CN103724377A

CN103724377A - 2,6-diene amine pyridine binuclear cobalt complex catalyst as well as preparation method and application thereof

Info

Publication number: CN103724377A
Application number: CN201410012648.0A
Authority: CN
Inventors: 邢其锋; 赵同; 杜世振; 孙文华
Original assignee: Institute of Chemistry CAS
Current assignee: Institute of Chemistry CAS
Priority date: 2014-01-10
Filing date: 2014-01-10
Publication date: 2014-04-16

Abstract

本发明公开了一种2,6-二烯胺吡啶双核钴配合物催化剂及其制备方法与应用。该类配合物的结构式如式Ⅰ所示，其中，R¹选自甲基、乙基和异丙基中的至少一种；R²为甲基或氢；R³为甲基、乙基或异丙基。制备方法如下：在室温条件下，使式Ⅴ所示的配体与CoCl₂反应，得到式Ⅰ所示配合物。本发明设计并合成了含有2,6-二烯胺吡啶配体以及钴金属配合物，该配合物在助催化剂甲基铝氧烷、改性甲基铝氧烷作用下，能够较好的催化乙烯聚合，得到高分子量的聚合物，同时其活性也很高，最高活性可以10⁷g·mol^–1(M)·h^–1；具有广泛的工业应用前景。

The invention discloses a 2,6-dienylamine pyridine binuclear cobalt complex catalyst as well as its preparation method and application. The structural formula of this type of complex is shown in formula I, wherein, R ¹ is at least one selected from methyl, ethyl and isopropyl; R ² is methyl or hydrogen; R ³ is methyl, ethyl or Isopropyl. The preparation method is as follows: at room temperature, the ligand represented by formula V is reacted with CoCl ₂ to obtain the complex represented by formula I. The present invention designs and synthesizes a complex containing 2,6-dienylamine pyridine ligand and cobalt metal, which can better catalyze Ethylene is polymerized to obtain a high molecular weight polymer, and its activity is also high, the highest activity can be 10 ⁷ g·mol ^–1 (M)·h ^–1 ; it has a wide range of industrial application prospects.

Description

2,6-, bis-enamine pyridine dinuclear cobalt complex Catalysts and its preparation method and application

Technical field

The present invention relates to a kind of 2,6-, bis-enamine pyridine dinuclear cobalt complex Catalysts and its preparation method and application.

Background technology

Polyolefine material is the pillar of modern science and technology and social development, in hard-core technology, national defense construction and national economy every field, become indispensable important materials, wherein polythene material is the synthetic resins that global evolution is the fastest, output is maximum, purposes is extremely wide, is widely used in many fields such as industry, agricultural, military affairs, health care, daily life.At present, industrialized polyethylene catalysts has Ziegler-Natta type catalyzer (DE Pat889229 (1953); IT Pat536899 (1955) and IT Pat545332 (1956); Chem.Rev., 2000,100,1169 and this special issue pertinent literature, Phillips type catalyzer (Belg.Pat.530617 (1955); Chem.Rev.1996,96,3327) and metallocene type catalyst (W.Kaminsky, Metalorganic Catalysts for Synthesis and Polymerization, Berlin:Springer, 1999), and efficient ethylene oligomerization and the polymerizing catalyst of the late transition metal complex type of development in recent years.Nineteen ninety-five, Brookhart study group has reported diimine coordination nickel, palladium complex catalyst vinyl polymerization (J.Am.Chem.Soc., 1995,117,6414), has obtained High molecular weight polyethylene.

1998, Brookhart and Gibbson reported respectively a class 2, the title complex of 6-bis-enamine pyridines, can high reactivity ground polymerising ethylene, its structure be shown below ((a) J.Am.Chem.Soc., 1998,120,4049; (b) Chem.Commun., 1998,849; (c) J.Am.Chem.Soc., 1999,121,8728.):

Round pyridine diimine iron cobalt complex catalyzer, we are doing a lot of work aspect such catalyzer at group, design and development ethylene oligomerization and the polymerizing catalyst of multiclass title complex: (figure below Fe1-3).Wherein tri-kinds of iron of Fe1-3 are that title complex has identical coordination skeleton, but, under promotor MAO exists, show distinct catalysis characteristics: Fe1 and there is no catalytic activity at all, Fe2 has higher ethylene oligomerization activity, and Fe3 has showed higher ethylene polymerization activity (Polym.Int., 2002,51,994; Chin.J.Polym.Sci., 2002,20,205).This shows, the solid by regulation and control part and electronic effect can be controlled the performance of its ethylene catalyst, have obtained the concern of international counterparts.These results of study also make us to the model of design high activated catalyst, have good basis simultaneously.

Our group had been designed and developed the catalyst system (M1-5) of several new tridentate coordinations afterwards, had obtained good result, and they all show excellent performance.Relevant work has been delivered or has been applied for a patent: Chinese patent ZL00132106.4, December 13 2000 applying date, January 28 2004 Granted publication day; Chinese patent ZL01118568.6, the June 4 calendar year 2001 applying date, December 3 2003 Granted publication day; Chinese patent ZL01120553.9, the July 20 calendar year 2001 applying date, September 1 2004 Granted publication day; Chinese Patent Application No. 01124240.X, the August 17 calendar year 2001 applying date; October 27 2004 200410086374.6 applying date of Chinese Patent Application No.; July 16 2007 Chinese Patent Application No. 200710119128.X applying date.Wherein, 2-benzoglyoxaline-6-amido pyridine iron and cobalt complex M1 can highly active catalytic ethylene oligomerization and polymerizations (200610165446.5 applyings date of Chinese Patent Application No.: on December 20th, 2006).

And 2-benzoxazole-6-amido pyridine iron and cobalt complex M2 can obtain oligopolymer and polyethylene wax (the Chinese Patent Application No. 200810239477.x applying date: on December 11st, 2008) with highly active catalytic ethylene oligomerization more.Particularly 2-amido-1 of seminar's exploitation in 2005, the title complex M3 of 10-phenanthroline iron and cobalt, has high ethylene oligomerization activity (200510066427.2 applyings date of Chinese Patent Application No.: on April 22nd, 2005; Granted publication day: on March 5th, 2008; Granted publication number: CN100372609C).This type of catalyst activity can compare favourably with classical pyridine diimine iron catalyst.

We organize two synthetic tooth 8-benzo miaows of design (oh or thiophene) azoles quinoline catalyst system M4 for catalyzed ethylene polymerization reaction in addition, also show high catalytic activity, and resulting polymers molecular weight is high, narrow molecular weight distribution, especially catalyzer has very strong tolerance to high temperature, has very strong prospects for commercial application.(Organometallics,2011,30,3658–3665)

We organize 2 of the synthetic N^N^N dentate of design simultaneously, 8-diimine quinoline M5 (Organometallics, 2010,29,1168) for catalyzed ethylene polymerization reaction, also show high catalytic activity, and resulting polymers molecular weight is high, narrow molecular weight distribution, catalyzer has very strong tolerance to high temperature, has prospects for commercial application widely.Due to the interaction existing before the different metal center in double-core metal complexes, double-core metal complexes shows some distinguished character.Advantageous property (the high reactivity showing in catalysis in olefine polymerization process due to dinuclear complex catalyzer in recent years; Temperature application range widely; The control of polymkeric substance proterties), our seminar has also carried out a large amount of research to double-core late transition metal complex catalyst, and has obtained some achievements, obtains a series of double-core late transition metal complexs (M6-8).Wherein comprise 2 of N^N^N tridentate ligand and N^N bidentate dentate simultaneously, the tall and erect M6 of 4-bis-(6-enamine pyridine)-3H-benzo nitrogen has also obtained oligomerization product (Organometallics when obtaining polymkeric substance, 2013,32,2309-2318).The tetramethyl biphenyl amine complex M7 catalysis of N^N bidentate dentate has obtained high molecular, the polymerisate (Chin.J.Polym.Sci., 2008,26,539) of narrow distribution.And the M8 of N^N bidentate dentate has also obtained oligomerization product (J.Organomet.Chem., 2005,690,1739) when obtaining polymkeric substance.

Make a general survey of the result of study of late transition metal catalyst for olefin polymerization nearly ten years, that late transition metal complex catalyst has is simpler than metallocene catalyst, cost is low and the advantage of good stability; And catalyst structure be also easy to modify with this, regulate and control product (polymkeric substance and oligopolymer) structure and molecular weight.But, as new catalyst system, still also have the difficult point of some fundamental researchs and advance industrialized restraining factors.First still the limitation of catalyst type, because this class research is at the early-stage, alternative catalyst system (saying exactly the catalyst type with good activity) is still few, has restricted the development of fundamental research.Secondly, because β-hydrogen chain shifts termination speed, be along with the rising of temperature increases, and the thermal stability of title complex itself is poor, this will certainly cause that activity raises and reduces with temperature of reaction.Moreover because each research system is in the pilot scale research stage, and this class polyolefin product performance study is still few.These have all limited the practical application of metal catalyst to a certain extent.Can, in the research of these catalyzer, how obtaining more highly active ethylene oligomerization and polymerizing catalyst becomes the core content of research, be also advance as early as possible industrialized key.The progress obtaining for the research of double-core late transition metal complex illustrates that such composition catalyst has the value of the research of advancing.

Summary of the invention

The object of this invention is to provide a kind of 2,6-, bis-enamine pyridine dinuclear cobalt complex Catalysts and its preparation methods.

