Nickel complex containing seven-membered ring pyridine imine, preparation method of nickel complex, catalyst composition and application of catalyst composition

Abstract

The invention discloses a nickel complex containing seven-membered ring pyridine imine, a preparation method of the nickel complex, a catalyst composition containing the complex and application of the catalyst composition. The complex can catalyze ethylene polymerization to obtain narrow-distribution (-2.8) branched polyethylene with medium molecular weight (15.0-27.0 kg.mol <-1 >), the activity of a nickel catalyst reaches 6.36 * 10 < 6 > g (PE) mol <-1 > (nickel) h <-1 >, and the molecular weight of a polyethylene product reaches 27.61 kgmol <-1 >.

Description

Technical Field

[0001] The invention relates to the field of olefin polymerization catalysis, and in particular to a seven-membered ring pyridine imine nickel complex and a preparation method thereof, a catalyst composition containing the complex and use thereof. Background Art

[0002] The chain-walking polymerization of ethylene catalyzed by late transition metals has become an efficient method for synthesizing a series of high-value polyethylene (including linear, branched and hyperbranched structures) from ethylene feedstock alone. The microstructure of the polyethylene chain determines the performance and application range of polyethylene, which requires the design of catalysts and the regulation of polymerization conditions. The late transition metal catalysts developed at the end of the 20th century were used to catalyze olefin polymerization, opening a new chapter in olefin polymerization research. Precise regulation of the polyethylene chain structure can be achieved by changing the central metal atom and its valence state of the catalyst, the electronic effect and steric effect of the ligand, as well as the polymerization method and polymerization conditions.

[0003] In 1995, Brookhart et al. pioneered the report of α-diimine nickel complex as an efficient catalyst for ethylene polymerization [Brookhart, M., et al., J. Am. Chem. Soc. 1995, 117, 6414-6415.], which can catalyze ethylene to prepare polymers with various properties, from linear high molecular weight to polyethylene with a certain degree of branching, and even hyperbranched elastic polyethylene [Wang Z. et al, Coord. Chem. Rev. 2017, 350, 68-83]. After twenty years of modification and improvement of the structure of nickel metal catalysts, the catalytic performance and product quality have made great progress [Gibson, VC et al, Top. Organomet. Chem. 2009, 26, 107-158]. The catalytic activity of the catalyst and the molecular weight, molecular weight distribution and microstructure of the polymer can be regulated by modifying the ligand skeleton [Wang Z. et al, Coord. Chem. Rev. 2017, 350, 68-83]. For example, the branching degree of the polymer can be regulated by a suitable nickel catalyst, so that the resulting polymer material sometimes shows properties similar to those of linear low-density polyethylene. Many pyridine imine nickel complexes A Examples of this type of catalyst have been reported [Zai, S., et al., ACS Catal. 2012, 2, 433–440; Chem. Commun. 2016, 52, 9113–9116], and this type of catalyst model exhibits high activity in ethylene polymerization (up to 10 7 g PE mol -1 (Ni)h -1), a polyethylene product with moderate branching and narrow distribution (PDI ≤ 2.52) was obtained. The steric hindrance and electronic effect of the imine aromatic ring substituents in the ligand skeleton largely affect the catalytic activity of the system [Wang Z. et al, Coord. Chem. Rev. 2017, 350, 68-83; Sun, W.-H., et, al., Dalton Trans. 2012, 41, 11999–12312].

[0004] In recent years, the research group of Sun Wenhua, a researcher at the Institute of Chemistry, Chinese Academy of Sciences, has systematically studied the catalytic performance of cycloalkylpyridine and cycloimine nickel catalysts [Wang Z. et al, Coord. Chem. Rev. 2017, 350, 68-83]. For example, 8-aryl imine-5,6,7-trihydroquinoline nickel (II) complex B containing a six-membered ring structure Shows high catalytic activity (about 10 7 g PE·mol -1 (Ni)·h -1 ), low molecular weight (M w =3.3-9.2kg·mol -1 ), narrow distribution polyethylene [CN105646597B]; 9-aryl imine-5,6,7,8-tetrahydrocycloheptyl pyridine nickel complex C containing a seven-membered ring structure It can efficiently catalyze ethylene polymerization. After activation with MMAO or Et2AlCl, it showed high catalytic activity (8.36×10 6 g PE mol -1 (Ni)h -1 ), the resulting polymer is highly branched (62-114 / 1000C) and has a low molecular weight (2.0-6.0 kg mol -1 ) and narrow distribution (PDI ~ 1.6) [CN105646599B; CN117466949A]; and 10-arylimine-5,6,7,8-tetrahydrocyclooctylpyridine nickel complex D containing an eight-membered ring and a more flexible structure [Zhang, R., et al., J. Polym. Sci., Part A: Polym. Chem., 2017, 55, 2601–2610], due to the overly flexible ring strain and poor chemical coordination environment, the catalytic activity of the complex in catalyzing ethylene polymerization was slightly lower than that of complexes B and C, which was only 3.44×10 6 g PE mol -1 (Ni)h -1 The resulting polymer is highly branched (68-71 / 1000C), low molecular weight (1.0-6.0 kg mol-1 ), polyethylene wax with narrow molecular weight (PDI ~ 1.8). And with the study of single active species of pyridine and cyclopentyl pyridine imine nickel complexes, it was found that the pyridine and cyclopentyl ligand skeleton can provide a rigid coordination environment around the nickel active center. However, this type of ligand structure is prone to imine-enamine interconversion [Huang, F., et al, Dalton Trans. 2015, 44, 14281-14292], which will lead to catalyst instability and multi-site catalytic behavior, resulting in a decrease in the catalytic activity of the system and a decrease in thermal stability [Wang Z. et al, Coord. Chem. Rev. 2017, 350, 68-83]. In particular, the design of 7-arylcyclopentylpyridine imine ligands with strong ring strain [Vierhapper, FW, et al., J. Org. Chem., 1975, 19, 2729-2734] and rigid structure cannot obtain such complexes. By fixing the imine structure with two methyl groups on the adjacent carbon of the aromatic imine, the imine-enamine interconversion is fundamentally suppressed, and a stable imine ligand is obtained, thereby obtaining a five-membered ring 6,6-dimethyl-7-arylimine-5,6-dihydrocyclopentylpyridinium nickel bromide complex E. It was used to catalyze ethylene polymerization to obtain a polyethylene wax product containing terminal groups and internal double bonds [Wang, Z., et al., J. Polym. Sci. Part A: Polym. Chem. 2017, 55, 3494–3505]. Summary of the invention

