CN111196824A - 一种蒽骨架磷氮配位双金属化合物的制备及其乙烯选择性齐聚催化 - Google Patents
一种蒽骨架磷氮配位双金属化合物的制备及其乙烯选择性齐聚催化 Download PDFInfo
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- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 125000005577 anthracene group Chemical group 0.000 title claims abstract description 38
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 239000005977 Ethylene Substances 0.000 title claims abstract description 25
- 238000006384 oligomerization reaction Methods 0.000 title claims abstract description 24
- 150000001875 compounds Chemical class 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 238000006555 catalytic reaction Methods 0.000 title abstract description 6
- 239000003446 ligand Substances 0.000 claims abstract description 13
- 238000006116 polymerization reaction Methods 0.000 claims description 36
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 31
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 27
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 125000005234 alkyl aluminium group Chemical group 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- YLZGEUWNNPEHBA-UHFFFAOYSA-N anthracene-1,8-diamine Chemical compound C1=CC(N)=C2C=C3C(N)=CC=CC3=CC2=C1 YLZGEUWNNPEHBA-UHFFFAOYSA-N 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- WCFQIFDACWBNJT-UHFFFAOYSA-N $l^{1}-alumanyloxy(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]O[Al] WCFQIFDACWBNJT-UHFFFAOYSA-N 0.000 claims description 2
- LWNGJAHMBMVCJR-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenoxy)boronic acid Chemical compound OB(O)OC1=C(F)C(F)=C(F)C(F)=C1F LWNGJAHMBMVCJR-UHFFFAOYSA-N 0.000 claims description 2
- NPNAXGKROXIVMJ-UHFFFAOYSA-N (2,3,4-trifluorophenyl)boron Chemical compound [B]C1=CC=C(F)C(F)=C1F NPNAXGKROXIVMJ-UHFFFAOYSA-N 0.000 claims description 2
- YVSMQHYREUQGRX-UHFFFAOYSA-N 2-ethyloxaluminane Chemical compound CC[Al]1CCCCO1 YVSMQHYREUQGRX-UHFFFAOYSA-N 0.000 claims description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical group [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical group [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical group BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 229910052804 chromium Chemical group 0.000 claims description 2
- 239000011651 chromium Chemical group 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Chemical group 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical group CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 claims description 2
