WO2021082278A1 - FLUORINE-CONTAINING α-DIIMINE NICKEL COMPLEXES FOR PREPARING POLYOLEFIN ELASTOMER AND INTERMEDIATES, AND PREPARATION METHOD AND USE - Google Patents

Abstract

Disclosed are a class of fluorine-containing α-diimine nickel complexes for preparing a polyolefin elastomer and intermediates thereof. The class of complexes have a single catalytic active center, the molecular weight of a polymer can be regulated and controlled by changing a ligand structure and the polymerization conditions, and the complexes have advantages including a high catalytic activity, a low cost and a stable performance. Also provided are methods for preparing an asymmetric α-diimine nickel complex containing a difluoro group and an intermediate thereof. The two preparation methods have advantages such as mild reaction conditions, short periods, and simple operation conditions. Also provided are the uses of a metal nickel complex and a catalyst system thereof for catalyzing ethylene polymerization, wherein the metal nickel complex and the catalyst system thereof exhibit a very good catalytic activity, and a polyethylene elastomer material with a narrow molecular weight distribution is thus obtained. The obtained polyethylene elastomer material has a high degree of branching, and also has a good tensile strength, elongation at break and elastic resilience. The obtained polyethylene elastomer material is a thermoplastic elastomer material and has excellent industrial application potential.

Description

A class of fluorine-containing α-diimine nickel complexes, intermediates, preparation methods and uses for preparing polyolefin elastomers Technical field

The invention belongs to the technical field of polyolefin catalysts, and specifically relates to a type of fluorine-containing α-diimine nickel complexes, intermediates, preparation methods and applications for preparing polyolefin elastomers.

Background technique

Among many late transition metal catalysts, nickel complexes have been widely studied because of their high catalytic activity, low cost, and low toxicity. As a highly active polyethylene (PE) and polypropylene (PP) catalyst, the α-diimine nickel complex is used in our daily life for food packaging, medical equipment, auto parts, etc. The huge economic achievements that followed were mainly based on the design of new catalysts, reaction engineering and polyolefin processes.

Thermoplastic elastomers (TPEs) have become important industrial materials due to the low cost and ease of manufacture brought about by rapid and reversible thermoplastic processing. At present, the application examples of TPEs replacing vulcanized rubber are sealing rings, gaskets, industrial hoses and footwear. The mechanical properties of polyethylene elastomers prepared by diarylimine acenaphthylene nickel catalyst catalyzed by the homopolymerization of ethylene are similar to thermoplastic elastomers (TPEs), and are valuable substitutes for commercial TPEs.

For example, the asymmetric diarylimine acenaphthylene nickel halide can catalyze the production of elastomeric polyethylene with medium to high molecular weight and high elastic recovery and elongation at break. The traditional synthetic methods of elastomers involve time-consuming and expensive controlled/living radical polymerization (CRP) and living anionic polymerization. Therefore, the use of late transition metal catalysts can more conveniently obtain TPEs. In addition to achieving high activity polymerization, synthetic polyethylene has aroused great interest due to its unique properties, such as high degree of branching, narrow polydispersity, and the properties of new elastomeric polymers that may exist.

Therefore, in order to develop better performance polyethylene elastomers, the research on the structure of ethylene polymer catalysts has become a key link in the study of ethylene polymerization. By controlling the type and valence state of the metal in the center of the catalyst and the structure of the ligand, such as electronic effects and stereo effects, the catalyst structure can be adjusted to study its influence on the polymerization performance.

Since the Brookhart research group reported in 1995 that α-diimine coordination nickel and palladium complexes catalyzed the polymerization of ethylene (J. Am. Chem. S° C., 1995, 117, 6414), there has been more and more information about nickel coordination The research of chemical catalysts has been reported one after another (Coord.Chem.Rev., 2017, 350, 68).

In the past few years, the inventor’s research group has been committed to the research of ethylene oligomerization and polymerization catalysts and catalytic processes, and has researched and developed various types of nickel complex ethylene polymerization catalysts. For example, the α-diimine complex catalyst containing 2-diphenylmethylnaphthaleneimine structure shown in Formula 1 can efficiently catalyze the polymerization of ethylene to form polymers with high molecular weight and low branching degree (Organometallics 2014, 33, 7223) ;Subsequently, the research team continued to design different large hindered substituents on the basis of α-diimine, and introduced electron withdrawing fluorine groups, as shown in formula 2 (Organometallics 2015, 34, 582). The catalyst exhibits high activity and better thermal stability in ethylene polymerization, and can obtain polymers with high degree of branching and good elasticity.

However, the catalytic performance of the above catalysts, as well as the conditions and efficiency of their preparation methods, still need to be further improved.

Summary of the invention

The technical problem to be solved by the present invention is to further improve the prior art, and provide a fluorine-containing α-diimine nickel complex and intermediates and their respective preparation methods, as well as a catalyst made from the nickel complex. The prepared nickel complex exhibits good performance in regulating the molecular weight of polyolefin when catalyzing olefin polymerization, and while obtaining a polyolefin elastomer with a narrow molecular weight distribution, it also improves the degree of branching of the elastomer.

In order to achieve the above technical objectives, the basic idea of the technical solution adopted by the present invention is:

The present invention provides a type of fluorine-containing α-diimine nickel complexes for preparing polyolefin elastomers, and the fluorine-containing α-diimine nickel complexes have a structure as shown in formula (I):

Wherein, R ^{1 is the} same or different, each independently selected from methyl, ethyl or isopropyl; R ^{2 is the} same or different, each independently selected from H or methyl; X is the same or different, each independently selected from halogen .

A further scheme of the nickel complex provided by the present invention is: the fluorine-containing α-diimine nickel complex includes, but is not limited to, formula (I-1), formula (I-2), and formula (I-3) , The structure shown in formula (I-4) or formula (I-5):

Wherein, X is the same or different, and each is independently selected from Br or Cl.

The present invention also provides a fluorine-containing α-diimine ligand compound. The fluorine-containing α-diimine ligand compound has a structure as shown in formula (II):

Wherein, R ^{1 is the} same or different, and each is independently selected from methyl, ethyl or isopropyl; R ^{2 is the} same or different, and each is independently selected from H or methyl.

The intermediate further solution provided by the present invention is: the fluorine-containing α-diimine ligand compound includes, but is not limited to, formula (II-1), formula (II-2), formula (II-3), formula The structure shown in (II-4) or formula (II-5):

The present invention also provides a 2-aniline acenaphthene compound containing two fluorine substituents, and the 2-aniline acenaphthene compound has a structure as shown in formula (III):

The present invention also provides an aniline compound containing two fluorine substituents and two benzhydryl substituents, and the aniline compound has a structure as shown in formula (IV):

The present invention also provides a method for preparing the fluorine-containing α-diimine nickel complex as described above, and the fluorine-containing α-diimine nickel complex is based on the fluorine-containing α-diimine ligand compound as described above. Prepared from intermediate raw materials;

It includes: formula (II), formula (II-1), formula (II-2), formula (II-3), formula (II-4) or formula (II-5) described fluorine-containing α- The diimine intermediate and the nickel-containing compound are mixed in a solvent at a molar ratio of 1 to 2:1, and reacted at 0 to 35°C for 8 to 24 hours to obtain a fluorine-containing α-diimine nickel complex;

Preferably, the nickel-containing compound is selected from nickel-containing halides, such as (DME)NiBr ₂ ;

Preferably, the molar ratio of the fluorine-containing α-diimine intermediate to the nickel-containing compound is 1 to 1.5:1, more preferably 1:1;

Preferably, the temperature of the reaction is 10-30°C, more preferably 20-25°C;

Preferably, the reaction time is 12-24 hours, more preferably 18-24 hours;

Preferably, the solvent is selected from one or more of halogenated alkanes and alcohol solvents, more preferably in dichloromethane and/or ethanol.

The present invention also provides a method for preparing the above-mentioned fluorine-containing α-diimine ligand compound. The fluorine-containing α-diimine ligand compound is the above-mentioned 2-aniline acenaphthylene compound containing two fluorine substituents. (Formula (III)) is prepared from intermediate raw materials:

It includes: taking the 2-aniline acenaphthylene ketone represented by the formula (III) and the compound represented by the formula (V) at a molar ratio of 1:1 to 2 and dissolving in a solvent, adding a catalyst and heating to reflux at a temperature of 120°C Condensation reaction is carried out for 12 to 18 hours to obtain a fluorine-containing α-diimine ligand compound as shown in formula (II);

Preferably, the catalyst is selected from p-toluenesulfonic acid, and the solvent is selected from aromatic hydrocarbon reagents, preferably toluene;

Preferably, the molar ratio of the 2-anilineacenaphthylene ketone represented by the formula (III) to the compound represented by the formula (V) is 1:1, and the condensation reaction time is 12 to 16 hours;

The structure of the formula (V) is as follows:

Wherein, R ¹ and R ² have the definitions as described above.

The preparation method also includes the purification of the fluorine-containing α-diimine ligand compound, which specifically includes:

(a) Dissolving the compound represented by formula (II) in dichloromethane;

(b) Use basic alumina for support, basic alumina column for column chromatography, and use a mixed solvent of petroleum ether and ethyl acetate (the volume ratio of petroleum ether and ethyl acetate is preferably 5:1) as the leaching The lotion is eluted, the eluted fraction is detected by thin-layer chromatography, and the third fraction is collected;

(c) The solvent is removed to obtain a purified compound represented by formula (II).