[0005] The purpose of the present invention is to provide a cycloheptylpyridine imine nickel complex containing a polar carbonyl group, which has a catalytic performance that is significantly better than the complexes provided by invention patents CN105646599B and CN117466949A, and exhibits several times higher catalytic activity in catalyzing ethylene polymerization reactions, and the weight-average molecular weight of the resulting polyethylene product is higher.

[0006] In order to achieve the above object, the present invention adopts the following technical scheme:

[0007] The compound represented by formula I,

[0008]

[0009] In formula I, Ar is Where * is the connection site, R 1 , R 2 , R 3 independently selected from H, F, Cl, Br, I, C 1-6 Alkyl, C 3-6 Cycloalkyl, C substituted by halogen 1-6 Alkyl, halogen-substituted C3-6 Cycloalkyl, methyl substituted with phenyl, methyl substituted with diphenyl, methyl substituted with halophenyl, methyl substituted with two halophenyls, wherein the two halophenyls are the same or different;

[0010] X is selected from Cl or Br, and two X in formula I are the same or different.

[0011] Preferably, the R 1 , R 2 , R 3 They are independently selected from H, methyl (Me), ethyl (Et), propyl (Pr), isopropyl (i-Pr), CHPh2, CH(p-YPh)2, CH(o-YPh)2, CH(m-YPh)2, Cl, Br, OMe (methoxy), and Y is F, Cl, Br or I. Ph represents phenyl.

[0012] Further preferably, the compound shown in Formula I includes the following specific structure:

[0013] Complex Ni1:R 1 =R 3 =Me, R 2 is H, X is Br;

[0014] Complex Ni2:R 1 =R 3 =Et, R 2 is H, X is Br;

[0015] Complex Ni3:R 1 =R 3 =i-Pr, R 2 is H, X is Br;

[0016] Complex Ni4:R 1 =R 2 =R 3 =Me, X is Br;

[0017] Complex Ni5: R 1 =R 3 =Et, R 2 =Me, X is Br;

[0018] Complex Ni6:R 1 =Et, R 2 =R 3 =CHPh2, X is Br;

[0019] Complex Ni7: R 1 =i-Pr, R 2 =R 3 =CHPh2, X is Br;

[0020] Complex Ni8: R 1 =R 3 =CHPh2, R 2 =Cl, X is Br;

[0021] Complex Ni9: R 1 =R 3 =CHPh2, R 2 =Br, X is Br;

[0022] Complex Ni10: R 1 =R 3 =CHPh2, R 2 =OMe, X is Br.

[0023] Another object of the present invention is to provide a method for preparing the compound of formula I, comprising the following steps:

[0024] Formula II and the corresponding aniline are subjected to template reaction at 95-140° C. for 6-24 hours in the presence of acetic acid to obtain a compound of formula I:

[0025]

[0026] Where Ar is Where * is the connection site, R 1 , R 2 , R 3 independently selected from H, F, Cl, Br, I, C 1-6 Alkyl, C 3-6 Cycloalkyl, C substituted by halogen 1-6 Alkyl, halogen-substituted C 3-6 Cycloalkyl, methyl substituted with phenyl, methyl substituted with diphenyl, methyl substituted with halophenyl, methyl substituted with two halophenyls, wherein the two halophenyls are the same or different;

[0027] X is selected from Cl or Br, and two X in formula I are the same or different.

[0028] Preferably, the compound of formula II and the corresponding aniline are subjected to template reaction in the presence of acetic acid at 120° C. for 12 h to obtain the compound of formula I.

[0029] The present invention also provides a catalyst composition, comprising the compound shown in formula I and an auxiliary agent.

[0030] Preferably, the auxiliary agent is one or more of aluminoxane, alkyl aluminum or alkyl aluminum chloride.

[0031] Further preferably, the auxiliary agent is sesquiethylaluminum chloride, and the molar ratio of the metal Al in the auxiliary agent to the metal nickel in the compound represented by formula I is 200 to 1000:1.

[0032] The present invention also provides the use of the catalyst composition for catalyzing olefin polymerization reaction. The olefin is preferably ethylene.

[0033] In the present invention, the term "C 1-6 The term "alkyl" refers to a straight or branched alkane having 1 to 6 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, hexyl, etc.

