摘要
采用邻苯二甲醛(酮)与氨基取代苯酚反应得到配体Ll-L4,然后与过渡金属卤化物反应,即得到非茂催化剂Cat.1-Cat.12。采用1H NMR,元素分析等手段对配体L1-L4的微观结构进行了表征。采用非茂催化剂(Cat.1-Cat.12)与MAO组成催化体系,催化乙烯聚合及乙烯/丙烯腈共聚合。探讨了催化剂结构及金属中心原子、聚合温度、A1/M摩尔比、催化剂浓度对乙烯聚合及乙烯/丙烯腈共聚合的影响。采用WAXD, DSC,13C NMR, FT-IR及GPC等手段对聚乙烯及乙烯/丙烯腈共聚物的结构和性能进行了表征。本文主要做了三方面的工作,即非茂催化剂(Cat.1-Cat.12)的合成,乙烯聚合[由(Cat.1-Cat.12)/MAO催化聚合]及乙烯/丙烯腈共聚合[由(Cat.4-Cat.12)/MAO催化聚合]。
首先,采用邻苯二甲醛(酮)与氨基取代苯酚(2-氨基-4-甲基苯酚,2-氨基-5-甲基苯酚,2-氨基-4-叔丁基苯酚)反应得到四种化合物,即配体L1-L4,然后与过渡金属卤化物(TiCl4, ZrCl4, YCl3)反应,得到一系列新型苯氧基亚胺非茂催化剂Cat.1-Cat.12。
其次,采用催化剂(Cat.1-Cat.12)/MAO催化乙烯聚合。结果发现催化剂结构、金属中心原子及反应条件对催化剂的催化活性影响较大,其中催化剂Cat.10的催化活性(2.93×106g PE/mol.Y.h)最大,分子量大,分子量分布窄(MW=3.35×105 g/mol, MWD=1.84)。此外,催化剂的催化活性在40-60℃范围内随温度的升高先上升后下降,在50℃达到最大值;随A1/M摩尔比及催化剂浓度的增加先上升后下降,在n(Al)/n(M)=300及催化剂浓度为1.0×104mol/L时达到最大值。聚合物的FT-IR,13C NMR结果表明所得聚乙烯为线型结构。
第三,采用催化剂(Cat.4-Cat.12)/MAO催化乙烯/丙烯腈进行共聚合。结果发现以前过渡金属Ti为活性中心的催化剂Cat.6的催化活性最好,为1.77×104g P/mol.Ti.h,且具有较强的耐杂原子能力。WAXD, DSC表明共聚物中丙烯腈的插入量随着反应体系中丙烯腈浓度的增加而增加,丙烯腈的插入在一定程度上破坏了聚乙烯链的规整性,使其结晶度降低,熔点降低;13C NMR, FT-IR结果表明共聚物中丙烯腈摩尔浓度可达2.29%,共聚单体丙烯腈在大分子链中呈无规分布,不存在长序列结构单元,有利于共聚物性能的均匀化;GPC结果表明共聚物的重均分子量可达36500 g/mol,分子量分布小于2,呈单一分布。
Phthaldialdehyde (ketone) was treated with substituted phenol to obtain ligands(L1-L4) which were then treated with transition metal halide, and obtained a series of novel non-metallocene catalysts(Cat.1-Cat.12). The structures of the ligands(L1-L4) were characterized by 1H-NMR and Elemental Analysis. These catalysts(Cat.1-Cat.12) were used to promote ethylene polymerization and ethylene/acrylonitrile copolymerization. The effects of the ligand structures and the metal center atoms(Ti, Zr) of these catalysts, polymetization temperature, Al/M molar ratio and concentration of catalyst on polymerization performance were investigated in detail. The structures and properties of polyethylene and ethylene/acrylonitrile copolymer obtained were characterized by WAXD, DSC,13C NMR, FT-IR and GPC. The main work in this thesis is composed of non-metallocene catalysts(Cat.1-Cat.12) synthesis, ethylene polymerization catalyzed by catalysts(Cat.1-Cat.12)/MAO and ethylene/acrylontrile copolymerization catalyzed by catalysts(Cat.4-Cat.12)/MAO.
