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

2,8-diimine-4,5,6 hydro quinoline transition metal complex, preparation method thereof, and application thereof Download PDF

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CN102731578A
CN102731578A CN2012101894801A CN201210189480A CN102731578A CN 102731578 A CN102731578 A CN 102731578A CN 2012101894801 A CN2012101894801 A CN 2012101894801A CN 201210189480 A CN201210189480 A CN 201210189480A CN 102731578 A CN102731578 A CN 102731578A
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孙文华
张文娟
柴文斌
孔少亮
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Abstract

The invention discloses a 2,8-diimine-4,5,6 hydro quinoline transition metal complex, a preparation method thereof, and an application thereof. The structural formula of the complex is shown as the formula I, wherein R1 is selected from hydrogen, methyl, ethyl, and propyl; R2, R3, R4, R5 and R6 are independantly selected from hydrogen, alkyl, nitro, and halogen; and M is transition metal. The preparation method of the transition metal complex comprises the steps that: (1) 2-aldehyde(ketone)-4,5,6-hydrogenated-8-quinolinone shown in the formula II and substituted phenylamine shown in the formula III are subjected to a reaction under the existence of a catalyst, such that a 2,8-diimine-4,5,6 hydro quinoline compound is obtained; (2) the 2,8-diimine-4,5,6 hydro quinoline compound is subjected to a reaction with MCl2, such that the metal complex is obtained. The metal complex is used for catalyzing an ethylene polymerization reaction. The obtained ethylene has a characteristic of high linearity, and is suitable to be used for producing high-density polyethylene or polyethylene wax. The catalyst has high tolerance to a relatively high reaction temperature, and has a good application prospect in industrialized productions.

Description

2,8-diimine-4,5,6 hydrogenated quinoline class transition metal complexes and preparation method thereof and application
Technical field
The present invention relates to a kind of 2,8-diimine-4,5,6 hydrogenated quinoline class transition metal complexes and preparation method thereof and application are specially the application in catalyzed ethylene polymerization.
Background technology
Polyolefine mainly comprises Vilaterm, Vestolen PP 7052 and gathers 1-butylene etc. that it accounts for the half the of macromolecular material as measuring maximum product.And because its excellent material performance, polyolefine material is widely used in all respects of producing and living.Wherein Vilaterm is a synthetic resins material with fastest developing speed, that output is maximum, purposes is extremely wide.And Vilaterm comprises many types, wherein Vilaterm be molecular weight bigger more than hundreds of thousands of, be Vilaterm, be the main raw material(s) of plastics; And polyethylene wax be molecular weight below several ten thousand, be commonly used to use as lubricant, be characterized in that softening temperature is higher, approach High molecular weight polyethylene, obtain should general application because of its good winter hardiness, thermotolerance, chemical resistant properties and wear resistance.At present, no matter be high density polyethylene(HDPE) or polyethylene wax, Ziegler-type catalyst remains the most frequently used catalyzer.Usually divide by unit, the compound that remains chromium in the transition metal, vanadium, zirconium, titanium four big metals is a Primary Catalysts, is aided with promotor and carrier composition catalystsystem that Primary Catalysts and polyreaction adapt.And our nearest result of study shows, no matter late transition metal catalyst is at preparation high density polyethylene(HDPE) or polyethylene wax all has the potential great potential.
At first in 1998, Brookhart and Gibson reported the title complex of pyridine diimine iron (II) and cobalt (II) when being equal to, through regulating the substituting group on the phenyl ring; Oligomerisation or polymerising ethylene well, its structure is suc as formula (J.Am.Chem.Soc., 1998 shown in the A; 120,4049-4050; Chem.Commun.1998,849-850):
Figure BDA00001741759500011
Formula A
Afterwards, round pyridine diimine iron cobalt complex catalyzer, people have carried out number of research projects, and catalyst structure is improved.From at first to the imitation of pyridine diimine iron cobalt complex catalyzer model, the model of independent design and development of new catalyzer till now, the seminar that the contriver belongs to has successfully developed a series of late transition metal catalyst model in the past 13 years.
2005, this seminar developed 2-amido-1, and the composition catalyst of 10-phenanthroline iron and cobalt (formula B), such catalyzer not only show the activity 8.95 * 10 of high catalyzed ethylene oligomerisation 7Gmol -1(Fe) h -1, simultaneously terminal olefin being had very high selectivity, oligomerization product distributes and approximately to meet the Schluz-Flory rule (Organometallics 2006,25,666-677, one Chinese patent application number 200510066427.2 applyings date: on April 22nd, 2005; Granted publication day: on March 5th, 2008; Granted publication number: CN100372609C).This type of catalyst activity can compare favourably with classical pyridine diimine iron catalyst.
Figure BDA00001741759500021
Formula B
Afterwards; This seminar has developed 2-benzoglyoxaline-6-amido pyridine iron and cobalt complex catalyzer (formula C) again; Such catalyzer can the highly active catalytic ethylene oligomerization and polymerization activity (Organometallics 2007; 26,2720-2734, one Chinese patent application number 200610165446.5 applyings date: on December 20th, 2006).Iron (II) title complex shows very high oligomerisation and polymerization activity to ethene, has reached 10 7G mol Fe -1h -1Oligomerization product comprises C 4, C 6, C 8, C 10, C 12, C 14, C 16, C 18, C 20And C 22Deng, the selectivity of terminal olefin is up to more than 99%; Polymkeric substance is low molecular weight polyethylene and polyethylene wax.
Formula C formula D
These catalyst systems can highly actively obtain high density polyethylene(HDPE) in the above result of study, perhaps contain some polyethylene waxs in the product.In the research and development of catalyzer; Exploitation high reactivity and be convenient to industrialized ethylene oligomerization and polymerizing catalyst always is the core content of Study of Novel Catalyst; Although exist various difficult problems to need to solve; But, be on theoretical knowledge or design experiences, all can obtain more accumulation along with to the more deep research and development of new catalyst.
