CN102731578A - 2,8-diimine-4,5,6 hydro quinoline transition metal complex, preparation method thereof, and application thereof - Google Patents

Abstract

The invention discloses a 2,8-diimine-4,5,6 hydroquinoline transition metal complex, a preparation method and an application thereof. Its structural formula is shown in formula I. In formula I, R ¹ is selected from hydrogen, methyl, ethyl and propyl, and R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently selected from hydrogen, alkyl , Nitro and halogen; M is a transition metal. The preparation method of the above-mentioned transition metal complexes provided by the present invention comprises the following steps: (1) 2-aldehyde(ketone)-4,5,6-hydrogenated-8-quinolinone represented by formula II and The substituted aniline is reacted in the presence of a catalyst to obtain a 2,8-diimine-4,5,6-hydroquinoline compound; (2) the 2,8-diimine-4,5,6-hydrogenated Quinoline compounds can be obtained by reacting with MCl ₂ . The metal complex is used to catalyze the polymerization of ethylene. The obtained polyethylene has highly linear characteristics and is suitable for the production of high-density polyethylene or polyethylene wax. The catalyst has strong tolerance to high reaction temperature and has a wide range of industrial applications. Application prospects.

Description

2,8-diimine-4,5,6 hydroquinoline transition metal complex and its preparation method and application

technical field

The invention relates to a 2,8-diimine-4,5,6 hydroquinoline transition metal complex and a preparation method and application thereof, specifically an application in catalyzing ethylene polymerization.

Background technique

Polyolefin mainly includes polyethylene, polypropylene and poly-1-butene, etc., as the largest product, it accounts for about half of polymer materials. And because of its excellent material properties, polyolefin materials are widely used in all aspects of production and life. Among them, polyethylene is a synthetic resin material with the fastest development, the largest output, and a wide range of uses. And polyethylene includes many types, among which polyethylene is called polyethylene with a molecular weight of more than hundreds of thousands, which is the main raw material of plastics; and polyethylene wax has a molecular weight of less than tens of thousands, which is usually used as a lubricant. It is characterized by high softening point, which is close to high molecular weight polyethylene, and is widely used because of its excellent cold resistance, heat resistance, chemical resistance and abrasion resistance. At present, whether it is high-density polyethylene or polyethylene wax, Ziegler-type catalysts are still the most commonly used catalysts. Divided by elements, it is still the compound of the four major metals of chromium, vanadium, zirconium and titanium among the transition metals as the main catalyst, supplemented by the main catalyst and the co-catalyst and carrier suitable for the polymerization reaction to form the catalytic system. However, our recent research results show that late transition metal catalysts have potentially great potential in the preparation of high-density polyethylene or polyethylene wax.

Firstly, in 1998, Brookhart and Gibson et al. simultaneously reported the complexes of pyridyl diimide iron (II) and cobalt (II), which could well oligomerize or polymerize ethylene by adjusting the substituents on the benzene ring. The structure As shown in Formula A (J. Am. Chem. Soc., 1998, 120, 4049-4050; Chem. Commun. 1998, 849-850):

Formula A

Afterwards, around the pyridinediimide iron-cobalt complex catalyst, people have carried out a lot of research work and improved the catalyst structure. From the initial imitation of the pyridinediimide iron-cobalt complex catalyst model to the independent design and development of new catalyst models, the inventor's research group has successfully developed a series of late transition metal catalysts in the past 13 years Model.

In 2005, our research group developed a complex catalyst of 2-amino-1,10-phenanthroline iron and cobalt (Formula B), which not only exhibited a very high activity of 8.95×10 ⁷ g·mol ^-1 (Fe)·h ^-1 , and has high selectivity to α-olefins, and the distribution of oligomerization products approximately conforms to the Schluz-Flory rule (Organometallics 2006,25,666-677, Chinese patent application number 200510066427.2 application Date: April 22, 2005; Authorization announcement date: March 5, 2008; Authorization announcement number: CN100372609C). The activity of this kind of catalyst is comparable to that of the classical iron pyridinediimide catalyst.

Formula B

Afterwards, our research group developed 2-benzimidazole-6-aminopyridine iron and cobalt complex catalysts (Formula C), which can catalyze ethylene oligomerization and polymerization with high activity (Organometallics 2007, 26, 2720 -2734, Chinese patent application number 200610165446.5 filing date: December 20, 2006). The iron(II) complex exhibits high oligomerization and polymerization activity towards ethylene, reaching 10 ⁷ g mol Fe ^-1 h ^-1 . Oligomerization products include C ₄ , C ₆ , C ₈ , C ₁₀ , C ₁₂ , C ₁₄ , C ₁₆ , C ₁₈ , C ₂₀ and C ₂₂ , etc. The selectivity of α-olefin is as high as 99%; the polymer is low Molecular weight polyethylene and polyethylene wax.

Type C Type D

In the above research results, these catalyst systems can obtain high-density polyethylene with high activity, or the product contains some polyethylene wax. In the research and development of catalysts, the development of highly active and industrialized ethylene oligomerization and polymerization catalysts has always been the core content of new catalyst research. Although there are various problems to be solved, with the deepening of new catalysts Research and development can gain more accumulation in both theoretical knowledge and design experience.

Contents of the invention

The object of the present invention is to provide a 2,8-diimine-4,5,6 hydroquinoline transition metal complex and its preparation method and application.

The 2,8-diimine-4,5,6 hydroquinoline transition metal complex provided by the present invention has a structural formula as shown in formula I,

In formula I, R ¹ is selected from hydrogen, methyl, ethyl and propyl, R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently selected from hydrogen, alkyl, nitro and halogen; M is transition metals.

In the above-mentioned transition metal complexes, R ¹ is selected from hydrogen, methyl and ethyl; R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently selected from hydrogen, methyl, ethyl and isopropyl , Fluorine, chlorine, bromine and nitro; M is Fe or Co.

The present invention also provides a preparation method for the above-mentioned transition metal complex, comprising the following steps:

(1) 2-formyl (ketone)-4,5,6-hydrogenated-8-quinolinone represented by formula II reacts with substituted aniline represented by formula III in the presence of a catalyst to obtain 2,8-dimethoxy Amine-4,5,6-hydroquinoline compounds;

The structural formula of the 2,8-diimine-4,5,6-hydroquinoline compound is shown in formula IV and/or formula V;

Formula Ⅱ Formula Ⅲ

Formula IV Formula V

In the above formula, R ¹ is selected from hydrogen, methyl, ethyl and propyl, and R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently selected from hydrogen, alkyl, nitro and halogen;

(2) The 2,8-diimine-4,5,6-hydroquinoline compound is reacted with MCl ₂ to obtain the product; M is a transition metal.

In the above-mentioned preparation method, in step (1), the catalyst can be p-toluenesulfonic acid; the solvent of the reaction can be n-butanol; the temperature of the reaction can be 110 ~ 125 ° C, specifically 110 °C or 125°C, the time can be 6h~20h, specifically 6h or 20h.

In the above preparation method, when in formula III, R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each independently selected from fluorine or chlorine, the catalyst can be p-toluenesulfonic acid, and the solvent can be Tetraethyl orthosilicate, the temperature of described reaction can be 140～150 ℃, and the time can be 1～2 days.

In the above preparation method, in step (2), the molar ratio of MCl ₂ to the 2,8-diimine-4,5,6-hydroquinoline compound can be (1~1.5): (1 ~1.2), specifically it can be 1:1, 1:1.2 or 1.5:1, the temperature of the reaction can be 20~25°C, and the time can be 4~18h, preferably 4h, 10h or 18h.

The present invention further provides a catalyst composition, which is composed of the above-mentioned transition metal complex and a cocatalyst, and the cocatalyst is selected from one or more of aluminoxanes, alkylaluminum compounds and alkylaluminum chlorides. kind.

In the above catalyst composition, the aluminoxane can specifically be methylalumoxane (MAO) or methylalumoxane (MMAO) modified by tert-butylaluminum; the aluminum compound can be specifically trimethyl Aluminum, triethylaluminum, triisobutylaluminum, tri-n-hexylaluminum or tri-n-octylaluminum; the alkylaluminum chloride can specifically be diethylaluminum chloride or ethylaluminum dichloride;

In the above catalyst composition, the molar ratio of the aluminum in the cocatalyst to the central metal M in the transition metal complex may be (100~10000):1, specifically (500~2500): 1, 500:1, 750:1, 1000:1, 1250:1, 1500:1, 1750:1, 2000:1 or 2500:1.

The present invention further provides the application of the above-mentioned transition metal complex and the above-mentioned catalyst composition in catalyzing ethylene polymerization; when catalyzing ethylene polymerization, the polymerization temperature can be 20-100°C, specifically 30°C, 40°C C, 50°C, 60°C, 70°C or 80°C; the pressure can be 0.1~1.0MPa, specifically 0.5MPa or 1.0MPa.

The present invention designs and synthesizes 2,8-diimine-4,5,6-hydroquinoline transition metal complexes containing N^N^N ligands. The metal complexes are used to catalyze ethylene polymerization. The obtained polyethylene has highly linear characteristics, is suitable for producing high-density polyethylene or polyethylene wax, and exhibits excellent catalytic activity. The catalyst has strong tolerance to high reaction temperature and has wide industrial application prospects.

Description of drawings

Fig. 1 is the crystal structure figure of complex Fe1;

Fig. 2 is the crystal structure figure of complex Fe2;

Fig. 3 is the crystal structure figure of complex Co1;

Fig. 4 is the crystal structure figure of complex Co2;

Fig. 5 is a crystal structure diagram of the complex Co5.

Detailed ways

The experimental methods used in the following examples are conventional methods unless otherwise specified.

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

The synthesis of complex in the following examples is carried out according to the following equation:

Preferably, complexes Fe1-Fe8 and Co1-Co8 of the following substitution conditions can be obtained;

1.M=Fe,R ¹ =Me,R ² =R ⁶ =Me,R ³ =R ⁴ =R ⁵ =H; 2.M=Fe,R ¹ =Me,R ² =R ⁶ =Et,R ³ =R ⁴ =R ⁵ =H;

3. M=Fe, R ¹ =Me, R ² =R ⁶ = ⁱ Pr, R ³ =R ⁴ =R ⁵ =H; 4. M=Fe, R ¹ =Me, R ² =R ⁴ =R ⁶ =Me,R ³ =R ⁵ =H;

5. M=Fe, R ¹ =Me, R ² =R ⁶ =Et, R ⁴ =Me, R ³ =R ⁵ =H; 6. M=Fe, R ¹ =Me, R ² =R ⁶ =Cl ,R ³ =R ⁴ =R ⁵ =H;

7.M=Fe,R ¹ =H,R ² =R ⁶ =Me,R ³ =R ⁴ =R ⁵ =H; 8.M=Fe,R ¹ =Et,R ² =R ⁶ =Me,R ³ =R ⁴ =R ⁵ =H;

9.M=Co,R ¹ =R ² =R ⁶ =Me,R ³ =R ⁴ =R ⁵ =H; 10.M=Co,R ¹ =Me,R ² =R ⁶ =Et,R ³ = R ⁴ =R ⁵ =H;

11. M=Co, R ¹ =Me, R ² =R ⁶ = ⁱ Pr, R ³ =R ⁴ =R ⁵ =H; 12. M=Co, R ¹ =Me, R ² =R ⁴ =R ⁶ =Me,R ³ =R ⁵ =H;

13.M=Co,R ¹ =R ² =R ⁶ =Et,R ⁴ =Me,R ³ =R ⁵ =H; 14.M=Co,R ¹ =Me,R ² =R ⁶ =Cl,R ³ =R ⁴ =R ⁵ =H;

15. M=Co, R ¹ =R ³ =R ⁴ =R ⁵ =H; R ² =R6=Me, 16. M=Co, R ¹ =Et, R ² =R ⁶ =Me, R ³ =R ⁴ =R ⁵ =H.

Example 1, Synthesis of 2,8-(2,6-dimethylbenzimine)-4,5,6-hydroquinoline (L1/L1') ligand Put the raw material 2,8- into a 100ml two-necked bottle 4,5,6-hydroquinoline diketone (0.189g, 0.1mmol) and 2,6-dimethylaniline (0.302g, 0.25mmol)] and p-toluenesulfonic acid 0.015g, in n-butanol (30ml) After the reaction was carried out for about 6 hours, the reaction solution was concentrated and separated by silica gel column chromatography (PE:EA=50:1, v/v) to obtain 0.174 g of a yellow solid with a yield of 44.2%.

NMR showed that there were two isomers, among which the enamine isomer was the main product, L1:L1'=0.19:1(detected by ¹ HNMR).FT-IR(KBr,cm ^-1 ):3362(ν _NH ),2932,1644,1593,1469,1446,1363,1315,1199,1110,1094,844,764,666.Anal.Calcd.For C ₂₇ H ₂₉ N ₃ :C,81.99;H,7.39;N,10.62.Found: C,81.61;H,7.46;N,10.48.(L1'):8.27(d,1H,J=7.8HZ,Py-H),7.61(d,1H,J=7.9HZ,Py-H),7.14 (d,2H,J=7.3HZ,Ar-H),7.07(m,3H,Ar-H),6.94(t,1H,J=7.5HZ,Ar-H),6.83(s,1H,-NH -),4.63(t,1H,J=4.6,-CH=),2.94(t,2H,J=7.8HZ,-CH ₂ -),2.36(m,2H,-CH ₂ -),2.33(s ,6H,CH ₃ ),2.24(s,3H,N=CCH ₃ ),2.06(s,6H,CH ₃ ). ¹³ C NMR(100MHz;CDCl ₃ ;TMS):δ168.3,154.2,150.2,150.0,140.8 ,138.8,136.7,135.5,129.7,129.3,127.0,126.8,126.7,124.3,121.0,99.7,54.8,29.3,22.8,19.7,19.5,19.3,18.2,17.9.

Example 2, Synthesis of 2,8-(2,6-diethylphenylimine)-4,5,6-hydroquinoline (L2/L2') ligand

Put raw materials 2,8-4,5,6-hydroquinoline diketone (0.189g, 0.1mmol) and 2,6-diethylaniline (0.373g, 0.25mmol) and p-toluenesulfonic acid into 100ml two-necked bottle 0.015g was refluxed in n-butanol (30ml). After the reaction was carried out for about 6 hours, the reaction solution was concentrated and separated by silica gel column chromatography (PE:EA=50:1, v/v) to obtain 0.24g of a yellow solid. Yield 53%.