Provided by the present invention 2,6-bis-enamine pyridine dinuclear cobalt complexes, its structural formula is suc as formula shown in I:

In described formula I,

R ¹be selected from least one in methyl, ethyl and sec.-propyl;

R ²for methyl or hydrogen;

R ³for methyl, ethyl or sec.-propyl.

Preferred, metal complexes of the present invention is selected from following any one title complex:

Co-1:R ¹=Me;R ²=H;R ³=Me。

Co-2:R ¹=Et;R ²=H;R ³=Me。

Co-3:R ¹=i-Pr;R ²=H;R ³=Me。

Co-4:R ¹=Me;R ²=H;R ³=Et。

Co-5:R ¹=Et;R ²=H;R ³=Et。

Co-6:R ¹=i-Pr;R ²=H;R ³=Et。

Co-7:R ¹=Me;R ²=H;R ³=i-Pr。

Co-8:R ¹=Et;R ²=H;R ³=i-Pr。

Co-9:R ¹=i-Pr;R ²=H;R ³=i-Pr。

Co-10:R ¹=Me;R ²=Me;R ³=Me。

Co-11:R ¹=Et;R ²=Me;R ³=i-Pr。

Also as follows:

Preparation provided by the invention is described 2, and the method for 6-bis-enamine pyridine dinuclear cobalt complexes, comprises the steps: at room temperature, by ligand compound and CoCl shown in formula V ₂mix and carry out complex reaction, obtain shown in formula I 2,6-bis-enamine pyridine dinuclear cobalt complexes;

In described formula V,

R ¹be selected from least one in methyl, ethyl and sec.-propyl;

R ²for methyl or hydrogen;

R ³for methyl, ethyl or sec.-propyl.

In aforesaid method, ligand compound shown in formula V and CoCl ₂molar ratio be 1.0-1.2:2.0-2.1, be specially 1.1:2;

In described complex reaction step, temperature is room temperature; Time is 8-24 hour, is specially 12 hours;

Described complex reaction is carried out in organic solvent;

Described organic solvent is selected from least one in methylene dichloride, ethanol and methyl alcohol.

The present invention also provides ligand compound shown in a kind of formula V,

In described formula V, R ¹be selected from least one in methyl, ethyl and sec.-propyl;

Described R ²for methyl or hydrogen;

R ³for methyl, ethyl or sec.-propyl.

Described in the described formula V of preparation provided by the invention, the method for ligand compound, comprises the steps:

1) at formic acid or acetic acid, under the condition as catalyzer, amino benzenes compounds shown in DAP and formula II is mixed and in ice bath, carries out condensation reaction, obtain the enamine-6-of 2-shown in formula III acyl pyridine compound;

2) at tosic acid or trifluoroacetic acid, under the condition as catalyzer, benzidine compound shown in step 1) gained 2-enamine-6-acyl pyridine compound and formula IV is mixed to reflux and carry out condensation reaction, obtain ligand compound shown in described formula V;

Described formula II to formula IV, R ¹, R ²and R ³definition respectively with aforementioned formula I in R ¹, R ²and R ³definition identical.

In the step 1) of aforesaid method, the consumption of described catalyzer is the 5%-10% of DAP mole dosage;

Shown in DAP and formula II, the molar ratio of amino benzenes compounds is 1.1-1.2:1.0-1.1, is specially 1.2:1;

In described step of condensation, the time is 12-24 hour, is specially 24 hours;

Described condensation reaction is carried out in organic solvent; Described organic solvent is specifically selected from least one in ethanol, methyl alcohol and methylene dichloride;

Described step 2) in, the consumption of described catalyzer is the 5%-10% of 2-enamine-6-acyl pyridine compound mole dosage;

Shown in 2-enamine-6-acyl pyridine compound and formula IV, the molar ratio of benzidine compound is 2.0-1.0:2.0-1.2, is specially 2.0:1.1;

In described step of condensation, the time is 8-12 hour, is specially 12 hours;

Described condensation reaction is carried out in organic solvent; Described organic solvent is specifically selected from least one in toluene, dimethylbenzene and orthodichlorobenzene.

Described method also comprises the steps:

A) after described step 1), step 2) before, the compound of 2-enamine-6-acyl pyridine shown in step 1) gained formula III is carried out to purifying in accordance with the following steps:

The acyl pyridine of 2-enamine-6-shown in step 1) gained formula III compound is dissolved in methylene dichloride, silicagel column carries out column chromatography, take the mixed solvent of sherwood oil and ethyl acetate or the mixed solvent of sherwood oil and methylene dichloride as eluent, carry out wash-out, by thin-layer chromatography, detect wash-out flow point, except desolventizing, obtain the formula III compound of purifying;

B) to step 2) ligand compound shown in gained formula V carries out purifying in accordance with the following steps:

By step 2) ligand compound shown in gained formula V is dissolved in methylene dichloride, silicagel column carries out column chromatography, take the mixed solvent of sherwood oil and ethyl acetate or the mixed solvent of sherwood oil and methylene dichloride as eluent, carry out wash-out, by thin-layer chromatography, detect wash-out flow point, except desolventizing, obtain ligand compound shown in the formula V of purifying.

The reaction process of aforesaid method as shown in Figure 1.

In addition, the present invention also provides a kind of catalyst composition for vinyl polymerization; The activeconstituents of this catalyst composition comprises shown in formula I 2,6-bis-enamine pyridine dinuclear cobalt complexes.

Described catalyst composition also comprises promotor;

Described promotor is specifically selected from least one in methylaluminoxane (being called for short MAO) and modified methylaluminoxane (being called for short MMAO); Wherein, modified methylaluminoxane (be called for short MMAO) can be bought and obtain from various open commercial sources, as can be purchased from U.S. AkzoNobel company.

Certainly, this catalyzer also can only be comprised of above-mentioned two components.

Shown in metallic aluminium element in described promotor and formula I 2, the mol ratio of the cobalt element in 6-bis-enamine pyridine dinuclear cobalt complexes is 500-2000:1, is specially 500:1,1000:1,1500:1,2000:1,500-1500:1,1000-2000:1.

The present invention also provides one to prepare poly method, comprises the steps: former stating under the condition of catalyst composition provided by the invention as catalyzer, and catalyzed ethylene carries out polyreaction, reacts the complete described polyethylene that obtains.

In described polymerization procedure, temperature is 40-70 ℃, is specially 40 ℃, 50 ℃, 60 ℃, 70 ℃, 40-60 ℃ or 50-70 ℃;

Pressure is 1-10atm;

Time is 15min-60min, is specially 30min;

Described polyreaction is carried out in solvent;

Described solvent is selected from least one in toluene, isopropylcarbinol and normal hexane;

Described polyreaction is carried out in inert atmosphere;

Described inert atmosphere is specially nitrogen atmosphere.

The present invention has designed and synthesized and has contained 2 of N^N^N dentate, 6-bis-enamine pyridine dinuclear cobalt complexes, and this metal complexes, for catalyzed ethylene polymerization reaction, shows very high catalytic activity, obtains the high molecular polymer of highly linear, can reach 1.2 × 10 ⁷gmol ^-1(Co) h ^-1, and such composition catalyst (50 ℃) under comparatively high temps still can keep higher lasting activity, has prospects for commercial application widely.

Accompanying drawing explanation

Fig. 1 is the reacting flow chart of preparation title complex of the present invention.

Fig. 2 is the crystalline structure schematic diagram of ligand L 5.

Fig. 3 is the crystalline structure schematic diagram of title complex Co-4.

Fig. 4 is embodiment 23a resulting polymers high temperature nuclear-magnetism carbon spectrum data plot.

Embodiment

Below in conjunction with specific embodiment, the present invention is further elaborated, but the present invention is not limited to following examples.Described method is ordinary method if no special instructions.Described starting material all can obtain from open commercial sources if no special instructions.Modified methylaluminoxane used (being called for short MMAO) is all purchased from U.S. AkzoNobel company.In following embodiment 23-35, the definition of described Al/Co is shown in metallic aluminium element in promotor MAO and formula I 2, the mol ratio of the cobalt element in 6-bis-enamine pyridine dinuclear cobalt complexes.

Embodiment 1, preparation N, N ^/-bis-(1-(3-(1-(2,6-diethylbenzene imines) ethyl) pyridine-2-yl) ethylidene) tetraethyl-biphenyl (L5) (R ¹for ethyl, R ²for hydrogen, R ³for ethyl)

1) 2; 6-diacetyl pyridine (3.9g; 24mmol) with 2 of ownership formula II; 6-Diethyl Aniline (3.0g; the formic acid that adds catalytic amount (2ml) in ethanol (200mL) solution 20mmol), stirs 24h in ice bath, filter; obtaining 0.87g yellow solid, is ownership formula III (R ¹for ethyl, R ²for hydrogen) 2-enamine-6-acyl pyridine compound: 1-(6-(1-((2,6-diethylbenzene) enamine) ethyl) 2-pyridyl) acetyl, productive rate 29.5%.

2) 6.0g (40mmol) 2,6-Diethyl Aniline is dissolved in 50ml methylene dichloride, 20g (133mmol) copper sulfate and the abundant ground and mixed of 20g (126mmol) potassium permanganate, add stirring at normal temperature 15h. reaction solution in solution to confirm that by thin-layer chromatography reaction is complete, reaction solution, through column chromatography chromatogram, separates and obtains 2.9g red solid 1,2-bis-(2,6-diethyl phenyl) diazene, yield 23%.

