WO2015074343A1 - 一种混凝土水性修复剂的微胶囊化方法 - Google Patents

一种混凝土水性修复剂的微胶囊化方法 Download PDF

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WO2015074343A1
WO2015074343A1 PCT/CN2014/071293 CN2014071293W WO2015074343A1 WO 2015074343 A1 WO2015074343 A1 WO 2015074343A1 CN 2014071293 W CN2014071293 W CN 2014071293W WO 2015074343 A1 WO2015074343 A1 WO 2015074343A1
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water
concrete
phase
aqueous
repairing agent
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PCT/CN2014/071293
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English (en)
French (fr)
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朱光明
邢峰
宋超男
周玉明
汤皎宁
董必钦
王险峰
韩宁旭
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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
    • B01J13/18—In situ polymerisation with all reactants being present in the same phase
    • B01J13/185—In situ polymerisation with all reactants being present in the same phase in an organic phase
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
    • C04B20/10—Coating or impregnating
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/72—Repairing or restoring existing buildings or building materials

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  • the invention belongs to the technical field of self-healing materials, and in particular relates to a micro-encapsulation method for a concrete aqueous repairing agent.
  • Concrete is a hydraulic porous cementitious artificial stone material. Due to its small elongation and low tensile strength, it is easy to produce shrinkage cracks and load cracks. The existence of cracks greatly affects the durability of concrete engineering.
  • One solution is to repair the cracks. However, manual repair is only applicable to external cracks. Due to the unpredictability of cracks and the limitations of crack detection technology, a large number of internal cracks are difficult to be discovered and repaired. Therefore, it is necessary to develop "smart" concrete with self-repairing function.
  • One way to achieve self-repairing concrete is to pre-embed the restorative agent in the concrete matrix. When the crack propagates, the embedded repair agent is released by a physical or chemical factor to automatically repair the crack.
  • the restorative agent is generally embedded in a tiny fibrous tube or in a microcapsule.
  • microcapsule self-repairing concrete has certain technical advantages: one is easy to disperse in concrete, and the other is uniformity, which can repair cracks extending in any direction.
  • microcapsule-type self-repairing concrete the most commonly used epoxy resin is used as a repairing agent.
  • this organic polymer-based repairing agent and the inorganic concrete matrix not only have the problem of poor interface bonding force, but also have aging problems. Since the durability is much lower than that of the concrete matrix, the crack repaired by the organic repair agent gradually loses the ability to break the crack after several years, and the original crack is re-cracked, which becomes a safety hazard.
  • Some inorganic binders such as sodium silicate, aluminum dihydrogen phosphate, etc.
  • Some inorganic binders are also good concrete repair agents. They have a strong bond with the concrete interface and are as durable as concrete without aging problems.
  • most of them are water-soluble silicates, phosphates, borates, sulfates, molybdates, which need to be microencapsulated by water-in-oil (W/O), that is, they are to be
  • W/O water-in-oil
  • the aqueous solution is dispersed in a continuous oil phase, as opposed to the preparation of conventional epoxy microcapsules.
  • the particle size of the W/O microcapsules is relatively small, usually below 10 microns.
  • W/O microcapsules having a particle diameter of several tens to several hundreds of micrometers, and controlling the size and wall thickness of the microcapsules
  • a double emulsion method using water-in-oil-in-water can be used to prepare O/. W microcapsules.
  • the double emulsion method is a two-layer emulsion formed by dispersing an emulsion (commonly referred to as primary emulsion, referred to as colostrum) in another continuous phase, with W/O/W And O/W/O two types, but all have a "two-film three-phase" multi-compartment structure.
  • the W/O/W double emulsion is one in which one or more aqueous phase droplets are contained in the oil phase droplets, and the oil phase droplets containing the aqueous phase droplets are dispersed in a continuous aqueous phase to form a milky emulsion. liquid.
  • the W/O microcapsules are prepared by the double emulsion method of W/O/W, in which an oily polymer solution or an oily polymer monomer is used as an intermediate oil phase, and then the solvent in the polymer solution is evaporated or extracted.
  • the polymer is deposited to form a wall of the capsule, or an initiator or a catalyst is added to the outer aqueous phase (or internal aqueous phase) to polymerize the monomer into a polymer and deposit in the oil phase to form a wall of the capsule.