NMR showed that there were two isomers, among which the enamine isomer was the main product, L2:L2'=0.33:1(detected by ¹ HNMR).Mp:138-139°C.FT-IR(KBr,cm ^-1 ):3353(ν _NH ),2964,2931,2867,2821,2361,2335,1643,1580,1484,1455,1359,1315,1194,1101,1016,875,764,698. L2': ¹ H NMR:8.24 (d,1H,J=7.8Hz,Py-H),7.60(d,1H,J=7.8Hz,Py-H),7.16(s,3H,Ar-H),7.11(d,2H,J= 7.4,Ar-H),7.00(t,1H,J=7.9Hz,Ar-H),6.84(s,1H,-NH),4.60(t,J=4.6Hz,1H,=CH),2.91( t,2H,J=7.7Hz,-CH ₂ -),2.67(m,4H,-CH ₂ -),2.44(m,4H,-CH ₂ -),2.33(m,2H,-CH ₂ -) , 2.23 (s, 3H, N=CCH ₃ ), 1.21 (t, 6H, J=7.9Hz, -CH ₃ ), 1.14 (t, 6H, J=7.4Hz, -CH ₃ ). ¹³ C NMR (100MHz; CDCl ₃ ; TMS): δ166.8, 164.3, 153.1, 148.8, 148.1, 142.0, 138.9, 138.5, 135.6, 135.4, 134.3, 131.5, 131.4, 126.7, 126.2, 125.9, 124.8, 98 28.2,25.1,24.9,21.7,17.2,15.4,14.0.13.7.Anal.Calcd.for C ₃₁ H ₃₇ N ₃ :C,82.44,H,8.26,N,9.30;Found:C,82.44,H,8.32,N ,9.15.

Example 3, Synthesis of 2,8-(2,6-diisopropylphenylimine)-4,5,6-hydroquinoline (L3/L3') ligand

Put raw materials 2,8-4,5,6-hydroquinoline diketone (0.189g, 0.1mmol) and 2,6-isopropylaniline (0.443g, 0.25mmol) and 0.015 p-toluenesulfonic acid into 100ml two-necked bottle g, reflux in n-butanol (30ml) at a temperature of 110°C. After the reaction was carried out for about 20 hours, the reaction solution was concentrated and separated by silica gel column chromatography (PE:EA=50:1, v/v) to obtain 0.309 g yellow solid, yield 61.0%.

NMR showed two isomers, of which the enamine isomer was the main product. L3:L3'=0.3:1(detected by ¹ HNMR).Mp:183-184°C.FT-IR(KBr,cm ^-1 ):3370(ν _NH ),2960,2867,2361,1641,1580, 1460,1357,1311,1188,1106,1050,1018,799,764,696.Anal.Calcd.for C ₃₅ H ₄₅ N ₃ :C,82.79,H,8.93,N,8.28;Found:C,82.38,H,8.78, N, 7.92. ¹³ C NMR (100MHz; CDCl ₃ ; TMS): δ166.7, 153.0, 148.5, 146.9, 140.0, 136.8, 135.9, 135.7, 135.4, 134.1, 126.5, 123.5, 123.0, 119.7, 98.3, 20.3, 28. 23.2, 22.9, 21.5, 17.3. ^1H NMR: 8.23(d, 1H, J=7.7Hz, Py-H), 7.61(d, 1H, J=7.7Hz, Py-H), 7.16(t, 2H, Ar-H),7.11(d,3H,J=7.4,Ar-H),7.00(t,1H,J=7.9Hz,Ar-H),6.75(s,1H,-NH),4.61(t, 1H,J=4.5Hz,=CH),3.27(m,2H,-CH-),2.92(t,2H,J=7.7Hz,-CH ₂ -),2.32(t,2H,J=7.8Hz, -CH ₂ -),2.24(s,3H,N=CCH ₃ ),1.20(d,12H,J=6.4Hz,CH ₃ ),1.16(m,12H,CH ₃ ).

Example 4, Synthesis of 2,8-(2,4,6-trimethylbenzimine)-4,5,6-hydroquinoline (L4/L4') ligand

Put raw materials 2,8-4,5,6-hydroquinoline diketone (0.189g, 0.1mmol) and 2,4,6-trimethylaniline (0.338g (2.5eq)] and p-toluene into 100ml two-necked bottle Sulfonic acid 0.015g, reflux in n-butanol (30ml), the temperature is 125°C, after about 6 hours of reaction, the reaction solution is concentrated and separated by silica gel column chromatography (PE:EA=50:1, v/v) , to obtain 0.181g yellow solid, yield 43.0%.

NMR showed two isomers, of which the enamine isomer was the main product. L4:L4'=0.15:1(detected by ¹ HNMR).FT-IR(KBr,cm ^-1 ):3366(v _NH ),2922,1640,1572,1477,1442,1397,1360,1313,1204, 1148, 1106, 1017, 852, 789, 671. ¹ H NMR (400MHz, CDCl ₃ ): 8.25 (d, 1H, J=7.7Hz, Py-H), 7.59 (d, 1H, J=7.8Hz, Py-H), 6.95(s,2H,Ar-H),6.89(s,2H,Ar-H),6.74(s,1H,-NH),4.61(t,J=4.1Hz,1H,=CH),2.92(t ,J=7.9Hz,2H,-CH ₂ -),2.35(t,2H,J=7.5Hz,-CH ₂ ),2.31(s,6H,-CH ₃ ),2.28(s,6H,CH ₃ ) ,2.22(s,3H,N=CCH ₃ ),2.06(s,6H,-CH ₃ ). ¹³ C NMR(100MHz;CDCl ₃ ;TMS):δ168.5,154.3,150.0,147.7,139.1,138,2,136.6, 136.1, 135.4, 133.4, 130.4, 129.9, 126.8, 120.9, 99.4, 29.3, 22.8, 22.3, 22.1, 19.6, 19.5, 19.3, 17.9. Anal. Calcd. for C ₂₉ H ₃₃ N ₃ : C, 82.23, H, 7.85,N,9.92;Found:C,82.12,H,8.04,N,9.77.

Example 5, Synthesis of 2,8-(2,6-diethyl-4-methylbenzimine)-4,5,6-hydroquinoline (L5/L5') ligand

Add raw materials 2,8-4,5,6-hydroquinoline diketone (0.189g, 0.1mmol) and 2,6-diethyl-4-methylaniline (0.408g, 0.25mmol) and 0.015g of p-toluenesulfonic acid was refluxed in n-butanol (30ml). After the reaction was carried out for about 6 hours, the reaction solution was concentrated and separated by silica gel column chromatography (PE:EA=50:1, v/v) to obtain 0.234 g yellow solid, yield 47.0%.

NMR showed two isomers, of which the enamine isomer was the main product. L5:L5'=0.23:1.Mp:98-99°C.FT-IR(KBr,cm ^-1 ):3369(ν _NH ),2965,2929,2869,2828,1639,1570,1460,1359, 1313,1203,1148,1106,1018,883,857,793,773,702,671.(L5'): ¹ H NMR(400MHz,CDCl ₃ )8.23(d,1H,J=7.8Hz,Py-H),7.59(d,1H,J= 7.8Hz,Py-H),6.98(s,2H,Ar-H),6.93(s,2H,Ar-H),6.76(s,1H,-NH-),4.60(t,J=4.5Hz, 1H,=CH),2.91(t,J=7.7Hz,2H,-CH ₂ -),2.64(m,4H,-CH ₂ ),2.40(m,2H,-CH ₂ -),2.35(s, 3H,-CH ₃ ),2.34(s,3H,-CH ₃ ),2.31(m,4H,CH ₂ ),1.21(t,6H,J=7.6Hz,CH ₃ ),1.14(t,6H,J =7.5Hz, CH ₃ ). ¹³ C NMR (100MHz; CDCl ₃ ; TMS): 166.8, 152.9, 145.286, 141.545, 138.9, 135.5, 135.3, 133.9, 132.2, 131.2, 130.1, 127.2, 126.7, 126.6, 99.3, 24.7,24.6,24.5,24.3,21.4,21.1,20.9,16.9,15.2,13.8.Anal.Calcd.for C ₃₃ H ₄₁ N ₃ :C,82.63,H,8.61,N,8.76;Found:C,82.56, H, 8.47, N, 8.46.

Example 6, Synthesis of 2,8-(2,6-dichlorophenylimine)-4,5,6 hydroquinoline (L6) ligand

Put raw materials 2,8-4,5,6-hydroquinoline diketone (0.189g, 0.1mmol) and 2,6-dichloroaniline (0.405,0.25mmol) and p-toluenesulfonic acid 0.015g into 100ml two-necked bottle, Reflux in n-butanol (30ml), after the reaction was carried out for about 6 hours, the reaction solution was concentrated, and after separation by silica gel column chromatography (PE:EA=50:1, v/v), 0.144g of yellow solid was obtained, with a yield of 30.2 %.

NMR showed two isomers, of which the enamine isomer was the main product. L6:L6'=0.26:FT-IR (KBr, cm ^-1 ):3359(v _NH ),2965,2929,2869,2828,1634,1570,1460,1359,1313,1203,1148,1106,1018, 883,857,793,773,702,671.Anal.Calcd.for C ₂₃ H ₁₇ Cl ₄ N ₃ :C,57.89;H,3.59;N,8.81;Found:C,57.56, ^H ,3.47,N, _8.46 . ;TMS): 166.8, 152.9, 145.286, 141.545, 138.9, 135.5, 135.3, 133.9, 132.2, 131.2, 130.1, 127.2, 126.7, 126.6, 99.3. (L5'): ¹ H NMR (400MHz, CDCl ₃ ) 8.25 ( d,1H,J=7.8Hz,Py-H),7.56(d,1H,J=7.8Hz,Py-H),6.96(s,2H,Ar-H),6.93(s,2H,Ar-H ),6.76(s,1H,-NH-),4.60(t,J=4.5Hz,1H,=CH),2.91(t,J=7.7Hz,2H,-CH ₂ -),2.64(m,4H ,-CH ₂ ),2.35(s,3H,-CH ₃ ).

Example 7, (2,6-dimethylbenzimine)methyl)-5,6-dihydro-N-2,6-dimethyl)quinoline 8-amino (L7/L7') ligand Synthesis

Put raw materials 2-formyl-8-ketone-4,5,6-hydroquinoline (0.175g, 1mmol) and 2,6-dimethylaniline (0.302g, 2.5mmol) and p-toluenesulfonic acid into a 100ml two-necked bottle 0.015g was refluxed in n-butanol (30ml). After the reaction was carried out for about 6 hours, the reaction solution was concentrated and separated by silica gel column chromatography (PE:EA=50:1, v/v) to obtain 0.222g of a yellow solid. Yield 58.2%.

NMR showed two isomers, of which the enamine isomer was the main product. L7:L7'=0.23:1.Mp:98-99°C.FT-IR(KBr,cm ^-1 ):3369(v _NH ),2965,2929,2869,2828,1639,1570,1460,1359, 1313,1203,1148,1106,1018,883,857,793,773,702,671.Anal.Calcd.for C ₂₆ H ₂₇ N ₃ :C,81.85;H,7.13;N,11.01;Found:C,82.01;H,7.47,N,11.46. ¹ H NMR (400MHz, CDCl ₃ ) 8.17(d, 1H, J=7.8HZ, Py-H), 7.64(d, 1H, J=7.9HZ, Py-H), 7.53(s, 1H), 7.16( d,2H,J=7.3HZ,Ar-H),7.01(m,3H,Ar-H),6.90(t,1H,J=7.5HZ,Ar-H),6.82(s,1H,-NH- ),4.61(t,1H,J=4.6,-CH=),2.97(t,2H,J=7.8HZ,-CH ₂ -),2.39(m,2H,-CH ₂ -),2.34(s, 6H, CH ₃ ), 2.25(s, 3H, N=CCH ₃ ), 2.02(s, 6H, CH ₃ ). ¹³ C NMR: δ168.3, 154.2, 151.8, 150.0, 140.8, 138.8, 136.7, 135.5, 129.7, 129.3, 127.0, 126.8, 126.7, 124.3, 121.0, 99.7, 54.8, 22.8, 19.7, 19.5, 19.3, 18.2, 17.9.

Example 8, Synthesis of 2,8-(2,6-dimethylimine)-4,5,6 hydroquinoline (L8) ligand

Put the raw materials 2-propionyl-8-4,5,6 hydroquinolinone (0.203g, 1mmol) and 2,6-dimethylaniline (0.302g, 0.25mmol) and 0.015 p-toluenesulfonic acid into a 100ml two-necked bottle g, reflux in n-butanol (30ml), after the reaction was carried out for about 6 hours, the reaction solution was concentrated, and after separation by silica gel column chromatography (PE:EA=50:1, v/v), 0.10g of yellow solid was obtained. rate of 25.2%.

NMR showed two isomers, of which the enamine isomer was the main product. L8:L8'=0.15:1.FT-IR (KBr,cm ^-1 ):3369(v _NH ),2965,2929,2869,2828,1639,1570,1460,1359,1313,1203,1148,1106, 1018,883,857,793,773,702,671.Anal.Calcd.for C ₂₈ H ₃₁ N ₃ :C,82.11;H,7.63;N,10.26;Found:C,82.36;H,8.00;N,10.46. ¹¹ H NMR (400MHz,CDCl ₃ ):8.17(d,1H,J=7.8HZ,Py-H),7.64(d,1H,J=7.9HZ,Py-H),7.53(s,1H),7.16(d,2H,J=7.3 HZ,Ar-H),7.01(m,3H,Ar-H),6.90(t,1H,J=7.5HZ,Ar-H),6.82(s,1H,-NH-),4.61(t,1H ,J=4.6,-CH=),2.97(t,2H,J=7.8HZ,-CH ₂ -),2.39(m,2H,-CH ₂ -),2.35(m,2H),2.31(s, 6H,CH ₃ ),2.00(s,6H,CH ₃ ),1.65(t,3H,J=6.7Hz). ¹³ CNMR(100MHz;CDCl ₃ ):169.1,152.9,145.2,141.5,138.9,135.5,135.0 ,133.9,132.2,131.2,130.1,127.2,126.7,126.6,99.3,24.7,24.6,24.5,24.3,21.4,20.9,16.9,15.2,13.8,10.9.

Embodiment 9, the preparation of complex Fe1

Ligand L1/L1' (0.15g, 0.38mmol) and 1 equivalent of FeCl ₂ 4H ₂ O (0.070g, 0.35mmol) were placed in a Schlenk tube, and after vacuuming and filling with nitrogen three times, 5ml of degassed Water and ethanol were stirred and reacted at room temperature for 10 hours. After adding anhydrous ether, a large amount of precipitate was formed. The precipitate was filtered, washed with anhydrous ether, and dried to obtain a powder (0.16g, 76.2%).

Its characterization data are as follows: FT-IR (KBr, cm ^-1 ): 2951, 2914, 2324, 1621, 1586, 1468, 1428, 1369, 1264, 1242, 1195, 1092, 1038, 923, 835, 766.Anal.Calcd.for C ₂₇ H ₂₉ Cl ₂ FeN ₃ : C, 62.09, H, 5.60, N, 8.05; Found: C, 62.13, H, 5.47, N, 7.67.

