本文選題：胺基雙酚配體 + 鈦、鋯金屬催化劑　； 參考：《內(nèi)蒙古工業(yè)大學(xué)》2017年碩士論文

【摘要】：發(fā)展均相催化劑/引發(fā)劑已經(jīng)越來越受到人們的重視,因?yàn)樗梢源呋铣删哂辛己蒙锝到庑缘母叻肿泳酆衔?如聚乳酸(PLA),聚己內(nèi)酯(PCL)以及其它可以用可再生的資源來制備的聚合物,用來取代石化制品以緩解其被隨意丟棄后所帶來的環(huán)境壓力。近年來,這類聚合物已經(jīng)被廣泛用于藥物輔料,可被人體代謝掉的手術(shù)縫合線,醫(yī)學(xué)植入材料以及生物組織工程支架等方面。目前,聚乳酸的制備合成主要通過丙交酯的開環(huán)聚合反應(yīng)來實(shí)現(xiàn)。本文合成了兩個(gè)對(duì)稱N-胺丙基嗎啉雙酚配體、兩個(gè)對(duì)稱胺基雙酚類單配體異丙氧基鈦金屬催化劑(LM(O~iPr)_2,L=-OC_6H_2-4-R~1-6-R~2-2-CH_2-N[(CH_2)_3-N(CH_2CH_2)_2O]-CH_2-4-R~1-6-R~2-C_6H_2O-,R~1=Me,R~2=~tBu,M=Ti,催化劑1;R~1=R~2=~tBu,M=Ti,催化劑2)以及兩個(gè)對(duì)稱胺基雙酚類雙配體鋯金屬催化劑(L_2M,L=~tBu,M=Zr,催化劑3;R~1=R~2=~tBu,M=Zr,催化劑4),所合成的催化劑通過了核磁共振氫譜(~1H MNR),核磁共振碳譜(~(13)C NMR)以及元素分析鑒定。其中,催化劑1和4經(jīng)過X-ray射線單晶衍射的表征分析,確定了其結(jié)構(gòu)。催化劑4的變溫核磁測(cè)試結(jié)果表明,催化劑4中嗎啉基團(tuán)的旋轉(zhuǎn)引起了H信號(hào)峰的差異。在對(duì)催化劑1,2,3,4的催化性能研究過程中發(fā)現(xiàn),這4個(gè)催化劑均能高效地引發(fā)L-丙交酯(L-LA)和rac-丙交酯(rac-LA)開環(huán)聚合反應(yīng)。實(shí)驗(yàn)結(jié)果表明,在無溶劑的條件下,催化劑3和4甚至可以有效地實(shí)現(xiàn)L-丙交酯(L-LA)和rac-丙交酯(rac-LA)的“不死”開環(huán)聚合反應(yīng)。單體與催化劑的摩爾比高達(dá)200 000/1,這個(gè)比例是現(xiàn)有文獻(xiàn)報(bào)道中,對(duì)于丙交酯開環(huán)聚合反應(yīng)的最高比例。得到了具有較高分子量(8.64×10~4g/mol)和較窄分子量分布(1.11 1.58)的丙交酯聚合物。在聚合過程中,單體分子在單位時(shí)間內(nèi)的轉(zhuǎn)化頻率(TOF)值可達(dá)6593 h~(-1),而且,即使在空氣氣氛下,聚合反應(yīng)依然可以高效地進(jìn)行。另外,通過對(duì)催化劑1,2催化L-LA、rac-LA得到的丙交酯聚合物進(jìn)行核磁共振氫譜(~1H MNR),基質(zhì)輔助激光解吸電離飛行時(shí)間質(zhì)譜(MALDI-TOF-MS)表征,推測(cè)出催化劑1,2引發(fā)L-LA、rac-LA開環(huán)聚合的聚合機(jī)理是由異丙氧基基團(tuán)(O~iPr)引發(fā)的配位插入機(jī)理。根據(jù)對(duì)催化劑3,4催化L-LA、rac-LA開環(huán)聚合所得聚丙交酯的分析結(jié)果,推測(cè)出在不加入苯甲醇(Bn OH)時(shí)催化劑3,4引發(fā)L-LA、rac-LA開環(huán)聚合的聚合機(jī)理為配體酚氧基引發(fā)的配位插入機(jī)理,在加入Bn OH時(shí)催化劑3,4引發(fā)L-LA、rac-LA開環(huán)聚合的聚合機(jī)理為Bn O-引發(fā)的配位插入機(jī)理。
[Abstract]:More and more attention has been paid to the development of homogeneous catalysts / initiators because they can catalyze the synthesis of polymers with good biodegradability. Polylactic acid (PLA), polycaprolactone (PCL) and other polymers that can be prepared with renewable resources are used to replace petrochemical products to relieve environmental pressure when they are discarded at will. In recent years, such polymers have been widely used in pharmaceutical excipients, surgical sutures that can be metabolized, medical implants and scaffolds for biological tissue engineering. At present, the synthesis of polylactic acid is mainly achieved by ring-opening polymerization of lactide. Two symmetric N-aminopropyl morpholine bisphenol ligands were synthesized. 涓や釜瀵圭О鑳哄熀鍙岄厷綾誨崟閰嶄綋寮備笝姘у熀閽涢噾灞炲偓鍖栧墏(LM(O~iPr)_2,L=-OC_6H_2-4-R~1-6-R~2-2-CH_2-N[(CH_2)_3-N(CH_2CH_2)_2O]-CH_2-4-R~1-6-R~2-C_6H_2O-,R~1=Me,R~2=~tBu,M=Ti,鍌寲鍓，

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