[0034] The term "C 3-6 "Cycloalkyl" is to be understood as a straight-chain or branched saturated monovalent monocyclic hydrocarbon ring containing, for example, 3, 4, 5 or 6 carbon atoms.

[0035] The present invention has the following advantages:

[0036] 1. A new type of cycloheptylpyridine imine nickel complex ethylene polymerization catalyst containing a polar carbonyl group is provided. This type of complex can catalyze the polymerization of ethylene to obtain medium molecular weight (15.0-27.0 kg·mol -1 Compared with the pyridocycloheptane imine nickel complex provided by the invention patents CN105646599B and CN117466949A, the polar carbonyl group in this patent has a stronger protective effect on the active center, promotes the chain growth reaction during polymerization, and improves the catalytic activity. The nickel catalyst activity reaches 6.36×10 6 g(PE)mol -1 (Nickel)h -1 The weight average molecular weight of polyethylene product is as high as 27.61 kg mol -1 Compared with the patent CN110386954A, the activity of the nickel-centered catalyst using EASC as an additive is increased by 11%, and the weight-average molecular weight of the polyethylene product is increased by 15 times.

[0037] 2. A method for synthesizing the compound shown in formula I using a cycloheptylpyridone intermediate is provided. The intermediate can be used to synthesize the target catalyst in a one-pot process, which has the advantages of mild reaction conditions, simple operation, and high yield.

[0038] 3. The catalyst of the present invention can catalyze the preparation of branched double-bond polyethylene: the polyethylene product has a melting point of 118-124°C, and high-temperature nuclear magnetic resonance characterization can show the characteristic peak of carbon-carbon double bonds, and can also show that the polyethylene has certain branch chains. Such polyethylene products can be widely used in the fields of film products, medical devices, pharmaceutical and food packaging materials, extruded pipes, wires and cables, blow-molded hollow products, etc. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] Figure 1 This is the H NMR spectrum of the cycloheptyl[b]pyridine-5,9-dione of Formula II obtained in Example 2;

[0040] Figure 2 The polyethylene product obtained in Example 19 1 H NMR spectra

[0041] Figure 3 The polyethylene product obtained in Example 19 13 C NMR spectrum. DETAILED DESCRIPTION

[0042] Unless otherwise specified, the experimental methods used in the following examples are conventional methods.

[0043] Unless otherwise specified, the chemical reagents, materials, etc. used in the following examples can be obtained from commercial sources.

[0044] The methylaluminoxane (MAO), modified methylaluminoxane (MMAO), diethylaluminum chloride (Et2AlCl), and ethylaluminum sesquichloride (EASC) used were purchased from Anhui Botai Electronic Materials Co., Ltd.

[0045] Example 1 Preparation of intermediate, namely 5,9-dihydroxy-7H-cyclohepta(B)pyridine-6,8-dicarboxylic acid dimethyl ester (V)

[0046]

[0047] Add 117g (0.6mol) of dimethyl 2,3-pyridinedicarboxylate, 146g (0.9mol, 1.5eq.) of dimethyl glutarate, and 800mL of toluene to a 2000mL three-necked flask, stir for 10min, dropwise add 168g (1.5mol, 2.5eq.) of potassium tert-butoxide in tetrahydrofuran solution (800mL), control the temperature to less than 30°C, raise the temperature to 60°C after the addition, and continue the reaction for 1h. TLC detection shows that the reaction is complete. The reaction mixture is concentrated under reduced pressure to remove half of the solvent. The mixture is cooled to below 5°C, 1500mL of water and 1500mL of petroleum ether are added, and the mixture is adjusted to pH = 6-6.5 with 60mL of glacial acetic acid to produce a large amount of solids, which are filtered and the filter cake is washed with a small amount of water. 94g of yellow solid V is obtained.

[0048] Example 2 Preparation of intermediate, namely compound cyclohepta[b]pyridine-5,9-dione (II)

[0049]

[0050] Add 94g of the product obtained in the previous step to 500mL of hydrochloric acid (concentrated hydrochloric acid) and 250ml of water, stir and heat to 80 degrees for 5h, monitor the reaction by TLC, cool to 0 degrees, slowly add solid sodium bicarbonate (about 300g) to adjust the pH to 5.0-5.5, and extract with 500mL of dichloromethane*10 times. Combine the organic phases, wash once with saturated brine, dry and decolorize, spin dry the solvent to obtain 56g of crude product, add 10mL of ethyl acetate and 400mL of n-hexane, stir and beat, filter and dry 46g of white solid, the yield is 43% (calculated from 2,3-pyridinedicarboxylic acid dimethyl ester raw material), purity>98%. Mp=61-62℃; 1 H NMR (400 MHz, DMSO-d6, Figure 1 )δ8.90(dd,J=4.7,1.5Hz,1H),8.15(dd,J=7.9,1.6Hz,1H),7.74(dd,J=7.9, 4.7Hz, 1H), 2.93 (t, J = 6.7Hz, 2H), 2.89–2.84 (m, 2H), 2.04 (p, J = 6.6Hz, 2H).