Its crystal structure is shown in Figure 1.

Embodiment 10, the preparation of complex Fe2

Ligand L2/L2' (0.158g, 0.38mmol) and 1 equivalent of FeCl ₂ 4H ₂ O (0.070g, 0.35mmol) were placed in a Schlenk tube, and after vacuuming and filling with nitrogen three times, 5ml of degassed Water and ethanol were stirred and reacted at room temperature for 4 hours, anhydrous ether was added, a large amount of precipitate was formed, the precipitate was filtered, washed with anhydrous ether, and dried to obtain a powder (0.144g, 71.4%).

Its characterization data are as follows: FT-IR (KBr, cm ^-1 ): 2967, 2940, 2874, 2359, 1608, 1578, 1551, 1446, 1421, 1372, 1270, 1246, 1188, 1111, 1039, 867, 808, 777. Anal. Calcd.for C ₃₁ H ₃₇ Cl ₂ FeN ₃ :C,64.37,H,6.45,N,7.26;Found:C,64.22,H,6.24,N,7.02.

Its crystal structure is shown in Figure 2.

Embodiment 11, the preparation of complex Fe3

Ligand L3/L3' (0.192g, 0.38mmol) and 1.2 equivalents of FeCl ₂ 4H ₂ O (0.084g, 0.42mmol) were placed in a Schlenk tube, and after vacuuming and filling with nitrogen three times, 5ml of degassed Water and ethanol were stirred and reacted at room temperature for 18 hours. Anhydrous ether was added, and a large amount of precipitate was formed. The precipitate was filtered, washed with anhydrous ether, and dried to obtain a blue powder (0.131g, 59.1%).

Its characterization data are as follows: FT-IR (KBr, cm ^-1 ): 2964, 1864, 2360, 2341, 1602, 1577, 1554, 1461, 1441, 1364, 1324, 1270, 1247, 1186, 1103, 1042, 924, 831, 801, 777. Anal.Calcd.for C ₃₅ H ₄₅ Cl ₂ FeN ₃ :C,66.25,H,7.15,N,6.62;Found:C,66.24,H,7.02,N,6.48.

Embodiment 12, the preparation of complex Fe4

Ligand L4/L4' (0.15g, 0.38mmol) and 1 equivalent of FeCl ₂ 4H ₂ O (0.070g, 0.35mmol) were placed in a Schlenk tube. After vacuuming and filling with nitrogen three times, 5ml of degassed Water and ethanol were stirred and reacted at room temperature for 10 hours. Anhydrous ether was added, and a large amount of precipitate was formed. The precipitate was filtered, washed with anhydrous ether, and dried to obtain a blue powder (0.106 g, 55.5%).

Its characterization data are as follows: FT-IR (KBr, cm ^-1 ): 2948, 2913, 1359, 1618, 1581, 1479, 1416, 1368, 1278, 1230, 1153, 1036, 906, 862, 829, 761. Anal. Calcd. for C ₂₉ H ₃₃ Cl ₂ FeN ₃ :C,63.29,H,6.04,N,7.64; Found:C,63.11,H,7.16,N,6.48.

Embodiment 13, the preparation of complex Fe5

Ligand L5/L5' (0.182g, 0.38mmol) and 0.67 equivalents of FeCl ₂ 4H ₂ O (0.047g, 0.23mmol) were placed in a Schlenk tube, and after vacuuming and filling with nitrogen three times, 5ml of degassed Water and ethanol, stirred at room temperature for 10 hours, added anhydrous ether, a large amount of precipitate formed, the precipitate was filtered and washed with anhydrous ether, dried to obtain a blue powder (0.121g, 57.1%).

Its characterization data are as follows: FT-IR (KBr, cm ^-1 ): 2963, 2926, 2865, 2359, 1612, 1577, 1455, 1419, 1371, 1268, 1250, 1206, 1153, 1036, 857, 829, 796, 760. Anal. Calcd. for C ₃₃ H ₄₁ Cl ₂ FeN ₃ : C, 65.36, H, 6.81, N, 6.93; Found: C, 65.42, H, 6.79, N, 6.72.

Embodiment 14, the preparation of complex Fe6

Ligand L6/L6' (0.181g, 0.38mmol) and 1 equivalent of FeCl ₂ 4H ₂ O (0.070g, 0.35mmol) were placed in a Schlenk tube, and after vacuuming and filling with nitrogen three times, 5ml of degassed Water and ethanol were stirred and reacted at room temperature for 10 hours. Anhydrous ether was added, and a large amount of precipitate was formed. The precipitate was filtered, washed with anhydrous ether, and dried to obtain a blue powder (0.120 g, 57.1%).

Its characterization data are as follows: FT-IR (KBr, cm ^-1 ): 2963, 2926, 2865, 2359, 1612, 1577, 1455, 1419, 1371, 1268, 1250, 1206, 1153, 1036, 857, 829, 796, 760. Anal. Calcd. for C ₂₃ H ₁₇ Cl ₆ FeN ₃ : C, 45.74; H, 2.84; N, 6.96; Found: C, 45.42; H, 2.79; N, 6.72.

Embodiment 15, the preparation of complex Fe7

Ligand L7/L7' (0.145g, 0.38mmol) and 1 equivalent of FeCl ₂ 4H ₂ O (0.070g, 0.35mmol) were placed in a Schlenk tube, and after vacuuming and filling with nitrogen three times, 5ml of degassed Water and ethanol were stirred and reacted at room temperature for 10 hours. Anhydrous ether was added, and a large amount of precipitate was formed. The precipitate was filtered, washed with anhydrous ether, and dried to obtain a blue powder (0.107g, 60.1%).

Its characterization data are as follows: FT-IR (KBr, cm ^-1 ): 2963, 2926, 2865, 2359, 1612, 1577, 1455, 1419, 1371, 1268, 1250, 1206, 1153, 1036, 857, 829, 796, 760. Anal. Calcd. for C ₂₆ H ₂₇ Cl ₂ FeN ₃ : C, 61.44; H, 5.35; N, 8.27; Found: C, 61.42, H, 5.79, N, 8.32.

Embodiment 16, the preparation of complex Fe8

Ligand L8/L8' (0.156g, 0.38mmol) and 1 equivalent of FeCl ₂ 4H ₂ O (0.070g, 0.35mmol) were placed in a Schlenk tube, and after vacuuming and filling with nitrogen three times, 5ml of degassed Water and ethanol, stirred at room temperature for 10 hours, added anhydrous ether, a large amount of precipitate formed, the precipitate was filtered and washed with anhydrous ether, dried to obtain a blue powder (0.122g, 65.1%).

Its characterization data are as follows: FT-IR (KBr, cm ^-1 ): 2963, 2926, 2865, 2359, 1612, 1577, 1455, 1419, 1371, 1268, 1250, 1206, 1153, 1036, 857, 829, 796, 760. Anal. Calcd. for C ₂₈ H ₃₁ Cl ₂ FeN ₃ : C, 62.71; H, 5.83; N, 7.83; Found: C, 62.42, H, 5.79, N, 7.72.

Embodiment 17, the preparation of complex Co1

Ligand L1/L1' (0.15g, 0.38mmol) and 1 equivalent of CoCl ₂ (0.045g, 0.35mmol) were placed in a Schlenk tube, vacuumed and filled with nitrogen three times, then 5ml of degassed absolute ethanol was added, at room temperature The reaction was stirred for 10 hours, and anhydrous ether was added, and a large amount of precipitate was formed. The precipitate was filtered, washed with anhydrous ether, and dried to obtain a powder (0.126g, 68.5%).

Its characterization data are as follows: Anal.Calcd.For C ₂₇ H ₂₉ Cl ₂ CoN ₃ :C,61.72;H,5.56;N,8.00;Found:C,61.70;H,5.63;N,7.68.FT-IR(KBr ;cm ^-1 ):2914,2165,2030,1624,1585,1468,1429,1371,1264,1236,1198,1098,1039,834,767.

Its crystal structure is shown in Figure 3.

Embodiment 18, the preparation of complex Co2

Ligand L2/L2' (0.158g, 0.38mmol) and 1 equivalent of CoCl ₂ (0.045g, 0.35mmol) were placed in a Schlenk tube. After vacuuming and filling with nitrogen three times, 5ml of degassed absolute ethanol was added, and at room temperature The reaction was stirred for 10 hours, and anhydrous ether was added, and a large amount of precipitate was formed. The precipitate was filtered, washed with anhydrous ether, and dried to obtain a powder (0.132g, 65.0%).

Its characterization data are as follows: Anal.Calcd.For C ₃₁ H ₃₇ Cl ₂ CoN ₃ :C,64.03;H,6.41;N,7.23;Found:C,63.70;H,6.63;N,7.68.FT-IR(KBr ;cm ^-1 ):2968,2938,2874,2360,2031,2166,1621,1584,1446,1373,1244,1190,1108,869,809,779.

Its crystal structure is shown in Figure 4.

Embodiment 19, the preparation of complex Co3

Ligand L3/L3' (0.192g, 0.38mmol) and 1 equivalent of CoCl ₂ (0.045g, 0.35mmol) were placed in a Schlenk tube. After vacuuming and filling with nitrogen three times, 5ml of degassed absolute ethanol was added, and at room temperature The reaction was stirred for 10 hours, and anhydrous diethyl ether was added, and a large amount of precipitate was formed. The precipitate was filtered, washed with anhydrous diethyl ether, and dried to obtain a powder (0.130 g, 58.5%).

Its characterization data are as follows: Anal.Calcd.For C ₃₅ H ₄₅ Cl ₂ CoN ₃ :C,65.93,H,7.11,N,6.59.Found:C,65.72,H,6.77,N,6.83.FT-IR(Diamond ;cm ^-1 ):2965,2865,2166,2031,1617,1584,1458,1369,1320,1245,1186,1106,1044,929,802,775.

Embodiment 20, the preparation of complex Co4

Ligand L4/L4' (0.15g, 0.38mmol) and 1 equivalent of CoCl ₂ (0.045g, 0.35mmol) were placed in a Schlenk tube, vacuumed and filled with nitrogen three times, then 5ml of degassed absolute ethanol was added, at room temperature The reaction was stirred for 10 hours, anhydrous ether was added, and a large amount of precipitate was formed. The precipitate was filtered, washed with anhydrous ether, and dried to obtain a powder (0.165 g, 85.6%).

Its characterization data are as follows: Anal.Calcd.For C ₂₉ H ₃₃ Cl ₂ CoN ₃ :C,62.94;H,6.01;N,7.59.Found:C,62.62;H,6.18;N,7.42.FT-IR(KBr ;cm ^-1 ):2951,2913,2329,2166,2030,1625,1581,1476,1431,1371,1264,1238,1212,1152,1116,1034,852,760.

Embodiment 21, the preparation of complex Co5

Ligand L5/L5' (0.182g, 0.38mmol) and 1 equivalent of CoCl ₂ (0.045g, 0.35mmol) were placed in a Schlenk tube. After vacuuming and filling with nitrogen three times, 5ml of degassed absolute ethanol was added, and at room temperature The reaction was stirred for 10 hours, and anhydrous ether was added, and a large amount of precipitate was formed. The precipitate was filtered, washed with anhydrous ether, and dried to obtain a yellow powder (0.169g, 79.1%).

Its characterization data are as follows: Anal. Calcd. For C ₃₃ H ₄₁ Cl ₂ CoN ₃ : C, 65.03; H, 6.78; N, 6.89. Found: C, 64.79; H, 7.05; N, 6.41. FT-IR (KBr;cm ^-1 ):2965,2929,2868,2361,2167,2032,1618,1577,1456,1372,1244,1207,1142,1036,858,828,794.

Its crystal structure is shown in Figure 5.

Embodiment 22, the preparation of complex Co6

Ligand L6/L6' (0.181g, 0.38mmol) and 1 equivalent of CoCl ₂ (0.045g, 0.35mmol) were placed in a Schlenk tube, vacuumed and filled with nitrogen three times, then 5ml of degassed absolute ethanol was added, at room temperature The reaction was stirred for 10 hours, anhydrous ether was added, and a large amount of precipitate was formed. The precipitate was filtered, washed with anhydrous ether, and dried to obtain a yellow powder (0.168 g, 79.5%).

Its characterization data are as follows: Anal. Calcd. For C ₂₃ H ₁₇ Cl ₆ CoN ₃ : C, 45.51; H, 2.82; N, 6.92; Found: C, 64.79, H, 7.05, N, 6.41. FT-IR (KBr;cm ^-1 ):2965,2929,2868,2361,2167,2032,1618,1577,1456,1372,1244,1207,1142,1036,858,828,794.

Embodiment 23, the preparation of complex Co7

Ligand L7/L7' (0.145g, 0.38mmol) and 1 equivalent of CoCl ₂ (0.045g, 0.35mmol) were placed in a Schlenk tube. After vacuuming and filling with nitrogen three times, 5ml of degassed absolute ethanol was added, and at room temperature The reaction was stirred for 10 hours, and anhydrous ether was added, and a large amount of precipitate was formed. The precipitate was filtered, washed with anhydrous ether, and dried to obtain a yellow powder (0.143g, 80%).

Its characterization data are as follows: Anal. Calcd. For C ₂₆ H ₂₇ Cl ₂ CoN ₃ : C, 61.07; H, 5.32; N, 8.22; Found: C, 61.34; H, 5.28; N, 8.41. FT-IR (KBr; cm ^-1 ): 2965, 2929, 2868, 2361, 2167, 2032, 1618, 1577, 1456, 1372, 1244.

Embodiment 24, the preparation of complex Co8

Ligand L8/L8' (0.156g, 0.38mmol) and 1 equivalent of CoCl ₂ (0.045g, 0.35mmol) were placed in a Schlenk tube, vacuumed and filled with nitrogen for three times, then 5ml of degassed absolute ethanol was added, at room temperature The reaction was stirred for 10 hours, and anhydrous ether was added, and a large amount of precipitate was formed. The precipitate was filtered, washed with anhydrous ether, and dried to obtain a yellow powder (0.123 g, 65.5%).

Its characterization data are as follows: Anal. Calcd. For C ₂₈ H ₃₁ Cl ₂ CoN ₃ : C, 62.35; H, 5.79; N, 7.79; Found: C, 62.45; H, 5.65; N, 7.41. FT-IR (KBr; cm ^-1 ): 2965, 2929, 2868, 2361, 2167, 2032, 1618, 1577, 1456, 1372, 1244.

The following examples are examples of using the complexes prepared above to catalyze ethylene polymerization.

