CN102731578B - 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-5,6,7-trihydroquinoline 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)-5,6,7-hydrogenated-8-quinolinone shown in formula II and Substituted aniline reacts under the condition that catalyst exists to obtain 2,8-diimine-5,6,7-trihydroquinoline compound; (2) said 2,8-diimine-5,6,7- Trihydroquinoline compound reacts with MCl ₂ to get that. 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-5,6,7-trihydroquinoline transition metal complex and its preparation method and application

technical field

The invention relates to a 2,8-diimine-5,6,7-trihydroquinoline transition metal complex and a preparation method and application thereof, specifically an application in catalytic ethylene polymerization. the

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. the

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):

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. the

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 for α-olefins, and the distribution of oligomerization products approximately conforms to the Schluz-Flory rule (Organometallics2006, 25, 666-677, Chinese patent application number 200510066427.2 filing 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.

Afterwards, our research group developed a 2-benzimidazole-6-aminopyridine iron and cobalt complex catalyst (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.

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. the

Contents of the invention

The object of the present invention is to provide a 2,8-diimine-5,6,7-trihydroquinoline transition metal complex and its preparation method and application. the

The 2,8-diimine-5,6,7-trihydroquinoline 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 the preparation method of above-mentioned transition metal complex, comprises the following steps:

(1) 2-formyl (ketone)-5,6,7-hydrogenated-8-quinolinone shown in formula II reacts with substituted aniline shown in formula III in the presence of a catalyst to obtain 2,8-diethylene Amine-5,6,7-trihydroquinoline compounds;

The structural formula of the 2,8-diimine-5,6,7-trihydroquinoline compound is shown in formula IV and/or 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-5,6,7-trihydroquinoline compound is reacted with MCl ₂ to obtain the product; M is a transition metal.

In the above preparation method, in step (1), the catalyst can be p-toluenesulfonic acid; the solvent for 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 to 20h, specifically 6h or 20h. the

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 Ethyl orthosilicate, the temperature of the reaction may be 140-150° C., and the time may be 1-2 days.

In the above preparation method, in step (2), the molar ratio of _MCl2 to the 2,8-diimine-5,6,7-trihydroquinoline compound can be (1～1.5):( 1-1.2), specifically 1:1, 1:1.2 or 1.5:1, the reaction temperature may be 20-25°C, and the reaction time may 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. the

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 specific alkylaluminum chloride can 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

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, 50°C °C, 60 °C, 70 °C or 80 °C; the pressure can be 0.1-1.0 MPa, specifically 0.5 MPa or 1.0 MPa. the

The present invention designs and synthesizes 2,8-diimine-5,6,7-trihydroquinoline transition metal complexes containing N^N^N ligands, which are used to catalyze ethylene polymerization , the resulting polyethylene has highly linear characteristics, is suitable for the production of high-density polyethylene or polyethylene wax, and exhibits excellent catalytic activity, the catalyst has strong tolerance to higher reaction temperatures, and has a wide range of industrial application prospects . the

Description of drawings

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

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

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

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

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

Detailed ways

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

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

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 situations 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 = ^R4 = ^R5 = 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 = ^R4 = ^R5 = 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 = ^R4 = ^R5 = H;

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

Embodiment 1, the synthesis of 2,8-(2,6-dimethylbenzimine)-5,6,7-trihydroquinoline (L1/L1') ligand

Put raw materials 2,8-5,6,7-hydroquinoline diketone (0.189g, 0.1mmol) and 2,6-dimethylaniline (0.302g, 0.25mmol)] and p-toluenesulfonic acid into 100ml two-necked bottle 0.015 g was refluxed in n-butanol (30 ml). 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. Yield 44.2%. the

NMR showed that there were two isomers, among which the enamine isomer was the main product, L1:L1'=0.19:1(detected by ¹ H NMR).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.

Embodiment 2, the synthesis of 2,8-(2,6-diethylphenylimine)-5,6,7-trihydroquinoline (L2/L2') ligand

Put raw materials 2,8-5,6,7-hydroquinoline diketone (0.189g, 0.1mmol) and 2,6-diethylaniline (0.373g, 0.25mmol) and p-toluenesulfonic acid into 100ml two-necked bottle 0.015 g was refluxed in n-butanol (30 ml). 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 0.24 g of a yellow solid. Yield 53%. the

NMR showed that there were two isomers, among which the enamine isomer was the main product, L2:L2'=0.33:1(detected by ¹ H NMR).Mp:138-139℃.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 = 7.9 Hz, -CH ₃ ), 1.14 (t, 6H, J = 7.4 Hz, -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.

Embodiment 3, the synthesis of 2,8-(2,6-diisopropylphenylimine)-5,6,7-trihydroquinoline (L3/L3') ligand

Put raw materials 2,8-5,6,7-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%. the

NMR showed two isomers, of which the enamine isomer was the main product. L3:L3'＝0.3:1(detected by ¹ H NMR).Mp:183-184℃.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. ¹ H 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 ).

Embodiment 4, the synthesis of 2,8-(2,4,6-trimethylbenzimine)-5,6,7-trihydroquinoline (L4/L4') ligand

Put raw materials 2,8-5,6,7-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 the reaction is carried out for about 6 hours, 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 H NMR).FT-IR(KBr,cm ^-1 ):3366(ν _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.

Embodiment 5, the synthesis of 2,8-(2,6-diethyl-4-methylphenylimine)-5,6,7-trihydroquinoline (L5/L5') ligand

2,8-5,6,7-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), and 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%. the

NMR showed two isomers, of which the enamine isomer was the main product. L5:L5'＝0.23:1.Mp:98-99℃.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=7.8 Hz, 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, 97.3, ,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.