Firstly, Phthaldialdehyde(ketone) was treated with substituted phenol (2-amino-4-methylphenol,2-amino-5-methylphenol,2-amino-4-tert-butyl-Phenol) to obtain a series of ligands(L1-L4) which were then treated with transition metal halide(TiCl4, ZrCl4, YCl3), so that the novel non-metallocene catalysts(Cat.1-Cat.12) with phenoxy-imine ligands were obtained.
Secondly, the catalysts(Cat.1-Cat.12)/MAO were employed in study on ethylene polymerization. The results indicated that the catalytic activity was greatly affected by the structures, metal center atoms of catalysts and reaction conditions. Besides, the catalytic activity of the catalyst(Cat.10) is the highest, up to 2.93×106 g PE/mol.Y.h, and the weight-average molecular weight of the polyethylene obtained was relative high, and its molecular weight distribution narrow(Mw=3.35×105 g/mol, MWD=1.84). It was also found that the catalytic activity of catalysts increased with enhancing temperature in the range of 40-60℃, peaking at 50℃. It also at first increased with the increasing of Al/M molar ratio and catalysts concentration and then decreaced, reaching the maximum value when Al/M molar ratio was 300, catalysts concentration 1.0×10-4mol/L. The results of 13C NMR and WAXD confirmed the linear structure of polyethylene obtained.
Thirdly, ethylene/acrylonitrile copolymerization was catalyzed by the catalysts(Cat.4-Cat.12)/MAO. It was found that the catalyst(Cat.6) with early transition metal Ti as active centre had the strong capability of resistance to hetero atoms, so its catalytic activity was up to 1.77×104 g P/mol.Ti.h. WAXD, DSC results indicated that acrylonitrile incorporation content in copolymer increased with increasing of the acrylonitrile concentration of reaction system. The stereoregularity of polyethylene chain was demaged to some extent by the introduction of acrylonitrile unit, so the crystallinity, melting point(Tm) of copolymer were decreased.13C NMR and FT-IR results revealed that acrylonitrile content in molar of copolymer was up to 2.29%, acrylontrile unit was isolated in the copolymer chain homogeneously and there was no long sequence units which were good for performance homogenization of the whole copolymer molecular chain. GPC results showed that the Mw of copolymer was as high as 36500 g/mol, MWD less than 2, showing a single distribution.
引文
[1]潘祖仁.高分子化学[M].北京:化学工业出版社,2003(第三版):160-163.
[2]肖士镜,余赋生.烯烃配位聚合催化剂及聚烯烃[M].北京:北京工业大学出版社,2002:16-47.
[3]Luo Hekuan, Tang Ruiguo, Gao Kejing. Studies on the Formation of New, Highly Active Silica-Supported Ziegler-Natta Catalyst for Ethylene Polymerization[J]. Journal of Catalysis, 2002,210:328-339.
[4]陈辉,张学全,黄葆同.TiCl4/SiO2-MgCl2载体催化剂下的乙烯/己烯-1共聚反应[J].应用化学,1996,13(5):76-78.
[5]孔媛,汪红丽,义建军,张明革,黄启谷,杨万泰.TiCl4/XROH/MgCl2/Et3Al催化剂合成宽分子量分布乙烯/1-己烯共聚物[J].应用化学,2010,27(6):626-631.
[6]豆秀丽,刘伟娇,义建军,张明革,黄启谷,杨万泰.MgCl2/SiO2复合载体Ti系催化剂的制备及其催化乙烯/1-己烯共聚[J].石油化工,2010,39(7):744-749.
[7]Bialk M, Czaja K. The effect of the comonomer on the copolymerization of ethylene with long chain α-olefins using Ziegler-Natta catalysts supported on MgCl2(THF)2[J]. Polymer,2000,41: 7899-7904.
[8]Kong Yuan, Yi Jianjun, Dou Xiuli Liu, Weijiao, Huang Qigu, Gao Kejing, Yang Wantai. With different structure ligands heterogeneous ZieglereNatta catalysts for the preparation of copolymer of ethylene and 1-octene with high comonomer incorporation[J]. Polymer,2010,51: 3859-3866.
