Large-steric-hindrance substituent modified acenaphthenyl skeleton Ni complex as well as synthesis method and application thereof

Abstract

The invention belongs to the field of olefin polymerization catalysis, and particularly relates to an acenaphthenyl skeleton Ni complex modified by a large-steric-hindrance substituent as shown in a formula I and a synthesis method and application of the acenaphthenyl skeleton Ni complex. The complex has the catalytic performance obviously superior to that of a metal nickel complex with an acenaphthenyl skeleton modified by substituent groups without large steric hindrance, and shows better catalytic activity and good thermal stability in catalytic ethylene polymerization reaction, and the molecular weight of a polymer obtained through catalysis and the branching degree of polyethylene are higher; and the obtained polyethylene material shows good elastic property. # imgabs0 #

Description

Technical Field

[0001] The present invention belongs to the field of olefin polymerization catalysis, and particularly relates to an acenaphthyl-based skeleton Ni complex modified with a bulky substituent, and a synthesis method and application thereof. Background Art

[0002] Polyolefin materials have become the most widely used polymer materials due to their rich raw material sources, low prices, and excellent comprehensive properties. Among them, polyethylene is particularly remarkable, and its technical level is an important symbol to measure the development level of the petrochemical industry in a country. Polyethylene materials have the advantages of low price, simple preparation, good chemical tolerance and mechanical properties, and can be applied to many fields such as packaging, printing, and electronic devices. Ethylene monomers can be copolymerized with one or several of monomers such as propylene and butene to prepare elastic materials. In comparison, due to its unique "chain walking" process, the diimine nickel complex can use ethylene as the only monomer to prepare branched polyethylene, thus showing catalytic advantages.

[0003] In 1995, Brookhart et al. first used α-diimine nickel / palladium complexes for catalyzing ethylene polymerization and copolymerization, and obtained branched polyethylene products with certain branches and relatively high molecular weights.

[0004] However, the catalytic activity and thermal stability of the existing α-diimine nickel / palladium complexes still need to be further improved. Summary of the Invention

[0005] The object of the present invention is to provide a metal nickel complex with an acenaphthyl-based skeleton modified with a bulky substituent. This complex has catalytic performance significantly superior to that of a metal nickel complex with an acenaphthyl-based skeleton without bulky substituent modification, shows better catalytic activity in the catalytic ethylene polymerization reaction, has good thermal stability, higher molecular weight of the polymer obtained by catalysis and higher degree of polyethylene branching, and the obtained polyethylene material shows good elastic properties.

[0006] The technical solution of the present invention is as follows:

[0007] The complex shown in Formula I,

[0008]

[0009] wherein, R 1 is unsubstituted, or Ra optionally substituted by one, two or more Rs; the Rs are selected from C 1-6 alkyl, F, Cl, Br, I, NO 2 or C 1-6 alkoxy;

[0010] R 2 、R 3 、R 4 、R5 , R 6 , R 7 are the same or different and are each independently selected from H, F, Cl, Br, I, C 1-6 alkyl, C 3-6 cycloalkyl, C alkyl substituted with halogen, 1-6 alkyl, C cycloalkyl substituted with halogen, 3-6 cycloalkyl, C alkyl substituted with Rb, 1-6 alkyl, C alkyl substituted with two or more Rb, 1-6 alkyl, C alkyl substituted with halo Rc, 1-6 alkyl, or C alkyl substituted with two or more halo Rc, 1-6 alkyl;

[0011] Ra, Rb, and Rc are the same or different and are each independently selected from C 6-14 aryl having 6 to 14 carbon atoms or heteroaryl having 5 to 14 atoms;

[0012] X is selected from F, Cl, Br, I, C 1-6 alkyl, and the two Xs are the same or different.

[0013] According to an embodiment of the present invention, Ra, Rb, and Rc are the same or different and are each independently selected from phenyl, naphthyl, or anthracenyl.

[0014] According to an embodiment of the present invention, R 1 is unsubstituted or is optionally substituted with one, two, or more Rs and is the following group: phenyl, naphthyl, or anthracenyl; the Rs are selected from C 1-3 alkyl, F, Cl, Br, I, NO 2 or C 1-3 alkoxy;

[0015] R 2 , R 3 , R 4 , R 5 , R 6 , R 7 are the same or different and are each independently selected from H, F, Cl, Br, I, C 1-3 alkyl, C 3-6 cycloalkyl, C alkyl substituted with halogen, 1-6 alkyl, C cycloalkyl substituted with halogen, 3-6 cycloalkyl, methyl substituted with phenyl, methyl substituted with diphenyl, methyl substituted with halophenyl, or methyl substituted with two halophenyls;

[0016] X is selected from F, Cl, Br, or I, and the two Xs are the same or different.

[0017] According to an embodiment of the present invention, R 1 is wherein R8 , R 9 are the same or different and are each independently selected from H, Me, F, Cl, NO 2 , OCH 3 ;

[0018] R 2 , R 3 , R 4 , R 5 , R 6 , R 7 are the same or different and are each independently selected from H, F, Cl, Br, I, methyl, ethyl, isopropyl, CHPh 2 , CH(p-F-Ph) 2 ;

[0019] Two Xs are the same and are selected from Cl or Br.

[0020] According to an embodiment of the present invention, Formula I includes the following specific structures:

[0021] Complex Ni1: The R 2 = R 3 = R 5 = R 6 = Me, X is selected from Br, R 4 , R 7 , R 8 , R 9 is H;

[0022] Complex Ni2: The R 2 = R 3 = R 5 = R 6 = Et, X is selected from Br, R 4 , R 7 , R 8 , R 9 is H;

[0023] Complex Ni3: The R 2 = R 3 = R 5 = R 6 = i-Pr, X is selected from Br, R 4 , R 7 , R 8 , R 9 is H;

[0024] Complex Ni4: The R 2 = R 3 = R 4 = R5 = R 6 = R 7 = Me, X is selected from Br, R 8 , R 9 is H;

[0025] Complex Ni5: The R 2 = R 3 = R 5 = R 6 = Et, R 4 = R 7 = Me, X is selected from Br, R 8 , R 9 is H;

[0026] Complex Ni6: The R 2 = R 5 = Me, R 3 = R 6 = Cl, X is selected from Cl, R 4 , R 7 , R 8 , R 9 is H;

[0027] Complex Ni7: The R 2 = R 3 = R 5 = R 6 = Me, R 4 = R 7 = CHPh 2 , X is selected from Br, R 8 , R 9 is H;

[0028] Complex Ni8: The R 2 = R 3 = R 5 = R 6 = Et, R 4 = R 7 = CHPh 2 , X is selected from Br, R 8 , R 9 is H;

[0029] Complex Ni9: The R 2 = R 3 = R 5 = R 6 = i-Pr, R 4 = R 7 = CHPh 2, X is selected from Br, R 8 and R 9 is H;

[0030] Complex Ni10: The R 2 = R 3 = R 5 = R 6 = F, R 4 = R 7 = CHPh 2 , X is selected from Br, R 8 and R 9 is H;

[0031] Complex Ni11: The R 2 = R 5 = CHPh 2 , R 3 = R 4 = R 6 = R 7 = Me, X is selected from Br, R 8 and R 9 is H;

[0032] Complex Ni12: The R 2 = R 4 = R 5 = R 7 = CHPh 2 , R 3 = R 6 = Me, X is selected from Br, R 8 and R 9 is H;

[0033] Complex Ni13: The R 2 = R 3 = R 5 = R 6 = CHPh 2 , R 4 = R 7 = Me, X is selected from Br, R 8 and R 9 is H;

[0034] Complex Ni14: The R 2 = R 3 = R 5 = R 6 = CH(p-F-Ph) 2 , R 4 = R 7= Me, X is selected from Br, R 8 、R 9 is H;

[0035] Complex Ni15: The R 2 = R 3 = CH(p-F-Ph) 2 ,R 4 = R 5 = R 6 = Me, X is selected from Br, R 7 、R 8 、R 9 is H;

[0036] Complex Ni16: The R 2 = R 3 = CH(p-F-Ph) 2 ,R 4 = Me, R 5 = R 6 = Et, X is selected from Br, R 7 、R 8 、R 9 is H;

[0037] Complex Ni17: The R 2 = R 3 = CH(p-F-Ph) 2 ,R 4 = Me, R 5 = R 6 = i-Pr, X is selected from Br, R 7 、R 8 、R 9 is H;

[0038] Complex Ni18: The wherein R 8 = NO 2 ,X is selected from Br, R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 9 is H;

[0039] Complex Ni19: The wherein R 8 = NO 2 ,R 2 = R 5 = Me, X is selected from Br, R 2 、R4 , R 5 , R 7 , R 9 is H;

[0040] Complex Ni20: The where R 8 = NO 2 , R 2 = R 3 = R 5 = R 6 = Me, X is selected from Br, R 4 , R 7 , R 9 is H;

[0041] Complex Ni21: The where R 8 = NO 2 , R 2 = R 5 = Me, R 3 = R 6 = Et, X is selected from Br, R 4 , R 7 , R 9 is H;

[0042] Complex Ni22: The where R 8 = NO 2 , R 2 = R 3 = R 5 = R 6 = Et, X is selected from Br, R 4 , R 7 , R 9 is H;

[0043] Complex Ni23: The where R 8 = NO 2 , R 2 = R 3 = R 5 = R 6 = i-Pr, X is selected from Br, R 4 , R 7 , R 9 is H;

[0044] Complex Ni24: The where R 8 = R 9 = F, R 2 = R 3 = R 5 = R 6= i-Pr, X is selected from Br, R 4 、R 7 is H;

[0045] Complex Ni25: The R 2 = R 3 = R 5 = R 6 = Me, X is selected from Br, R 4 、R 7 is H;

[0046] Complex Ni26: The R 2 = R 3 = R 5 = R 6 = Et, X is selected from Br, R 4 、R 7 is H;

[0047] Complex Ni27: The R 2 = R 3 = R 5 = R 6 = i-Pr, X is selected from Br, R 4 、R 7 is H;

[0048] Complex Ni28: The R 2 = R 3 = R 4 = R 5 = R 6 = R 7 = Me, X is selected from Br;

[0049] Complex Ni29: The R 2 = R 3 = R 5 = R 6 = Et, R 4 = R 7 = Me, X is selected from Br;

[0050] Complex Ni30: The R 2 = R 3 = R 5 = R 6 = i-Pr, X is selected from Br, R 4 、R 7 is H;

[0051] Complex Ni31: The R2 = R 3 = R 5 = R 6 = i-Pr, X is selected from Br, R 4 , R 7 is H.

[0052] The present invention also provides a method for preparing the complex shown in the above formula I, comprising the following steps;

[0053] Compound IIa, IIb, IIc reacts with compound NiX 2 to obtain the complex shown in formula I;

[0054]

[0055] wherein, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , X has the definitions as described above.

[0056] According to an embodiment of the present invention, when R 2 and R 5 in compounds IIb and IIc have the same definition, R 3 and R 4 have the same definition; when R 4 and R 7 have the same definition, that is, when the complex shown in formula I is a symmetric structure, any one of compounds IIb or IIc is used to react with compound IIa and compound NiX 2 for reaction.

[0057] According to an embodiment of the present invention, when the complex shown in formula I is a symmetric structure, any one of compounds IIb or IIc is used to react with compound IIa and compound NiX 2 by refluxing in acetic acid.

[0058] According to an embodiment of the present invention, when any one of the definitions of R 2 and R 5 , R 3 and R 4 , R 4 and R 7 is different, that is, when the complex shown in formula I is an asymmetric structure, in the preparation of formula I, first react formula IIa with any one of IIb and IIc, and then react the obtained product with the remaining one of IIb and IIc and compound NiX 2 for reaction.

[0059] According to an embodiment of the present invention, when the complex shown in Formula I has an asymmetric structure, in the preparation of Formula I, either IIa and any one of IIb and IIc are first refluxed in toluene under the catalysis of p-toluenesulfonic acid; the resulting product is then reacted with the remaining one of IIb and IIc and the compound NiX 2 in acetic acid by refluxing.

[0060] The present invention also provides a catalyst composition, which comprises the complex shown in Formula I as described above and a co-catalyst, and the catalyst composition is used for catalyzing olefin polymerization reaction, and the olefin is preferably ethylene.