The present invention also provides a preparation method of the 2-aniline acenaphthene compound containing two fluorine substituents as described above, wherein the 2-aniline acenaphthene compound containing two fluorine substituents (formula (III)) is based on The aniline compound (formula (IV)) containing two fluorine substituents and two benzhydryl substituents is prepared as a raw material as described above;

It includes:

(1) Take 3,4-difluoroaniline represented by formula (VII) and benzhydrol represented by formula (VIII) at a molar ratio of 1:2, and dissolve them _{in hydrochloric acid containing ZnCl 2} at a temperature of 140°C Carry out the substitution reaction for 6 to 8 hours to obtain the 2,6-diphenylmethyl-3,4-difluoroaniline compound represented by formula (IV);

(2) Take the acenaphthylene dione represented by the formula (VI) and the 2,6-dibenzyl-3,4 represented by the formula (IV) prepared in step (1) at a molar ratio of 1:1～2 -The difluoroaniline compound is dissolved in a solvent, and a catalyst is added to carry out a substitution reaction for 10 to 16 hours at room temperature to obtain 2-anilineacenaphthenone as shown in formula (III);

Preferably, the catalyst in step (2) is selected from p-toluenesulfonic acid, and the solvent is selected from aromatic hydrocarbon reagents, preferably toluene;

Preferably, in the step (2), the molar ratio of the acenaphthylene dione represented by the formula (VI) to the aniline represented by the formula (IV) is 1:1, and the substitution reaction time is 12 to 14 hours;

The structures of the formula (VI), formula (VII) and formula (VIII) are as follows:

The preparation method also includes the purification of the 2-aniline acenaphthene represented by formula (III), which specifically includes:

(a') Dissolving the 2-aniline acenaphthylene ketone represented by the formula (III) in dichloromethane;

(b') Use basic alumina for support, alumina for column chromatography, and use a mixed solvent of petroleum ether and ethyl acetate (the volume ratio of petroleum ether and ethyl acetate is preferably 5:1) as the eluent Perform elution, and detect the eluted fraction by thin-layer chromatography (the developing solvent is a mixed solvent with a volume ratio of petroleum ether and ethyl acetate of 5:2, and the third fraction is collected);

(c') The solvent is removed to obtain the purified 2-aniline acenaphthlene represented by the formula (III).

Purification of the 2,6-dibenzyl-3,4-difluoroaniline compound prepared in step (1), the specific purification process is the same as the above steps (a′), (b′) and (c′) .

The present invention also provides a catalyst. The catalyst may include only a main catalyst or a main catalyst and a co-catalyst. The main catalyst is selected from the fluorine-containing α-diimine nickel complexes as described above. The co-catalyst is selected from one or more of aluminoxane, aluminum alkyl or aluminum alkyl chloride; when the catalyst includes both a main catalyst and a co-catalyst, the Al in the co-catalyst and Ni in the main catalyst The molar ratio of is 200-3500:1, preferably 400-3000:1, for example, it may preferably be 300:1, 400:1, 2000:1, 2500:1, 3000:1 or 3500:1.

Preferably, the aluminoxane is selected from one or two of methylaluminoxane (MAO) or triisobutylaluminum modified methylaluminoxane (MMAO), more preferably triisobutyl Aluminum modified methyl aluminoxane (MMAO);

Preferably, the alkyl aluminum chloride is selected from dimethyl aluminum chloride (Me ₂ AlCl) and/or sesquiethyl aluminum chloride (EASC), more preferably dimethyl aluminum chloride (Me ₂ AlCl) );

Preferably, when the co-catalyst is methylaluminoxane, the molar ratio of Al in the co-catalyst to Ni in the main catalyst is 1000-4000:1, more preferably 2000:1;

Preferably, when the co-catalyst is sesquiethyl aluminum chloride, the molar ratio of Al in the co-catalyst to Ni in the main catalyst is 100-1000:1, more preferably 500:1;

Preferably, when the co-catalyst is methylaluminoxane modified with triisobutyl aluminum, the molar ratio of Al in the co-catalyst to Ni in the main catalyst is 1000-4000:1, more preferably 1500-3500: 1. For example, it may preferably be 1500:1, 2000:1, 2500:1, 2750:1, 3000:1, 3250:1 or 3500:1;

Preferably, the co-catalyst is dimethyl aluminum chloride, and the molar ratio of Al in the co-catalyst to Ni in the main catalyst is 100-1000:1, more preferably 200-700:1, for example, 200: 1. 300:1, 400:1, 500:1, 600:1 or 700:1.

In the above scheme, when the co-catalyst is selected as the triisobutyl aluminum modified methylaluminoxane MMAO, the molecular weight distribution index of the obtained polyethylene elastomer is mostly between 1.5 and 1.7, which was previously studied by the inventor. The polyethylene elastomer catalyzed by α-diimine nickel complex (as shown in formula 1 or formula 2) and MMAO have a wide molecular weight distribution, which increases the number of molecules per unit volume and the number of chain ends. The strength of the elastomer is lower than that of the elastomer provided by the present invention.

The present invention also provides a method for preparing polyethylene. The preparation method includes: dissolving the catalyst, which may include only the main catalyst or the main catalyst and the promoter as described above, in a solvent, and the temperature is raised to 20-60 Pass in ethylene raw material after ℃, and carry out polymerization reaction for 5～120min under the pressure of 1～10atm;

Preferably, the solvent for the polymerization reaction is selected from one or more of toluene, dichloromethane, ethanol, tetrahydrofuran, hexane or cyclohexane, more preferably toluene;

Preferably, the polymerization reaction is carried out under an ethylene atmosphere.

In the above scheme, at 30℃ close to room temperature, the activity of the nickel complex to catalyze the polymerization of ethylene can be as high as 5.9×10 ⁶ g·mol ^-1 (Ni)·h ^-1 , and the weight average molecular weight of the prepared polyethylene is M _w fluctuates between 1.03～11.42×10 ⁵ g·mol ^-1 , showing extremely strong control performance on the molecular weight of polyethylene; and the reaction at a lower temperature further illustrates that the nickel complex provided by the present invention has a relatively high High catalytic efficiency.

In the above scheme, the melting temperature of the prepared polyethylene is between 32.8 and 94.5°C, indicating that the polyethylene elastomer material obtained by this type of catalyst has a wide temperature range of application. Moreover, the polyethylene prepared by the present invention is a polyethylene elastomer material with a higher degree of branching and better mechanical properties. In some embodiments of the present invention, the polyethylene elastomer material is supported at 50°C. The degree of conversion is 191 branches per 1000 carbons, and the tensile strain of the sample after lamination can be as high as 2592.67%, which has extremely high industrial application potential.

The above-mentioned catalyst provided by the present invention can be used in olefin polymerization reactions to produce olefin elastomers with higher degree of branching and good tensile properties.

After adopting the above technical solution, the present invention has the following beneficial effects compared with the prior art:

1. The present invention provides fluorine-containing α-diimine nickel complexes and intermediates thereof. This type of nickel complex has a single catalytic active center, can adjust the molecular weight of the polymer by changing the ligand structure and polymerization conditions, and has the advantages of high catalytic activity, low cost, stable performance and the like.

2. The present invention also provides a method for preparing the fluorine-containing α-diimine nickel complex and its intermediates. The two preparation methods have the advantages of mild reaction conditions, short cycle, simple operating conditions and the like.

3. The present invention also provides the use of the fluorine-containing α-diimine nickel complex. Its purpose is to be used as a catalyst to catalyze the polymerization of ethylene, and it exhibits very good catalytic activity during the reaction. While obtaining a polyethylene elastomer with a narrow molecular weight distribution, it also increases the degree of branching of the elastomer material, so that the elastomer is pressed into the film. The tensile properties of this type of polyethylene elastomer have been greatly improved. This type of polyethylene elastomer material with good tensile strength, elongation at break and elastic recovery has thermoplastic elastomer properties and has great industrial application potential.

The specific embodiments of the present invention will be described in further detail below in conjunction with the accompanying drawings.

Description of the drawings

The accompanying drawings are used as a part of the present invention to provide a further understanding of the present invention. The exemplary embodiments of the present invention and the description thereof are used to explain the present invention, but do not constitute an improper limitation of the present invention. Obviously, the drawings in the following description are only some embodiments. For those of ordinary skill in the art, other drawings can be obtained based on these drawings without creative work. In the attached picture:

Figure 1 is a schematic diagram of the crystal structure of the nickel complex represented by formula (I-2) of the present invention;

Figure 2 is a schematic diagram of the crystal structure of the nickel complex represented by formula (I-5) of the present invention;

Figure 3 is a temperature-rising nuclear magnetic carbon spectrogram of the polymer prepared by e in Example 13 of the present invention;

Figure 4 is a temperature-rising nuclear magnetic carbon spectrum of the polymer prepared in d in Example 18 of the present invention;

Figure 5 is a temperature-rising nuclear magnetic carbon spectrogram of the polymer prepared by i in Example 18 of the present invention;

Fig. 6 is a fracture drawing of the polymer prepared by i in Example 18 of the present invention;

Fig. 7 is a stress-strain curve diagram of the polymer prepared by i in Example 18 of the present invention at -10°C and 30°C.

It should be noted that these drawings and text descriptions are not intended to limit the scope of the present invention in any way, but to explain the concept of the present invention for those skilled in the art by referring to specific embodiments.