3) 2.9g (10mmol) nitrogen benzide is dissolved in 100ml ethanol, and anhydrous stannous chloride 22.5g (100mmol) is dissolved in 50ml dilute hydrochloric acid and is added dropwise to reaction solution, and reaction solution is heated to reflux, reaction 2h.By thin-layer chromatography, determine that reaction is complete, reaction solution adds 50ml water, adds sodium hydroxide to regulate pH value to alkalescence.Ethyl acetate extractive reaction liquid (100ml × 2).Organic layer is dry concentrated. and column chromatography for separation obtains 1.2g brown solid 3,3', 5,5'-tetraethyl--[1,1'-phenylbenzene]-4,4'-diamines, yield 40%.

4) by 0.75g (2.5mmol) step 1) gained 1-(6-(1-((2,6-diethylbenzene) enamine) ethyl) 2-pyridyl) acetyl and 0.28g (1.25mmol) step 3) gained 3,3', 5,5'-tetraethyl--[1,1'-phenylbenzene]-4,4'-diamines is dissolved in 100ml toluene, catalytic amount (50mg) tosic acid adds reaction solution, reaction solution reflux 12h.Silica gel column chromatography separates and obtains 0.24g yellow solid, yield 22.6% (fusing point: 272 ℃).

Structural identification data are as follows: crystalline structure schematic diagram as shown in Figure 2.

As seen from the figure, two phenyl ring in biphenyl structural in a copline, the simultaneously angle near normal between the phenyl ring in pyridine ring and biphenyl and aniline, the structure of this part exists symmetry in addition.

¹h NMR (400MHz, CDCl ₃): 8.51 (d, J=8.0Hz, 4H, Py-H), 7.95 (t, J=8.0Hz, 2H, Py-H), 7.13 (d, J=7.6Hz, 4H, Ph-H), 7.05 (t, J=8.0Hz, 2H, Ph-H), 6.29 (s, 4H, Ph-H), 2.40-2.53 (m, 8H, 4 × CH ₂), 2.24 (s, 6H, 2 × CH ₃), 2.10 (s, 6H, 2 × CH ₃), 1.14 (t, J=7.6Hz, 12H, 4 × CH ₃). ¹³c NMR:(100MHz, CDCl ₃): 167.5,166.9,155.2,155.0,147.9,136.9,136.0,131.2,126.4,126.0,125.8,123.4,122.3,24.7,18.2,16.9,16.7,13.8.FT-IR (cm ^-1): 2964 (m), 1637 (ν _c=N, s), 1567 (m), 1450 (s), 1362 (s), 1321 (w), 1296 (w), 1243 (m), 1200 (s), 1119 (m), 1098 (m), 857 (w), 828 (m), 769 (m), 689 (w). ultimate analysis: C ₅₈h ₆₈n ₆(848) theoretical value: N, 9.90; C, 82.03; H, 8.07. experimental value: N, 9.65; C, 81.96; H, 8.12.

Embodiment 2, preparation n,N ^/ -bis-(1-(3-(1-(2,6-dimethyl benzene imines) ethyl) pyridine-2-yl) ethylidene) tetramethyl- biphenyl [L1](R ¹for methyl, R ²for hydrogen, R ³for methyl)

Use with embodiment 1 same procedure and obtain 0.45g yellow solid, yield 49.3% (fusing point: 272 ℃).

Structural identification data are as follows: ¹h NMR:(400MHz, CDCl ₃): 8.53 (d, J=8.0Hz, 2H, Py-H), 7.96 (t, J=8.0Hz, 1H, Py-H), 7.37 (d, J=8.0Hz, 2H, Ph-H), 7.09 (t, J=8.0Hz, 1H, Ph-H), 6.96 (s, 2H, Ph-H), 2.31 (s, 3H, CH ₃), 2.26 (s, 3H, CH ₃), 2.14 (s, 6H, 2 × CH ₃), 2.07 (s, 6H, 2 × CH ₃). ¹³c NMR (100MHz, CDCl ₃): 167.5,167.3,155.2,155.1,148.8,148.7,136.9,136.0,128.0,126.4,125.8,125.5,123.1,122.4,18.2,18.0,16.7,16.5.FT-IR (cm ^-1): 2913 (m), 1639 (ν _c=N, s), 1569 (m), 1461 (s), 1429 (s), 1362 (s), 1324 (w), 1296 (w), 1247 (m), 1200 (s), 1120 (m), 1083 (m), 857 (m), 814 (m), 769 (s), 689 (w). ultimate analysis: C ₅₀h ₅₂n ₆(736) theoretical value: N, 11.40; C, 81.49; H, 7.11. experimental value: N, 10.99; C, 81.36; H, 6.92.

Embodiment 3, preparation N, N ^/-bis-(1-(3-(1-(2,6-diethylbenzene imines) ethyl) pyridine-2-yl) ethylidene) tetramethyl biphenyl [L2] (R ¹for ethyl, R ²for hydrogen, R ³for methyl)

Use with embodiment 1 same procedure and obtain 0.41g yellow solid, yield 42.6% (fusing point: 238 ℃).

Structural identification data are as follows: ¹h NMR (400MHz, CDCl ₃): 8.51 (d, J=8.0Hz, 4H, Py-H), 7.95 (t, J=8.0Hz, 2H, Py-H), 7.13 (d, J=7.6Hz, 4H, Ph-H), 7.05 (t, J=8.0Hz, 2H, Ph-H), 6.29 (s, 4H, Ph-H), 2.29-2.44 (m, 8H, 4 × CH ₂), 2.24 (s, 6H, 2 × CH ₃), 2.10 (s, 6H, 2 × CH ₃), 1.14 (t, J=7.6Hz, 12H, 4 × CH ₃). ¹³c NMR (100MHz, CDCl ₃): 167.5,166.9,155.2,155.0,147.9,136.9,136.0,131.2,126.4,126.0,125.8,123.4,122.3,24.7,18.2,16.9,16.7,13.8.FT-IR (cm ^-1): 2964 (m), 1637 (ν _c=N, s), 1567 (s), 1450 (m), 1362 (s), 1321 (w), 1296 (w), 1243 (s), 1200 (m), 1119 (m), 1098 (w), 857 (w), 828 (m), 769 (s), 689 (w). ultimate analysis: C ₅₆h ₆₀n ₆(792) theoretical value: N, 10.60; C, 81.78; H, 7.63. experimental value: N, 10.69; C, 81.95; H, 7.39.

Embodiment 4, preparation N, N ^/-bis-(1-(3-(1-(2,6-diisopropyl benzene imines) ethyl) pyridine-2-yl) ethylidene) tetramethyl benzidine [L3] (R ¹for sec.-propyl, R ²for hydrogen, R ³for methyl)

Use with embodiment 1 same procedure and obtain 0.26g yellow solid, yield 26.8% (fusing point: 245 ℃).

Structural identification data are as follows: ¹h NMR (400MHz, CDCl ₃): 8.56 (d, J=8.0Hz, 4H, Py-H), 7.96 (t, J=8.0Hz, 2H, Py-H), 7.36 (s, 4H, Ph-H), 7.19 (d, J=7.6Hz, 4H, Ph-H), 7.11 (t, J=8.0Hz, 2H, Ph-H), 2.71-2.83 (m, 4H, 2 × CH ₂), 2.31 (s, 6H, 2 × CH ₃), 2.29 (s, 6H, 2 × CH ₃), 2.14 (s, 12H, 4 × CH ₃), 1.18 (d, 12H, J=2.0Hz, 4 × CH ₃), 1.16 (d, 12H, J=2.0Hz, 4 × CH ₃). ¹³c NMR (100MHz, CDCl ₃): 167.5,166.5,155.3,155.2,152.6,137.4,136.4,131.2,126.9,126.0,125.7,124.5,123.2,122.1,28.4,25.6,23.3,23.0,18.2,17.9.FT-IR (cm ^-1): 2957 (m), 2015 (w), 1641 (ν _c=N, s), 1570 (w), 1460 (m), 1361 (s), 1322 (w), 1243 (m), 1204 (s), 1117 (m), 859 (w), 824 (m), 766 (s), 692 (w). ultimate analysis: C ₅₈h ₆₈n ₆(848) theoretical value: N, 9.90; C, 82.03; H, 8.07. experimental value: N, 9.55; C, 81.86; H, 8.15.

Embodiment 5, preparation N, N ^/-bis-(1-(3-(1-(2,6-dimethyl benzene imines) ethyl) pyridine-2-yl) ethylidene) tetraethyl-p-diaminodiphenyl [L4] (R ¹for methyl, R ²for hydrogen, R ³for ethyl)

Use with embodiment 1 same procedure and obtain 0.43g yellow solid, yield 23.6% (fusing point: 283 ℃).

Structural identification data are as follows: ¹h NMR (400MHz, CDCl ₃): 8.51 (d, J=8.0Hz, 4H, Py-H), 7.95 (t, J=8.0Hz, 2H, Py-H), 7.13 (d, J=7.6Hz, 4H, Ph-H), 7.05 (t, J=8.0Hz, 2H, Ph-H), 6.29 (s, 4H, Ph-H), 2.29-2.43 (m, 8H, 4 × CH ₂), 2.24 (s, 6H, 2 × CH ₃), 2.10 (s, 6H, 2 × CH ₃), 1.14 (t, J=7.6Hz, 12H, 4 × CH ₃). ¹³c NMR (100MHz, CDCl ₃): 167.5,166.9,155.2,155.0,147.9,136.9,136.0,131.2,126.4,126.0,125.8,123.4,122.3,24.7,18.2,16.9,16.7,13.8.FT-IR (cm ^-1): 2964 (m), 1637 (ν _c=N, s), 1567 (w), 1450 (m), 1362 (s), 1321 (w), 1296 (w), 1243 (m), 1200 (s), 1119 (s), 1098 (m), 857 (m), 828 (m), 769 (s), 689 (w). ultimate analysis: C ₅₄h ₆₀n ₆(792) theoretical value: N, 10.60; C, 81.78; H, 7.63. experimental value: N, 10.65; C, 81.95; H, 7.39.