Example 25,

Ethylene polymerization under pressure used a 300 ml stainless steel polymerization kettle equipped with a mechanical stirring paddle and temperature control device. The polymerization kettle was evacuated and heated to 100° C. for two hours. Under the condition of pre-replacing the nitrogen in the kettle with ethylene, the polymerization kettle was allowed to cool slowly to the envisaged polymerization temperature (30° C.). Then add 50mL of toluene, 20mL of toluene solution dissolved with 3μmol catalyst (Fe3), 2.05mL of cocatalyst (MAO, 1.46mol/L toluene solution) (Al/Fe=1000), the remaining toluene (making the total amount of toluene 100ml ). The kettle was closed, and ethylene was passed through to maintain a constant pressure of ethylene (10 atm). After the polymerization reaction reaches the preset time (30min), release the ethylene pressure in the kettle, add hydrochloric acid ethanol, filter and wash and dry to constant weight in an oven at 60°C to obtain 2.45g polymer. Polymerization activity was calculated from the yield. Polymerization activity: 1.63×10 ⁶ g ofPE·mol ^-1 (M)·h ^-1 , polymer M _w =203.4Kg·mol ^-1 , M _w /M _n =3.4, T _m =135.5.

Example 26,

Ethylene polymerization under pressure used a 300 ml stainless steel polymerization kettle equipped with a mechanical stirring paddle and temperature control device. The polymerization kettle was evacuated and heated to 100° C. for two hours. Under the condition of pre-replacing the nitrogen in the kettle with ethylene, the polymerization kettle was allowed to cool slowly to the envisaged polymerization temperature (30° C.). Then add 50mL of toluene, 20mL of toluene solution dissolved with 3μmol catalyst (Fe3), 3.08mL of cocatalyst (MAO, 1.46mol/L toluene solution) (Al/Fe=1500), the remaining toluene (making the total amount of toluene 100ml ). The kettle was closed, and ethylene was passed through to maintain a constant pressure of ethylene (10 atm). After the polymerization reaction reaches the preset time (30min), release the ethylene pressure in the kettle, add hydrochloric acid ethanol, filter and wash, and dry to constant weight in an oven at 60°C to obtain 3.12g polymer. Polymerization activity was calculated from the yield. Polymerization activity: 2.08×10 ⁶ g ofPE·mol ^-1 (M)·h ^-1 , polymer M _w =132.9Kg·mol ^-1 , M _w /M _n =8.5, T _m =133.3.

Example 27,

Ethylene polymerization under pressure used a 300 ml stainless steel polymerization kettle equipped with a mechanical stirring paddle and temperature control device. The polymerization kettle was evacuated and heated to 100° C. for two hours. Under the condition of pre-replacing the nitrogen in the kettle with ethylene, the polymerization kettle was allowed to cool slowly to the envisaged polymerization temperature (30° C.). Then add 50mL of toluene, 20mL of toluene solution dissolved with 3μmol catalyst (Fe3), 4.10mL of cocatalyst (MAO, 1.46mol/L toluene solution) (Al/Fe=2000), the remaining toluene (making the total amount of toluene 100ml ). The kettle was closed, and ethylene was passed through to maintain a constant pressure of ethylene (10 atm). After the polymerization reaction reaches the preset time (30min), release the ethylene pressure in the still, add hydrochloric acid ethanol, filter and wash and dry to constant weight in an oven at 60°C to obtain 4.90g polymer. Polymerization activity was calculated from the yield. Polymerization activity: 3.27×10 ⁶ g ofPE·mol ^-1 (M)·h ^-1 , polymer M _w =174.5Kg·mol ^-1 , M _w /M _n =32.5, T _m =130.6.

Example 28,

Ethylene polymerization under pressure used a 300 ml stainless steel polymerization kettle equipped with a mechanical stirring paddle and temperature control device. The polymerization kettle was evacuated and heated to 100° C. for two hours. Under the condition of pre-replacing the nitrogen in the kettle with ethylene, the polymerization kettle was allowed to cool slowly to the envisaged polymerization temperature (30° C.). Then add 50mL of toluene, 20mL of toluene solution dissolved with 3μmol catalyst (Fe3), 5.14mL of cocatalyst (MAO, 1.46mol/L toluene solution) (Al/Fe=2500), the remaining toluene (making the total amount of toluene 100ml ). The kettle was closed, and ethylene was passed through to maintain a constant pressure of ethylene (10 atm). After the polymerization reaction reached the preset time (30min), the ethylene pressure in the still was released, hydrochloric acid ethanol was added, and after filtering and washing, it was dried to a constant weight in a 60°C oven to obtain 3.79g polymer. Polymerization activity was calculated from the yield. Polymerization activity: 2.53×10 ⁶ g of PE·mol ^-1 (M)·h ^-1 , polymer M _w =78.9Kg·mol ^-1 , M _w /M _n =35.9, T _m =128.8.

Example 29,

Ethylene polymerization under pressure used a 300 ml stainless steel polymerization kettle equipped with a mechanical stirring paddle and temperature control device. The polymerization kettle was evacuated and heated to 100° C. for two hours. Under the condition of pre-replacing the nitrogen in the kettle with ethylene, allow the polymerization kettle to be slowly cooled to the envisaged polymerization temperature (40° C.). Then add 50mL of toluene, 20mL of toluene solution dissolved with 3μmol catalyst (Fe3), 4.10mL of cocatalyst MAO (1.46mol/L toluene solution) (Al/Fe=2000), and the remaining toluene (making the total amount of toluene 100ml) . The kettle was closed, and ethylene was passed through to maintain a constant pressure of ethylene (10 atm). After the polymerization reaction reaches the preset time (30min), release the ethylene pressure in the kettle, add hydrochloric acid ethanol, filter and wash and dry to constant weight in an oven at 60°C to obtain 5.95g polymer, according to polymer Polymerization activity was calculated from the yield. Polymerization activity: 3.97×10 ⁶ g ofPE·mol ^-1 (M)·h ^-1 , polymer M _w =77.0Kg·mol ^-1 , M _w /M _n =23.5, T _m =128.

Example 30,

Ethylene polymerization under pressure used a 300 ml stainless steel polymerization kettle equipped with a mechanical stirring paddle and temperature control device. The polymerization kettle was evacuated and heated to 100° C. for two hours. Under the condition of pre-replacing the nitrogen in the kettle with ethylene, the polymerization kettle was allowed to cool slowly to the envisaged polymerization temperature (50° C.). Then add 50mL of toluene, 20mL of toluene solution dissolved with 3μmol catalyst (Fe3), 4.10mL of cocatalyst MAO (1.46mol/L toluene solution) (Al/Fe=2000), and the remaining toluene (making the total amount of toluene 100ml) . The kettle was closed, and ethylene was passed through to maintain a constant pressure of ethylene (10 atm). After the polymerization reaction reached the preset time (30min), the ethylene pressure in the kettle was released, hydrochloric acid ethanol was added, and after filtering and washing, it was dried to constant weight in a 60°C oven to obtain 13.2g polymer. Polymerization activity was calculated from the yield. Polymerization activity: 8.80×10 ⁶ g ofPE·mol ^-1 (M)·h ^-1 , polymer M _w =121.6Kg·mol ^-1 , M _w /M _n =13.9, T _m =130.7.

Example 31,

Ethylene polymerization under pressure used a 300 ml stainless steel polymerization kettle equipped with a mechanical stirring paddle and temperature control device. The polymerization kettle was evacuated and heated to 100° C. for two hours. Under the condition of pre-replacing the nitrogen in the kettle with ethylene, the polymerization kettle was slowly cooled to the envisaged polymerization temperature (60° C.). Then add 50mL of toluene, 20mL of toluene solution dissolved with 3μmol catalyst (Fe3), 4.10mL of cocatalyst MAO (1.46mol/L toluene solution) (Al/Fe=2000), and the remaining toluene (making the total amount of toluene 100ml) . The kettle was closed, and ethylene was passed through to maintain a constant pressure of ethylene (10 atm). After the polymerization reaction reaches the preset time (30min), release the ethylene pressure in the kettle, add hydrochloric acid ethanol, filter and wash and dry to constant weight in an oven at 60°C to obtain 11.0g polymer, according to polymer Polymerization activity was calculated from the yield. Polymerization activity: 7.34×10 ⁶ g ofPE·mol ^-1 (M)·h ^-1 , polymer M _w =13.3Kg·mol ^-1 , M _w /M _n =2.8, T _m =128.1.

Example 32,

Ethylene polymerization under pressure used a 300 ml stainless steel polymerization kettle equipped with a mechanical stirring paddle and temperature control device. The polymerization kettle was evacuated and heated to 100° C. for two hours. Under the condition of pre-replacing the nitrogen in the kettle with ethylene, the polymerization kettle was allowed to cool slowly to the envisaged polymerization temperature (80° C.). Then add 50mL of toluene, 20mL of toluene solution dissolved with 3μmol catalyst (Fe3), 4.10mL of cocatalyst MAO (1.46mol/L toluene solution) (Al/Fe=2000), and the remaining toluene (making the total amount of toluene 100ml) . The kettle was closed, and ethylene was passed through to maintain a constant pressure of ethylene (10 atm). After the polymerization reaction reaches the preset time (30min), release the ethylene pressure in the kettle, add hydrochloric acid ethanol, filter and wash and dry to constant weight in an oven at 60°C to obtain 10.2g polymer. Polymerization activity was calculated from the yield. Polymerization activity: 6.81×10 ⁶ g ofPE·mol ^-1 (M)·h ^-1 , polymer M _w =18.5Kg·mol ^-1 , M _w /M _n =4.3, T _m =127.6.

Example 33,

Ethylene polymerization under pressure used a 300 ml stainless steel polymerization kettle equipped with a mechanical stirring paddle and temperature control device. The polymerization kettle was evacuated and heated to 100° C. for two hours. Under the condition of pre-replacing the nitrogen in the kettle with ethylene, the polymerization kettle was allowed to cool slowly to the envisaged polymerization temperature (50° C.). Then add 50 mL of toluene, 20 mL of toluene solution dissolved with 3 μmol catalyst (Fe1), 4.10 mL of cocatalyst MAO (1.46 mol/L toluene solution) (Al/Fe=2000), and the remaining toluene (making the total amount of toluene 100 mL) . The kettle was closed, and ethylene was passed through to maintain a constant pressure of ethylene (10 atm). After the polymerization reaction reached the preset time (30min), the ethylene pressure in the kettle was released, hydrochloric acid ethanol was added, and after filtering and washing, it was dried to constant weight in an oven at 60°C to obtain 8.41g polymer. Polymerization activity was calculated from the yield. Polymerization activity: 5.61×10 ⁶ g ofPE·mol ^-1 (M)·h ^-1 , polymer M _w =22.8Kg·mol ^-1 , M _w /M _n =4.7, T _m =128.7.

Example 34,

Ethylene polymerization under pressure used a 300 ml stainless steel polymerization kettle equipped with a mechanical stirring paddle and temperature control device. The polymerization kettle was evacuated and heated to 100° C. for two hours. Under the condition of pre-replacing the nitrogen in the kettle with ethylene, the polymerization kettle was allowed to cool slowly to the envisaged polymerization temperature (50° C.). Then add 50mL of toluene, 20mL of toluene solution dissolved with 3μmol catalyst (Fe2), 4.10mL of cocatalyst MAO (1.46mol/L toluene solution) (Al/Fe=2000), and the remaining toluene (making the total amount of toluene 100ml) . The kettle was closed, and ethylene was passed through to maintain a constant pressure of ethylene (10 atm). After the polymerization reaction reached the preset time (30min), the ethylene pressure in the kettle was released, hydrochloric acid ethanol was added, and after filtering and washing, it was dried to a constant weight in a 60°C oven to obtain 23.4g polymer. Polymerization activity was calculated from the yield. Polymerization activity: 15.6×10 ⁶ g ofPE·mol ^-1 (M)·h ^-1 , polymer M _w =22.7Kg·mol ^-1 , M _w /M _n =6.3, T _m =129.9.

Example 35,

Ethylene polymerization under pressure used a 300 ml stainless steel polymerization kettle equipped with a mechanical stirring paddle and temperature control device. The polymerization kettle was evacuated and heated to 100° C. for two hours. Under the condition of pre-replacing the nitrogen in the kettle with ethylene, the polymerization kettle was allowed to cool slowly to the envisaged polymerization temperature (50° C.). Then add 50mL of toluene, 20mL of toluene solution dissolved with 3μmol catalyst (Fe4), 4.10mL of cocatalyst MAO (1.46mol/L toluene solution) (Al/Fe=2000), and the remaining toluene (making the total amount of toluene 100ml) . The kettle was closed, and ethylene was passed through to maintain a constant pressure of ethylene (10 atm). After the polymerization reaction reached the preset time (30min), the ethylene pressure in the kettle was released, hydrochloric acid ethanol was added, and after filtering and washing, it was dried to a constant weight in a 60°C oven to obtain 8.34g polymer. Polymerization activity was calculated from the yield. Polymerization activity: 5.56×10 ⁶ g ofPE·mol ^-1 (M)·h ^-1 , polymer M _w =31.5Kg·mol ^-1 , M _w /M _n =7.2, T _m =128.6.

Example 36,

Ethylene polymerization under pressure used a 300 ml stainless steel polymerization kettle equipped with a mechanical stirring paddle and temperature control device. The polymerization kettle was evacuated and heated to 100° C. for two hours. Under the condition of pre-replacing the nitrogen in the kettle with ethylene, the polymerization kettle was allowed to cool slowly to the envisaged polymerization temperature (50° C.). Then add 50mL of toluene, 20mL of toluene solution dissolved with 3μmol catalyst (Fe5), 4.10mL of cocatalyst MAO (1.46mol/L toluene solution) (Al/Fe=2000), and the remaining toluene (making the total amount of toluene 100ml) . The kettle was closed, and ethylene was passed through to maintain a constant pressure of ethylene (10 atm). After the polymerization reaction reached the preset time (30min), the ethylene pressure in the kettle was released, hydrochloric acid ethanol was added, and after filtering and washing, it was dried to constant weight in an oven at 60°C to obtain 12.4g polymer. Polymerization activity was calculated from the yield. Polymerization activity: 8.25×10 ⁶ g ofPE·mol ^-1 (M)·h ^-1 , polymer M _w =29.7Kg·mol ^-1 , M _w /M _n =5.3, T _m =129.8.

Example 37,

Ethylene polymerization under pressure used a 300 ml stainless steel polymerization kettle equipped with a mechanical stirring paddle and temperature control device. The polymerization kettle was evacuated and heated to 100° C. for two hours. Under the condition of pre-replacing the nitrogen in the kettle with ethylene, the polymerization kettle was allowed to cool slowly to the envisaged polymerization temperature (30° C.). Then add 50mL toluene successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyst (Fe3), 1.55mL cocatalyst (MMAO, the heptane solution of 1.93mol/L) (Al/Fe=1000), remaining toluene (make toluene total amount be 100ml). The kettle was closed, and ethylene was passed through to maintain a constant pressure of ethylene (10 atm). After the polymerization reaction reached the preset time (30min), the ethylene pressure in the kettle was released, hydrochloric acid ethanol was added, and after filtering and washing, it was dried to constant weight in a 60°C oven to obtain 2.91g polymer. Polymerization activity was calculated from the yield. Polymerization activity: 1.94×10 ⁶ g ofPE·mol ^-1 (M)·h ^-1 , polymer M _w =37.8Kg·mol ^-1 , M _w /M _n =28.0, T _m =123.6.