[0061] According to an embodiment of the present invention, the polymerization is the polymerization of the same olefin monomer or the copolymerization reaction of multiple olefin monomers.

[0062] According to an embodiment of the present invention, the co-catalyst is one or several of aluminoxane, alkylaluminum or alkylaluminum chloride.

[0063] According to an embodiment of the present invention, the molar ratio of metal Al in the co-catalyst to metal Ni in the complex shown in Formula (I) is (100 - 5000):1, for example (200 - 4000):1, such as (500 - 3000):1, (800 - 2500):1 or (1000 - 2000):1.

[0064] According to an embodiment of the present invention, the co-catalyst is at least one of methylaluminoxane (MAO), methylaluminoxane modified with triisobutylaluminum (MMAO), sesquiethylaluminum chloride (EASC), EtAlCl 2 among others.

[0065] According to an embodiment of the present invention, when the co-catalyst is methylaluminoxane (MAO), the molar ratio of metal Al in methylaluminoxane (MAO) to metal Ni in the complex shown in Formula (I) is (200 - 2500):1, such as (1000 - 2000):1, such as 1875:1.

[0066] According to an embodiment of the present invention, when the co-catalyst is methylaluminoxane modified with triisobutylaluminum (MMAO), the molar ratio of metal Al in the co-catalyst to metal Ni in the compound shown in Formula I is (200 - 3800):1, such as (625 - 3750):1.

[0067] According to an embodiment of the present invention, when the co-catalyst is methylaluminoxane modified with triisobutylaluminum (MMAO), the molar ratio of metal Al in the co-catalyst to metal Ni in the compound shown in Formula I is (200 - 3800):1, such as (625 - 3750):1.

[0068] According to an embodiment of the present invention, when the co-catalyst is sesquiethylaluminum chloride (EASC), the molar ratio of metal Al in the co-catalyst to metal Ni in the compound shown in Formula I is (200-2500):1, for example (100-600):1.

[0069] According to an embodiment of the present invention, the co-catalyst is EtAlCl 2 When, the molar ratio of metal Al in the co-catalyst to metal Ni in the compound shown in Formula I is (200-2500):1, for example (100-600):1.

[0070] The present invention also provides a method for catalyzing olefin polymerization, including polymerizing an olefin in the presence of the catalyst composition as described above.

[0071] The complex of the present invention has the following advantages:

[0072] 1. The present invention provides a new class of acenaphthylene-based skeleton α-diimine type ethylene polymerization catalysts containing rigid bulky substituents. The complexes are rigidly bulky modified at the distal end of the acenaphthylene, significantly increasing the axial steric hindrance, and showing good catalytic activity and extremely strong thermal stability in the catalytic polymerization of ethylene. Using EASC as the co-catalyst, at a polymerization temperature of 60 °C, the catalytic activity can reach 1.1×10 7 g·mol -1 (Ni)·h -1 , which is 1.2 - 1.5 times that of the unmodified catalyst on the acenaphthenequinone skeleton under the same catalytic conditions; at a polymerization temperature of 80 °C, using EASC as the co-catalyst, the catalytic activity of Ni2 can reach 8.8×10 6 g·mol -1 (Ni)·h -1 ; at a polymerization temperature of 80 °C, the catalytic activity is still 6×10 6 g·mol -1 (Ni)·h -1 , while the activity of the complex without modification on the acenaphthylene skeleton under the same conditions is less than 1×10 6 g·mol -1 (Ni)·h -1 . The high thermal stability endows the catalyst with good industrial application prospects.

[0073] 2. The present invention provides a synthesis method for a class of acenaphthylene-based skeleton Ni complexes modified with bulky substituents. The present invention uses a one-pot method to synthesize the target catalyst. The method has the advantages of mild reaction conditions, simple operation, and easy post-treatment, providing a new idea and method for preparing acenaphthenequinone compounds modified with bulky substituents.

[0074] 3. Compared with the Ni catalyst without modification on the acenaphthyl skeleton, the degree of branching and molecular weight of the polyethylene sample catalyzed by the catalyst of the present invention have both been improved. The catalyst of the present invention can catalyze the preparation of polyethylene with low to medium to high degrees of branching or even hyperbranched polyethylene (48 - 172 / 1000C’s), and has a wide range of applications. The melting points of the obtained polymers are mostly distributed in the range of 70–120 °C. The weight-average molecular weight M w of the prepared polyethylene can be adjusted between 5–26×10 4 g·mol -1 , and the molecular weight distribution is relatively narrow (less than 2). In addition, the polymer catalyzed by this catalyst has good elastic properties and toughness. When a tensile test is carried out, the maximum strain can exceed 2000% (while the stress exceeds 9 MPa), which has great academic and industrial research value. BRIEF DESCRIPTION OF THE DRAWINGS

[0075] Figure 1 is a schematic structural diagram of complexes Ni1–Ni31.

[0076] Figure 2 is a schematic crystal structure diagram of complex Ni3 prepared in Example 3.

[0077] Figure 3 is a stress-strain curve diagram of the polymers obtained in Examples 38 and 43.

[0078] Figure 4 is a nuclear magnetic carbon spectrum diagram of the polymer obtained in Example 47 at 100 °C.

[0079] TERMINOLOGY DEFINITIONS AND EXPLANATIONS

[0080] In the present invention, the "*" in some groups represents the connection site.

[0081] In the present invention, the term "C 1-6 alkyl" refers to a straight-chain or branched-chain alkane having 1 to 6 carbon atoms, and examples of the alkyl include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, or hexyl, etc.

[0082] The term "C 3-6 cycloalkyl" should be understood as a straight-chain or branched-chain saturated monocyclic hydrocarbon ring containing, for example, 3, 4, 5, or 6 carbon atoms.

[0083] The term "C 6-14 aryl" should be understood to represent a monocyclic, bicyclic, or tricyclic hydrocarbon ring having 6, 7, 8, 9, 10, 11, 12, 13, or 14 carbon atoms and being monovalent aromatic or partially aromatic ("C 6-14 aryl"), especially a ring having 6 carbon atoms ("C 6"Aryl"), such as phenyl; or biphenyl, or a ring having 9 carbon atoms ("C 9 "Aryl"), such as indanyl or indenyl, or a ring having 10 carbon atoms ("C 10 "Aryl"), such as tetrahydronaphthyl, dihydronaphthyl or naphthyl, or a ring having 13 carbon atoms ("C 13 "Aryl"), such as fluorenyl, or a ring having 14 carbon atoms ("C 14 "Aryl"), such as anthryl. When the C 6-20 "Aryl" is substituted, it may be mono-substituted or multi-substituted. And there is no restriction on its substitution site, for example, it can be ortho-substituted, para-substituted or meta-substituted.

[0084] The term "5-14-membered heteroaryl" should be understood to include such monovalent monocyclic, bicyclic or tricyclic aromatic ring systems: having 5, 6, 7, 8, 9, 10, 11, 12, 13 or 14 ring atoms, especially 5 or 6 or 9 or 10 carbon atoms, and containing 1-5, preferably 1-3 heteroatoms independently selected from N, O and S. And, in each case, it may be benzo-fused. In particular, heteroaryl is selected from thienyl, furyl, pyrrolyl, oxazolyl, thiazolyl, imidazolyl, pyrazolyl, isoxazolyl, isothiazolyl, oxadiazolyl, triazolyl, thiadiazolyl, thia-4H-pyrazolyl, etc. and their benzo derivatives, such as benzofuryl, benzothienyl, benzoxazolyl, benzisoxazolyl, benzimidazolyl, benzotriazolyl, indazolyl, indolyl, isoindolyl, etc.; or pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, etc., and their benzo derivatives, such as quinolinyl, quinazolinyl, isoquinolinyl, etc.; or azocinyl, indolizinyl, purinyl, etc. and their benzo derivatives; or cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, naphthyridinyl, pteridinyl, carbazolyl, acridinyl, phenazinyl, phenothiazinyl, phenoxazinyl, etc. Detailed implementation mode

[0085] The experimental methods used in the following examples are all conventional methods unless otherwise specified.

[0086] The chemical reagents, materials, etc. used in the following examples can be obtained from commercial sources unless otherwise specified.

[0087] The methylaluminoxane (abbreviation: MAO) and modified methylaluminoxane (abbreviation: MMAO) used in the following examples and comparative examples are all purchased from Anhui Botai Electronic Materials Co., Ltd.

[0088] Example 1 Preparation of N,N'-bis(2,6-dimethylphenyl)-5-phenylacenaphthylene-1,2-diimine·nickel(II) bromide complex, Ni1

[0089] A suspension of compound 5-phenylacenaphthenequinone (0.10 g, 0.387 mmol), 2,6-dimethylaniline (0.314 g, 1.55 mmol) and (DME)·NiBr 2 (0.114 g, 0.368 mmol) in acetic acid (8 mL) was refluxed for 6 hours. After cooling to room temperature, an excess of diethyl ether (20 mL) was added to induce precipitation. The red precipitate was collected by filtration and dried in an oven at 60 °C for 8 hours to obtain a red powder Ni1 (0.14 g, 53.0%).

[0090] Structural characterization is as follows: FT-IR (cm -1 ): 3335 (m), 2979 (m), 2909 (m), 1651 (w, v C＝N ), 1624 (m, v C＝N ), 1597 (s), 1579 (s), 1467 (m), 1422 (m), 1380 (w), 1338 (w), 1311 (w), 1261 (w), 1230 (w), 1196 (w), 1165 (w), 1129 (w), 1071 (w), 1034 (w), 997 (w), 850 (w), 825 (w), 781 (s), 763 (s), 701 (s). Elemental analysis: C 34 H 28 Br 2 N 2 Ni (683.11) Theoretical values: C, 59.78; H, 4.13; N, 4.10. Experimental values: C, 59.60; H, 4.00; N, 4.15.

[0091] Example 2 Preparation of N,N'-bis(2,6-diethylphenyl)-5-phenylacene-1,2-diimine nickel(II) complex, Ni2 is similar to Example 1, replacing 2,6-dimethylaniline with 2,6-diethylaniline, and adjusting the feeding amounts of other substances according to the corresponding molar ratios, and the operation is similar. A red powder Ni2 (0.43 g, 83.5%) was obtained.

[0092] Structural characterization is as follows: FT-IR (cm -1 ): 3353 (m), 2965 (w), 2931 (w), 2875 (w), 1648 (w, v C＝N ), 1621 (m, v C＝N), 1600 (m), 1579 (m), 1444 (m), 1423 (m), 1377 (w), 1334 (w), 1300 (w), 1257 (w), 1183 (w), 1129 (w), 1069 (w), 973 (w), 849 (m), 810 (m), 763 (s), 701 (s). Elemental analysis: C 38 H 36 Br 2 N 2 Ni (739.22) Theoretical values: C, 61.74; H, 4.91; N, 3.79. Experimental values: C, 61.28; H, 4.76; N, 3.77.

[0093] Example 3 Preparation of N,N'-bis(2,6-diisopropylphenyl)-5-phenylacenaphthylene-1,2-diimine·nickel(II) bromide complex, Ni3 is similar to Example 1, replace 2,6-dimethylaniline with 2,6-diisopropylaniline, and adjust the feeding amounts of other substances according to the corresponding molar ratios, and the operation is similar. Obtain red powder Ni3 (0.08 g, 48.7%). Its crystal structure diagram is as Figure 3 shown.

[0094] Structure characterization is as follows: FT-IR (cm -1 ): 3356 (w), 2960 (m), 2922 (w), 1649 (w, v C＝N ), 1619 (w, v C＝N ), 1579 (m), 1418 (w), 1383 (w), 1358 (w), 1323 (w), 1252 (w), 1183 (w), 1063 (s), 971 (w), 932 (w), 851 (w), 828 (m), 759 (s), 700 (s). Elemental analysis: C 42 H 44 Br 2 N 2 Ni (795.33) Theoretical values: C, 63.43; H, 5.58; N, 3.52. Experimental values: C, 63.28; H, 5.56; N, 3.51.