Embodiment 6, preparation N, N ^/-bis-(1-(3-(1-(2,6-diisopropyl benzene imines) ethyl) pyridine-2-yl) ethylidene) tetraethyl-p-diaminodiphenyl [L6] (R ¹for sec.-propyl, R ²for hydrogen, R ³for ethyl)

Use with embodiment 1 same procedure and obtain 0.34g yellow solid, yield 30.5% (fusing point: 270 ℃).

Structural identification data are as follows: ¹h NMR (400MHz, CDCl ₃): 8.53 (d, J=8.0Hz, 4H, Py-H), 7.96 (t, J=8.0Hz, 2H, Py-H), 7.40 (s, 4H, Ph-H), 7.17 (d, J=7.6Hz, 4H, Ph-H), 7.11 (t, J=8.0Hz, 2H, Ph-H), 2.78-2.91 (m, 4H, 4 × CH), 2.34-2.51 (m, 8H, 4 × CH ₂), 2.29 (s, 6H, 2 × CH ₃), 2.26 (s, 6H, 2 × CH ₃), 1.22 (t, 12H, J=7.6Hz, 4 × CH ₃), 1.16 (d, 24H, J=5.6Hz, 8 × CH ₃). ¹³c NMR (100MHz, CDCl ₃): 167.2,167.0,155.3,155.2,146.8,146.6,136.9,136.6,135.9,131.7,124.7,123.6,123.1,122.3,28.4,25.0,23.3,23.0,17.2,17.0,14.0.FTIR (cm ^-1): 2962 (m), 1635 (ν _c=N, s), 1569 (w), 1454 (m), 1362 (s), 1322 (w), 1241 (m), 1196 (s), 1120 (s), 1103 (m), 869 (w), 824 (m), 766 (s), 692 (m). ultimate analysis: C ₆₂h ₇₆n ₆(904) theoretical value: N, 9.28; C, 82.26; H, 8.46. experimental value: N, 8.89; C, 81.95; H, 8.43.

Embodiment 7, preparation N, N ^/-bis-(1-(3-(1-(2,6-dimethyl benzene imines) ethyl) pyridine-2-yl) ethylidene) tetra isopropyl p-diaminodiphenyl [L7] (R ¹for methyl, R ²for hydrogen, R ³for sec.-propyl)

Use with embodiment 1 same procedure and obtain 0.36g yellow solid, yield 34.4% (fusing point: 279 ℃).

Structural identification data are as follows: ¹h NMR (400MHz, CDCl ₃): 8.57 (d, J=8.0Hz, 4H, Py-H), 7.97 (t, J=8.0Hz, 2H, Py-H), 7.42 (s, 4H, Ph-H), 7.10 (d, J=7.6Hz, 4H, Ph-H), 6.97 (t, J=7.6Hz, 2H, Ph-H), 2.79-2.90 (m, 4H, 4 × CH), 2.35 (s, 6H, 2 × CH ₃), 2.28 (s, 6H, 2 × CH ₃), 2.10 (s, 12H, 4 × CH ₃), 1.41 (d, J=7.2Hz, 24H, 8 × CH ₃). ¹³c NMR (100MHz, CDCl ₃): 167.3,167.2,155.2,155.0,148.8,137.3,137.0,136.1,128.0,125.5,123.1,122.4,122.3,121.8,28.6,23.4,23.0,18.1,17.4,16.6.FT-IR (cm ^-1): 2958 (m), 1636 (ν _c=Ns), 1569 (w), 1460 (m), 1362 (s), 1321 (w), 1244 (w), 1200 (m), 1117 (s), 868 (w), 822 (m), 760 (m). ultimate analysis: C ₅₈h ₆₈n ₆(848) theoretical value: N, 9.90; C, 82.03; H, 8.07. experimental value: N, 9.59; C, 81.93; H, 8.05.

Embodiment 8, preparation N, N ^/-bis-(1-(3-(1-(2,6-diethylbenzene imines) ethyl) pyridine-2-yl) ethylidene) tetra isopropyl p-diaminodiphenyl [L8] (R ¹for ethyl, R ²for hydrogen, R ³for sec.-propyl)

Use with embodiment 1 same procedure and obtain 0.36g yellow solid, yield 31.9% (fusing point: 276 ℃).

Structural identification data are as follows: ¹h NMR (400MHz, CDCl ₃): 8.53 (d, J=8.0Hz, 4H, Py-H), 7.96 (t, J=8.0Hz, 2H, Py-H), 7.42 (s, 4H, Ph-H), 7.13 (d, J=7.6Hz, 4H, Ph-H), 7.05 (d, J=8.0Hz, 2H, Ph-H), 2.73-2.81 (m, 4H, 4 × CH), 2.40-2.54 (m, 8H, 4 × CH ₂), 2.36 (s, 6H, 2 × CH ₃), 2.28 (s, 6H, 2 × CH ₃), 1.24 (d, J=7.2Hz, 24H, 8 × CH ₃), 1.16 (t, J=7.6Hz, 12H, 4 × CH ₃). ¹³c NMR (100MHz, CDCl ₃): 167.5,167.0,155.3,155.0,145.6,139.3,137.3,136.1,131.3,128.3,126.0,123.4,122.4,121.8,28.6,24.7,23.4,23.0,16.9,13.8.FT-IR (cm ^-1): 2960 (m), 2015 (w), 1636 (ν _c=N, s), 1582 (w), 1444 (m), 1362 (s), 1322 (w), 1240 (m), 1196 (w), 1117 (s), 868 (m), 823 (m), 783 (m), 762 (s). ultimate analysis: C ₆₂h ₇₆n ₆(904) theoretical value: N, 9.28; C, 82.26; H, 8.46. experimental value: N, 8.97; C, 82.03; H, 8.43.

Embodiment 9, preparation N, N ^/-bis-(1-(3-(1-(2,6-diisopropyl benzene imines) ethyl) pyridine-2-yl) ethylidene) tetra isopropyl p-diaminodiphenyl [L9] (R ¹for sec.-propyl, R ²for hydrogen, R ³for sec.-propyl)

Use with embodiment 1 same procedure and obtain 0.42g yellow solid, yield 35.0% (fusing point: 202 ℃).

Structural identification data are as follows: ¹h NMR (400MHz, CDCl ₃): 8.60 (d, J=8.0Hz, 4H, Py-H), 7.99 (t, J=8.0Hz, 2H, Py-H), 7.43 (s, 4H, Ph-H), 7.17 (d, J=7.6Hz, 4H, Ph-H), 7.12 (t, J=8.0Hz, 2H, Ph-H), 2.71-2.89 (m, 8H, 4 × CH ₂), 2.30 (s, 6H, 2 × CH ₃), 2.27 (s, 6H, 2 × CH ₃), 1.25 (d, J=5.6Hz, 24H, 8 × CH ₃), 1.19 (d, J=5.6Hz, 24H, 8 × CH ₃). ¹³c NMR (100MHz, CDCl ₃): 167.2,167.0,155.2,155.1,146.6,146.3,145.6,137.4,137.3,136.9,136.1,135.8,135.7,124.6,123.8,123.6,123.1,123.1,122.6,122.3,121.8,28.6,28.4,23.4,23.3,23.3,23.0,22.9,17.3,17.2,17.1.FT-IR (cm ^-1): 2960 (m), 2158 (w), 2015 (w), 1639 (ν _c=N, s), 1570 (m), 1455 (s), 1361 (s), 1323 (w), 1239 (m), 1194 (s), 1117 (m), 961 (w), 868 (m), 823 (m), 763 (s), 691 (m). ultimate analysis: C ₆₆h ₈₄n ₆(960) theoretical value: N, 8.74; C, 82.45; H, 8.81. experimental value: N, 8.59; C, 82.15; H, 8.66.

Embodiment 10, preparation N, N ^/-bis-(1-(3-(1-2,4,6-trimethylammonium) pyridine-2-yl) ethylidene) tetramethyl benzidine [L10] (R ¹for methyl, R ²for methyl, R ³for methyl)

Use with embodiment 1 same procedure and obtain 0.30g yellow solid, yield 32.0% (fusing point: 228 ℃).

Structural identification data are as follows: ¹h NMR (400MHz, CDCl ₃): 8.49 (d, J=7.6Hz, 2H, Py-H), 7.93 (t, J=8.0Hz, 1H, Py-H), 7.36 (s, 2H, Ph-H), 6.91 (s, 2H, Ph-H), 2.31 (s, 6H, 2 × CH ₃), 2.29 (s, 3H, CH ₃), 2.27 (s, 6H, 2 × CH ₃), 2.10 (s, 6H, 2 × CH ₃). ¹³c NMR:(100MHz, CDCl ₃): 167.5,167.3,155.3,148.8,147.8,137.0,136.0,131.1,128.0,126.5,126.3,125.8,125.5,122.5,18.2,18.0,16.7,16.5.FT-IR (cm ^-1): 2964 (m), 2030 (w), 1643 (ν _c=N, s), 1574 (m), 1454 (s), 1362 (s), 1322 (w), 1205 (s), 1150 (w), 1120 (m), 859 (m), 817 (m), 741 (w), 694 (w). ultimate analysis: C ₅₃h ₅₈n ₆(764) theoretical value: N, 10.79; C, 81.71; H, 7.50. experimental value: N, 10.59; C, 82.15; H, 7.66.