  • the method for preparing the microcapsules does not need to adjust the pH value, does not need to change the temperature greatly, has low solvent residual amount, is simple in method, and is convenient to operate, and is suitable for coating biologically active water-soluble substances like polypeptides and proteins, and thus in medicine, food and The field of cosmetics and other fields has been widely used.
  • the double emulsion is essentially a non-thermodynamically stable system that is highly unstable and undergoes Ostwald ripening (Ostwald). Ripening), flocculation, coalescence and stratification.
  • the present invention provides a microencapsulation method for a concrete aqueous repair agent.
  • a microencapsulation method for a concrete aqueous repairing agent comprising the following steps:
  • the inner water phase is prepared, and the inner water phase is 0.5 to 3 mol/L of inorganic water-based concrete repairing agent and 0.01 to 2 a wt% aqueous solution of gelling agent;
  • the oil phase being a styrene organic solution having a volume concentration of 50 to 100%;
  • an outer aqueous phase Forming an outer aqueous phase, the outer aqueous phase comprising 0.01 to 3 wt% of a water-soluble styrene polymerization initiator;
  • the double emulsion is heated to 35 to 70 ° C and stirred to obtain microcapsules of the concrete aqueous repairing agent.
  • the microencapsulation method of the concrete water-based repairing agent provided by the invention has low cost, stable and simple process, and is suitable for industrial production.
  • Example 1 is an optical micrograph of a microcapsule of a concrete aqueous repairing agent prepared in Example 1;
  • FIG. 2 is a scanning electron microscope image of a microcapsule of a concrete aqueous repairing agent prepared in the first embodiment
  • Example 3 is a scanning electron micrograph of microcapsules of a concrete aqueous repairing agent prepared in Example 2.
  • the embodiment of the invention provides a microencapsulation method for a concrete aqueous repairing agent, which comprises the following steps:
  • S05 preparing a double emulsion; adding 3 to 5 wt% of an oil-in-water surfactant to the outer aqueous phase, and dissolving and mixing with the colostrum;
  • the inorganic water-based concrete repairing agent is sodium silicate, potassium silicate, lithium silicate, aluminum phosphate (P 2 O 5 /Al 2 O 3 molar ratio of 2.0 to 3.0), sodium tetraborate, tetraboric acid Potassium, sodium molybdate, potassium molybdate, ammonium dimolybdate [(NH 4 ) 2 Mo 2 O 7 • 4H 2 O], ammonium heptamolybdate [(NH 4 ) 6 Mo 7 O 24 • 4H 2 O], Potassium alum [KAl(SO 4 ) 2 •12H 2 O], ammonium alum [NH 4 Al(SO 4 ) 2 •12H 2 O], sodium aluminoquinone [NaAl(SO 4 ) 2 •12H 2 O], aluminum sulfate At least one of zinc sulfate, manganese sulfate, magnesium sulfate, and calcium sulfate.
  • the internal aqueous phase contains 0.01 to 2% by weight of a gelling agent, which is a natural water-soluble polymer, preferably gelatin, carrageenan, Xanthan gum, alginic acid.
  • a gelling agent which is a natural water-soluble polymer, preferably gelatin, carrageenan, Xanthan gum, alginic acid.
  • Sodium alginate (NaAlg) konjac flour, Acacia gum, pectin, agar, carboxymethylcellulose (CMC), hydroxypropyl modified starch (Hydroxypropyl starch) And at least one of carboxymethyl starch (CMS).
  • CMC carboxymethylcellulose
  • CMS carboxymethyl starch
  • the styrene solution does not contain a polymerization inhibitor, and the solvent of the styrene solution is an organic solvent that is not miscible with water, preferably chloroform (chloroform), toluene, xylene, cyclohexanol, methyl At least one of ethyl ketone and diethyl ether.
  • chloroform chloroform
  • toluene xylene
  • cyclohexanol methyl At least one of ethyl ketone and diethyl ether.
  • the water-soluble styrene polymerization initiator means a water-soluble azo initiator or a water-soluble oxidation-reduction initiator.
  • the water-soluble azo initiator is preferably azobisisobutylphosphonium hydrochloride (AIBA, V-50 initiator), azobisisobutyrazoline hydrochloride (AIBI, VA-044 initiator), or Nitrodiacyanate (ACVA, V-501 initiator), azodiisopropylimidazoline (AIP, VA-061 initiator);
  • the oxidant is preferably hydrogen peroxide ( H 2 O 2 ), ammonium persulfate [(NH 4 ) 2 S 2 O 8 ], sodium persulfate (Na 2 S 2 O 8 ), potassium persulfate (K 2 S 2 O 8 ), isopropyl hydrogen peroxide Benzene (CHP), t-but
  • the water-in-oil (W/O) surfactant has an HLB value of 4 to 6 at room temperature in pure water.