[0095] Example 4 Preparation of N,N'-bis(2,4,6-trimethylphenyl)-5-phenylacenaphthylene-1,2-diimine·nickel(II) bromide complex, Ni4 is similar to Example 1, replace 2,6-dimethylaniline with 2,4,6-trimethylaniline, and adjust the feeding amounts of other substances according to the corresponding molar ratios, and the operation is similar. Obtain red powder Ni4 (0.24 g, 87.3%).

[0096] Structure characterization is as follows: FT-IR (cm -1): 3233 (w), 2917 (w), 1649 (w, v C＝N ), 1579 (w), 1539 (w), 1480 (w), 1421 (w), 1370 (w), 1342 (w), 1313 (w), 1290 (w), 1263 (w), 1233 (w), 1206 (w), 1120 (w), 1039 (w), 1017 (w), 969 (w), 940 (w), 854 (w), 820 (s). Elemental analysis: C 36 H 32 Br 2 N 2 Ni(711.17) Theoretical values: C, 60.80; H, 4.54; N, 3.94. Experimental values: C, 59.40; H, 4.66; N, 3.77.

[0097] Example 5 Preparation of N,N'-bis(2,6-diethyl-4-methylphenyl)-5-phenylacenaphthylene-1,2-diimine·nickel(II) bromide complex, Ni5

[0098] Similar to Example 1, replace 2,6-dimethylaniline with 2,6-diethyl-4-methylaniline, and adjust the feeding amounts of other substances according to the corresponding molar ratios, and the operation is similar. A red powder Ni5 (0.20 g, 66.6%) is obtained.

[0099] Structure characterization is as follows: FT-IR (cm -1 ): 2964 (w), 2938 (w), 2876 (w), 1626 (w, v C＝N ), 1563 (w), 1519 (w), 1457 (w), 1417 (w), 1373 (w), 1337 (w), 1303 (w), 1230 (w), 1203 (w), 1154 (w), 1115 (w), 1063 (w), 1023 (w), 856 (w), 825 (w), 760 (s). Elemental analysis: C 40 H 40 Br 2 N 2 Ni(767.28) Theoretical values: C, 62.62; H, 5.25; N, 3.56. Experimental values: C, 62.80; H, 5.43; N, 3.53.

[0100] Example 6 Preparation of N,N'-bis(2-methyl-6-chlorophenyl)-5-phenylacenaphthylene-1,2-diimine·nickel(II) chloride complex, Ni6 is similar to Example 1, replace 2,6-dimethylaniline with 2-methyl-6-chloroaniline, and replace (DME)·NiBr 2Replace it with nickel chloride, and adjust the feeding amounts of other substances according to the corresponding molar ratios. The operation is similar. A brownish-yellow powder Ni6 (0.05 g, 68.5%) is obtained.

[0101] The structural characterization is as follows: FT-IR (cm -1 ): 3233 (w), 2917 (w), 2876 (w), 1645 (w, v C＝N ), 1579 (w), 1539 (w), 1421 (w), 1290 (w), 1017 (w), 853 (w), 760 (s). Elemental analysis: C 32 H 22 Cl 4 N 2 Ni (635.04) Theoretical values: C, 60.52; H, 3.49; N, 4.41. Experimental values: C, 60.80; H, 3.43; N, 4.43.

[0102] Example 7 Preparation of N,N'-bis(2,6-dimethyl-4-diphenylmethylphenyl)-5-phenylacenaphthylene-1,2-diimine·nickel(II) bromide complex, Ni7

[0103] Similar to Example 1, replace 2,6-dimethylaniline with 2,6-dimethyl-4-diphenylmethylaniline, and adjust the feeding amounts of other substances according to the corresponding molar ratios. The operation is similar. A brownish-red powder Ni7 (0.15 g, 53.5%) is obtained.

[0104] The structural characterization is as follows: FT-IR (cm -1 ): 3018 (m), 2999 (m), 1648 (w, v C＝N ), 1618 (m, v C＝N ), 1602 (s), 1585 (s), 1469 (m), 1423 (m), 1380 (w), 1340 (w), 1291 (w), 1250 (w), 1107 (w), 1071 (w), 1035 (w), 997 (w), 850 (w), 771 (w), 763 (s), 701 (s). Elemental analysis: C 60 H 48 Br 2 N 2 Ni (1015.56) Theoretical values: C, 70.96; H, 4.76; N, 2.76. Experimental values: C, 70.80; H, 4.56; N, 2.73.

[0105] Example 8 Preparation of N,N'-bis(2,6-diethyl-4-diphenylmethylphenyl)-5-phenylacenaphthylene-1,2-diimine·nickel(II) bromide complex, Ni8

[0106] Similar to Example 1, 2,6-dimethylaniline was replaced with 2,6-diethyl-4-diphenylmethylaniline, and the feeding amounts of other substances were adjusted according to the corresponding molar ratios, and the operations were similar. A brownish-red powder Ni8 (0.20 g, 70.6%) was obtained.

[0107] The structural characterization is as follows: FT-IR (cm -1 ): 3142 (m), 3005 (m), 2985 (m), 2907 (m), 1650 (w, v C＝N ), 1624 (m, v C＝N ), 1597 (s), 1550 (m), 1467 (m), 1423 (m), 1380 (w), 1335 (w), 1311 (w), 1261 (w), 1230 (w), 1196 (w), 1129 (w), 1071 (w), 1034 (w), 997 (w), 850 (w), 825 (w), 780 (m), 763 (s), 698 (s). Elemental analysis: C 64 H 56 Br 2 N 2 Ni(1071.67) Theoretical values: C, 71.73; H, 5.27; N, 2.61. Experimental values: C, 71.80; H, 5.26; N, 2.63.

[0108] Example 9 Preparation of N,N'-bis(2,6-diisopropyl-4-diphenylmethylphenyl)-5-phenylacenaphthylene-1,2-diimine·nickel(II) bromide complex, Ni9

[0109] Similar to Example 1, 2,6-dimethylaniline was replaced with 2,6-diisopropyl-4-diphenylmethylaniline, and the feeding amounts of other substances were adjusted according to the corresponding molar ratios, and the operations were similar. A brownish-red powder Ni9 (0.18 g, 61.2%) was obtained.

[0110] The structural characterization is as follows: FT-IR (cm -1 ): 3058 (m), 2995 (m), 1657 (w, v C＝N ), 1618 (m, v C＝N ), 1597 (s), 1550 (m), 1467 (m), 1423 (m), 1380 (w), 1335 (w), 1311 (w), 1261 (w), 1230 (w), 1205 (w), 1129 (w), 1075 (w), 1034 (w), 997 (w), 850 (w), 825 (w), 789 (s), 733 (s), 705 (s). Elemental analysis: C 68 H 64 Br2 N 2 Theoretical values of Ni(1127.78): C, 72.42; H, 5.72; N, 2.48. Experimental values: C, 72.25; H, 5.56; N, 2.43.

[0111] Example 10 Preparation of N,N'-bis(2,6-difluoro-4-diphenylmethylphenyl)-5-phenylacenaphthylene-1,2-diimine·nickel(II) bromide complex, Ni10

[0112] Similar to Example 1, replace 2,6-dimethylaniline with 2,6-difluoro-4-diphenylmethylaniline, and adjust the feeding amounts of other substances according to the corresponding molar ratios, and the operations are similar. A red powder Ni10 (0.11 g, 44.4%) is obtained.

[0113] The structure characterization is as follows: FT-IR (cm -1 ): FT-IR (cm -1 ): 3353 (m), 2911 (m), 1655 (w, v C＝N ), 1619 (m, v C＝N ), 1598 (s), 1550 (m), 1465 (m), 1423 (m), 1385 (w), 1335 (w), 1311 (w), 1255 (w), 1205 (w), 1129 (w), 1065 (w), 1034 (w), 997 (w), 850 (w), 825 (w), 766 (m), 704 (s). Elemental analysis: C 56 H 36 Br 2 F 4 N 2 Theoretical values of Ni(1031.41): C, 65.21; H, 3.52; N, 2.72. Experimental values: C, 65.00; H, 3.48; N, 2.73.

[0114] Example 11 Preparation of N,N'-bis(2,4-dimethyl-6-diphenylmethylphenyl)-5-phenylacenaphthylene-1,2-diimine·nickel(II) bromide complex, Ni11

[0115] Similar to Example 1, replace 2,6-dimethylaniline with 2,4-dimethyl-6-diphenylmethylaniline, and adjust the feeding amounts of other substances according to the corresponding molar ratios, and the operations are similar. A red powder Ni11 (0.13 g, 50.4%) is obtained.

[0116] The structure characterization is as follows: FT-IR (cm -1 ): 3275 (m), 2999 (m), 1642 (w, v C＝N ), 1619 (m, vC＝N ), 1598 (s), 1558 (s), 1446 (m), 1385 (w), 1339 (w), 1311 (w), 1251 (w), 1230 (w), 1197 (w), 1165 (w), 1150 (w), 1075 (w), 1034 (w), 997 (w), 850 (w), 825 (w), 777 (s), 702 (s). Elemental analysis: C 60 H 48 Br 2 N 2 Ni (1015.56) Theoretical values: C, 70.96; H, 4.76; N, 2.76. Experimental values: C, 70.52; H, 4.58; N, 2.73.

[0117] Example 12 Preparation of N,N'-bis[2-methyl-4,6-bis(diphenylmethyl)phenyl]-5-phenylacenaphthylene-1,2-diimine·nickel(II) bromide complex, Ni12

[0118] Similar to Example 1, replace 2,6-dimethylaniline with 2-methyl-4,6-bis(diphenylmethyl)aniline, and adjust the feeding amounts of other substances according to the corresponding molar ratios, and the operations are similar. A red powder Ni12 (0.13 g, 50.4%) is obtained.

[0119] Structural characterization is as follows: FT-IR (cm -1 ): 3222 (m), 2925 (m), 1655 (w, v C＝N ), 1629 (m, v C＝N ), 1588 (s), 1558 (m), 1467 (m), 1422 (m), 1380 (w), 1338 (w), 1311 (w), 1261 (w), 1230 (w), 1196 (w), 1144 (w), 1071 (w), 1034 (w), 992 (w), 850 (w), 825 (w), 780 (m), 763 (s), 693 (s). Elemental analysis: C 84 H 64 Br 2 N 2 Ni (1319.95) Theoretical values: C, 76.44; H, 4.89; N, 2.12. Experimental values: C, 76.33; H, 4.88; N, 2.09.

[0120] Example 13 Preparation of N,N'-bis[2,6-bis(diphenylmethyl)-4-methylphenyl]-5-phenylacenaphthylene-1,2-diimine·nickel(II) bromide complex, Ni13

[0121] Similar to Example 1, 2,6-dimethylaniline was replaced with 2,6-bis(diphenylmethyl)-4-methylaniline, and the feed amounts of other substances were adjusted according to the corresponding molar ratios, and the operation was similar. A brownish-red powder Ni13 (0.13 g, 50.4%) was obtained.

[0122] The structure characterization is as follows: FT-IR (cm -1 ): 3333 (m), 2898 (m), 1631 (w, v C＝N ), 1597 (s), 1579 (s), 1465 (m), 1452 (m), 1370 (w), 1338 (w), 1312 (w), 1261 (w), 1235 (w), 1196 (w), 1166 (w), 1129 (w), 1071 (w), 1034 (w), 997 (w), 850 (w), 825 (w), 781 (s), 764 (s), 706 (s). Elemental analysis: C 84 H 64 Br 2 N 2 Ni (1319.95) Theoretical values: C, 76.44; H, 4.89; N, 2.12. Experimental values: C, 76.39; H, 4.78; N, 2.06.

[0123] Example 14 Preparation of N,N'-bis(2,6-di[bis(p-fluorodiphenyl)methyl)-4-methylphenyl]-5-phenylacenaphthylene-1,2-diimine·nickel(II) bromide complex, Ni14

[0124] Similar to Example 1, 2,6-dimethylaniline was replaced with 2,6-bis[bis(p-fluorodiphenyl)methyl]-4-methylaniline, and the feed amounts of other substances were adjusted according to the corresponding molar ratios, and the operation was similar. A brownish-red powder Ni14 (0.13 g, 50.4%) was obtained.