Embodiment 6, the synthesis of 2,8-(2,6-dichlorophenylimine)-5,6,7-trihydroquinoline (L6) ligand

Put raw materials 2,8-5,6,7-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, It was refluxed in n-butanol (30ml), and 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 0.144g of a yellow solid with a yield of 30.2 %. the

NMR showed two isomers, of which the enamine isomer was the main product. L6:L6'＝0.26:FT-IR(KBr,cm ^-1 ):3359(ν _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-5,6,7-hydroquinoline (0.175g, 1mmol) and 2,6-dimethylaniline (0.302g, 2.5mmol) and p-toluenesulfonic acid into 100ml two-necked bottle 0.015 g was refluxed in n-butanol (30 ml). 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 0.222 g of a yellow solid. Yield 58.2%. the

NMR showed two isomers, of which the enamine isomer was the main product. L7:L7'＝0.23:1.Mp:98-99℃.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.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.

Embodiment 8, the synthesis of 2,8-(2,6-dimethylimine)-5,6,7-trihydroquinoline (L8) ligand

Put raw materials 2-propionyl-8-5,6,7-hydroquinolinone (0.203g, 1mmol) and 2,6-dimethylaniline (0.302g, 0.25mmol) and p-toluenesulfonic acid into a 100ml two-necked bottle 0.015 g was refluxed in n-butanol (30 ml). 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 0.10 g of a yellow solid. Yield 25.2%. the

NMR showed two isomers, of which the enamine isomer was the main product. L8:L8'=0.15:1.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.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. ):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 C NMR (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, 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 (0.16g, 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. the

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. the

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, a large amount of precipitate was formed, the precipitate was filtered, washed with anhydrous ether, and dried to obtain a blue powder (0.106g, 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 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 (0.121g, 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 _{C26H27Cl2FeN3} : 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 were stirred and reacted at room temperature for 10 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 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 _{C28H31Cl2FeN3} : 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, anhydrous ether was added, a large amount of precipitate was formed, the precipitate was filtered and 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. the

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 (0.132 g, 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. the

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, anhydrous ether was added, and a large amount of precipitate was formed, which was filtered, washed with anhydrous 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, which 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. the

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, 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 (0.143 g, 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, anhydrous ether was added, a large amount of precipitate was formed, the precipitate was filtered and washed with anhydrous ether, and dried to obtain a yellow powder (0.123g, 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. the

Embodiment 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 that the nitrogen in the kettle was replaced with ethylene in advance, the polymerization kettle was allowed to cool down slowly to the expected polymerization temperature (30° C.). Then add 50mL toluene successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyst (Fe3), 2.05mL cocatalyst (MAO, 1.46mol/L toluene solution) (Al/Fe=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 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 of PE·mol ^-1 (M)·h ^-1 , polymer M _w =203.4Kg·mol ^-1 , M _w /M _n =3.4, T _m =135.5.

Embodiment 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 that the nitrogen in the kettle was replaced with ethylene in advance, the polymerization kettle was allowed to cool down slowly to the expected polymerization temperature (30° C.). Then add 50mL toluene successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyst (Fe3), 3.08mL cocatalyst (MAO, 1.46mol/L toluene solution) (Al/Fe=1500), 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 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 of PE·mol ^-1 (M)·h ^-1 , polymer M _w =132.9Kg·mol ^-1 , M _w /M _n =8.5, T _m =133.3.

Embodiment 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 that the nitrogen in the kettle was replaced with ethylene in advance, the polymerization kettle was allowed to cool down slowly to the expected polymerization temperature (30° C.). Then add 50mL toluene successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyst (Fe ), 4.10mL cocatalyst (MAO, 1.46mol/L toluene solution) (Al/Fe=2000), 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 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 4.90g polymer. Polymerization activity was calculated from the yield. Polymerization activity: 3.27×10 ⁶ g of PE·mol ^-1 (M)·h ^-1 , polymer M _w =174.5Kg·mol ^-1 , M _w /M _n =32.5, T _m =130.6.

Embodiment 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 that the nitrogen in the kettle was replaced with ethylene in advance, the polymerization kettle was allowed to cool down slowly to the expected polymerization temperature (30° C.). Then add 50mL toluene successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyst (Fe3), 5.14mL cocatalyst (MAO, 1.46mol/L toluene solution) (Al/Fe=2500), 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, and after filtering and washing, it was dried to a constant weight in an oven at 60°C to obtain 3.79g of a 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.

Embodiment 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, the polymerization kettle was allowed to cool down slowly to the expected polymerization temperature (40° C.). Then add 50mL toluene successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyst (Fe3), 4.10mL promoter MAO (1.46mol/L toluene solution) (Al/Fe=2000), 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 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 of polymer. Polymerization activity was calculated from the yield. Polymerization activity: 3.97×10 ⁶ g of PE·mol ^-1 (M)·h ^-1 , polymer M _w =77.0Kg·mol ^-1 , M _w /M _n =23.5, T _m =128.

Embodiment 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 that the nitrogen in the kettle was replaced with ethylene in advance, the polymerization kettle was allowed to cool down slowly to the expected polymerization temperature (50° C.). Then add 50mL toluene successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyst (Fe3), 4.10mL promoter MAO (1.46mol/L toluene solution) (Al/Fe=2000), 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 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 13.2g of polymer. Polymerization activity was calculated from the yield. Polymerization activity: 8.80×10 ⁶ g of PE·mol ^-1 (M)·h ^-1 , polymer M _w =121.6Kg·mol ^-1 , M _w /M _n =13.9, T _m =130.7.

