【摘要】：本論文中合成并研究了12個新的金屬化合物。以苯胺的衍生物Ph N(Li)Si Me_3(L~1)為起始原料,分別與兩倍量的二甲基氨基腈或哌啶腈進行加成反應后,再與三分之一量Ti Cl_4(THF)_2反應,培養(yǎng)晶體,最終得到了3個1,3,5-三氮雜戊二烯Ti化合物2a-2c。按照得到化合物2b的實驗過程反應后,再與等摩爾量的CH_3Li反應,得到化合物2d-2d'。以2-氨基吡啶的衍生物(2-C_5H_4N)N(H)Si Me_3(L~2)為起始原料,先經(jīng)等摩爾量的正丁基鋰鋰化后,再分別與等摩爾量的二甲基氨基腈或哌啶腈進行加成反應后,然后分別與無水Cr Cl_2、Fe Cl_2、Cu Cl_2、Sn Cl_2以不同的比例發(fā)生復分解反應,得到了8個1,3,5-三氮雜戊二烯化合物3a-3h。通過X-射線單晶衍射、核磁共振(NMR)、元素分析和熔點測定對這12個化合物進行了詳細表征。通過改變反應溫度、助催化劑含量等實驗條件,對其中兩種Ti化合物(2a和2c)對乙烯聚合的催化活性進行研究。具體內(nèi)容分為三章:第一章,介紹了本論文工作的研究背景、研究意義、研究目的和研究進展。主要內(nèi)容包括引言、1,3,5-三氮雜戊二烯金屬有機化合物、吡啶衍生物類金屬有機化合物、金屬有機Ti化合物等三個部分。第二章,簡述了金屬Ti化合物的研究現(xiàn)狀。以Ph N(Li)Si Me_3(L~1)為原料,與兩倍摩爾量的二甲氨基腈或1-哌啶腈加成后,再與Ti Cl_4(THF)_2發(fā)生復分解反應,得到了1,3,5-三氮雜戊二烯Ti化合物2a-2c(Scheme 1)。按照得到2b的實驗過程,與Ti Cl_4(THF)_2反應后,再與CH_3Li反應,得到化合物2d-2d'(Scheme 1)。通過X-射線單晶衍射、核磁共振(NMR)、熔點測定和元素分析等手段,對它們的物理和化學性質(zhì)進行了詳細表征。將化合物2a和2c作為主催化劑催化乙烯的聚合反應,通過改變反應溫度和Al/Ti對其催化性能進行了具體研究。實驗結(jié)果為在溫度為70℃、Al/Ti為1000時,化合2a的活性達到最大為5.66×10~(4 )g PE·mol~(-1)·h~(-1),化合物2c的催化活性達到最大為4.5×10~(4 )g PE·mol~(-1)·h~(-1)。第三章,簡述了吡啶衍生物配體的研究背景和研究現(xiàn)狀。以(2-C_5H_4N)N(H)Si Me_3(L~2)為原料,與等摩爾量的正丁基鋰反應后,然后與等摩爾量的二甲氨基腈或哌啶腈加成后,再分別與無水Cr Cl_2、Fe Cl_2、Cu Cl_2、Sn Cl_2發(fā)生復分解反應,最終得到了8個新的1,3,5-三氮雜戊二烯Cr(II)、Fe(II)、Cu(II)、Sn(II)化合物3a-3h(Scheme 1)。通過X-射線單晶衍射、核磁共振(NMR)、熔點測定和元素分析等手段,對它們的物理和化學性質(zhì)進行了詳細表征。圖1化合物2a-2c,和2d-2d'的合成路線Scheme 1 Synthetic routes to complexes 2a-2c,and 2d-2d'Reagents and conditions:i 2Me_2NCN,Et_2O,ca.-78℃;1/3 Ti Cl_4(THF)_2,Et_2O,ca.-78℃.ii 2Me_2NCN,Et_2O,ca.-78℃;1/3 TiCl_4(THF)_2,Et_2O,ca.-78℃.iii 2 1-Piperidinecarbonitrile,Et_2O,ca.-78℃;1/3 TiCl_4(THF)_2,Et_2O,ca.-78℃.iv 2Me_2NCN,Et_2O,ca.-78℃;TiCl_4(THF)_2,Et_2O,ca.-78℃;1/3 CH_3Li,Et_2O,ca.0℃.圖2化合物3a-3h的合成路線Scheme 2 Synthetic routes to complexes 3a-3hReagents and conditions:i Bu~(n )Li,Et_2O,0℃;Me_2NCN,Et_2O,ca.-78℃;1/2 Cr Cl_2,Et_2O,ca.-78℃.ii Bu~(n )Li,Et_2O,0℃;1-Piperidinecarbonitrile,Et_2O,ca.-78℃;1/2 Cr Cl_2,Et_2O,ca.-78℃.iii Bu~(n )Li,THF,0℃;Me_2NCN,THF,ca.-78℃;1/2 Fe Cl_2,THF,ca.-78℃;CH_2Cl_2.iv Bu~(n )Li,Et_2O,0℃;Me_2NCN,Et_2O,ca.-78℃;1/2 Cu Cl_2,Et_2O,ca.-78℃.v Bu~(n )Li,Et_2O,0℃;Me_2NCN,Et_2O,ca.-78℃;1/2 Cu Cl_2,Et_2O,ca.-78℃.vi Bu~(n )Li,Et_2O,0℃;1-Piperidinecarbonitrile,Et_2O,ca.-78℃;1/2 Cu Cl_2,Et_2O,ca.-78℃.vii Bu~(n )Li,Et_2O,0℃;Me_2NCN,Et_2O,ca.-78℃;Sn Cl_2,Et_2O,ca.-78℃.