- CQYBWJYIKCZXCN-UHFFFAOYSA-N diethylaluminum Chemical compound CC[Al]CC CQYBWJYIKCZXCN-UHFFFAOYSA-N 0.000 claims description 2
- UAIZDWNSWGTKFZ-UHFFFAOYSA-L ethylaluminum(2+);dichloride Chemical compound CC[Al](Cl)Cl UAIZDWNSWGTKFZ-UHFFFAOYSA-L 0.000 claims description 2
- 239000011630 iodine Chemical group 0.000 claims description 2
- 229910052740 iodine Chemical group 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical group C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 2
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 claims description 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical group C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 2
- OLFPYUPGPBITMH-UHFFFAOYSA-N tritylium Chemical compound C1=CC=CC=C1[C+](C=1C=CC=CC=1)C1=CC=CC=C1 OLFPYUPGPBITMH-UHFFFAOYSA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 10
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 10
- 230000037048 polymerization activity Effects 0.000 description 10
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 6
- 150000002816 nickel compounds Chemical class 0.000 description 5
- 150000001336 alkenes Chemical class 0.000 description 4
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 239000004711 α-olefin Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 150000001869 cobalt compounds Chemical class 0.000 description 2
- 239000012967 coordination catalyst Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 238000004679 31P NMR spectroscopy Methods 0.000 description 1
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 1
- 229910021585 Nickel(II) bromide Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- -1 anthracene-anthracene compound Chemical class 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- RAABOESOVLLHRU-UHFFFAOYSA-N diazene Chemical compound N=N RAABOESOVLLHRU-UHFFFAOYSA-N 0.000 description 1
- 229910000071 diazene Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 229920000092 linear low density polyethylene Polymers 0.000 description 1
- 239000004707 linear low-density polyethylene Substances 0.000 description 1
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical compound [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
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- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/04—Nickel compounds
- C07F15/045—Nickel compounds without a metal-carbon linkage
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2442—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring comprising condensed ring systems