[9]Nomura K, Oya K, Komatsu T, Imanishi Y. Effect of the Cyclopentadienyl Fragment onMonomer Reactivities and Monomer sequence Distributions in Ethylene/a-Olefin opolymerization by a Nonbridged (Cyclopentadienyl)(aryloxy)titanium(Ⅳ) complex MAO Catalyst System[J]. Macromolecules,2000,33:3187-3189.
[10]Suhm J, Schneider M J, Mulhaupt R. Influence of metallocene structures on ethene copolymerization with 1-butene and 1-octene [J]. J Mole Catal A:Chem,1998,128:215-227.
[11]Koppl A, Babel Al, Alt AG Homopolymerization of ethylene and copolymerization of ethylene and 1-hexene with bridged metallocene/methylaluminoxane catalysts:the influence of the bridging moiety[J]. J Mol Catal, A:Chem,2000,153:109-119.
[12]Koivumaki J, Fink G, Seppala J V. Copolymerization of Ethene 1-Dodecene and Ethene 1-Octadecene with the Stereorigid Zirconium Catalyst Systems iPr(Flu-Cp)ZrCl2 Mao and Me2Si(Ind)2ZrCl2 Mao-Influence of the Comonomer Chain-Length[J]. Macromolecules,1994, 27:6254-6258.
[13]Cabrera A R, Schneider Y, Valderrama M, Galland G B, Rojas R S. Synthesis and Characterization of Materials Prepared via the Copolymerization of Ethylene with 1-Octadecene and Norbornene Using a [(π-Cyano-nacnac)Cp] Zirconium Complex[J]. J Polym Sci, Part A: Polym. Chem,2011,49:1535-1542.
[14]黄启谷,马利福,邓坤学,盛亚平,赵扬锋.一种催化剂及用该催化剂制备超低密度乙烯共聚物的方法[P],CN101148487,2008.
[15]Chung T C, Lu H L, Ding R D. Synthesis of Polyethylene-g-polystyrene and Polyethylene-g-poly(p-methylstyrene) Graft Copolymers[J]. Macromolecules,1997,30: 1272-1278.
[16]盛亚平,闭涛,吕明,马利福,黄启谷,高克京,吴一弦,杨万泰.二茂钛/锡/环氧化合物引发苯乙烯活性自由基聚合的研究[J].高分子学报,2008,2:179-182.
[17]Kaita S, Yamanaka M, Horiuchi A C, Wakatsuki Y. Butadiene Polymerization Catalyzed by Lanthanide Metallocene Alkylaluminum Complexes with Cocatalysts:Metal-Dependent Control of 1,4-Cis/Trans Stereoselectivity and Molecular Weight[J]. Macromolecules,2006,39, 1359-1363.
[18]Yoshida Y, Mohri J, Ishii S, Mitani M, Saito J, Matsui S, Makio H, Nakano T, Tanaka Hi, Onda M, Yamamoto Y, Mizuno A, Fujita T. Living Copolymerization of Ethylene with Norbornene Catalyzed by Bis(Pyrrolide Imine) Titanium Complexes with MAO[J]. J Am Chem Soc,2004, 126:12023-12032.
[19]Nomura K, Wang Wei, Fujiki M, Liu Jingyu. Notable norbornene (NBE) incorporation in ethylene-NBE copolymerization catalysed by nonbridged half-titanocenes:better correlation between NBE incorporation and coordination energy[J]. Chem Commum,2006,25:2659-2661.
[20]Curran K, Risse W, Boggioni L, Tritto I. Addition Polymers of Strained Cyclic Olefins-Transition Metal Catalysed Polymerisations of the Cyclobutene Derivative Bicyclo[3.2.0]hept-6-ene[J]. Macromol Chem Phys,2008,209:707-714.
[21]Rodriguez-Delgado A, Mariott W R, Chen E YX. Synthesis and MMA polymerization of chiral ansa-zirconocene ester enolate complexes with C2- and Cs-ligation[J]. J of Organometallic Chem,2006,691:3490-3497.
[22]Yuetao Zhang, Yalan Ning, Lucia Caporaso, Luigi Cavallo, Eugene Y.-X. Chen. Catalyst-Site-Controlled Coordination Polymerization of Polar Vinyl Monomers to Highly Syndiotactic Polymers[J]. J Am Chem Soc,2010,132:2695-2709.