[Abstract]:Twelve new metal compounds were synthesized and studied in this paper. Three 1,3,5-triazapentadiene Ti compounds 2a-1 were synthesized from aniline derivative Ph N(Li)Si Me_3(L~1) by addition reaction with two times of dimethylaminonitrile or piperidinitrile respectively and then with one third of Ti Cl_4(THF)_2. 2c. Compound 2d-2d'. Starting from 2-aminopyridine derivative (2-C_5H_4N) N (H) Si Me_3 (L~2), the compound 2B was lithized with n-butyl lithium and then reacted with dimethylaminonitrile or piperidinitrile respectively. Eight 1,3,5-triazapentadiene compounds 3a-3h were synthesized by double decomposition reaction with anhydrous Cr Cl_2, Fe Cl_2, Cu Cl_2 and Sn Cl_2 in different ratios. The 12 compounds were characterized by X-ray single crystal diffraction, nuclear magnetic resonance (NMR), elemental analysis and melting point determination. The catalytic activities of two Ti compounds (2a and 2c) for ethylene polymerization were studied under different experimental conditions, including the content of Ti, the content of Ti, the content of Ti, the content of Ti, the content of Ti, the content of Ti, the content of Ti, the content of Ti, the content of Ti, the content of Ti, the content of Ti, the content of Ti, the content of Ti, the content of Ti, the content of Ti, the Metallo-organic compounds, organometallic Ti compounds and so on. In the second chapter, the research status of metal Ti compounds is briefly reviewed. The 1,3,5-triazapentadiene Ti compound 2 was synthesized from Ph N (Li) Si Me_3 (L~1) as raw material, which was added with dimethylaminonitrile (DMN) or 1-piperidinitrile (1-piperidinitrile), and then reacted with Ti Cl_4 (THF) _2. A-2c (Scheme 1). According to the experimental process of obtaining 2b, reacting with Ti Cl_4 (THF) _2 and CH_3Li, compounds 2d-2d'(Scheme 1) were obtained. Their physical and chemical properties were characterized by X-ray single crystal diffraction, nuclear magnetic resonance (NMR), melting point determination and elemental analysis. Compounds 2a and 2C were used as main catalysts. The results showed that the activity of 2A reached the maximum of 5.66 (4) g PE (mol) (-1) (-1) (-1) (-1) and compound 2C reached the maximum of 4.5 (4) g PE (mol) (-1) (-1) when the temperature was 70, and Al/Ti was 1000. In this chapter, the research background and present situation of pyridine derivative ligands are briefly described. Eight new compounds are obtained by the reaction of (2-C_5H_4N) N (H) Si Me_3 (L~2) with n-butyl lithium at the same molar amount, then with dimethylaminonitrile or piperidinitrile at the same molar amount, and then with anhydrous Cr Cl_2, Fe Cl_2, Cu Cl_2, Sn Cl_2 respectively. The physical and chemical properties of 1,3,5-triazapentadiene Cr (II), Fe (II), Cu (II), Sn (II) compounds 3a-3h (Scheme 1) were characterized in detail by X-ray single crystal diffraction, nuclear magnetic resonance (NMR), melting point determination and elemental analysis. a-2c,and 2d-2d'Reagents and conditions:i 2Me_2NCN,Et_2O,ca.-78鈩，

本文編號：2184687