  • the volume ratio of the internal aqueous phase to the oil phase during mixing is 1:3 to 4, and the stirring rate is greater than 5000 r/min.
  • the oil-in-water (O/W) surfactant has an HLB value of 8 to 12 at room temperature in pure water.
  • the volume ratio of the colostrum to the external aqueous phase during mixing (colostrum: external aqueous phase) is 1:1.5 to 2.5, and the agitation rate is 15 to 100 r/min.
  • the W/O surfactant and the O/W surfactant are preferably one or more of the following surfactants: sorbitan fatty acid ester polycondensation Oxyethylene ether, grade Tween 20 ⁇ Tween 80; sorbitan fatty acid ester, grade Span 20 ⁇ Span 80; PEG-30 dipolyhydroxystearate, grade Arlacel P135; castor oil polyoxyethylene ether, grades EL35 and EL40; alkylphenol ethoxylates, grades OP 4 ⁇ OP 7; fatty alcohol polyoxyethylene ether, grades AEO3 ⁇ AEO10.
  • the reaction temperature is 35 to 70 ° C
  • the reaction time is 10 to 120 minutes
  • the stirring rate is 15 to 100 r / min.
  • An inert gas is introduced during the reaction.
  • the microencapsulation method of the concrete water-based repairing agent provided by the embodiment of the invention is mainly characterized by selecting and selecting suitable surfactants for oil-in-water (O/W) and water-in-oil (W/O).
  • the amount of the appropriate amount of the gelling agent is added to the internal aqueous phase to block the mutual leakage of water in the internal and external aqueous phases; the stirring rate is slower in the formation of the double emulsion, and the polymerization reaction is rapid.
  • the HLB value of the surfactant is controlled within the range of 4 to 7; in the case of oil-in-water, the HLB value of the surfactant is controlled within the range of 8 to 18.
  • the HLB value of the surfactant varies with temperature, pH, salinity in the aqueous phase, and polarity of the oil phase solvent, and thus different surfactants correspond to different process conditions.
  • the microcapsules are prepared by the W/O/W double emulsion method. If the composition of the core material (internal water phase) and the wall material (oil phase) are defined, then the surfactant, the organic solvent are selected, and the temperature, pH, and The control of salinity and agitation rate is unique.
  • microencapsulation method of the above-mentioned concrete aqueous repairing agent is exemplified below by way of specific examples.
  • Embodiment 1 is a diagrammatic representation of Embodiment 1:
  • S14 Formulating colostrum.
  • the class 80 and Tween 80 were mixed at a mass ratio of 9:1, and as a W/O surfactant, the HLB value at room temperature was 5.4.
  • S15 Formulating a W/O/W type double emulsion.
  • the class 80 and Tween 80 were mixed at a mass ratio of 6:4, and as an O/W surfactant, the HLB value at room temperature was 8.6.
  • Embodiment 2 is a diagrammatic representation of Embodiment 1:
  • S21 preparing an internal aqueous phase, preparing 30 mL of a sodium silicate solution having a concentration of 1 mol/L, and dropping 2 drops (about 0.1 ml) of a 5 wt% aqueous solution of xanthan gum to adjust the viscosity of the internal water phase;
  • S25 Formulating a W/O/W type double emulsion.