Summary of the invention
The purpose of this invention is to provide a kind of 2,8-diimine-4,5,6 hydrogenated quinoline class transition metal complexes and preparation method thereof and application.
Provided by the present invention 2,8-diimine-4,5,6 hydrogenated quinoline class transition metal complexes, its structural formula be suc as formula shown in the I,
Figure BDA00001741759500031
In the formula I, R 1Be selected from hydrogen, methyl, ethyl and propyl group, R 2, R 3, R 4, R 5And R 6Be selected from hydrogen, alkyl, nitro and halogen independently of one another; M is a transition metal.
In the above-mentioned transition metal complex, 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.
The present invention also provides the preparation method of above-mentioned transition metal complex, comprises the steps:
(1) 2-aldehyde radical shown in the formula II (ketone)-4,5, substituted aniline shown in 6-hydrogenation-8-quinolinone and the formula III react under the condition that catalyzer exists and obtain 2,8-diimine-4,5,6-hydrogenated quinoline compound;
Said 2,8-diimine-4,5, the structural formula of 6-hydrogenated quinoline compound are shown in formula IV and/or the formula V;
Figure BDA00001741759500032
Formula II formula III
Formula IV formula V
In the following formula, R 1Be selected from hydrogen, methyl, ethyl and propyl group, R 2, R 3, R 4, R 5And R 6Be selected from hydrogen, alkyl, nitro and halogen independently of one another;
(2) said 2,8-diimine-4,5,6-hydrogenated quinoline compound and MCl 2Reaction promptly gets product; M is a transition metal.
Among the above-mentioned preparation method, in the step (1), said catalyzer can be tosic acid; The solvent of said reaction can be propyl carbinol; The temperature of said reaction can be 110 ~ 125 ° of C, specifically can be 110 ° of C or 125 ° of C, and the time can be 6h ~ 20h, specifically can be 6h or 20h.
Among the above-mentioned preparation method, in the formula III, R 2, R 3, R 4, R 5And R 6When being selected from fluorine or chlorine independently of one another, said catalyzer can be tosic acid, and said solvent can be tetraethoxy, and the temperature of said reaction can be 140 ~ 150 ° of C, and the time can be 1 ~ 2 day.
Among the above-mentioned preparation method, in the step (2), MCl 2With said 2,8-diimine-4,5; The molfraction ratio of 6-hydrogenated quinoline compound can be (1 ~ 1.5): (1 ~ 1.2), specifically can be 1:1,1:1.2 or 1.5:1, the temperature of said reaction can be 20 ~ 25 ° of C; Time can be 4 ~ 18h, is preferably 4h, 10h or 18h.
The present invention also further provides a kind of catalyst composition, and it is made up of above-mentioned transition metal complex and promotor, and said promotor is selected from one or more in aikyiaiurnirsoxan beta, alkylaluminium cpd and the chlorination aluminum alkyls.
In the above-mentioned catalyst composition, said aikyiaiurnirsoxan beta specifically can be the MAO (MMAO) of MAO (MAO) or the modification of tertiary butyl aluminium; Said aluminum compound specifically can be trimethylaluminium, triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum or tri-n-octylaluminium; Said chlorination aluminum alkyls specifically can be diethylaluminum chloride or ethylaluminium dichloride;
In the above-mentioned catalyst composition; The molfraction ratio of central metal M in aluminium in the said promotor and the said transition metal complex can be (100 ~ 10000): 1, specifically can be (500 ~ 2500): 1,500:1,750:1,1000:1,1250:1,1500:1,1750:1,2000:1 or 2500:1.
The present invention further provides above-mentioned transition metal complex and the application of above-mentioned catalyst composition in the catalyzed ethylene polymerization reaction; When catalyzed ethylene polymerization, polymerization temperature can be 20 ~ 100 ° of C, specifically can be 30 ° of C, 40 ° of C, 50 ° of C, 60 ° of C, 70 ° of C or 80 ° of C; Pressure can be 0.1 ~ 1.0MPa, specifically can be 0.5MPa or 1.0MPa.
The present invention has designed and synthesized 2, the 8 – diimines-4,5 that contain the N^N^N dentate; 6-hydrogenated quinoline class transition metal complex, this metal complexes are used for the catalyzed ethylene polymerization reaction, and the gained Vilaterm has the characteristic of highly linear; Be suitable for producing high density polyethylene(HDPE) or polyethylene wax; And show excellent catalytic activity, catalyzer has very strong tolerance to higher reaction temperatures, has the wide industrial application prospect.
Description of drawings
Fig. 1 is the crystalline structure figure of title complex Fe1;
Fig. 2 is the crystalline structure figure of title complex Fe2;
Fig. 3 is the crystalline structure figure of title complex Co1;
Fig. 4 is the crystalline structure figure of title complex Co2;
Fig. 5 is the crystalline structure figure of title complex Co5.
Embodiment
Employed experimental technique is ordinary method like no specified otherwise among the following embodiment.
Used material, reagent etc. like no specified otherwise, all can obtain from commercial sources among the following embodiment.