Embodiment 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 allowed to cool down slowly to the expected polymerization temperature (60° C.). Then add 50mL toluene successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyst (Fe3), 4.10mL promoter MAO (1.46mol/L toluene solution) (Al/Fe=2000), 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 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. Polymerization activity was calculated from the yield. Polymerization activity: 7.34×10 ⁶ g of PE·mol ^-1 (M)·h ^-1 , polymer M _w =13.3Kg·mol ^-1 , M _w /M _n =2.8, T _m =128.1.

Embodiment 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 that the nitrogen in the kettle was replaced with ethylene in advance, the polymerization kettle was allowed to cool down slowly to the expected polymerization temperature (80° C.). Then add 50mL toluene successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyst (Fe3), 4.10mL promoter MAO (1.46mol/L toluene solution) (Al/Fe=2000), 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 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 of PE·mol ^-1 (M)·h ^-1 , polymer M _w =18.5Kg·mol ^-1 , M _w /M _n =4.3, T _m =127.6.

Embodiment 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 that the nitrogen in the kettle was replaced with ethylene in advance, the polymerization kettle was allowed to cool down slowly to the expected polymerization temperature (50° C.). Then add 50mL toluene successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyst (Fe1), 4.10mL promoter MAO (1.46mol/L toluene solution) (Al/Fe=2000), 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 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 8.41g of polymer. Polymerization activity was calculated from the yield. Polymerization activity: 5.61×10 ⁶ g of PE·mol ^-1 (M)·h ^-1 , polymer M _w =22.8Kg·mol ^-1 , M _w /M _n =4.7, T _m =128.7.

Embodiment 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 that the nitrogen in the kettle was replaced with ethylene in advance, the polymerization kettle was allowed to cool down slowly to the expected polymerization temperature (50° C.). Then add 50mL toluene successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyst (Fe ), 4.10mL promoter MAO (1.46mol/L toluene solution) (Al/Fe=2000), 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 reaches the preset time (30min), release the ethylene pressure in the kettle, add hydrochloric acid ethanol, filter and wash, and then dry to constant weight in an oven at 60°C to obtain 23.4g polymer. Polymerization activity was calculated from the yield. Polymerization activity: 15.6×10 ⁶ g of PE·mol ^-1 (M)·h ^-1 , polymer M _w =22.7Kg·mol ^-1 , M _w /M _n =6.3, T _m =129.9.

Embodiment 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 that the nitrogen in the kettle was replaced with ethylene in advance, the polymerization kettle was allowed to cool down slowly to the expected polymerization temperature (50° C.). Then add 50mL toluene successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyst (Fe4), 4.10mL promoter MAO (1.46mol/L toluene solution) (Al/Fe=2000), 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 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 8.34g of polymer. Polymerization activity was calculated from the yield. Polymerization activity: 5.56×10 ⁶ g of PE·mol ^-1 (M)·h ^-1 , polymer M _w =31.5Kg·mol ^-1 , M _w /M _n =7.2, T _m =128.6.

Embodiment 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 that the nitrogen in the kettle was replaced with ethylene in advance, the polymerization kettle was allowed to cool down slowly to the expected polymerization temperature (50° C.). Then add 50mL toluene successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyst (Fe5), 4.10mL promoter MAO (1.46mol/L toluene solution) (Al/Fe=2000), 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 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 12.4g polymer. Polymerization activity was calculated from the yield. Polymerization activity: 8.25×10 ⁶ g of PE·mol ^-1 (M)·h ^-1 , polymer M _w =29.7Kg·mol ^-1 , M _w /M _n =5.3, T _m =129.8.

Embodiment 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 that the nitrogen in the kettle was replaced with ethylene in advance, the polymerization kettle was allowed to cool down slowly to the expected polymerization temperature (30° C.). Then add 50mL toluene successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyst (Fe ), 1.55mL cocatalyst (MMAO, the heptane solution of 1.93mol/L) (Al/Fe=1000), remaining toluene (making 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 an oven at 60°C to obtain 2.91g of polymer. Polymerization activity was calculated from the yield. Polymerization activity: 1.94×10 ⁶ g of PE·mol ^-1 (M)·h ^-1 , polymer M _w =37.8Kg·mol ^-1 , M _w /M _n =28.0, T _m =123.6.

Embodiment 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 that the nitrogen in the kettle was replaced with ethylene in advance, the polymerization kettle was allowed to cool down slowly to the expected polymerization temperature (30° C.). Then add 50mL toluene successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyst (Fe3), 2.33mL cocatalyst (MMAO, the heptane solution of 1.93mol/L) (/Fe=1500), remaining toluene (making toluene total amount be 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 4.72g of 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 that the nitrogen in the kettle was replaced with ethylene in advance, the polymerization kettle was allowed to cool down slowly to the expected polymerization temperature (30° C.). Then add 50mL toluene successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyst (Fe ), 3.10mL cocatalyst (MMAO, the heptane solution of 1.93mol/L) (Al/Fe=2000), remaining toluene (making 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 an oven at 60°C to obtain 6.49g of 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.

Embodiment 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 that the nitrogen in the kettle was replaced with ethylene in advance, the polymerization kettle was allowed to cool down slowly to the expected polymerization temperature (30° C.). Then add 50mL toluene successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyst (Fe3), 3.89mL cocatalyst (MMAO, the heptane solution of 1.93mol/L) Al/Fe=2500), remaining toluene (making toluene total amount be 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 of polymer. Polymerization activity was calculated from the yield. Polymerization activity: 4.00×10 ⁶ g of PE·mol ^-1 (M)·h ^-1 , polymer M _w =8.1Kg·mol ^-1 , M _w /M _n =5.7, T _m =120.5.