Detailed ways

In order to make the objectives, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments will be described clearly and completely in conjunction with the accompanying drawings in the embodiments of the present invention. The following embodiments are used to illustrate the present invention. , But not used to limit the scope of the present invention.

Unless otherwise specified, the experimental methods used in the following examples are all conventional methods.

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

Unless otherwise specified, the concentrations in the following examples are molar concentrations.

The molecular weight and molecular weight distribution of the polymer obtained in the following ethylene polymerization examples are measured according to the conventional high temperature GPC method, and the melting point is measured according to the conventional DSC method. The polymerization activity of the polymer is calculated according to the following formula. Obtained: polymerization activity = polymer output/(catalyst amount x polymerization time). The calculation method of branching degree refers to the literature (Macromolecules, 1999, 32, 1620-1625; Polym., J. 1984, 16, 731-738).

All the following synthesized compounds have been confirmed by nuclear magnetic, infrared and elemental analysis.

As a preferred embodiment, the synthesis of the complexes in the following examples is carried out according to the following reaction equation:

Example 1

In this example, 2-(2,6-bis(benzyl)-3,4-difluoroaniline)acenaphthenone represented by formula (V) was prepared.

In 2,6-bis(benzyl)-3,4-difluoroaniline (4.61g, 10.0mmol) and acenaphthenedione (1.82g, 10.0mmol) in dichloromethane (150mL) and ethanol (30mL) A catalyst amount (0.57g) of p-toluenesulfonic acid was added to the mixed solution, and the reaction was carried out at room temperature for 12h. The solvent is removed, and the residue is subjected to basic alumina column chromatography with a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 5:1, and the elution fraction is detected through a thin-layer silica gel plate. The developing solvent is petroleum ether and ethyl acetate. The volume ratio of the ester is a mixed solvent of 5:1, the third fraction is collected, and the solvent is removed to obtain a yellow solid. Yield: 49%.

The structure confirmation data is as follows:

¹ H NMR (400MHz, CDCl ₃ , TMS): δ 7.98 (d, J = 8.0 Hz, 2H), 7.71 (d, J = 9.6 Hz, 2H), 7.15 (d, J = 8.2 Hz, 7H), 7.05 (t, J = 8.4 Hz, 5H), 6.93 (d, J = 7.2 Hz, 4H), 6.90 (d, J = 8.4 Hz, 2H), 6.82 (d, J = 10.4 Hz, 2H), 6.62 ( d, J = 8.2, 2H), 6.59-6.47 (m, 1H), 5.84 (d, J = 8.0 Hz, 2H), 5.4 (s, 2H).

¹³ C NMR (100MHz, CDCl ₃ , TMS): δ 189.4, 163.9, 149.5, 146.9, 144.9, 142.6, 142.5, 142.0, 139.9, 132.0, 129.5, 129.3, 128.6, 128.4, 128.0, 127.6, 127.1, 126.7, 126.3, 126.1, 125.7, 123.9, 122.0, 121.9, 121.8, 117.2, 117.0, 51.9, 49.7.

FT-IR(cm ^-1 ): 3657(w), 3059(w), 3027(w), 1956(m), 1723(vs), 1649(s), 1594(s), 1475(s), 1448 (w), 1418(w), 1271(m), 1179(m), 1073(w), 1027(m), 1005(m), 935(m), 886(s), 862(m), 761 (m).

¹⁹ F NMR (470MHz, CDCl ₃ ): δ-134.9, -141.9.

Elemental analysis: C ₄₄ H ₂₉ F ₂ NO (625.72). Theoretical value: C, 84.46; H, 4.67; N, 2.24. Experimental value: C, 84.61; H, 4.55; N, 2.08.

Example 2

In this example, the α-diimine intermediate represented by formula (II) was prepared: 1-(2,6-dimethylaniline)-2-(2,6-bis(benzyl)-3 ,4-Difluoroaniline)acenaphthene [L1], wherein R ¹ is methyl and R ² is hydrogen.

Take the 2-(2,6-bis(benzyl)-3,4-difluoroaniline)acenaphthene (0.625g, 1.0mmol) and 2,6-dimethylaniline (0.111 g, 1.0 mmol) in toluene solution (50 mL) was added with a catalytic amount of p-toluenesulfonic acid, and heated to reflux for 12 h. The solvent toluene was removed, and the residue was subjected to basic alumina column chromatography with a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 5:1. The eluted fraction was detected by a thin-layer silica gel plate, the third fraction was collected, and the solvent was removed to obtain a red solid. Yield: 17%.

The structure confirmation data is as follows:

¹ H NMR (400MHz, CDCl ₃ , TMS): δ 7.69 (d, J = 11.2 Hz, 1H), 7.49 (d, J = 10.8 Hz, 1H), 7.28 (s, 1H), 7.20 (d, J = 10.0 Hz, 3H), 7.17 (d, J = 8.4 Hz, 5H), 7.10 (t, J = 10.2 Hz, 6H), 7.02 (d, J = 9.6 Hz, 2H), 6.89 (t, J = 9.6 Hz, 3H), 6.86 (d, J = 10.4 Hz, 1H), 6.56-6.51 (m, 5H), 6.43 (t, J = 9.6 Hz, 1H), 6.30 (t, J = 10.0 Hz, 1H), 5.77(d, J=9.6Hz, 1H), 5.65(s, 1H), 5.63(s, 1H), 2.26(s, 3H), 2.21(s, 3H).

¹³ C NMR (100MHz, CDCl ₃ , TMS): δ 165.2, 161.4, 149.0, 145.7, 142.7, 142.3, 140.6, 140.1, 139.9, 129.7, 129.6, 129.4, 128.8, 128.7, 128.4, 128.4, 128.2, 128.1, 128.1, 127.9, 127.8, 127.5, 126.8, 126.5, 126.1, 125.6, 124.7, 124.6, 124.1, 123.9, 122.4, 122.3, 121.8, 118.1, 117.1, 116.9, 51.9, 50.0, 18.1, 17.6.

¹⁹ F NMR (470MHz, CDCl ₃ ): δ-135.1, -142.7.

FT-IR (cm ^-1 ): 3344 (m), 3059 (w), 3023 (m), 1663 (v _{C = N} , s), 1635 (v _{C = N} , s), 1594 (s), 1474 (vs), 1445(m), 1418(w), 1321(m), 1274(s), 1223(s), 1081(w), 1030(m), 1003(w), 940(m), 916 (w), 860(w), 829(w), 762(vs), 698(vs).

Elemental analysis: C ₅₂ H ₃₈ F ₂ N ₂ (728.89) Theoretical value: C, 85.69; H, 5.26; N, 3.84. Experimental value: C, 85.35; H, 5.38; N, 4.10.

Example 3

In this example, the α-diimine intermediate represented by formula (II) was prepared: 1-(2,6-diethylaniline)-2-(2,6-bis(benzyl)-3 ,4-Difluoroaniline)acenaphthene [L2], wherein R ¹ is ethyl and R ² is hydrogen.

Take the 2-(2,6-bis(benzyl)-4-methylaniline)acenaphthenone (0.625g, 1.0mmol) and 2,6-diethylaniline (0.149g, A catalytic amount of p-toluenesulfonic acid was added to a 1.0 mmol) toluene (50 mL) solution, and the mixture was heated to reflux for 12 hours. The solvent toluene was removed, and the residue was subjected to basic alumina column chromatography with a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 5:1. The eluted fraction was detected by a thin-layer silica gel plate, the third fraction was collected, and the solvent was removed to obtain a yellow solid. Yield: 13%.

The structure confirmation data is as follows:

¹ H NMR (400MHz, CDCl ₃ , TMS): δ 7.65 (d, J = 11.2 Hz, 1H), 7.45 (d, J = 11.2 Hz, 1H), 7.27 (s, 2H), 7.20 (d, J = 6.0Hz, 8H), 7.08 (t, J = 11.0Hz, 4H), 6.97 (d, J = 10.4Hz, 2H) 6.90 (d, J = 30.2Hz, 3H), 6.84 (t, J = 11.8Hz , 1H), 6.61-6.39(m, 6H), 6.29(t, J=10.0Hz, 1H), 5.72(d, J=9.2Hz, 1H), 5.65(s, 1H), 5.62(s, 1H) , 2.72-2.61 (m, 2H), 2.58-2.48 (m, 2H), 1.19 (t, J=10.4Hz, 3H), 1.11 (t, J=10.0Hz, 3H).

¹³ C NMR (100MHz, CDCl ₃ , TMS): δ 161.5, 148.1, 142.5, 140.5, 140.1, 139.9, 130.6, 130.5, 129.6, 129.6, 129.4, 128.7, 128.4, 128.3, 128.1, 127.9, 127.8, 127.2, 126.8, 126.5, 126.4, 126.2, 126.1, 126.0, 125.7, 124.2, 124.1, 122.4, 117.4, 51.8, 50.0, 24.7, 24.5, 14.4, 14.3.

¹⁹ F NMR (470MHz, CDCl ₃ ): δ-135.7, -139.4.

FT-IR (cm ^-1 ): 3667 (m), 2971 (s), 2904 (w), 1669 (v _{C = N} , m), 1640 (v _{C = N} , m), 1595 (s), 1472 (s), 1449(m), 1412(m), 1317(w), 1225(m), 1071(s), 948(m), 862(w), 829(s), 760(s), 698 (vs).

