【摘要】：合成親水高分子,因其原料易得,結(jié)構(gòu)和性能可控而在增稠、吸水樹脂及智能微凝膠等方面得到廣泛應(yīng)用。進(jìn)一步提高水凝膠的吸水性及使用安全性、賦予聚合物高效性、功能性、智能性成為該領(lǐng)域的研究熱點。本論文基于丙烯酸及共聚物展開,設(shè)計并制備了一系列功能性親水聚合物,并對其結(jié)構(gòu)和性能進(jìn)行了詳細(xì)地表征和研究。(1)化學(xué)交聯(lián)丙烯酸微凝膠的合成與應(yīng)用研究。使用沉淀聚合法,將丙烯酸與三官能單體季戊四醇三烯丙基醚共聚,合成主要用作水性增稠劑的丙烯酸微凝膠。通過核磁共振、紅外光譜、掃描電鏡對凝膠結(jié)構(gòu)進(jìn)行了表征,并對凝膠的動態(tài)模量、粘度、透光率、聚合穩(wěn)定性等方面進(jìn)行了研究。結(jié)果表明,在聚合溫度為68oC,交聯(lián)劑用量為單體質(zhì)量分?jǐn)?shù)的0.4%,單體濃度為14%,分散劑用量為單體質(zhì)量分?jǐn)?shù)的1.2%,引發(fā)劑LPO用量為單體摩爾分?jǐn)?shù)的0.15%時,所得丙烯酸均聚物微凝膠綜合性能最為優(yōu)異,其0.5%凝膠分散液粘度為8.08×104 mPa·s,0.2%分散液粘度為1.45×104mPa·s,透光率為97.4%。同時,采用與具有長疏水鏈的單體丙烯酸十八酯共聚,改善其凝膠的耐鹽性及抗稀釋性。結(jié)果表明,通過疏水單體丙烯酸十八酯的共聚改性,在分子網(wǎng)絡(luò)中形成物理交聯(lián)點,可提高凝膠的耐稀釋性、耐鹽性等流變學(xué)性質(zhì);盡管添加共聚單體會使粉末潤濕時間提高,但當(dāng)共聚單體添加量為3%時,凝膠于低濃度、酸堿環(huán)境、離子環(huán)境、有機溶劑環(huán)境、較高溫度下具有優(yōu)異的流變學(xué)性質(zhì)。(2)基于配位作用的超分子凝膠的合成與性能。對2,2':6',2″-三聯(lián)吡啶的苯基4'位進(jìn)行修飾,形成含有可聚合雙鍵的4'-(苯乙烯基)-2,2':6',2″-三聯(lián)吡啶單體,將此單體與丙烯酸共聚,即得水溶性的含三聯(lián)吡啶配體基團的線性聚合物,在水溶液中可迅速與過渡金屬離子配位形成超分子凝膠。由特性粘數(shù)、動態(tài)流變、吸水倍率、熱分析及微觀形貌分析對溶膠及凝膠性能進(jìn)行測試表征,并將配體配制成低濃度溶液,以微量金屬離子絡(luò)合,進(jìn)行光譜性能的測試研究。結(jié)果表明,高濃度配體溶液可瞬間與金屬離子配位形成三維結(jié)構(gòu),溶膠和凝膠的動態(tài)模量發(fā)生大幅轉(zhuǎn)變;且凝膠表現(xiàn)出智能環(huán)境響應(yīng)性,酸堿和離子環(huán)境可降低凝膠吸水倍率,但其交聯(lián)結(jié)構(gòu)并未因此破壞,表明金屬配位鍵具有一定的結(jié)合強度。將低濃度配體溶液及絡(luò)合物進(jìn)行光譜測試,結(jié)果表明,配體溶液的紫外-可見吸收峰值為305nm,分別添加一定濃度的Fe2+、Ni2+、Cu2+、Cd2+、Zn2+,其吸收峰值發(fā)生不同程度的紅移,吸收強度也有一定的變化,并在某些離子濃度區(qū)間具有比較明顯的線性關(guān)系;配體具有熒光發(fā)射性能,而Fe2+、Ni2+、Cu2+可使配體熒光猝滅,配體與Cd2+、Zn2+絡(luò)合后具有熒光發(fā)射,并使熒光發(fā)射峰值紅移。該類分子顯示出優(yōu)異的離子傳感功能,可望在水體系中對特定金屬離子的痕量分析方面得到應(yīng)用。
[Abstract]:Hydrophilic polymers are widely used in thickening, absorbent resins and intelligent microgels due to their easily obtained raw materials, controllable structure and properties. Further improving the water absorption and safety of hydrogels and endowing polymers with high efficiency, functionality and intelligence has become a research hotspot in this field. A series of functional hydrophilic polymers were designed and prepared based on acrylic acid and copolymers. The structure and properties of these polymers were characterized and studied in detail. (1) Synthesis and application of chemically crosslinked acrylic microgels. Acrylic acid microgel was synthesized by precipitation polymerization of acrylic acid and trifunctional monomer pentaerythritol triallyl ether. The structure of the gel was characterized by NMR, IR and SEM. The dynamic modulus, viscosity, transmittance and polymerization stability of the gel were studied. The results show that when the polymerization temperature is 68oC, the amount of crosslinking agent is 0.4wt% of monomer, the concentration of monomer is 14%, the amount of dispersant is 1.2 mass fraction of monomer, the amount of initiator LPO is 0.15 mol fraction of monomer. The obtained acrylic acid homopolymer microgel has the most excellent comprehensive properties, the viscosity of 0.5% gel dispersion is 8.08 脳 10 ~ 4 mPa / s, the viscosity of 0.2wt% dispersion solution is 1.45 脳 104mPa / s, and the transmittance is 97.4%. The salt resistance and dilution resistance of the gel were improved by copolymerization with octadecyl acrylate, a monomer with long hydrophobic chain. The results show that the physical crosslinking point can be formed in the molecular network by copolymerization modification of hydrophobic monomer octadecyl acrylate, which can improve the rheological properties of gel, such as dilute resistance and salt resistance, although adding copolymer monomer can increase the wetting time of powder. However, the gel has excellent rheological properties at low concentration, acid-base environment, ionic environment, organic solvent environment and higher temperature when the amount of monomer is 3. (2) Synthesis and properties of supramolecular gel based on coordination. The phenyl 4 'site of 2o 2: 6: 6 "-tripyridine was modified to form a 4n- (styrene group) -2o 2: 6: 6" -tripyridine monomer containing polymerizable double bonds. The monomer was copolymerized with acrylic acid to form a water-soluble linear polymer containing tripyridine ligand group. Supramolecular gels can be rapidly coordinated with transition metal ions in aqueous solution. The properties of sol and gel were characterized by intrinsic viscosity, dynamic rheology, water absorbency, thermal analysis and micromorphology analysis. The ligand was prepared into a low concentration solution, and the spectral properties were studied by complexing with trace metal ions. The results showed that the solution of high concentration ligand could coordinate with metal ions to form three dimensional structure, and the dynamic modulus of sol and gel changed greatly, and the gel showed intelligent environmental response, and acid base and ion environment could reduce the absorbency of gel. However, the crosslinking structure was not destroyed, indicating that the metal coordination bond has a certain binding strength. The spectra of low concentration ligands and their complexes were measured. The results showed that the UV-Vis absorption peak value of ligand solution was 305 nm, and the absorption peak value of ligands was shifted to different degrees by adding certain concentration of Fe2 Ni2 / Cu2 / CD2 / Zn2 / Zn2 +, respectively. The absorption intensity of ligands also changed, and the linear relationship was obvious in some ion concentration ranges. The ligands have fluorescence emission properties, while Fe2 Ni2Cu2 can quench the fluorescence of ligands, and the ligand complexes with Cd2 + Zn2 + have fluorescence emission, and the luminescence of ligands can be quenched when the ligands are complexed with Cd2 ~ (2 +) Zn _ (2). And the fluorescence emission peak red shift. These molecules exhibit excellent ion sensing function and are expected to be applied to trace analysis of specific metal ions in water systems.
【學(xué)位授予單位】：青島科技大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O648.17

