CN111233939A - 一种不对称亚胺苊合卤化镍配合物及其制备方法和应用 - Google Patents
一种不对称亚胺苊合卤化镍配合物及其制备方法和应用 Download PDFInfo
- Publication number
- CN111233939A CN111233939A CN202010113135.4A CN202010113135A CN111233939A CN 111233939 A CN111233939 A CN 111233939A CN 202010113135 A CN202010113135 A CN 202010113135A CN 111233939 A CN111233939 A CN 111233939A
- Authority
- CN
- China
- Prior art keywords
- asymmetric
- nickel
- complex
- iminacenaphthylene
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 23
- -1 nickel halide Chemical class 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000010668 complexation reaction Methods 0.000 title description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000005977 Ethylene Substances 0.000 claims abstract description 23
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 22
- 239000003446 ligand Substances 0.000 claims abstract description 15
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 30
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 claims description 27
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 229910021585 Nickel(II) bromide Inorganic materials 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 12
- 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 12
- JBXIOAKUBCTDES-UHFFFAOYSA-N 2h-acenaphthylen-1-one Chemical compound C1=CC(C(=O)C2)=C3C2=CC=CC3=C1 JBXIOAKUBCTDES-UHFFFAOYSA-N 0.000 claims description 9
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 8
- 239000013067 intermediate product Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- HXGDTGSAIMULJN-UHFFFAOYSA-N acetnaphthylene Natural products C1=CC(C=C2)=C3C2=CC=CC3=C1 HXGDTGSAIMULJN-UHFFFAOYSA-N 0.000 claims description 5
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N N-phenyl amine Natural products NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 4
- AFPRJLBZLPBTPZ-UHFFFAOYSA-N acenaphthoquinone Chemical compound C1=CC(C(C2=O)=O)=C3C2=CC=CC3=C1 AFPRJLBZLPBTPZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000004440 column chromatography Methods 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical group 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- BLTMLQFLPRYEJB-UHFFFAOYSA-N 2,4-bis[bis(4-methoxyphenyl)methyl]-6-methylaniline Chemical compound COC1=CC=C(C=C1)C(C1=C(N)C(=CC(=C1)C(C1=CC=C(C=C1)OC)C1=CC=C(C=C1)OC)C)C1=CC=C(C=C1)OC BLTMLQFLPRYEJB-UHFFFAOYSA-N 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 229910052794 bromium Inorganic materials 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims description 2
- 229910052801 chlorine Inorganic materials 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 claims description 2
- CWRYPZZKDGJXCA-UHFFFAOYSA-N acenaphthene Chemical compound C1=CC(CC2)=C3C2=CC=CC3=C1 CWRYPZZKDGJXCA-UHFFFAOYSA-N 0.000 claims 2
- 150000002466 imines Chemical class 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 16
- 239000003054 catalyst Substances 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 239000004698 Polyethylene Substances 0.000 abstract description 4
- 229920000573 polyethylene Polymers 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract 2
- 125000001424 substituent group Chemical group 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 56
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 26
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 239000000843 powder Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- 238000005160 1H NMR spectroscopy Methods 0.000 description 9
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical compound [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 description 9