Embodiment 11, preparation N, N ^/-bis-(1-(3-(1-(2,6-diethyl-4-methylbenzene) imines) ethyl) pyridine-2-yl) ethylidene) tetra isopropyl p-diaminodiphenyl [L11] (R ¹for ethyl, R ²for methyl, R ³for sec.-propyl)

Use with embodiment 1 same procedure and obtain 0.25g yellow solid, yield 22.1% (fusing point: 265 ℃).

Structural identification data are as follows: ¹h NMR (400MHz, CDCl ₃): 8.50 (d, J=7.6Hz, 2H, Py-H), 7.94 (t, J=8.0Hz, 1H, Py-H), 7.41 (s, 1H, Ph-H), 7.27 (s, 1H, Ph-H), 6.94 (s, 2H, Ph-H), 2.78-2.87 (m, 2H, 2 × CH), 2.36-2.43 (m, 4H, 2 × CH ₂), 2.35 (s, 3H, CH ₃), 2.27 (s, 3H, CH ₃), 1.26 (d, J=1.6Hz, 12H, 4 × CH ₃), 1.15 (t, J=7.6Hz, 6H, 2 × CH ₃). ¹³c NMR:(100MHz, CDCl ₃): 167.2,155.4,155.2,145.6,145.4,137.3,136.9,136.1,132.5,131.2,126.8,122.3,121.9,121.8,28.6,24.7,23.4,23.4,23.1,23.0,21.1,17.3,16.8,13.9.FT-IR (cm ^-1): 2964 (m), 1643 (ν _c=N, m), 1577 (m), 1456 (s), 1365 (s), 1325 (w), 1254 (m), 1195 (s), 1121 (w), 857 (m), 814 (m), 779 (w), 694 (w). ultimate analysis: C ₆₄h ₈₀n ₆(932) theoretical value: N, 9.00; C, 82.36; H, 8.64. experimental value: N, 8.71; C, 82.03; H, 8.59.

Embodiment 12, preparation N, N ^/-bis-(1-(3-(1-(2,6-dimethyl benzene imines) ethyl) pyridine-2-yl) ethylidene) tetramethyl benzidine closes cobalt chloride [Co-1] (R ¹for methyl, R ²for hydrogen, R ³for methyl)

By embodiment 2 gained N, N ^/-bis-(1-(3-(1-(2,6-dimethyl benzene imines) ethyl) pyridine-2-yl) ethylidene) tetramethyl benzidine (L1) (0.080g, 0.11mmol) and CoCl ₂(0.024g, 0.20mmol) is at CH ₂cl ₂(5mL) stirring at room 12h. reaction solution is concentrated and in the mixing solutions of EtOH (5mL), adds a large amount of ether sedimentations, and throw out is collected by filtration, and washs with a large amount of ether.Obtain yellow powder (0.063g, 66.5%yield).FT-IR ( ^-1cm): 2970 (w), 1626 (ν _c=N, m), 1522 (w), 1457 (s), 1436 (s), 1403 (s), 1269 (m), 1248 (m), 1214 (w), 852 (m), 810 (m), 762 (m), 733 (w). ultimate analysis: C ₅₀h ₅₂n ₆co ₂cl ₄(996) theoretical value: N, 8.43; C, 60.25; H, 5.26. experimental value: N, 8.36; C, 59.92; H, 5.71.MS (MALDI-TOF, m/z): 996.16. experimental value: m/z984.1[M-CoCl ₄+ CCA] ⁺, 735.8[M-Co ₂cl ₄] ⁺.

Embodiment 13, preparation N, N ^/-bis-(1-(3-(1-(2,6-diethylbenzene imines) ethyl) pyridine-2-yl) ethylidene) tetramethyl benzidine closes cobalt chloride [Co-2] (R ¹for ethyl, R ²for hydrogen, R ³for methyl)

By embodiment 3 gained N, N ^/-bis-(1-(3-(1-(2,6-diethylbenzene imines) ethyl) pyridine-2-yl) ethylidene) tetramethyl-aniline (L2) (0.088g, 0.11mmol) and CoCl ₂(0.024g, 0.20mmol) mixing is dissolved in CH ₂cl ₂(5mL) stirring at room 12h. reaction solution is concentrated and in the mixing solutions of EtOH (5mL), adds a large amount of ether sedimentations, and throw out is collected by filtration, and washs with a large amount of ether.Obtain yellow powder (0.056g, 53.6%yield) .FT-IR (cm ^-1): 2960 (m), 1630 (ν _c=N, m), 1587 (s), 1448 (m), 1368 (s), 1321 (w), 1263 (s), 1208 (s), 1097 (m), 870 (m), 818 (s), 791 (w), 742 (m), 695 (m). ultimate analysis: C ₅₆h ₆₀n ₆co ₂cl ₄(1052) theoretical value: N, 7.98; C, 61.61; H, 5.74. experimental value: N, 8.06; C, 61.64; H, 5.72.MS (MALDI-TOF, m/z): 1052.23. experimental value: m/z1040.1[M-CoCl ₄+ CCA] ⁺, 852.0[M-CoCl ₄] ⁺.

Embodiment 14, preparation N, N ^/-bis-(1-(3-(1-(2,6-diisopropyl benzene imines) ethyl) pyridine-2-yl) ethylidene) tetramethyl benzidine closes cobalt chloride [Co-3] (R ¹for sec.-propyl, R ²for hydrogen, R ³for methyl)

By embodiment 3 gained N, N ^/-bis-(1-(3-(1-(2,6-diisopropyl benzene imines) ethyl) pyridine-2-yl) ethylidene) tetramethyl benzidine (L3) (0.092g, 0.11mmol) and CoCl ₂(0.024g, 0.20mmol) mixing is dissolved in CH ₂cl ₂(5mL) stirring at room 12h. reaction solution is concentrated and in the mixing solutions of EtOH (5mL), adds a large amount of ether sedimentations, and throw out is collected by filtration, and washs with a large amount of ether.Obtain yellow powder (0.054g, 49.0%yield) .2958 (m), 2019 (w), 1636 (ν _c=N, m), 1584 (s), 1465 (m), 1367 (s), 1322 (w), 1263 (s), 1211 (s), 1101 (m), 892 (w), 807 (s), 762 (m), 739 (m), 697 (w). ultimate analysis: C ₅₈h ₆₈n ₆co ₂cl ₄(1108) theory: N, 7.58; C, 62.82; H, 6.18. experimental value: N, 7.59; C, 62.89; H, 6.10.MS (MALDI-TOF, m/z): 1108.29. experimental value: m/z1096.2[M-CoCl ₄+ CCA] ⁺, 943.1[M-CoCl ₃] ⁺, 908.1[M-CoCl ₄] ⁺, 850.1[M-Co ₂cl ₄] ⁺.

Embodiment 15, preparation N, N ^/-bis-(1-(3-(1-(2,6-dimethyl benzene imines) ethyl) pyridine-2-yl) ethylidene) tetraethyl-p-diaminodiphenyl closes cobalt chloride [Co-4] (R ¹for methyl, R ²for hydrogen, R ³for ethyl)

By embodiment 4 gained N, N ^/-bis-(1-(3-(1-(2,6-dimethyl benzene imines) ethyl) pyridine-2-yl) ethylidene) tetraethyl-p-diaminodiphenyl (L4) (0.087g, 0.11mmol) and CoCl ₂(0.024g, 0.20mmol) mixing is dissolved in CH ₂cl ₂(5mL) stirring at room 12h. reaction solution is concentrated and in the mixing solutions of EtOH (5mL), adds a large amount of ether sedimentations, and throw out is collected by filtration, and washs with a large amount of ether.Obtain yellow powder (0.078g, 75.5%yield).

Crystalline structure schematic diagram as shown in Figure 3.

As seen from the figure, compared with the structure of part, in title complex, two of biphenyl structural phenyl ring are no longer in a copline, but deflection mutually, pyridine ring is no longer vertical with the angle of the phenyl ring in biphenyl and aniline simultaneously, and angle diminishes, and title complex has symmetry equally; Not directly contact between two metal centers.

FT-IR (cm- ¹): 2968 (w), 1621 (ν _c=N, m), 1584 (s), 1464 (m), 1369 (s), 1320 (w), 1259 (s), 1210 (s), 1099 (m), 1056 (w), 865 (m), 806 (s), 765 (m). ultimate analysis: C ₅₄h ₆₀n ₆co ₂cl ₄(1052) theoretical value: N, 7.58; C, 62.82; H, 6.18. experimental value: N, 7.46; C, 62.69; H, 6.45.MS (MALDI-TOF, m/z): 1052.23. experimental value: m/z1040.2[M-CoCl ₄+ CCA] ⁺, 887.0[M-CoCl ₃] ⁺, 852.0[M-CoCl ₄] ⁺.