[0125] The structure characterization is as follows: FT-IR (cm -1 ): 3235 (w), 2928 (w), 1644 (w, v C＝N ), 1624 (w, v C＝N ), 1579 (w), 1539 (w), 1480 (w), 1421 (w), 1370 (w), 1342 (w), 1313 (w), 1290 (w), 1263 (w), 1233 (w), 1206 (w), 1120 (w), 1039 (w), 1015 (w), 979 (w), 922 (w), 804 (w), 720 (s). Elemental analysis: C 84 H 64 Br 2 N 2Theoretical values of Ni(1319.95): C, 76.44; H, 4.89; N, 2.12. Experimental values: C, 76.39; H, 4.78; N, 2.06.

[0126] Example 15 Preparation of N 1 -[2,6-bis(p-fluorodiphenyl)methyl-4-methylphenyl]-N 2 -(2,6-dimethylphenyl)-5-phenylacenaphthylene-1,2-diimine·nickel(II) bromide complex, Ni15

[0127] In a 100 ml round-bottom flask, add 2,6-bis(p-fluorodibenzyl)-4-methylaniline (2 mmol), 5-phenylacenaphthenequinone (2 mmol), a catalytic amount of p-toluenesulfonic acid (0.3 mmol) and toluene (30 mL), heat under reflux for 8 h. Remove the solvent using a rotary evaporator, recrystallize with dichloromethane and methanol, filter and dry to obtain an orange-yellow solid (Formula III). Yield: 49.0%.

[0128]

[0129] A suspension of the compound shown in Formula III (0.387 mmol), 2,6-dimethylaniline (0.387 mmol) and (DME)·NiBr 2 (0.368 mmol) in acetic acid (8 mL) was refluxed for 6 hours. After cooling to room temperature, an excess of diethyl ether (20 mL) was added to induce precipitation. The red precipitate was collected by filtration and dried in an oven at 60 °C for 8 hours to obtain a red powder Ni15, yield: 67.5%.

[0130] Structure characterization is as follows: FT-IR (cm -1 ): 3346(w), 2925(w), 1655(w,v C＝N ), 1625(w,v C＝N ), 1579(w), 1540(w), 1480(w), 1425(w), 1385(w), 1323(w), 1298(w), 1253(w), 1229(w), 1207(w), 1120(w), 1045(w), 1017(w), 969(w), 940(w), 853(w), 770(s). Elemental analysis: C 59 H 42 Br 2 F 4 N 2 Ni(1073.49) Theoretical values: C, 66.01; H, 3.94; N, 2.61. Experimental values: C, 65.39; H, 3.70; N, 2.23.

[0131] Example 16 Preparation of N 1 -(2,6-Bis(p-fluorodiphenyl)methyl-4-methylphenyl)-N 2 -(2,6-Diethylphenyl)-5-phenylacenaphthylene-1,2-diimine·nickel(II) bromide complex, Ni16

[0132] Similar to Example 15, 2,6-dimethylaniline was replaced with 2,6-diethylaniline, and the feed amounts of other substances were adjusted according to the corresponding molar ratios, and the operations were similar. A brownish-red powder Ni16 was obtained, yield: 70.5%.

[0133] The structure was characterized as follows: FT-IR (cm -1 ): 3403 (m), 2933 (m), 1655 (w, v C＝N ), 1625 (m, v C＝N ), 1603 (s), 1550 (s), 1467 (m), 1422 (m), 1370 (w), 1339 (m), 1311 (w), 1261 (w), 1230 (w), 1196 (w), 1165 (w), 1129 (w), 1071 (w), 1034 (w), 845 (w), 781 (m), 763 (s). Elemental analysis: C 61 H 46 Br 2 F 4 N 2 Ni (1101.55) Theoretical values: C, 66.51; H, 4.21; N, 2.54. Experimental values: C, 65.99; H, 4.05; N, 2.21.

[0134] Example 17 Preparation of N 1 -(2,6-Bis(p-fluorodiphenyl)methyl-4-methylphenyl)-N 2 -(2,6-Diisopropylphenyl)-5-phenylacenaphthylene-1,2-diimine·nickel(II) bromide complex, Ni17

[0135] Similar to Example 15, 2,6-dimethylaniline was replaced with 2,6-diisopropylaniline, and the feed amounts of other substances were adjusted according to the corresponding molar ratios, and the operations were similar. A brownish-red powder Ni17 was obtained, yield: 68.6%.

[0136] The structure was characterized as follows: FT-IR (cm -1 ): 3238 (m), 2937 (m), 2944 (m), 1645 (w, v C＝N ), 1629 (m, v C＝N), 1599(s), 1550(s), 1463(m), 1402(m), 1338(w), 1312(w), 1230(w), 1196(w), 1164(w), 1129(w), 1071(w), 1034(w), 997(w), 951(w), 845(w), 763(s), 702(s). Elemental analysis: C 63 H 50 Br 2 F 4 N 2 Ni(1129.60) Theoretical values: C, 66.99; H, 4.46; N, 2.48. Experimental values: C, 66.99; H, 4.45; N, 2.50.

[0137] Example 18 Preparation of N,N'-bis(phenyl)-5-(3-nitrophenyl)acenaphthylene-1,2-diamine·nickel(II) bromide complex, Ni18

[0138] Similar to Example 1, 5-phenylacenaphthenequinone was replaced with 5-(3-nitrophenyl)acenaphthenequinone, 2,6-dimethylaniline was replaced with aniline, and the feed amounts of other substances were adjusted according to the corresponding molar ratios, and the operation was similar. A red powder Ni18 (0.046 g, 48.9%) was obtained.

[0139] Structure characterization is as follows: FT-IR (cm -1 ): 3050(m), 2923(m), 2894(m), 1650(w, v C＝N ), 1614(m, v C＝N ), 1599(s), 1465(m), 1416(m), 1338(w), 1306(w), 1267(w), 1230(w), 1196(w), 1160(w), 1128(w), 1069(w), 1035(w), 996(w), 850(w), 825(w), 699(s). Elemental analysis: C 30 H 19 Br 2 N 3 NiO 2 (672.00) Theoretical values: C, 53.62; H, 2.85; N, 6.25. Experimental values: C, 53.62; H, 2.86; N, 6.23.

[0140] Example 19 Preparation of N,N'-bis(2-methylphenyl)-5-(3-nitrophenyl)acenaphthylene-1,2-diamine·nickel(II) bromide complex, Ni19

[0141] Similar to Example 1, 5-phenylacenaphthenequinone was replaced with 5-(3-nitrophenyl)acenaphthenequinone, and 2,6-dimethylaniline was replaced with 2-methylaniline. The feeding amounts of other substances were adjusted according to the corresponding molar ratios, and the operations were similar. A red powder Ni19 (0.13 g, 50.6%) was obtained.

[0142] The structure characterization is as follows: FT-IR (cm -1 ): 3285 (m), 2999 (m), 1650 (w, v C＝N ), 1618 (m, v C＝N ), 1599 (s), 1465 (m), 1420 (m), 1377 (w), 1340 (w), 1315 (w), 1269 (w), 1230 (w), 1196 (w), 1165 (w), 1129 (w), 1071 (w), 1034 (w), 997 (w), 850 (w), 825 (w), 798 (s), 709 (s). Elemental analysis: C 32 H 23 Br 2 N 3 NiO 2 (672.00) Theoretical values: C, 54.90; H, 3.31; N, 6.00. Experimental values: C, 54.62; H, 3.26; N, 5.95.

[0143] Example 20 Preparation of N,N'-bis(2,6-dimethylphenyl)-5-(3-nitrophenyl)acenaphthylene-1,2-diimine·nickel(II) bromide complex, Ni20

[0144] Similar to Example 1, 5-phenylacenaphthenequinone was replaced with 5-(3-nitrophenyl)acenaphthenequinone, and the feeding amounts of other substances were adjusted according to the corresponding molar ratios, and the operations were similar. A red powder Ni20 (0.057 g, 48.9%) was obtained.

[0145] The structure characterization is as follows: FT-IR (cm -1 ): 3243 (w), 2918 (w), 1645 (w, v C＝N ), 1569 (w), / 1478 (w), 1419 (w), 1369 (w), 1342 (w), 1313 (w), 1290 (w), 1263 (w), 1233 (w), 1206 (w), 1022 (w), 950 (w), 814 (w), 790 (s). Elemental analysis: C 30 H 19 Br 2 N 3 NiO 2(672.00) Theoretical values: C, 53.62; H, 2.85; N, 6.25. Experimental values: C, 53.62; H, 2.86; N, 6.23.

[0146] Example 21 Preparation of N,N'-bis(2-methyl-6-ethylphenyl)-5-(3-nitrophenyl)acenaphthylene-1,2-diamine·nickel(II) bromide complex, Ni21

[0147] Similar to Example 1, replace 5-phenylacenaphthenequinone with 5-(3-nitrophenyl)acenaphthenequinone, and replace 2,6-dimethylaniline with 2-methyl-6-ethylaniline. Adjust the feeding amounts of other substances according to the corresponding molar ratios, and the operation is similar. A red powder Ni21 (0.26 g, 60.5%) is obtained.

[0148] Structure characterization is as follows: FT-IR (cm -1 ): 2998 (m), 2917 (m), 2903 (m), 1650 (w, v C＝N ), 1616 (m, v C＝N ), 1598 (s), 1467 (m), 1423 (m), 1319 (w), 1306 (w), 1260 (w), 1230 (w), 1190 (w), 1175 (w), 1139 (w), 1071 (w), 1005 (w), 850 (w), 829 (w), 782 (s), 763 (s), 663 (s). Elemental analysis: C 36 H 31 Br 2 N 3 NiO 2 (756.16) Theoretical values: C, 57.18; H, 4.13; N, 5.56. Experimental values: C, 56.59; H, 3.96; N, 5.22.

[0149] Example 22 Preparation of N,N'-bis(2,6-diethylphenyl)-5-(3-nitrophenyl)acenaphthylene-1,2-diamine·nickel(II) bromide complex, Ni22

[0150] Similar to Example 1, replace 5-phenylacenaphthenequinone with 5-(3-nitrophenyl)acenaphthenequinone, and replace 2,6-dimethylaniline with 2,6-diethylaniline. Adjust the feeding amounts of other substances according to the corresponding molar ratios, and the operation is similar. A brownish-red powder Ni22 (0.086 g, 39.2%) is obtained.

[0151] Structure characterization is as follows: FT-IR (cm -1 ): 3202 (m), 1650 (w, v C＝N), 1598 (s), 1579 (s), 1467 (m), 1379 (w), 1311 (w), 1261 (w), 1220 (w), 1196 (w), 1165 (w), 1129 (w), 1071 (w), 1034 (w), 1002 (w), 850 (w), 793 (s), 720 (s). Elemental analysis: C 38 H 35 Br 2 N 3 NiO 2 (784.22) Theoretical values: C, 58.20; H, 4.50; N, 5.36. Experimental values: C, 58.52; H, 4.36; N, 5.25.

[0152] Example 23 Preparation of N,N'-bis(2,6-diisopropylphenyl)-5-(3-nitrophenyl)acenaphthylene-1,2-diimine·nickel(II) bromide complex, Ni23

[0153] Similar to Example 1, 5-phenylacenaphthenequinone was replaced with 5-(3-nitrophenyl)acenaphthenequinone, and 2,6-dimethylaniline was replaced with 2,6-diisopropylaniline. The feed amounts of other substances were adjusted according to the corresponding molar ratios, and the operations were similar. A dark red powder Ni23 (0.038 g, 63.3%) was obtained.

[0154] Structural characterization is as follows: FT-IR (cm -1 ): 3322 (m), 2999 (m), 1659 (w, v C＝N ), 1634 (m, v C＝N ), 1590 (s), 1425 (m), 1360 (w), 1311 (w), 1261 (w), 1230 (w), 1196 (w), 1165 (w), 1129 (w), 1071 (w), 998 (w), 860 (w), 783 (s), 705 (s). Elemental analysis: C 42 H 43 Br 2 N 3 NiO 2 (840.33) Theoretical values: C, 60.03; H, 5.16; N, 5.00. Experimental values: C, 59.25; H, 4.85; N, 4.85.