Example 38,

Ethylene polymerization under pressure used a 300 ml stainless steel polymerization kettle equipped with a mechanical stirring paddle and temperature control device. The polymerization kettle was evacuated and heated to 100° C. for two hours. Under the condition of pre-replacing the nitrogen in the kettle with ethylene, the polymerization kettle was allowed to cool slowly to the envisaged polymerization temperature (30° C.). Then add 50mL of toluene, 20mL of toluene solution dissolved with 3μmol catalyst (Fe3), 2.33mL of cocatalyst (MMAO, 1.93mol/L heptane solution) (Fe=1500), the remaining toluene (making the total amount of toluene 100ml ). The kettle was closed, and ethylene was passed through to maintain a constant pressure of ethylene (10 atm). After the polymerization reaction reaches the preset time (30min), release the ethylene pressure in the kettle, add hydrochloric acid ethanol, filter and wash and dry to constant weight in an oven at 60°C to obtain 4.72g polymer. Polymerization activity was calculated from the yield. Polymerization activity: 3.14×10 ⁶ g of PE·mol ^-1 (M)·h ^-1 , polymer M _w =19.2Kg·mol ^-1 , M _w /M _n =12.8, T _m =123.2.

Example 39/

Ethylene polymerization under pressure used a 300 ml stainless steel polymerization kettle equipped with a mechanical stirring paddle and temperature control device. The polymerization kettle was evacuated and heated to 100° C. for two hours. Under the condition of pre-replacing the nitrogen in the kettle with ethylene, the polymerization kettle was allowed to cool slowly to the envisaged polymerization temperature (30° C.). Then add 50mL of toluene, 20mL of toluene solution dissolved with 3μmol catalyst (Fe3), 3.10mL of cocatalyst (MMAO, 1.93mol/L heptane solution) (Al/Fe=2000), the remaining toluene (so that the total amount of toluene is 100ml). The kettle was closed, and ethylene was passed through to maintain a constant pressure of ethylene (10 atm). After the polymerization reaction reaches the preset time (30min), release the ethylene pressure in the kettle, add hydrochloric acid ethanol, filter and wash and dry to constant weight in an oven at 60°C to obtain 6.49g polymer. Polymerization activity was calculated from the yield. Polymerization activity: 4.33×10 ⁶ g of PE·mol ^-1 (M)·h ^-1 , polymer M _w =13.0Kg·mol ^-1 , M _w /M _n =9.3, T _m =123.5.

Example 40,

Ethylene polymerization under pressure used a 300 ml stainless steel polymerization kettle equipped with a mechanical stirring paddle and temperature control device. The polymerization kettle was evacuated and heated to 100° C. for two hours. Under the condition of pre-replacing the nitrogen in the kettle with ethylene, the polymerization kettle was allowed to cool slowly to the envisaged polymerization temperature (30° C.). Then add 50mL toluene, 20mL toluene solution dissolved with 3μmol catalyst (Fe3), 3.89mL cocatalyst (MMAO, 1.93mol/L heptane solution) Al/Fe=2500), the remaining toluene (so that the total amount of toluene is 100 ml). The kettle was closed, and ethylene was passed through to maintain a constant pressure of ethylene (10 atm). After the polymerization reaction reaches the preset time (30min), release the ethylene pressure in the kettle, add hydrochloric acid ethanol, filter and wash and dry to constant weight in an oven at 60°C to obtain 6.00g polymer. Polymerization activity was calculated from the yield. Polymerization activity: 4.00×10 ⁶ g ofPE·mol ^-1 (M)·h ^-1 , polymer M _w =8.1Kg·mol ^-1 , M _w /M _n =5.7, T _m =120.5.

Example 41,

Ethylene polymerization under pressure used a 300 ml stainless steel polymerization kettle equipped with a mechanical stirring paddle and temperature control device. The polymerization kettle was evacuated and heated to 100° C. for two hours. Under the condition of pre-replacing the nitrogen in the kettle with ethylene, allow the polymerization kettle to be slowly cooled to the envisaged polymerization temperature (40° C.). Then add 50mL of toluene, 20mL of toluene solution dissolved with 3μmol catalyst (Fe3), 3.10mL of cocatalyst (MMAO, 1.93mol/L heptane solution) (Al/Fe=2000), the remaining toluene (so that the total amount of toluene is 100ml). The kettle was closed, and ethylene was passed through to maintain a constant pressure of ethylene (10 atm). After the polymerization reaction reaches the preset time (30min), release the ethylene pressure in the kettle, add hydrochloric acid ethanol, filter and wash and dry to constant weight in an oven at 60°C to obtain 7.04g polymer, according to polymer Polymerization activity was calculated from the yield. Polymerization activity: 4.69×10 ⁶ g of PE·mol ^-1 (M)·h ^-1 , polymer M _w =17.4Kg·mol ^-1 , M _w /M _n =9.1, T _m =123.1.

Example 42,

Ethylene polymerization under pressure used a 300 ml stainless steel polymerization kettle equipped with a mechanical stirring paddle and temperature control device. The polymerization kettle was evacuated and heated to 100° C. for two hours. Under the condition of pre-replacing the nitrogen in the kettle with ethylene, the polymerization kettle was allowed to cool slowly to the envisaged polymerization temperature (50° C.). Then add 50mL of toluene, 20mL of toluene solution dissolved with 3μmol catalyst (Fe3), 3.10mL of cocatalyst (MMAO, 1.93mol/L heptane solution) (Al/Fe=2000), the remaining toluene (so that the total amount of toluene is 100ml). The kettle was closed, and ethylene was passed through to maintain a constant pressure of ethylene (10 atm). After the polymerization reaction reached the preset time (30min), the ethylene pressure in the still was released, hydrochloric acid ethanol was added, and after filtering and washing, it was dried to constant weight in a 60°C oven to obtain 22.3g polymer. Polymerization activity was calculated from the yield. Polymerization activity: 14.8×10 ⁶ g ofPE·mol ^-1 (M)·h ^-1 , polymer M _w =32.7Kg·mol ^-1 , M _w /M _n =8.9, T _m =128.2.

Example 43,

Ethylene polymerization under pressure used a 300 ml stainless steel polymerization kettle equipped with a mechanical stirring paddle and temperature control device. The polymerization kettle was evacuated and heated to 100° C. for two hours. Under the condition of pre-replacing the nitrogen in the kettle with ethylene, the polymerization kettle was slowly cooled to the envisaged polymerization temperature (60° C.). Then add 50mL of toluene, 20mL of toluene solution dissolved with 3μmol catalyst (Fe3), 3.10mL of cocatalyst (MMAO, 1.93mol/L heptane solution) (Al/Fe=2000), the remaining toluene (so that the total amount of toluene is 100ml). The kettle was closed, and ethylene was passed through to maintain a constant pressure of ethylene (10 atm). After the polymerization reaction reached the preset time (30min), the ethylene pressure in the kettle was released, hydrochloric acid ethanol was added, and after filtration and washing, it was dried to a constant weight in a 60°C oven to obtain 18.9g polymer. Polymerization activity was calculated from the yield. Polymerization activity: 12.6×10 ⁶ g ofPE·mol ^-1 (M)·h ^-1 , polymer M _w =29.9Kg·mol ^-1 , M _w /M _n =8.9, T _m =127.7.

Example 44,

Ethylene polymerization under pressure used a 300 ml stainless steel polymerization kettle equipped with a mechanical stirring paddle and temperature control device. The polymerization kettle was evacuated and heated to 100° C. for two hours. Under the condition of pre-replacing nitrogen in the kettle with ethylene, the polymerization kettle was slowly cooled to the envisaged polymerization temperature (70° C.). Then add 50mL of toluene, 20mL of toluene solution dissolved with 3μmol catalyst (Fe3), 3.10mL of cocatalyst (MMAO, 1.93mol/L heptane solution) (Al/Fe=2000), the remaining toluene (so that the total amount of toluene is 100ml). The kettle was closed, and ethylene was passed through to maintain a constant pressure of ethylene (10 atm). After the polymerization reaction reached the preset time (30min), the ethylene pressure in the kettle was released, hydrochloric acid ethanol was added, and after filtering and washing, it was dried to constant weight in a 60°C oven to obtain 17.3g polymer. Polymerization activity was calculated from the yield. Polymerization activity: 11.5×10 ⁶ g ofPE·mol ^-1 (M)·h ^-1 , polymer M _w =15.1Kg·mol ^-1 , M _w /M _n =4.5, T _m =127.2.

Example 45,

Ethylene polymerization under pressure used a 300 ml stainless steel polymerization kettle equipped with a mechanical stirring paddle and temperature control device. The polymerization kettle was evacuated and heated to 100° C. for two hours. Under the condition of pre-replacing the nitrogen in the kettle with ethylene, the polymerization kettle was allowed to cool slowly to the envisaged polymerization temperature (50° C.). Then add 50mL toluene successively, 20mL is dissolved with 3μmol catalyst (Fe1's toluene solution, 3.10mL cocatalyst (MMAO, 1.93mol/L heptane solution) (Al/Fe=2000), remaining toluene (making toluene total amount be 100 Milliliters).The still is sealed, leads to ethylene and maintains the constant pressure (10atm) of ethylene.After the polymerization reaction reaches the preset time (30min), the ethylene pressure in the still is released, and hydrochloric acid ethanol is added, after filtering and washing at 60 Dry to constant weight in an oven at °C to obtain 22.5g polymer, and calculate the polymerization activity according to the output of the polymer. Polymerization activity: 14.8×10 ⁶ g of PE·mol ^-1 (M)·h ^-1 , polymer M _w = 11.7Kg·mol ^-1 , M _w /M _n = 4.0, T _m = 126.3.

Example 46,

Ethylene polymerization under pressure used a 300 ml stainless steel polymerization kettle equipped with a mechanical stirring paddle and temperature control device. The polymerization kettle was evacuated and heated to 100° C. for two hours. Under the condition of pre-replacing the nitrogen in the kettle with ethylene, the polymerization kettle was allowed to cool slowly to the envisaged polymerization temperature (50° C.). Then add 50mL toluene successively, 20mL is dissolved with 3μmol catalyst (Fe2 toluene solution, 3.10mL cocatalyst (MMAO, the heptane solution of 1.93mol/L) (Al/Fe=2000), remaining toluene (make toluene total amount be 100 Milliliters).The still is sealed, leads to ethylene and maintains the constant pressure (10atm) of ethylene.After the polymerization reaction reaches the preset time (30min), the ethylene pressure in the still is released, and hydrochloric acid ethanol is added, after filtering and washing at 60 Dry to constant weight in an oven at °C to obtain 14.7g polymer, and calculate the polymerization activity according to the output of the polymer. Polymerization activity: 9.81×10 ⁶ g of PE·mol ^-1 (M)·h ^-1 , polymer M _w = 12.9 Kg·mol ^-1 , M _w /M _n = 5.1, T _m = 125.2.

Example 47,

Ethylene polymerization under pressure used a 300 ml stainless steel polymerization kettle equipped with a mechanical stirring paddle and temperature control device. The polymerization kettle was evacuated and heated to 100° C. for two hours. Under the condition of pre-replacing the nitrogen in the kettle with ethylene, the polymerization kettle was allowed to cool slowly to the envisaged polymerization temperature (50° C.). Then add 50mL toluene successively, 20mL is dissolved with 3μmol catalyst (Fe4 toluene solution, 3.10mL co-catalyst (MMAO, 1.93mol/L heptane solution) (Al/Fe=2000), remaining toluene (making toluene total amount be 100 Milliliters).The still is sealed, leads to ethylene and maintains the constant pressure (10atm) of ethylene.After the polymerization reaction reaches the preset time (30min), the ethylene pressure in the still is released, and hydrochloric acid ethanol is added, after filtering and washing at 60 Dry to constant weight in an oven at °C to obtain 23.0g polymer, and calculate the polymerization activity according to the yield of the polymer. Polymerization activity: 15.4×10 ⁶ g of PE·mol ^-1 (M)·h ^-1 , polymer M _w = 14.8 Kg·mol ^-1 , M _w /M _n = 6.0, T _m = 127.4.

Example 48,

Ethylene polymerization under pressure used a 300 ml stainless steel polymerization kettle equipped with a mechanical stirring paddle and temperature control device. The polymerization kettle was evacuated and heated to 100° C. for two hours. Under the condition of pre-replacing the nitrogen in the kettle with ethylene, the polymerization kettle was allowed to cool slowly to the envisaged polymerization temperature (50° C.). Then add 50mL toluene successively, 20mL is dissolved with 3μmol catalyst (Fe5 toluene solution, 3.10mL cocatalyst (MMAO, the heptane solution of 1.93mol/L) (Al/Fe=2000), remaining toluene (making toluene total amount be 100 Milliliters).The still is sealed, leads to ethylene and maintains the constant pressure (10atm) of ethylene.After the polymerization reaction reaches the preset time (30min), the ethylene pressure in the still is released, and hydrochloric acid ethanol is added, after filtering and washing at 60 Dry to constant weight in an oven at °C to obtain 20.3g polymer, and calculate the polymerization activity according to the yield of the polymer. Polymerization activity: 13.5×10 ⁶ g of PE·mol ^-1 (M)·h ^-1 , polymer M _w = 12.8 Kg·mol ^-1 , M _w /M _n = 5.8, T _m = 126.7.

Example 49,

Ethylene polymerization under pressure used a 300 ml stainless steel polymerization kettle equipped with a mechanical stirring paddle and temperature control device. The polymerization kettle was evacuated and heated to 100° C. for two hours. Under the condition of pre-replacing the nitrogen in the kettle with ethylene, the polymerization kettle was allowed to cool slowly to the envisaged polymerization temperature (50° C.). Then add 50mL of toluene, 20mL of toluene solution dissolved with 3μmol catalyst (Fe3), 3.10mL of cocatalyst (MMAO, 1.93mol/L heptane solution) (Al/Fe=2000), the remaining toluene (so that the total amount of toluene is 100ml). The kettle was closed, and ethylene was passed through to maintain a constant pressure of ethylene (10 atm). After the polymerization reaction reached the preset time (15min), the ethylene pressure in the kettle was released, hydrochloric acid ethanol was added, and after filtering and washing, it was dried to constant weight in a 60°C oven to obtain 18.0g polymer. Polymerization activity was calculated from the yield. Polymerization activity: 24.0×10 ⁶ g of PE·mol ^-1 (M)·h ^-1 , polymer M _w =9.8Kg·mol ^-1 , M _w /M _n =2.7, T _m =127.5.