【參考文獻(xiàn)】

相關(guān)期刊論文 前10條

1 華慢;龔元元;梁暉;盧江;;反相懸浮聚合法制備球狀卡波樹脂的研究[J];高分子學(xué)報;2013年09期

2 王一龍;畢彩豐;趙宇;王強;申云霞;;卡波樹脂的合成及性能研究[J];中國海洋大學(xué)學(xué)報(自然科學(xué)版);2010年09期

3 張群;王振華;方偉;白競冰;武愛軍;;吸水膨脹橡膠的研究進(jìn)展[J];世界橡膠工業(yè);2010年03期

4 薛鐵中;華慢;袁立新;;卡波樹脂在化妝品中的應(yīng)用[J];日用化學(xué)品科學(xué);2009年11期

5 楊瑞成;楊娟;穆元春;陳奎;;聚丙烯酸高吸水性聚合物的制備與性能[J];蘭州理工大學(xué)學(xué)報;2008年05期

6 朱維平;徐玉芳;錢旭紅;;具有重要生物學(xué)意義的重金屬及過渡金屬離子熒光分子探針[J];化學(xué)進(jìn)展;2007年09期

7 盧毅;張彤;陶建生;;卡波姆在藥劑學(xué)中的應(yīng)用[J];中國醫(yī)藥工業(yè)雜志;2007年06期

8 張國梅,雙少敏,鈔建賓,潘景浩;環(huán)糊精超分子化學(xué)在生命科學(xué)研究中的新進(jìn)展[J];分析科學(xué)學(xué)報;2005年02期

9 李小迪;水溶性高分子化合物在化妝品配方中的應(yīng)用[J];香料香精化妝品;2004年05期

10 李旭東,史顯宗,王進(jìn),張鋒,于善普;影響涂料印花增稠劑增稠及抗?jié)B化性能的因素[J];青島化工學(xué)院學(xué)報;1998年04期

相關(guān)博士學(xué)位論文 前2條

1 董盛誼;基于冠醚的超分子聚合物和超分子凝膠的研究[D];浙江大學(xué);2012年

2 于智莘;基于-C=O…H-N-氫鍵的有機小分子凝膠的自組織行為及性質(zhì)研究[D];吉林大學(xué);2011年

相關(guān)碩士學(xué)位論文 前3條

1 耿慶霞;以瓜環(huán)為主體的超分子探針對金屬離子的識別作用[D];貴州大學(xué);2016年

2 劉立星;沉淀聚合法合成卡波樹脂的研究[D];廣東工業(yè)大學(xué);2013年

3 王賽;基于脲基氫鍵組裝的光響應(yīng)性偶氮苯功能超分子凝膠的設(shè)計、合成與表征[D];南京大學(xué);2013年

，

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