本文選題：形狀記憶材料　切入點(diǎn)：水凝膠　出處：《中國科學(xué)技術(shù)大學(xué)》2017年博士論文　論文類型：學(xué)位論文

【摘要】：目前智能材料的研究是一個(gè)熱門學(xué)科,形狀記憶材料便是智能材料中的一種。形狀記憶材料能夠在某一種或多種刺激環(huán)境(如pH、光照、氧化還原、電、磁場(chǎng)、溫度)中,外力作用下固定住某一臨時(shí)形狀,當(dāng)再受到刺激時(shí)能夠恢復(fù)到原來的永久形狀。形狀記憶材料從最初的Ti-Ni為主體的形狀記憶金屬到各種塑料和橡膠類的形狀記憶聚合物,再到新興的形狀記憶水凝膠的形狀記憶材料發(fā)展。從形狀記憶材料的發(fā)展趨勢(shì)可以看出形狀記憶水凝膠綜合了形狀記憶聚合物和智能水凝膠的各種優(yōu)點(diǎn),創(chuàng)造了新的研究領(lǐng)域,挖掘出了在分子元器件、微型機(jī)器人、生物醫(yī)學(xué)等高新技術(shù)領(lǐng)域中巨大的應(yīng)用潛力。但目前對(duì)于形狀記憶智能水凝膠的研究大部分還集中在通過疏水作用形成的熱響應(yīng)性形狀記憶水凝膠,因此開發(fā)研究新型的熱響應(yīng)型形狀記憶水凝膠、其它響應(yīng)型形狀記憶水凝膠以及多種響應(yīng)型水凝膠,以及拓展形狀記憶水凝膠的應(yīng)用領(lǐng)域,成為未來的發(fā)展趨勢(shì)。另外,目前主要的形狀記憶水凝膠都是通過化學(xué)交聯(lián)固定水凝膠骨架,利用物理交聯(lián)來賦予水凝膠形狀記憶的功能。因?yàn)橛谢瘜W(xué)交聯(lián)的存在,水凝膠不能重復(fù)利用,對(duì)材料來說很浪費(fèi)。因此,綜合以上分析,本論文結(jié)合金屬離子與一些基團(tuán)之間的配位交聯(lián)作用、疏水鏈段之間的疏水作用以及主客體相互作用,制備了幾種新型的形狀記憶水凝膠體系并進(jìn)行機(jī)理和性能研究。具體研究?jī)?nèi)容如下:(1)利用丙烯酰胺(AM)、異丙烯膦酸(IPPA)和大分子交聯(lián)劑聚乙二醇雙丙烯酸酯(PEGDA)合成了一種新型的水凝膠。該水凝膠中的磷酸根可以與三價(jià)鐵離子(Fe~(3+))配位交聯(lián),通過氧化還原反應(yīng)使三價(jià)鐵離子還原為二價(jià)鐵離子(Fe2+),從而破壞磷酸根與三價(jià)鐵離子之間的交聯(lián)作用。另外,通過加入絡(luò)合劑EDTA·2Na,用更強(qiáng)的絡(luò)合作用與磷酸根搶奪三價(jià)鐵離子,從而也使磷酸根和三價(jià)鐵離子之間的交聯(lián)破壞。通過兩種方式都可控制交聯(lián)和解交聯(lián),從而使水凝膠具有兩種刺激響應(yīng)性形狀記憶。我們利用流變儀對(duì)水凝膠的性能進(jìn)行研究,對(duì)形狀記憶的原理和影響因素進(jìn)行了分析。(2)利用可聚合陽離子表面活性劑甲基丙烯酸二甲氨基乙酯溴代十六烷(C16DMAEMA)、丙烯酰胺(AM)為單體進(jìn)行膠束聚合,以甲叉雙丙烯酰胺(MBA)為化學(xué)交聯(lián)劑,與α-環(huán)糊精混合制備疏水改性聚丙烯酰胺水凝膠。其中利用主客體相互作用,將環(huán)糊精引入到疏水鏈段上,形成疏水鏈穿插多個(gè)環(huán)糊精的聚輪烷拓?fù)浣Y(jié)構(gòu)。XRD、固態(tài)~(13)C-NMR、DSC等表征手段證明引入到疏水基團(tuán)上的環(huán)糊精之間的氫鍵相互作用形成結(jié)晶區(qū),并通過結(jié)晶區(qū)的熔融和結(jié)晶形成可使水凝膠實(shí)現(xiàn)熱響應(yīng)形狀記憶功能。(3)利用丙烯酰胺(AM)、丙烯酸(AA)和疏水單體丙烯酸十八烷酯(C18)共聚合成了一種沒有化學(xué)交聯(lián)劑,而是通過疏水締合作用物理交聯(lián)的聚合物水凝膠,并通過加入三價(jià)鐵離子利用與水凝膠中羧基之間的配位絡(luò)合作用形成第二種物理交聯(lián)。該水凝膠體系中由于同時(shí)存在疏水相互作用和能與三價(jià)鐵離子配位絡(luò)合的相互作用,屬于由兩種物理交聯(lián)構(gòu)成的水凝膠。利用疏水作用固定水凝膠的形狀,凝膠中的丙烯酸基團(tuán)與三價(jià)鐵離子交聯(lián),通過還原和絡(luò)合作用解交聯(lián),從而實(shí)現(xiàn)水凝膠的形狀記憶功能,賦予水凝膠多重響應(yīng)形狀記憶特性。同時(shí),由于水凝膠中不存在化學(xué)交聯(lián)鍵,大大豐富了水凝膠的種類和應(yīng)用。
[Abstract]:The research of intelligent materials is a hot subject, shape memory material is a kind of smart material. The shape memory materials can stimulate the environment in one or more (such as pH, light, redox, electric, magnetic field, temperature), under the action of external force to fix a temporary shape. When can be restored to the original permanent shape again when stimulated. The shape memory materials from the original Ti-Ni as the main body of the shape memory metal to shape memory polymer plastic and rubber, and then to the development of shape memory materials shape memory gel. Emerging from the development trend of shape memory materials can be seen shape memory gel synthesis all the advantages of shape memory polymer and intelligent hydrogels, create a new field of study, excavated in the molecular components, micro robot, the use of biomedical and other high-tech fields in large Force. But the shape memory gel response of shape memory of intelligent hydrogels most concentrated in the form of heat through hydrophobic interaction, the study of new type thermal response type shape memory gel so developed, other response type shape memory gel and a variety of responsive hydrogels, and the expansion of the application of shape memory