Example 50,

Ethylene polymerization under pressure used a 300 ml stainless steel polymerization kettle equipped with a mechanical stirring paddle and temperature control device. The polymerization kettle was evacuated and heated to 100° C. for two hours. Under the condition of pre-replacing the nitrogen in the kettle with ethylene, the polymerization kettle was allowed to cool slowly to the envisaged polymerization temperature (50° C.). Then add 50mL of toluene, 20mL of toluene solution dissolved with 3μmol catalyst (Fe3), 3.10mL of cocatalyst (MMAO, 1.93mol/L heptane solution) (Al/Fe=2000), the remaining toluene (so that the total amount of toluene is 100ml). The kettle was closed, and ethylene was passed through to maintain a constant pressure of ethylene (10 atm). After the polymerization reaction reaches the preset time (40min), release the ethylene pressure in the kettle, add hydrochloric acid ethanol, filter and wash, and dry to constant weight in an oven at 60°C to obtain 28.0g polymer. Polymerization activity was calculated from the yield. Polymerization activity: 12.5×10 ⁶ g of PE·mol ^-1 (M)·h ^-1 , polymer M _w =46.2Kg·mol ^-1 , M _w /M _n =11.1, T _m =128.9.

Example 51,

Ethylene polymerization under pressure used a 300 ml stainless steel polymerization kettle equipped with a mechanical stirring paddle and temperature control device. The polymerization kettle was evacuated and heated to 100° C. for two hours. Under the condition of pre-replacing the nitrogen in the kettle with ethylene, the polymerization kettle was allowed to cool slowly to the envisaged polymerization temperature (50° C.). Then add 50 mL of toluene, 20 mL of toluene solution dissolved with 3 μmol catalyst (Co4), 1.03 mL of cocatalyst MAO (1.46 mol/L toluene solution) (Al/Co=500), and the remaining toluene (making the total amount of toluene 100 mL) . The kettle was closed, and ethylene was passed through to maintain a constant pressure of ethylene (10 atm). After the polymerization reaction reached the preset time (30min), the ethylene pressure in the kettle was released, hydrochloric acid ethanol was added, after filtering and washing, it was dried to constant weight in an oven at 60°C, and the polymerization activity was calculated according to the output of the polymer. Polymerization activity: 9.29×10 ⁶ g ofPE·mol ^-1 (M)·h ^-1 , polymer M _w =1124g·mol ^-1 , M _w /M _n =1.7, T _m =102.2

Example 52,

The ethylene polymerization under pressure used a 300 ml stainless steel polymerization kettle equipped with a mechanical stirring paddle and temperature control device. The polymerization kettle was evacuated and heated to 100° C. for two hours. Under the condition of pre-replacing the nitrogen in the kettle with ethylene, the polymerization kettle was allowed to cool slowly to the envisaged polymerization temperature (50° C.). Then add 50mL of toluene, 20mL of toluene solution dissolved with 3μmol catalyst (Co4), 1.54mL of cocatalyst MAO (1.46mol/L toluene solution) (Al/Co=750), and the remaining toluene (making the total amount of toluene 100ml) . The kettle was closed, and ethylene was passed through to maintain a constant pressure of ethylene (10 atm). After the polymerization reaction reached the preset time (30min), the ethylene pressure in the kettle was released, hydrochloric acid ethanol was added, after filtering and washing, it was dried to constant weight in an oven at 60°C, and the polymerization activity was calculated according to the output of the polymer. Polymerization activity: 12.63×10 ⁶ g ofPE·mol ^-1 (M)·h ^-1 , polymer M _w =1000 g·mol ^-1 , M _w /M _n =1.5, T _m =101.4°C.

Example 53,

Ethylene polymerization under pressure used a 300 ml stainless steel polymerization kettle equipped with a mechanical stirring paddle and temperature control device. The polymerization kettle was evacuated and heated to 100° C. for two hours. Under the condition of pre-replacing the nitrogen in the kettle with ethylene, the polymerization kettle was allowed to cool slowly to the envisaged polymerization temperature (50° C.). Then add 50mL of toluene, 20mL of toluene solution dissolved with 3μmol catalyst (Co4), 2.05mL of cocatalyst MAO (1.46mol/L toluene solution) (Al/Co=1000), and the remaining toluene (making the total amount of toluene 100ml) . The kettle was closed, and ethylene was passed through to maintain a constant pressure of ethylene (10 atm). After the polymerization reaction reached the preset time (30min), the ethylene pressure in the kettle was released, hydrochloric acid ethanol was added, after filtering and washing, it was dried to constant weight in an oven at 60°C, and the polymerization activity was calculated according to the output of the polymer. Polymerization activity: 14.76×10 ⁶ g ofPE·mol ^-1 (M)·h ^-1 , polymer M _w =949 g·mol ^-1 , M _w /M _n =1.5, T _m =99.6°C.

Example 54,

Ethylene polymerization under pressure used a 300 ml stainless steel polymerization kettle equipped with a mechanical stirring paddle and temperature control device. The polymerization kettle was evacuated and heated to 100° C. for two hours. Under the condition of pre-replacing the nitrogen in the kettle with ethylene, the polymerization kettle was allowed to cool slowly to the envisaged polymerization temperature (50° C.). Then add 50mL of toluene, 20mL of toluene solution dissolved with 3μmol catalyst (Co4), 2.57mL of cocatalyst MAO (1.46mol/L toluene solution) (Al/Co=1250), and the remaining toluene (making the total amount of toluene 100ml) . The kettle was closed, and ethylene was passed through to maintain a constant pressure of ethylene (10 atm). After the polymerization reaction reached the preset time (30min), the ethylene pressure in the kettle was released, hydrochloric acid ethanol was added, after filtering and washing, it was dried to constant weight in an oven at 60°C, and the polymerization activity was calculated according to the output of the polymer. Polymerization activity: 13.29×10 ⁶ g of PE·mol ^-1 (M)·h ^-1 , polymer M _w =998 g·mol ^-1 , M _w /M _n =1.6T _m =100.9°C.

Example 55,

Ethylene polymerization under pressure used a 300 ml stainless steel polymerization kettle equipped with a mechanical stirring paddle and temperature control device. The polymerization kettle was evacuated and heated to 100° C. for two hours. Under the condition of pre-replacing the nitrogen in the kettle with ethylene, the polymerization kettle was allowed to cool slowly to the envisaged polymerization temperature (50° C.). Then add 50mL of toluene, 20mL of toluene solution dissolved with 3μmol catalyst (Co4), 3.08mL of cocatalyst MAO (1.46mol/L toluene solution) (Al/Co=1500), and the remaining toluene (making the total amount of toluene 100ml) . The kettle was closed, and ethylene was passed through to maintain a constant pressure of ethylene (10 atm). After the polymerization reaction reached the preset time (30min), the ethylene pressure in the kettle was released, hydrochloric acid ethanol was added, after filtering and washing, it was dried to constant weight in an oven at 60°C, and the polymerization activity was calculated according to the output of the polymer. Polymerization activity: 12.00×10 ⁶ g ofPE·mol ^-1 (M)·h ^-1 , polymer M _w =1029 g·mol ^-1 , M _w /M _n =1.5, T _m =102.3°C.

Example 56,

Ethylene polymerization under pressure used a 300 ml stainless steel polymerization kettle equipped with a mechanical stirring paddle and temperature control device. The polymerization kettle was evacuated and heated to 100° C. for two hours. Under the condition of pre-replacing the nitrogen in the kettle with ethylene, the polymerization kettle was allowed to cool slowly to the envisaged polymerization temperature (30° C.). Then add 50mL of toluene, 20mL of toluene solution dissolved with 3μmol catalyst (Co4), 2.05mL of cocatalyst MAO (1.46mol/L toluene solution) (Al/Co=1000), and the remaining toluene (making the total amount of toluene 100ml) . The kettle was closed, and ethylene was passed through to maintain a constant pressure of ethylene (10 atm). After the polymerization reaction reached the preset time (30min), the ethylene pressure in the kettle was released, hydrochloric acid ethanol was added, after filtering and washing, it was dried to constant weight in an oven at 60°C, and the polymerization activity was calculated according to the output of the polymer. Polymerization activity: 6.72×10 ⁶ g ofPE·mol ^-1 (M)·h ^-1 , polymer M _w =1219 g·mol ^-1 , M _w /M _n =1.6, T _m =100.9°C.

Example 57,

Ethylene polymerization under pressure used a 300 ml stainless steel polymerization kettle equipped with a mechanical stirring paddle and temperature control device. The polymerization kettle was evacuated and heated to 100° C. for two hours. Under the condition of pre-replacing the nitrogen in the kettle with ethylene, allow the polymerization kettle to be slowly cooled to the envisaged polymerization temperature (40° C.). Then add 50mL toluene successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyst (Co4), 2.05mL promoter MAO (1.46mol/L toluene solution) (Al/Co=1000), remaining toluene (making toluene total amount be 100 milliliters ). The kettle was closed, and ethylene was passed through to maintain a constant pressure of ethylene (10 atm). After the polymerization reaction reached the preset time (30min), the ethylene pressure in the kettle was released, hydrochloric acid ethanol was added, after filtering and washing, it was dried to constant weight in an oven at 60°C, and the polymerization activity was calculated according to the output of the polymer. Polymerization activity: 7.66×10 ⁶ g ofPE·mol ^-1 (M)·h ^-1 , polymer M _w =960 g·mol ^-1 , M _w /M _n =1.6, T _m =100.3°C.

Example 58,

Ethylene polymerization under pressure used a 300 ml stainless steel polymerization kettle equipped with a mechanical stirring paddle and temperature control device. The polymerization kettle was evacuated and heated to 100° C. for two hours. Under the condition of pre-replacing the nitrogen in the kettle with ethylene, the polymerization kettle was slowly cooled to the envisaged polymerization temperature (60° C.). Then add 50mL toluene successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyst (Co4), 2.05mL promoter MAO (1.46mol/L toluene solution) (Al/Co=1000), remaining toluene (making toluene total amount be 100 milliliters ). The kettle was closed, and ethylene was passed through to maintain a constant pressure of ethylene (10 atm). After the polymerization reaction reached the preset time (30min), the ethylene pressure in the kettle was released, hydrochloric acid ethanol was added, after filtering and washing, it was dried to constant weight in an oven at 60°C, and the polymerization activity was calculated according to the output of the polymer. Polymerization activity: 16.37×10 ⁶ g ofPE·mol ^-1 (M)·h ^-1 , polymer M _w =910 g·mol ^-1 , M _w /M _n =1.5, T _m =99.6°C.

Example 59,

Ethylene polymerization under pressure used a 300 ml stainless steel polymerization kettle equipped with a mechanical stirring paddle and temperature control device. The polymerization kettle was evacuated and heated to 100° C. for two hours. Under the condition of pre-replacing nitrogen in the kettle with ethylene, the polymerization kettle was slowly cooled to the envisaged polymerization temperature (70° C.). Then add 50mL of toluene, 20mL of toluene solution dissolved with 3μmol catalyst (Co4), 2.05mL of cocatalyst MAO (1.46mol/L toluene solution) (Al/Co=1000), and the remaining toluene (making the total amount of toluene 100ml) . The kettle was closed, and ethylene was passed through to maintain a constant pressure of ethylene (10 atm). After the polymerization reaction reached the preset time (30min), the ethylene pressure in the kettle was released, hydrochloric acid ethanol was added, after filtering and washing, it was dried to constant weight in an oven at 60°C, and the polymerization activity was calculated according to the output of the polymer. Polymerization activity: 15.60×10 ⁶ g ofPE·mol ^-1 (M)·h ^-1 , polymer M _w =880 g·mol ^-1 , M _w /M _n =1.6, T _m =99.0°C.

Example 60,

Ethylene polymerization under pressure used a 300 ml stainless steel polymerization kettle equipped with a mechanical stirring paddle and temperature control device. The polymerization kettle was evacuated and heated to 100° C. for two hours. Under the condition of pre-replacing the nitrogen in the kettle with ethylene, the polymerization kettle was slowly cooled to the envisaged polymerization temperature (60° C.). Then add 50mL of toluene, 20mL of toluene solution dissolved with 3μmol catalyst (Co4), 2.05mL of cocatalyst MAO (1.46mol/L toluene solution) (Al/Co=1000), and the remaining toluene (making the total amount of toluene 100ml) . The kettle was closed, and ethylene was passed through to maintain a constant pressure of ethylene (10 atm). After the polymerization reaction reached the preset time (5min), the ethylene pressure in the kettle was released, hydrochloric acid ethanol was added, after filtering and washing, it was dried to constant weight in an oven at 60°C, and the polymerization activity was calculated according to the output of the polymer. Polymerization activity: 4.83×10 ⁶ g ofPE·mol ^-1 (M)·h ^-1 , polymer M _w =891 g·mol ^-1 , M _w /M _n =1.5, T _m =100.5°C.

