水杨醛亚胺催化剂的制备及其催化烯烃聚合性能评价
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摘要
双核水杨醛亚胺催化剂相对于单金属催化剂由于双金属之间的协同作用以及各不相同取代基的空间位阻和电子效应可能会使催化体系中活性中心发生变化,对烯烃聚合课题研究有着重要的意义。本文利用两种新型结构的二醛和不同取代苯胺反应合成了六种不同的配体,进而将之与金属化合物配合得到了六种不同结构的催化剂(Cat1-Cat6),并将其应用于不同单体聚合研究,主要研究内容和结果如下:
1.合成了六种双核水杨醛亚胺金属催化剂,并利用IR、UV和~1HNMR对催化剂的结构进行了表征。
2.采用双核水杨醛亚胺锆催化剂催化乙烯聚合进行了研究。分别从主催化剂、反应时间、温度、摩尔比、助催化剂等聚合条件考察了对乙烯聚合的影响。结果发现,配体中苯胺的邻对位取代基为供电子基团的邻异丙基时(Cat1)催化剂的催化烯烃聚合活性较高,其催化乙烯最高活性达到3.6×10~5g/molZr·h。通过GPC研究所得到的聚乙烯,发现在较低聚合温度下(0℃-40℃)聚合物分子量分布较宽,达到32.5-37.6。而在较高聚和温度(60℃-80℃)下得到的聚合物分子量分布却很窄,只有1.00-1.30。进一步通过FTIR、~(13)C NMR及DSC表征,证明得到了具有一定支化度的聚乙烯。
3.采用双核水杨醛亚胺镍催化剂催化降冰片烯聚合进行了研究。结果发现,配体中苯胺的邻对位取代基为供电子基团的邻异丙基时(Cat4)催化剂的催化降冰片烯聚合活性较高,其催化最高活性达到1.16×10~6g/molNi·h。通过GPC研究所得到的聚降冰片烯,发现聚合温度对其影响不大,其聚合产物成单峰分布分子量分布为2.20左右。进一步通过FTIR、1H-NMR表征,证明我们得到的是乙烯基加成聚降冰片烯。
4.采用双核水杨醛亚胺镍催化剂催化甲基丙烯酸甲酯聚合进行了研究。结果发现,配体中苯胺的邻对位取代基为供电子基团的邻异丙基时(Cat4)催化剂的催化甲基丙烯酸甲酯聚合活性较高,其催化最高活性达到1.42×10~5g/molNi·h。通过FTIR、~1H-NMR和DSC表征所得到的聚甲基丙烯酸甲酯,证明得到了间规度为73%,玻璃化转变温度为108℃的间规聚甲基丙烯酸甲酯。
In this thesis, six salicylideneiminato double metal complexes with different substituted groups (Cat1-Cat6) were prepared and their catalytic performance to ethylene, norbornene, and methyl methacrylate polymerization were investigated. The results were summarized as follows:
1. 5,5’-methyl-bis-t-butyl hydroxybenzaldehyde 2-isopropyl aniline zirconium complexes(Cat1), 5,5’-methyl-bis-t-butyl hydroxybenzaldehyde 2,6-diisopropylamine zirconium complexes(Cat2), 5,5’-methyl-bis-t-butyl hydroxybenzaldehyde 2-fluoro aniline zirconium complexes(Cat3), 5,5’-methyl-bis-hydroxybenzaldehyde 2-isopropyl aniline nickel complexes (Cat4), 5,5’-methyl-bis-hydroxybenzaldehyde 2,6-diisopropylamine nickel complexes (Cat5), and 5,5’-methyl-bis-hydroxybenzaldehyde 2-fluoro aniline nickel complexes (Cat6) were succesfully synthesized and characterizate by IR, ~1H NMR and UV.
2. The ethylene polymerization was carried out under Cat1-Cat3 catalyst system. The results indicated that the catalyst with giving electronic isopropyl groups substituents (Cat1) had highest catalytic activity among the catalyst investigated, reached 3.6×10~5g/molZr.h. The effects of reaction conditions on the polymerization were systematically investigated, such as main catalyst, reaction time, temperature, molar ratio of catalysts to cocatalysts, and different cocatalysts. The wide molecular weight distribution (Mw/Mn)polymers around 32.5-37.6 were obtained under lower polymerization temperature (0℃-40℃) for Cat1, while Mw/Mn of polymers obtained is between 1.00 and 1.30 under higher polymerization temperature (60℃-80℃) by GPC. Furthermore, It proofed a certain degree of branched polyethylene was gotten, characterizate by IR, ~1C NMR and DSC.
