基于側(cè)鏈型含胺聚合物的功能高分子材料設(shè)計合成與應(yīng)用
發(fā)布時間：2019-07-06 19:46
【摘要】：含胺聚合物由于結(jié)構(gòu)豐富、反應(yīng)活性高等特點可被用來構(gòu)筑性能優(yōu)異的功能高分子材料。高分子合成技術(shù)和胺基修飾方法的發(fā)展進一步為此提供了強有力的支撐。本論文則主要圍繞側(cè)鏈型含胺聚合物,設(shè)計、合成新型功能高分子材料,并開展應(yīng)用化研究。內(nèi)容主要包含以下五個方面:在第二章,通過自由基共聚反應(yīng)和高碘酸鈉氧化法分別合成了烯丙基胺兩親共聚物P(AH-co-AHH)和具有二醛結(jié)構(gòu)的交聯(lián)劑。進而通過這兩種前驅(qū)體物質(zhì)之間的希夫堿反應(yīng)構(gòu)筑了可降解的水凝膠材料,并探究了其在阻斷膽酸鹽肝腸循環(huán),治療高血脂疾病中的應(yīng)用。通過多種手段對所合成聚合物前驅(qū)體和凝膠材料進行了系統(tǒng)地表征。更重要的是,等溫微量熱滴定(iTC)實驗揭示了甘氨膽酸鈉與P(AH-co-AHH)之間的結(jié)合作用主要依賴靜電相互作用和疏水締合作用的協(xié)同效應(yīng)。此外,所報道凝膠材料在模擬小腸環(huán)境中表現(xiàn)出可降解性能以及對甘氨膽酸鈉優(yōu)異的吸附性能。在第三章,通過表面原子轉(zhuǎn)移自由基聚合(SIATRP)和側(cè)鏈型胺基的二硫代氨基甲酸鹽(DTC)官能化修飾制備了 DTC聚合物梳接枝的納米二氧化硅復(fù)合材料(DTC-PGMA@SiO2),并將其作為高效的納米型重金屬離子吸附材料。反應(yīng)動力學(xué)數(shù)據(jù)表明SI-ATPR聚合反應(yīng)具有高度可控的特征。我們詳細(xì)研究了DTC-PGMA@SiO2對重金屬離子的吸附行為,包括pH影響、吸附動力學(xué)、吸附等溫線、吸附熱力學(xué)和吸附機理等。得益于規(guī)整的核-刷型結(jié)構(gòu)、高的比表面積和DTC基團的強重金屬離子吸附性能,DTC-PGMA@SiO2材料表現(xiàn)出快平衡、高容量的優(yōu)異吸附性能。循環(huán)再生實驗表明所報道的吸附材料兼具成本經(jīng)濟性和可持續(xù)應(yīng)用性。在第四章,通過可逆加成-斷裂鏈轉(zhuǎn)移(RAFT)自由基聚合,制備了包含貽貝啟發(fā)的黏附性多巴胺嵌段和草本植物啟發(fā)的抗菌性茨醇嵌段的雙嵌段共聚物(PDA-b-PBA),并將其應(yīng)用于構(gòu)筑具有持久黏附、抗菌性能的聚合物涂層。所合成的單體、聚合物、以及涂層材料通過多種手段得到了充分的表征。通過掃描電鏡和原子力顯微鏡觀測發(fā)現(xiàn)所制備的聚合物涂層具有光滑、均勻的表面形貌。得益于豐富的側(cè)鏈型多巴胺和茨醇結(jié)構(gòu),PDA-b-PBA聚合物涂層在二氧化硅、氧化鋁片、硅片和不銹鋼等多種基材表面展現(xiàn)出強健的黏附性能和優(yōu)異的廣譜抗菌性能。值得注意的是,PDA-b-PBA聚合物涂層還可構(gòu)筑在在棉布、紗布等織物表面,從而發(fā)展具有高度生物相容性和耐水洗性能的抗菌織物。在第五章,基于呋喃官能化的烯丙基胺兩親共聚物P(AH-co-AHH)和馬來酰亞胺官能化的PEG聚合物構(gòu)筑了 Diels-Alder水凝膠材料,并將其應(yīng)用于疏水性藥物的長效緩釋。通過多種手段對所合成的聚合物前驅(qū)體以及凝膠樣品進行了系統(tǒng)表征。通過分子動力學(xué)模擬、等溫微量熱滴定(iTC)等手段著重研究了P(AH-co-AHH)對苯丁酸氮芥(CBL)藥物的增溶作用。載藥凝膠在模擬胃腸道環(huán)境中,均能夠表現(xiàn)出長效的CBL緩釋行為。體外細(xì)胞實驗表明,所報道的Diels-Alder水凝膠材料具有優(yōu)異的生物相容性,且凝膠緩釋給藥方案能顯著提高CBL藥物的安全性。在第六章,首先基于N-乙烯基乙酰胺合成了新型的雙烯單體,并用以制備Fe304納米顆粒摻雜的磁性凝膠基材。依此通過堿性水解和胺基的二硫代氨基甲酸鹽(DTC)官能化構(gòu)筑了具有牢靠網(wǎng)絡(luò)骨架結(jié)構(gòu)的磁性凝膠吸附材料(DTC-PNB@Fe304),并將其應(yīng)用于處理水體重金屬離子污染。通過研究其吸附行為發(fā)現(xiàn),得益于多孔結(jié)構(gòu)和DTC基團的強配位能力,該材料表現(xiàn)出較高的金屬離子吸附容量。和傳統(tǒng)的凝膠吸附材料相比,Fe304納米顆粒的引入還賦予了DTC-PNB@Fe304材料更便捷的磁場輔助分離性能。
文內(nèi)圖片：
圖片說明：圖５－５ａ呈現(xiàn)了邋Ｇｅｌ－ＫＧｅＩ－２和Ｇｅｌｌ－３樣品的儲能模量（Ｇ，，）?
[Abstract]:The amine-containing polymer can be used to construct the functional high molecular material with excellent performance due to the rich structure and high reactivity. The development of the polymer synthesis technology and the amine modification method further provides a strong support for this purpose. The paper mainly focuses on the side chain type amine-containing polymer, and designs and synthesizes the novel functional high molecular material, and