- 230000037048 polymerization activity Effects 0.000 description 9
- 239000007787 solid Substances 0.000 description 8
- 238000000921 elemental analysis Methods 0.000 description 7
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 229910001848 post-transition metal Inorganic materials 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- UFFBMTHBGFGIHF-UHFFFAOYSA-N 2,6-dimethylaniline Chemical compound CC1=CC=CC(C)=C1N UFFBMTHBGFGIHF-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000006384 oligomerization reaction Methods 0.000 description 2
- GMEQPKCGYROUQA-UHFFFAOYSA-N 2,4-bis[(4,4-dimethoxycyclohexa-1,5-dien-1-yl)-phenylmethyl]-6-methylaniline Chemical compound CC1=CC(=CC(=C1N)C(C2=CCC(C=C2)(OC)OC)C3=CC=CC=C3)C(C4=CCC(C=C4)(OC)OC)C5=CC=CC=C5 GMEQPKCGYROUQA-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 229910000071 diazene Inorganic materials 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920013716 polyethylene resin Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
- C07F15/04—Nickel compounds
- C07F15/045—Nickel compounds without a metal-carbon linkage
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F10/02—Ethene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/847—Nickel
Abstract
本发明提供了一种不对称亚胺苊合卤化镍配合物及其制备方法和应用，所述的镍配合物晶体结构显示其主体部分与卤素呈扭曲的四面体几何结构。用Me2AlCl进行激活，此类镍配合物对乙烯聚合反应都表现出高活性，达到106g PE(mol of Ni)‑1h‑1，并产生具有高分子量、窄分子量分布和中等分支度的通用型聚合物，配体上的取代基的变化对镍配合物的催化性能及聚乙烯的微观结构都有很大影响。该镍配合物可作为催化剂在乙烯聚合中应用。
Description
技术领域
本发明涉及后过渡金属配合物，特别涉及卤化镍配合物，更具体地说是一种不对称亚胺苊合卤化镍配合物及其制备方法和应用。
背景技术
聚乙烯树脂是通用合成树脂中产量最大的品种，因其性能好、价格低等特点，应用相当广泛，如注塑制品、薄膜、中空制品、电线电缆等都在其消费结构中占有较大的比例。工业化的烯烃聚合催化剂主要以前过渡金属为主。自1995年，Brookhart课题组报道了α-二亚胺配位镍、钯配合物催化乙烯聚合(J.Am.Chem.Soc.,1995,117,6414)获得了高分子量、高支化聚乙烯后，后过渡金属配合物催化剂设计合成与催化乙烯(齐聚和聚合)研究成为科学家们研究的核心内容，无论是对经典催化剂模型的改良还是在研究新模型催化剂体系中都获得了良好突破。近年来发展的后过渡金属配合物的乙烯齐聚和聚合高效催化剂，不仅制备简单，催化活性高，而且能够控制聚合物分子量和分子量的分布，迅速成为应用研究的热点。
发明内容
本发明的目的是提供一种不对称亚胺苊合卤化镍配合物及其制备方法，以及该配合物作为催化剂可在乙烯聚合中应用。
本发明提供的一种不对称亚胺苊合卤化镍配合物，具有如下的结构式：
其中：
R1、R2各自独立地选自氢、1-10个碳原子的烷基、芳基、烷芳基、芳烷基和烷氧基中的一种；R1和R2相同或不同。
R1、R2各自独立地优选自氢、甲基、乙基、异丙基和甲氧基中的一种。
X为卤素，优选氯或溴。
本发明还提供了一种不对称亚胺苊合卤化镍配合物的制备方法，包括如下步骤：
(1)配体的制备：将适量的对甲基苯磺酸溶于甲醇中，搅拌下分批加入到等摩尔量的2-(2,4-二(4,4’-二甲氧基二苯甲基)-6-甲基苯胺与苊醌的二氯甲烷混合液中，室温搅拌18-24小时，将所得溶液浓缩，然后通过柱色谱法纯化，得到苊酮中间产物A；将苊酮中间产物溶于二氯甲烷中分批加入到苯胺化合物的甲醇溶液中，回流20-24小时，反应完全后，浓缩，洗涤，抽滤，结晶，制得不对称亚胺苊合配体化合物B；所述的苊酮与苯胺化合物的摩尔比为1：1-2；
(2)镍配合物的制备：在氮气氛围下，将一定量的(DME)NiBr2或NiCl2·6H2O分批加入到不对称亚胺苊合配体化合物B的乙醇溶液中，不对称亚胺苊合配体化合物B与(DME)NiBr2或六水合氯化镍的摩尔比为1:1，搅拌下恢复室温，继续反应10-12小时后，反应结束浓缩，洗涤，抽滤，重结晶，制得不对称亚胺苊合卤化镍配合物C。具体的合成路线如下：
不对称亚胺苊合卤化镍配合物作为催化剂可在乙烯聚合中应用。在乙烯聚合的实验中催化剂聚合活性最高可达：8.61×106g of PE(mol of Ni)-1h-1，聚合物分子量最高可达：3.85×105g mol-1。
与现有技术相比本发明的有益效果：合成卤化镍配合物所用原料易得、制备步骤少、方法简单，且产率较高；作为催化剂用于乙烯聚合可以制备出高催化活性的聚合物而非齐聚物，并且可得到具有中等支化度和窄分子量分布的高分子量通用型聚合物。
附图说明
图1为溴化镍配合物C2的晶体结构；
图2为氯化镍配合物C5的晶体结构；
具体实施方式
下面仅仅为说明而给出的实施例，这些实施例并非用于限制本发明的保护范围。
实施例1 不对称亚胺苊合溴化镍配合物的制备、表征和应用
(1)配体的制备
将催化量的对甲基苯磺酸溶于甲醇中，搅拌下分批加入到2-(2,4-二(4,4-二甲氧基二苯甲基)-6-甲基苯胺(6.11g，10.9mmol)与苊醌(1.98g，10.9mmol)的二氯甲烷混合液中，室温搅拌18-24小时，将所得溶液浓缩，然后通过碱性氧化铝柱色谱法纯化，洗脱剂和洗脱比例为石油醚/乙酸乙酯为50：1，得到苊酮中间产物A；
将苊酮中间产物A(1.08g，1.50mmol)溶于二氯甲烷中，分批加入到2,6-二甲基苯胺(0.27g，2.25mmol)的甲醇溶液中，回流20-24小时，反应完全后，浓缩，洗涤，抽滤，结晶，制得不对称亚胺苊合配体化合物B1；
B2(R1＝Et,R2＝H),B3(R1＝iPr,R2＝H)和B4(R1＝Et,R2＝Me)的制备方法同B1；
苊酮中间体A表征的数据：1H-NMR(400MHz,CDCl3,TMS):δ8.07(t,J＝6.0Hz,2H,Ph-H),7.87(d,J＝12.0Hz,1H,Ph-H),7.75(d,J＝8.0Hz,1H,Ph-H),7.02(t,J＝8.0Hz,4H,Ph-H),6.84(m,7H,Ph-H),6.64(m,5H,Ph-H),6.37(d,J＝8Hz,1H,Ph-H),5.88(d,J＝8Hz,3H,Ph-H),5.39(s,2H,2×CH),3.81(s,6H,2×OCH3),3.73(s,3H,OCH3),3.11(s,3H,OCH3),1.98(s,3H,CH3).13C-NMR(100MHz,CDCl3,TMS):δ188.9,161.1,157.7,157.6,156.7,146.1,141.9,140.0,136.3,134.7,130.4,133.8,132.2,131.6,130.1,129.9,129.6,128.7,127.9,127.6,122.4,120.8,116.9,113.2,112.9,112.5,54.5,53.8,50.5,16.5.