The synthetic of title complex carries out according to following equation among the following embodiment:
The title complex Fe1-Fe8 and the Co1-Co8 that preferably, can be replaced situation as follows;
1.M=Fe,R 1=Me,R 2=R 6=Me,R 3=R 4=R 5=H;2.M=Fe,R 1=Me,R 2=R 6=Et,R 3=R 4=R 5=H;
3.M=Fe,R 1=Me,R 2=R 6= iPr,R 3=R 4=R 5=H;4.M=Fe,R 1=Me,R 2=R 4=R 6=Me,R 3=R 5=H;
5.M=Fe,R 1=Me,R 2=R 6=Et,R 4=Me,R 3=R 5=H;6.M=Fe,R 1=Me,R 2=R 6=Cl,R 3=R 4=R 5=H;
7.M=Fe,R 1=H,R 2=R 6=Me,R 3=R 4=R 5=H;8.M=Fe,R 1=Et,R 2=R 6=Me,R 3=R 4=R 5=H;
9.M=Co,R 1=R 2=R 6=Me,R 3=R 4=R 5=H;10.M=Co,R 1=Me,R 2=R 6=Et,R 3=R 4=R 5=H;
11.M=Co,R 1=Me,R 2=R 6= iPr,R 3=R 4=R 5=H;12.M=Co,R 1=Me,R 2=R 4=R 6=Me,R 3=R 5=H;
13.M=Co,R 1=R 2=R 6=Et,R 4=Me,R 3=R 5=H;14.M=Co,R 1=Me,R 2=R 6=Cl,R 3=R 4=R 5=H;
15.M=Co,R 1=R 3=R 4=R 5=H;R 2=R6=Me,16.M=Co,R 1=Et,R 2=R 6=Me,R 3=R 4=R 5=H.
Embodiment 1,2, and 8-(2,6-dimethyl benzene imines)-4,5 drops into raw material 2 in the synthetic 100ml two-mouth bottle of 6-hydrogenated quinoline (L1/L1 ') part; 8-4,5,6-hydrogenated quinoline diketone (0.189g, 0.1mmol) with 2,6-xylidine (0.302g; 0.25mmol)] and tosic acid 0.015g, in propyl carbinol (30ml), refluxing, after reaction was carried out about 6 hours, reaction solution concentrated; (PE:EA=50:1 v/v) after the separation, gets the 0.174g yellow solid, yield 44.2% to silica gel column chromatography.
Nuclear-magnetism shows has two kinds of isomer, and wherein the eneamines isomer is a primary product, L1:L1 '=0.19:1 (detected by 1HNMR) .FT-IR (KBr, cm -1): 3362 (ν N-H), 2932,1644,1593,1469,1446,1363,1315,1199,1110,1094,844,764,666.Anal.Calcd.For C 27H 29N 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). 13C NMR (100MHz; CDCl 3; TMS): δ 168.3,154.2,150.2,150.0,140.8,138.8,136.7,135.5,129.7,129.3,127.0,126.8,126.7,124.3,121.0,99.7,54.8,29.3,22.8,19.7,19.5,19.3,18.2,17.9.
Embodiment 2,2,8-(2,6-diethylbenzene imines)-4,5,6-hydrogenated quinoline (L2/L2 ') part synthetic
Drop into raw material 2,8-4,5,6--hydrogenated quinoline diketone (0.189g in the 100ml two-mouth bottle; 0.1mmol) and 2, (0.373g's 6-Diethyl Aniline 0.25mmol) and tosic acid 0.015g, refluxes in propyl carbinol (30ml); After reaction was carried out about 6 hours, reaction solution concentrated, silica gel column chromatography (PE:EA=50:1; V/v) after the separation, get the 0.24g yellow solid, yield 53%.
Nuclear-magnetism shows has two kinds of isomer, and wherein the eneamines isomer is a primary product, L2:L2 '=0.33:1 (detected by 1HNMR) .Mp:138-139 ° of C.FT-IR (KBr, cm -1): 3353 (ν N-H), 2964,2931,2867,2821,2361,2335,1643,1580,1484,1455,1359,1315,1194,1101,1016,875,764,698.L2 ': 1H NMR:8.24 (d, 1H, J=7.8Hz, Py-H), 7.60 (d, 1H, J=7.8Hz, Py-H), 7.16 (s, 3H; Ar-H), 7.11 (d, 2H, J=7.4, Ar-H), 7.00 (t, 1H, J=7.9Hz, Ar-H), 6.84 (s; 1H ,-NH), 4.60 (t, J=4.6Hz, 1H ,=CH), 2.91 (t, 2H, J=7.7Hz ,-CH 2-), 2.67 (m, 4H ,-CH 2-), 2.44 (m, 4H ,-CH 2-), 2.33 (m, 2H ,-CH 2-), 2.23 (s, 3H, N=CCH 3), 1.21 (t, 6H, J=7.9Hz ,-CH 3), 1.14 (t, 6H, J=7.4Hz ,-CH 3). 13C?NMR(100MHz;CDCl 3;TMS):δ166.8,164.3,153.1,148.8,148.1,142.0,138.9,138.5,135.6,135.4,134.3,131.5,131.4,126.7,126.2,125.9,123.4,119.8,98.4,28.2,25.1,24.9,21.7,17.2,15.4,14.0.13.7.Anal.Calcd.forC 31H 37N 3:C,82.44,H,8.26,N,9.30;Found:C,82.44,H,8.32,N,9.15.
Embodiment 3,2,8-(2,6-diisopropyl benzene imines)-4,5,6-hydrogenated quinoline (L3/L3 ') part synthetic
Drop into raw material 2,8-4,5,6-hydrogenated quinoline diketone (0.189g in the 100ml two-mouth bottle; 0.1mmol) and 2, (0.443g's 6-isopropyl aniline 0.25mmol) and tosic acid 0.015g, refluxes in propyl carbinol (30ml); Temperature is 110 ℃, and after reaction was carried out about 20 hours, reaction solution concentrated, silica gel column chromatography (PE:EA=50:1; V/v) after the separation, get the 0.309g yellow solid, yield 61.0%.