gel, become the trend of development the future. In addition, the shape memory gel is mainly fixed by chemical crosslinking hydrogels, using physical crosslinking to give hydrogel shape memory function. Because of the existence of chemical crosslinking, the hydrogel can not be reused, a waste of materials. Therefore, based on the above analysis, this paper combines between metal ions and some groups Coordination Crosslinking, hydrophobic interaction between the hydrophobic segment and the interaction between subject and object, the preparation of several new Study on the mechanism and performance of shape memory and hydrogel system. The specific contents are as follows: (1) using acrylamide (AM), isopropenyl phosphonic acid (IPPA) and macromolecular crosslinking agent of polyethylene glycol diacrylate (PEGDA) is a new type of hydrogel was synthesized. The hydrogel in phosphate and ferric iron can ion (Fe~ (3+)) Coordination Crosslinking, the ferric ion reduction of two valent iron ions through redox reaction (Fe2+), thus undermining the cross-linking between phosphate and ferric ion. In addition, by adding the complexing agent EDTA 2Na, with a stronger complexation with phosphate from ferric ion thus, the cross-linking between phosphate and ferric ion damage. By two ways can control the settlement so that the crosslinking crosslinking hydrogel with two kinds of stimuli responsive shape memory. We use the research on properties of hydrogel rheometer The principle and influencing factors of shape memory were analyzed. (2) using a polymerizable cationic surfactant two dimethylamino ethyl methacrylate methyl sixteen alkyl bromide (C16DMAEMA), acrylamide (AM) by micellar polymerization monomers with methylene bisacrylamide (MBA) as crosslinking agent, and alpha cyclodextrin mixed preparation of hydrophobically modified polyacrylamide hydrogel. The interaction between subject and object, the cyclodextrin into hydrophobic segments, forming a hydrophobic chain with multiple cyclodextrin polyrotaxanes topology.XRD, solid state ~ (13) C-NMR, DSC characterization means that introduced between the cyclodextrin hydrophobic groups the hydrogen bonding between the formation of crystalline region, and can realize the thermal response of shape memory functional hydrogel formed by melting and crystallization of the crystalline region. (3) using acrylamide (AM), acrylic acid (AA) and hydrophobic acrylic acid alkyl ester eighteen memo (C18) Co The polymerization did not become a chemical cross-linking agent, but by hydrophobic association polymer hydrogel physical crosslinking, and by the addition of ferric ion and using between hydrogel complexation with carboxyl groups to form second kinds of physical crosslinking. The interaction and hydrophobic interaction and ferric ion complexing with the hydrogel in the system, is composed of two physically crosslinked hydrogels. Using shape hydrophobic hydrogel fixed in the gel, acrylic acid groups and ferric ion crosslinking by crosslinking and co reduction, so as to realize the function of shape memory hydrogels, with multiple response shape memory properties of hydrogels. At the same time, due to the chemical crosslinking key does not exist the hydrogel, greatly enriched the types and applications of hydrogels.

