丙烯酸系親水聚合物的分子設計、制備及應用研究
發(fā)布時間：2018-09-12 17:00
【摘要】：合成親水高分子,因其原料易得,結構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用。進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、智能性成為該領域的研究熱點。本論文基于丙烯酸及共聚物展開,設計并制備了一系列功能性親水聚合物,并對其結構和性能進行了詳細地表征和研究。(1)化學交聯丙烯酸微凝膠的合成與應用研究。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、掃描電鏡對凝膠結構進行了表征,并對凝膠的動態(tài)模量、粘度、透光率、聚合穩(wěn)定性等方面進行了研究。結果表明,在聚合溫度為68oC,交聯劑用量為單體質量分數的0.4%,單體濃度為14%,分散劑用量為單體質量分數的1.2%,引發(fā)劑LPO用量為單體摩爾分數的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。結果表明,通過疏水單體丙烯酸十八酯的共聚改性,在分子網絡中形成物理交聯點,可提高凝膠的耐稀釋性、耐鹽性等流變學性質;盡管添加共聚單體會使粉末潤濕時間提高,但當共聚單體添加量為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)異的流變學性質。(2)基于配位作用的超分子凝膠的合成與性能。對2,2':6',2″-三聯吡啶的苯基4'位進行修飾,形成含有可聚合雙鍵的4'-(苯乙烯基)-2,2':6',2″-三聯吡啶單體,將此單體與丙烯酸共聚,即得水溶性的含三聯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、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,以微量金屬離子絡合,進行光譜性能的測試研究。結果表明,高濃度配體溶液可瞬間與金屬離子配位形成三維結構,溶膠和凝膠的動態(tài)模量發(fā)生大幅轉變;且凝膠表現出智能環(huán)境響應性,酸堿和離子環(huán)境可降低凝膠吸水倍率,但其交聯結構并未因此破壞,表明金屬配位鍵具有一定的結合強度。將低濃度配體溶液及絡合物進行光譜測試,結果表明,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.
【學位授予單位】：青島科技大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：O648.17
本文編號：2239645
[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.
【學位授予單位】：青島科技大學
【學位級別】：碩士
【學位授予年份】：2017
【分類號】：O648.17
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