3. The polymerization of norbornene was catalyzed by Cat4-Cat6. The catalytic activity of Cat4 is up to 1.16×10~6gPNB/molNi.h. The resulted polynorbornenes were characterized by IR, 1H NMR in detail, indicating that norbornene polymerization via addition polymerization route. The temperature play a silm role in molecular weight distribution of resulted polynorbronene.
4. The polymerization of methyl methacrylate was performed under Cat4-Cat6 catalyst system. The catalytic activity of Cat4 reached 1.42×10~5 g PMMA/molNi.h. Poly(methyl methacrylate) with 73% regularity degrees was obtained, whose glass transition temperature is about 108℃.
1.合成了六种双核水杨醛亚胺金属催化剂,并利用IR、UV和~1HNMR对催化剂的结构进行了表征。
2.采用双核水杨醛亚胺锆催化剂催化乙烯聚合进行了研究。分别从主催化剂、反应时间、温度、摩尔比、助催化剂等聚合条件考察了对乙烯聚合的影响。结果发现,配体中苯胺的邻对位取代基为供电子基团的邻异丙基时(Cat1)催化剂的催化烯烃聚合活性较高,其催化乙烯最高活性达到3.6×10~5g/molZr·h。通过GPC研究所得到的聚乙烯,发现在较低聚合温度下(0℃-40℃)聚合物分子量分布较宽,达到32.5-37.6。而在较高聚和温度(60℃-80℃)下得到的聚合物分子量分布却很窄,只有1.00-1.30。进一步通过FTIR、~(13)C NMR及DSC表征,证明得到了具有一定支化度的聚乙烯。
3.采用双核水杨醛亚胺镍催化剂催化降冰片烯聚合进行了研究。结果发现,配体中苯胺的邻对位取代基为供电子基团的邻异丙基时(Cat4)催化剂的催化降冰片烯聚合活性较高,其催化最高活性达到1.16×10~6g/molNi·h。通过GPC研究所得到的聚降冰片烯,发现聚合温度对其影响不大,其聚合产物成单峰分布分子量分布为2.20左右。进一步通过FTIR、1H-NMR表征,证明我们得到的是乙烯基加成聚降冰片烯。
4.采用双核水杨醛亚胺镍催化剂催化甲基丙烯酸甲酯聚合进行了研究。结果发现,配体中苯胺的邻对位取代基为供电子基团的邻异丙基时(Cat4)催化剂的催化甲基丙烯酸甲酯聚合活性较高,其催化最高活性达到1.42×10~5g/molNi·h。通过FTIR、~1H-NMR和DSC表征所得到的聚甲基丙烯酸甲酯,证明得到了间规度为73%,玻璃化转变温度为108℃的间规聚甲基丙烯酸甲酯。
In this thesis, six salicylideneiminato double metal complexes with different substituted groups (Cat1-Cat6) were prepared and their catalytic performance to ethylene, norbornene, and methyl methacrylate polymerization were investigated. The results were summarized as follows:
1. 5,5’-methyl-bis-t-butyl hydroxybenzaldehyde 2-isopropyl aniline zirconium complexes(Cat1), 5,5’-methyl-bis-t-butyl hydroxybenzaldehyde 2,6-diisopropylamine zirconium complexes(Cat2), 5,5’-methyl-bis-t-butyl hydroxybenzaldehyde 2-fluoro aniline zirconium complexes(Cat3), 5,5’-methyl-bis-hydroxybenzaldehyde 2-isopropyl aniline nickel complexes (Cat4), 5,5’-methyl-bis-hydroxybenzaldehyde 2,6-diisopropylamine nickel complexes (Cat5), and 5,5’-methyl-bis-hydroxybenzaldehyde 2-fluoro aniline nickel complexes (Cat6) were succesfully synthesized and characterizate by IR, ~1H NMR and UV.
2. The ethylene polymerization was carried out under Cat1-Cat3 catalyst system. The results indicated that the catalyst with giving electronic isopropyl groups substituents (Cat1) had highest catalytic activity among the catalyst investigated, reached 3.6×10~5g/molZr.h. The effects of reaction conditions on the polymerization were systematically investigated, such as main catalyst, reaction time, temperature, molar ratio of catalysts to cocatalysts, and different cocatalysts. The wide molecular weight distribution (Mw/Mn)polymers around 32.5-37.6 were obtained under lower polymerization temperature (0℃-40℃) for Cat1, while Mw/Mn of polymers obtained is between 1.00 and 1.30 under higher polymerization temperature (60℃-80℃) by GPC. Furthermore, It proofed a certain degree of branched polyethylene was gotten, characterizate by IR, ~1C NMR and DSC.