[0155] Example 24 Preparation of N,N'-bis(2,6-diisopropylphenyl)-5-(3,5-difluorophenyl)acenaphthylene-1,2-diimine·nickel(II) bromide complex, Ni24

[0156] Similar to Example 1, 5-phenylacenaphthenequinone was replaced with 5-(3,5-difluorophenyl)acenaphthenequinone, and 2,6-dimethylaniline was replaced with 2,6-diisopropylaniline. The feeding amounts of other substances were adjusted according to the corresponding molar ratios, and the operation was similar. A dark red powder Ni24 (0.12 g, 68.5%) was obtained.

[0157] The structural characterization is as follows: FT-IR (cm -1 ): 3353 (w), 2997 (w), 1649 (w, v C＝N ), 1620 (w, v C＝N ), 1579 (w), 1538 (w), 1480 (w), 1421 (w), 1370 (w), 1342 (w), 1313 (w), 1290 (w), 1263 (w), 1222 (w), 1020 (w), 1089 (w), 999 (w), 840 (w), 744 (w), 720 (s). Elemental analysis: C 42 H 42 Br 2 F 2 N 2 Ni(831.31) Theoretical values: C, 60.68; H, 5.09; N, 3.37. Experimental values: C, 60.25; H, 4.98; N, 3.25.

[0158] Example 25 Preparation of N,N'-bis(2,6-dimethylphenyl)-5-(1-naphthyl)acene-1,2-diamine nickel(II) bromide complex, Ni25

[0159] Similar to Example 1, 5-phenylacenaphthenequinone was replaced with 5-(1-naphthyl)acenaphthenequinone, and the feeding amounts of other substances were adjusted according to the corresponding molar ratios, and the operation was similar. A yellowish-brown powder Ni25 (0.110 g, 51.4%) was obtained.

[0160] The structural characterization is as follows: FT-IR (cm -1 ): 3305 (w), 2998 (m), 2922 (w), 1648 (w, v C＝N ), 1620 (w, v C＝N ), 1550 (m), 1420 (w), 1383 (w), 1359 (w), 1323 (w), 1252 (w), 1183 (w), 1064 (s), 970 (w), 934 (w), 855 (w), 825 (m), 770 (s), 739 (s). Elemental analysis: C 38 H 30 Br 2 N 2Theoretical values for Ni(733.17): C, 62.25; H, 4.12; N, 3.82. Experimental values: C, 62.25; H, 4.22; N, 3.85.

[0161] Example 26 Preparation of N,N'-bis(2,6-diethylphenyl)-5-(1-naphthyl)acenaphthylene-1,2-diimine·nickel(II) bromide complex, Ni26

[0162] Similar to Example 1, 5-phenylacenaphthenequinone was replaced with 5-(1-naphthyl)acenaphthenequinone, and 2,6-dimethylaniline was replaced with 2,6-diethylaniline. The feed amounts of other substances were adjusted according to the corresponding molar ratios, and the operations were similar. A dark red powder Ni26 (0.125 g, 54.6%) was obtained.

[0163] Structural characterization is as follows: FT-IR (cm -1 ): 3265(m), 2929(m), 1650(w,v C＝N ), 1620(m,v C＝N ), 1597(s), 1558(s), 1445(m), 1380(w), 1338(w), 1311(w), 1261(w), 1230(w), 1196(w), 1165(w), 1130(w), 1071(w), 1034(w), 997(w), 850(w), 825(w), 780(s), 709(s). Elemental analysis: C 42 H 38 Br 2 N 2 Theoretical values for Ni(789.28): C, 63.91; H, 4.85; N, 3.55. Experimental values: C, 63.88; H, 4.85; N, 3.55.

[0164] Example 27 Preparation of N,N'-bis(2,6-diisopropylphenyl)-5-(1-naphthyl)acenaphthylene-1,2-diimine·nickel(II) bromide complex, Ni27

[0165] Similar to Example 1, 5-phenylacenaphthenequinone was replaced with 5-(1-naphthyl)acenaphthenequinone, and 2,6-dimethylaniline was replaced with 2,6-diisopropylaniline. The feed amounts of other substances were adjusted according to the corresponding molar ratios, and the operations were similar. A dark red powder Ni27 (0.04 g, 36.9%) was obtained.

[0166] Structural characterization is as follows: FT-IR (cm -1 ): 3344(m), 2927(m), 1649(w,v C＝N ), 1612(m,v C＝N), 1590(s), 1579(s), 1463(m), 1422(m), 1380(w), 1340(w), 1270(w), 1210(w), 1196(w), 1144(w), 1071(w), 1034(w), 1002(w), 850(w), 825(w), 781(s), 763(s), 699(s). Elemental analysis: C 46 H 46 Br 2 N 2 Ni(845.39) Theoretical values: C, 65.36; H, 5.48; N, 3.31. Experimental values: C, 64.44; H, 5.01; N, 2.95.

[0167] Example 28 Preparation of N,N'-bis(2,4,6-trimethylphenyl)-5-(1-naphthyl)acenaphthylene-1,2-diamine·nickel(II) bromide complex, Ni28

[0168] Similar to Example 1, replace 5-phenylacenaphthenequinone with 5-(1-naphthyl)acenaphthenequinone, and replace 2,6-dimethylaniline with 2,4,6-trimethylaniline. Adjust the feeding amounts of other substances according to the corresponding molar ratios, and the operation is similar. A dark red powder Ni28 (0.208 g, 94.5%) is obtained.

[0169] Structural characterization is as follows: FT-IR (cm -1 ): 3344(m), 2980(m), 2914(m), 1644(w,v C＝N ), 1625(m,v C＝N ), 1597(s), 1579(s), 1467(m), 1422(m), 1380(w), 1338(w), 1314(w), 1261(w), 1230(w), 1196(w), 1165(w), 1129(w), 1071(w), 1034(w), 997(w), 850(w), 825(w), 782(m), 767(s), 700(s). Elemental analysis: C 40 H 34 Br 2 N 2 Ni(761.23) Theoretical values: C, 63.11; H, 4.50; N, 3.18. Experimental values: C, 62.58; H, 4.05; N, 3.05.

[0170] Example 29 Preparation of N,N'-bis(2,6-diethyl-4-methylphenyl)-5-(1-naphthyl)acenaphthylene-1,2-diamine·nickel(II) bromide complex, Ni29

[0171] Similar to Example 1, 5-phenylacenaphthenequinone was replaced with 5-(1-naphthyl)acenaphthenequinone, and 2,6-dimethylaniline was replaced with 2,6-diethyl-4-methylaniline. The feeding amounts of other substances were adjusted according to the corresponding molar ratios, and the operation was similar. A brick-red powder Ni29 (0.09 g, 38.0%) was obtained.

[0172] The structural characterization is as follows: FT-IR (cm -1 ): 3022 (m), 2950 (m), 1644 (w, v C＝N ), 1615 (m, v C＝N ), 1597 (s), 1579 (s), 1467 (m), 1422 (m), 1388 (w), 1311 (w), 1230 (w), 1196 (w), 1165 (w), 1098 (w), 1035 (w), 996 (w), 860 (w), 805 (w), 771 (s), 699 (s). Elemental analysis: C 44 H 42 Br 2 N 2 Ni (817.34) Theoretical values: C, 64.66; H, 5.18; N, 3.43. Experimental values: C, 63.98; H, 5.05; N, 3.45.

[0173] Example 30 Preparation of N,N'-bis(2,6-diisopropylphenyl)-5-(2-naphthyl)acenaphthylene-1,2-diamine·nickel(II) bromide complex, Ni30

[0174] Similar to Example 1, 5-phenylacenaphthenequinone was replaced with 5-(2-naphthyl)acenaphthenequinone, and 2,6-dimethylaniline was replaced with 2,6-diisopropylaniline. The feeding amounts of other substances were adjusted according to the corresponding molar ratios, and the operation was similar. A dark red powder Ni30 (0.106 g, 72.1%) was obtained.

[0175] The structural characterization is as follows: FT-IR (cm -1 ): 3339 (m), 2988 (m), 2889 (m), 1650 (w, v C＝N ), 1624 (m, v C＝N ), 1598 (s), 1550 (m), 1467 (m), 1405 (m), 1380 (w), 1340 (w), 1309 (w), 1230 (w), 1197 (w), 1130 (w), 1071 (w), 997 (w), 850 (w), 829 (w), 791 (s), 763 (s), 701 (s). Elemental analysis: C 46 H 46 Br 2 N 2Theoretical values of Ni(845.39): C, 65.36; H, 5.48; N, 3.31. Experimental values: C, 65.25; H, 5.45; N, 3.35.

[0176] Example 31 Preparation of N,N'-bis(2,6-diisopropylphenyl)-5-(9-anthryl)acenaphthylene-1,2-diamine nickel(II) bromide complex, Ni31

[0177] Similar to Example 1, 5-phenylacenaphthenequinone was replaced with 5-(9-anthryl)acenaphthenequinone, and 2,6-dimethylaniline was replaced with 2,6-diisopropylaniline. The feeding amounts of other substances were adjusted according to the corresponding molar ratios, and the operations were similar. A red powder Ni31 (0.055 g, 43.3%) was obtained.

[0178] Structural characterization is as follows: FT-IR (cm -1 ): 3033(m), 2909(m), 1644(w,v C＝N ), 1619(m,v C＝N ), 1597(s), 1467(m), 1422(m), 1380(w), 1338(w), 1311(w), 1261(w), 1230(w), 1196(w), 1150(w), 1035(w), 996(w), 849(w), 825(w), 763(s), 701(s). Elemental analysis: C 50 H 48 Br 2 N 2 Theoretical values of Ni(895.45): C, 67.07; H, 5.40; N, 3.13. Experimental values: C, 66.53; H, 5.25; N, 2.95.

[0179] Example 32 Polymerization of ethylene using complex Ni2 and cocatalyst MAO

[0180] Select a dry 250 mL high-pressure reactor, displace nitrogen twice, then evacuate and replace it with ethylene gas. Add toluene (25 mL × 2) to the reactor, stir for five minutes and then let it stand. When the temperature of the reactor reaches 50 °C, add 2.5 mL of the cocatalyst MAO (1.5 mol / L, toluene solution), then add another 25 mL of toluene, and continue to add the pre-prepared Ni2 catalyst solution (2 μmol, 25 mL). At this time, the aluminum-nickel ratio (the molar ratio of metallic aluminum in the cocatalyst to metallic nickel in the catalyst) is 1875:1. Turn on the mechanical stirrer with a speed of 400 revolutions per minute, and at the same time, charge ethylene into the reactor to keep the pressure of the reaction system at 10 atm of ethylene gas, and the reaction proceeds for 30 minutes. After the reaction is completed, treat the reaction solution with an ethanol solution acidified with 10% hydrochloric acid to precipitate a white solid. Stir it in the hydrochloric acid-ethanol solution for 1 hour, then filter it by suction. Place the obtained white solid in a vacuum oven at 60 °C and dry it to a constant weight to obtain 2.55 g of a white polymer, and the polymerization activity is 2.55×10 6 g(PE)mol -1 (Ni)h -1 , and the weight-average molecular weight M of the polymer w = 169 kg / mol, and the molecular weight distribution M of the polymer w / M n = 1.98 (both M w and M n are measured by GPC), and the melting point T of the polymer m = 107.28 °C (measured by DSC).

[0181] Example 33: Polymerization of ethylene catalyzed by complex Ni2 and cocatalyst MMAO

[0182] Basically the same as Example 32 of this example, the difference is that 1.5 mL of the cocatalyst MMAO (2.5 mol / L, toluene solution) is used, and the aluminum-nickel ratio (the molar ratio of metallic aluminum in the cocatalyst to metallic nickel in the catalyst) is 1875:1. 4.22 g of a white polymer is obtained, and the polymerization activity is 4.22×10 6 g(PE)mol -1 (Ni)h -1 , and the weight-average molecular weight M of the polymer w = 156 kg / mol, and the molecular weight distribution M of the polymer w / M n = 1.77 (both M w and M n are measured by GPC).

[0183] Example 34: Polymerization of ethylene catalyzed by complex Ni2 and cocatalyst EtAlCl 2

[0184] ​Basically the same as Example 32, the difference is that the cocatalyst is EtAlCl 2 1 mL (1 mol / L, toluene solution), and the aluminum-nickel ratio (the molar ratio of metallic aluminum in the cocatalyst to metallic nickel in the catalyst) is 500:1. 5.35 g of white polymer was obtained, and the polymerization activity was 5.35×10 6 g(PE)mol -1 (Ni)h -1 , the weight-average molecular weight M w of the polymer = 147 kg / mol, and the molecular weight distribution M w / M n = 1.75 (M w and M n are both measured by GPC), and the melting point T m of the polymer = 77.74 °C (measured by DSC).