Elemental analysis: C ₅₄ H ₄₂ F ₂ N ₂ (756.94) Theoretical value: C, 85.69; H, 5.59; N, 3.70. Experimental value: C, 85.72; H, 5.65; N, 3.75.

Example 4

In this example, the α-diimine intermediate represented by formula (II) was prepared: 1-(2,6-diisopropylaniline)-2-(2,6-bis(benzyl)- 3,4-Difluoroaniline)acenaphthene [L3], wherein R ¹ is diisopropyl and R ² is hydrogen.

Take the 2-(2,6-bis(diphenylmethyl)-4-methylaniline)acenaphthene (0.625g, 1.0mmol) and 2,6-diisopropylaniline (0.177g) prepared in Example 1. , 1.0mmol) in toluene (50mL) solution was added with a catalytic amount of p-toluenesulfonic acid, and heated to reflux for 12h. The solvent toluene was removed, and the residue was subjected to basic alumina column chromatography with a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 5:1. The eluted fraction was detected by a thin-layer silica gel plate, the third fraction was collected, and the solvent was removed to obtain a yellow solid. Yield: 30%.

The structure confirmation data is as follows:

¹ H NMR (400MHz, CDCl ₃ , TMS): δ 7.62 (d, J = 8.0 Hz, 1H), 7.41 (d, J = 8.0 Hz, 1H), 7.20 (d, J = 8.0 Hz, 3H), 7.18-7.14 (m, 8H), 7.07 (dd, J = 8.0, 4.0 Hz, 4H), 6.95 (d, J = 8.0 Hz, 2H), 6.87 (t, J = 8.0 Hz, 3H), 6.76 (t , J=8.0Hz, 1H), 6.52-6.39(m, 5H), 6.27(t, J=8.0Hz, 1H), 5.66(d, J=8.0Hz, 1H), 5.64(s, 1H), 5.61 (s, 1H), 3.18-3.08 (m, 2H), 1.27 (d, J = 8.0 Hz, 3H), 1.22 (d, J = 8.0 Hz, 3H), 1.02 (d, J = 8.0 Hz, 3H) , 0.95 (d, J=8.0Hz, 3H).

¹³ C NMR (100MHz, CDCl ₃ , TMS): δ 165.3, 162.0, 146.9, 145.8, 142.9, 142.6, 140.5, 140.1, 139.9, 135.6, 135.5, 129.6, 129.5, 129.4, 129.3, 128.8, 128.7, 128.3, 128.1, 128.0, 127.9, 126.9, 126.8, 126.5, 126.1, 126.0, 125.7, 124.7, 124.1, 123.6, 123.5, 122.9, 122.5, 122.4, 117.1, 116.9, 51.8, 50.0, 28.6, 24.0, 23.6, 23.5.

¹⁹ F NMR (470MHz, CDCl ₃ ): δ-134.7, -142.6.

FT-IR(cm ^-1 ): 3676(s), 2980(vs), 2901(s), 2376(w), 2043(w), 1663(v _C=N ,w), 1595(v _C=N , M), 1581(w), 1473(m), 1401(s), 1249(m), 1057(s), 889(m), 763(w), 697(s).

Elemental analysis: C ₅₆ H ₄₆ F ₂ N ₂ (784.99) Theoretical value: C, 85.68; H, 5.91; N, 3.57. Experimental value: C, 85.46; H, 5.89; N, 3.60.

Example 5

In this embodiment, the α-diimine intermediate represented by formula (II) is prepared: 1-(2,4,6-trimethylaniline)-2-(2,6-bis(benzyl) -3,4-Difluoroaniline)acenaphthene [L4], wherein R ¹ is a methyl group and R ² is a methyl group.

Take the 2-(2,6-bis(benzyl)-4-methylaniline)acenaphthenone (0.625g, 1.0mmol) and 2,4,6-trimethylaniline (0.187 g, 1.0 mmol) in toluene (50 mL) was added with a catalytic amount of p-toluenesulfonic acid, and heated to reflux for 12 h. The solvent toluene was removed, and the residue was subjected to basic alumina column chromatography with a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 5:1. The eluted fraction was detected by a thin-layer silica gel plate, the third fraction was collected, and the solvent was removed to obtain a red solid. Yield: 18%.

The structure confirmation data is as follows:

¹ H NMR (400MHz, CDCl ₃ , TMS): δ 7.49 (d, J = 8.0 Hz, 1H), 7.25 (d, J = 8.0 Hz, 1H), 7.22 (t, J = 8.0 Hz, 3H), 7.16 (d, J = 8.0 Hz, 2H), 7.10 (t, J = 8.0 Hz, 1H), 7.00 (d, J = 10.2 Hz, 4H), 6.90 (d, J = 8.0, 4.0 Hz, 4H), 6.85(t, J=8.0Hz, 4H), 6.76(s, 2H), 6.60(d, J=8.0Hz, 1H), 6.57-6.49(m, 3H), 6.44(t, J=6.0Hz, 1H ), 6.31(t, J=6.0Hz, 1H), 5.79(d, J=4.0Hz, 1H), 5.65(s, 1H), 5.63(s, 1H), 2.39(s, 3H), 2.15(s , 6H).

¹³ C NMR (101MHz, CDCl ₃ , TMS): δ 165.3, 161.5, 146.5, 145.8, 142.8, 142.4, 140.6, 140.2, 140.0, 139.9, 133.1, 129.6, 129.4, 129.1, 129.1, 128.8, 128.7, 128.6, 128.5, 128.3, 128.2, 128.0, 127.9, 127.8, 127.5, 127.1, 126.8, 126.7, 126.5, 126.0, 125.6, 124.5, 124.4, 124.0, 122.4, 122.3, 121.8, 121.8, 117.1, 116.9, 51.9, 50.0, 20.9, 17.5.

¹⁹ F NMR (470MHz, CDCl ₃ ): δ-135.1, -142.8.

FT-IR(cm ^-1 ): 3728(m), 3687(w), 2980(s), 2901(s), 2374(m), 1724(v _C=N , m), 1649(v _C=N , M), 1482(s), 1446(m), 1412(w), 1274(w), 1229(vs), 1072(m), 857(m), 741(w), 697(vs).

Elemental analysis: C ₅₃ H ₄₀ F ₂ N ₂ (742.91) Theoretical value: C, 85.69; H, 5.43; N, 3.77. Experimental value: C, 85.30; H, 5.51; N, 3.81.

Example 6

In this example, the α-diimine intermediate represented by formula (II) was prepared: 1-(2,6-diethyl-4-methylaniline)-2-(2,6-bis(diphenyl) (Methyl)-3,4-difluoroaniline)acenaphthylene [L5], wherein R ¹ is ethyl and R ² is methyl.

Take the 2-(2,6-bis(benzyl)-4-methylaniline)acenaphthene (0.625g, 1.0mmol) and 2,6-diethyl-4-methyl prepared in Example 1 A catalytic amount of p-toluenesulfonic acid was added to a toluene (50 mL) solution of aniline (0.163 g, 1.0 mmol), and the mixture was heated to reflux for 12 h. The solvent toluene was removed, and the residue was subjected to basic alumina column chromatography with a mixed solvent of petroleum ether and ethyl acetate in a volume ratio of 25:1. The eluted fraction was detected by a thin-layer silica gel plate, the third fraction was collected, and the solvent was removed to obtain a red solid. Yield: 26%.

The structure confirmation data is as follows:

¹ H NMR (400MHz, CDCl ₃ , TMS): δ 7.66 (d, J = 12.0 Hz, 1H), 7.47 (d, J = 8.0 Hz, 1H), 7.28 (d, J = 8.0 Hz, 3H), 7.21 (d, J = 8.0 Hz, 4H), 7.17 (d, J = 4.2 Hz, 1H), 7.10 (dd, J = 8.0, 4.0 Hz, 4H), 7.03 (dd, J = 8.0, 4.0 Hz, 4H) ), 6.91 (d, J = 8.0 Hz, 3H), 6.82 (t, J = 8.0 Hz, 1H), 6.59 (dd, J = 8.0, 8.0 Hz, 2H), 6.53 (t, J = 8.0 Hz, 4H ), 6.44 (t, J = 8.0 Hz, 2H), 6.30 (t, J = 8.0 Hz, 1H), 5.74 (d, J = 4.0 Hz, 1H), 5.66 (s, 1H), 5.64 (s, 1H) ), 2.67-2.58 (m, 2H), 2.53-2.43 (m, 2H), 1.19 (t, J = 8.0 Hz, 3H), 1.11 (t, J = 8.0 Hz, 3H).

¹³ C NMR (100MHz, CDCl ₃ , TMS): δ 165.3, 161.7, 145.6, 142.9, 141.8, 140.5, 140.3, 139.9, 138.9, 133.4, 130.4, 129.6, 129.4, 129.3, 128.8, 128.7, 128.6, 128.5, 128.3, 128.1, 127.9, 127.8, 127.2, 127.0, 126.8, 126.8, 126.7, 126.5, 126.1, 126.0, 125.7, 124.0, 122.4, 117.1, 51.8, 50.0, 24.3, 21.2, 14.6, 13.2.