[0051] The reaction formula for preparing the target complex through Examples 3-12 is as follows:

[0052]

[0053] Example 3 Preparation of 9-(2,6-dimethylphenyl)imino)-6,7,8,9-tetrahydro-5H-cycloheptane[b]pyridin-5-one nickel(II) chloride complex Ni1

[0054] Under nitrogen atmosphere, 0.437g (2.5mmol) of cycloheptyl[b]pyridine-5,9-dione II, 2,6-dimethylaniline (0.305g, 2.5mmol), 0.537g (2.5mmol) of nickel bromide and 10mL of acetic acid were placed in a Shrek bottle, and the mixture was reacted at 120°C (oil bath temperature) for 12h. After the reaction mixture was cooled to room temperature, the acetic acid solvent was concentrated under reduced pressure to obtain a brown oily substance. After a small amount of dichloromethane was added to dissolve it, the insoluble substances (inorganic salts) were filtered out, and the filtrate was concentrated to about 1.0mL. A large amount of ether was added to produce a suspension, and stirring was continued for 0.5h. After the mixture was filtered, the filter cake was washed 3 times with a small amount of ether, and the filter cake solid was dried to obtain 0.68g of brown powder with a yield of 53%. The structural characterization is as follows: FT-IR (cm -1 ):3395(s),1629(s,v C＝O ),1578(m,v C＝N),1527(w),1469(w),1440(w),1382(w),1342(w),1269(w),1194(w),1122(w),1094(w),1039(w),905(w),776(w),675(w),612(w).Elemental analysis [C 18 H 18 Br2N2NiO(M w :493.91)]: Theoretical value C, 43.51; H, 3.65; N, 5.64. Experimen...

[0055] Example 4 Preparation of 9-(2,6-diethylphenyl)imino)-6,7,8,9-tetrahydro-5H-cycloheptane[b]pyridin-5-one nickel(II) chloride complex Ni2

[0056] Similar to Example 3, 2,6-dimethylaniline was replaced with 2,6-diethylaniline (0.407 g, 2.5 mmol) to obtain 0.76 g of brown solid powder with a yield of 58%. FT-IR (KBr, cm -1 ):3422(w),2966(w),2059(w),1631(s,v C＝O ),1591(s,v C＝N ),1523(w),1452(w),1383(w),1343(w),1280(w),1145(w),Elemental Analysis[C 20 H 22 Br2N2NiO(M w :521.94)] Theoretical value: C, 45.76; H, 4.22; N, 5.34. Experimental value: C, 45.91; H, 4.45; N, 5.41%.

[0057] Example 5 Preparation of 9-(2,6-diisopropylphenyl)imino)-6,7,8,9-tetrahydro-5H-cycloheptane[b]pyridin-5-one nickel(II) chloride complex Ni3

[0058] Similar to Example 3, 2,6-dimethylaniline was replaced with 2,6-diisopropylamine (0.442 g, 2.5 mmol) to obtain 0.87 g of brown solid powder with a yield of 70%. FT-IR (KBr, cm -1 ):3404(s),2966(w),2548(w),2355(w),1632(s,v C＝O ),1581(s,v C＝N),1553(w),1501(w),1462(w),1385(w),1344(w),1285(w),1181(w),1056(w),804(w).Elemental analysis[C 22 H 26 Br2N2NiO (Mw: 549.97)] Theoretical value: C, 47.79; H, 4.74; N, 5.07. Experimental value: C, 47.85; H, 4.81; N, 5.02%.

[0059] Example 6 Preparation of 9-(2,4,6-trimethylphenyl)imino)-6,7,8,9-tetrahydro-5H-cycloheptane[b]pyridin-5-one nickel(II) chloride complex Ni4

[0060] Similar to Example 3, 2,6-dimethylaniline was replaced with 2,4,6-trimethylaniline (0.337 g, 2.5 mmol) to obtain 1.09 g of brown solid powder with a yield of 86%. FT-IR (KBr, cm -1 ):3405(s),1644(s,v C＝O ),1577(m,v C＝N ),1530(w),1481(w),1441(w),1382(w),1343(w),1315(w),1275(w),1206(w),1152(w),1116(w),1019(w),905(w),855(w),817(w)Elemental analysis[C 19 H 20 Br2N2NiO (Mw: 507.92)] Theoretical value: C, 44.67; H, 3.95; N, 5.48. Experimental value: C, 44.71; H, 3.99; N, 5.54%.

[0061] Example 7 Preparation of 9-(2,6-diethyl-4-methylphenyl)imino)-6,7,8,9-tetrahydro-5H-cycloheptane[b]pyridin-5-one nickel(II) chloride complex Ni5

[0062] Similar to Example 3, 2,6-dimethylaniline was replaced with 2,6-diethyl-4-methylaniline (0.407 g, 2.5 mmol) to obtain 0.962 g of brown solid powder with a yield of 72%. FT-IR (KBr, cm -1 ):3387(s),2966(w),1627(s,v C＝O ),1578(s,v C＝N),1525(w),1454(w),1342(w),1276(w),1147(w),1057(w),1021(w),860(w).Elemental analysis[C 21 H 24 Br2N2NiO (Mw: 535.96)] Theoretical value: C, 46.80; H, 4.49; N, 5.20. Experimen...

[0063] Example 8 Preparation of 9-(2-ethyl-4,6-diphenylmethylphenyl)imino)-6,7,8,9-tetrahydro-5H-cycloheptane[b]pyridin-5-one nickel(II) chloride complex Ni6

[0064] Similar to Example 3, 2,6-dimethylaniline was replaced with 2-ethyl-4,6-dibenzhydrylaniline (1.132 g, 2.5 mmol) to obtain 1.445 g of brown solid powder with a yield of 70%. FT-IR (KBr, cm -1 ):3416(s),2961(w),1640(s,v C=O),1629(s,v C=N),1571(w),1552(w),1527(w),1493(w),1451(w),1383(w),1342(w),131 4(w),1272(w),1178(w),1138(w),1079(w),1033(w),811(w),768(w).Elemental analysis[C 44 H 38 Br2N2NiO (Mw: 826.07)] Theoretical value: C, 63.73; H, 4.62; N, 3.38. Experimental value: C, 63.69; H, 4.72; N, 3.31%.