3. The polymerization of norbornene was catalyzed by Cat4-Cat6. The catalytic activity of Cat4 is up to 1.16×10~6gPNB/molNi.h. The resulted polynorbornenes were characterized by IR, 1H NMR in detail, indicating that norbornene polymerization via addition polymerization route. The temperature play a silm role in molecular weight distribution of resulted polynorbronene.
4. The polymerization of methyl methacrylate was performed under Cat4-Cat6 catalyst system. The catalytic activity of Cat4 reached 1.42×10~5 g PMMA/molNi.h. Poly(methyl methacrylate) with 73% regularity degrees was obtained, whose glass transition temperature is about 108℃.
引文
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2 Bao F, Li X, Kang B, Wu Q. Vinyl polymerization of norbornene catalyzed by a series of bis(b-ketoiminato)nickel(II) complexes in the presence of methylaluminoxane. Eur. Polym. J., 2006, 42: 928-934
3 Wang L Y, Li Y F, Zhu F M, Wu Q. Homo- and copolymerization of norbornene and norbornene derivative with Ni and Pd-basedβ-ketoiminato complexes and MAO. Eur. Polym. J., 2006, 42: 322-327
4 He X H, Chen Y W, Liu Y M, Yu S X, Wu Q. Addition polymerization of norbornene using bis(β-ketoamino) nickel(II)/tris(penta.uorophenyl) borane catalytic systems. J. Polym. Sci. Part A: Polym. Chem., 2007, 45: 4733-4743
5 Gao H Y, Zhang J K, Chen Y, Zhu F M, Wu Q, Vinyl-polymerization of norbornene with novel anilido-imino nickel complexes/ethylaluminoxane: abnormal influence of polymerization temperature on molecular weight of polynorbornenes. J. Mol. Catal. A: Chem., 2005, 240: 178-185
6 Guo W J, Bao F, Gui G Q, Zhu F M, Wu Q. Synthesis, molecular structure, and solution-dependent behavior of nickel complexes chelating anilido-imine donors and their catalytic activity toward olefin polymerization. Organometallics, 2004, 23: 6273-6280
7 LüX Q, Bao F, Kang B S, Wu Q, Liu H Q, Zhu F M. Syntheses, structures and catalytic activity of copper(II) complexes bearing N,O-chelate ligands. J. Organomet. Chem., 2006, 691: 821-828
8 Younkin T R, Conner E F, Henderson J I, Friedrich S K, Grubbs R H, Bansleben D A. Neutral, single-component nickel(II) polyolefin catalysts that tolerate heteroatoms. Science, 2000, 287: 460-462
9 Frederik B, Christoph J. Metal catalysts for the vinyl/addition polymerization of norbornene. Coord. Chem. Rev., 2009, 253: 827-861
10 Daisuke T. Recent progress in olefin polymerization catalyzed by transition metal complexes: new catalysts and new reactions. Dalton Trans., 2010, 39: 311-328
11 Wang C M, Fredrich S, Gruss R H. Neutral nickel(Ⅱ) based diimine catalysts for ethylene polymerization. Organometallics, 1998, 17: 3149-3151
12李立辉,冯燕,闫卫东,任鸿萍,王佰全.邻-酚羟基取代N-杂环卡宾[C,O]螯合双配体镍/MAO催化降冰片烯加成聚合的研究.高分子学报, 2008, (6): 582-586
13 Li Y S, Li Y R, Li X F. New neutral nickel(Ⅱ) complexes bearing pyrrole-imine chelate ligands: synthesis, structure and norbornene polymerization behavior. J. Organomet. Chem., 2003, 667: 185-191
14 Li X F, Li Y S. Vinylic polymerization of norbornene by neutral nickel(II)-based catalysts. J. Polym. Sci. Part A: Polym. Chem., 2002, 40: 2680-2685
15张启兴,林少全,吴志勇,王海华.α-二亚胺镍(Ⅱ)配合物-TiCl4复合催化剂催化乙烯原位聚合制备支化聚乙烯.高等学校化学学报, 2004, 25(11): 2166-2170
16李贺新,石金永,闫卫东,胡友良.铁系亚胺基吡啶复配催化乙烯原位共聚产物表征.高分子学报, 2004, (6): 935-938
17 Xu H, Guo C Y, Zhang M G. In situ copolymerization of ethylene to linear low-density polyethylene (LLDPE) with calcosilicate (CAS-1) supported dual-functional catalytic system. Catal. Commun., 2007, 8(2): 2143-2149
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