  • the class 80 and Tween 80 were mixed at a mass ratio of 1:1, and as an O/W surfactant, the HLB value at room temperature was 9.9.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
  • Manufacturing Of Micro-Capsules (AREA)

Abstract

一种混凝土水性修复剂的微胶囊化方法，包括如下步骤：配制内水相，所述内水相为0.5-3mol/L的无机水性混凝土修复剂和0.01-2wt%的胶凝剂水溶液；配制油相，所述油相为体积浓度50-100%的苯乙烯有机溶液；配制外水相，所述外水相包含0.01-3wt%的水溶性苯乙烯聚合引发剂；向所述油相中加入3-15wt%的油包水表面活性剂，溶解后与所述内水相搅拌混合，得初乳；配制双乳液，在所述外水相中加入3-5wt%的水包油表面活性剂，溶解后与所述初乳搅拌混合；对所述双乳液升温至35-70°C，搅拌，得混凝土水性修复剂的微胶囊。

Description

一种混凝土水性修复剂的微胶囊化方法 技术领域
本发明属于自修复材料技术领域，具体涉及一种混凝土水性修复剂的微胶囊化方法。
背景技术
混凝土是一种水硬性的多孔胶凝人造石材料，由于其延伸率微小，抗拉强度低，所以极易产生收缩裂缝和荷载裂缝。裂纹的存在极大地影响了混凝土工程的耐久性，解决的一个方法就是对裂纹进行修复。但人工修复仅适用于外部裂纹，由于裂纹发生的不可预测性以及裂纹探测技术的局限，大量存在的内裂纹很难被发现和修复，为此需要开发具有自主修复功能的“智能型”混凝土。
自修复混凝土的一种实现方法是在混凝土基体中预先包埋修复剂，当裂纹扩展时，包埋的修复剂被某个物理或化学因素所触发而被释放，对裂纹进行自动修复。在现有技术中，修复剂一般被包埋在微小的纤维管中或者微胶囊里。相比较而言，两者中，微胶囊型自修复混凝土具有一定的技术优势：一是易在混凝土中分散，二是各相同性，可修复任意方向扩展的裂纹。
在微胶囊型自修复混凝土中，最常用环氧树脂作为修复剂，然而这种有机聚合物类修复剂与无机的混凝土基体不仅存在界面结合力差的问题，还存在老化问题。由于其耐久性远远低于混凝土基体，因此被有机修复剂修复的裂纹，在经若干年后，会逐渐失去弥合裂纹的能力，使原裂纹重新开裂，成为安全隐患。
有些无机粘接剂，如硅酸钠、磷酸二氢铝等，也是很好的混凝土修复剂。它们与混凝土界面结合力强，且与混凝土一样耐久，不存在老化问题。但它们大多是水溶性的硅酸盐、磷酸盐、硼酸盐、硫酸盐、钼酸盐，需要采取油包水（W/O）的方法使其微胶囊化，也就是说，要将它们的水溶液分散在连续的油相中，这与一般的环氧微胶囊的制备方法相反。W/O微胶囊的粒径比较小，通常在10微米以下。为了获得几十至几百微米粒径的W/O微胶囊，并对微胶囊的大小和壁厚进行控制，可采用水包油包水（W/O/W）的双乳液方法制备O/W微胶囊。
双乳液法是将一种乳状液(通常称为初级乳状液，简称初乳)分散在另外的连续相中形成的双层乳状液，有W/O/W 和O/W/O两种类型，但都具有“两膜三相”的多隔室结构。W/O/W型双乳液是油相液滴中含有一个或多个的水相液滴，这种含有水相液滴的油相液滴又被分散在连续的水相中而形成的乳状液。采用W/O/W的双乳液方法制备W/O微胶囊，就是在以油性的聚合物溶液或者油性的聚合物单体作为中间的油相，然后使聚合物溶液中的溶剂蒸发或者发生萃取，使聚合物沉积形成囊壁，或者在外水相（或者内水相）中加入引发剂或者催化剂，使单体聚合成高分子而在油相中沉积而形成囊壁。这种制备微胶囊的方法无需调节pH值，无需大幅改变温度，溶剂残留量低，方法简单，操作方便，适合包覆像多肽、蛋白质等具有生物活性的水溶性物质，因而在医药、食品和化妆品等领域获得了广泛的应用。但是双乳液本质上是一个非热力学稳定体系,极易失稳，发生奥氏熟化（Ostwald ripening）、絮凝、聚结和分层等现象。