Embodiment 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, the polymerization kettle was allowed to cool down slowly to the expected polymerization temperature (40° C.). Then add 50mL toluene successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyst (Fe ), 3.10mL cocatalyst (MMAO, the heptane solution of 1.93mol/L) (Al/Fe=2000), remaining toluene (making 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 an oven at 60°C to obtain 7.04g of 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.

Embodiment 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 that the nitrogen in the kettle was replaced with ethylene in advance, the polymerization kettle was allowed to cool down slowly to the expected polymerization temperature (50° C.). Then add 50mL toluene successively, 20mL is dissolved with the toluene solution of 3 _μ mol catalyst (Fe3), 3.10mL cocatalyst (MMAO, the heptane solution of 1.93mol/L) (Al/Fe=2000), remaining toluene (making toluene total volume 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 22.3g of polymer. Polymerization activity was calculated from the yield. Polymerization activity: 14.8×10 ⁶ g of PE·mol ^-1 (M)·h ^-1 , polymer M _w =32.7Kg·mol ^-1 , M _w /M _n =8.9, T _m =128.2.

Embodiment 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 allowed to cool down slowly to the expected polymerization temperature (60° C.). Then add 50mL toluene successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyst (Fe ), 3.10mL cocatalyst (MMAO, the heptane solution of 1.93mol/L) (Al/Fe=2000), remaining toluene (making 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 an oven at 60°C to obtain 18.9g polymer. Polymerization activity was calculated from the yield. Polymerization activity: 12.6×10 ⁶ g of PE·mol ^-1 (M)·h ^-1 , polymer M _w =29.9Kg·mol ^-1 , M _w /M _n =8.9, T _m =127.7.

Embodiment 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 that the nitrogen in the kettle was replaced with ethylene in advance, the polymerization kettle was allowed to cool down slowly to the expected polymerization temperature (70° C.). Then add 50mL toluene successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyst (Fe ), 3.10mL cocatalyst (MMAO, the heptane solution of 1.93mol/L) (Al/Fe=2000), remaining toluene (making toluene total amount be 100ml). The still is closed, and ethylene is passed through to maintain a constant (10 atm) pressure of ethylene. 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 17.3g of polymer. Polymerization activity was calculated from the yield. Polymerization activity: 11.5×10 ⁶ g of PE·mol ^-1 (M)·h ^-1 , polymer M _w =15.1Kg·mol ^-1 , M _w /M _n =4.5, T _m =127.2.

Embodiment 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 that the nitrogen in the kettle was replaced with ethylene in advance, the polymerization kettle was allowed to cool down slowly to the expected polymerization temperature (50° C.). Then add 50mL toluene successively, 20mL is dissolved with 3 μ mol catalyst (the toluene solution of Fe1, 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 ℃ to constant weight to obtain 22.5g polymer, and calculate the polymerization activity according to the yield 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.

Embodiment 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 that the nitrogen in the kettle was replaced with ethylene in advance, the polymerization kettle was allowed to cool down slowly to the expected polymerization temperature (50° C.). Then add 50mL toluene successively, 20mL is dissolved with 3 μ mol catalyst (Fe2 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 ℃ to constant weight to obtain 14.7g polymer, and calculate the polymerization activity according to the yield 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.

Embodiment 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 that the nitrogen in the kettle was replaced with ethylene in advance, the polymerization kettle was allowed to cool down slowly to the expected polymerization temperature (50° C.). Then add 50mL toluene successively, 20mL is dissolved with 3 μ mol catalyst (Fe4 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 ℃ to constant weight to obtain 23.0 g of 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.

Embodiment 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 that the nitrogen in the kettle was replaced with ethylene in advance, the polymerization kettle was allowed to cool down slowly to the expected polymerization temperature (50° C.). Then add 50mL toluene successively, 20mL is dissolved with 3 μ mol 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 in an oven at ℃ to constant weight 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.

Embodiment 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 that the nitrogen in the kettle was replaced with ethylene in advance, the polymerization kettle was allowed to cool down slowly to the expected polymerization temperature (50° C.). Then add 50mL toluene successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyst (Fe ), 3.10mL cocatalyst (MMAO, the heptane solution of 1.93mol/L) (Al/Fe=2000), remaining toluene (making 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 (15min), 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 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.

Embodiment 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 that the nitrogen in the kettle was replaced with ethylene in advance, the polymerization kettle was allowed to cool down slowly to the expected polymerization temperature (50° C.). Then add 50mL toluene successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyst (Fe ), 3.10mL cocatalyst (MMAO, the heptane solution of 1.93mol/L) (Al/Fe=2000), remaining toluene (making 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 (40min), release the ethylene pressure in the kettle, add hydrochloric acid ethanol, filter and wash, and then 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.