Nuclear-magnetism shows has two kinds of isomer, and wherein the eneamines isomer is a primary product.L3:L3’=0.3:1(detected?by 1HNMR).Mp:183-184°C.FT-IR(KBr,cm -1):3370(ν N-H),2960,2867,2361,1641,1580,1460,1357,1311,1188,1106,1050,1018,799,764,696.Anal.Calcd.for?C 35H 45N 3:C,82.79,H,8.93,N,8.28;Found:C,82.38,H,8.78,N,7.92. 13C?NMR(100MHz;CDCl 3;TMS):δ166.7,153.0,148.5,146.9,140.0,136.8,135.9,135.7,135.4,134.1,126.5,123.5,123.0,119.7,98.3,28.3,28.0,23.2,22.9,21.5,17.3. 1H?NMR:8.23(d,1H,J=7.7Hz,Py-H),7.61(d,1H,J=7.7Hz,Py-H),7.16(t,2H,Ar-H),7.11(d,3H,J=7.4,Ar-H),7.00(t,1H,J=7.9Hz,Ar-H),6.75(s,1H,-NH),4.61(t,1H,J=4.5Hz,=CH),3.27(m,2H,-CH-),2.92(t,2H,J=7.7Hz,-CH 2-),2.32(t,2H,J=7.8Hz,-CH 2-),2.24(s,3H,N=CCH 3),1.20(d,12H,J=6.4Hz,CH 3),1.16(m,12H,CH 3).
Embodiment 4,2,8-(2,4,6-Three methyl Benzene imines)-4,5,6-hydrogenated quinoline (L4/L4 ') part synthetic
Drop into raw material 2,8-4,5,6-hydrogenated quinoline diketone (0.189g in the 100ml two-mouth bottle; 0.1mmol) and 2 (0.338g (2.5eq)] and tosic acid 0.015g, in propyl carbinol (30ml), reflux; Temperature is 125 ℃, and after reaction was carried out about 6 hours, reaction solution concentrated, silica gel column chromatography (PE:EA=50:1; V/v) after the separation, get the 0.181g yellow solid, yield 43.0%.
Nuclear-magnetism shows has two kinds of isomer, and wherein the eneamines isomer is a primary product.L4:L4’=0.15:1(detected?by 1HNMR).FT-IR(KBr,cm -1):3366(v N-H),2922,1640,1572,1477,1442,1397,1360,1313,1204,1148,1106,1017,852,789,671. 1H?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). 13C?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 29H 33N 3:C,82.23,H,7.85,N,9.92;Found:C,82.12,H,8.04,N,9.77.
Embodiment 5,2,8-(2,6-diethylammonium-4-methylbenzene imines)-4,5,6-hydrogenated quinoline (L5/L5 ') part synthetic
Drop into raw material 2,8-4,5,6-hydrogenated quinoline diketone (0.189g in the 100ml two-mouth bottle; 0.1mmol) and 2, (0.408g's 6-diethylammonium-4-monomethylaniline 0.25mmol) and tosic acid 0.015g, refluxes in propyl carbinol (30ml); After reaction was carried out about 6 hours, reaction solution concentrated, silica gel column chromatography (PE:EA=50:1; V/v) after the separation, get the 0.234g yellow solid, yield 47.0%.
Nuclear-magnetism shows has two kinds of isomer, and wherein the eneamines isomer is a primary product.L5:L5’=0.23:1.Mp:98-99°C.FT-IR(KBr,cm -1):3369(ν N-H),2965,2929,2869,2828,1639,1570,1460,1359,1313,1203,1148,1106,1018,883,857,793,773,702,671.(L5’): 1H?NMR(400MHz,CDCl 3)8.23(d,1H,J=7.8Hz,Py-H),7.59(d,1H,J=7.8Hz,Py-H),6.98(s,2H,Ar-H),6.93(s,2H,Ar-H),6.76(s,1H,-NH-),4.60(t,J=4.5Hz,1H,=CH),2.91(t,J=7.7Hz,2H,-CH 2-),2.64(m,4H,-CH 2),2.40(m,2H,-CH 2-),2.35(s,3H,-CH 3),2.34(s,3H,-CH 3),2.31(m,4H,CH 2),1.21(t,6H,J=7.6Hz,CH 3),1.14(t,6H,J=7.5Hz,CH 3). 13C?NMR(100MHz;CDCl 3;TMS):166.8,152.9,145.286,141.545,138.9,135.5,135.3,133.9,132.2,131.2,130.1,127.2,126.7,126.6,99.3,24.7,24.6,24.5,24.3,21.4,21.1,20.9,16.9,15.2,13.8.Anal.Calcd.for?C 33H 41N 3:C,82.63,H,8.61,N,8.76;Found:C,82.56,H,8.47,N,8.46。
Embodiment 6,2,8-(2,6-dichlorobenzene imines)-4,5,6 hydrogenated quinolines (L6) part synthetic
Drop into raw material 2,8-4,5,6-hydrogenated quinoline diketone (0.189g in the 100ml two-mouth bottle; 0.1mmol) and 2, the 6-dichlorphenamide bulk powder (0.405,0.25mmol) and tosic acid 0.015g, in propyl carbinol (30ml), reflux; After reaction was carried out about 6 hours, reaction solution concentrated, silica gel column chromatography (PE:EA=50:1; V/v) after the separation, get the 0.144g yellow solid, yield 30.2%.
Nuclear-magnetism shows has two kinds of isomer, and wherein the eneamines isomer is a primary product.L6:L6’=0.26:FT-IR?(KBr，cm -1):3359(v N-H),2965,2929,2869,2828,1634,1570,1460,1359,1313,1203,1148,1106,1018,883,857,793,773,702,671.Anal.Calcd.for?C 23H 17Cl 4N 3:C,57.89;H,3.59;N,8.81;Found:C,57.56,H,3.47,N,8.46. 13C?NMR(100MHz;CDCl 3;TMS):166.8,152.9,145.286,141.545,138.9,135.5,135.3,133.9,132.2,131.2,130.1,127.2,126.7,126.6,99.3.(L5’): 1H?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).
Embodiment 7, (2,6-dimethyl benzene imines) methyl)-5,6-dihydro-N-2,6-dimethyl-) quinoline 8-amino (L7/L7 ') part synthetic
Drop into raw material 2-aldehyde radical-8 ketone-4,5 in the 100ml two-mouth bottle, (0.175g is 1mmol) with 2 for the 6-hydrogenated quinoline; (0.302g's 6-xylidine 2.5mmol) and tosic acid 0.015g, refluxes in propyl carbinol (30ml); After reaction was carried out about 6 hours, reaction solution concentrated, silica gel column chromatography (PE:EA=50:1; V/v) after the separation, get the 0.222g yellow solid, yield 58.2%.
