鋅、鋁配合物的合成、表征及催化環(huán)酯開環(huán)聚合
發(fā)布時間：2018-12-08 08:32
【摘要】：脂肪族聚酯如聚己內(nèi)酯(PCL)、聚丙交酯(PLA)、聚丁內(nèi)酯(PHB)及其共聚物,因具有良好的生物相容性、生物降解性和滲透性而被廣泛應(yīng)用于生物、醫(yī)藥、材料領(lǐng)域,金屬催化環(huán)酯開環(huán)聚合是合成這些聚合物的有效方法。單活性位點(diǎn)催化劑因其在酯開環(huán)聚合中良好的反應(yīng)活性和可控性得到了廣泛的研究,可以從鏈末端機(jī)理和活性基團(tuán)控制機(jī)理闡述具體的聚合過程。可以通過精心設(shè)計(jì)配體、選擇中心金屬、引發(fā)劑從而精確調(diào)控聚合速率、聚合物分子量、聚合物分子量分布以及聚合的立構(gòu)選擇性。第一章闡述可降解脂肪族聚酯研究背景,環(huán)酯單體開環(huán)聚合的機(jī)理研究,重點(diǎn)介紹丙交酯的選擇性聚合,并詳細(xì)介紹了各種開環(huán)聚合的金屬催化體系。第二章描述一系列卡賓配位的鋅配合物的合成、表征及其對外消旋丙交酯(rac-LA)開環(huán)聚合的催化作用。在芐醇的存在下,所有的鋅催化劑都能夠有效地催化外消旋丙交酯開環(huán)聚合,聚合物的分子量可控,分子量分布窄,聚合反應(yīng)有活性聚合的特征。第三章介紹了含氮雜環(huán)卡賓的C,N,O-三齒配體穩(wěn)定的鋅配合物的合成、表征及其對rac-LA開環(huán)聚合的催化作用。催化劑具有高活性、可控性好的特征。第四章介紹了含吡咯基配體([2-{5-R'2NCH2(C4H2N)}]2CR2)配位的雙核和三核鋅配合物的合成、表征及催化研究。配體的取代基位阻決定配合物的結(jié)構(gòu),當(dāng)R為乙基時得到三核鋅配合物,當(dāng)R為芳基如苯基和1,1'-聯(lián)苯-2,2'-二取代基時,產(chǎn)生雙核配合物。三核鋅配合物不穩(wěn)定,實(shí)際引發(fā)聚合過程的活性物種較復(fù)雜,聚合可控性較差,動力學(xué)實(shí)驗(yàn)表明聚合對單體的濃度既不是一級也不是二級反應(yīng)。相同條件下雙核鋅的催化活性和可控性都較好,聚合對單體的濃度是一級反應(yīng)。第五章介紹了含鄰菲羅啉配體配位的N,N,O-三齒鋁配合物的合成、表征及催化環(huán)酯開環(huán)聚合作用研究。在芐醇的存在下,該催化體系能有效催化ε-己內(nèi)酯、rac-丙交酯、β-丁內(nèi)酯開環(huán)聚合。配體上取代基對聚合活性有顯著影響,該催化體系能有效地催化ε-CL開環(huán)聚合,所得聚合物的分子量可控,分子量分布窄。丙交酯開環(huán)聚合得到等規(guī)傾向的PLA,動力學(xué)研究揭示聚合對于單體濃度和催化劑濃度都是一級反應(yīng)。聚合丁內(nèi)酯,可控性較差,得到無規(guī)聚合物。利用聚合反應(yīng)的活性特征也得到一些嵌段聚合物。
[Abstract]:Aliphatic polyester, such as polycaprolactone (PCL), polylactide (PLA), polybutyllactone (PHB) and its copolymers, have been widely used in the fields of biology, medicine and materials because of their good biocompatibility, biodegradability and permeability. Metal-catalyzed ring-opening polymerization of cycloesters is an effective method for the synthesis of these polymers. Single active site catalyst has been widely studied for its good reaction activity and controllability in the ring-opening polymerization of ester. The polymerization process can be explained from the chain end mechanism and the active group control mechanism. The polymerization rate, molecular weight distribution and structural selectivity of polymers can be precisely regulated by carefully designed ligands, selection of central metals and initiators. In the first chapter, the research background of degradable aliphatic polyester, the mechanism of ring opening polymerization of cycloester monomer, the selective polymerization of lactide and the metal catalytic system of ring opening polymerization are introduced in detail. Chapter 2 describes the synthesis and characterization of a series of carbine-coordinated zinc complexes and their catalytic effects on ring-opening polymerization of racemic lactide (rac-LA). In the presence of benzyl alcohol, all zinc catalysts can effectively catalyze the ring-opening polymerization of racemic lactide, the molecular weight of the polymer is controllable, the molecular weight distribution is narrow, and the polymerization has the characteristics of active polymerization. In chapter 3, the synthesis, characterization and catalytic effect of C ~ (2 +) N _ (10) O ~ (3 +) -tridentate ligand stabilized zinc complex on rac-LA ring opening polymerization were introduced. The catalyst has the characteristics of high activity and good controllability. In chapter 4, the synthesis, characterization and catalytic study of binuclear and trinuclear zinc complexes with pyrrole ligand ([2- {5-R'2NCH2 (C4H2N)}] 2CR2) were introduced. The structure of the complexes is determined by the substituent steric hindrance of ligands. The trinuclear zinc complexes are obtained when R is ethyl, and binuclear complexes are produced when R is aryl such as phenyls and 1tau-1, biphenyls, 2o 2o 2 or disubstituted groups. The complex of trinuclear zinc complex is unstable, the active species that actually initiated the polymerization process are more complex, and the polymerization controllability is poor. The kinetic experiments show that the polymerization concentration to the monomer is neither a first-order nor a second-order reaction. The catalytic activity and controllability of binuclear zinc were good under the same conditions, and the concentration of monomers was the first order reaction. In chapter 5, the synthesis, characterization and catalytic ring-opening polymerization of ring opening polymerization of cycloester were studied. In the presence of benzyl alcohol, the system can effectively catalyze the ring-opening polymerization of 蔚 -caprolactone, rac- lactide and 尾 -butyrolactone. The ligand substituents have a significant effect on the polymerization activity. The catalyst system can effectively catalyze the ring-opening polymerization of 蔚-CL. The molecular weight of the obtained polymer is controllable and the molecular weight distribution is narrow. The PLA, kinetic study of isotactic tendency obtained by ring-opening polymerization of lactide shows that the polymerization is a first-order reaction for monomer concentration and catalyst concentration. Polymerization of butyrolactone, poor controllability, a random polymer. Some block polymers were also obtained by using the active characteristics of the polymerization reaction.