Embodiment 16, preparation N, N ^/-bis-(1-(3-(1-(2,6-diethylbenzene imines) ethyl) pyridine-2-yl) ethylidene) tetraethyl-p-diaminodiphenyl closes cobalt chloride [Co-5] (R ¹for ethyl, R ²for hydrogen, R ³for ethyl)

By embodiment 1 gained N, N ^/-bis-(1-(3-(1-(2,6-diethylbenzene imines) ethyl) pyridine-2-yl) ethylidene) tetraethyl-p-diaminodiphenyl (L5) (0.092g, 0.11mmol) and CoCl ₂(0.024g, 0.20mmol) mixing is dissolved in CH ₂cl ₂(5mL) stirring at room 12h. reaction solution is concentrated and in the mixing solutions of EtOH (5mL), adds a large amount of ether sedimentations, and throw out is collected by filtration, and washs with a large amount of ether.Obtain yellow powder (0.083g, 76.2%yield) .FT-IR (cm ^-1): 2963 (m), 2163 (w), 1623 (ν _c=Nm), 1586 (s), 1447 (s), 1368 (s), 1260 (s), 1207 (m), 1105 (w), 1026 (w), 868 (m), 807 (m), 765 (m). ultimate analysis: C ₅₈h ₆₈n ₆co ₂cl ₄(1108) theoretical value: N, 7.58; C, 62.82; H, 6.18. experimental value: N, 7.26; C, 63.20; H, 6.10.MS (MALDI-TOF, m/z): 1108.29. experimental value: m/z1096.2[M-CoCl ₄+ CCA] ⁺, 908.2[M-CoCl ₄] ⁺.

Embodiment 17, preparation 2N, N ^/-bis-(1-(3-(1-(2,6-diisopropyl benzene imines) ethyl) pyridine-2-yl) ethylidene) tetraethyl-p-diaminodiphenyl closes cobalt chloride [Co-6] (R ¹for sec.-propyl, R ²for hydrogen, R ³for ethyl)

By embodiment 6 gained N, N ^/-bis-(1-(3-(1-(2,6-diisopropyl benzene imines) ethyl) pyridine-2-yl) ethylidene) tetraethyl-p-diaminodiphenyl (L6) (0.099g, 0.11mmol) and CoCl ₂(0.024g, 0.20mmol) mixing is dissolved in CH ₂cl ₂(5mL) stirring at room 12h. reaction solution is concentrated and in the mixing solutions of EtOH (5mL), adds a large amount of ether sedimentations, and throw out is collected by filtration, and washs with a large amount of ether.Obtain yellow powder (0.052g, 45.2%yield) .FT-IR (cm ^-1): 2962 (m), 1621 (ν _c=N, m), 1585 (s), 1449 (s), 1370 (s), 1322 (w), 1248 (s), 1208 (m), 1104 (w), 868 (m), 814 (m), 794 (s), 764 (m). ultimate analysis: C ₆₂h ₇₆n ₆co ₂cl ₄(1164) theoretical value: N, 7.21; C, 63.92; H, 6.58. experimental value: N, 6.96; C, 64.29; H, 6.51.MS (MALDI-TOF, m/z): 1164.35. experimental value: m/z1152.3[M-CoCl ₄+ CCA] ⁺, 999.2[M-CoCl ₃] ⁺, 964.2[M-CoCl ₄] ⁺, 906.2[M-Co ₂cl ₄] ⁺.

Embodiment 18, preparation N, N ^/-bis-(1-(3-(1-(2,6-dimethyl benzene imines) ethyl) pyridine-2-yl) ethylidene) tetra isopropyl p-diaminodiphenyl closes cobalt chloride [Co-7] (R ¹for methyl, R ²for hydrogen, R ³for sec.-propyl)

By embodiment 7 gained N, N ^/-bis-(1-(3-(1-(2,6-dimethyl benzene imines) ethyl) pyridine-2-yl) ethylidene) tetra isopropyl p-diaminodiphenyl (L7) (0.092g, 0.11mmol) and CoCl ₂(0.024g, 0.20mmol) mixing is dissolved in CH ₂cl ₂(5mL) stirring at room 12h. reaction solution is concentrated and in the mixing solutions of EtOH (5mL), adds a large amount of ether sedimentations, and throw out is collected by filtration, and washs with a large amount of ether.Obtain yellow powder (0.070g, 63.7%yield) .FT-IR (cm ^-1): 2958 (m), 1636 (ν _c=Nm), 1569 (s), 1460 (s), 1362 (s), 1321 (w), 1244 (s), 1200 (m), 1117 (m), 868 (m), 822 (s), 760 (m). ultimate analysis: C ₅₈h ₆₈n ₆co ₂cl ₄(1108) theoretical value: N, 7.58; C, 62.82; H, 6.18. experimental value: N, 7.57; C, 62.98; H, 6.05.MS (MALDI-TOF, m/z): 1108.29. experimental value: m/z1096.3[M-CoCl ₄+ CCA] ⁺, 908.1[M-CoCl ₄] ⁺.

Embodiment 19, N, N ^/-bis-(1-(3-(1-(2,6-diethylbenzene imines) ethyl) pyridine-2-yl) ethylidene) tetra isopropyl p-diaminodiphenyl closes cobalt chloride [Co-8] (R ¹for ethyl, R ²for hydrogen, R ³for sec.-propyl)

By embodiment 8 gained N, N ^/-bis-(1-(3-(1-(2,6-diethylbenzene imines) ethyl) pyridine-2-yl) ethylidene) tetra isopropyl p-diaminodiphenyl (L8) (0.099g, 0.11mmol) and CoCl ₂(0.024g, 0.20mmol) mixing is dissolved in CH ₂cl ₂(5mL) stirring at room 12h. reaction solution is concentrated and in the mixing solutions of EtOH (5mL), adds a large amount of ether sedimentations, and throw out is collected by filtration, and washs with a large amount of ether.Obtain yellow powder (0.096g, 82.9%yield) .FT-IR (cm ^-1): 2962 (s), 2019 (w), 1621 (ν _c=N, m), 1585 (s), 1461 (s), 1368 (s), 1320 (m), 1262 (s), 1206 (m), 1104 (m), 870 (m), 806 (m). ultimate analysis: C ₆₂h ₇₆n ₆co ₂cl ₄(1164) theoretical value: N, 7.21; C, 63.92; H, 6.58. experimental value: N, 6.99; C, 64.14; H, 6.60.MS (MALDI-TOF, m/z): 1164.35. experimental value: m/z1152.3[M-CoCl ₄+ CCA] ⁺, 999.2[M-CoCl ₃] ⁺, 964.2[M-CoCl ₄] ⁺, 906.2[M-Co ₂cl ₄] ⁺.

Embodiment 20, preparation N, N ^/-bis-(1-(3-(1-(2,6-diisopropyl benzene imines) ethyl) pyridine-2-yl) ethylidene) tetra isopropyl p-diaminodiphenyl closes cobalt chloride [Co-9] (R ¹for sec.-propyl, R ²for hydrogen, R ³for sec.-propyl)

By embodiment 9 gained N, N ^/-bis-(1-(3-(1-(2,6-diisopropyl benzene imines) ethyl) pyridine-2-yl) ethylidene) tetra isopropyl p-diaminodiphenyl (L9) (0.11g, 0.11mmol) and CoCl ₂(0.024g, 0.20mmol) mixing is dissolved in CH ₂cl ₂(5mL) stirring at room 12h. reaction solution is concentrated and in the mixing solutions of EtOH (5mL), adds a large amount of ether sedimentations, and throw out is collected by filtration, and washs with a large amount of ether.Obtain yellow powder (0.071g, 58.4%yield) .FT-IR (cm ^-1): 2960 (s), 2160 (w), 2019 (w), 1621 (ν _c=N, m), 1585 (s), 1462 (s), 1368 (s), 1321 (m), 1262 (s), 1207 (m), 1103 (w), 1024 (w), 940 (w), 869 (m), 802 (s). ultimate analysis: C ₆₆h ₈₄n ₆co ₂cl ₄(1220) theoretical value: N, 6.88; C, 64.92; H, 6.93. experimental value: N, 6.74; C, 65.26; H, 6.89.MS (MALDI-TOF, m/z): 1220.41. experimental value: m/z1208.4[M-CoCl ₃+ CCA] ⁺, 1055.2[M-CoCl ₃] ⁺, 1020.3[M-CoCl ₄] ⁺, 962.2[M-Co ₂cl ₄] ⁺.

Embodiment 21, preparation N, N ^/-bis-(1-(3-(1-2,4,6-trimethylammonium) pyridine-2-yl) ethylidene) tetramethyl benzidine closes cobalt chloride [Co-10] (R ¹for methyl, R ²for methyl, R ³for methyl)

By embodiment 10 gained N, N ^/-bis-(1-(3-(1-2,4,6-trimethylammonium) pyridine-2-yl) ethylidene) tetramethyl benzidine (L10) (0.084g, 0.11mmol) and CoCl ₂(0.024g, 0.20mmol) mixing is dissolved in CH ₂cl ₂(5mL) stirring at room 12h. reaction solution is concentrated and in the mixing solutions of EtOH (5mL), adds a large amount of ether sedimentations, and throw out is collected by filtration, and washs with a large amount of ether.Obtain yellow powder (0.081g, 79.6%yield) .FT-IR ( ^-1cm): 2962 (m), 2030 (w), 1645 (ν _c=N, w), 1579 (m), 1455 (m), 1366 (s), 1322 (w), 1256 (m), 1208 (s), 1121 (w), 857 (m), 815 (m), 740 (w), 698 (w). ultimate analysis: C ₅₂h ₅₆n ₆co ₂cl ₄(1024) theoretical value: N, 8.20; C, 60.95; H, 5.51. experimental value: N, 7.81; C, 61.26; H, 5.47.MS (MALDI-TOF, m/z): 1024.20. experimental value: m/z1012.3[M-CoCl ₄+ CCA] ⁺, 859.1[M-CoCl ₃] ⁺, 824.1[M-CoCl ₄] ⁺, 766.1[M-Co ₂cl ₄] ⁺.