[0185] Example 35 uses complex Ni2 and cocatalyst Et 2 AlCl to catalyze ethylene polymerization

[0186] Basically the same as Example 32, the difference is that the cocatalyst is Et 2 AlCl 1 mL (1 mol / L, toluene solution), and the aluminum-nickel ratio (the molar ratio of metallic aluminum in the cocatalyst to metallic nickel in the catalyst) is 500:1. 6.73 g of white polymer was obtained, and the polymerization activity was 6.73×10 6 g(PE)mol -1 (Ni)h -1 , the weight-average molecular weight M w of the polymer = 108 kg / mol, and the molecular weight distribution M w / M n = 1.65 (M w and M n are both measured by GPC), and the melting point T m of the polymer = 60.89 °C (measured by DSC).

[0187] Example 36 uses complex Ni2 and cocatalyst EASC to catalyze ethylene polymerization

[0188] Basically the same as Example 32, the difference is that the cocatalyst is EASC 1 mL (1 mol / L, toluene solution), and the aluminum-nickel ratio (the molar ratio of metallic aluminum in the cocatalyst to metallic nickel in the catalyst) is 500:1. 7.51 g of white polymer was obtained, and the polymerization activity was 7.51×10 6 g(PE)mol -1 (Ni)h -1 , the weight-average molecular weight M w of the polymer = 126 kg / mol, and the molecular weight distribution Mw / M n = 1.37 (M w and M n both measured by GPC), the melting point T of the polymer m = 63.93 °C (measured by DSC).

[0189] Example 37: Ethylene polymerization was catalyzed by complex Ni2 and cocatalyst MMAO at 60 °C

[0190] Basically the same as Example 32 of this invention, except that the cocatalyst MMAO was 1.5 mL (2.5 mol / L, toluene solution), the aluminum-to-nickel ratio (the molar ratio of metallic aluminum in the cocatalyst to metallic nickel in the catalyst) was 1875:1, and the polymerization temperature was 60 °C. 5.23 g of white polymer was obtained, and the polymerization activity was 5.23×10 6 g(PE)mol -1 (Ni)h -1 , the weight-average molecular weight M of the polymer w = 139 kg / mol, the molecular weight distribution M of the polymer w / M n = 1.83 (M w and M n both measured by GPC), the melting point T of the polymer m = 87.59 °C (measured by DSC), and the degree of branching of this polyethylene sample was calculated to be 69 / 1000 C's from high-temperature NMR data.

[0191] Example 38: Ethylene polymerization was catalyzed by complex Ni2 and cocatalyst MMAO at 80 °C

[0192] Basically the same as Example 32 of this invention, except that the cocatalyst MMAO was 1.5 mL (2.5 mol / L, toluene solution), the aluminum-to-nickel ratio (the molar ratio of metallic aluminum in the cocatalyst to metallic nickel in the catalyst) was 1875:1, and the polymerization temperature was 80 °C. 2.20 g of white polymer was obtained, and the polymerization activity was 2.20×10 6 g(PE)mol -1 (Ni)h -1 , the weight-average molecular weight M of the polymer w = 198 kg / mol, the molecular weight distribution M of the polymer w / M n = 2.28 (M w and M n both measured by GPC), the melting point T of the polymer m = 100.36 °C (measured by DSC), and the degree of branching of this polyethylene sample was calculated to be 64 / 1000 C's from high-temperature NMR data. The stress-strain curve of the polymer is as Figure 3 shown.

[0193] Example 39: Catalytic ethylene polymerization using complex Ni1 and cocatalyst MMAO

[0194] Basically the same as Example 32, except that the catalyst is Ni1, the cocatalyst is 1.5 mL of MMAO (2.5 mol / L, toluene solution), the aluminum-nickel ratio (the molar ratio of metallic aluminum in the cocatalyst to metallic nickel in the catalyst) is 1875:1, and the polymerization temperature is 60 °C. 6.08 g of white polymer was obtained, and the polymerization activity was 6.08×10 6 g(PE)mol -1 (Ni)h -1 , and the weight-average molecular weight M w of the polymer = 66 kg / mol, and the molecular weight distribution M w / M n = 2.56 (both M w and M n were measured by GPC), and the melting point T m of the polymer = 111.50 °C (measured by DSC).

[0195] Example 40: Catalytic ethylene polymerization using complex Ni3 and cocatalyst MMAO

[0196] Basically the same as Example 32, except that the catalyst is Ni3, the cocatalyst is 1.5 mL of MMAO (2.5 mol / L, toluene solution), the aluminum-nickel ratio (the molar ratio of metallic aluminum in the cocatalyst to metallic nickel in the catalyst) is 1875:1, and the polymerization temperature is 60 °C. 5.57 g of white polymer was obtained, and the polymerization activity was 5.57×10 6 g(PE)mol -1 (Ni)h -1 , and the weight-average molecular weight M w of the polymer = 205 kg / mol, and the molecular weight distribution M w / M n = 2.09 (both M w and M n were measured by GPC).

[0197] Example 41: Catalytic ethylene polymerization using complex Ni4 and cocatalyst MMAO

[0198] Basically the same as Example 32, except that the catalyst is Ni4, the cocatalyst is 1.5 mL of MMAO (2.5 mol / L, toluene solution), the aluminum-nickel ratio (the molar ratio of metallic aluminum in the cocatalyst to metallic nickel in the catalyst) is 1875:1, and the polymerization temperature is 60 °C. 3.54 g of white polymer was obtained, and the polymerization activity was 3.54×10 6 g(PE)mol-1 (Ni)h -1 , the weight-average molecular weight M of the polymer w = 58 kg / mol, and the molecular weight distribution M of the polymer w / M n = 2.42 (both M w and M n are measured by GPC), and the melting point T of the polymer m = 116.66 °C (measured by DSC).

[0199] Example 42: Ethylene polymerization was catalyzed using complex Ni5 and cocatalyst MMAO

[0200] Basically the same as Example 32 of this invention, except that the catalyst was Ni5, the cocatalyst was 1.5 mL of MMAO (2.5 mol / L, toluene solution), the aluminum-to-nickel ratio (the molar ratio of metallic aluminum in the cocatalyst to metallic nickel in the catalyst) was 1875:1, and the polymerization temperature was 60 °C. 3.15 g of white polymer was obtained, and the polymerization activity was 3.15×10 6 g(PE)mol -1 (Ni)h -1 , the weight-average molecular weight M of the polymer w = 171 kg / mol, and the molecular weight distribution M of the polymer w / M n = 2.02 (both M w and M n are measured by GPC), and the melting point T of the polymer m = 97.75 °C (measured by DSC).

[0201] Example 43: Ethylene polymerization was catalyzed using complex Ni2 and cocatalyst EASC at 80 °C

[0202] Basically the same as Example 32 of this invention, except that the cocatalyst was 1 mL of EASC (1 mol / L, toluene solution), the aluminum-to-nickel ratio was 500:1, and the polymerization temperature was 60 °C. 8.78 g of white polymer was obtained, and the polymerization activity was 8.78×10 6 g(PE)mol -1 (Ni)h -1 , the weight-average molecular weight M of the polymer w = 89 kg / mol, and the molecular weight distribution M of the polymer w / M n = 2.20 (both M w and M n are measured by GPC), and the melting point T of the polymer m = 51.64 °C (measured by DSC). The degree of branching of this polyethylene sample was calculated to be 167 / 1000 C's from high-temperature NMR data. The stress-strain curve of the polymer is asFigure 3 as shown

[0203] Example 44: Polymerization of ethylene was catalyzed by complex Ni2 and cocatalyst EASC at 90 °C

[0204] It was basically the same as Example 32 of this invention, except that 1 mL (1 mol / L, toluene solution) of cocatalyst EASC was used, the aluminum-nickel ratio was 500:1, and the polymerization temperature was 90 °C. 6.01 g of white polymer was obtained, and the polymerization activity was 6.01×10 6 g(PE) / mol -1 (Ni) / h -1 , and the weight-average molecular weight M w of the polymer was 110 kg / mol, and the molecular weight distribution M w / M n was 2.80 (both M w and M n were measured by GPC).

[0205] Example 45: Polymerization of ethylene was catalyzed by complex Ni2 and cocatalyst EASC at 60 °C

[0206] It was basically the same as Example 32 of this invention, 0.2 mL (1 mol / L, toluene solution) of cocatalyst EASC was used, the aluminum-nickel ratio was 200:1, and the polymerization temperature was 60 °C. The polymerization activity was 9.01×10 6 g(PE) / mol -1 (Ni) / h -1 , and the weight-average molecular weight M w of the polymer was 192 kg / mol, and the molecular weight distribution M w / M n was 2.40 (both M w and M n were measured by GPC), the melting point T m of the polymer was 58.48 °C (measured by DSC), and the degree of branching of this polyethylene sample was calculated to be 123 / 1000 C's through high-temperature NMR data.

[0207] Example 46: Polymerization of ethylene was catalyzed by complex Ni1 and cocatalyst EASC

[0208] It was basically the same as Example 32 of this invention, except that the catalyst was Ni1, 0.2 mL (1 mol / L, toluene solution) of cocatalyst EASC was used, the aluminum-nickel ratio was 200:1, and the polymerization temperature was 60 °C. 11.27 g of white polymer was obtained, and the polymerization activity was 11.27×10 6 g(PE) / mol -1 (Ni) / h -1 , and the weight-average molecular weight M w= 54 kg / mol, the polymer molecular weight distribution M w / M n = 2.00 (M w and M n are both measured by GPC), the polymer melting point T m = 93.71 °C (measured by DSC). The degree of branching of this polyethylene sample is calculated to be 65 / 1000 C's from the high-temperature NMR data.

[0209] Example 47: Polymerization of ethylene is catalyzed by complex Ni3 and cocatalyst EASC

[0210] It is basically the same as Example 32 of this invention, except that the catalyst is Ni3, the cocatalyst EASC is 0.2 mL (1 mol / L, toluene solution), the aluminum-nickel ratio is 200:1, and the polymerization temperature is 60 °C. 9.22 g of white polymer is obtained, and the polymerization activity is 9.22×10 6 g(PE)mol -1 (Ni)h -1 , the weight-average molecular weight M w = 261 kg / mol, the polymer molecular weight distribution M w / M n = 2.41 (M w and M n are both measured by GPC). The degree of branching of this polyethylene sample is calculated to be 172 / 1000 C's from the high-temperature NMR data. The high-temperature NMR carbon spectrum of the polymer is as shown in Figure 4 Example 48: Polymerization of ethylene is catalyzed by complex Ni4 and cocatalyst EASC

[0211] It is basically the same as Example 32 of this invention, except that the catalyst is Ni4, the cocatalyst EASC is 0.2 mL (1 mol / L, toluene solution), the aluminum-nickel ratio is 200:1, and the polymerization temperature is 60 °C. 10.94 g of white polymer is obtained, and the polymerization activity is 10.94×10 6 g(PE)mol -1 (Ni)h -1 , the weight-average molecular weight M w = 54 kg / mol, the polymer molecular weight distribution M w / M n = 1.70 (M w and M n are both measured by GPC), the polymer melting point T m = 108.29 °C (measured by DSC). The degree of branching of this polyethylene sample is calculated to be 48 / 1000 C's from the high-temperature NMR data.

[0212] Example 49: Polymerization of ethylene catalyzed by complex Ni5 and cocatalyst EASC

[0213] Basically the same as Example 32 of this invention, except that the catalyst is Ni5, the cocatalyst EASC is 0.2 mL (1 mol / L, toluene solution), the aluminum-nickel ratio is 200:1, and the polymerization temperature is 60 °C. 8.79 g of white polymer is obtained, and the polymerization activity is 8.79×10 6 g(PE)mol -1 (Ni)h -1 , the weight-average molecular weight M w of the polymer = 114 kg / mol, the molecular weight distribution M w / M n = 2.11 (M w and M n are both measured by GPC), the melting point T m of the polymer = 62.23 °C (measured by DSC), and the degree of branching of this polyethylene sample is calculated to be 97 / 1000 C‘s through high-temperature NMR data.