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Abstract
本发明涉及一种蒽骨架磷氮配位双金属化合物的制备及其乙烯齐聚的应用。本发明引入了蒽骨架，设计合成了蒽骨架磷氮配位双金属化合物，结合了磷氮配体和双金属催化，实现乙烯高效高选择性齐聚。本发明报道的蒽骨架磷氮配位双金属化合物具有制备简单、活性高、耐高温、选择性好的特点。因此，本发明报道的蒽骨架磷氮配位双金属化合物具有原始创新性。
Description
技术领域
本发明涉及一种双金属化合物及其制备方法，以及该金属化合物在催化乙烯齐聚中的应用。
背景技术
乙烯齐聚是一种工业化生产α-烯烃的方法。而α-烯烃是制备清洁剂、塑化剂、精细化学品以及生产线性低密度聚乙烯共聚单体的重要原料。目前一个主要的工业生产线性α烯烃的方法是应用SHOP型催化剂(Angew.Chem.,Int.Ed.Engl.1978,17,466–467)。1998年，Brookhart和Gibson等又同时报道了吡啶二亚胺Fe(II)和Co(II)的配合物，通过调节苯环上的取代基，可以很好地催化乙烯齐聚或聚合(J.Am.Chem.Soc.1998,120,4049-4050；Chem.Commun.1998,849-850)。Braunstein等报道了一系列磷氮配位过渡金属化合物，能够高效的催化乙烯齐聚(Acc.Chem.Res.2005,38,784-793)。最近有研究报道，双金属催化剂能够模拟仿生酶，通过协同催化，进一步提高金属催化剂的烯烃催化性能(Chem.Rev.2011,111,2450-2485)。本发明将磷氮配位过渡金属化合物和双金属催化结合起来，报道了基于蒽骨架磷氮配位双金属化合物，并应用也催化烯烃齐聚；通过协同催化，不但提高了聚合活性，对选择性也有显著的提高。因此，本发明报道的蒽骨架磷氮配位双金属化合物具有原始创新性，能够增强我国α-烯烃制备技术市场的竞争能力。
发明内容
本发明的目的是提供一种蒽骨架磷氮配位双金属化合物的制备方法及其在烯烃齐聚中的应用。
本发明提供一种式(I)所示蒽骨架磷氮配位双金属化合物：
其中，M选自镍、钴、铁、铬；R1选自甲基，乙基，异丙基，叔丁基，苯基；R2选自甲基，乙基，异丙基，叔丁基，苯基；X选自氯、溴、碘；n为X的个数，为1-3的自然数。
本发明提供了上述蒽骨架磷氮配位双金属化合物的制备方法，包括以下步骤：
在氮气氛围下，1,8-二胺基蒽与2-磷苯甲醛按1：2～3摩尔比例混合，加入催化剂量的对甲基苯磺酸5mg～10mg，在二氯甲烷中反应6-18小时；减压除去二氯甲烷后，加入甲醇洗涤得到蒽骨架磷氮配体；
将蒽骨架磷氮配体与金属盐按1：2摩尔比例混合，加入溶剂，搅拌反应6-18小时；减压除去溶剂，用乙醚洗涤，得到蒽骨架磷氮配位双金属化合物。
本发明还提供了上述式(I)所示蒽骨架磷氮配位双金属化合物做为催化剂在催化乙烯齐聚反应中的应用。
上述催化乙烯齐聚反应中还加有助催化剂，助催化剂为三五氟苯基硼、三苯碳鎓四(五氟苯基)硼酸盐、铝氧烷、烷基铝和氯化烷基铝中的一种或几种。所述铝氧烷为甲基铝氧烷、乙基铝氧烷或异丁基铝氧烷；烷基铝为三甲基铝、三乙基铝、三异丁基铝或三正己基铝；氯化烷基铝为一氯二乙基铝、倍半一氯二乙基铝或二氯化乙基铝。
在上述聚合反应中，聚合温度为0-120℃，聚合压力为0.1-4Mpa，聚合溶剂为甲苯、己烷、庚烷中的一种或几种。
本发明提供了蒽骨架磷氮配位双金属化合物的制备，以及该化合物催化烯烃聚合的应用。本发明报道的蒽骨架磷氮配位双金属化合物具有制备简单、活性高、耐高温、选择性好的特点。
附图说明
图1为蒽骨架磷氮配体的核磁共振氢谱图，
图2为蒽骨架磷氮配体的核磁共振氢谱图，
图3为蒽骨架磷氮配体的核磁共振氢谱图，
图4为蒽骨架磷氮配位双金属镍化合物的晶体结构图，
图5为实施例5产物气象色谱图，
图6为实施例10产物气象色谱图。
具体实施方式
通过实施例进一步说明本发明，但本发明并不限于此。本发明的实施例可以使本专业的技术人员更全面的理解本发明。
下述实施例中所使用的实验方法如无特殊说明，均为常规方法。
以下以具体的实施例描述本发明。
实施例1、蒽骨架磷氮配体2-Ph2P-C6H4-CH＝N-C14H8-N＝CH-C6H4-2-Ph2P的制备。
在氮气氛围下，1,8-二胺基蒽(0.416g,2.00mmol)与2-磷苯甲醛(1.16g,4.00mmol)混合，加入催化剂量的对甲基苯磺酸10mg，在二氯甲烷中反应12小时；减压除去二氯甲烷后，加入甲醇洗涤得到蒽骨架磷氮配体2-Ph2P-C6H4-CH＝N-C14H8-N＝CH-C6H4-2-Ph2P(1.33g,1.76mmol,88％)。1H NMR(CDCl3):δ9.41(s,1H),9.29(d,J＝5.2Hz,2H),8.63-8.60(m,2H),8.35(s,1H),7.79(d,J＝8.6Hz,2H),7.48(t,J＝7.3Hz,2H),7.41-7.29(m,24H),6.99-6.96(m,2H),6.45(d,J＝8.6Hz,2H)ppm.13C NMR(CDCl3):δ158.70(d,J＝24.3Hz),149.73,139.83(d,J＝16.8Hz),138.92(d,J＝19.6Hz),136.24(d,J＝9.9Hz),134.45,134.25,133.42,132.42,131.10,129.20,129.10,128.90(d,J＝7.2Hz),128.06(d,J＝3.9Hz),127.66,125.92,125.51,119.93,111.26ppm.31P NMR(CDCl3):δ-13.84ppm.Anal.Calcd for C52H38N2P2:C,82.96；H,5.09；N,3.72.Found:C,82.79；H,5.12；N,3.63。