配体B1(R1＝Me,R2＝H),B2(R1＝Et,R2＝H),B3(R1＝iPr,R2＝H)和B4(R1＝Et,R2＝Me)的产率和表征的数据如下：
B1:黄色粉末，产率为32.3％。1H-NMR(400MHz,CDCl3,TMS):δ7.79(d,J＝8.0Hz,1H,Ph-H),7.75(d,J＝8.0Hz,1H,Ph-H),7.30(t,J＝16.0Hz,1H,Ph-H),7.18(t,J＝12.0Hz,1H,Ph-H),7.05(m,6H,Ph-H),6.86(m,8H,Ph-H),6.75(d,J＝8.0Hz,2H,Ph-H),6.68(d,J＝8.0Hz,2H,Ph-H),6.63(s,1H,Ph-H),6.59(d,J＝8.0Hz,1H,Ph-H),6.33(d,J＝8.0Hz,1H,Ph-H),5.91(d,J＝8.0Hz,2H,Ph-H),5.57(s,1H,CH),5.41(s,1H,CH),3.81(s,6H,2×OCH3),3.74(s,3H,OCH3),3.10(s,3H,OCH3),2.30(s,3H,CH3),2.04(s,6H,2×CH3).13C-NMR(100MHz,CDCl3,TMS):δ162.6,161.4,158.0,157.8,156.8,149.3,147.4,140.3,139.7,137.1,136.0,134.4,133.5,130.9,130.5,130.4,130.3,129.3,129.2,128.8,128.7,128.5,128.3,127.9,127.6,125.1,124.9,124.8,123.8,123.2,122.0,113.7,113.6,113.4,112.9,55.4,55.3,54.8,51.0,18.3,17.9,17.7.FT-IR(cm-1):3057(w),2156(w),1673(νC＝N,m),1644(νC＝N,m),1606(m),1509(s),1463(w),1442(w),1300(m),1251(s),1205(w),1178(s),1109(w),1031(w),924(m),831(m),814(m),778(m),568(m).元素分析：C57H50N2O4(827.04)，理论值:C,82.78；H,6.09；N,3.39％.实际值:C,82.58；H,6.03；N,3.50％.
B2：黄色粉末，产率31.2％。1H-NMR(400MHz,CDCl3,TMS):δ7.78(d,J＝8.0Hz,1H,Ph-H),7.73(d,J＝8.0Hz,1H,Ph-H),7.30(d,J＝8.0Hz,1H,Ph-H),7.16(t,J＝12.0Hz,3H,Ph-H),7.05(t,J＝8.0Hz,4H,Ph-H),6.85(m,8H,Ph-H),6.76(d,J＝8.0Hz,2H,Ph-H),6.69(d,J＝8.0Hz,2H,Ph-H),6.64(s,1H,Ph-H),6.58(d,J＝8.0Hz,1H,Ph-H),6.30(d,J＝8.0Hz,1H,Ph-H),5.92(d,J＝8.0Hz,2H,Ph-H),5.59(s,1H,CH),5.41(s,1H,CH),3.82(s,6H,2×OCH3),3.75(s,3H,OCH3),3.11(s,3H,OCH3),2.77-2.33(m,4H,CH2),2.04(s,3H,CH3),1.26(t,J＝16.0Hz,3H,CH3),1.05(t,J＝16.0Hz,3H,CH3).13C-NMR(100MHz,CDCl3,TMS):δ162.6,161.5,158.0,157.8,156.8,148.5,147.4,140.3,139.7,137.1,136.0,134.4,133.5,130.9,130.7,130.5,130.4,130.3,129.4,129.2,128.7,128.3,127.7,127.5,126.6,126.4,124.8,124.1,123.2,122.5,113.7,113.6,113.4,112.9,55.4,55.3,54.8,54.7,51.0,24.9,24.7,17.7,14.6,13.8.FT-IR(cm-1):3052(w),2156(w),1671(νC＝N,m),1657(νC＝N,m),1586(m),1608(m),1509(s),1462(w),1437(w),1298(m),1248(s),1177(s),1034(w),927(m),832(m),813(m),782(m),574(m).元素分析：C59H54N2O4(855.09)，理论值:C,82.87；H,6.37；N,3.28％.实际值:C,83.02；H,6.25；N,3.17％.