[0065] Example 9 Preparation of 9-(2-propyl-4,6-diphenylmethylphenyl)imino)-6,7,8,9-tetrahydro-5H-cycloheptane[b]pyridin-5-one nickel(II) chloride complex Ni7

[0066] Similar to Example 3, 2,6-dimethylaniline was replaced with 2-propyl-4,6-dibenzhydrylaniline (1.16 g, 2.5 mmol) to obtain 1.76 g of brown solid powder with a yield of 84%. FT-IR (KBr, cm -1 ):3422(s),2967(w),1639(s,v C＝O ),1629(s,v C＝N),1571(w),1547(w),1528(w),1493(w),1450(w),1383(w),1342(w),1314(w),1 273(w),1257(w),1178(w),1099(w),1084(w),1032(w),903(w),812(w).Elemental analysis[C 45 H 50 Br2N2NiO (exact mass: 840.08)] Theoretical value: C, 64.09; H, 4.78; N, 3.32. Experimental value: C, 64.11; H, 4.82; N, 3.37%.

[0067] Example 10 Preparation of 9-(2,6-diphenylmethyl-4-chlorophenyl)imino)-6,7,8,9-tetrahydro-5H-cycloheptane[b]pyridin-5-one nickel(II) chloride complex Ni8

[0068] Similar to Example 3, 2,6-dimethylaniline was replaced with 2,6-diphenylmethyl-4-chloroaniline (1.14 g, 2.5 mmol) to obtain 0.915 g of brown solid powder with a yield of 44%. FT-IR (KBr, cm -1 ):3405(s),1630(s,v C＝O ),1588(s,v C＝N ),1552(w),1528(w),1493(w),1441(w),1383(w),1343(w),1277(w),1135(w),702(w).Elemental analysis[C 42 H 33 Br2ClN2NiO (exact mass: 832.00)] Theoretical value: C, 60.36; H, 3.98; N, 3.35. Experimen...

[0069] Example 11 Preparation of 9-(2,6-diphenylmethyl-4-bromophenyl)imino)-6,7,8,9-tetrahydro-5H-cycloheptane[b]pyridin-5-one nickel(II) chloride complex Ni9

[0070] Similar to Example 3, 2,6-dimethylaniline was replaced with 2,6-dibenzhydryl-4-bromoaniline (1.25 g, 2.5 mmol) to obtain 1.24 g of brown solid powder with a yield of 57%. FT-IR (KBr, cm -1 ):3405(s),1629(s,v C＝O ),1588(s,v C＝N),1551(w),1528(w),1493(w),1450(w),1383(w),1343(w),1274(w),1144(w),1084(w),701(w).Elemental analysis [C 42 H 33 Br3N2NiO (Mw: 875.94)] Theoretical value: C, 57.32; H, 3.78; N, 3.18. Experimen...

[0071] Example 12 Preparation of 9-(2,6-diphenylmethyl-4-methoxyphenyl)imino)-6,7,8,9-tetrahydro-5H-cycloheptane[b]pyridin-5-one nickel(II) chloride complex Ni10

[0072] Similar to Example 3, 2,6-dimethylaniline was replaced with 2,6-diphenylmethyl-4-methoxyaniline (1.13 g, 2.5 mmol) to obtain 1.73 g of brown solid powder with a yield of 84%. FT-IR (KBr, cm -1 ):3405(s),1634(s,v C＝O ),1600(s,v C＝N ),1528(w),1493(w),1461(w),1450(w),1343(w),1315(w),1275(w),1201(w), 1138(w),1118(w),1080(w),1048(w),1032(w),905(w),864(w),814(w).Elemental analysis[C 43 H 36 Br3N2NiO (exact mass: 828.04)] Theoretical value: C, 62.13; H, 4.37; N, 3.37. Experimental value: C, 62.21; H, 4.42; N, 3.42%.

[0073] Example 13 Screening of different co-catalysts: Using nickel complex Ni3 as catalyst

[0074] a) Ni3 (3 μmol) complex was placed in a dry 250 mL autoclave, and the nitrogen was replaced by vacuum twice, and then replaced by ethylene gas. Toluene (25 mL×2) was added to the autoclave, and the mixture was stirred for five minutes and then allowed to stand. When the temperature of the autoclave reached 30°C, the required amount (5.0 mL) of cocatalyst MAO (1.46 mol / L in toluene) was added, and toluene (25 mL×2) was added to make the total volume of the solvent 100 mL. At this time, the aluminum-nickel ratio (the molar ratio of the metal aluminum in the cocatalyst to the metal cobalt in the catalyst) was 2500. The mechanical stirring was turned on at a speed of 400 rpm, and ethylene was simultaneously charged into the autoclave, and the pressure of the reaction system was kept at 10 atm of ethylene gas, and the reaction was carried out for 30 minutes. After the reaction, the reaction solution was treated with 10% hydrochloric acid ethanol solution to obtain a white precipitate, which was stirred in the hydrochloric acid ethanol solution for 1 hour, filtered, and the obtained white solid was placed in a 100°C oven to dry to constant weight to obtain 1.20 g of white polymer with a polymerization activity of 0.80×10 6 g(PE)mol -1 (Ni)h -1 , polymer weight average molecular weight M w =9.62kg / mol, polymer molecular weight distribution M w / M n =2.68(M w and M n All measured by GPC), polymer melting point T m =120.0°C (measured by DSC).