[0214] Example 50: Polymerization of ethylene catalyzed by complex Ni6 and cocatalyst MAO

[0215] Basically the same as Example 32 of this invention, except that the catalyst is Ni6. 6.21 g of white polymer is obtained, and the polymerization activity is 6.21×10 6 g(PE)mol -1 (Ni)h -1 .

[0216] Example 51: Polymerization of ethylene catalyzed by complex Ni7 and cocatalyst MAO

[0217] Basically the same as Example 32 of this invention, except that the catalyst is Ni7. 10.45 g of white polymer is obtained, and the polymerization activity is 10.45×10 6 g(PE)mol -1 (Ni)h -1 .

[0218] Example 52: Polymerization of ethylene catalyzed by complex Ni8 and cocatalyst MAO

[0219] Basically the same as Example 32 of this invention, except that the catalyst is Ni8. 6.33 g of white polymer is obtained, and the polymerization activity is 6.33×10 6 g(PE)mol -1 (Ni)h -1 .

[0220] Example 53: Polymerization of ethylene catalyzed by complex Ni9 and cocatalyst MAO

[0221] Basically the same as Example 32, except that the catalyst is Ni9. 6.50 g of white polymer was obtained, and the polymerization activity was 6.50×10 6 g(PE) / mol -1 (Ni) / h -1 .

[0222] Example 54: Polymerization of ethylene was catalyzed by complex Ni10 and cocatalyst MAO

[0223] Basically the same as Example 32, except that the catalyst is Ni10. 9.02 g of white polymer was obtained, and the polymerization activity was 9.02×10 6 g(PE) / mol -1 (Ni) / h -1 .

[0224] Example 55: Polymerization of ethylene was catalyzed by complex Ni11 and cocatalyst MAO

[0225] Basically the same as Example 32, except that the catalyst is Ni11. 5.46 g of white polymer was obtained, and the polymerization activity was 5.46×10 6 g(PE) / mol -1 (Ni) / h -1 .

[0226] Example 56: Polymerization of ethylene was catalyzed by complex Ni12 and cocatalyst MAO

[0227] Basically the same as Example 32, except that the catalyst is Ni12. 4.75 g of white polymer was obtained, and the polymerization activity was 4.75×10 6 g(PE) / mol -1 (Ni) / h -1 .

[0228] Example 57: Polymerization of ethylene was catalyzed by complex Ni13 and cocatalyst MAO

[0229] Basically the same as Example 32, except that the catalyst is Ni13. 1.97 g of white polymer was obtained, and the polymerization activity was 1.97×10 6 g(PE) / mol -1 (Ni) / h -1 .

[0230] Example 58: Polymerization of ethylene was catalyzed by complex Ni14 and cocatalyst MAO

[0231] Basically the same as Example 32, except that the catalyst is Ni14. 2.02 g of white polymer was obtained, and the polymerization activity was 2.02×10 6 g(PE) / mol -1(Ni)h -1 。

[0232] Example 59: Polymerization of ethylene catalyzed by complex Ni15 and cocatalyst MAO

[0233] Basically the same as Example 32 of this invention, except that the catalyst is Ni15. 13.05 g of white polymer was obtained, and the polymerization activity was 13.05×10 6 g(PE)mol -1 (Ni)h -1 。

[0234] Example 60: Polymerization of ethylene catalyzed by complex Ni16 and cocatalyst MAO

[0235] Basically the same as Example 32 of this invention, except that the catalyst is Ni16. 10.11 g of white polymer was obtained, and the polymerization activity was 10.11×10 6 g(PE)mol -1 (Ni)h -1 。

[0236] Example 61: Polymerization of ethylene catalyzed by complex Ni17 and cocatalyst MAO

[0237] Basically the same as Example 32 of this invention, except that the catalyst is Ni17. 4.03 g of white polymer was obtained, and the polymerization activity was 4.03×10 6 g(PE)mol -1 (Ni)h -1 。

[0238] Example 62: Polymerization of ethylene catalyzed by complex Ni18 and cocatalyst MAO

[0239] Basically the same as Example 32 of this invention, except that the catalyst is Ni18. 1.12 g of white polymer was obtained, and the polymerization activity was 1.12×10 6 g(PE)mol -1 (Ni)h -1 。

[0240] Example 63: Polymerization of ethylene catalyzed by complex Ni19 and cocatalyst MAO

[0241] Basically the same as Example 32 of this invention, except that the catalyst is Ni19. 0.93 g of white polymer was obtained, and the polymerization activity was 0.93×10 6 g(PE)mol -1 (Ni)h -1 。

[0242] Example 64: Polymerization of ethylene catalyzed by complex Ni20 and cocatalyst MAO

[0243] Basically the same as Example 32, except that the catalyst is Ni20. 7.62 g of white polymer was obtained, and the polymerization activity was 7.62×10 6 g(PE)mol -1 (Ni)h -1 .

[0244] Example 65 Polymerization of ethylene using complex Ni21 and cocatalyst MAO

[0245] Basically the same as Example 32, except that the catalyst is Ni21. 5.66 g of white polymer was obtained, and the polymerization activity was 5.66×10 6 g(PE)mol -1 (Ni)h -1 .

[0246] Example 66 Polymerization of ethylene using complex Ni22 and cocatalyst MAO

[0247] Basically the same as Example 32, except that the catalyst is Ni22. 3.54 g of white polymer was obtained, and the polymerization activity was 3.54×10 6 g(PE)mol -1 (Ni)h -1 .

[0248] Example 67 Polymerization of ethylene using complex Ni23 and cocatalyst MAO

[0249] Basically the same as Example 32, except that the catalyst is Ni23. 3.32 g of white polymer was obtained, and the polymerization activity was 3.32×10 6 g(PE)mol -1 (Ni)h -1 .

[0250] Example 68 Polymerization of ethylene using complex Ni24 and cocatalyst MAO

[0251] Basically the same as Example 32, except that the catalyst is Ni24. 5.55 g of white polymer was obtained, and the polymerization activity was 5.55×10 6 g(PE)mol -1 (Ni)h -1 .

[0252] Example 69 Polymerization of ethylene using complex Ni25 and cocatalyst MAO

[0253] Basically the same as Example 32, except that the catalyst is Ni25. 4.34 g of white polymer was obtained, and the polymerization activity was 4.34×10 6 g(PE)mol-1 (Ni)h -1 。

[0254] Example 70: Polymerization of ethylene was catalyzed by complex Ni26 and cocatalyst MAO

[0255] It was basically the same as Example 32, except that the catalyst was Ni26. 4.55 g of white polymer was obtained, and the polymerization activity was 4.55×10 6 g(PE)mol -1 (Ni)h -1 。

[0256] Example 71: Polymerization of ethylene was catalyzed by complex Ni27 and cocatalyst MAO

[0257] It was basically the same as Example 32, except that the catalyst was Ni27. 4.69 g of white polymer was obtained, and the polymerization activity was 4.69×10 6 g(PE)mol -1 (Ni)h -1 。

[0258] Example 72: Polymerization of ethylene was catalyzed by complex Ni28 and cocatalyst MAO

[0259] It was basically the same as Example 32, except that the catalyst was Ni28. 3.85 g of white polymer was obtained, and the polymerization activity was 3.85×10 6 g(PE)mol -1 (Ni)h -1 。

[0260] Example 73: Polymerization of ethylene was catalyzed by complex Ni29 and cocatalyst MAO

[0261] It was basically the same as Example 32, except that the catalyst was Ni29. 4.35 g of white polymer was obtained, and the polymerization activity was 4.35×10 6 g(PE)mol -1 (Ni)h -1 。

[0262] Example 74: Polymerization of ethylene was catalyzed by complex Ni30 and cocatalyst MAO

[0263] It was basically the same as Example 32, except that the catalyst was Ni30. 4.64 g of white polymer was obtained, and the polymerization activity was 4.64×10 6 g(PE)mol -1 (Ni)h -1 。

[0264] Example 75: Polymerization of ethylene was catalyzed by complex Ni31 and cocatalyst MAO

[0265] Basically the same as Example 32, except that the catalyst is Ni31. 4.97 g of white polymer was obtained, and the polymerization activity was 4.97×10 6 g(PE)mol -1 (Ni)h -1 .

[0266] Example 76 Polymerization of ethylene was catalyzed by complex Ni2 and cocatalyst EASC at 100 °C

[0267] Basically the same as Example 44, except that the polymerization temperature was 100 °C. 4.52 g of white polymer was obtained, and the polymerization activity was 4.52×10 6 g(PE)mol -1 (Ni)h -1 .

[0268] Comparative Example 1

[0269] Polymerization of ethylene was catalyzed by complex N,N'-bis(2,6-dimethylphenyl)acenaphthylene-1,2-diimine·nickel(II) bromide (Formula IV) and cocatalyst EASC at 60 °C

[0270]

[0271] A dry 250 mL high-pressure reactor was selected, purged with nitrogen twice, then evacuated and replaced with ethylene gas. Toluene (25 mL×2) was added to the reactor, and after stirring for five minutes, it was allowed to stand. When the temperature of the reactor reached 60 °C, 0.4 mL of cocatalyst EASC was added, followed by 25 mL of toluene. Then, the pre-prepared catalyst solution (2 μmol, 25 mL) was added. At this time, the aluminum-nickel ratio (the molar ratio of metal aluminum in the cocatalyst to metal nickel in the catalyst) was 200:1. The mechanical stirring was turned on at a speed of 400 revolutions per minute, and at the same time, ethylene was charged into the reactor to maintain the pressure of the reaction system at 10 atm of ethylene gas, and the reaction was carried out for 30 minutes. After the reaction was completed, the reaction solution was treated with an ethanol solution acidified with 10% hydrochloric acid to precipitate a white solid, which was stirred in the hydrochloric acid-ethanol solution for 1 hour, filtered by suction, and the obtained white solid was placed in a vacuum oven at 60 °C and dried to a constant weight to obtain 2.55 g of white polymer, and the polymerization activity was 8.96×10 6 g(PE)mol -1 (Ni)h -1 , the weight-average molecular weight M w = 48 kg / mol, the molecular weight distribution M w / M n = 1.99 (M w and M n were both measured by GPC), and the melting point T m= 100.94 °C (measured by DSC). The catalytic results of the complex Ni1 of this application under the same conditions are as shown in Example 46 above.

[0272] In addition, when a tensile test was performed on the polymer obtained by the catalysis of Formula IV, the maximum strain was 556%. When a tensile test was performed on the polymer obtained by the complex Ni1 of this application, the maximum strain was 890%.

[0273] Comparative Example 2 used the complex N,N'-bis(2,6-diethylphenyl)acenaphthyl-1,2-diamine nickel(II) bromide (Formula V) and the cocatalyst EASC to catalyze ethylene polymerization at 60 °C

[0274]

[0275] Basically the same as Example 32 of this example, the difference is that the catalyst is N,N'-bis(2,6-diethylphenyl)acenaphthyl-1,2-diamine nickel(II) bromide (Formula V), and the aluminum-nickel ratio is 200:1. 6.09 g of white polymer was obtained, and the polymerization activity was 6.09×10 6 g(PE)mol -1 (Ni)h -1 , the weight-average molecular weight M of the polymer w = 133 kg / mol, the molecular weight distribution M of the polymer w / M n = 1.78 (M w and M n were both measured by GPC), and the melting point T of the polymer m = 72.47 °C (measured by DSC). The catalytic results of the complex Ni2 of this application under the same conditions are as shown in Example 45 above.

[0276] Comparative Example 3 used the complex N,N'-bis(2,6-diisopropylphenyl)acenaphthyl-1,2-diamine nickel(II) bromide (Formula VI) and the cocatalyst EASC to catalyze ethylene polymerization at 60 °C

[0277]

[0278] Basically the same as Example 32 of this example, the difference is that the catalyst is N,N'-bis(2,6-diisopropylphenyl)acenaphthyl-1,2-diamine nickel(II) bromide (Formula VI), and the aluminum-nickel ratio is 200:1. 6.95 g of white polymer was obtained, and the polymerization activity was 6.95×10 6 g(PE)mol -1 (Ni)h -1 , the weight-average molecular weight M of the polymer w = 154 kg / mol, the molecular weight distribution M of the polymer w / M n= 2.00 (M w and M n both measured by GPC). The catalytic results of the complex Ni3 of this application under the same conditions are as shown in Example 47 above.