B3：黄色粉末，产率为62.2％。1H-NMR(400MHz,CDCl3,TMS):δ7.78(d,J＝8.0Hz,1H,Ph-H),7.73(d,J＝8.0Hz,1H,Ph-H),7.30(t,J＝8.0Hz,2H,Ph-H),7.25(s,2H,Ph-H),7.15(t,J＝12.0Hz,1H,Ph-H),7.05(t,4H,J＝8.0Hz,Ph-H),6.88(m,7H,Ph-H),6.76(d,J＝8.0Hz,2H,Ph-H),6.70(d,J＝8.0Hz,2H,Ph-H),6.65(s,1H,Ph-H),6.55(d,J＝8.0Hz,1H,Ph-H),6.29(d,J＝4.0Hz,1H,Ph-H),5.92(d,J＝8.0Hz,2H,Ph-H),5.60(s,1H,CH),5.42(s,1H,CH),3.82(s,6H,2×OCH3),3.75(s,3H,OCH3),3.26(m,1H,CH),3.11(s,3H,OCH3),2.91(m,1H,CH),2.04(s,3H,CH3),1.33(d,J＝8.0Hz,3H,CH3)1.20(d,J＝4.0Hz,3H,CH3)1.16(d,J＝8.0Hz,3H,CH3),0.87(d,J＝4.0Hz,3H,CH3).13C-NMR(100MHz,CDCl3,TMS):δ162.7,161.6,158.0,157.8,156.8,147.4,147.3,140.4,139.7,137.1,136.0,135.7,135.6,134.3,133.6,130.9,130.5,130.4,130.3,129.2,128.7,128.3,127.5,124.8,124.5,123.7,123.4,123.2,123.0,113.7,113.6,113.4,112.9,55.4,55.3,54.8,54.6,51.0,24.0,23.7,23.4,23.2,17.7.FT-IR(cm-1):3054(w),2331(w),2156(w),1663(νC＝N,m),1640(νC＝N,m),1609(m),1585(w),1506(s),1461(w),1433(w),1296(w),1237(s),1174(s),1032(w),926(m),832(m),814(m),775(m),748(m),570(m).元素分析：C61H58N2O4(883.15)，理论值:C,82.96；H,6.62；N,3.17％.实际值:C,82.64；H,6.55；N,3.33％.
B4:黄色粉末产物0.40g，产率为28.9％。1H-NMR(400MHz,CDCl3,TMS):δ7.78(d,J＝8.0Hz,1H,Ph-H),7.73(d,J＝8.0Hz,1H,Ph-H),7.31(t,J＝16.0Hz,1H,Ph-H),7.15(s,1H,Ph-H),7.02(t,J＝8.0Hz,6H,Ph-H),6.88(m,8H,Ph-H),6.76(d,J＝8.0Hz,2H,Ph-H),6.69(d,J＝8.0Hz,2H,Ph-H),6.64(s,1H,Ph-H),6.30(d,J＝8.0Hz,1H,Ph-H),5.92(d,J＝8.0Hz,2H,Ph-H),5.59(s,1H,CH),5.41(s,1H,CH),3.82(s,6H,2×OCH3),3.75(s,3H,OCH3),3.11(s,3H,OCH3),2.74-2.52(m,2H,CH2),2.42(s,3H,CH3),2.33-2.28(m,2H,CH2),2.04(s,3H,CH3),1.25(t,J＝12.0Hz,3H,CH3),1.04(t,J＝12.0Hz,3H,CH3).13C-NMR(100MHz,CDCl3,TMS):δ162.5,161.4,157.9,157.7,156.7,147.3,145.9,140.1 139.5,137.0,136.8,135.9,134.3,133.4,133.2 130.8,130.7,130.4,130.3,130.2,129.3,129.2,129.1,128.6,128.4 128.2,127.8,127.6,127.4,127.2,127.0,124.7,123.0,122.5,113.7,113.6,113.5,113.2,112.8,55.3,55.2,54.7,54.5,50.9,24.8,24.6,21.2,17.6,14.5,13.8.FT-IR(cm-1):3036(w),2833(w),2325(w),2160(w),1659(νC＝N,m),1638(νC＝N,m),1608(m),1509(s),1461(w),1439(w),1330(w),1298(w),1248(s),1177(s),1035(m),926(m),833(m),813(m),783(m),566(m).元素分析：C60H56N2O4(827.04)，理论值：C,82.92；H,6.49；N,3.22％.实际值:C,82.85；H,6.41；N,3.26％.
(2)溴化镍配合物的制备
在氮气氛围下，将一定量的(DME)NiBr2(0.06g，0.20mmol)分批加入到不对称亚胺苊合配体化合物B1(0.17g，0.20mmol)的乙醇溶液中，搅拌下恢复室温，继续反应10小时后，反应结束浓缩，洗涤，抽滤，重结晶，制得不对称亚胺苊合溴化镍配合物C1。
溴化镍配合物C2(R1＝Et,R2＝H),C3(R1＝iPr,R2＝H)和C4(R1＝Et,R2＝Me)的制备条件同溴化镍配合物C1的制备。
溴化镍配合物C1(R1＝Me,R2＝H),C2(R1＝Et,R2＝H),C3(R1＝iPr,R2＝H)和C4(R1＝Et,R2＝Me)的产率和表征的数据如下：
C1：深红色固体粉末产物，产率为92.1％。1H-NMR(400MHz,CDCl3,TMS):δ30.28(s,1H,An-H),28.50(s,3H,CH3),27.86(s,3H,CH3),26.74(s,3H,CH3),26.30(s,1H,An-H),25.24(s,1H,An-H),24.76(s,1H,An-H),23.97(s,1H,An-H),21.67(s,1H,An-H),20.98(s,1H,An-H),18.87(broad,0.36H,Ar-CH(Ph)2),17.24(s,1H,Ar-H),16.42(s,1H,Ar-H),8.33(s,4H,Ar-H),7.85(s,2H,Ar-H),7.65(s,4H,Ar-H),7.02(s,2H,Ar-H),6.77(s,2H,Ar-H),5.84(s,1H,Ar-H),5.57(s,1H,Ar-H),5.44(s,1H,Ar-H),4.07(s,6H,OCH3),3.69(s,3H,OCH3),2.85(s,3H,OCH3),-17.20(s,1H,Ar-Hp).FT-IR(cm-1):2327(w),2157(w),1652(νC＝N,w),1607(νC＝N,m),1582(m),1509(s),1464(w),1442(w),1298(m),1249(s),1176(s),1031(w),833(m),775(m),578(m).元素分析：C57H50Br2N2O4Ni(1045.54)，理论值:C,65.48；H,4.82；N,2.68％.实际值:C,65.20；H,4.78；N,2.76％.