[0075] b) is basically the same as method a) in this embodiment, except that the co-catalyst is MMAO (2.5 mol L -1 ) The required amount is 3.0 mL, and the aluminum-nickel ratio is 2500. The polymerization activity is 0.50×10 6 g(PE)mol -1 (Ni)h -1 , polymer weight average molecular weight M w =5.77kg / mol, polymer molecular weight distribution M w / M n =1.67, polymer melting point T m =119.0℃.

[0076] c) is basically the same as method a) in this embodiment, except that the co-catalyst is Et2AlCl (1 mol L -1 ) The required amount is 1.2 mL, and the aluminum-nickel ratio is 400. The polymerization activity is 0.83×10 6 g(PE)mol -1 (Ni)h -1 , polymer weight average molecular weight M w=10.18kg / mol, polymer molecular weight distribution M w / M n =2.45, polymer melting point T m =125.3℃.

[0077] d) is basically the same as method a) in this embodiment, except that the co-catalyst is EASC (1 mol L -1 ) The required amount is 1.2 mL, and the aluminum-nickel ratio is 400. The polymerization activity is 2.34×10 6 g(PE)mol -1 (Ni)h -1 , polymer weight average molecular weight M w =5.41kg / mol, polymer molecular weight distribution M w / M n =2.19, polymer melting point T m =123.6°C. The above results are shown in Table 1.

[0078] Table 1 Ni3 ethylene polymerization performance under different co-catalysts a

[0079]

[0080] a Conditions: 3 μmol Ni3, 30 min, 10 atm CH2=CH2, 100 mL toluene, 30 min, 30 °C;

[0081] b 10 6 g PE mol -1 (Ni)h -1 ; c Determined by differential scanning calibration (DSC); d M w :kg / mol,M w andM w / M n determined by GPC.

[0082] Example 14 Polymerization Condition Screening

[0083] (a) The same as Example 13a, except that the cocatalyst was EASC, the required amount was 0.6 mL, and the aluminum-nickel ratio was 200. The polymerization activity was 1.24×10 6 g(PE)mol -1 (Ni)h -1 , polymer weight average molecular weight Mw =5.17kg / mol, polymer molecular weight distribution M w / M n =2.25, polymer melting point T m =124.9℃.

[0084] (b) is basically the same as Example (a), except that the cocatalyst is EASC, the required amount is 1.8 mL, and the aluminum-nickel ratio is 600. The polymerization activity is 3.00×10 6 g(PE)mol -1 (Ni)h -1 , polymer weight average molecular weight M w =12.51kg / mol, polymer molecular weight distribution M w / M n =2.94, polymer melting point T m =123.7℃.

[0085] (c) is basically the same as Example (a), except that the cocatalyst is EASC, the required amount is 2.4 mL, and the aluminum-nickel ratio is 800. The polymerization activity is 2.25×10 6 g(PE)mol -1 (Ni)h -1 , polymer weight average molecular weight M w =5.50kg / mol, polymer molecular weight distribution M w / M n =2.09, polymer melting point T m =124.2℃.

[0086] (d) is basically the same as Example (a), except that the cocatalyst is EASC, the required amount is 3.0 mL, and the aluminum-nickel ratio is 1000. The polymerization activity is 1.66×10 6 g(PE)mol -1 (Ni)h -1 , polymer weight average molecular weight M w =6.54kg / mol, polymer molecular weight distribution M w / M n =2.35, polymer melting point T m =124.2℃.

[0087] (e) Same as method (b) in this embodiment, except that the polymerization temperature is 10°C and the aluminum-nickel ratio is 600. The polymerization activity is 3.96×10 6 g(PE)mol -1 (Ni)h -1 , polymer weight average molecular weight M w =21.19 kg / mol, polymer molecular weight distribution Mw / M n =4.50, polymer melting point T m =123.8℃.

[0088] (f) is basically the same as method (b) in this embodiment, except that the polymerization temperature is 20°C and the aluminum-nickel ratio is 600. The polymerization activity is 4.00×10 6 g(PE)mol -1 (Ni)h -1 , polymer weight average molecular weight M w =15.47kg / mol, polymer molecular weight distribution M w / M n =3.45, polymer melting point T m =121.3℃.

[0089] (g) Same as method (b) in this example, except that the polymerization temperature is 40°C and the aluminum-nickel ratio is 600. The polymerization activity is 3.16×10 6 g(PE)mol -1 (Ni)h -1 , polymer weight average molecular weight M w =5.60kg / mol, polymer molecular weight distribution M w / M n =2.62, polymer melting point T m =123.7℃.

[0090] (h) is basically the same as method (b) in this embodiment, except that the polymerization temperature is 50°C and the aluminum-nickel ratio is 600. The polymerization activity is 1.90×10 6 g(PE)mol -1 (Ni)h -1 , polymer weight average molecular weight M w =3.61kg / mol, polymer molecular weight distribution M w / M n =2.08, polymer melting point T m =124.1℃.