Nuclear-magnetism shows has two kinds of isomer, and wherein the eneamines isomer is a primary product.L7:L7’=0.23:1.Mp:98-99°C.FT-IR(KBr,cm -1):3369(v N-H),2965,2929,2869,2828,1639,1570,1460,1359,1313,1203,1148,1106,1018,883,857,793,773,702,671.Anal.Calcd.for?C 26H 27N 3:C,81.85;H,7.13;N,11.01;Found:C,82.01;H,7.47,N,11.46. 1H?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). 13C?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 8,2,8-(2,6-dimethyl-imines)-4,5,6 hydrogenated quinolines (L8) part synthetic
Drop into raw material 2-propionyl group-8-4 in the 100ml two-mouth bottle, (0.203g is 1mmol) with 2 for 5,6 hydrogenated quinoline ketone; (0.302g's 6-xylidine 0.25mmol) and tosic acid 0.015g, refluxes in propyl carbinol (30ml); After reaction was carried out about 6 hours, reaction solution concentrated, silica gel column chromatography (PE:EA=50:1; V/v) after the separation, get the 0.10g yellow solid, yield 25.2%.
Nuclear-magnetism shows has two kinds of isomer, and wherein the eneamines isomer is a primary product.L8:L8’=0.15:1.FT-IR?(KBr,cm -1):3369(v N-H),2965,2929,2869,2828,1639,1570,1460,1359,1313,1203,1148,1106,1018,883,857,793,773,702,671.Anal.Calcd.for?C 28H 31N 3:C,82.11;H,7.63;N,10.26;Found:C,82.36;H,8.00;N,10.46. 11H?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-),2.35(m,2H),2.31(s,6H,CH 3),2.00(s,6H,CH 3),1.65(t,3H,J=6.7Hz). 13CNMR(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.
The preparation of embodiment 9, title complex Fe1
(0.15g is 0.38mmol) with 1 normal FeCl with ligand L 1/L1 ' 24H 2(0.070g 0.35mmol) places Schlenk pipe to O, behind the vacuum nitrogen filling gas three times; The absolute ethyl alcohol that adds the 5ml degassing; Stirring reaction is 10 hours under the room temperature, adds anhydrous diethyl ether, has a large amount of depositions to generate; With sedimentation and filtration and with obtaining powder (0.16g, 76.2%) after anhydrous diethyl ether washing, the drying.
Its characterization data is following: 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 27H 29Cl 2FeN 3: C, 62.09, H, 5.60, N, 8.05; Found:C, 62.13, H, 5.47, N, 7.67.
Its crystalline structure is as shown in Figure 1.
The preparation of embodiment 10, title complex Fe2
(0.158g is 0.38mmol) with 1 normal FeCl with ligand L 2/L2 ' 24H 2(0.070g 0.35mmol) places Schlenk pipe to O, behind the vacuum nitrogen filling gas three times; The absolute ethyl alcohol that adds the 5ml degassing; Stirring reaction is 4 hours under the room temperature, adds anhydrous diethyl ether, has a large amount of depositions to generate; With sedimentation and filtration and with obtaining powder (0.144g, 71.4%) after anhydrous diethyl ether washing, the drying.
Its characterization data is following: 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 31H 37Cl 2FeN 3: C, 64.37, H, 6.45, N, 7.26; Found:C, 64.22, H, 6.24, N, 7.02.
Its crystalline structure is as shown in Figure 2.
The preparation of embodiment 11, title complex Fe3
(0.192g is 0.38mmol) with 1.2 normal FeCl with ligand L 3/L3 ' 24H 2(0.084g 0.42mmol) places Schlenk pipe to O, behind the vacuum nitrogen filling gas three times; The absolute ethyl alcohol that adds the 5ml degassing; Stirring reaction is 18 hours under the room temperature, adds anhydrous diethyl ether, has a large amount of depositions to generate; With sedimentation and filtration and with obtaining blue powder (0.131g, 59.1%) after anhydrous diethyl ether washing, the drying.
Its characterization data is following: 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 35H 45Cl 2FeN 3: C, 66.25, H, 7.15, N, 6.62; Found:C, 66.24, H, 7.02, N, 6.48.
The preparation of embodiment 12, title complex Fe4
(0.15g is 0.38mmol) with 1 normal FeCl with ligand L 4/L4 ' 24H 2(0.070g 0.35mmol) places Schlenk pipe to O, behind the vacuum nitrogen filling gas three times; The absolute ethyl alcohol that adds the 5ml degassing; Stirring reaction is 10 hours under the room temperature, adds anhydrous diethyl ether, has a large amount of depositions to generate; With sedimentation and filtration and with obtaining blue powder (0.106g, 55.5%) after anhydrous diethyl ether washing, the drying.
Its characterization data is following: 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 29H 33Cl 2FeN 3: C, 63.29, H, 6.04, N, 7.64; Found:C, 63.11, H, 7.16, N, 6.48.
The preparation of embodiment 13, title complex Fe5
(0.182g is 0.38mmol) with 0.67 normal FeCl with ligand L 5/L5 ' 24H 2(0.047g 0.23mmol) places Schlenk pipe to O, behind the vacuum nitrogen filling gas three times; The absolute ethyl alcohol that adds the 5ml degassing; Stirring reaction is 10 hours under the room temperature, adds anhydrous diethyl ether, has a large amount of depositions to generate; With sedimentation and filtration and with obtaining blue powder (0.121g, 57.1%) after anhydrous diethyl ether washing, the drying.
Its characterization data is following: 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 33H 41Cl 2FeN 3: C, 65.36, H, 6.81, N, 6.93; Found:C, 65.42, H, 6.79, N, 6.72.