[23]Marques M M, Correia S G,Asceso J R, Ribeiro A F G, Gomes P T, Dias A R, Foster P, Rausch M D, Chien J CW. Polymerization with TMA-Protected Polar Vinyl Comonomers. I. Catalyzed by Group 4 Metal Complexes withrη5-type Ligands[J]. J Polym Sci, Part A:Polym. Chem,1999, 37:2457-2469.
[24]Hakala K, Helaja T, Lofgren, B. Metallocene/Methylaluminoxane-Catalyzed Copolymerizations of Oxygen-Functionalized Long-Chain Olefins with Ethylene[J]. J Polym Sci, Part A:Polym. Chem,2000,38:1966-1971.
[25]Hagihara, H.; Murata, M.; Uozumi, T. Alternating Copolymerization of Ethylene and 5-Hexen-1-ol with [Ethylene(1-indenyl)(9-fluorenyl)]-zirconium Dichloride/Methyl-aluminoxane as the Catalyst[J]. Macromol. Rapid Commun,2001,22:353-357.
[26]Imuta J, Kashiwa N. Catalytic Regioselective Introduction of Allyl Alcohol into the Nonpolar Polyolefins:Development of One-Pot Synthesis of Hydroxyl-Capped Polyolefins Mediated by a New Metallocene IF Catalyst[J]. J. Am. Chem. Soc,2002,124:1176-1177
[27]Kotzabasakis V, Petzetakis N, Pitsikalis M, Adjichristidis N, Lohse D J. Copolymerization of Tetradecene-1 and Octene-1 with Silyl-Protected 10-Undecen-1-ol Using a Cs-Symmetry Hafnium Metallocene Catalyst. A Route to Functionalized Poly(a-olefins)[J]. J Polym Sci, Part A:Polym Chem,2009,47:876-886.
[28]Ishii S, Saito J, Mitani M, Mohri J, Matsukawa N, Tohi Y, Matsui S, Kashiwa N, Fujita T. Highly active ethylene polymerization catalysts based on titanium complexes having two phenoxy-imine chelate ligands[J]. J Mol Catal A:Chem[J],2002,179:11-16.
[29]Ye Weiping, Zhan Jie, Pan Li, Hu Ninghai, Li Yuesheng. Synthesis and Characterization of Titanium Complexes Bearing Two β-Enaminoketonato Ligands with Electron-Withdrawing Groups and Their Behavior in Ethylene Polymerization[J]. Organometallics,2008,27: 3642-3653.
[30]Ma Lifu, Sheng Yaping, Huang Qigu, Zhao Yangfeng Deng Kunxue, Yi Jianjun Yang Wantai. A Kind of Novel Nonmetallocene Catalysts for Ethylene Polymerizaiton[J]. J Polym Sci:Part A: Polym Chem,2008,46:33-37.
[31]Ma Lifu, Wang Hongli, Yi Jianjun, Huang Qigu, Gao Kejing, Yang Wantai. Copolymerization of Ethylene with 1-Hexene Promoted by Novel Multi-Chelated Non-Metallocene Complexes with Imine Bridged Imidazole Ligand[J]. J Polym Sci, Part A:Polym Chem,2010,48:417-424.
[32]Li Gang, Lamberti M, D'Amora S, Pellecchia C. C1-Symmetric Pentacoordinate Anilidopyridylpyrrolide Zirconium(IV) Complexes as Highly Isospecific Olefin Polymerization Catalysts[J]. Macromolecules 2010,43:8887-8891.
[33]Figueroa R, Froese R D, He Yiyong, Klosin J, Theriault C N. Synthesis of Imino-Enamido Hafnium and Zirconium Complexes:A New Family of Olefin Polymerization Catalysts with Ultrahigh-Molecular-Weight Capabilities[J]. Organometallics,2011,30:1695-1709.
[34]Wu Jiqian, Li Baixiang, Zhang Senwang, Li Yuesheng. Bis(b-enaminoketonato) Vanadium (Ⅲ or IV) Complexes as Catalysts for Olefin Polymerization[J]. J Polym Sci, Part A:Polym Chem, 2010,48:3062-3072.