FT-IR (cm ^-1 ): 3720 (w), 2963 (m), 2039 (w), 1663 (v _{C = N} , m), 1636 (v _{C = N} , m), 1595 (s), 1471 (vs), 1449(m), 1415(m), 1319(w), 1270(w), 1222(s), 1153(m), 1073(s), 1035(m), 1001(m), 937 (m), 914(w), 857(s), 826(vs), 768(s), 746(s), 696(vs).

Elemental analysis: C ₅₅ H ₄₄ F ₂ N ₂ (770.97) Theoretical value: C, 85.69; H, 5.75; N, 3.63. Experimental value: C, 85.30; H, 5.58; N, 3.78.

Example 7

In this example, the α-diimine nickel complex represented by formula (I) was prepared: [1-(2,6-dimethylaniline)-2-(2,6-bis(benzyl) -3,4-Difluoroaniline)acenaphthylene] nickel(II) bromide [complex C1], wherein R ¹ is methyl, R ² is hydrogen, and X is bromine.

At room temperature, mix (DME)NiBr ₂ (0.030g, 0.10mmol) and 1-(2,6-dimethylaniline)-2-(2,6-bis(benzyl) prepared in Example 2) -3,4-Difluoroaniline)acenaphthene (0.079g, 0.10mmol) was mixed and dissolved in dichloromethane, stirred for 24h under nitrogen protection, dichloromethane was removed under reduced pressure, and ether was added to precipitate a brown solid, filtered, and washed with ether , Dried to obtain a brown solid. Yield: 66%.

The structure confirmation data is as follows:

FT-IR (cm ^-1 ): 3025 (w), 1649 (v _{C = N} , m), 1628 (v _{C = N} , w), 1583 (m), 1494 (vs), 1473 (m), 1416 (m), 1322(w), 1292(w), 1225(m), 1191(m), 1075(m), 1032(m), 1000(m), 959(s), 923(m), 863 (m), 828(m), 771(s), 698(vs).

Elemental analysis: C ₅₂ H ₃₈ Br ₂ F ₂ N ₂ Ni (947.39). Theoretical value: C, 57.13; H, 4.02; N, 2.43. Experimental value: C, 57.24; H, 4.42; N, 2.88.

Example 8

In this example, the α-diimine nickel complex represented by formula (I) was prepared: [1-(2,6-diethylaniline)-2-(2,6-bis(benzyl) -3,4-Difluoroaniline)acenaphthylene] nickel(II) bromide [complex C2], wherein R ¹ is ethyl, R ² is hydrogen, and X is bromine.

At room temperature, mix (DME)NiBr ₂ (0.030g, 0.1mmol) and 1-(2,6-diethylaniline)-2-(2,6-bis(benzyl) prepared in Example 3) -3,4-Difluoroaniline)acenaphthene (0.076g, 0.10mmol) was mixed and dissolved in dichloromethane, stirred for 16h under nitrogen protection, dichloromethane was removed under reduced pressure, and ether was added to precipitate a brown solid, filtered, and washed with ether , Dried to obtain a brown solid. Yield: 73%.

The structure confirmation data is as follows:

FT-IR (cm ^-1 ): 2969 (w), 1644 (v _{C = N} , m), 1620 (v _{C = N} , w), 1579 (m), 1474 (s), 1447 (m), 1415 (m), 1322(m), 1292(m), 1224(w), 1183(m), 1074(m), 1000(m), 960(w), 864(m), 826(m), 768 (s), 697(vs).

Elemental analysis: C ₅₄ H ₄₂ Br ₂ F ₂ N ₂ Ni (972.10). Theoretical value: C, 66.49; H, 4.34; N, 2.87. Experimental value: C, 66.59; H, 4.54; N, 2.88.

Example 9

In this example, the α-diimine nickel complex represented by the formula (I) was prepared: [1-(2,6-diisopropylaniline)-2-(2,6-bis(diphenylmethyl) )-3,4-Difluoroaniline)acenaphthylene] nickel(II) bromide [complex C3], wherein R ¹ is isopropyl, R ² is hydrogen, and X is bromine.

At room temperature, (DME)NiBr ₂ (0.030g, 0.1mmol) and 1-(2,6-diisopropylaniline)-2-(2,6-bis(diphenylmethyl) prepared in Example 4 )-3,4-Difluoroaniline)acenaphthene (0.079g, 0.10mmol) was dissolved in dichloromethane and stirred for 16h under nitrogen protection. After the dichloromethane was removed under reduced pressure, a brown solid precipitated after the addition of diethyl ether. Filtered, diethyl ether After washing and drying, a brown solid was obtained. Yield: 65%.

The structure confirmation data is as follows:

FT-IR (cm ^-1 ): 2968 (s), 2901 (w), 2374 (w), 2044 (w), 1668 (v _{C = N} , w), 1644 (v _{C = N} , m), 1597 (s), 1474(s), 1416(w), 1323(w), 1290(w), 1226(w), 1073(w), 1003(m), 936(m), 829(s), 761 (s), 698(vs).

Elemental analysis: C ₅₆ H ₄₆ Br ₂ F ₂ N ₂ Ni (1003.50): Theoretical value: C, 67.03; H, 4.62; N, 2.79. Experimental value: C, 67.21; H, 4.86; N, 2.81.

Example 10

In this example, the α-diimine nickel complex represented by formula (I) was prepared: [1-(2,4,6-trimethylaniline)-2-(2,6-bis(diphenylmethyl) (Base)-3,4-difluoroaniline)acenaphthylene]nickel(II) bromide [complex C4], wherein R ¹ is methyl, R ² is methyl, and X is bromine.

At room temperature, (DME)NiBr ₂ (0.030g, 0.1mmol) and 1-(2,4,6-trimethylaniline)-2-(2,6-bis(diphenylmethyl) prepared in Example 5 Benzene)-3,4-difluoroaniline)acenaphthene (0.074g, 0.10mmol) was mixed and dissolved in dichloromethane and stirred for 16h under nitrogen protection. After the dichloromethane was removed under reduced pressure, a brown solid precipitated out after the addition of diethyl ether, which was filtered. Wash with ether and dry to obtain a brown solid. Yield: 60%.

The structure confirmation data is as follows:

FT-IR (cm ^-1 ): 3024 (w), 2984 (w), 2903 (w), 1643 (v _{C = N} , s), 1581 (v _{C = N} , vs), 1474 (s), 1448 (s), 1415(m), 1320(w), 1294(w), 1228(w), 1188(w), 1074(m), 1031(m), 1001(m), 961(m), 921 (m), 864(w), 827(m), 768(s), 697(vs).

Elemental analysis: C ₅₃ H ₄₀ Br ₂ F ₂ N ₂ Ni(961.42)+CH ₂ Cl ₂ Theoretical value: C, 61.99; H, 4.05; N, 2.68. Experimental value: C, 61.71; H, 4.18; N, 2.75.

Example 11

In this example, the α-diimine nickel complex represented by formula (I) was prepared: [1-(2,6-diethyl-4-methylaniline)-2-(2,6-bis( Diphenylmethyl)-3,4-difluoroaniline)acenaphthylene]nickel(II) bromide [complex C5], wherein R ¹ is ethyl, R ² is methyl, and X is bromine.

At room temperature, (DME)NiBr ₂ (0.030g, 0.1mmol) and 1-(2,6-diethyl-4-methylaniline)-2-(2,6-bis() prepared in Example 6 Diphenylmethyl)-3,4-difluoroaniline)acenaphthene (0.077g, 0.10mmol) was mixed and dissolved in dichloromethane and stirred for 16h under nitrogen protection. After dichloromethane was removed under reduced pressure, a brown solid was precipitated when diethyl ether was added. , Filtered, washed with ether, and dried to obtain a brown solid. Yield: 86%.

The structure confirmation data is as follows:

FT-IR(cm ^-1 ): 3025(w), 2962(w), 1651(v(C=N), w), 1622(v(C=N), m), 1583(m), 1494( m), 1452(s), 1363(w), 1293(m), 1261(w), 1186(m), 1075(w), 1048(w), 1032(m), 962(w), 897( m), 866(s).

Elemental analysis: C ₅₅ H ₄₄ Br ₂ F ₂ N ₂ Ni (989.47). Theoretical value: C, 66.76; H, 4.48; N, 2.83. Experimental value: C, 67.17; H, 4.60; N, 2.86.

Example 12

In this embodiment, the α-diimine nickel complex represented by formula (II-1) is used as the main catalyst, and methylaluminoxane (MAO) is used as the co-catalyst, and the ethylene polymerization reaction is carried out under a 10atm environment:

In an ethylene atmosphere, add 20 mL of toluene, 30 mL of toluene solution of catalyst C1 (2 μmol), 2.7 mL of co-catalyst MAO (1.46 mol/L toluene solution), and 50 mL of toluene into a 250 mL stainless steel autoclave. At this time, Al/ Ni=2000:1. The mechanical stirring was started and kept at 400 rpm. When the polymerization temperature reached 30°C, the reactor was filled with ethylene, and the polymerization reaction started. Maintain an ethylene pressure of 10 atm at 30°C and stir for 30 minutes. The reaction solution was neutralized with an ethanol solution acidified with 5% hydrochloric acid to obtain a polymer precipitate, which was washed several times with ethanol, dried in a vacuum to a constant weight, and weighed.

Polymerization activity: 0.54×10 ⁶ g·mol ^-1 (Ni)·h ^-1 , polymer T _m =113.4°C. (T _m is the melting temperature of the polymer, measured by DSC), the molecular weight of the polymer M _w =4.67×10 ⁵ g·mol ^-1 , PDI=2.7 (M _w is the mass average molecular weight of the polymer, measured by GPC at elevated temperature Income).