【學(xué)位授予單位】：中國科學(xué)技術(shù)大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2017
【分類號(hào)】：O648.17;TB381

【相似文獻(xiàn)】

相關(guān)博士學(xué)位論文 前10條

1 艾克熱木.牙生;基于不同相互作用的形狀記憶水凝膠的設(shè)計(jì)和性能表征[D];中國科學(xué)技術(shù)大學(xué);2017年

2 賈羽潔;聚苯胺—聚對(duì)苯乙烯磺酸水凝膠基活性炭的制備與應(yīng)用基礎(chǔ)研究[D];中國林業(yè)科學(xué)研究院;2017年

3 楊伯光;聚噻吩基導(dǎo)電水凝膠研制及其在心肌組織工程中的應(yīng)用研究[D];天津大學(xué);2016年

4 高利龍;多官能度聚乙二醇衍生物的合成、凝膠化及其生物醫(yī)學(xué)應(yīng)用[D];浙江大學(xué);2016年

5 余瀚森;利用動(dòng)態(tài)共價(jià)鍵構(gòu)筑可注射自修復(fù)水凝膠[D];中國科學(xué)技術(shù)大學(xué);2017年

6 張松松;仿生減阻涂層的制備及性能研究[D];哈爾濱工程大學(xué);2016年

7 于珊;細(xì)胞選擇性梯度生物材料的構(gòu)建及其調(diào)控細(xì)胞遷移行為研究[D];浙江大學(xué);2017年

8 葉磊;兩性離子改性淀粉衍生物的制備及其用于藥物遞送和埋植材料的研究[D];天津大學(xué);2016年

9 張亞彬;基于聚乙烯醇制備仿生軟骨組織工程支架[D];天津大學(xué);2016年

10 梅斌;酶促自組裝紫杉醇水凝膠的合成與應(yīng)用[D];中國科學(xué)技術(shù)大學(xué);2017年

相關(guān)碩士學(xué)位論文 前1條

1 廖悅;光敏感自變形水凝膠作為無接觸式3D宏觀/微觀光打印平臺(tái)的研究[D];天津大學(xué);2016年

，

本文編號(hào)：1611013