The preparation of embodiment 14, title complex Fe6
(0.181g is 0.38mmol) with 1 normal FeCl with ligand L 6/L6 ' 24H 2(0.070g 0.35mmol) places Schlenk pipe to O, behind the vacuum nitrogen filling gas three times; The absolute ethyl alcohol that adds the 5ml degassing; Stirring reaction is 10 hours under the room temperature, adds anhydrous diethyl ether, has a large amount of depositions to generate; With sedimentation and filtration and with obtaining blue powder (0.120g, 57.1%) after anhydrous diethyl ether washing, the drying.
Its characterization data is following: 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 23H 17Cl 6FeN 3: C, 45.74; H, 2.84; N, 6.96; Found:C, 45.42; H, 2.79; N, 6.72.
The preparation of embodiment 15, title complex Fe7
(0.145g is 0.38mmol) with 1 normal FeCl with ligand L 7/L7 ' 24H 2(0.070g 0.35mmol) places Schlenk pipe to O, behind the vacuum nitrogen filling gas three times; The absolute ethyl alcohol that adds the 5ml degassing; Stirring reaction is 10 hours under the room temperature, adds anhydrous diethyl ether, has a large amount of depositions to generate; With sedimentation and filtration and with obtaining blue powder (0.107g, 60.1%) after anhydrous diethyl ether washing, the drying.
Its characterization data is following: 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 26H 27Cl 2FeN 3: C, 61.44; H, 5.35; N, 8.27; Found:C, 61.42, H, 5.79, N, 8.32.
The preparation of embodiment 16, title complex Fe8
(0.156g is 0.38mmol) with 1 normal FeCl with ligand L 8/L8 ' 24H 2(0.070g 0.35mmol) places Schlenk pipe to O, behind the vacuum nitrogen filling gas three times; The absolute ethyl alcohol that adds the 5ml degassing; Stirring reaction is 10 hours under the room temperature, adds anhydrous diethyl ether, has a large amount of depositions to generate; With sedimentation and filtration and with obtaining blue powder (0.122g, 65.1%) after anhydrous diethyl ether washing, the drying.
Its characterization data is following: 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 28H 31Cl 2FeN 3: C, 62.71; H, 5.83; N, 7.83; Found:C, 62.42, H, 5.79, N, 7.72.
The preparation of embodiment 17, title complex Co1
(0.15g is 0.38mmol) with 1 normal CoCl with ligand L 1/L1 ' 2(0.045g 0.35mmol) places Schlenk pipe, behind the vacuum nitrogen filling gas three times; Add the absolute ethyl alcohol of the 5ml degassing, stirring reaction is 10 hours under the room temperature, adds anhydrous diethyl ether; There are a large amount of depositions to generate; With sedimentation and filtration and with obtaining powder, (0.126g, 68.5%) after anhydrous diethyl ether washing, the drying.
Its characterization data is following: Anal.Calcd.For C 27H 29Cl 2CoN 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 crystalline structure is as shown in Figure 3.
The preparation of embodiment 18, title complex Co2
(0.158g is 0.38mmol) with 1 normal CoCl with ligand L 2/L2 ' 2(0.045g 0.35mmol) places Schlenk pipe, behind the vacuum nitrogen filling gas three times; The absolute ethyl alcohol that adds the 5ml degassing; Stirring reaction is 10 hours under the room temperature, adds anhydrous diethyl ether, has a large amount of depositions to generate; With sedimentation and filtration and with obtaining powder (0.132g, 65.0%) after anhydrous diethyl ether washing, the drying.
Its characterization data is following: Anal.Calcd.For C 31H 37Cl 2CoN 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 crystalline structure is as shown in Figure 4.
The preparation of embodiment 19, title complex Co3
(0.192g is 0.38mmol) with 1 normal CoCl with ligand L 3/L3 ' 2(0.045g 0.35mmol) places Schlenk pipe, behind the vacuum nitrogen filling gas three times; The absolute ethyl alcohol that adds the 5ml degassing; Stirring reaction is 10 hours under the room temperature, adds anhydrous diethyl ether, has a large amount of depositions to generate; With sedimentation and filtration and with obtaining powder (0.130g, 58.5%) after anhydrous diethyl ether washing, the drying.
Its characterization data is following: Anal.Calcd.For C 35H 45Cl 2CoN 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.
The preparation of embodiment 20, title complex Co4
(0.15g is 0.38mmol) with 1 normal CoCl with ligand L 4/L4 ' 2(0.045g 0.35mmol) places Schlenk pipe, behind the vacuum nitrogen filling gas three times; The absolute ethyl alcohol that adds the 5ml degassing; Stirring reaction is 10 hours under the room temperature, adds anhydrous diethyl ether, has a large amount of depositions to generate; With sedimentation and filtration and with obtaining powder (0.165g, 85.6%) after anhydrous diethyl ether washing, the drying.
Its characterization data is following: Anal.Calcd.For C 29H 33Cl 2CoN 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.
The preparation of embodiment 21, title complex Co5
(0.182g is 0.38mmol) with 1 normal CoCl with ligand L 5/L5 ' 2(0.045g 0.35mmol) places Schlenk pipe, behind the vacuum nitrogen filling gas three times; The absolute ethyl alcohol that adds the 5ml degassing; Stirring reaction is 10 hours under the room temperature, adds anhydrous diethyl ether, has a large amount of depositions to generate; With sedimentation and filtration and with obtaining yellow powder (0.169g, 79.1%) after anhydrous diethyl ether washing, the drying.
Its characterization data is following: Anal.Calcd.For C 33H 41Cl 2CoN 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 crystalline structure is as shown in Figure 5.
The preparation of embodiment 22, title complex Co6
(0.181g is 0.38mmol) with 1 normal CoCl with ligand L 6/L6 ' 2(0.045g 0.35mmol) places Schlenk pipe, behind the vacuum nitrogen filling gas three times; The absolute ethyl alcohol that adds the 5ml degassing; Stirring reaction is 10 hours under the room temperature, adds anhydrous diethyl ether, has a large amount of depositions to generate; With sedimentation and filtration and with obtaining yellow powder (0.168g, 79.5%) after anhydrous diethyl ether washing, the drying.