[0091] (j) is basically the same as method (b) in this embodiment, except that the polymerization temperature is 60°C and the aluminum-nickel ratio is 600. The polymerization activity is 0.84×10 6 g(PE)mol -1 (Ni)h -1 , polymer weight average molecular weight M w =2.55kg / mol, polymer molecular weight distribution M w / M n =1.64, polymer melting point T m =118.4℃.

[0092] (k) is basically the same as method (f) in this embodiment, except that the polymerization time is 5 min and the aluminum-nickel ratio is 600. The polymerization activity is 7.99×10 6 g(PE)mol -1 (Ni)h -1 , polymer weight average molecular weight M w =12.58kg / mol.

[0093] (l) is basically the same as method (f) in this embodiment, except that the polymerization time is 15 min and the aluminum-nickel ratio is 600. The polymerization activity is 4.60×10 6 g(PE)mol -1 (Ni)h -1 , polymer weight average molecular weight M w =12.74kg / mol, polymer molecular weight distribution M w / M n =2.11, polymer melting point T m =123.4℃.

[0094] (m) is basically the same as method (f) in this embodiment, except that the polymerization time is 45 min and the aluminum-nickel ratio is 600. The polymerization activity is 2.71×10 6 g(PE)mol -1 (Ni)h -1 , polymer weight average molecular weight M w =15.77kg / mol, polymer molecular weight distribution M w / M n =1.87, polymer melting point T m =122.7℃.

[0095] (n) is basically the same as method (f) in this embodiment, except that the polymerization time is 60 min and the aluminum-nickel ratio is 600. The polymerization activity is 2.56×10 6 g(PE)mol -1 (Ni)h -1 , polymer weight average molecular weight M w =17.77kg / mol, polymer molecular weight distribution M w / M n =1.91, polymer melting point T m =121.2℃.

[0096] (o) is basically the same as method (f) in this embodiment, except that the ethylene pressure is 5 atm and the polymerization activity is 1.93×10 6 g(PE)mol -1 (Ni)h -1, polymer weight average molecular weight M w =8.29kg / mol, polymer molecular weight distribution M w / M n =1.82, polymer melting point T m =122.3°C. The above results are shown in Table 2.

[0097] Table 2 Optimization conditions a

[0098]

[0099] a Reaction conditions: 3 μmol Ni3, 5-60 min, 10 atm of ethylene, 100 mL toluene; b 10 6 g PE mol -1 (Ni)h -1 ; c Determined by differential scanning calorimetry; d M w :kg / mol,M w andM w / M n determined by GPC; e 5 atm.

[0100] Example 15: Ethylene polymerization catalyzed by complex Ni1 and cocatalyst EASC

[0101] The same as Example (14f), except that the main catalyst is Ni1. The polymerization activity is 4.84×10 6 g(PE)mol -1 (Ni)h -1 , polymer weight average molecular weight M w =15.28kg / mol, polymer molecular weight distribution M w / M n =2.12, polymer melting point T m =124.8℃.

[0102] Example 16: Ethylene polymerization catalyzed by complex Ni2 and cocatalyst EASC

[0103] The same as Example (14f), except that the main catalyst is Ni2. The polymerization activity is 2.40×10 6 g(PE)mol -1 (Ni)h -1 , polymer weight average molecular weight M w=10.86kg / mol, polymer molecular weight distribution M w / M n =2.33, polymer melting point T m =121.5℃.

[0104] Example 17: Ethylene polymerization catalyzed by complex Ni4 and cocatalyst EASC

[0105] The same as Example (14f), except that the main catalyst is Ni4. The polymerization activity is 4.74×10 6 g(PE)mol -1 (Ni)h -1 , polymer weight average molecular weight M w =12.43kg / mol, polymer molecular weight distribution M w / M n =2.31, polymer melting point T m =122.3℃.

[0106] Example 18 The polymerization of ethylene using the complex Ni5 and the cocatalyst EASC is basically the same as Example (14f), except that the main catalyst is Ni5. The polymerization activity is 1.33×10 6 g(PE)mol -1 (Ni)h -1 , polymer weight average molecular weight M w =14.29kg / mol, polymer molecular weight distribution M w / M n =2.34, polymer melting point T m =123.2℃.

[0107] Example 19: Ethylene polymerization catalyzed by complex Ni6 and cocatalyst EASC

[0108] The same as Example (14f), except that the main catalyst is Ni6. The polymerization activity is 6.36×10 6 g(PE)mol -1 (Ni)h -1 , polymer weight average molecular weight M w =27.61kg / mol, polymer molecular weight distribution M w / M n =2.24, polymer melting point T m =125.3℃.

[0109] Take 30 mg of the obtained polymer and dissolve it in 0.6 mL of deuterated 1,1,2,2-tetrachloroethane at 120°C. 1 H NMR data ( Figure 2), at δ 5.90 ppm (multiplet) and 5.20 ppm (triplet), and the corresponding peak area ratio was 1:2, proving that it contained terminal vinyl groups.

[0110] Take 30 mg of the obtained polymer and dissolve it in 0.6 mL of deuterated 1,1,2,2-tetrachloroethane at 120°C. 13 C NMR data ( Figure 3 ), two groups of signal peaks were obtained at δ3138.91ppm and 114.38ppm, indicating the vinyl end of polyethylene. At the same time, there were many carbon chain signal peaks in the high field region. According to the literature report [Galland, GB et al Macromolecules, 1999, 32: 1620–1625], by 13 C NMR analysis revealed that the polymer sample contained 34 branches per 1000 carbon atoms in the main chain, including methyl branches (28.0%), ethyl branches (5.1%) and long chain branches (66.9%).