C2：深红色固体粉末产物，产率为88.1％。1H-NMR(400MHz,CDCl3,TMS):δ30.16(s,1H,An-H),27.97(s,1H,An-H),26.55(s,3H,CH3),26.24(s,1H,An-H),24.94(s,1H,An-H),24.34(s,2H,CH2),23.83(s,2H,CH2),21.72(s,1H,An-H),21.03(s,1H,An-H),19.27(broad,0.35H,Ar-CH(Ph)2),17.08(s,1H,Ar-H),16.36(s,1H,Ar-H),8.34(s,4H,Ar-H),7.90(s,2H,Ar-H),7.65(s,4H,Ar-H),6.78(s,4H,Ar-H),5.83(s,1H,An-H),5.64(s,1H,An-H),5.53(s,2H,An-H),4.13(s,6H,OCH3),3.69(s,6H,OCH3),2.88(s,6H,CH3),-16.59(s,1H,Ar-Hp).FT-IR(cm-1):2963(w),2930(w),2903(w),2835(w),1651(νC＝N,w),1608(νC＝N,m),1583(m),1509(s),1462(w),1442(w),1298(m),1249(s),1175(s),1109(w),1034(w),832(m),813(m),776(m).元素分析：C59H54Br2N2O4Ni(1073.59)，理论值:C,66.01；H,5.07；N,2.61％.实际值:C,66.24；H,5.02；N,2.69％.
C3：深红色固体粉末产物，产率为60.6％。1H-NMR(400MHz,CDCl3,TMS):δ30.85(s,1H,An-H),27.95(s,3H,CH3),26.65(s,1H,An-H),24.42(s,1H,An-H),24.15(s,2H,CH),22.62(s,1H,An-H),21.59(s,1H,An-H),19.66(broad,0.27H,Ar-CH(Ph)2),17.49(s,1H,Ar-H),16.57(s,1H,Ar-H),8.42(s,5H,Ar-H),7.69(s,7H,Ar-H),7.01(s,1H,Ar-H),6.70(s,3H,Ar-H),5.71(s,3H,Ar-H),5.52(s,2H,Ar-H),4.14(s,6H,OCH3),3.65(s,6H,OCH3),2.91(s,3H,CH3),2.19(s,3H,CH3),1.44(s,6H,CH3),-16.07(s,1H,Ar-Hp).FT-IR(cm-1):2962(w),2833(w),1648(νC＝N,w),1608(νC＝N,m),1582(m),1508(s),1462(w),1439(w),1384(w),1359(w),1296(w),1243(s),1174(s),1110(w),1033(w),960(m),934(m),835(m),813(m),777(m),751(m).元素分析：C61H58Br2N2O4Ni(1101.65)，理论值:C,66.51；H,5.31；N,2.54％.实际值:C,66.27；H,5.07；N,2.43％.
C4：深红色固体粉末产物，产率为71.5％。1H-NMR(400MHz,CDCl3,TMS):δ33.49(s,3H,CH3),30.30(s,2H,An-H),27.95(s,1H,An-H),26.58(s,3H,CH3),26.34(s,1H,An-H),24.77(s,2H,An-H),24.49(s,2H,CH2),24.15(s,1H,CH2),21.62(s,1H,An-H),21.12(s,1H,An-H),19.16(broad,0.40H,Ar-CH(Ph)2),17.11(s,1H,Ar-H),16.43(s,1H,Ar-H),8.34(s,4H,Ar-H),7.96(s,2H,Ar-H),7.66(s,4H,Ar-H),6.80(s,2H,Ar-H),5.91(s,1H,Ar-H),5.57(s,4H,Ar-H),4.14(s,6H,OCH3),3.71(s,3H,OCH3),2.89(s,3H,OCH3),1.44(s,3H,CH3),0.78(s,3H,CH3).FT-IR(cm-1):2959(w),2835(w),2159(w),1651(νC＝N,w),1608(νC＝N,m),1582(m),1509(s),1460(w),1439(w),1297(m),1249(s),1174(s),1110(w),1032(m),831(m),813(m),779(m),754(w),735(w),658(w).元素分析：C60H56Br2N2O4Ni(1087.62)，理论值:C,66.26；H,5.19；N,2.58％.实际值:C,66.38；H,5.13；N,2.54％.