Its characterization data is following: Anal.Calcd.For C 23H 17Cl 6CoN 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.
The preparation of embodiment 23, title complex Co7
(0.145g is 0.38mmol) with 1 normal CoCl with ligand L 7/L7 ' 2(0.045g 0.35mmol) places Schlenk pipe, behind the vacuum nitrogen filling gas three times; The absolute ethyl alcohol that adds the 5ml degassing; Stirring reaction is 10 hours under the room temperature, adds anhydrous diethyl ether, has a large amount of depositions to generate; With sedimentation and filtration and with obtaining yellow powder (0.143g, 80%) after anhydrous diethyl ether washing, the drying.
Its characterization data is following: Anal.Calcd.For C 26H 27Cl 2CoN 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.
The preparation of embodiment 24, title complex Co8
(0.156g is 0.38mmol) with 1 normal CoCl with ligand L 8/L8 ' 2(0.045g 0.35mmol) places Schlenk pipe, behind the vacuum nitrogen filling gas three times; The absolute ethyl alcohol that adds the 5ml degassing; Stirring reaction is 10 hours under the room temperature, adds anhydrous diethyl ether, has a large amount of depositions to generate; With sedimentation and filtration and with obtaining yellow powder (0.123g, 65.5%) after anhydrous diethyl ether washing, the drying.
Its characterization data is following: Anal.Calcd.For C 28H 31Cl 2CoN 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.
Following embodiment utilizes the title complex of above-mentioned preparation to carry out the embodiment of catalyzed ethylene polymerization.
Embodiment 25,
Add the vinyl polymerization of depressing and use 300 milliliters of stainless steel polymeric kettles that are equipped with mechanical stirring oar and temperature-control device.Polymeric kettle is vacuumized and be heated to 100 ° of C, and continue two hours heat-up time.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (30 ° of C) of imagination.Add 50mL toluene then successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyzer (Fe3), 2.05mL promotor (MAO, 1.46mol/L toluene solution) (Al/Fe=1000), residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, add acidic alcohol, in the baking oven of 60 ° of C, be dried to constant weight behind the filtration washing, obtain the 2.45g polymkeric substance, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 1.63 * 10 6G ofPEmol -1(M) h -1, polymkeric substance M w=203.4Kgmol -1, M w/ M n=3.4, T m=135.5.
Embodiment 26,
Add the vinyl polymerization of depressing and use 300 milliliters of stainless steel polymeric kettles that are equipped with mechanical stirring oar and temperature-control device.Polymeric kettle is vacuumized and be heated to 100 ° of C, and continue two hours heat-up time.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (30 ° of C) of imagination.Add 50mL toluene then successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyzer (Fe3), 3.08mL promotor (MAO, 1.46mol/L toluene solution) (Al/Fe=1500), residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, add acidic alcohol, in the baking oven of 60 ° of C, be dried to constant weight behind the filtration washing, obtain the 3.12g polymkeric substance, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 2.08 * 10 6G ofPEmol -1(M) h -1, polymkeric substance M w=132.9Kgmol -1, M w/ M n=8.5, T m=133.3.
Embodiment 27,
Add the vinyl polymerization of depressing and use 300 milliliters of stainless steel polymeric kettles that are equipped with mechanical stirring oar and temperature-control device.Polymeric kettle is vacuumized and be heated to 100 ° of C, and continue two hours heat-up time.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (30 ° of C) of imagination.Add 50mL toluene then successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyzer (Fe3), 4.10mL promotor (MAO, 1.46mol/L toluene solution) (Al/Fe=2000), residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, add acidic alcohol, in the baking oven of 60 ° of C, be dried to constant weight behind the filtration washing, obtain the 4.90g polymkeric substance, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 3.27 * 10 6G ofPEmol -1(M) h -1, polymkeric substance M w=174.5Kgmol -1, M w/ M n=32.5, T m=130.6.
Embodiment 28,
Add the vinyl polymerization of depressing and use 300 milliliters of stainless steel polymeric kettles that are equipped with mechanical stirring oar and temperature-control device.Polymeric kettle is vacuumized and be heated to 100 ° of C, and continue two hours heat-up time.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (30 ° of C) of imagination.Add 50mL toluene then successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyzer (Fe3), 5.14mL promotor (MAO, 1.46mol/L toluene solution) (Al/Fe=2500), residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, add acidic alcohol, in the baking oven of 60 ° of C, be dried to constant weight behind the filtration washing, obtain the 3.79g polymkeric substance, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 2.53 * 10 6G of PEmol -1(M) h -1, polymkeric substance M w=78.9Kgmol -1, M w/ M n=35.9, T m=128.8.
Embodiment 29,
Add the vinyl polymerization of depressing and use 300 milliliters of stainless steel polymeric kettles that are equipped with mechanical stirring oar and temperature-control device.Polymeric kettle is vacuumized and be heated to 100 ° of C, and continue two hours heat-up time.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (40 ° of C) of imagination.Add 50mL toluene then successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyzer (Fe3), 4.10mL promotor MAO (1.46mol/L toluene solution) (Al/Fe=2000), residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, add acidic alcohol, in the baking oven of 60 ° of C, be dried to constant weight behind the filtration washing, obtain the 5.95g polymkeric substance, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 3.97 * 10 6G ofPEmol -1(M) h -1, polymkeric substance M w=77.0Kgmol -1, M w/ M n=23.5, T m=128.