Embodiment 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 that the nitrogen in the kettle was replaced with ethylene in advance, the polymerization kettle was allowed to cool down slowly to the expected polymerization temperature (50° C.). Then add 50mL toluene successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyst (Co4), 1.03mL cocatalyst MAO (1.46mol/L toluene solution) (Al/Co=500), remaining toluene (making toluene total amount be 100 milliliters) . The still is closed, and ethylene is passed through to maintain a constant (10 atm) pressure of ethylene. After the polymerization reaction reached the preset time (30min), the ethylene pressure in the kettle was released, hydrochloric acid ethanol was added, filtered and washed, dried in an oven at 60°C to constant weight, and the polymerization activity was calculated according to the yield of the polymer. Polymerization activity: 9.29×10 ⁶ g of PE·mol ^-1 (M)·h ^-1 , polymer M _w =1124g·mol ^-1 , M _w /M _n =1.7, T _m =102.2

Embodiment 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 that the nitrogen in the kettle was replaced with ethylene in advance, the polymerization kettle was allowed to cool down slowly to the expected polymerization temperature (50° C.). Then add 50mL toluene successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyst (Co4), 1.54mL cocatalyst MAO (1.46mol/L toluene solution) (Al/Co=750), 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, filtered and washed, dried in an oven at 60°C to constant weight, and the polymerization activity was calculated according to the yield of the polymer. Polymerization activity: 12.63×10 ⁶ g of PE·mol ^-1 (M)·h ^-1 , polymer M _w =1000 g·mol ^-1 , M _w /M _n =1.5, T _m =101.4°C.

Embodiment 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 that the nitrogen in the kettle was replaced with ethylene in advance, the polymerization kettle was allowed to cool down slowly to the expected polymerization temperature (50° C.). Then add 50mL toluene successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyst (Co ), 2.05mL cocatalyst 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, filtered and washed, dried in an oven at 60°C to constant weight, and the polymerization activity was calculated according to the yield of the polymer. Polymerization activity: 14.76×10 ⁶ g of PE·mol ^-1 (M)·h ^-1 , polymer M _w =949 g·mol ^-1 , M _w /M _n =1.5, T _m =99.6°C.

Embodiment 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 that the nitrogen in the kettle was replaced with ethylene in advance, the polymerization kettle was allowed to cool down slowly to the expected polymerization temperature (50° C.). Then add 50mL toluene successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyst (Co4), 2.57mL cocatalyst MAO (1.46mol/L toluene solution) (Al/Co=1250), 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, filtered and washed, dried in an oven at 60°C to constant weight, and the polymerization activity was calculated according to the yield 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.

Embodiment 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 that the nitrogen in the kettle was replaced with ethylene in advance, the polymerization kettle was allowed to cool down slowly to the expected polymerization temperature (50° C.). Then add 50mL toluene successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyst (Co ), 3.08mL cocatalyst MAO (1.46mol/L toluene solution) (Al/Co=1500), 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, filtered and washed, dried in an oven at 60°C to constant weight, and the polymerization activity was calculated according to the yield of the polymer. Polymerization activity: 12.00×10 ⁶ g of PE·mol ^-1 (M)·h ^-1 , polymer M _w =1029 g·mol ^-1 , M _w /M _n =1.5, T _m =102.3°C.

Embodiment 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 that the nitrogen in the kettle was replaced with ethylene in advance, the polymerization kettle was allowed to cool down slowly to the expected polymerization temperature (30° C.). Then add 50mL toluene successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyst (Co ), 2.05mL cocatalyst 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, filtered and washed, dried in an oven at 60°C to constant weight, and the polymerization activity was calculated according to the yield of the polymer. Polymerization activity: 6.72×10 ⁶ g of PE·mol ^-1 (M)·h ^-1 , polymer M _w =1219 g·mol ^-1 , M _w /M _n =1.6, T _m =100.9°C.

Embodiment 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, the polymerization kettle was allowed to cool down slowly to the expected polymerization temperature (40° C.). Then add 50mL toluene successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyst (Co4), 2.05mL cocatalyst 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, filtered and washed, dried in an oven at 60°C to constant weight, and the polymerization activity was calculated according to the yield of the polymer. Polymerization activity: 7.66×10 ⁶ g of PE·mol ^-1 (M)·h ^-1 , polymer M _w =960 g·mol ^-1 , M _w /M _n =1.6, T _m =100.3°C.

Embodiment 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 allowed to cool down slowly to the expected polymerization temperature (60° C.). Then add 50mL toluene successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyst (Co4), 2.05mL cocatalyst 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, filtered and washed, dried in an oven at 60°C to constant weight, and the polymerization activity was calculated according to the yield of the polymer. Polymerization activity: 16.37×10 ⁶ g of PE·mol ^-1 (M)·h ^-1 , polymer M _w =910 g·mol ^-1 , M _w /M _n =1.5, T _m =99.6°C.

Embodiment 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 that the nitrogen in the kettle was replaced with ethylene in advance, the polymerization kettle was allowed to cool down slowly to the expected polymerization temperature (70° C.). Then add 50mL toluene successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyst (Co ), 2.05mL cocatalyst 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, filtered and washed, dried in an oven at 60°C to constant weight, and the polymerization activity was calculated according to the yield of the polymer. Polymerization activity: 15.60×10 ⁶ g of PE·mol ^-1 (M)·h ^-1 , polymer M _w =880 g·mol ^-1 , M _w /M _n =1.6, T _m =99.0°C.

Embodiment 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 allowed to cool down slowly to the expected polymerization temperature (60° C.). Then add 50mL toluene successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyst (Co ), 2.05mL cocatalyst 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 (5min), the ethylene pressure in the kettle was released, hydrochloric acid ethanol was added, filtered and washed, dried in an oven at 60°C to constant weight, and the polymerization activity was calculated according to the yield of the polymer. Polymerization activity: 4.83×10 ⁶ g of PE·mol ^-1 (M)·h ^-1 , polymer M _w =891 g·mol ^-1 , M _w /M _n =1.5, T _m =100.5°C.