[35]He Lipeng, Mu Hongliang, Li Baixiang, Li Yuesheng. Ethylene Polymerization by the Chromium Catalysts Based on Bidentate [O, P=O] or [S, P] Ligands[J]. J Polym Sci, Part A: Polym Chem,2010,48:311-319.
[36]Xu Tieqi, An Haiyan, Gao Wei, Mu Ying. Chromium(Ⅲ) Complexes with Chelating Anilido-Imine Ligands:Synthesis Structures, and Catalytic Properties for Ethylene Polymerization[J]. Eur. J. Inorg. Chem.2010,3360-3364.
[37]Zhang Xiaofan, Chen Shangtao, Li Huayi, Zhang Zhicheng, Lu Yingying, Wu Chunhong, Hu Youliang. Highly Active Copolymerization of Ethylene with 10-Undecen-1-ol Using Phenoxy-Based Zirconium/Methylaluminoxane Catalysts[J]. J Polym Sci, Part A:Polym Chem, 2005,43:5944-5952.
[38]Zhang Xiaofan, Chen Shangtao, Li Huayi, Zhang Zhicheng, Lu Yingying, Wu Chunhong, Hu Youliang. Copolymerizations of Ethylene and Polar Comonomers with Bis(phenoxyketimine) Group IV Complexes:Effects of the Central Metal Properties[J]. J Polym Sci, Part A:Polym Chem,2007,45:59-68.
[39]Terao H, Ishii S, Mitani M, Tanaka H, Fujita T. Ethylene/Polar Monomer Copolymerization Behavior of Bis(phenoxy-imine)Ti Complexes:Formation of Polar Monomer Copolymers[J]. J. Am. Chem. Soc,2008,130:17636-17637.
[40]Sudhakar P, Vijayakrishna K. Highly Stereoselective Living Polymerization of Vinyl Ethers at Ambient Temperature Mediated by Chiral Titanium Complexes[J]. ChemCatChem,2010,2: 649-652.
[41]Small B L, Brookhart M. Methods for forming amorphous ultra-high molecular weight polyalphaolefin drag reducing agents using non-metallocene catalysts and alkylaluminoxane[J]. J Am Chem Soc,1998,120:7143-7149.
[42]Abu-Surrah A S, Lappalainen K, Piironen U, Lehmus P, Repo T, Leskela M. New bis(imino)pyridine-iron(Ⅱ)-and cobalt(Ⅱ)-based catalysts:synthesis, characterization and activity towards polymerization of ethylene[J]. J of Organometallic Chemistry,2002,648: 55-61.
[43]姜涛,陈红霞,宁英男,贾辉,匡洞庭,曲广淼,宁伟,卢艳.均相后过渡金属镍络合物/烷基铝化物催化剂[P].CN 1657171A,2004.
[44]Liu Jingyu, Li Yanguo, Li Yuesheng, Hu Ninghai. Ethylene Polymerization by (a-Diimine)Nickel(Ⅱ) Complexes Bearing Different Substituents on para-Position of Imines Activated with MMAO[J]. J Appl Polym Sci,2008,109:700-707.
[45]Song Chunlei, Tang Liming, Li Yanguo, Li Xiaofang, Chen Jie, Li Yuesheng. Preparation of Linear a-Olefins to High-Molecular Weight Polyethylenes Using Cationic a-Diimine Nickel(Ⅱ) Complexes Containing Chloro-Substituted Ligands[J]. J Polym Sci Part A:Polym Chem,2006, 44:1964-1974.
[46]Guo CunYue, Peulecke N, Basvani K R, Kindermann M K, Heinicke J.2-Phosphinophenolate Nickel Catalysts:Formation of Ethylene Copolymers with Isolated sec-Alkyl, Aryl, and Functionally Substituted Alkyl Groups[J]. Macromolecules,2010,43:1416-1424.
[47]Popeney C S, Levins C M, Guan Zhibin. Systematic Investigation of Ligand Substitution Effects in Cyclophane-Based Nickel(Ⅱ) and Palladium(Ⅱ) Olefin Polymerization Catalysts[J]. Organometallics, Received:2011, March 1.