(3)溴化镍配合物C1、C2、C3、C4作为催化剂在乙烯聚合中的应用
①C1用于乙烯聚合：
在乙烯气氛下，将20mL甲苯、30mL的催化剂C1(2μmol)的甲苯溶液、1.2mL的助催化剂Me2AlCl(1.00mol/L甲苯溶液)、50mL甲苯依次加入到250mL不锈钢高压釜中。此时Al/Ni＝600:1。机械搅拌开始，保持400转/分，当聚合温度达到30℃时，往反应釜中充入乙烯，聚合反应开始。在30℃下保持10atm的乙烯压力，搅拌30min。用5％盐酸酸化的乙醇溶液中和反应液，得到聚合物沉淀，用乙醇洗数次，真空烘干至恒重，称重。聚合活性：8.61×106g·mol-1(Ni)·h-1，聚合物Tm＝121.2℃(Tm为聚合物的熔融温度，通过DSC测试所得)，聚合物分子量Mw＝2.87×105g·mol-1，PDI＝3.44(Mw为聚合物的质均分子量，通过升温GPC测试所得)。
②C2用于乙烯聚合：方法条件同①，聚合活性：6.51×106g·mol-1(Ni)·h-1，聚合物Tm＝121.1℃，Mw＝3.85×105g·mol-1，PDI＝3.41。
③C3用于乙烯聚合：方法条件同①，聚合活性：6.09×106g·mol-1(Ni)·h-1，聚合物Tm＝120.7℃，Mw＝3.52×105g·mol-1，PDI＝3.80。
④C4用于乙烯聚合：方法条件同①，聚合活性：6.46×106g·mol-1(Ni)·h-1，聚合物Tm＝122.2℃，Mw＝3.26×105g·mol-1，PDI＝3.30。
实施例2 不对称亚胺苊合氯化镍配合物的制备、表征和应用
(1)配体的制备同实施例1；
(2)氯化镍配合物的制备及表征
在氮气氛围下，将一定量的NiCl2·6H2O(0.05g，0.20mmol)分批加入到不对称亚胺苊合配体化合物B1(0.17g，0.20mmol)的乙醇溶液中，搅拌下恢复室温，继续反应10小时后，反应结束浓缩，洗涤，抽滤，重结晶，制得不对称亚胺苊合镍配合物C5。
氯化镍配合物C6(R1＝Et,R2＝H),C7(R1＝iPr,R2＝H)和C8(R1＝Et,R2＝Me)的制备条件同氯化镍配合物C5的制备。
氯化镍配合物C5(R1＝Me,R2＝H),C6(R1＝Et,R2＝H),C7(R1＝iPr,R2＝H)和C8(R1＝Et,R2＝Me)的产率和表征的数据如下：
C5:浅红色固体粉末产物，产率为58.1％。FT-IR(cm-1):2964(w),2935(w),2904(w),2834(w),1656(νC＝N,w),1606(νC＝N,m),1585(m),1508(s),1461(w),1440(w),1425(w),1296(m),1240(s),1176(s),1134(w),1109(w),1032(m),953(m),871(m),830(m),811(w),774(w),656(w).元素分析：C59H54Cl2N2O4Ni(956.63)，理论值:C,71.57；H,5.27；N,2.93％.实际值:C,71.26；H,5.05；N,2.77％.
C6：浅红色固体粉末产物，产率为45.1％。FT-IR(cm-1):2964(w),2935(w),2904(w),2834(w),1656(νC＝N,w),1606(νC＝N,m),1585(m),1508(s),1461(w),1440(w),1425(w),1296(m),1240(s),1176(s),1134(w),1109(w),1032(m),953(m),871(m),830(m),811(w),774(w),656(w).元素分析：C59H54Cl2N2O4Ni(984.68)，理论值:C,71.97；H,5.53；N,2.84％.实际值:C,71.59；H,5.40；N,2.65％.
C7：浅红色固体粉末产物，产率为76.8％。FT-IR(cm-1):2967(w),2899(w),2838(w),1658(νC＝N,w),1606(νC＝N,m),1583(m),1508(s),1461(w),1439(w),1418(w),1384(w),1297(w),1240(s),1175(s),1107(w),1033(m),954(m),871(m),830(m),811(m),774(m),656(m).Anal.calcd for C61H58Cl2N2O4Ni(1012.74):C,72.35；H,5.77；N,2.77％.Found:C,72.05；H,5.75；N,2.73％.
C8：浅红色固体粉末产物，产率为83.4％。FT-IR(cm-1):2967(w),2906(w),2840(w),1654(νC＝N,w),1608(νC＝N,m),1582(m),1509(s),1460(w),1418(w),1387(w),1296(m),1249(s),1175(s),1111(w),1034(m),832(m),811(m),778(m),756(w),731(w),658(w).元素分析：C60H56Cl2N2O4Ni(998.71)，理论值:C,72.16；H,5.65；N,2.81％.实际值:C,72.26；H,5.63；N,2.65％.