carries out the application research. The content mainly includes five aspects: in the second chapter, the allyl amine amphiphilic copolymer P (AH-co-AHH) and the cross-linking agent with the dialdehyde structure are respectively synthesized by the free-radical copolymerization and the sodium periodate oxidation method. And then the degradable hydrogel material is constructed by the Schiff base reaction between the two precursor substances, and the application of the degradable hydrogel material in the treatment of high blood lipid diseases by blocking the liver-intestinal circulation of the bile acid salt is also explored. The synthesized polymer precursor and the gel material were systematically characterized by various means. More importantly, the isothermal microthermal titration (iTC) experiment revealed that the combination of sodium glycocholate and P (AH-co-AHH) mainly depends on the synergistic effect of electrostatic interaction and hydrophobic association. In addition, that gel material have been reported to exhibit biodegradability in the simulated small intestine environment and excellent adsorption properties to the sodium glycocholate. In the third chapter, a DTC polymer comb-grafted nano-silica composite (DTC-PGMA@SiO2) was prepared by functional modification of a surface atom transfer free radical polymerization (SIATRP) and a dithio carbamate (DTC) functional modification of a side chain type amine group, And is used as an efficient nano-type heavy metal ion adsorbing material. The reaction kinetic data indicate that the SI-ATPR polymerization has a highly controllable characteristic. The adsorption behavior of DTC-PGMA@SiO2 to heavy metal ions was studied in detail, including pH, adsorption kinetics, adsorption isotherm, adsorption thermodynamics and adsorption mechanism. Due to the regular core-brush type structure, the high specific surface area and the strong heavy metal ion adsorption performance of the DTC group, the DTC-PGMA@SiO2 material exhibits the excellent adsorption performance of fast balance and high capacity. The cyclic regeneration experiments show that the reported adsorption materials are both cost-effective and sustainable. in chap. IV, a bi-block copolymer (PDA-b-PBA) containing mussels-inspired, adhesive dopamine block and herbal-inspired antimicrobial peptide block was prepared by free-radical polymerization of a reversible addition-break chain transfer (RAFT), A polymeric coating of antimicrobial properties. The synthesized monomers, polymers, and coating materials are sufficiently