本文選題：層層自組裝法　切入點(diǎn)：聚電解質(zhì)微膠囊　出處：《深圳大學(xué)》2017年碩士論文

【摘要】：兩種荷異種電荷的聚電解質(zhì)之間存在庫侖引力,利用這個(gè)性質(zhì)可以讓它們通過交替的層層自組裝方式形成微膠囊,這種微膠囊具有離子敏感的特性,可以被多種離子所觸發(fā),釋放內(nèi)容物,在生物醫(yī)藥領(lǐng)域備受關(guān)注,可用于人體的靶向給藥或者定向組織移植。本文針對(duì)混凝土中的氯害和碳酸化這兩個(gè)嚴(yán)重影響混凝土耐久性的重大工程問題,提出了將這種具有離子響應(yīng)特性的通過層層自組裝法制備的聚電解質(zhì)微膠囊加入到混凝土中,為混凝土建立一個(gè)抗有害離子入侵的免疫系統(tǒng),以實(shí)現(xiàn)混凝土的化學(xué)自修復(fù)。用于生物體的聚電解質(zhì)微膠囊不能直接包裹芯材,通常在制備時(shí)是以固體微球作為模板,進(jìn)行聚電解質(zhì)層層自組裝后再溶去模板,注入液體的芯材,同時(shí),所制得的微膠囊也只能存在于水相中。一旦除去連續(xù)的水相,微膠囊將會(huì)潰散。為了使這種微膠囊適用于混凝土,本文對(duì)聚電解質(zhì)層層自組裝法制備微膠囊的工藝進(jìn)行了改進(jìn),實(shí)現(xiàn)了:(1)在流動(dòng)的環(huán)氧液滴表面直接包覆聚電解質(zhì),形成微膠囊;(2)通過聚電解質(zhì)層間的交聯(lián)穩(wěn)定微膠囊的殼層結(jié)構(gòu),使聚電解質(zhì)微膠囊可以在混凝土的無水環(huán)境下穩(wěn)定存在。此外,為了提高包覆效率,適應(yīng)混凝土應(yīng)用的“量大價(jià)廉”的要求,本文還采用了可聚合乳化劑,在液體芯材表面進(jìn)行光聚合,先形成一荷電網(wǎng)狀穩(wěn)定層,再進(jìn)行聚電解質(zhì)層層自組裝,這種方法可以克服微膠囊形成初期聚電解質(zhì)層數(shù)很低時(shí),在高速離心過程中的破裂問題,大大提高了微膠囊化的效率。實(shí)驗(yàn)遞進(jìn)地分為三個(gè)部分,分別是:(1)傳統(tǒng)的模板法制備環(huán)氧微膠囊:在CaCO_3沉積時(shí),加入PSS調(diào)控CaCO_3結(jié)晶形態(tài)。當(dāng)PSS的濃度為5 mg/mL時(shí)制得良好的球形微粒,平均粒徑為8.6±0.6μm,比表面積約為8.8±0.5 m2/g,表面電位-45 mV左右。以此CaCO_3微球?yàn)槟０?在其表面上離子型聚電解質(zhì)PAH和PSS的交替自組裝,達(dá)到預(yù)定層數(shù)后除去碳酸鈣模板,得到中空微膠囊(PSS/PAH)n,向里面包埋脂環(huán)族環(huán)氧T8210后,浸入戊二醛溶液對(duì)壁材進(jìn)行交聯(lián),得到環(huán)氧/聚電解質(zhì)微膠囊;(2)銨基陽離子型表面活性劑乳化液體芯材,然后聚電解質(zhì)層層自組裝直接包覆:用陽離子型表面活性劑雙十二烷基二甲基溴化銨乳化十二烷,其銨基陽離子油性大于水性,固基本溶于油相十二烷,在十二烷液滴的表面鋪展,使乳液荷正電并使其穩(wěn)定,然后在乳液液滴表面上進(jìn)行PSS和PAH的交替層層自組裝,達(dá)到預(yù)定層數(shù)后,用戊二醛對(duì)壁材進(jìn)行交聯(lián),得到十二烷/聚電解質(zhì)微膠囊;(3)UV界面聚合法在液體環(huán)氧乳液液滴的表面上形成荷負(fù)電的網(wǎng)狀聚合物膜,然后聚電解質(zhì)層層自組裝制備液態(tài)環(huán)氧微膠囊:環(huán)氧是很好的混凝土修復(fù)劑。將環(huán)氧E44與可聚合的表面活性劑,不飽和酯環(huán)氧丙烯酸酯、丙烯酰胺、和甲基丙烯酸羥丙磺酸鈉混合,乳化后在液滴表面進(jìn)行UV聚合,形成一層荷負(fù)電的網(wǎng)狀薄膜。這層膜既能保護(hù)芯材在低速攪拌時(shí)不流失,也不影響后面的觸發(fā)效果,在薄膜基礎(chǔ)上組裝聚電解質(zhì)至預(yù)定層數(shù),再進(jìn)行壁材的交聯(lián),得到易于保存且穩(wěn)定的環(huán)氧/聚電解質(zhì)微膠囊。實(shí)驗(yàn)表明,利用戊二醛(GA)對(duì)囊壁中的PAH組分進(jìn)行交聯(lián),生成一種吡啶結(jié)構(gòu),使囊壁形成類似于互穿聚合物的網(wǎng)絡(luò)結(jié)構(gòu),可以穩(wěn)定整個(gè)多層膜,既能很好地加固微膠囊的穩(wěn)定性,也不影響膠囊對(duì)離子的響應(yīng)。三種方法制備的聚電解質(zhì)微膠囊都能在PH≥12的堿性溶液中觸發(fā),釋放液體芯材。本論文通過制備方法的不斷改進(jìn),在模板法的基礎(chǔ)上完成了聚電解質(zhì)在液體芯材上的直接包覆,簡(jiǎn)化了制備流程,拓寬了聚電解質(zhì)微膠囊的應(yīng)用范圍。通過采用戊二醛對(duì)聚電解質(zhì)壁材中PAH的交聯(lián),成功制備出了可以在無水狀態(tài)下穩(wěn)定存在的聚電解質(zhì)自修復(fù)微膠囊干粉,在重新注水后未失去對(duì)離子的響應(yīng)特性。采用可聚合表面活性劑,在液體表面預(yù)先形成單分子厚度的穩(wěn)定殼層,使乳液液滴在高速離心過程中不破碎,不合并,可以大大提高聚電解質(zhì)包覆液體芯材的效率。總之,本文的實(shí)驗(yàn)表明,通過層層自組裝制備的聚電解質(zhì)微膠囊可以用于混凝土,通過離子自動(dòng)觸發(fā),實(shí)行混凝土的化學(xué)自修復(fù)。