Example 61,

Ethylene polymerization under pressure used a 300 ml stainless steel polymerization kettle equipped with a mechanical stirring paddle and temperature control device. The polymerization kettle was evacuated and heated to 100° C. for two hours. Under the condition of pre-replacing the nitrogen in the kettle with ethylene, the polymerization kettle was slowly cooled to the envisaged polymerization temperature (60° C.). Then add 50mL of toluene, 20mL of toluene solution dissolved with 3μmol catalyst (Co4), 2.05mL of cocatalyst MAO (1.46mol/L toluene solution) (Al/Co=1000), and the remaining toluene (making the total amount of toluene 100ml) . The kettle was closed, and ethylene was passed through to maintain a constant pressure of ethylene (10 atm). After the polymerization reaction reached the preset time (10min), the ethylene pressure in the kettle was released, hydrochloric acid ethanol was added, after filtering and washing, it was dried to constant weight in an oven at 60°C, and the polymerization activity was calculated according to the output of the polymer. Polymerization activity: 10.13×10 ⁶ g ofPE·mol ^-1 (M)·h ^-1 , polymer M _w =896g·mol ^-1 , M _w /M _n =1.5, T _m =99.8°C

Example 62,

Ethylene polymerization under pressure used a 300 ml stainless steel polymerization kettle equipped with a mechanical stirring paddle and temperature control device. The polymerization kettle was evacuated and heated to 100° C. for two hours. Under the condition of pre-replacing the nitrogen in the kettle with ethylene, the polymerization kettle was slowly cooled to the envisaged polymerization temperature (60° C.). Then add 50mL of toluene, 20mL of toluene solution dissolved with 3μmol catalyst (Co4), 2.05mL of cocatalyst MAO (1.46mol/L toluene solution) (Al/Co=1000), and the remaining toluene (making the total amount of toluene 100ml) . The kettle was closed, and ethylene was passed through to maintain a constant pressure of ethylene (10 atm). After the polymerization reaction reached the preset time (60min), the ethylene pressure in the kettle was released, hydrochloric acid ethanol was added, after filtering and washing, it was dried to constant weight in an oven at 60°C, and the polymerization activity was calculated according to the output of the polymer. Polymerization activity: 18.43×10 ⁶ g ofPE·mol ^-1 (M)·h ^-1 , polymer M _w =1016g·mol ^-1 , M _w /M _n =1.5, T _m =99.8°C

Example 63,

Ethylene polymerization under pressure used a 300 ml stainless steel polymerization kettle equipped with a mechanical stirring paddle and temperature control device. The polymerization kettle was evacuated and heated to 100° C. for two hours. Under the condition of pre-replacing the nitrogen in the kettle with ethylene, the polymerization kettle was slowly cooled to the envisaged polymerization temperature (60° C.). Then add 50mL of toluene, 20mL of toluene solution dissolved with 3μmol catalyst (Co4), 2.05mL of cocatalyst MAO (1.46mol/L toluene solution) (Al/Co=1000), and the remaining toluene (making the total amount of toluene 100ml) . The kettle was closed, and ethylene was passed through to maintain a constant pressure of ethylene (5 atm). After the polymerization reaction reached the preset time (30min), the ethylene pressure in the kettle was released, hydrochloric acid ethanol was added, after filtering and washing, it was dried to constant weight in an oven at 60°C, and the polymerization activity was calculated according to the output of the polymer. Polymerization activity: 8.20×10 ⁶ g ofPE·mol ^-1 (M)·h ^-1 , polymer M _w =914g·mol ^-1 , M _w /M _n =1.4, T _m =100.5°C.

Example 64,

The ethylene polymerization under pressure used a 300 ml stainless steel polymerization kettle equipped with a mechanical stirring paddle and temperature control device. The polymerization kettle was evacuated and heated to 100° C. for two hours. Under the condition of pre-replacing the nitrogen in the kettle with ethylene, the polymerization kettle was slowly cooled to the envisaged polymerization temperature (60° C.). Then add 50 mL of toluene, 20 mL of toluene solution dissolved with 3 μmol catalyst (Co1), 2.05 mL of cocatalyst MAO (1.46 mol/L toluene solution) (Al/Co=1000), and the remaining toluene (making the total amount of toluene 100 mL) . The kettle was closed, and ethylene was passed through to maintain a constant pressure of ethylene (5 atm). After the polymerization reaction reached the preset time (30min), the ethylene pressure in the kettle was released, hydrochloric acid ethanol was added, after filtering and washing, it was dried to constant weight in an oven at 60°C, and the polymerization activity was calculated according to the output of the polymer. Polymerization activity: 16.29×10 ⁶ g ofPE·mol ^-1 (M)·h ^-1 , polymer M _w =827g·mol ^-1 , M _w /M _n =1.6, T _m =99.0°C.

Example 65,

Ethylene polymerization under pressure used a 300 ml stainless steel polymerization kettle equipped with a mechanical stirring paddle and temperature control device. The polymerization kettle was evacuated and heated to 100° C. for two hours. Under the condition of pre-replacing the nitrogen in the kettle with ethylene, the polymerization kettle was slowly cooled to the envisaged polymerization temperature (60° C.). Then add 50mL of toluene, 20mL of toluene solution dissolved with 3μmol catalyst (Co2), 2.05mL of cocatalyst MAO (1.46mol/L toluene solution) (Al/Co=1000), and the remaining toluene (making the total amount of toluene 100ml) . The kettle was closed, and ethylene was passed through to maintain a constant pressure of ethylene (5 atm). After the polymerization reaction reached the preset time (30min), the ethylene pressure in the kettle was released, hydrochloric acid ethanol was added, after filtering and washing, it was dried to constant weight in an oven at 60°C, and the polymerization activity was calculated according to the output of the polymer. Polymerization activity: 13.37×10 ⁶ g ofPE·mol ^-1 (M)·h ^-1 , polymer M _w =1955g·mol ^-1 , M _w /M _n =1.9, T _m =117.4°C.

Example 66,

Ethylene polymerization under pressure used a 300 ml stainless steel polymerization kettle equipped with a mechanical stirring paddle and temperature control device. The polymerization kettle was evacuated and heated to 100° C. for two hours. Under the condition of pre-replacing the nitrogen in the kettle with ethylene, the polymerization kettle was slowly cooled to the envisaged polymerization temperature (60° C.). Then add 50mL of toluene, 20mL of toluene solution dissolved with 3μmol catalyst (Co3), 2.05mL of cocatalyst MAO (1.46mol/L toluene solution) (Al/Co=1000), and the remaining toluene (making the total amount of toluene 100ml) . The kettle was closed, and ethylene was passed through to maintain a constant pressure of ethylene (5 atm). After the polymerization reaction reached the preset time (30min), the ethylene pressure in the kettle was released, hydrochloric acid ethanol was added, after filtering and washing, it was dried to constant weight in an oven at 60°C, and the polymerization activity was calculated according to the output of the polymer. Polymerization activity: 6.70×10 ⁶ g ofPE·mol ^-1 (M)·h ^-1 , polymer M _w =10189g·mol ^-1 , M _w /M _n =2.0, T _m =128.9°C.

Example 67,

Ethylene polymerization under pressure used a 300 ml stainless steel polymerization kettle equipped with a mechanical stirring paddle and temperature control device. The polymerization kettle was evacuated and heated to 100° C. for two hours. Under the condition of pre-replacing the nitrogen in the kettle with ethylene, the polymerization kettle was slowly cooled to the envisaged polymerization temperature (60° C.). Then add 50mL of toluene, 20mL of toluene solution dissolved with 3μmol catalyst (Co5), 2.05mL of cocatalyst MAO (1.46mol/L toluene solution) (Al/Co=1000), and the remaining toluene (making the total amount of toluene 100ml) . The kettle was closed, and ethylene was passed through to maintain a constant pressure of ethylene (5 atm). After the polymerization reaction reached the preset time (30min), the ethylene pressure in the kettle was released, hydrochloric acid ethanol was added, after filtering and washing, it was dried to constant weight in an oven at 60°C, and the polymerization activity was calculated according to the output of the polymer. Polymerization activity: 16.21×10 ⁶ g ofPE·mol ^-1 (M)·h ^-1 , polymer M _w =2009g·mol ^-1 , M _w /M _n =1.9, T _m =117.6°C.

Example 68,

Ethylene polymerization under pressure used a 300 ml stainless steel polymerization kettle equipped with a mechanical stirring paddle and temperature control device. The polymerization kettle was evacuated and heated to 100° C. for two hours. Under the condition of pre-replacing the nitrogen in the kettle with ethylene, the polymerization kettle was allowed to cool slowly to the envisaged polymerization temperature (50° C.). Then add 50mL toluene successively, 20mL is dissolved with the toluene solution of 3μmol catalyst (Co4), 1.55mL co-catalyst (MMAO, the heptane solution of 1.93mol/L) (Al/Co=1000), remaining toluene (making toluene total amount is 100ml). The kettle was closed, and ethylene was passed through to maintain a constant pressure of ethylene (10 atm). After the polymerization reaction reached the preset time (30min), the ethylene pressure in the kettle was released, hydrochloric acid ethanol was added, after filtering and washing, it was dried to constant weight in an oven at 60°C, and the polymerization activity was calculated according to the output of the polymer. Polymerization activity: 9.35×10 ⁶ g of PE·mol ^-1 (M)·h ^-1 , polymer M _w =1031 g·mol ^-1 , M _w /M _n =1.5, T _m =102.0°C.

Example 69,

The polymerization kettle was evacuated and heated to 100° C. for two hours. Under the condition of pre-replacing the nitrogen in the kettle with ethylene, the polymerization kettle was allowed to cool slowly to the envisaged polymerization temperature (50° C.). Then add 50mL toluene successively, 20mL is dissolved with the toluene solution of 3μmol catalyst (Co4), 1.94mL cocatalyst (MMAO, the heptane solution of 1.93mol/L) (Al/Co=1250), remaining toluene (making toluene total amount is 100ml). The kettle was closed, and ethylene was passed through to maintain a constant pressure of ethylene (10 atm). After the polymerization reaction reached the preset time (30min), the ethylene pressure in the kettle was released, hydrochloric acid ethanol was added, after filtering and washing, it was dried to constant weight in an oven at 60°C, and the polymerization activity was calculated according to the output of the polymer. Polymerization activity: 10.05×10 ⁶ g ofPE·mol ^-1 (M)·h ^-1 , polymer M _w =1064 g·mol ^-1 , M _w /M _n =1.5, T _m =101.6°C.

Example 70,

The polymerization kettle was evacuated and heated to 100° C. for two hours. Under the condition of pre-replacing the nitrogen in the kettle with ethylene, the polymerization kettle was allowed to cool slowly to the envisaged polymerization temperature (50° C.). Then add 50mL toluene successively, 20mL is dissolved with the toluene solution of 3μmol catalyst (Co4), 2.33mL co-catalyst (MMAO, the heptane solution of 1.93mol/L) (Al/Co=1500), remaining toluene (making toluene total amount is 100ml). The kettle was closed, and ethylene was passed through to maintain a constant pressure of ethylene (10 atm). After the polymerization reaction reached the preset time (30min), the ethylene pressure in the kettle was released, hydrochloric acid ethanol was added, after filtering and washing, it was dried to constant weight in an oven at 60°C, and the polymerization activity was calculated according to the output of the polymer. Polymerization activity: 11.52×10 ⁶ g of PE·mol ^-1 (M)·h ^-1 , polymer M _w =1056 g·mol ^-1 , M _w /M _n =1.6, T _m =99.5°C.

Example 71,

The polymerization kettle was evacuated and heated to 100° C. for two hours. Under the condition of pre-replacing the nitrogen in the kettle with ethylene, the polymerization kettle was allowed to cool slowly to the envisaged polymerization temperature (50° C.). Then add 50mL toluene successively, 20mL is dissolved with the toluene solution of 3μmol catalyst (Co4), 2.72mL cocatalyst (MMAO, the heptane solution of 1.93mol/L) (Al/Co=1750), remaining toluene (making toluene total amount is 100ml). The kettle was closed, and ethylene was passed through to maintain a constant pressure of ethylene (10 atm). After the polymerization reaction reached the preset time (30min), the ethylene pressure in the kettle was released, hydrochloric acid ethanol was added, after filtering and washing, it was dried to constant weight in an oven at 60°C, and the polymerization activity was calculated according to the output of the polymer. Polymerization activity: 11.05×10 ⁶ g ofPE·mol ^-1 (M)·h ^-1 , polymer M _w =1088 g·mol ^-1 , M _w /M _n =1.6, T _m =100.8°C.

Example 72,

The polymerization kettle was evacuated and heated to 100° C. for two hours. Under the condition of pre-replacing the nitrogen in the kettle with ethylene, the polymerization kettle was allowed to cool slowly to the envisaged polymerization temperature (30° C.). Then add 50mL toluene successively, 20mL is dissolved with the toluene solution of 3μmol catalyst (Co4), 2.33mL co-catalyst (MMAO, the heptane solution of 1.93mol/L) (Al/Co=1500), remaining toluene (making toluene total amount is 100ml). The kettle was closed, and ethylene was passed through to maintain a constant pressure of ethylene (10 atm). After the polymerization reaction reached the preset time (30min), the ethylene pressure in the kettle was released, hydrochloric acid ethanol was added, after filtering and washing, it was dried to constant weight in an oven at 60°C, and the polymerization activity was calculated according to the output of the polymer. Polymerization activity: 5.89×10 ⁶ g ofPE·mol ^-1 (M)·h ^-1 , T _m =100.4°C

Example 73,

The polymerization kettle was evacuated and heated to 100° C. for two hours. Under the condition of pre-replacing the nitrogen in the kettle with ethylene, allow the polymerization kettle to be slowly cooled to the envisaged polymerization temperature (40° C.). Then add 50mL toluene successively, 20mL is dissolved with the toluene solution of 3μmol catalyst (Co4), 2.33mL co-catalyst (MMAO, the heptane solution of 1.93mol/L) (Al/Co=1500), remaining toluene (making toluene total amount is 100ml). The kettle was closed, and ethylene was passed through to maintain a constant pressure of ethylene (10 atm). After the polymerization reaction reached the preset time (30min), the ethylene pressure in the kettle was released, hydrochloric acid ethanol was added, after filtering and washing, it was dried to constant weight in an oven at 60°C, and the polymerization activity was calculated according to the output of the polymer. Polymerization activity: 8.68×10 ⁶ g ofPE·mol ^-1 (M)·h ^-1 , polymer M _w =927Kg·mol ^-1 , M _w /M _n =1.6, T _m =99.4°C.

Example 74,

The polymerization kettle was evacuated and heated to 100° C. for two hours. Under the condition of pre-replacing the nitrogen in the kettle with ethylene, the polymerization kettle was slowly cooled to the envisaged polymerization temperature (60° C.). Then add 50mL toluene successively, 20mL is dissolved with the toluene solution of 3μmol catalyst (Co4), 2.33mL co-catalyst (MMAO, the heptane solution of 1.93mol/L) (Al/Co=1500), remaining toluene (making toluene total amount is 100ml). The kettle was closed, and ethylene was passed through to maintain a constant pressure of ethylene (10 atm). After the polymerization reaction reached the preset time (30min), the ethylene pressure in the kettle was released, hydrochloric acid ethanol was added, after filtering and washing, it was dried to constant weight in an oven at 60°C, and the polymerization activity was calculated according to the output of the polymer. Polymerization activity: 13.21×10 ⁶ g ofPE·mol ^-1 (M)·h ^-1 , polymer M _w =951 g·mol ^-1 , M _w /M _n =1.5, T _m =98.7°C.

Example 75,

The polymerization kettle was evacuated and heated to 100° C. for two hours. Under the condition of pre-replacing nitrogen in the kettle with ethylene, the polymerization kettle was slowly cooled to the envisaged polymerization temperature (70° C.). Then add 50mL toluene successively, 20mL is dissolved with the toluene solution of 3μmol catalyst (Co4), 2.33mL co-catalyst (MMAO, the heptane solution of 1.93mol/L) (Al/Co=1500), remaining toluene (making toluene total amount is 100ml). The kettle was closed, and ethylene was passed through to maintain a constant pressure of ethylene (10 atm). After the polymerization reaction reached the preset time (30min), the ethylene pressure in the kettle was released, hydrochloric acid ethanol was added, after filtering and washing, it was dried to constant weight in an oven at 60°C, and the polymerization activity was calculated according to the output of the polymer. Polymerization activity: 4.92×10 ⁶ g ofPE·mol ^-1 (M)·h ^-1 , polymer M _w =950 g·mol ^-1 , M _w /M _n =1.5, T _m =100.3°C.