characterized by a variety of means. The surface morphology of the prepared polymer coating was observed by scanning electron microscope and atomic force microscope. The PDA-b-PBA polymer coating has strong adhesion performance and excellent broad-spectrum antibacterial performance on various substrate surfaces such as silicon dioxide, aluminum oxide sheet, silicon chip and stainless steel due to the rich side chain type dopamine and the Tzol structure. It is to be noted that the PDA-b-PBA polymer coating can also be constructed on the surface of a fabric such as cotton, gauze, etc., thereby developing an antibacterial fabric having a high degree of biocompatibility and water-washing performance. In the fifth chapter, the Diels-Alder hydrogel material is constructed based on the functionalized allyl amine amphiphilic copolymer P (AH-co-AHH) and the maleimino-functionalized PEG polymer, and is applied to the long-acting sustained-release of the hydrophobic drug. The synthesized polymer precursor and the gel sample were characterized by various means. The effect of P (AH-co-AHH) on the drug of chlorambucil (CBL) was studied by means of molecular dynamics simulation and isothermal microthermal titration (iTC). The drug-loaded gel can show long-acting CBL sustained-release behavior in the simulated gastrointestinal tract. In vitro cell experiments show that the reported Diels-Alder hydrogel material has excellent biocompatibility, and the gel sustained-release administration scheme can significantly improve the safety of the CBL drug. In chapter 6, the novel diolefin monomer is first synthesized based on N-vinylethenamine and used to prepare the Fe304 nano-particle-doped magnetic gel base material. The magnetic gel adsorption material (DTC-PNB@Fe304) with a solid network framework structure is constructed by the function of the dithio carbamate (DTC) of the basic hydrolysis and the amino group, and is applied to the treatment of the heavy metal ion pollution of the water body. By studying its adsorption behavior, it is found that the material exhibits high metal ion adsorption capacity due to the strong coordination ability of the porous structure and the DTC group. Compared with the traditional gel adsorption material, the introduction of the Fe304 nano-particles also gives a more convenient magnetic field-assisted separation performance of the DTC-PNB@Fe304 material.
【學(xué)位授予單位】：山東大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2017
【分類號】：TQ317
本文編號：2511281
文內(nèi)圖片：
圖片說明：圖５－５ａ呈現(xiàn)了邋Ｇｅｌ－ＫＧｅＩ－２和Ｇｅｌｌ－３樣品的儲能模量（Ｇ，，）?