[Abstract]:There are two kinds of heterogeneous charge Coulomb attraction between charged polyelectrolytes, may make use of this property to let them through the alternate layer by layer self-assembly to form microcapsules, the micro capsule has the characteristics of ion sensitive, can be triggered by various ions, releasing the contents, has attracted much attention in the field of biological medicine, can be used for human targeting the medicine or directional tissue transplantation. Aiming at the concrete carbonation and chloride and the two major engineering problems seriously affect the durability of concrete, put forward the ion response characteristics through layers of self-assembly of polyelectrolyte microcapsules prepared by adding into concrete, establish an anti immune intrusion of harmful ions in order to realize the system for concrete, concrete chemical self repair. For the biological polyelectrolyte microcapsules can not directly coated core material, usually at the time of preparation is a solid micro The ball as a template for polyelectrolyte layer by layer self-assembly after dissolving the template into the liquid core material, at the same time, microcapsules can only exist in the water phase. Once removed continuous aqueous phase, micro capsule will be scattered. In order to make this kind of microcapsule is suitable for concrete, preparation of microcapsules in this paper the polyelectrolyte layer by layer self-assembly method was improved and realized: (1) on the surface of epoxy droplet flow directly coated polyelectrolyte microcapsules are formed; (2) the shell structure of poly electrolyte layer between the crosslinked stable microcapsules, the polyelectrolyte microcapsules can exist stably in the anhydrous environment of concrete the next. In addition, in order to improve the coating efficiency, adapt to the concrete application of the "large quantity of cheap" requirement, this paper uses the emulsifier for photo polymerization in liquid core material surface, forming a grid shaped charge stable layer, and then poly electric The quality of the solution self-assembly, this method can overcome the early formation of polyelectrolyte microcapsules layers are low, fracture problems in high-speed centrifugal process, greatly improving the efficiency of microencapsulation. The order is divided into three parts, namely: (1) the traditional template preparation of microcapsules in epoxy the deposition of CaCO_3, adding PSS regulation of CaCO_3 crystal morphology. When PSS concentration was 5 mg/mL for spherical particles with good, average particle size is 8.6 + 0.6 m, about 8.8 + 0.5 m2/g specific surface area, surface potential of -45 mV. This CaCO_3 microspheres on the surface of ion type polyelectrolyte PAH and PSS self-assembly, calcium carbonate template removal reaches a predetermined number, get the hollow capsules (PSS/PAH n), to which the embedding of alicyclic epoxy T8210, the wall material is immersed in glutaraldehyde crosslinking, epoxy / polyelectrolyte microcapsules; (2) ammonium cation Ionic surfactant emulsion liquid core material, then the polyelectrolyte layer by layer self-assembly coated directly with cationic surfactant dodecyl bromide emulsion two methyl twelve alkyl ammonium