[48]Camacho D H, Guan Zhibin. Living Polymerization of α-Olefins at Elevated Temperatures Catalyzed by a Highly Active and Robust Cyclophane-Based Nickel Catalyst[J]. Macromolecules,2005,38:2544-2546.
[49]Popeney C S, Camacho D H, Guan Zhibin. Efficient Incorporation of Polar Comonomers in Copolymerizations with Ethylene Using a Cyclophane-Based Pd(Ⅱ)-Diimine Catalyst[J]. J Am Chem Soc,2007,129:10062-10063.
[50]刘伟娇,黄启谷,义建军,豆秀丽,张明革,杨万泰,马利福,李俊拢,汪红丽,孔媛,盛亚平,赵扬锋.烯烃配位聚合催化剂的研究进展[J].高分子通报,(6):1-33.
[51]Dong Weimin, Masuda T. Novel Neodymium (Ⅲ) Isopropoxide Methylaluminoxane Catalyst for Isoprene Polymerization[J]. J Polym Sci Part A:Polym Chem,2002,40:1838-1844.
[52]Fang Xiangdong, Deng Yuanfu, Xie Qinxing, Moingeon F. A Bis (1,2-Azaborolyl)yttrium Alkyl Complex:Synthesis, Structure, and Polymerization Study[J]. Organometallics,2008,27: 2892-2895.
[53]Mahrova T V, Fukin G K., Cherkasov A V, Trifonov A A, Ajellal N, Carpentier F. Yttrium Complexes Supported by Linked Bis(amide) Ligand:Synthesis,Structure, and Catalytic Activity in the Ring-Opening Polymerization of Cyclic Esters[J]. Inorg Chem,2009,48:4258-4266.
[54]Valente A, Zinck P, Mortreux A, Visseaux M. Borohydrido Rare Earth Based Coordinative Chain Transfer Copolymerization:A Convenient Tool for Tuning the Microstructure of Isoprene/Styrene Copolymers[J]. J Polym Sci Part A:Polym Chem,2011,49:1615-1620.
[55]Nomura K, Komatsu T, Imanishi Y. Ligand effect in olefin polymerization catalyzed by (cyclopentadienyl) (aryloxy) titanium(Ⅳ) complexes, Cp'TiCl (OAr)-MAO system. Ethylenerl-hexene copolymerization by 1,3-iBu2C5H3TiCl2 (O-2,6-iPr2C6H3)-MAO catalyst system[J]. Journal of Molecular Catalysis A:Chemical,2000,159:127-137.
[56]Huang Jiling, Lian Bing, Qian Yanlong, Zhou Weizhen. Syntheses of Titanium(Ⅳ) Complexes with Mono-Cp and Schiff Base Ligands and Their Catalytic Activities for Ethylene Polymerization and Ethylene/1-Hexene Copolymerization [J]. Macromolecules,2002,35: 4871-4874.
[57]Killian C M., Tempel D J, Johnson L K, Brookhart M. Living Polymerization of a-Olefins Using NiⅡ-α-Diimine Catalysts. Synthesis of New Block Polymers Based on a-Olefins[J]. J Am Chem Soc,1996,118:11664-11665.
[58]Killian C M., Johnson L K., Brookhartd M. Preparation of Linear a-Olefins Using Cationic Nickel(II)-Diimine Catalysts[J]. Organometallics,1997,16:2005-2007.
[59]Lyubov D M., Fukin G K, Trifonov A. N, N'-Diisopropyl-N"-bis(trimethylsilyl)guanidinate Ligand as a Supporting Coordination Environment in Yttrium Chemistry. Synthesis, Structure, and Properties of Complexes [(Me3Si)2NC(N/-Pr)2]YCl2(THF)2, [(Me3Si)2NC(Ni-Pr)2]Y(CH2Si-Me3)2(THF)2, and [(Me3Si)2NC(Ni-Pr)2]Y[(μ-H)(μ-Et)2BEt]2 (THF)[J]. Inorg Chem.,2007,46: 11450-11456.
[60]Quijada R, Rabagliati F M, Benavente R, Bello A. Synthesis and characterization of copolymers of ethylene and 1-octadecene using the rac-Et(Ind)2ZrCl2/MAO catalyst system[J]. Macromol Chem Phys,1999,200:1306-1310.