Embodiment 22, preparation N, N ^/-bis-(1-(3-(1-(2,6-diethyl-4-methylbenzene) imines) ethyl) pyridine-2-yl) ethylidene) tetra isopropyl p-diaminodiphenyl closes cobalt chloride [Co-11] (R ¹for ethyl, R ²for methyl, R ³for sec.-propyl)

By embodiment 11 gained N, N ^/-bis-(1-(3-(1-(2,6-diethyl-4-methylbenzene) imines) ethyl) pyridine-2-yl) ethylidene) tetra isopropyl p-diaminodiphenyl (L11) (0.10g, 0.11mmol) and CoCl ₂(0.024g, 0.20mmol) mixing is dissolved in CH ₂cl ₂(5mL) stirring at room 12h. reaction solution is concentrated and in the mixing solutions of EtOH (5mL), adds a large amount of ether sedimentations, and throw out is collected by filtration, and washs with a large amount of ether.Obtain yellow powder (0.070g, 94.2%yield): FT-IR (cm ^-1): 2963 (s), 2017 (w), 1624 (ν _c=N, w), 1584 (m), 1451 (s), 1367 (s), 1323 (w), 1262 (s), 1205 (m), 1104 (w), 868 (m), 798 (m), 764 (m), 739 (w). ultimate analysis: C ₆₄h ₈₀n ₆co ₂cl ₄(1192) theoretical value: N, 7.04; C, 64.43; H, 6.76. experimental value: N, 6.59; C, 64.26; H, 6.86.MS (MALDI-TOF, m/z): 1192.38. experimental value: m/z1180.6[M-CoCl ₄+ CCA] ⁺, 1027.4[M-CoCl ₃] ⁺, 992.4[M-CoCl ₄] ⁺, 934.4[M-Co ₂cl ₄] ⁺.

Embodiment 23, utilize title complex Co-3 and MAO associating catalysis to add the vinyl polymerization of depressing:

A) under nitrogen protection; the toluene solution of CATALYST Co-3 (1.5 μ mol) of the promotor MAO of 50ml toluene and 1.4ml (1.46mol/L in toluene) and 30ml is joined in 250ml stainless steel autoclave successively, and making cumulative volume is 100ml.Now Al/Co=1000:1.Mechanical stirring starts, and keeps 400 revs/min, when polymerization temperature reaches 40 ℃, in reactor, is filled with ethene, and polyreaction starts.At 40 ℃, keep the ethene pressure of 10atm, stir and carry out polyreaction 30min.With the ethanolic soln neutralization reaction liquid of 5% hcl acidifying, obtain polymkeric substance precipitation, to wash for several times with ethanol, vacuum drying is to constant weight, the 9.3g polymkeric substance of weighing to obtain, polymerization activity: 6.20 × 10 ⁶g/mol (Co) h ^-1, polymkeric substance T _m=130.8 ℃ of (T _mfor the melt temperature of polymkeric substance, by DSC, test gained).

Get resulting polymers 100mg, be dissolved in the deuterated orthodichlorobenzene of 5ml, under 135 ℃ of conditions, test this polymkeric substance ¹³c data, as shown in Figure 4.Signal accumulation 1000 times, obtains fignal center displacement and locates at 29.96 (ppm), is indicated as methylene group displacement, proves that resulting polymers is extended chain polyethylene.

B) substantially same a), difference is: polymerization temperature is 50 ℃.Polymerization activity: 6.70 × 10 ⁶g/mol (Co) h ^-1, polymkeric substance T _m=131.4 ℃.

C) substantially same a), difference is: polymerization temperature is 60 ℃.Polymerization activity: 4.30 × 10 ⁶g/mol (Co) h ^-1, polymkeric substance T _m=129.6 ℃.

D) substantially same a), difference is: polymerization temperature is 70 ℃.Polymerization activity: 2.80 × 10 ⁶g/mol (Co) h ^-1, polymkeric substance T _m=128.6 ℃.

E) substantially same a), difference is: polymerization temperature is 40 ℃.Promotor consumption is the MAO (1.46mol/L in toluene) of 0.7ml, makes Al/Co=500:1.Polymerization activity: 5.00 × 10 ⁶g/mol (Co) h ^-1, polymkeric substance T _m=125.8 ℃.

F) substantially same a), difference is: polymerization temperature is 40 ℃.Promotor consumption is the MAO (1.46mol/L in toluene) of 1.4ml, makes Al/Co=1500:1.Polymerization activity: 5.10 × 10 ⁶g/mol (Co) h ^-1, polymkeric substance T _m=128.8 ℃.

G) substantially same a), difference is: polymerization temperature is 40 ℃.Promotor consumption is the MAO (1.46mol/L in toluene) of 2.7ml, makes Al/Co=2000:1.Polymerization activity: 4.40 × 10 ⁶g/mol (Co) h ^-1, polymkeric substance T _m=126.0 ℃.

H) substantially same a) difference is: Primary Catalysts is Co-1, and polymerization temperature is 50 ℃.Make Al/Co=1000:1.Polymerization time is 15min.Polymerization activity: 11.8 × 10 ⁶g/mol (Co) h ^-1, polymkeric substance T _m=120.9 ℃.

I) substantially same a) difference is: Primary Catalysts is Co-1, and polymerization temperature is 50 ℃.Make Al/Co=1000:1.Polymerization time is 30min.Polymerization activity: 7.30 × 10 ⁶g/mol (Co) h ^-1, polymkeric substance T _m=124.5 ℃.

J) substantially same a) difference is: Primary Catalysts is Co-1, and polymerization temperature is 50 ℃.Make Al/Co=1000:1.Polymerization time is 45min.Polymerization activity: 5.90 × 10 ⁶g/mol (Co) h ^-1, polymkeric substance T _m=121.6 ℃.

K) substantially same a) difference is: Primary Catalysts is Co-1, and polymerization temperature is 50 ℃.Make Al/Co=1000:1.Polymerization time is 60min.Polymerization activity: 4.70 × 10 ⁶g/mol (Co) h ^-1, polymkeric substance T _m=122.1 ℃.

L) substantially same a) difference is: Primary Catalysts is Co-1, and polymerization temperature is 50 ℃.Make Al/Co=1000:1.Polymerization time is 30min.Polymerization pressure is 1atm.Polymerization activity: 0.30 × 10 ⁶g/mol (Co) h ^-1, polymkeric substance T _m=104.6 ℃.

M) substantially same a) difference is: Primary Catalysts is Co-1, and polymerization temperature is 50 ℃.Make Al/Co=1000:1.Polymerization time is 30min.Polymerization pressure is 5atm.Polymerization activity: 4.10 × 10 ⁶g/mol (Co) h ^-1, polymkeric substance T _m=122.7 ℃.

Embodiment 24, utilize title complex Co-1 and MMAO associating catalysis to add the vinyl polymerization of depressing

Substantially same a) difference is: Primary Catalysts is Co-1, and the MMAO (1.93mol/L in toluene) that promotor consumption is 1.5ml, makes Al/Co=1500:1; Polymerization temperature is 30 ℃.Polymerization activity: 3.80 × 10 ⁶g/mol (Co) h- ¹, polymkeric substance T _m=117.0 ℃.

Substantially same b) difference is: Primary Catalysts is Co-1, and the MMAO (1.93mol/L in toluene) that promotor consumption is 1.5ml, makes Al/Co=1500:1; Polymerization temperature is 40 ℃.Polymerization activity: 4.50 × 10 ⁶g/mol (Co) h ^-1, polymkeric substance T _m=116.5 ℃.

Substantially same c) difference is: Primary Catalysts is Co-1, and the MMAO (1.93mol/L in toluene) that promotor consumption is 1.5ml, makes Al/Co=1500:1; Polymerization temperature is 50 ℃.Polymerization activity: 3.60 × 10 ⁶g/mol (Co) h ^-1, polymkeric substance T _m=115.8 ℃.

Substantially same d) difference is: Primary Catalysts is Co-1, and the MMAO (1.93mol/L in toluene) that promotor consumption is 1.5ml, makes Al/Co=1500:1; Polymerization temperature is 60 ℃.Polymerization activity: 2.00 × 10 ⁶g/mol (Co) h ^-1, polymkeric substance T _m=115.1 ℃.

Substantially same e) difference is: Primary Catalysts is Co-1, and the MMAO (1.93mol/L in toluene) that promotor consumption is 1.5ml, makes Al/Co=1500:1; Polymerization temperature is 70 ℃.Polymerization activity: 0.87 × 10 ⁶g/mol (Co) h ^-1, polymkeric substance T _m=112.96 ℃.

Substantially same f) difference is: Primary Catalysts is Co-1, and the MMAO (1.93mol/L in toluene) that promotor consumption is 0.5ml, makes Al/Co=500:1; Polymerization temperature is 50 ℃.Polymerization activity: 9.00 × 10 ⁶g/mol (Co) h ^-1, polymkeric substance T _m=131.24 ℃.

Substantially same g) difference is: Primary Catalysts is Co-1, and the MMAO (1.93mol/L in toluene) that promotor consumption is 1.0ml, makes Al/Co=1000:1; Polymerization temperature is 50 ℃.Polymerization activity: 7.70 × 10 ⁶g/mol (Co) h ^-1, polymkeric substance T _m=130.2 ℃.

Substantially same h) difference is: Primary Catalysts is Co-1, and the MMAO (1.93mol/L in toluene) that promotor consumption is 2.1ml, makes Al/Co=2000:1; Polymerization temperature is 60 ℃.Polymerization activity: 10.5 × 10 ⁶g/mol (Co) h ^-1, polymkeric substance T _m=129.0 ℃.