Example 13

In this embodiment, the α-diimine nickel complex represented by formula (II-1) is used as the main catalyst, and methylaluminoxane (MMAO) modified with triisobutylaluminum is used as the co-catalyst. Undertake ethylene polymerization reaction:

(a) In an ethylene atmosphere, add 20 mL of toluene, 30 mL of the toluene solution of the main catalyst (2 μmol), 2.0 mL of the co-catalyst MMAO (2.00 mol/L toluene solution), and 50 mL of toluene into a 250 mL stainless steel autoclave. At this time, Al/Ni=2000:1. The mechanical stirring was started and kept at 400 rpm. When the polymerization temperature reached 30°C, the reactor was filled with ethylene, and the polymerization reaction started. Maintain an ethylene pressure of 10 atm at 30°C and stir for 30 minutes. The reaction solution was neutralized with an ethanol solution acidified with 5% hydrochloric acid to obtain a polymer precipitate, which was washed several times with ethanol, dried in a vacuum to a constant weight, and weighed.

Polymerization activity: 2.76×10 ⁶ g·mol ^-1 (Ni)·h ^-1 , polymer T _m =65.6°C. (T _m is the melting temperature of the polymer, measured by DSC), the molecular weight of the polymer M _w =5.23×10 ⁵ g·mol ^-1 , PDI = 1.6 (M _w is the mass average molecular weight of the polymer, measured by heating GPC Income).

(b) is basically the same as (a), except that the amount of the co-catalyst is 1.5 mL of co-catalyst MMAO (2.0 mol/L toluene solution), so that Al/Ni=1500:1. Polymerization activity: 1.47×10 ⁶ g·mol ^-1 (Ni)·h ^-1 , polymer T _m = 82.2° C., M _w =4.58×10 ⁵ g·mol ^-1 , PDI = 1.6.

(c) is basically the same as (a), except that the amount of the co-catalyst is 2.5 mL of co-catalyst MMAO (2.0 mol/L toluene solution), so that Al/Ni=2500:1. Polymerization activity: 3.06×10 ⁶ g·mol ^-1 (Ni)·h ^-1 , polymer T _m =89.7° C., M _w =9.39×10 ⁵ g·mol ^-1 , PDI=1.7.

(d) is basically the same as (a), except that the amount of the co-catalyst is 2.7 mL of co-catalyst MMAO (2.0 mol/L toluene solution), so that Al/Ni=2750:1. Polymerization activity: 3.74×10 ⁶ g·mol ^-1 (Ni)·h ^-1 , polymer T _m =61.3° C., M _w =3.46×10 ⁵ g·mol ^-1 , PDI=1.6.

(e) is basically the same as (a), except that the amount of the co-catalyst is 3.0 mL of the co-catalyst MMAO (2.0 mol/L toluene solution), so that Al/Ni=3000:1. Polymerization activity: 5.90×10 ⁶ g·mol ^-1 (Ni)·h ^-1 , polymer T _m =94.5° C., M _w =6.30×10 ⁵ g·mol ^-1 , PDI=1.7.

Take 100 mg of the polymer obtained in (e), dissolve it in 5 mL of deuterium tetrachloroethane, and test the ¹³ C data of the polymer at 30°C. The signal was accumulated for 2000 times, and the signal peak shift was between 20-40 (ppm), indicating the shift of methyl, methylene and methine groups, which proved that the polymer obtained was branched polyethylene (see Figure 3 for specific information) ). After calculation, the branching degree of this sample is 123 branches per 1000 carbons, containing 57% methyl branches.

(f) is basically the same as (a), except that the amount of the co-catalyst is 3.2 mL of co-catalyst MMAO (2.0 mol/L toluene solution), so that Al/Ni=3250:1. Polymerization activity: 4.13×10 ⁶ g·mol ^-1 (Ni)·h ^-1 , polymer T _m =58.8° C., M _w =3.06×10 ⁵ g·mol ^-1 , PDI=1.7.

(g) is basically the same as (a), except that the amount of the co-catalyst is 3.5 mL of co-catalyst MMAO (2.0 mol/L toluene solution), so that Al/Ni=3500:1. Polymerization activity: 3.25×10 ⁶ g·mol ^-1 (Ni)·h ^-1 , polymer T _m =70.8° C., M _w =4.58×10 ⁵ g·mol ^-1 , PDI=1.6.

(h) is basically the same as (e), except that the polymerization temperature is 20°C. Polymerization activity: 4.92×10 ⁶ g·mol ^-1 (Ni)·h ^-1 , polymer T _m =92.6° C., M _w =6.02×10 ⁵ g·mol ^-1 , PDI=1.9.

(i) is basically the same as (e), except that the polymerization temperature is 40°C. Polymerization activity: 3.43×10 ⁶ g·mol ^-1 (Ni)·h ^-1 , polymer T _m =51.9° C., M _w =2.62×10 ⁵ g·mol ^-1 , PDI=1.5.

(j) is basically the same as (e), except that the polymerization temperature is 50°C. Polymerization activity: 1.84×10 ⁶ g·mol ^-1 (Ni)·h ^-1 , polymer T _m =53.4° C., M _w =2.58×10 ⁵ g·mol ^-1 , PDI=1.5.

(k) is basically the same as (e), except that the polymerization temperature is 60°C. Polymerization activity: 1.25×10 ⁶ g·mol ^-1 (Ni)·h ^-1 , polymer T _m =57.0° C., M _w =2.55×10 ⁵ g·mol ^-1 , PDI=1.5.

(l) Basically the same as (e), except that the polymerization time is 5 min. Polymerization activity: 1.95×10 ⁶ g·mol ^-1 (Ni)·h ^-1 , polymer T _m = 68.4° C., M _w = 3.91×10 ⁵ g·mol ^-1 , PDI = 1.6.

(m) is basically the same as (e), except that the polymerization time is 15 minutes. Polymerization activity: 4.31×10 ⁶ g·mol ^-1 (Ni)·h ^-1 , polymer T _m =79.5° C., M _w =7.15×10 ⁵ g·mol ^-1 , PDI=1.6.

(n) is basically the same as (e), except that the polymerization time is 45 minutes. Polymerization activity: 4.85×10 ⁶ g·mol ^-1 (Ni)·h ^-1 , polymer T _m = 83.9° C., M _w =7.79×10 ⁵ g·mol ^-1 , PDI = 1.5.

(o) is basically the same as (e), except that the polymerization time is 60 minutes. Polymerization activity: 3.80×10 ⁶ g·mol ^-1 (Ni)·h ^-1 , polymer T _m = 64.9° C., M _w =4.06×10 ⁵ g·mol ^-1 , PDI = 1.6.

(p) is basically the same as (e), except that the polymerization pressure is 5 atm. Polymerization activity: 2.42×10 ⁶ g·mol ^-1 (Ni)·h ^-1 , polymer T _m =51.1° C., M _w =2.70×10 ⁵ g·mol ^-1 , PDI=1.5.

(q) is basically the same as (e), except that the polymerization pressure is 1 atm. Polymerization activity: 0.47×10 ⁶ g·mol ^-1 (Ni)·h ^-1 , polymer T _m = 32.8° C., M _w =1.03×10 ⁵ g·mol ^-1 , PDI = 1.5.

Example 14

In this embodiment, the α-diimide nickel complex represented by formula (II-2) is used as the main catalyst, and methylaluminoxane (MMAO) modified with triisobutylaluminum is used as the co-catalyst. Undertake ethylene polymerization reaction:

The process is basically the same as that in Example 13(e), except that the main catalyst is the α-diimine nickel complex described in formula (II-2). Polymerization activity: 3.07×10 ⁶ g·mol ^-1 (Ni)·h ^-1 , polymer T _m = 58.7° C., M _w = 3.80×10 ⁵ g·mol ^-1 , PDI = 1.7.

Example 15

In this embodiment, the α-diimine nickel complex represented by formula (II-3) is used as the main catalyst, and methylaluminoxane (MMAO) modified with triisobutylaluminum is used as the co-catalyst. Undertake ethylene polymerization reaction:

The process is basically the same as in Example 13(e), except that the main catalyst is the α-diimine nickel complex described in formula (II-3). Polymerization activity: 1.70×10 ⁶ g·mol ^-1 (Ni)·h ^-1 , polymer T _m = 82.6° C., M _w = 11.42×10 ⁵ g·mol ^-1 , PDI = 1.9.

Example 16

In this embodiment, the α-diimine nickel complex represented by formula (II-4) is used as the main catalyst, and methylaluminoxane (MMAO) modified with triisobutylaluminum is used as the co-catalyst. Undertake ethylene polymerization reaction:

The process is basically the same as in Example 13(e), except that the main catalyst is the α-diimine nickel complex described in formula (II-4). Polymerization activity: 3.92×10 ⁶ g·mol ^-1 (Ni)·h ^-1 , polymer T _m =56.3° C., M _w =2.55×10 ⁵ g·mol ^-1 , PDI=1.5.