cations, the oil than water, solid basic oil soluble phase twelve alkanes, twelve alkane droplet spreading on the surface, the a positively charged emulsion and make it stable, then in alternating emulsion droplets on the surface of PSS and PAH layers of self-assembly, reaches a predetermined number after crosslinking for wall material with glutaraldehyde, twelve alkane / polyelectrolyte microcapsules; (3) reticular polymer film UV interface polymerization on the surface of liquid epoxy emulsion droplets on the formation of negatively charged polyelectrolyte layers, then prepared by the self-assembly of liquid epoxy microcapsules: epoxy concrete repairing agent is good. The epoxy E44 and a polymerizable surfactant, unsaturated ester epoxy acrylate, acrylamide, Mixed with methyl acrylic acid hydroxypropyl sodium sulfonate, emulsified in droplet surface UV polymerization, forming a layer of negatively charged mesh film. This film can protect the core material loss at low speed, also does not affect the triggering effect, to set pre assembled polyelectrolyte layers in thin films based on cross-linked again for the wall material, are easy to preserve and stable epoxy / polyelectrolyte microcapsules. Experiments show that using glutaraldehyde (GA) of PAH group in the cyst wall was crosslinked to generate a pyridine structure, the cystic wall similar to the formation of interpenetrating polymer network structure, which can stabilize the whole multilayer film. Good to reinforce the stability of the microcapsule, does not affect the response of capsule ions. Three kinds of preparation methods of microcapsules can trigger in alkaline solution PH = 12, the release of liquid core material. Through preparation methods of this paper are improved in mold Based on the method of plate to complete the direct coating of polyelectrolytes in liquid core materials, simplifies the preparation process, broaden the scope of application of polyelectrolyte microcapsules. By using glutaraldehyde on polyelectrolyte wall material of PAH crosslinking, successfully prepared can exist stably in the anhydrous state of polyelectrolyte self repair the micro capsule powder in water after re not lost on response of ions. The polymerizable surfactant, on the surface of the liquid in advance to form a stable shell thickness of a single molecule, the emulsion droplets in high speed centrifugal process is not broken, do not merge, can greatly improve the efficiency of polyelectrolyte coated liquid core material. In a word, the experiments in this paper show that through the layers prepared by the self-assembly of polyelectrolyte microcapsules can be used in concrete, automatically triggered by the ion chemistry to implement concrete self repair.

【學(xué)位授予單位】：深圳大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：TU528

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