Embodiment 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 allowed to cool down slowly to the expected polymerization temperature (60° C.). Then add 50mL toluene successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyst (Co ), 2.05mL cocatalyst 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 (10min), the ethylene pressure in the kettle was released, hydrochloric acid ethanol was added, filtered and washed, dried in an oven at 60°C to constant weight, and the polymerization activity was calculated according to the yield of the polymer. Polymerization activity: 10.13×10 ⁶ g of PE·mol ^-1 (M)·h ^-1 , polymer M _w =896g·mol ^-1 , M _w /M _n =1.5, T _m =99.8°C

Embodiment 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 allowed to cool down slowly to the expected polymerization temperature (60° C.). Then add 50mL toluene successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyst (Co ), 2.05mL cocatalyst 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 (60min), the ethylene pressure in the kettle was released, hydrochloric acid ethanol was added, filtered and washed, dried in an oven at 60°C to constant weight, and the polymerization activity was calculated according to the yield of the polymer. Polymerization activity: 18.43×10 ⁶ g of PE·mol ^-1 (M)·h ^-1 , polymer M _w =1016g·mol ^-1 , M _w /M _n =1.5, T _m =99.8°C

Embodiment 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 that the nitrogen in the kettle was previously replaced with ethylene, the polymerization kettle was allowed to cool slowly to the intended polymerization temperature (60°C). Then add 50mL toluene successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyst (Co ), 2.05mL cocatalyst 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 (5 atm). After the polymerization reaction reached the preset time (30min), the ethylene pressure in the kettle was released, hydrochloric acid ethanol was added, filtered and washed, dried in an oven at 60°C to constant weight, and the polymerization activity was calculated according to the yield of the polymer. Polymerization activity: 8.20×10 ⁶ g of PE·mol ^-1 (M)·h ^-1 , polymer M _w ＝914 _g mol ^-1 , M _w /M _n ＝1.4, T _m ＝100.5℃.

Embodiment 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 allowed to cool down slowly to the expected polymerization temperature (60° C.). Then add 50mL toluene successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyst (Co1), 2.05mL cocatalyst 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 (5 atm). After the polymerization reaction reached the preset time (30min), the ethylene pressure in the kettle was released, hydrochloric acid ethanol was added, filtered and washed, dried in an oven at 60°C to constant weight, and the polymerization activity was calculated according to the yield of the polymer. Polymerization activity: 16.29×10 ⁶ g of PE·mol ^-1 (M)·h ^-1 , polymer M _w =827g·mol ^-1 , M _w /M _n =1.6, T _m =99.0°C.

Embodiment 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 allowed to cool down slowly to the expected polymerization temperature (60° C.). Then add 50mL toluene successively, 20mL is dissolved with 3 μ mol catalyst (Co ) Toluene solution, 2.05mL cocatalyst 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 (5 atm). After the polymerization reaction reached the preset time (30min), the ethylene pressure in the kettle was released, hydrochloric acid ethanol was added, filtered and washed, dried in an oven at 60°C to constant weight, and the polymerization activity was calculated according to the yield of the polymer. Polymerization activity: 13.37×10 ⁶ g of PE·mol ^-1 (M)·h ^-1 , polymer M _w =1955g·mol ^-1 , M _w /M _n =1.9, T _m =117.4°C.

Embodiment 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 allowed to cool down slowly to the expected polymerization temperature (60° C.). Then add 50mL toluene successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyst (Co3), 2.05mL cocatalyst 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 (5 atm). After the polymerization reaction reached the preset time (30min), the ethylene pressure in the kettle was released, hydrochloric acid ethanol was added, filtered and washed, dried in an oven at 60°C to constant weight, and the polymerization activity was calculated according to the yield of the polymer. Polymerization activity: 6.70×10 ⁶ g of PE·mol ^-1 (M)·h ^-1 , polymer M _w =10189g·mol ^-1 , M _w /M _n =2.0, T _m =128.9°C.

Embodiment 67,

Polymerization of ethylene 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 down slowly to the expected polymerization temperature (60° C.). Then add 50mL toluene successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyst (Co5), 2.05mL cocatalyst 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 (5 atm). After the polymerization reaction reached the preset time (30min), the ethylene pressure in the kettle was released, hydrochloric acid ethanol was added, filtered and washed, dried in an oven at 60°C to constant weight, and the polymerization activity was calculated according to the yield of the polymer. Polymerization activity: 16.21×10 ⁶ g of PE·mol ^-1 (M)·h ^-1 , polymer M _w =2009g·mol ^-1 , M _w /M _n =1.9, T _m =117.6°C.

Embodiment 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 that the nitrogen in the kettle was replaced with ethylene in advance, the polymerization kettle was allowed to cool down slowly to the expected polymerization temperature (50° C.). Then add 50mL toluene successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyst (Co4), 1.55mL cocatalyst (MMAO, the heptane solution of 1.93mol/L) (Al/Co=1000), remaining toluene (making 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, filtered and washed, dried in an oven at 60°C to constant weight, and the polymerization activity was calculated according to the yield 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.

Embodiment 69,

The polymerization kettle was evacuated and heated to 100° C. for two hours. Under the condition that the nitrogen in the kettle was replaced with ethylene in advance, the polymerization kettle was allowed to cool down slowly to the expected polymerization temperature (50° C.). Then add 50mL toluene successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyst (Co4), 1.94mL cocatalyst (MMAO, the heptane solution of 1.93mol/L) (Al/Co=1250), remaining toluene (making 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, filtered and washed, dried in an oven at 60°C to constant weight, and the polymerization activity was calculated according to the yield of the polymer. Polymerization activity: 10.05×10 ⁶ g of PE·mol ^-1 (M)·h ^-1 , polymer M _w =1064 g·mol ^-1 , M _w /M _n =1.5, T _m =101.6°C.