Example 17

In this embodiment, the α-diimide nickel complex represented by formula (II-5) is used as the main catalyst, and methylaluminoxane (MMAO) modified with triisobutylaluminum is used as the co-catalyst. Undertake ethylene polymerization reaction:

The process is basically the same as that of Example 13(e), except that the main catalyst is the α-diimine nickel complex described in formula (II-5). Polymerization activity: 3.24×10 ⁶ g·mol ^-1 (Ni)·h ^-1 , polymer T _m =57.7° C., M _w =4.53×10 ⁵ g·mol ^-1 , PDI=1.4.

Example 18

In this embodiment, the α-diimine nickel complex represented by formula (II-1) is used as the main catalyst, and dimethyl aluminum chloride (Me ₂ AlCl) is used as the co-catalyst, and the ethylene polymerization reaction is carried out in a pressurized environment. :

(a) In an ethylene atmosphere, add 20 mL of toluene, 30 mL of the toluene solution of the main catalyst (2 μmol), 1.2 mL of the promoter Me ₂ AlCl (1.17 mol/L toluene solution), and 50 mL of toluene into a 250 mL stainless steel autoclave. . At this time, Al/Ni=500:1. The mechanical stirring was started and kept at 400 rpm. When the polymerization temperature reached 30°C, the reactor was filled with ethylene, and the polymerization reaction started. Maintain an ethylene pressure of 10 atm at 30°C and stir for 30 minutes. The reaction solution was neutralized with an ethanol solution acidified with 5% hydrochloric acid to obtain a polymer precipitate, which was washed several times with ethanol, dried in a vacuum to a constant weight, and weighed.

Polymerization activity: 3.75×10 ⁶ g·mol ^-1 (Ni)·h ^-1 , polymer T _m = 69.3°C. (T _m is the melting temperature of the polymer, measured by DSC), the molecular weight of the polymer M _w = 3.82×10 ⁵ g·mol ^-1 , PDI = 1.8 (M _w is the mass average molecular weight of the polymer, measured by heating GPC Income).

(b) is basically the same as (a), except that the amount of the co-catalyst is 0.34 mL of the co-catalyst Me ₂ AlCl (1.17 mol/L toluene solution), so that Al/Ni=200:1. Polymerization activity: 2.64×10 ⁶ g·mol ^-1 (Ni)·h ^-1 , polymer T _m =65.2° C., M _w =3.32×10 ⁵ g·mol ^-1 , PDI=1.6.

(c) is basically the same as (a), except that the amount of the co-catalyst is _{0.51 mL of the co-catalyst Me 2} AlCl (1.17 mol/L toluene solution), so that Al/Ni=300:1. Polymerization activity: 3.16×10 ⁶ g·mol ^-1 (Ni)·h ^-1 , polymer T _m = 68.3° C., M _w = 3.27×10 ⁵ g·mol ^-1 , PDI = 1.8.

(d) is basically the same as (a), except that: the amount of the co-catalyst is 0.68 mL of the co-catalyst Me ₂ AlCl (1.17 mol/L toluene solution), so that Al/Ni=400:1. Polymerization activity: 4.41×10 ⁶ g·mol ^-1 (Ni)·h ^-1 , polymer T _m =79.3° C., M _w =2.03×10 ⁵ g·mol ^-1 , PDI=1.5.

Take 100 mg of the polymer obtained in (d), dissolve it in 5 mL of deuterium tetrachloroethane, and test the ¹³ C data of the polymer at 30°C. The signal is accumulated 2000 times, and the signal peak shift is between 20-40 (ppm), indicating the shift of methyl, methylene and methine groups, which proves that the obtained polymer is branched polyethylene (see Figure 4 for specific information) ). After calculation, the branching degree of this sample is 178 branches per 1000 carbons, containing 92% methyl branches.

(e) is basically the same as (a), except that the amount of the co-catalyst is 1.02 mL of the co-catalyst Me ₂ AlCl (1.17 mol/L toluene solution), so that Al/Ni=600:1. Polymerization activity: 3.16×10 ⁶ g·mol ^-1 (Ni)·h ^-1 , polymer T _m =689° C., M _w =2.14×10 ⁵ g·mol ^-1 , PDI=1.3.

(f) is basically the same as (a), except that the amount of the co-catalyst is _{1.20 mL of the co-catalyst Me 2} AlCl (1.17 mol/L toluene solution), so that Al/Ni=700:1. Polymerization activity: 2.62×10 ⁶ g·mol ^-1 (Ni)·h ^-1 , polymer T _m = 63.6° C., M _w =1.94×10 ⁵ g·mol ^-1 , PDI = 1.5.

(g) is basically the same as (d), except that the polymerization temperature is 20°C. Polymerization activity: 3.09×10 ⁶ g·mol ^-1 (Ni)·h ^-1 , polymer T _m = 85.2° C., M _w =5.73×10 ⁵ g·mol ^-1 , PDI = 1.5.

(h) is basically the same as (d), except that the polymerization temperature is 40°C. Polymerization activity: 3.66×10 ⁶ g·mol ^-1 (Ni)·h ^-1 , polymer T _m = 65.5° C., M _w =1.48×10 ⁵ g·mol ^-1 , PDI = 1.5.

(i) is basically the same as (d), except that the polymerization temperature is 50°C. Polymerization activity: 2.96×10 ⁶ g·mol ^-1 (Ni)·h ^-1 , polymer T _m =44.8° C., M _w =1.40×10 ⁵ g·mol ^-1 , PDI=1.5. ,

Take 100 mg of the polymer obtained in (i), dissolve it in 5 mL of deuterium tetrachloroethane, and test the ¹³ C data of the polymer at 30°C. The signal was accumulated for 2000 times, and the signal peak shift was between 20-40 (ppm), indicating the shift of methyl, methylene and methine groups, which proved that the obtained polymer is branched polyethylene (see Figure 5 for specific information) ). After calculation, the branching degree of this sample is 191 branches per 1000 carbons, containing 70% methyl branches.

Take 2 g of the polymer obtained in (i) and press the film at 50°C to prepare a film sample. The sample was used to test the tensile test at break and the corresponding stress-strain curve was obtained. The result showed that the tensile strain of the sample bar can reach 2592.67% when the tensile stress is 0.97 MPa, and no sample bar fracture is observed in the process. This indicates that the sample has good mechanical tensile properties (see Figure 6 for specific information).

Similarly, the elastic recovery rate test was performed on the dynamic mechanical analyzer (DMA) with the above sample strips. These tests were carried out at -10 and 30°C, and each cycle was repeated up to 10 times. The strain recovery value (SR) is calculated using the standard formula SR=100(εa-εr)/εa, where εa is the applied strain and εr is the strain in 10 zero-load cycles. The test results of all the splines obtained satisfactory results, and the elastic recovery rate did not decrease much. Even after 10 cycles, the samples could still maintain elasticity. As the temperature increases from -10°C to 30°C, the elastic recovery rate of the spline increases, and the SR value increases from 45% to 63% (see Figure 7 for specific information). The sample has good tensile strength, elongation at break and elastic recovery, and has good thermoplastic elastomer (TPEs) properties, and is expected to replace the current industrial TPEs.

(j) is basically the same as (d), except that the polymerization time is 5 min. Polymerization activity: 2.44×10 ⁶ g·mol ^-1 (Ni)·h ^-1 , polymer T _m = 49.4° C., M _w =1.79×10 ⁵ g·mol ^-1 , PDI = 1.7.

(k) is basically the same as (d), except that the polymerization time is 15 minutes. Polymerization activity: 3.27×10 ⁶ g·mol ^-1 (Ni)·h ^-1 , polymer T _m =55.2° C., M _w =2.86×10 ⁵ g·mol ^-1 , PDI=1.6.

(l) is basically the same as (d), except that the polymerization time is 45 minutes. Polymerization activity: 1.44×10 ⁶ g·mol ^-1 (Ni)·h ^-1 , polymer T _m =58.8° C., M _w =1.89×10 ⁵ g·mol ^-1 , PDI=1.7.

(m) is basically the same as (d), except that the polymerization time is 60 minutes. Polymerization activity: 0.93×10 ⁶ g·mol ^-1 (Ni)·h ^-1 , polymer T _m = 66.3° C., M _w = 2.57×10 ⁵ g·mol ^-1 , PDI = 1.6.

(n) is basically the same as (d), except that the polymerization pressure is 5 atm. Polymerization activity: 2.72×10 ⁶ g·mol ^-1 (Ni)·h ^-1 , polymer T _m =73.1° C., M _w =3.52×10 ⁵ g·mol ^-1 , PDI=1.7.

(o) Basically the same as (d), except that the aggregation time is 1 atm. Polymerization activity: 0.61×10 ⁶ g·mol ^-1 (Ni)·h ^-1 , polymer T _m =34.0° C., M _w =1.08×10 ⁵ g·mol ^-1 , PDI=1.5.

Example 19

In this embodiment, the α-diimine nickel complex described in formula (II-2) is used as the main catalyst, and dimethyl aluminum chloride (Me ₂ AlCl) is used as the co-catalyst, and the ethylene polymerization reaction is carried out in a pressurized environment. :

The process is basically the same as that in Example 18(d), except that the main catalyst is the α-diimine nickel complex described in formula (II-2). Polymerization activity: 3.11×10 ⁶ g·mol ^-1 (Ni)·h ^-1 , polymer T _m =54.9° C., M _w =3.75×10 ⁵ g·mol ^-1 , PDI=2.1.

