所述以异氰酸酯封端的聚氨酯预聚体与环氧树脂混合，加入乳化剂和水，搅拌，乳化制成水包油乳液；
    S3：升温，界面反应形成囊壁；
    S4：过滤，将滤出物用水漂洗，干燥，即得以聚氨酯为壁材的环氧微胶囊。
  2. 根据权利要求1所述的制备方法，其特征在于，所述制备以异氰酸酯封端的聚氨酯预聚体的步骤包括：将羟基化合物、异氰酸酯、溶剂、催化剂混合，升温至50~80℃，以100~500 rpm转速搅拌反应2~3小时得到聚氨酯预聚体；所述羟基化合物为二羟基化合物或多羟基化合物；所述异氰酸酯包括二异氰酸酯或多异氰酸酯。
  3. 根据权利要求2所述的制备方法，其特征在于，所述羟基化合物与所述异氰酸酯的-OH/-NCO基团摩尔比为1: 1.8~2.2。
  4. 根据权利要求2或3所述的制备方法，其特征在于，所述羟基化合物为1,4-丁二醇或季戊四醇。
  5. 根据权利要求2或3所述的制备方法，其特征在于，所述异氰酸酯选自4,4′-二苯基甲烷二异氰酸酯、甲苯二异氰酸酯、2,2′-二甲基-3,3′,5,5′-三苯基甲烷四异氰酸酯。
  6. 根据权利要求1所述的制备方法，其特征在于，所述以异氰酸酯封端的聚氨酯预聚体、环氧、乳化剂和水的质量比为1: 1~2 : 0.05~0.15 : 4~20。
  7. 根据权利要求1所述的制备方法，其特征在于，步骤S2中所述搅拌的速率为600~1200 rpm，所述乳化的温度为3~30℃，所述乳化的时间5~10分钟。
  8. 根据权利要求1所述的制备方法，其特征在于，所述乳化剂选自苯乙烯-马来酸酐嵌段共聚物、聚乙烯醇中的至少一种。
  9. 根据权利要求1所述的制备方法，其特征在于，所述界面反应的温度为50 ~ 75℃，界面反应的时间为1 ~ 3小时。
  10. 根据权利要求1所述的制备方法，其特征在于，所述催化剂选自辛酸亚锡、二丁基锡二月桂酸酯、异辛酸铅、辛酸铅、异辛酸锌、辛酸锌、乙酰丙酮铁、环烷酸锌、环烷酸钴、油酸钾中的一种或几种的混合，所述催化剂的加入量为二异氰酸酯或多异氰酸酯总质量的0.2 ~ 0.4 %。
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