(3)氯化镍配合物C5、C6、C7、C8作为催化剂在乙烯聚合中的应用
①C5用于乙烯聚合：方法条件同实施例1，聚合活性：6.58×106g·mol-1(Ni)·h-1，聚合物Tm＝124.9℃，Mw＝2.97×105g·mol-1，PDI＝3.46。
②C6用于乙烯聚合：方法条件同实施例1，聚合活性：5.35×106g·mol-1(Ni)·h-1，聚合物Tm＝119.9℃，Mw＝2.67×105g·mol-1，PDI＝3.07。
③C7用于乙烯聚合：方法条件同实施例1，聚合活性：4.38×106g·mol-1(Ni)·h-1，聚合物Tm＝120.6℃，Mw＝3.04×105g·mol-1，PDI＝2.94。
④C8用于乙烯聚合：方法条件同实施例1，聚合活性：4.58×106g·mol-1(Ni)·h-1，聚合物Tm＝121.5℃，Mw＝2.98×105g·mol-1，PDI＝3.21。
Claims (6)
1.一种不对称亚胺苊合卤化镍配合物，其特征在于，具有如下的结构式：
其中：
R1、R2各自独立地选自氢、1-10个碳原子的烷基、芳基、烷芳基、芳烷基和烷氧基中的一种。
X为卤素。
2.如权利要求1所述的一种不对称亚胺苊合卤化镍配合物，其特征在于，所述的R1、R2各自独立地选自氢、甲基、乙基、异丙基和甲氧基中的一种；所述卤素选自Cl或Br。
3.如权利要求1或2所述的一种不对称亚胺苊合镍配合物的制备方法，其特征在于，包括如下步骤：
(1)配体的制备：将适量的对甲基苯磺酸溶于甲醇中，搅拌下分批加入到等摩尔量的2-(2,4-二(4,4’-二甲氧基二苯甲基)-6-甲基苯胺与苊醌的二氯甲烷混合液中，室温搅拌18-24小时，将所得溶液浓缩，然后通过柱色谱法纯化，得到苊酮中间产物；将苊酮中间产物溶于二氯甲烷中分批加入到苯胺化合物的甲醇溶液中，回流20-24小时，反应完全后，浓缩，洗涤，抽滤，结晶，制得不对称亚胺苊合配体化合物；
(2)镍配合物的制备：在氮气氛围下，将一定量的(DME)NiBr2或NiCl2·6H2O分批加入到亚胺苊合配体化合物的乙醇溶液中，搅拌下恢复室温，继续反应10-12小时后，反应结束浓缩，洗涤，抽滤，重结晶，制得不对称亚胺苊合卤化镍配合物。
4.如权利要求3所述的一种不对称亚胺苊合镍配合物的制备方法，其特征在于，所述步骤(1)中的苊酮与苯胺化合物的摩尔比为1：1-2。
5.如权利要求3所述的一种不对称亚胺苊合镍配合物的制备方法，其特征在于，所述步骤(2)中的不对称亚胺苊合配体化合物B与(DME)NiBr2或六水合氯化镍的摩尔比为1:1。
6.如权利要求1或2所述的一种不对称亚胺苊合卤化镍配合物在乙烯聚合中的应用。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010113135.4A CN111233939B (zh) | 2020-02-24 | 2020-02-24 | 一种不对称亚胺苊合卤化镍配合物及其制备方法和应用 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010113135.4A CN111233939B (zh) | 2020-02-24 | 2020-02-24 | 一种不对称亚胺苊合卤化镍配合物及其制备方法和应用 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111233939A true CN111233939A (zh) | 2020-06-05 |
| CN111233939B CN111233939B (zh) | 2021-12-31 |
Family
ID=70870602
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010113135.4A Active CN111233939B (zh) | 2020-02-24 | 2020-02-24 | 一种不对称亚胺苊合卤化镍配合物及其制备方法和应用 |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111233939B (zh) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112142801A (zh) * | 2020-10-10 | 2020-12-29 | 山西大学 | 一种不对称吡啶亚胺钴配合物及其制备方法和应用 |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102180910A (zh) * | 2011-03-11 | 2011-09-14 | 中国科学院化学研究所 | 不对称α二亚胺镍配合物催化剂及其制备方法与应用 |
| CN105693896A (zh) * | 2014-11-25 | 2016-06-22 | 中国石油天然气股份有限公司 | 苊醌-1,2-不对称二亚胺镍配合物催化剂及其制备方法与应用 |
| CN106632506A (zh) * | 2016-09-26 | 2017-05-10 | 中国科学院化学研究所 | 一类含4,4’‑二氟二苯甲基的不对称α‑二亚胺镍配合物、其中间体、制备方法及其应用 |
| CN108794545A (zh) * | 2017-04-28 | 2018-11-13 | 中国科学院化学研究所 | 用于制备超高分子量聚乙烯弹性体的含叔丁基不对称α-二亚胺镍配合物、制备方法及用途 |
| CN109942638A (zh) * | 2019-04-19 | 2019-06-28 | 常州大学 | 用于乙烯聚合的含邻位二对甲基苯甲基取代的不对称α-二亚胺镍（Ⅱ）配合物 |
-
2020
- 2020-02-24 CN CN202010113135.4A patent/CN111233939B/zh active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102180910A (zh) * | 2011-03-11 | 2011-09-14 | 中国科学院化学研究所 | 不对称α二亚胺镍配合物催化剂及其制备方法与应用 |
| CN105693896A (zh) * | 2014-11-25 | 2016-06-22 | 中国石油天然气股份有限公司 | 苊醌-1,2-不对称二亚胺镍配合物催化剂及其制备方法与应用 |