【學(xué)位授予單位】：中國科學(xué)技術(shù)大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2017
【分類號】：O643.36;O631.5
本文編號：2368042
[Abstract]:Aliphatic polyester, such as polycaprolactone (PCL), polylactide (PLA), polybutyllactone (PHB) and its copolymers, have been widely used in the fields of biology, medicine and materials because of their good biocompatibility, biodegradability and permeability. Metal-catalyzed ring-opening polymerization of cycloesters is an effective method for the synthesis of these polymers. Single active site catalyst has been widely studied for its good reaction activity and controllability in the ring-opening polymerization of ester. The polymerization process can be explained from the chain end mechanism and the active group control mechanism. The polymerization rate, molecular weight distribution and structural selectivity of polymers can be precisely regulated by carefully designed ligands, selection of central metals and initiators. In the first chapter, the research background of degradable aliphatic polyester, the mechanism of ring opening polymerization of cycloester monomer, the selective polymerization of lactide and the metal catalytic system of ring opening polymerization are introduced in detail. Chapter 2 describes the synthesis and characterization of a series of carbine-coordinated zinc complexes and their catalytic effects on ring-opening polymerization of racemic lactide (rac-LA). In the presence of benzyl alcohol, all zinc catalysts can effectively catalyze the ring-opening polymerization of racemic lactide, the molecular weight of the polymer is controllable, the molecular weight distribution is narrow, and the polymerization has the characteristics of active polymerization. In chapter 3, the synthesis, characterization and catalytic effect of C ~ (2 +) N _ (10) O ~ (3 +) -tridentate ligand stabilized zinc complex on rac-LA ring opening polymerization were introduced. The catalyst has the characteristics of high activity and good controllability. In chapter 4, the synthesis, characterization and catalytic study of binuclear and trinuclear zinc complexes with pyrrole ligand ([2- {5-R'2NCH2 (C4H2N)}] 2CR2) were introduced. The structure of the complexes is determined by the substituent steric hindrance of ligands. The trinuclear zinc complexes are obtained when R is ethyl, and binuclear complexes are produced when R is aryl such as phenyls and 1tau-1, biphenyls, 2o 2o 2 or disubstituted groups. The complex of trinuclear zinc complex is unstable, the active species that actually initiated the polymerization process are more complex, and the polymerization controllability is poor. The kinetic experiments show that the polymerization concentration to the monomer is neither a first-order nor a second-order reaction. The catalytic activity and controllability of binuclear zinc were good under the same conditions, and the concentration of monomers was the first order reaction. In chapter 5, the synthesis, characterization and catalytic ring-opening polymerization of ring opening polymerization of cycloester were studied. In the presence of benzyl alcohol, the system can effectively catalyze the ring-opening polymerization of 蔚 -caprolactone, rac- lactide and 尾 -butyrolactone. The ligand substituents have a significant effect on the polymerization activity. The catalyst system can effectively catalyze the ring-opening polymerization of 蔚-CL. The molecular weight of the obtained polymer is controllable and the molecular weight distribution is narrow. The PLA, kinetic study of isotactic tendency obtained by ring-opening polymerization of lactide shows that the polymerization is a first-order reaction for monomer concentration and catalyst concentration. Polymerization of butyrolactone, poor controllability, a random polymer. Some block polymers were also obtained by using the active characteristics of the polymerization reaction.
【學(xué)位授予單位】：中國科學(xué)技術(shù)大學(xué)
【學(xué)位級別】：博士
【學(xué)位授予年份】：2017
【分類號】：O643.36;O631.5
【參考文獻(xiàn)】
相關(guān)博士學(xué)位論文 前3條
1 麻文安;鋁、鋅、錫配合物的合成、表征及催化環(huán)酯開環(huán)聚合[D];中國科學(xué)技術(shù)大學(xué);2011年
2 張成;鋁、鋅、鈷、鎳絡(luò)合物的合成及催化作用研究[D];中國科學(xué)技術(shù)大學(xué);2008年
3 齊春艷;含新型膦亞胺配體的鋰、鎂、鋁、錫（Ⅱ）和鋅化合物的合成、表征及其催化環(huán)酯開環(huán)聚合研究[D];中國科學(xué)技術(shù)大學(xué);2006年
，本文編號：2368042
本文鏈接：http://sikaile.net/kejilunwen/huaxue/2368042.html
最近更新
教材專著