Embodiment 25, utilize title complex Co-1 and MAO associating catalysis to add the vinyl polymerization of depressing

Substantially same a), difference is: Primary Catalysts is Co-1; Promotor consumption is the MAO (1.46mol/L in toluene) of 1.4ml, makes Al/Co=1000:1; Polymerization temperature is 50 ℃.Polymerization activity: 7.30 × 10 ⁶g/mol (Co) h ^-1, polymkeric substance T _m=124.5 ℃.

Embodiment 26, utilize title complex Co-2 and MAO associating catalysis to add the vinyl polymerization of depressing

Substantially same a), difference is: Primary Catalysts is Co-2; Promotor consumption is the MAO (1.46mol/Lin toluene) of 1.4ml, makes Al/Co=1000:1; Polymerization temperature is 50 ℃.Polymerization activity: 6.8 × 10 ⁶g/mol (Co) h- ¹, polymkeric substance T _m=126.9 ℃.

Embodiment 27, utilize title complex Co-3 and MAO associating catalysis to add the vinyl polymerization of depressing

Substantially same a), difference is: Primary Catalysts is Co-3; Promotor consumption is the MAO (1.46mol/L in toluene) of 1.4ml, makes Al/Co=1000:1; Polymerization temperature is 50 ℃.Polymerization activity: 6.70 × 10 ⁶g/mol (Co) h ^-1, polymkeric substance T _m=131.4 ℃.

Embodiment 28, utilize title complex Co-4 and MAO associating catalysis to add the vinyl polymerization of depressing

Substantially same a), difference is: Primary Catalysts is Co-4; Promotor consumption is the MAO (1.46mol/L in toluene) of 1.4ml, makes Al/Co=1000:1; Polymerization temperature is 50 ℃.Polymerization activity: 7.00 × 10 ⁶g/mol (Co) h ^-1, polymkeric substance T _m=124.6 ℃.

Embodiment 29, utilize title complex Co-5 and MAO associating catalysis to add the vinyl polymerization of depressing

Substantially same a), difference is: Primary Catalysts is Co-5; Promotor consumption is the MAO (1.46mol/L in toluene) of 1.4ml, makes Al/Co=1000:1; Polymerization temperature is 50 ℃.Polymerization activity: 3.90 × 10 ⁶g/mol (Co) h ^-1, polymkeric substance T _m=129.0 ℃.

Embodiment 30, utilize title complex Co-6 and MAO associating catalysis to add the vinyl polymerization of depressing

Substantially same a), difference is: Primary Catalysts is Co-6; Promotor consumption is the MAO (1.46mol/L in toluene) of 1.4ml, makes Al/Co=1000:1; Polymerization temperature is 50 ℃.Polymerization activity: 1.30 × 10 ⁶g/mol (Co) h ^-1, polymkeric substance T _m=131.0 ℃.

Embodiment 31, utilize title complex Co-7 and MAO associating catalysis to add the vinyl polymerization of depressing

Substantially same a), difference is: Primary Catalysts is Co-7; Promotor consumption is the MAO (1.46mol/L in toluene) of 1.4ml, makes Al/Co=1000:1; Polymerization temperature is 50 ℃.Polymerization activity: 7.70 × 10 ⁶g/mol (Co) h ^-1, polymkeric substance T _m=130.0 ℃.

Embodiment 32, utilize title complex Co-8 and MAO associating catalysis to add the vinyl polymerization of depressing

Substantially same a), difference is: Primary Catalysts is Co-8; Promotor consumption is the MAO (1.46mol/L in toluene) of 1.4ml, makes Al/Co=1000:1; Polymerization temperature is 50 ℃.Polymerization activity: 4.50 × 10 ⁶g/mol (Co) h ^-1, polymkeric substance T _m=132.4 ℃.

Embodiment 33, utilize title complex Co-9 and MAO associating catalysis to add the vinyl polymerization of depressing

Substantially same a), difference is: Primary Catalysts is Co-9; Promotor consumption is the MAO (1.46mol/L in toluene) of 1.4ml, makes Al/Co=1000:1; Polymerization temperature is 50 ℃.Polymerization activity: 2.10 × 10 ⁶g/mol (Co) h ^-1, polymkeric substance T _m=133.4 ℃.

Embodiment 34, utilize title complex Co-10 and MAO associating catalysis to add the vinyl polymerization of depressing

Substantially same a), difference is: Primary Catalysts is Co-10; Promotor consumption is the MAO (1.46mol/L in toluene) of 1.4ml, makes Al/Co=1000:1; Polymerization temperature is 50 ℃.Polymerization activity: 5.50 × 10 ⁶g/mol (Co) h- ¹, polymkeric substance T _m=124.2 ℃.

Embodiment 35, utilize title complex Co-11 and MAO associating catalysis to add the vinyl polymerization of depressing

Substantially same a), difference is: Primary Catalysts is Co-11; Promotor consumption is the MAO (1.46mol/L in toluene) of 1.4ml, makes Al/Co=1000:1; Polymerization temperature is 50 ℃.Polymerization activity: 0.93 × 10 ⁶g/mol (Co) h ^-1, polymkeric substance T _m=132.9 ℃.

Claims

1. 2,6-dienylamine pyridine binuclear cobalt complex shown in formula I,

In said formula I,

R ^is at least one selected from methyl, ethyl and isopropyl;

R ² is methyl or hydrogen;

R ³ is methyl, ethyl or isopropyl.

2. a method for preparing the described 2,6-dienamine pyridine binuclear cobalt complex of claim 1, comprising the steps of: at room temperature, the ligand compound shown in formula V is mixed with CoCl _and carried out complexation reaction , to obtain the 2,6-dienylamine pyridine binuclear cobalt complex shown in formula I;

In the formula V,

R ^is at least one selected from methyl, ethyl and isopropyl;

R ² is methyl or hydrogen;

R ³ is methyl, ethyl or isopropyl.

3. The method according to claim 2, characterized in that: the ratio of the ligand compound shown in formula V to CoCl ₂ is 1.0-1.2:2.0-2.1, specifically 1.1:2;

In the complexation reaction step, the temperature is room temperature; the time is 8-24 hours, specifically 12 hours;

The complexation reaction is carried out in an organic solvent;

The organic solvent is specifically selected from at least one of methylene chloride, ethanol and methanol.

4. Ligand compounds shown in formula V,

In the formula V, R ^is selected from at least one of methyl, ethyl and isopropyl;

The R ² is methyl or hydrogen;

R ³ is methyl, ethyl or isopropyl.

5. A method for preparing the ligand compound of formula V described in claim 4, comprising the steps of:

1) Under the condition of formic acid or acetic acid as a catalyst, mix 2,6-diacetylpyridine and aniline compound represented by formula II in an ice bath for condensation reaction to obtain 2-enamine-6 represented by formula III - Acylpyridine compounds;

2) Under the condition of p-toluenesulfonic acid or trifluoroacetic acid as a catalyst, the 2-enamino-6-acylpyridine compound obtained in step 1) is mixed with the benzidine compound shown in formula IV and refluxed for condensation reaction to obtain the Ligand compounds shown in formula V;

In the formulas II to IV, the definitions of R ¹ , R ² and R ³ are the same as the definitions of R ¹ , R ² and R ³ in claim 1, respectively.

6. The method according to claim 5, characterized in that: in the step 1), the amount of the catalyst is 5%-10% of the molar amount of 2,6-diacetylpyridine;

The molar ratio of the 2,6-diacetylpyridine to the aniline compound represented by formula II is 1.1-1.2:1.0-1.1, specifically 1.2:1;

In the condensation reaction step, the time is 12-24 hours, specifically 24 hours;

The condensation reaction is carried out in an organic solvent; the organic solvent is specifically selected from at least one of ethanol, methanol and methylene chloride;

In the step 2), the amount of the catalyst is 5%-10% of the molar amount of the 2-enamine-6-acylpyridine compound;

The molar ratio of the 2-enamine-6-acylpyridine compound to the benzidine compound shown in formula IV is 2.0-1.0:2.0-1.2, specifically 2.0:1.1;

In the condensation reaction step, the time is 8-12 hours, specifically 12 hours;

The condensation reaction is carried out in an organic solvent; the organic solvent is specifically selected from at least one of toluene, xylene and o-dichlorobenzene.

7. A catalyst composition for ethylene polymerization, the active component of which comprises the 2,6-dienylamine pyridine binuclear cobalt complex shown in formula I of claim 1.

8. The catalyst composition according to claim 7, characterized in that: the catalyst composition also includes a co-catalyst; the co-catalyst is specifically selected from at least one of methyl aluminoxane and modified methyl aluminoxane A sort of;

The molar ratio of the metal aluminum element in the cocatalyst to the cobalt element in the 2,6-dienaminopyridine binuclear cobalt complex shown in formula I is 500-2000:1, specifically 500:1, 1000:1, 1500: 1, 2000: 1, 500-1500: 1, 1000-2000: 1.

9. A method for preparing polyethylene, comprising the following steps: under the condition that the catalyst composition according to any one of claims 7-8 is used as a catalyst, catalyzing ethylene for polymerization reaction, and obtaining the polyethylene after the reaction is completed.

10. The method according to claim 9, characterized in that: in the polymerization reaction step, the temperature is 40-70°C; specifically 40°C, 50°C, 60°C, 70°C, 40-60°C or 50- 70°C;

The pressure is 1-10atm;

The time is 15min-60min;

The polymerization reaction is carried out in a solvent;

The solvent is selected from at least one of toluene, isobutanol and n-hexane;

The polymerization reaction is carried out in an inert atmosphere;

The inert atmosphere is specifically a nitrogen atmosphere.