[0279] Comparative Example 4 Use the complex N,N'-bis(2,6-diethylphenyl)acenaphthyl-1,2-diimine nickel(II) bromide (Formula V) and the cocatalyst EASC to catalyze ethylene polymerization at 100 °C

[0280] Basically the same as Comparative Example 1 of this application, the difference is that the catalyst is N,N'-bis(2,6-diethylphenyl)acenaphthyl-1,2-diimine nickel(II) bromide (Formula V), the aluminum-nickel ratio is 500:1, and the polymerization temperature is 100 °C. 0.17 g of white polymer was obtained, and the polymerization activity was 0.17×10 6 g(PE)mol -1 (Ni)h -1 , the weight-average molecular weight M of the polymer w = 97 kg / mol, the molecular weight distribution M of the polymer w / M n = 3.42 (M w and M n both measured by GPC), the melting point T of the polymer m = 122.04 °C (measured by DSC). The catalytic results of the complex Ni2 of this application under the same conditions are as shown in Example 76 above.

[0281] Comparative Example 5

[0282] Use the complex N,N'-bis(2,6-diisopropylphenyl)-5-phenoxyacenaphthyl-1,2-diimine nickel(II) bromide (Formula VII) and the cocatalyst EASC to catalyze ethylene polymerization at 60 °C

[0283]

[0284] Basically the same as Example 32 of this application, the difference is that the catalyst is N,N'-bis(2,6-diisopropylphenyl)-5-phenoxyacenaphthyl-1,2-diimine nickel(II) bromide (Formula VII), and the aluminum-nickel ratio is 200:1. 4.55 g of white polymer was obtained, and the polymerization activity was 4.55×10 6 g(PE)mol -1 (Ni)h -1 . The catalytic results of the complex Ni3 of this application under the same conditions are as shown in Example 47 above.

[0285] In summary, the complex of the present application has significantly better catalytic activity than the Ni catalyst without modification in the acenaphthylene backbone or the complex containing a non-bulky substituent under the same conditions. Moreover, the catalytic activity of the complex at high temperatures is also significantly better than that of the above two types of compounds, that is, the complex of the present application has obvious advantages in terms of catalytic activity and thermal stability.

[0286] In addition, the above test results also show that the elastic properties and toughness of the polymer obtained by catalysis with the complex of the present invention are also significantly better than those of the Ni complex catalyst without modification in the acenaphthylene backbone.

[0287] The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiments. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. The complex shown in Formula I, wherein, R 1 Ra is unsubstituted or optionally substituted by one, two or more Rs; the Rs are selected from C 1-6 alkyl, F, Cl, Br, I, NO 2 or C 1-6 alkoxy; R 2 、R 3 、R 4 、R 5 、R 6 、R 7 are the same or different and are each independently selected from H, F, Cl, Br, I, C 1-6 alkyl, C 3-6 cycloalkyl, C alkyl substituted with halogen, C 1-6 cycloalkyl substituted with halogen, C 3-6 alkyl substituted with Rb, C 1-6 alkyl substituted with two or more Rb, C 1-6 alkyl substituted with halo Rc, C 1-6 alkyl, or C alkyl substituted with two or more halo Rc 1-6 alkyl; Ra, Rb, and Rc are the same or different and are each independently selected from C 6-14 arylene or 5- to 14-membered heteroarylene; X is selected from F, Cl, Br, I, C 1-6 alkyl groups, and the two Xs are the same or different.

2. The complex according to claim 1, characterized in that, Ra, Rb, and Rc are the same or different and are each independently selected from phenyl, naphthyl, or anthracenyl.

3. The complex according to claim 1 or 2, characterized in that, R 1 is a group selected from the group consisting of phenyl, naphthyl or anthracenyl, which is unsubstituted or optionally substituted by one, two or more Rs; the Rs are selected from C 1-3 alkyl, F, Cl, Br, I, NO 2 or C 1-3 alkoxy; R 2 、R 3 、R 4 、R 5 、R 6 、R 7 are the same or different and are each independently selected from H, F, Cl, Br, I, C 1-3 alkyl, C 3-6 cycloalkyl, C 1-6 alkyl substituted by halogen, C 3-6 cycloalkyl substituted by halogen, methyl substituted by phenyl, methyl substituted by diphenyl, methyl substituted by halogenated phenyl or methyl substituted by two halogenated phenyls; X is selected from F, Cl, Br, or I, and the two Xs are the same or different.

4. The complex according to any one of claims 1-3, characterized in that, R 1 is wherein R 8 , R 9 are the same or different and are each independently selected from H, Me, F, Cl, NO 2 , OCH 3 ; R 2 、R 3 、R 4 、R 5 、R 6 、R 7 are the same or different and are each independently selected from H, F, Cl, Br, I, methyl, ethyl, isopropyl, CHPh 2 、CH(p-F-Ph) 2 ; the two Xs are the same and are selected from Cl or Br.

5. The complex according to any one of claims 1-4, characterized in that, Formula I includes the following specific structures: Complex Ni1: The R 2 = R 3 = R 5 = R 6 = Me, X is selected from Br, R 4 、R 7 、R 8 、R 9 is H; Complex Ni2: The R 2 = R 3 = R 5 = R 6 = Et, X is selected from Br, R 4 、R 7 、R 8 、R 9 is H; Complex Ni3: The R 2 = R 3 = R 5 = R 6 = i-Pr, X is selected from Br, R 4 、R 7 、R 8 、R 9 are H; Complex Ni4: The R 2 = R 3 = R 4 = R 5 = R 6 = R 7 = Me, X is selected from Br, R 8 、R 9 is H; Complex Ni5: The R 2 = R 3 = R 5 = R 6 = Et, R 4 = R 7 = Me, X is selected from Br, R 8 、R 9 is H; Complex Ni6: The R 2 = R 5 = Me, R 3 = R 6 = Cl, X is selected from Cl, R 4 、R 7 、R 8 、R 9 is H; Complex Ni7: The R 2 = R 3 = R 5 = R 6 = Me, R 4 = R 7 = CHPh 2 , X is selected from Br, R 8 , R 9 is H; Complex Ni8: The R 2 = R 3 = R 5 = R 6 = Et, R 4 = R 7 = CHPh 2 , X is selected from Br, R 8 , R 9 is H; Complex Ni9: The R 2 = R 3 = R 5 = R 6 = i-Pr, R 4 = R 7 = CHPh 2 , X is selected from Br, R 8 , R 9 is H; Complex Ni10: The R 2 = R 3 = R 5 = R 6 = F, R 4 = R 7 = CHPh 2 , X is selected from Br, R 8 , R 9 is H; Complex Ni11: The R 2 = R 5 = CHPh 2 , R 3 = R 4 = R 6 = R 7 = Me, X is selected from Br, R 8 , R 9 is H; Complex Ni12: The R 2 =R 4 =R 5 =R 7 =CHPh 2 ,R 3 =R 6 =Me, X is selected from Br, R 8 、R 9 is H; Complex Ni13: The R 2 =R 3 =R 5 =R 6 =CHPh 2 ,R 4 =R 7 =Me, X is selected from Br, R 8 、R 9 is H; Complex Ni14: The R 2 = R 3 = R 5 = R 6 = CH(p-F-Ph) 2 ,R 4 = R 7 = Me, X is selected from Br, R 8 、R 9 is H; Complex Ni15: The R 2 = R 3 = CH(p-F-Ph) 2 R 4 = R 5 = R 6 = Me, X is selected from Br, R 7 R 8 R 9 is H; Complex Ni16: The R 2 = R 3 = CH(p-F-Ph) 2 R 4 = Me, R 5 = R 6 = Et, X is selected from Br, R 7 R 8 R 9 is H; Complex Ni17: The R 2 = R 3 = CH(p-F-Ph) 2 R 4 = Me, R 5 = R 6 = i-Pr, X is selected from Br, R 7 R 8 R 9 is H; Complex Ni18: The wherein R 8 = NO 2 , X is selected from Br, R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 9 is H; Complex Ni19: The where R 8 = NO 2 , R 2 = R 5 = Me, X is selected from Br, R 2 , R 4 , R 5 , R 7 , R 9 is H; Complex Ni20: The where R 8 = NO 2 , R 2 = R 3 = R 5 = R 6 = Me, X is selected from Br, R 4 , R 7 , R 9 are H; Complex Ni21: The where R 8 = NO 2 , R 2 = R 5 = Me, R 3 = R 6 = Et, X is selected from Br, R 4 , R 7 , R 9 is H; Complex Ni22: The where R 8 = NO 2 , R 2 = R 3 = R 5 = R 6 = Et, X is selected from Br, R 4 , R 7 , R 9 are H; Complex Ni23: The where R 8 = NO 2 , R 2 = R 3 = R 5 = R 6 = i-Pr, X is selected from Br, R 4 , R 7 , R 9 is H; Complex Ni24: The where R 8 = R 9 = F, R 2 = R 3 = R 5 = R 6 = i-Pr, X is selected from Br, R 4 , R 7 is H; Complex Ni25: The R 2 =R 3 =R 5 =R 6 =Me, X is selected from Br, R 4 、R 7 is H; Complex Ni26: The R 2 = R 3 = R 5 = R 6 = Et, X is selected from Br, R 4 、R 7 is H; Complex Ni27: The R 2 = R 3 = R 5 = R 6 = i-Pr, X is selected from Br, R 4 、R 7 is H; Complex Ni28: The R 2 = R 3 = R 4 = R 5 = R 6 = R 7 = Me, X is selected from Br; Complex Ni29: The R 2 = R 3 = R 5 = R 6 = Et, R 4 = R 7 = Me, X is selected from Br; Complex Ni30: The R 2 = R 3 = R 5 = R 6 = i-Pr, X is selected from Br, R 4 、R 7 is H; Complex Ni31: The R 2 = R 3 = R 5 = R 6 = i-Pr, X is selected from Br, R 4 、R 7 is H.

6. The preparation method of the complex shown in Formula I according to any one of claims 1-5, characterized in that, it includes the following steps; Compound IIa, IIb, IIc and compound NiX 2 react to obtain the complex shown by formula I; Among them, R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , X has the definition described in any one of claims 1-5.

7. The preparation method according to claim 6, characterized in that, When R in Compounds IIb and IIc 2 is the same as the definition of R 5 , and R 3 is the same as the definition of R 4 ; when R 4 is the same as the definition of R 7 , that is, when the complex shown in Formula I is a symmetric structure, any one of Compounds IIb or IIc is used to react with Compound IIa and Compound NiX 2 ; Preferably, when the complex represented by Formula I has a symmetric structure, any one of Compound IIb or IIc is used together with Compound IIa and Compound NiX 2 Reflux the reaction in acetic acid.

8. The preparation method according to claim 6, characterized in that, When R 2 is different from the definition of R 5 , R 3 is different from the definition of R 4 , R 4 is different from the definition of R 7 , that is, when the complex shown in formula I is an asymmetric structure, in the preparation of formula I, first react IIa with any one of IIb and IIc, and then react the obtained product with the remaining one of IIb and IIc and the compound NiX 2 for reaction; Preferably, when the complex shown in Formula I is an asymmetric structure, in the process of preparing Formula I, either IIa and any one of IIb and IIc are first refluxed in toluene under the catalysis of p-toluenesulfonic acid; the obtained product is then refluxed in acetic acid with the remaining one of IIb and IIc and the compound NiX 2 ​ 9. A catalyst composition, characterized in that, it includes the complex shown in Formula I according to any one of claims 1-5 and a promoter, and the catalyst composition is used for catalyzing olefin polymerization reaction, and the olefin is preferably ethylene; Preferably, the promoter is one or more of aluminoxane, alkylaluminum, or alkylaluminum chloride; Preferably, the molar ratio of metal Al in the promoter to metal Ni in the complex shown in Formula (I) is (100-5000):

1.

10. A method for catalyzing olefin polymerization reaction, characterized in that, it includes carrying out the polymerization reaction of olefin in the presence of the catalyst composition according to claim 9.

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