 技术问题
有鉴于此，本发明提供一种混凝土水性修复剂的微胶囊化方法。
技术解决方案
一种混凝土水性修复剂的微胶囊化方法，其包括如下步骤：
配制内水相，所述内水相为0.5～3 mol/L的无机水性混凝土修复剂和0.01～2 wt%的胶凝剂水溶液；
配制油相，所述油相为体积浓度50～100%的苯乙烯有机溶液；
配制外水相，所述外水相包含0.01～3wt%的水溶性苯乙烯聚合引发剂；
向所述油相中加入3～15 wt%的油包水表面活性剂，溶解后与所述内水相搅拌混合，得初乳；
配制双乳液；在所述外水相中加入3～5 wt%的水包油表面活性剂，溶解后与所述初乳搅拌混合；
对所述双乳液升温至35～70℃，搅拌，得混凝土水性修复剂的微胶囊。
 有益效果
本发明提供的混凝土水性修复剂的微胶囊化方法成本低、工艺稳定、简单，适合工业化生产。
附图说明
图1是实施例一制备的混凝土水性修复剂的微胶囊的光学显微镜照片；
图2是实施例一制备的混凝土水性修复剂的微胶囊的扫描电镜图片；
图3是实施例二制备的混凝土水性修复剂的微胶囊的扫描电镜图片。
 本发明的实施方式
为了使本发明的目的、技术方案及优点更加清楚明白，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。
本发明实施例提供一种混凝土水性修复剂的微胶囊化方法，其包括如下步骤：
S01：配制内水相，所述内水相为0.5～3 mol/L的无机水性混凝土修复剂和0.01～2 wt%的胶凝剂水溶液；
S02：配制油相，所述油相为体积浓度50～100%的苯乙烯有机溶液；
S03：配制外水相，所述外水相包含0.01～3wt%的水溶性苯乙烯聚合引发剂；
S04：向所述油相中加入3～15wt%的油包水表面活性剂，溶解后与所述内水相搅拌混合，得初乳；
S05：配制双乳液；在所述外水相中加入3～5wt%的水包油表面活性剂，溶解后与所述初乳搅拌混合；
S06：对所述双乳液升温至35～70℃，搅拌，得混凝土水性修复剂的微胶囊。
步骤S01中，所述无机水性混凝土修复剂为硅酸钠、硅酸钾、硅酸锂、磷酸铝（P2O5/Al2O3摩尔比为2.0～3.0）、四硼酸钠、四硼酸钾、钼酸钠、钼酸钾、二钼酸铵[(NH4)2Mo2O7•4H2O]、七钼酸铵[(NH4)6Mo7O24•4H2O]，钾明矾[KAl(SO4)2•12H2O]、铵明矾[NH4Al(SO4)2•12H2O]、铝钠矾[NaAl(SO4)2•12H2O]、硫酸铝、硫酸锌、硫酸锰、硫酸镁、硫酸钙中的至少一种。所述内水相含有0.01～2wt%的胶凝剂，所述胶凝剂为天然水溶性高分子，优选为明胶（gelatin）、卡拉胶（Carrageenan）、黄原胶（Xanthan gum）、海藻酸钠（sodium alginate，NaAlg）、魔芋粉（konjac flour）、阿拉伯胶（Acacia gum）、果胶（pectin）、琼脂（agar）、羧甲基纤维素（CMC）、羟丙基变性淀粉（Hydroxypropyl starch ）、羧甲基淀粉（CMS）中的至少一种。
步骤S02中，所述苯乙烯溶液不含阻聚剂，苯乙烯溶液的溶剂为不与水混溶的有机溶剂，优选为三氯甲烷(氯仿)、甲苯、二甲苯、环己醇、甲基乙基酮、乙醚中的至少一种。
步骤S03中，所述水溶性苯乙烯聚合引发剂是指水溶性偶氮类引发剂或水溶性氧化——还原引发剂。其中水溶性偶氮类引发剂优选偶氮二异丁基脒盐酸盐（AIBA，V-50引发剂）、偶氮二异丁咪唑啉盐酸盐（AIBI，VA-044引发剂）、偶氮二氰基戊酸（ACVA，V-501引发剂）、偶氮二异丙基咪唑啉（AIP，VA-061引发剂）；在水溶性氧化一还原引发剂中，氧化剂优选过氧化氢（H2O2）、过硫酸铵[(NH4)2S2O8]、过硫酸钠（Na2S2O8）、过硫酸钾（K2S2O8）、过氧化氢异丙苯（CHP）、叔丁基过氧化氢（TBHP）；过硫酸盐、氢过氧化物，还原剂优选硫酸亚铁（FeSO4）、亚硫酸钠（Na2SO3）、葡萄糖、草酸、三乙醇胺（TEA）、过碳酸酰胺（尿素）。