[61]Nomura K, Fukuda H, Katao S, Fujiki M, Kim H J, Kim D H, Saeed I. Olefin Polymerization by Half-Titanocenes Containing η2-Pyrazolato Ligands-MAO Catalyst Systems[J]. Macromolecules, Revised:February 6,2011.
[62]Hu Ping, Wang Fosong, Jin Guoxin. Syntheses, Characterization, and Ethylene Polymerization of Half-Sandwich Zirconium Complexes with Tridentate Imino-Quinolinol Ligands[J]. Organometallics,2011,30:1008-1012.
[63]Tsurugi H, Ohnishi R, Kaneko H, Panda T K., Mashima K. Controlled Benzylation of -Diimine Ligands Bound to Zirconium and Hafnium:An Alternative Method for Preparing Mono- and Bis(amido)M(CH2Ph)n (n=2,3) Complexes as Catalyst Precursors for Isospecific Polymerization of -Olefins[J]. Organometallics,2009,28:680-687.
[64]Hasumi S, Itagaki K, Zhang Shu, Nomura K. Ethylene Polymerization by Phenoxy Substituted Tris(pyrazolyl)borate Ti(IV) Methyl Complexes[J]. Macromolecules,2011,44:773-777.
[65]Froese R D J, Jazdzewski B A., Klosin J, Kuhlman R L, Theriault C N, Wels D M. Imino-Amido Hf and Zr Complexes:Synthesis, Isomerization, andOlefin Polymerization[J]. Organometallics, 2011,30:251-262.
[66]Eisenbach C D, Sperlich B. Copolymerization of Acrylonitrile and Ethene in the Presence of Trifluoroacetic Acid as Complexing Agent[J]. Macromolecules,1996,29:7748-7752.
[67]Wu Fan, Foley S R, Burns C T, Jordan R F. Acrylonitrile Insertion Reactions of Cationic Palladium Alkyl Complexes[J]. J Am Chem Soc,2005,127:1841-1853.
[68]Wu Fan, Jordan, R. F. Acrylonitrile Insertion Reactions of Palladium Alkyl Complexes that Contain Neutral or Anionic Bidentate Phosphine Ligands[J]. Organometallics,2006,25:5631-5637.
[69]Groux, L. F, Weiss T, Reddy D N, Chase P A, Piers W E, Ziegler T, Parvez, M, Benet-Buchholz J. Insertion of Acrylonitrile into Palladium Methyl Bonds in Neutral and Anionic Pd(Ⅱ) Complexes[J]. J Am Chem Soc,2005,127:1854-1869.
[70]Kochi T, Noda S, Yoshimura K, Nozaki K. Formation of Linear Copolymers of Ethylene and Acrylonitrile Catalyzed by Phosphine Sulfonate Palladium Complexes[J]. J Am Chem Soc, 2007,129:8948-8949.
[71]王建国,刘宇,黄葆同.极低密度聚乙烯与其它聚乙烯的共混[J].高分子学报,1998,(4):471-476.
[72]黄启谷,林尚安,祝方明,伍青.单茂钛催化剂催化丁烯-1聚合及高分子量无规聚丁烯-1的合成及表征[J].高等学校化学学报,2002,23(1):167-169.
[73]杨立娟,任鸿平,李传峰,陈韶辉,田稼薇.FI烯烃聚合催化剂研究进展[J].现代塑料加工应用,2010,22(5):60-63.
[74]Murray M C, Baird M C. Copolymerization of 1-hexene and ethylene catalyzed by the Ziegler catalyst Cp*TiMe3/B(C6F5;h[J]. J Polym Sci Chem,2000,38:3966-3976.
[75]Nomura K, Komatus T, Imanish Y. Ligand effect in olefin polymerization catalyzed by (cyclopentadienyl) (aryloxy) titanium(Ⅳ) complexes, CpTiCl2(OAr)-MAO system.: Ethylene/1-hexene copolymerization by (1,3-'Bu2C5H3)TiCl2(O-2,6-iPr2C6H3)-MAO catalyst system[J]. J Mol Catal, A:Chem,2000,159:127-137.