Embodiment 70,

The polymerization kettle was evacuated and heated to 100° C. for two hours. Under the condition that the nitrogen in the kettle was replaced with ethylene in advance, the polymerization kettle was allowed to cool down slowly to the expected polymerization temperature (50° C.). Then add 50mL toluene successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyst (Co4), 2.33mL cocatalyst (MMAO, the heptane solution of 1.93mol/L) (Al/Co=1500), remaining toluene (making 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, filtered and washed, dried in an oven at 60°C to constant weight, and the polymerization activity was calculated according to the yield 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.

Embodiment 71,

The polymerization kettle was evacuated and heated to 100° C. for two hours. Under the condition that the nitrogen in the kettle was replaced with ethylene in advance, the polymerization kettle was allowed to cool down slowly to the expected polymerization temperature (50° C.). Then add 50mL toluene successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyst (Co4), 2.72mL cocatalyst (MMAO, the heptane solution of 1.93mol/L) (Al/Co=1750), remaining toluene (making 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, filtered and washed, dried in an oven at 60°C to constant weight, and the polymerization activity was calculated according to the yield of the polymer. Polymerization activity: 11.05×10 ⁶ g of PE·mol ^-1 (M)·h ^-1 , polymer M _w =1088 g·mol ^-1 , M _w /M _n =1.6, T _m =100.8°C.

Embodiment 72,

The polymerization kettle was evacuated and heated to 100° C. for two hours. Under the condition that the nitrogen in the kettle was replaced with ethylene in advance, the polymerization kettle was allowed to cool down slowly to the expected polymerization temperature (30° C.). Then add 50mL toluene successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyst (Co4), 2.33mL cocatalyst (MMAO, the heptane solution of 1.93mol/L) (Al/Co=1500), remaining toluene (making 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, filtered and washed, dried in an oven at 60°C to constant weight, and the polymerization activity was calculated according to the yield of the polymer. Polymerization activity: 5.89×10 ⁶ g of PE·mol ^-1 (M)·h ^-1 , T _m =100.4°C

Embodiment 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, the polymerization kettle was allowed to cool down slowly to the expected polymerization temperature (40° C.). Then add 50mL toluene successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyst (Co4), 2.33mL cocatalyst (MMAO, the heptane solution of 1.93mol/L) (Al/Co=1500), remaining toluene (making 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, filtered and washed, dried in an oven at 60°C to constant weight, and the polymerization activity was calculated according to the yield of the polymer. Polymerization activity: 8.68×10 ⁶ g of PE·mol ^-1 (M)·h ^-1 , polymer M _w =927Kg·mol ^-1 , M _w /M _n =1.6, T _m =99.4°C.

Embodiment 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 allowed to cool down slowly to the expected polymerization temperature (60° C.). Then add 50mL toluene successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyst (Co4), 2.33mL cocatalyst (MMAO, the heptane solution of 1.93mol/L) (Al/Co=1500), remaining toluene (making 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, filtered and washed, dried in an oven at 60°C to constant weight, and the polymerization activity was calculated according to the yield of the polymer. Polymerization activity: 13.21×10 ⁶ g of PE·mol ^-1 (M)·h ^-1 , polymer M _w =951 g·mol ^-1 , M _w /M _n =1.5, T _m =98.7°C.

Embodiment 75,

The polymerization kettle was evacuated and heated to 100° C. for two hours. Under the condition that the nitrogen in the kettle was replaced with ethylene in advance, the polymerization kettle was allowed to cool down slowly to the expected polymerization temperature (70° C.). Then add 50mL toluene successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyst (Co4), 2.33mL cocatalyst (MMAO, the heptane solution of 1.93mol/L) (Al/Co=1500), remaining toluene (making 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, filtered and washed, and dried in an oven at 60°C to constant weight, and the polymerization activity was calculated according to the yield of the polymer. Polymerization activity: 4.92×10 ⁶ g of PE·mol ^-1 (M)·h ^-1 , polymer M _w =950 g·mol ^-1 , M _w /M _n =1.5, T _m =100.3°C.

Embodiment 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 allowed to cool down slowly to the expected 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 (making 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, filtered and washed, dried in an oven at 60°C to constant weight, and the polymerization activity was calculated according to the yield of the polymer. Polymerization activity: 8.83×10 ⁶ g of PE·mol ^-1 (M)·h ^-1 , polymer M _w =996g·mol ^-1 , M _w /M _n =1.5, T _m =100.4°C.

Embodiment 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 allowed to cool down slowly to the expected polymerization temperature (60° C.). Then add 50mL toluene successively, 20mL is dissolved with 3 μ mol catalyst (Co The toluene solution of ), 2.33mL cocatalyst (MMAO, the heptane solution of 1.93mol/L) (Al/Co=1500), remaining toluene (making 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, filtered and washed, dried in an oven at 60°C to constant weight, and the polymerization activity was calculated according to the yield of the polymer. Polymerization activity: 5.72×10 ⁶ g of PE·mol ^-1 (M)·h ^-1 , polymer M _w =2162g·mol ^-1 , M _w /M _n =1.9, T _m =118.4°C.

Embodiment 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 allowed to cool down slowly to the expected polymerization temperature (60° C.). Then add 50mL toluene successively, 20mL is dissolved with 3 μ mol catalyst (Co The toluene solution of ), 2.33mL cocatalyst (MMAO, the heptane solution of 1.93mol/L) (Al/Co=1500), remaining toluene (making 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, filtered and washed, dried in an oven at 60°C to constant weight, and the polymerization activity was calculated according to the yield 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.