Example 76,

The polymerization kettle was evacuated and heated to 100° C. for two hours. Under the condition of pre-replacing the nitrogen in the kettle with ethylene, the polymerization kettle was slowly cooled to the envisaged polymerization temperature (60° C.). Then add 50mL toluene successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyst (Co1), 2.33mL cocatalyst (MMAO, the heptane solution of 1.93mol/L) (Al/Co=1500), remaining toluene (make toluene total amount be 100ml). The kettle was closed, and ethylene was passed through to maintain a constant pressure of ethylene (10 atm). After the polymerization reaction reached the preset time (30min), the ethylene pressure in the kettle was released, hydrochloric acid ethanol was added, after filtering and washing, it was dried to constant weight in an oven at 60°C, and the polymerization activity was calculated according to the output of the polymer. Polymerization activity: 8.83×10 ⁶ g ofPE·mol ^-1 (M)·h ^-1 , polymer M _w =996g·mol ^-1 , M _w /M _n =1.5, T _m =100.4°C.

Example 77,

The polymerization kettle was evacuated and heated to 100° C. for two hours. Under the condition of pre-replacing the nitrogen in the kettle with ethylene, the polymerization kettle was slowly cooled to the envisaged polymerization temperature (60° C.). Then add 50mL of toluene, 20mL of toluene solution with 3μmol catalyst (Co2), 2.33mL of cocatalyst (MMAO, 1.93mol/L heptane solution) (Al/Co=1500), the remaining toluene (so that the total amount of toluene is 100ml). The kettle was closed, and ethylene was passed through to maintain a constant pressure of ethylene (10 atm). After the polymerization reaction reached the preset time (30min), the ethylene pressure in the kettle was released, hydrochloric acid ethanol was added, after filtering and washing, it was dried to constant weight in an oven at 60°C, and the polymerization activity was calculated according to the output of the polymer. Polymerization activity: 5.72×10 ⁶ g ofPE·mol ^-1 (M)·h ^-1 , polymer M _w =2162g·mol ^-1 , M _w /M _n =1.9, T _m =118.4°C.

Example 78,

The polymerization kettle was evacuated and heated to 100° C. for two hours. Under the condition of pre-replacing the nitrogen in the kettle with ethylene, the polymerization kettle was slowly cooled to the envisaged polymerization temperature (60° C.). Then add 50mL toluene, 20mL toluene solution with 3μmol catalyst (Co3), 2.33mL co-catalyst (MMAO, 1.93mol/L heptane solution) (Al/Co=1500), remaining toluene (so that the total amount of toluene is 100ml). The kettle was closed, and ethylene was passed through to maintain a constant pressure of ethylene (10 atm). After the polymerization reaction reached the preset time (30min), the ethylene pressure in the kettle was released, hydrochloric acid ethanol was added, after filtering and washing, it was dried to constant weight in an oven at 60°C, and the polymerization activity was calculated according to the output of the polymer. Polymerization activity: 3.41×10 ⁶ g of PE·mol ^-1 (M)·h ^-1 , polymer M _w =8096g·mol ^-1 , M _w /M _n =3.2, T _m =129.1°C.

Example 79,

The polymerization kettle was evacuated and heated to 100° C. for two hours. Under the condition of pre-replacing the nitrogen in the kettle with ethylene, the polymerization kettle was slowly cooled to the envisaged polymerization temperature (60° C.). Then add 50mL toluene successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyst (Co5), 2.33mL cocatalyst (MMAO, the heptane solution of 1.93mol/L) (Al/Co=1500), remaining toluene (make toluene total amount be 100ml). The kettle was closed, and ethylene was passed through to maintain a constant pressure of ethylene (10 atm). After the polymerization reaction reached the preset time (30min), the ethylene pressure in the kettle was released, hydrochloric acid ethanol was added, after filtering and washing, it was dried to constant weight in an oven at 60°C, and the polymerization activity was calculated according to the output of the polymer. Polymerization activity: 7.81×10 ⁶ g ofPE·mol ^-1 (M)·h ^-1 , polymer M _w =2052g·mol ^-1 , M _w /M _n =1.9, T _m =119.0°C.

Example 80,

Ethylene polymerization under pressure used a 300 ml stainless steel polymerization kettle equipped with a mechanical stirring paddle and temperature control device. The polymerization kettle was evacuated and heated to 100° C. for two hours. Under the condition of pre-replacing the nitrogen in the kettle with ethylene, the polymerization kettle was allowed to cool slowly to the envisaged polymerization temperature (50° C.). Then add 50mL toluene successively, 20mL is dissolved with 3μmol catalyst (Fe6 toluene solution, 3.10mL cocatalyst (MMAO, the heptane solution of 1.93mol/L) (Al/Fe=2000), remaining toluene (making toluene total amount be 100 Milliliters).The still is sealed, leads to ethylene and maintains the constant pressure (10atm) of ethylene.After the polymerization reaction reaches the preset time (30min), the ethylene pressure in the still is released, and hydrochloric acid ethanol is added, after filtering and washing at 60 Dry in an oven at °C to constant weight to obtain 11.5g polymer, and calculate the polymerization activity according to the output of the polymer. Polymerization activity: 7.8×10 ⁶ g of PE·mol ^-1 (M)·h ^-1 , polymer M _w = 23.8 Kg·mol ^-1 , M _w /M _n = 4.0, T _m = 127.4.

Example 81,

Ethylene polymerization under pressure used a 300 ml stainless steel polymerization kettle equipped with a mechanical stirring paddle and temperature control device. The polymerization kettle was evacuated and heated to 100° C. for two hours. Under the condition of pre-replacing the nitrogen in the kettle with ethylene, the polymerization kettle was allowed to cool slowly to the envisaged polymerization temperature (50° C.). Then add 50mL toluene successively, 20mL is dissolved with 3μmol catalyst (Fe7 toluene solution, 3.10mL cocatalyst (MMAO, the heptane solution of 1.93mol/L) (Al/Fe=2000), remaining toluene (making toluene total amount be 100 Milliliters).The still is sealed, leads to ethylene and maintains the constant pressure (10atm) of ethylene.After the polymerization reaction reaches the preset time (30min), the ethylene pressure in the still is released, and hydrochloric acid ethanol is added, after filtering and washing at 60 Dry in an oven at °C to constant weight to obtain 20.0g polymer, and calculate the polymerization activity according to the yield of the polymer. Polymerization activity: 13.4×10 ⁶ g of PE·mol ^-1 (M)·h ^-1 , polymer M _w = 20Kg·mol ^-1 , M _w /M _n = 8.4, T _m = 124.4.

Example 82,

Ethylene polymerization under pressure used a 300 ml stainless steel polymerization kettle equipped with a mechanical stirring paddle and temperature control device. The polymerization kettle was evacuated and heated to 100° C. for two hours. Under the condition of pre-replacing the nitrogen in the kettle with ethylene, the polymerization kettle was allowed to cool slowly to the envisaged polymerization temperature (50° C.). Then add 50mL toluene successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyst (Fe8), 3.10mL cocatalyst (MMAO, the heptane solution of 1.93mol/L) (Al/Fe=2000), remaining toluene (make toluene total amount be 100ml). The kettle was closed, and ethylene was passed through to maintain a constant pressure of ethylene (10 atm). After the polymerization reaction reaches the preset time (30min), release the ethylene pressure in the kettle, add hydrochloric acid ethanol, filter and wash and dry to constant weight in a 60°C oven to obtain 8.0g polymer, according to polymer Polymerization activity was calculated from the yield. Polymerization activity: 5.3×10 ⁶ g of PE·mol ^-1 (M)·h ^-1 , polymer M _w =40.8Kg·mol ^-1 , M _w /M _n =2.0, T _m =127.4.

Example 83,

Ethylene polymerization under pressure used a 300 ml stainless steel polymerization kettle equipped with a mechanical stirring paddle and temperature control device. The polymerization kettle was evacuated and heated to 100° C. for two hours. Under the condition of pre-replacing the nitrogen in the kettle with ethylene, the polymerization kettle was slowly cooled to the envisaged polymerization temperature (60° C.). Then add 50mL of toluene, 20mL of toluene solution dissolved with 3μmol catalyst (Co6), 2.05mL of cocatalyst MAO (1.46mol/L toluene solution) (Al/Co=1000), and the remaining toluene (making the total amount of toluene 100ml) . The kettle was closed, and ethylene was passed through to maintain a constant pressure of ethylene (5 atm). After the polymerization reaction reached the preset time (30min), the ethylene pressure in the kettle was released, hydrochloric acid ethanol was added, after filtering and washing, it was dried to constant weight in an oven at 60°C, and the polymerization activity was calculated according to the output of the polymer. Polymerization activity: 3.70×10 ⁶ g ofPE·mol ^-1 (M)·h ^-1 , polymer M _w =5400g·mol ^-1 , M _w /M _n =1.8, T _m =124.9°C.

Example 84,

Ethylene polymerization under pressure used a 300 ml stainless steel polymerization kettle equipped with a mechanical stirring paddle and temperature control device. The polymerization kettle was evacuated and heated to 100° C. for two hours. Under the condition of pre-replacing the nitrogen in the kettle with ethylene, the polymerization kettle was slowly cooled to the envisaged polymerization temperature (60° C.). Then add 50mL of toluene, 20mL of toluene solution dissolved with 3μmol catalyst (Co7), 2.05mL of cocatalyst MAO (1.46mol/L toluene solution) (Al/Co=1000), and the remaining toluene (making the total amount of toluene 100ml) . The kettle was closed, and ethylene was passed through to maintain a constant pressure of ethylene (5 atm). After the polymerization reaction reached the preset time (30min), the ethylene pressure in the kettle was released, hydrochloric acid ethanol was added, after filtering and washing, it was dried to constant weight in an oven at 60°C, and the polymerization activity was calculated according to the output of the polymer. Polymerization activity: 23.21×10 ⁶ g ofPE·mol ^-1 (M)·h ^-1 , polymer M _w =2002g·mol ^-1 , M _w /M _n =1.6, T _m =110.6°C.

Example 85,

Ethylene polymerization under pressure used a 300 ml stainless steel polymerization kettle equipped with a mechanical stirring paddle and temperature control device. The polymerization kettle was evacuated and heated to 100° C. for two hours. Under the condition of pre-replacing the nitrogen in the kettle with ethylene, the polymerization kettle was allowed to cool slowly to the envisaged polymerization temperature (50° C.). Then add 50mL toluene successively, 20mL is dissolved with the toluene solution of 3μmol catalyst (Co8), 2.05mL co-catalyst (MMAO, the heptane solution of 1.93mol/L) (Al/Fe=1000), remaining toluene (making toluene total amount is 100ml). The kettle was closed, and ethylene was passed through to maintain a constant pressure of ethylene (10 atm). After the polymerization reaction reached the preset time (30min), the ethylene pressure in the kettle was released, hydrochloric acid ethanol was added, after filtering and washing, it was dried to constant weight in an oven at 60°C, and the polymerization activity was calculated according to the output of the polymer. Polymerization activity: 10.4×10 ⁶ g ofPE·mol ^-1 (M)·h ^-1 , polymer M _w =7000 g·mol ^-1 , M _w /M _n =1.8, T _m =126.4.

Claims (10)

1.2 8-diimine-4,5,6 hydrogenated quinoline class transition metal complexes, its structural formula be suc as formula shown in the I,

The formula I

In the formula I, R ¹Be selected from hydrogen, methyl, ethyl and propyl group, R ², R ³, R ⁴, R ⁵And R ⁶Be selected from hydrogen, alkyl, nitro and halogen independently of one another; M is a transition metal.

2. transition metal complex according to claim 1 is characterized in that: R ¹Be selected from hydrogen, methyl and ethyl; R ², R ³, R ⁴, R ⁵And R ⁶Be selected from hydrogen, methyl, ethyl, sec.-propyl, fluorine, chlorine, bromine and nitro independently of one another; M is Fe or Co.

3. the preparation method of claim 1 or 2 said transition metal complexes comprises the steps:

(1) 2-aldehyde radical shown in the formula II (ketone)-4,5, substituted aniline shown in 6-hydrogenation-8-quinolinone and the formula III react under the condition that catalyzer exists and obtain 2,8-diimine-4,5,6-hydrogenated quinoline compound;

Said 2,8-diimine-4,5, the structural formula of 6-hydrogenated quinoline compound is suc as formula shown in IV and/or the formula V;

Formula II formula III

Formula IV formula V

In the following formula, R ¹Be selected from hydrogen, methyl, ethyl and propyl group, R ², R ³, R ⁴, R ⁵And R ⁶Be selected from hydrogen, alkyl, nitro and halogen independently of one another;

(2) said 2,8-diimine-4,5,6-hydrogenated quinoline compound and MCl ₂Reaction promptly gets product; M is a transition metal.

4. method according to claim 3 is characterized in that: in the step (1), said catalyzer is a tosic acid; The solvent of said reaction is a propyl carbinol; The temperature of said reaction is 110 ~ 125 ° of C, and the time is 6h ~ 20h.

5. method according to claim 3 is characterized in that: in the formula III, and R ², R ³, R ⁴, R ⁵And R ⁶When being selected from fluorine or chlorine independently of one another, catalyzer is a tosic acid described in the step (1), and said solvent is a tetraethoxy, and the temperature of said reaction is 140 ~ 150 ° of C, and the time is 1 ~ 2 day.

6. according to arbitrary described method among the claim 3-5, it is characterized in that: in the step (2), MCl ₂With said 2,8-diimine-4,5, the molfraction of 6-hydrogenated quinoline compound is than being (1 ~ 1.5): (1 ~ 1.2), the temperature of said reaction are 20 ~ 25 ° of C, and the time is 4 ~ 18h.

7. catalyst composition is made up of claim 1 or 2 said transition metal complexes and promotor, and said promotor is selected from one or more in aikyiaiurnirsoxan beta, alkylaluminium cpd and the chlorination aluminum alkyls.

8. compsn according to claim 7 is characterized in that: said aikyiaiurnirsoxan beta is the MAO of MAO or the modification of tertiary butyl aluminium; Said aluminum compound is trimethylaluminium, triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum or tri-n-octylaluminium; Said chlorination aluminum alkyls is diethylaluminum chloride or ethylaluminium dichloride; The molfraction of central metal M in aluminium in the said promotor and the said transition metal complex is than being (100 ~ 10000): 1.

9. claim 1 or 2 said transition metal complexes and claim 7 or the 8 said catalyst compositions application in the catalyzed ethylene polymerization reaction.

10. application according to claim 9 is characterized in that: the temperature of said ethylene polymerization is 20 ~ 100 ° of C, and pressure is 0.1 ~ 1.0MPa.

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