[Abstract]:The amine-containing polymer can be used to construct the functional high molecular material with excellent performance due to the rich structure and high reactivity. The development of the polymer synthesis technology and the amine modification method further provides a strong support for this purpose. The paper mainly focuses on the side chain type amine-containing polymer, and designs and synthesizes the novel functional high molecular material, and carries out the application research. The content mainly includes five aspects: in the second chapter, the allyl amine amphiphilic copolymer P (AH-co-AHH) and the cross-linking agent with the dialdehyde structure are respectively synthesized by the free-radical copolymerization and the sodium periodate oxidation method. And then the degradable hydrogel material is constructed by the Schiff base reaction between the two precursor substances, and the application of the degradable hydrogel material in the treatment of high blood lipid diseases by blocking the liver-intestinal circulation of the bile acid salt is also explored. The synthesized polymer precursor and the gel material were systematically characterized by various means. More importantly, the isothermal microthermal titration (iTC) experiment revealed that the combination of sodium glycocholate and P (AH-co-AHH) mainly depends on the synergistic effect of electrostatic interaction and hydrophobic association. In addition, that gel material have been reported to exhibit biodegradability in the simulated small intestine environment and excellent adsorption properties to the sodium glycocholate. In the third chapter, a DTC polymer comb-grafted nano-silica composite (DTC-PGMA@SiO2) was prepared by functional modification of a surface atom transfer free radical polymerization (SIATRP) and a dithio carbamate (DTC) functional modification of a side chain type amine group, And is used as an efficient nano-type heavy metal ion adsorbing material. The reaction kinetic data indicate that the SI-ATPR polymerization has a highly controllable characteristic. The adsorption behavior of DTC-PGMA@SiO2 to heavy metal ions was studied in detail, including pH, adsorption kinetics, adsorption isotherm, adsorption thermodynamics and adsorption mechanism. Due to the regular core-brush type structure, the high specific surface area and the strong heavy metal ion adsorption performance of the DTC group, the DTC-PGMA@SiO2 material exhibits the excellent adsorption performance of fast balance and high capacity. The cyclic regeneration experiments show that the reported adsorption materials are both cost-effective and sustainable. in chap. IV, a bi-block copolymer (PDA-b-PBA) containing mussels-inspired, adhesive dopamine block and herbal-inspired antimicrobial peptide block was prepared by free-radical polymerization of a reversible addition-break chain transfer (RAFT), A polymeric coating of antimicrobial properties. The synthesized monomers, polymers, and coating materials are sufficiently characterized by a variety of means. The surface morphology of the prepared polymer coating was observed by scanning electron microscope and atomic force microscope. The PDA-b-PBA polymer coating has strong adhesion performance and excellent broad-spectrum antibacterial performance on various substrate surfaces such as silicon dioxide, aluminum oxide sheet, silicon chip and stainless steel due to the rich side chain type dopamine and the Tzol structure. It is to be noted that the PDA-b-PBA polymer coating can also be constructed on the surface of a fabric such as cotton, gauze, etc., thereby developing an antibacterial fabric having a high degree of biocompatibility and water-washing performance. In the fifth chapter, the Diels-Alder hydrogel material is constructed based on the functionalized allyl amine amphiphilic copolymer P (AH-co-AHH) and the maleimino-functionalized PEG polymer, and is applied to the long-acting sustained-release of the hydrophobic drug. The synthesized polymer precursor and the gel sample were characterized by various means. The effect of P (AH-co-AHH) on the drug of chlorambucil (CBL) was studied by means of molecular dynamics simulation and isothermal microthermal titration (iTC). The drug-loaded gel can show long-acting CBL sustained-release behavior in the simulated gastrointestinal tract. In vitro cell experiments show that the reported Diels-Alder hydrogel material has excellent biocompatibility, and the gel sustained-release administration scheme can significantly improve the safety of the CBL drug. In chapter 6, the novel diolefin monomer is first synthesized based on N-vinylethenamine and used to prepare the Fe304 nano-particle-doped magnetic gel base material. The magnetic gel adsorption material (DTC-PNB@Fe304) with a solid network framework structure is constructed by the function of the dithio carbamate (DTC) of the basic hydrolysis and the amino group, and is applied to the treatment of the heavy metal ion pollution of the water body. By studying its adsorption behavior, it is found that the material exhibits high metal ion adsorption capacity due to the strong coordination ability of the porous structure and the DTC group. Compared with the traditional gel adsorption material, the introduction of the Fe304 nano-particles also gives a more convenient magnetic field-assisted separation performance of the DTC-PNB@Fe304 material.
【學(xué)位授予單位】：山東大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2017
【分類號】：TQ317
本文編號：2511281
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