在所述步骤S04中，所述油包水（W/O）表面活性剂在纯水中室温时的HLB值为4～6。混合时所述内水相与油相的体积比（内水相：油相）为1:3～4，搅拌速率大于5000r/min。
步骤S05中，所述水包油（O/W）表面活性剂在纯水中室温时的HLB值为8～12。混合时所述初乳与外水相的体积比（初乳：外水相）为1:1.5～2.5，搅拌速率为15～100r/min。
在所述步骤S04和S05中，所述W/O表面活性剂和O/W表面活性剂，优选下列表面活性剂中的一种或两种以上的复配：失水山梨醇脂肪酸酯聚氧乙烯醚，牌号Tween 20～Tween 80；失水山梨醇脂肪酸酯，牌号Span 20～Span 80； PEG-30二聚羟基硬脂酸酯，牌号Arlacel P135；蓖麻油聚氧乙烯醚，牌号EL35和EL40；烷基酚聚氧乙烯醚，牌号OP 4～OP 7；脂肪醇聚氧乙烯醚，牌号AEO3～AEO10。
在所述步骤S06中，反应温度为35～70℃，反应时间为10～120分钟，搅拌速率为15～100r/min。反应时通入惰性气体。
本发明实施例提供的混凝土水性修复剂的微胶囊化方法，其技巧性主要表现在选取合适的水包油（O/W）和油包水（W/O）的表面活性剂的选取和适当的用量；在内水相中加入适量的以及合适的胶凝剂，以阻滞内外水相中水的相互渗漏；在形成双乳液时搅拌速率要慢，而聚合反应要迅速。通常，油包水时，表面活性剂的HLB值控制在4～7范围之内；水包油时，表面活性剂的HLB值控制在8～18范围内。但表面活性剂的HLB值随温度、pH值、水相中的盐度、油相溶剂的极性而变，因而不同的表面活性剂对应着不同的工艺条件。W/O/W型双乳液法制备微胶囊，如果限定了芯材（内水相）和壁材（油相）的组成，那么对表面活性剂、有机溶剂选取，以及对温度、pH值、盐度和搅拌速率的控制均具有独特性。
以下通过具体实施例来举例说明上述混凝土水性修复剂的微胶囊化方法。
实施例一：
S11：配制内水相，配制30 mL 浓度为1 mol/L的磷酸二氢铝溶液，滴入5滴（约0.25毫升）5wt%明胶水溶液，调节内水相黏度；
S12：配制油相，往市售苯乙烯中倒入适量的浓度为5 wt% NaOH水溶液作洗液，振荡、分液，去掉洗后略带红色的NaOH洗液，重复多次，直至NaOH洗液无色。然后加入5 g无水硫酸钠，密闭，于避光处干燥3天以上，以除去水分。最后再减压蒸馏，将中间馏分避光低温保存，此为不含阻聚剂（对苯二酚）的苯乙烯。
取15 mL经上述处理过的苯乙烯，与15 mL经蒸馏处理过的甲苯混合，制成苯乙烯的甲苯溶液，作为油相。
S13：配制外水相。取70 mL去离子水中，加入0.20 g过硫酸钾和0.11 g亚硫酸钠作为引发剂。
S14：配制初乳。将司班80和吐温80按9：1的质量比混合，作为W/O表面活性剂，室温时的HLB值为5.4。
取上述W/O表面活性剂4.4 g，加入到步骤2所制的油相中，搅拌混合均匀，再与步骤1所制内水相混合，均质机高速搅拌2分钟，转速10000 r/min，得白色牛奶状初乳。
S15：配制W/O/W型双乳液。将司班80和吐温80按6：4的质量比混合，作为O/W表面活性剂，室温时的HLB值为8.6。
取上述O/W表面活性剂10 g，加入到步骤S13所制的外水相中，搅拌混合均匀，倒入500 mL三口烧瓶中，再小心加入步骤S14所制的初乳，通氮气，低速搅拌，转速20 r/min，得W/O/W型双乳液。
S16：向步骤5所制W/O/W型双乳液中通氮气，升温至70℃，反应40分钟后停止，过滤，得磷酸二氢铝溶液的聚苯乙烯微胶囊。光学显微镜和扫描电子显微镜观察，微胶囊的形貌分别如图1和图2所示。
实施例二：
S21：配制内水相，配制30mL浓度为1mol/L的硅酸钠溶液，滴入2滴（约0.1毫升）5wt%黄原胶水溶液，调节内水相黏度；