Example 20

In this embodiment, the α-diimine nickel complex of formula (II-3) is used as the main catalyst, and dimethyl aluminum chloride (Me ₂ AlCl) is used as the co-catalyst, and the ethylene polymerization reaction is carried out in a pressurized environment. :

The process is basically the same as that in Example 18(d), except that the main catalyst is the α-diimine nickel complex described in formula (II-3). Polymerization activity: 1.35×10 ⁶ g·mol ^-1 (Ni)·h ^-1 , polymer T _m = 60.7° C., M _w = 3.67×10 ⁵ g·mol ^-1 , PDI = 2.0.

Example 21

In this embodiment, the α-diimine nickel complex of formula (II-4) is used as the main catalyst, and dimethyl aluminum chloride (Me ₂ AlCl) is used as the co-catalyst, and the ethylene polymerization reaction is carried out in a pressurized environment. :

The process is basically the same as in Example 18(d), except that the main catalyst is the α-diimine nickel complex described in formula (II-4). Polymerization activity: 4.16×10 ⁶ g·mol ^-1 (Ni)·h ^-1 , polymer T _m = 68.3° C., M _w =3.02×10 ⁵ g·mol ^-1 , PDI = 1.6.

Example 22

In this embodiment, the α-diimine nickel complex of formula (II-5) is used as the main catalyst, and dimethyl aluminum chloride (Me ₂ AlCl) is used as the co-catalyst, and the ethylene polymerization reaction is carried out in a pressurized environment. :

The process is basically the same as that of Example 18(d), except that the main catalyst is the α-diimine nickel complex described in formula (II-5). Polymerization activity: 2.87×10 ⁶ g·mol ^-1 (Ni)·h ^-1 , polymer T _m = 63.4° C., M _w = 3.72×10 ⁵ g·mol ^-1 , PDI = 1.9.

The above are only the preferred embodiments of the present invention and do not limit the present invention in any form. Although the present invention has been disclosed as above in preferred embodiments, it is not intended to limit the present invention. Any technology familiar with this patent Without departing from the scope of the technical solution of the present invention, the personnel can use the technical content suggested above to make slight changes or modification into equivalent embodiments with equivalent changes. However, any content that does not deviate from the technical solution of the present invention is based on the technology of the present invention. Essentially, any simple modifications, equivalent changes and modifications made to the above embodiments still fall within the scope of the solution of the present invention.

Claims (10)

1. A type of fluorine-containing α-diimine nickel complexes for preparing polyolefin elastomers, characterized in that the fluorine-containing α-diimine nickel complexes have the structure shown in formula (I):

   

   Wherein, R ^{1 is the} same or different, each independently selected from methyl, ethyl or isopropyl; R ^{2 is the} same or different, each independently selected from H or methyl; X is the same or different, each independently selected from halogen ；

   Preferably, the fluorine-containing α-diimine nickel complex includes the structure shown below:

   

   Wherein, X is the same or different, and each is independently selected from Br or Cl.
2. A fluorine-containing α-diimine ligand compound is characterized in that the fluorine-containing α-diimine ligand compound has a structure as shown in formula (II):

   

   Wherein, R ¹ and R ² have the definition as described in claim 1;

   Preferably, the fluorine-containing α-diimine ligand compound includes the structure shown below:

   
3. A 2-aniline acenaphthene compound containing two fluorine substituents, characterized in that the 2-aniline acenaphthene compound has a structure as shown in formula (III):

   
4. An aniline compound containing two fluorine substituents and two benzhydryl substituents, characterized in that the aniline compound has a structure as shown in formula (IV):

   
5. A method for preparing the fluorine-containing α-diimine nickel complex according to claim 1, wherein the fluorine-containing α-diimine nickel complex is the fluorine-containing α-diimine nickel complex according to claim 2. The imine ligand compound is prepared as an intermediate raw material;

   It comprises: mixing the fluorine-containing α-diimine ligand compound according to claim 2 and the nickel-containing compound in a solvent at a molar ratio of 1 to 2:1, and reacting at 0 to 35° C. for 8 to 24 hours to prepare Obtain fluorine-containing α-diimine nickel complex;

   Preferably, the nickel-containing compound is selected from nickel-containing halides;

   Preferably, the molar ratio of the fluorine-containing α-diimine ligand compound to the nickel-containing compound is 1 to 1.5:1, more preferably 1:1;

   Preferably, the temperature of the reaction is 10-30°C, more preferably 20-25°C;

   Preferably, the reaction time is 12-24 hours, more preferably 18-24 hours;

   Preferably, the solvent is selected from one or more of halogenated alkanes and alcohol solvents, more preferably in dichloromethane and/or ethanol.
6. A method for preparing the fluorine-containing α-diimine ligand compound according to claim 2, wherein the fluorine-containing α-diimine ligand compound is substituted with two fluorine-containing compounds according to claim 3. The 2-anilinoacenaphthylene ketone compound is prepared as an intermediate raw material;

   It comprises: taking the 2-aniline acenaphthylene ketone represented by the formula (III) in claim 3 and the compound represented by the formula (V) in a molar ratio of 1:1-2 to dissolve in a solvent, and adding the catalyst at a temperature of 120°C Under heating and refluxing for 12 to 18 hours, the condensation reaction is carried out to obtain the fluorine-containing α-diimine ligand compound as shown in the formula (II) in claim 2;

   Preferably, the catalyst is selected from p-toluenesulfonic acid, and the solvent is selected from aromatic hydrocarbon reagents, preferably toluene;

   Preferably, the molar ratio of the 2-anilineacenaphthylene ketone represented by the formula (III) to the compound represented by the formula (V) is 1:1, and the condensation reaction time is 12 to 16 hours;

   The structure of the formula (V) is as follows:

   

   Wherein, R ¹ and R ² have the definitions described in claim 1.
7. A method for preparing 2-aniline acenaphthlenone compound containing two fluorine substituents as claimed in claim 3, wherein the 2-aniline acenaphthene compound containing two fluorine substituents is described in claim 4 The aniline compound containing two fluorine substituents and two benzhydryl substituents is prepared as raw materials;

   It includes:

   (1) Take 3,4-difluoroaniline represented by formula (VII) and benzhydrol represented by formula (VIII) at a molar ratio of 1:2, and dissolve them _{in hydrochloric acid containing ZnCl 2} at a temperature of 140°C Carrying out the substitution reaction for 6 to 8 hours to obtain the 2,6-dibenzyl-3,4-difluoroaniline compound represented by the formula (IV) in claim 4;

   (2) Take the acenaphthylene dione represented by the formula (VI) and the 2,6-dibenzyl-3,4 represented by the formula (IV) prepared in step (1) at a molar ratio of 1:1～2 -The difluoroaniline compound is dissolved in a solvent, and a catalyst is added to carry out a substitution reaction for 10 to 16 hours at room temperature to obtain the 2-anilineacenaphthlene represented by the formula (III) in claim 3;

   Preferably, the catalyst in step (2) is selected from p-toluenesulfonic acid, and the solvent is selected from aromatic hydrocarbon reagents, preferably toluene;

   Preferably, in the step (2), the molar ratio of the acenaphthylene dione represented by the formula (VI) to the aniline represented by the formula (IV) is 1:1, and the substitution reaction time is 12 to 14 hours;

   The structures of the formula (VI), formula (VII) and formula (VIII) are as follows:

   
8. A catalyst, characterized in that the catalyst comprises only a main catalyst, or a main catalyst and a promoter, the main catalyst is selected from the fluorine-containing α-diimine nickel complex according to claim 1, and the promoter The catalyst is selected from one or more of aluminoxane, aluminum alkyl or aluminum alkyl chloride; when the catalyst includes both a main catalyst and a co-catalyst, the Al in the co-catalyst and Ni in the main catalyst The molar ratio is 200-3500:1, preferably 400-3000:1.

   Preferably, the aluminoxane is selected from one or two of methylaluminoxane and triisobutylaluminum-modified methylaluminoxane, more preferably triisobutylaluminum-modified methyl Aluminoxane

   Preferably, the alkyl aluminum chloride is selected from dimethyl aluminum chloride and/or sesquiethyl aluminum chloride, more preferably dimethyl aluminum chloride;

   Preferably, when the co-catalyst is methylaluminoxane, the molar ratio of Al in the co-catalyst to Ni in the main catalyst is 1000-4000:1, more preferably 2000:1;

   Preferably, when the co-catalyst is sesquiethyl aluminum chloride, the molar ratio of Al in the co-catalyst to Ni in the main catalyst is 100-1000:1, more preferably 500:1;

   Preferably, when the co-catalyst is methylaluminoxane modified with triisobutyl aluminum, the molar ratio of Al in the co-catalyst to Ni in the main catalyst is 1000-4000:1, more preferably 1500-3500: 1;

   Preferably, the co-catalyst is dimethyl aluminum chloride, and the molar ratio of Al in the co-catalyst to Ni in the main catalyst is 100-1000:1, more preferably 200-700:1.
9. A preparation method of polyethylene, characterized in that, the preparation method comprises: dissolving the catalyst according to claim 5 in a solvent, heating to 20-60°C and passing ethylene raw material into it, and under a pressure of 1-10atm Perform 5～120min polymerization reaction;

   Preferably, the solvent is selected from one or more of toluene, dichloromethane, ethanol, tetrahydrofuran, hexane or cyclohexane, more preferably toluene;

   Preferably, the polymerization reaction is carried out under an ethylene atmosphere.
10. An application of the catalyst according to claim 7 in olefin polymerization.

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