Embodiment 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 allowed to cool down slowly to the expected polymerization temperature (60° C.). Then add 50mL toluene successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyst (Co ), 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, filtered and washed, dried in an oven at 60°C to constant weight, and the polymerization activity was calculated according to the yield of the polymer. Polymerization activity: 7.81×10 ⁶ g of PE·mol ^-1 (M)·h ^-1 , polymer M _w =2052g·mol ^-1 , M _w /M _n =1.9, T _m =119.0°C.

Embodiment 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 that the nitrogen in the kettle was replaced with ethylene in advance, the polymerization kettle was allowed to cool down slowly to the expected polymerization temperature (50° C.). Then add 50mL toluene successively, 20mL is dissolved with 3 μ mol 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 ℃ to constant weight to obtain 11.5g polymer, and calculate the polymerization activity according to the yield of the polymer. Polymerization activity: 7.8×10 ⁶ g of PE·mol ^-1 (M)·h ^-1 , polymer M _w =23.8Kg·mol ^-1 , M _w /M _n =4.0, T _m =127.4.

Embodiment 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 that the nitrogen in the kettle was replaced with ethylene in advance, the polymerization kettle was allowed to cool down slowly to the expected polymerization temperature (50° C.). Then add 50mL toluene successively, 20mL is dissolved with 3 μ mol 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 ℃ to constant weight to obtain 20.0 g of 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.

Embodiment 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 that the nitrogen in the kettle was replaced with ethylene in advance, the polymerization kettle was allowed to cool down slowly to the expected 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 (making 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 an oven at 60°C to obtain 8.0g 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.

Embodiment 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 allowed to cool down slowly to the expected polymerization temperature (60° C.). Then add 50mL toluene successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyst (Co ), 2.05mL cocatalyst 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 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, filtered and washed, dried in an oven at 60°C to constant weight, and the polymerization activity was calculated according to the yield of the polymer. Polymerization activity: 3.70×10 ⁶ g of PE·mol ^-1 (M)·h ^-1 , polymer M _w =5400g·mol ^-1 , M _w /M _n =1.8, T _m =124.9°C.

Embodiment 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 allowed to cool down slowly to the expected polymerization temperature (60° C.). Then add 50mL toluene successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyst (Co7), 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 (5 atm). After the polymerization reaction reached the preset time (30min), the ethylene pressure in the kettle was released, hydrochloric acid ethanol was added, filtered and washed, dried in an oven at 60°C to constant weight, and the polymerization activity was calculated according to the yield of the polymer. Polymerization activity: 23.21×10 ⁶ g of PE·mol ^-1 (M)·h ^-1 , polymer M _w =2002g·mol ^-1 , M _w /M _n =1.6, T _m =110.6°C.

Embodiment 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 that the nitrogen in the kettle was replaced with ethylene in advance, the polymerization kettle was allowed to cool down slowly to the expected polymerization temperature (50° C.). Then add 50mL toluene successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyst (Co8), 2.05mL 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, filtered and washed, dried in an oven at 60°C to constant weight, and the polymerization activity was calculated according to the yield of the polymer. Polymerization activity: 10.4×10 ⁶ g of PE·mol ^-1 (M)·h ^-1 , polymer M _w =7000 g·mol ^-1 , M _w /M _n =1.8, T _m =126.4.

Claims (9)

1.2,8-diimine-5,6,7-tri-hydrogen quinoline transition metal complex, its structural formula such as formula shown in I,

In formula I, 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.

2. the preparation method of transition metal complex described in claim 1, comprises the steps:

(1) substituted aniline shown in 2-aldehyde radical shown in formula II (ketone)-5,6,7-tri-hydrogen-8-quinolinone and formula III carries out being obtained by reacting 2,8-diimine-5,6,7-tri-hydrogen quinoline compound under catalyzer existent condition;

The structural formula of described 2,8-diimine-5,6,7-tri-hydrogen quinoline compounds is such as formula IV;

In above formula, 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, nitro, fluorine, chlorine and bromine independently of one another;

(2) described 2,8-diimine-5,6,7-tri-hydrogen quinoline compound and MCl ₂react and obtain product; M is Fe or Co.

3. method according to claim 2, is characterized in that: in step (1), and described catalyzer is tosic acid; The solvent of described reaction is propyl carbinol; The temperature of described reaction is 110 ~ 125 DEG C, and the time is 6h ~ 20h.

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

5. the method according to claim 3 or 4, is characterized in that: in step (2), MCl ₂compare for (1 ~ 1.5) with the molfraction of described 2,8-diimine-5,6,7-tri-hydrogen quinoline compounds: (1 ~ 1.2), the temperature of described reaction is 20 ~ 25 DEG C, and the time is 4 ~ 18h.

6. a catalyst composition, is made up of transition metal complex described in claim 1 and promotor, and described promotor is selected from one or more in aikyiaiurnirsoxan beta, alkylaluminium cpd and chlorination aluminum alkyls.

7. composition according to claim 6, is characterized in that: described aikyiaiurnirsoxan beta is the methylaluminoxane of methylaluminoxane or the modification of tertiary butyl aluminium; Described alkylaluminium cpd is trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum or tri-n-octylaluminium; Described chlorination aluminum alkyls is diethylaluminum chloride or ethylaluminium dichloride; Aluminium in described promotor is (100 ~ 10000) with the molfraction ratio of the central metal M in described transition metal complex: 1.

8. the application of catalyst composition described in transition metal complex described in claim 1 or claim 6 or 7 in catalyzed ethylene polymerization reaction.

9. application according to claim 8, is characterized in that: the temperature of described ethylene polymerization is 20 ~ 100 DEG C, and pressure is 0.1 ~ 1.0MPa.