实施例2、蒽骨架磷氮配位双金属镍化合物Ni2的制备。
将蒽骨架磷氮配体(0.735g,1.00mmol)与金属盐NiBr2(DME)(0.618g,2.00mmol)混合，加入二氯甲烷，搅拌反应12小时；减压除去溶剂，用乙醚洗涤，得到蒽骨架磷氮配位双金属镍化合物Ni2(1.10g,0.93mmol,93％)。Anal.Calcd for C52H38Br4N2Ni2P2:C,52.49；H,3.22；N,2.35.Found:C,52.22；H,3.18；N,2.21。
实施例3、蒽骨架磷氮配位双金属镍化合物Co2的制备。
将蒽骨架磷氮配体(0.735g,1.00mmol)与金属盐CoCl2(0.260g,2.00mmol)混合，加入二氯甲烷，搅拌反应12小时；减压除去溶剂，用乙醚洗涤，得到蒽骨架磷氮配位双金属钴化合物Co2(0.98g,0.97mmol,97％)。Anal.Calcd for C52H38Cl4N2Co2P2:C,61.69；H,3.78；N,2.77.Found:C,61.55；H,3.65；N,2.70。
实施例4、蒽骨架磷氮配位双金属镍化合物Fe2的制备。
将蒽骨架磷氮配体(0.735g,1.00mmol)与金属盐FeCl2(0.254g,2.00mmol)混合，加入二氯甲烷，搅拌反应12小时；减压除去溶剂，用乙醚洗涤，得到蒽骨架磷氮配位双金属钴化合物Fe2(0.95g,0.95mmol,95％)。Anal.Calcd for C52H38Cl4N2Fe2P2:C,62.06；H,3.81；N,2.78.Found:C,61.96；H,3.71；N,2.68。
实施例5、Ni2催化乙烯齐聚。
在手套箱中，将1.19mg(1μmol)Ni2装入有磁搅拌子的350ml聚合瓶，然后拿出手套箱接到聚合线上，抽真空并用乙烯气置换3次。用注射器注入50ml的甲苯和助催化剂0.11mLEtAlCl2(Al/Ni＝100)，在20℃下，保持5atm的乙烯压力，剧烈搅拌反应30min。反应结束后，取少量反应液，用5％盐酸中和，取上层有机相进行气相色谱分析。聚合活性:2.04×106g·mol-1(Ni)·h-1；丁烯选择性99％。
实施例6、Ni2催化乙烯齐聚。
聚合反应过程与反应条件同实施例5，所用助催化剂为MAO(Al/Ni＝1000)。聚合活性:0.25×106g·mol-1(Ni)·h-1；丁烯选择性99％。
实施例7、Ni2催化乙烯齐聚。
聚合反应过程与反应条件同实施例5，所用助催化剂为Et2AlCl(Al/Ni＝100)。聚合活性:0.15×106g·mol-1(Ni)·h-1；丁烯选择性99％。
实施例8、Ni2催化乙烯齐聚。
聚合反应过程与反应条件同实施例5，所用聚合温度为40摄氏度。聚合活性:6.28×106g·mol-1(Ni)·h-1；丁烯选择性94％。
实施例9、Ni2催化乙烯齐聚。
聚合反应过程与反应条件同实施例5，所用聚合温度为60摄氏度。聚合活性:5.96×106g·mol-1(Ni)·h-1；丁烯选择性95％。
实施例10、Ni2催化乙烯齐聚。
聚合反应过程与反应条件同实施例5，所用聚合温度为40摄氏度，所用Al/Ni＝200。聚合活性:9.10×106g·mol-1(Ni)·h-1；丁烯选择性98％。
实施例11、Ni2催化乙烯齐聚。
聚合反应过程与反应条件同实施例5，所用聚合温度为40摄氏度，所用Al/Ni＝250。聚合活性:5.78×106g·mol-1(Ni)·h-1；丁烯选择性98％。
实施例11、Ni2催化乙烯齐聚。
聚合反应过程与反应条件同实施例5，所用聚合温度为40摄氏度，所用Al/Ni＝200，聚合压力为1atm乙烯。聚合活性:1.36×106g·mol-1(Ni)·h-1；丁烯选择性99％。
实施例13、Co2催化乙烯齐聚。
聚合反应过程与反应条件同实施例5，所用催化剂为Co2，聚合温度为40摄氏度，所用Al/Ni＝200。聚合活性:0.66×106g·mol-1(Co)·h-1；丁烯选择性99％。
实施例4、Fe2催化乙烯齐聚。
聚合反应过程与反应条件同实施例5，所用催化剂为Fe2，聚合温度为40摄氏度，所用Al/Ni＝200。聚合活性:0.40×106g·mol-1(Co)·h-1；丁烯选择性55％。
Claims (6)
1.一类蒽骨架磷氮配位双金属化合物，其结构如式(I)所示：
其中，M选自镍、钴、铁、铬；R1选自甲基，乙基，异丙基，叔丁基，苯基；R2选自甲基，乙基，异丙基，叔丁基，苯基；X选自氯、溴、碘；n为X的个数，为1-3的自然数。
2.权利要求1所述蒽骨架磷氮配位双金属化合物的制备方法，包括如下步骤：
在氮气氛围下，1,8-二胺基蒽与2-磷苯甲醛按1：2～3摩尔比例混合，加入催化剂量的对甲基苯磺酸5mg～10mg，在二氯甲烷中反应6-18小时；减压除去二氯甲烷后，加入甲醇洗涤得到蒽骨架磷氮配体；将蒽骨架磷氮配体与金属盐按1：2摩尔比例混合，加入溶剂，搅拌反应6-18小时；减压除去溶剂，用乙醚洗涤，得到蒽骨架磷氮配位双金属化合物。
3.一种进行乙烯齐聚反应的方法，其特征在于：反应的催化剂为权利要求1所述蒽骨架磷氮配位双金属化合物。
4.根据权利要求3所述的方法，其特征在于：所述乙烯齐聚反应中还加有助催化剂，助催化剂为三五氟苯基硼、三苯碳鎓四(五氟苯基)硼酸盐、铝氧烷、烷基铝和氯化烷基铝中的一种或几种。
5.根据权利要求3和4所述的方法，其特征在于：所述铝氧烷为甲基铝氧烷、乙基铝氧烷或异丁基铝氧烷；烷基铝为三甲基铝、三乙基铝、三异丁基铝或三正己基铝；氯化烷基铝为一氯二乙基铝、倍半一氯二乙基铝或二氯化乙基铝。
6.根据权利要求3所述的方法，其特征在于：聚合温度为0-120℃，聚合压力为0.1-4Mpa，聚合溶剂为甲苯、己烷、庚烷中的一种或几种。
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