[0111] Example 20: Ethylene polymerization catalyzed by complex Ni7 and cocatalyst EASC

[0112] The same as Example (14f), except that the main catalyst is Ni7. The polymerization activity is 3.72×10 6 g(PE)mol -1 (Ni)h -1 , polymer weight average molecular weight M w =28.62kg / mol, polymer molecular weight distribution M w / M n =2.53, polymer melting point T m =123.6℃.

[0113] Example 21 Ethylene polymerization catalyzed by complex Ni8 and cocatalyst EASC

[0114] Basically the same as Example (14f), except that the main catalyst is Ni8. A trace amount of polyethylene product is obtained.

[0115] Example 22: Ethylene polymerization catalyzed by complex Ni9 and cocatalyst EASC

[0116] The same as in Example (14f), except that the main catalyst is Ni9. A trace amount of polyethylene product is obtained. Example 23 Ethylene polymerization catalyzed by complex Ni10 and cocatalyst EASC is basically the same as in Example (14f), except that the main catalyst is Ni10. The polymerization activity is 1.70×10 6 g(PE)mol -1 (Ni)h -1, polymer weight average molecular weight M w =35.45kg / mol, polymer molecular weight distribution M w / M n =3.5, polymer melting point T m =126.0°C. The above results are shown in Table 3.

[0117] Table 3 Catalytic performance of different nickel catalysts

[0118]

[0119] a Conditions: 3μmol of Ni; 30min; 10atm of ethylene; 100mL toluene, 30min; b 10 6 gPE mol -1 (Ni)h -1 ; c Determined by differential scanning calorimetry; d M w :kg / mol,M w andM w / M n determined by GPC.

Claims

1. A compound of formula I, In formula I, Ar is Where * is the connection site, R 1 , R 2 , R 3 independently selected from H, F, Cl, Br, I, C 1-6 Alkyl, C 3-6 Cycloalkyl, C substituted by halogen 1-6 Alkyl, halogen-substituted C 3-6 Cycloalkyl, phenyl-substituted methyl, diphenyl-substituted methyl, halogenated phenyl-substituted methyl, two halogenated phenyl-substituted methyl, the two halogenated phenyl groups being the same or different; X is selected from Cl or Br, and two X in formula I are the same or different.

2. The compound according to claim 1, characterized in that: The R 1 , R 2 , R 3 They are independently selected from H, methyl, ethyl, propyl, isopropyl, CHPh2, CH(p-YPh)2, CH(o-YPh)2, CH(m-YPh)2, Cl, Br, OMe, and Y is F, Cl, Br or I.

3. The compound according to claim 2, characterized in that The specific structure includes the following: Complex Ni1:R 1 =R 3 =Me, R 2 is H, X is Br; Complex Ni2:R 1 =R 3 =Et, R 2 is H, X is Br; Complex Ni3:R 1 =R 3 =i-Pr, R 2 is H, X is Br; Complex Ni4:R 1 =R 2 =R 3 =Me, X is Br; Complex Ni5: R 1 =R 3 =Et, R 2 =Me, X is Br; Complex Ni6: R 1 =Et, R 2 =R 3 =CHPh2, X is Br; Complex Ni7: R 1 =i-Pr, R 2 =R 3 =CHPh2, X is Br; Complex Ni8: R 1 =R 3 =CHPh2, R 2 =Cl, X is Br; Complex Ni9: R 1 =R 3 =CHPh2, R 2 =Br, X is Br; Complex Ni10: R 1 =R 3 =CHPh2, R 2 =OMe, X is Br.

4. A method for preparing a compound of formula I, characterized in that The steps include: Formula II and the corresponding aniline are subjected to template reaction at 95-140° C. for 6-24 hours in the presence of acetic acid to obtain a compound of formula I: Where Ar is Where * is the connection site, R 1 , R 2 , R 3 independently selected from H, F, Cl, Br, I, C 1-6 Alkyl, C 3-6 Cycloalkyl, C substituted by halogen 1-6 Alkyl, halogen-substituted C 3-6 Cycloalkyl, phenyl-substituted methyl, diphenyl-substituted methyl, halogenated phenyl-substituted methyl, two halogenated phenyl-substituted methyl, the two halogenated phenyl groups being the same or different; X is selected from Cl or Br, and two X in formula I are the same or different.

5. The preparation method according to claim 4, characterized in that The compound of formula II and the corresponding aniline are subjected to template reaction at 120° C. for 12 h in the presence of acetic acid to obtain the compound of formula I.

6. A catalyst composition comprising a compound as shown in formula I of claim 1, 2 or 3 and an auxiliary agent.

7. The catalyst composition according to claim 6, characterized in that The auxiliary agent is one or more of aluminoxane, alkyl aluminum or alkyl aluminum chloride.

8. The catalyst composition according to claim 6, characterized in that The auxiliary agent is sesquiethylaluminum chloride, and the molar ratio of the metal Al in the auxiliary agent to the metal nickel in the compound represented by formula I is 200-1000:

1.

9. Use of the catalyst composition according to claim 6, 7 or 8, characterized in that The catalyst composition is used for catalyzing olefin polymerization reaction.

10. The use according to claim 9, characterized in that The olefin is ethylene.

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