S22：配制油相，往市售苯乙烯中倒入适量的浓度为5 wt% NaOH水溶液作洗液，振荡、分液，去掉洗后略带红色的NaOH洗液，重复多次，直至NaOH洗液无色。然后加入5 g无水硫酸钠，密闭，于避光处干燥3天以上，以除去水分。最后再减压蒸馏，将中间馏分避光低温保存，此为不含阻聚剂（对苯二酚）的苯乙烯。
取30 mL经上述处理过的苯乙烯，与15 mL经蒸馏处理过的氯仿混合，制成苯乙烯的氯仿溶液，作为油相。
S23：配制外水相，取70 mL去离子水中，加入20 mL 20 wt% V-50引发剂的甲醇溶液。
S24：配制初乳，将0.15g Arlacel P135作为W/O表面活性剂（室温时的HLB值为5.5），加入到步骤2所制的油相中，搅拌混合均匀，再与步骤1所制内水相混合，均质机高速搅拌5分钟，转速10000r/min，得白色牛奶状初乳。
S25：配制W/O/W型双乳液。将司班80和吐温80按1：1的质量比混合，作为O/W表面活性剂，室温时的HLB值为9.9。
取上述O/W表面活性剂10g，加入到步骤S23所制的外水相中，搅拌混合均匀，倒入500 mL三口烧瓶中，再小心加入步骤S24所制的初乳，通氮气，低速搅拌，转速20 r/min，得W/O/W型双乳液。
S26：向步骤S25所制W/O/W型双乳液中通氮气，升温至70℃，反应60分钟后停止，过滤，得硅酸钠溶液的聚苯乙烯微胶囊。扫描电子显微镜观察，微胶囊的形貌如图3所示。
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. 一种混凝土水性修复剂的微胶囊化方法，其特征在于，包括如下步骤：
    配制内水相，所述内水相为0.5～3 mol/L的无机水性混凝土修复剂和0.01～2 wt%的胶凝剂水溶液；
    配制油相，所述油相为体积浓度50～100%的苯乙烯有机溶液；
    配制外水相，所述外水相包含0.01～3wt%的水溶性苯乙烯聚合引发剂；
    向所述油相中加入3～15 wt%的油包水表面活性剂，溶解后与所述内水相搅拌混合，得初乳；
    配制双乳液；在所述外水相中加入3～5 wt%的水包油表面活性剂，溶解后与所述初乳搅拌混合；
    对所述双乳液升温至35～70℃，搅拌，得混凝土水性修复剂的微胶囊。
  2. 如权利要求1所述的混凝土水性修复剂的微胶囊化方法，其特征在于，所述无机水性混凝土修复剂为硅酸钠、硅酸钾、硅酸锂、磷酸铝、四硼酸钠、四硼酸钾、钼酸钠、钼酸钾、二钼酸铵、七钼酸铵，钾明矾、铵明矾、铝钠矾、硫酸铝、硫酸锌、硫酸锰、硫酸镁、硫酸钙中的至少一种。
  3. 如权利要求1所述的混凝土水性修复剂的微胶囊化方法，其特征在于，所述胶凝剂为明胶、卡拉胶、黄原胶、海藻酸钠、魔芋粉、阿拉伯胶、果胶、琼脂、羧甲基纤维素、羟丙基变性淀粉、羧甲基淀粉中的至少一种。
  4. 如权利要求1所述的混凝土水性修复剂的微胶囊化方法，其特征在于，所述苯乙烯有机溶液的溶剂为三氯甲烷、甲苯、二甲苯、环己醇、甲基乙基酮、乙醚中的至少一种。
  5. 如权利要求1所述的混凝土水性修复剂的微胶囊化方法，其特征在于，所述水溶性苯乙烯聚合引发剂为水溶性偶氮类引发剂或水溶性氧化-还原引发剂。
  6. 如权利要求1所述的混凝土水性修复剂的微胶囊化方法，其特征在于，所述油包水表面活性剂在纯水中室温下的HLB值为4～6。
  7. 如权利要求1所述的混凝土水性修复剂的微胶囊化方法，其特征在于，所述配制外水相时，所述内水相与油相的体积比为1:3～4。
  8. 如权利要求1所述的混凝土水性修复剂的微胶囊化方法，其特征在于，所述水包油表面活性剂在纯水中室温下的HLB值为8～12。
  9. 如权利要求1所述的混凝土水性修复剂的微胶囊化方法，其特征在于，所述配制双乳液时，所述初乳与外水相的体积比为1:1.5～2.5。
  10. 如权利要求1所述的混凝土水性修复剂的微胶囊化方法，其特征在于，所述双乳液升温至35～70℃，搅拌速率为15～100 r/min，时间为10～120分钟。
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