| CN106632506A (zh) * | 2016-09-26 | 2017-05-10 | 中国科学院化学研究所 | 一类含4,4’‑二氟二苯甲基的不对称α‑二亚胺镍配合物、其中间体、制备方法及其应用 |
| CN108794545A (zh) * | 2017-04-28 | 2018-11-13 | 中国科学院化学研究所 | 用于制备超高分子量聚乙烯弹性体的含叔丁基不对称α-二亚胺镍配合物、制备方法及用途 |
| CN109942638A (zh) * | 2019-04-19 | 2019-06-28 | 常州大学 | 用于乙烯聚合的含邻位二对甲基苯甲基取代的不对称α-二亚胺镍（Ⅱ）配合物 |
Non-Patent Citations (3)
| Title |
|---|
| SHIFANG YUAN等: "Alkylaluminum activator effects on polyethylene branching using a N,N-nickel precatalyst appended with bulky 4,4-dimethoxybenzhydryl groups", 《APPL ORGANOMETAL CHEM.》 * |
| YANJUN CHEN等: "Balancing High Thermal Stability with High Activity in Diaryliminoacenaphthene-Nickel(II) Catalysts for Ethylene Polymerization", 《JOURNAL OF POLYMER SCIENCE, PART A: POLYMER CHEMISTRY》 * |
| 袁世芳等: "镍配位催化乙烯聚合新进展", 《高分子通报》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112142801A (zh) * | 2020-10-10 | 2020-12-29 | 山西大学 | 一种不对称吡啶亚胺钴配合物及其制备方法和应用 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111233939B (zh) | 2021-12-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101531725B (zh) | α-二亚胺镍配合物烯烃聚合催化剂及其制备方法与制备支化聚乙烯的方法 | |
| CN101812145B (zh) | α-二亚胺镍配合物烯烃聚合催化剂及其制备方法与制备支化聚乙烯的方法 | |
| CN105294778A (zh) | 一种镍基配合物及其制备方法和应用 | |
| CN104250270A (zh) | 一种不对称二苯甲基α-二亚胺镍配合物及其制备与应用 | |
| CN111233939B (zh) | 一种不对称亚胺苊合卤化镍配合物及其制备方法和应用 | |
| CN109957049B (zh) | 不对称（α-二亚胺）镍烯烃催化剂及其制备方法和应用 | |
| CN105693896A (zh) | 苊醌-1,2-不对称二亚胺镍配合物催化剂及其制备方法与应用 | |
| CN110092744A (zh) | 一类高热稳定的含叔丁基不对称二亚胺吡啶配合物、其制备方法及应用 | |
| CN109762027B (zh) | 一种对位含芳基取代的α-二亚胺镍配合物及其制备方法和应用 | |
| CN101613425B (zh) | 具有双峰和/或宽峰分布分子量分布的聚乙烯的催化剂 | |
| CN109956980B (zh) | 亚乙基苊不对称α-二亚胺镍催化剂及其制备方法和应用 | |
| CN109988100B (zh) | 硝基强化热稳定性和催化活性的不对称二亚胺吡啶配合物、其制备方法及应用 | |
| CN106397263A (zh) | 配体化合物、其制备及含所述配体化合物的配合物 | |
| CN112142801B (zh) | 一种不对称吡啶亚胺钴配合物及其制备方法和应用 | |
| CN109957051B (zh) | 亚乙烯基苊α-二亚胺镍烯烃催化剂及其制备方法和应用 | |
| CN108794544A (zh) | 用于制备超高分子量聚乙烯的含硝基不对称α-二亚胺镍配合物、中间体、制备方法及用途 | |
| CN110938164A (zh) | 一锅法串联催化共聚乙烯与1,2-二取代极性内烯烃的方法及其产物 | |
| CN112898352B (zh) | 一种不对称钯配合物和制备方法及其催化烯烃聚合应用 | |
| CN112920300B (zh) | 一类大位阻α-二亚胺配体、镍催化剂及其制备方法与应用 | |
| CN105646599A (zh) | 吡啶并环庚烷亚胺镍配合物催化剂及其制备方法与应用 | |
| CN110183496A (zh) | 吡啶二亚胺类双核金属配合物，其制备方法及应用 | |
| CN109956978B (zh) | 基于菲醌的不对称α-二亚胺镍催化剂及其制备方法和应用 | |
| CN112175018B (zh) | 含有二苯甲氧基的吡啶亚胺钴配合物及其制备方法和应用 | |
| CN113620968A (zh) | 具有环状缩醛结构的刚性生物基二醇单体、其制法与应用 | |
| CN113024613A (zh) | 一种不对称亚胺铁配合物及其制备方法和应用 |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20231220 Address after: 201400 1st floor, No. 281-289 (single), Lixin Road, Fengxian District, Shanghai Patentee after: Pramita Technical Services (Shanghai) Co.,Ltd. Address before: 030006, No. 92, Hollywood Road, Xiaodian District, Shanxi, Taiyuan Patentee before: SHANXI University |
|
| TR01 | Transfer of patent right |