Embodiment 30,
Add the vinyl polymerization of depressing and use 300 milliliters of stainless steel polymeric kettles that are equipped with mechanical stirring oar and temperature-control device.Polymeric kettle is vacuumized and be heated to 100 ° of C, and continue two hours heat-up time.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (50 ° of C) of imagination.Add 50mL toluene then successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyzer (Fe3), 4.10mL promotor MAO (1.46mol/L toluene solution) (Al/Fe=2000), residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, add acidic alcohol, in the baking oven of 60 ° of C, be dried to constant weight behind the filtration washing, obtain the 13.2g polymkeric substance, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 8.80 * 10 6G ofPEmol -1(M) h -1, polymkeric substance M w=121.6Kgmol -1, M w/ M n=13.9, T m=130.7.
Embodiment 31,
Add the vinyl polymerization of depressing and use 300 milliliters of stainless steel polymeric kettles that are equipped with mechanical stirring oar and temperature-control device.Polymeric kettle is vacuumized and be heated to 100 ° of C, and continue two hours heat-up time.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (60 ° of C) of imagination.Add 50mL toluene then successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyzer (Fe3), 4.10mL promotor MAO (1.46mol/L toluene solution) (Al/Fe=2000), residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, add acidic alcohol, in the baking oven of 60 ° of C, be dried to constant weight behind the filtration washing, obtain the 11.0g polymkeric substance, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 7.34 * 10 6G ofPEmol -1(M) h -1, polymkeric substance M w=13.3Kgmol -1, M w/ M n=2.8, T m=128.1.
Embodiment 32,
Add the vinyl polymerization of depressing and use 300 milliliters of stainless steel polymeric kettles that are equipped with mechanical stirring oar and temperature-control device.Polymeric kettle is vacuumized and be heated to 100 ° of C, and continue two hours heat-up time.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (80 ° of C) of imagination.Add 50mL toluene then successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyzer (Fe3), 4.10mL promotor MAO (1.46mol/L toluene solution) (Al/Fe=2000), residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, add acidic alcohol, in the baking oven of 60 ° of C, be dried to constant weight behind the filtration washing, obtain the 10.2g polymkeric substance, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 6.81 * 10 6G ofPEmol -1(M) h -1, polymkeric substance M w=18.5Kgmol -1, M w/ M n=4.3, T m=127.6.
Embodiment 33,
Add the vinyl polymerization of depressing and use 300 milliliters of stainless steel polymeric kettles that are equipped with mechanical stirring oar and temperature-control device.Polymeric kettle is vacuumized and be heated to 100 ° of C, and continue two hours heat-up time.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (50 ° of C) of imagination.Add 50mL toluene then successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyzer (Fe1), 4.10mL promotor MAO (1.46mol/L toluene solution) (Al/Fe=2000), residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, add acidic alcohol, in the baking oven of 60 ° of C, be dried to constant weight behind the filtration washing, obtain the 8.41g polymkeric substance, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 5.61 * 10 6G ofPEmol -1(M) h -1, polymkeric substance M w=22.8Kgmol -1, M w/ M n=4.7, T m=128.7.
Embodiment 34,
Add the vinyl polymerization of depressing and use 300 milliliters of stainless steel polymeric kettles that are equipped with mechanical stirring oar and temperature-control device.Polymeric kettle is vacuumized and be heated to 100 ° of C, and continue two hours heat-up time.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (50 ° of C) of imagination.Add 50mL toluene then successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyzer (Fe2), 4.10mL promotor MAO (1.46mol/L toluene solution) (Al/Fe=2000), residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, add acidic alcohol, in the baking oven of 60 ° of C, be dried to constant weight behind the filtration washing, obtain the 23.4g polymkeric substance, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 15.6 * 10 6G ofPEmol -1(M) h -1, polymkeric substance M w=22.7Kgmol -1, M w/ M n=6.3, T m=129.9.
Embodiment 35,
Add the vinyl polymerization of depressing and use 300 milliliters of stainless steel polymeric kettles that are equipped with mechanical stirring oar and temperature-control device.Polymeric kettle is vacuumized and be heated to 100 ° of C, and continue two hours heat-up time.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (50 ° of C) of imagination.Add 50mL toluene then successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyzer (Fe4), 4.10mL promotor MAO (1.46mol/L toluene solution) (Al/Fe=2000), residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, add acidic alcohol, in the baking oven of 60 ° of C, be dried to constant weight behind the filtration washing, obtain the 8.34g polymkeric substance, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 5.56 * 10 6G ofPEmol -1(M) h -1, polymkeric substance M w=31.5Kgmol -1, M w/ M n=7.2, T m=128.6.
Embodiment 36,
Add the vinyl polymerization of depressing and use 300 milliliters of stainless steel polymeric kettles that are equipped with mechanical stirring oar and temperature-control device.Polymeric kettle is vacuumized and be heated to 100 ° of C, and continue two hours heat-up time.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (50 ° of C) of imagination.Add 50mL toluene then successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyzer (Fe5), 4.10mL promotor MAO (1.46mol/L toluene solution) (Al/Fe=2000), residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, add acidic alcohol, in the baking oven of 60 ° of C, be dried to constant weight behind the filtration washing, obtain the 12.4g polymkeric substance, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 8.25 * 10 6G ofPEmol -1(M) h -1, polymkeric substance M w=29.7Kgmol -1, M w/ M n=5.3, T m=129.8.
Embodiment 37,
Add the vinyl polymerization of depressing and use 300 milliliters of stainless steel polymeric kettles that are equipped with mechanical stirring oar and temperature-control device.Polymeric kettle is vacuumized and be heated to 100 ° of C, and continue two hours heat-up time.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (30 ° of C) of imagination.Add 50mL toluene then successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyzer (Fe3), 1.55mL promotor (MMAO, the n-heptane solution of 1.93mol/L) (Al/Fe=1000), residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, add acidic alcohol, in the baking oven of 60 ° of C, be dried to constant weight behind the filtration washing, obtain the 2.91g polymkeric substance, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 1.94 * 10 6G ofPEmol -1(M) h -1, polymkeric substance M w=37.8Kgmol -1, M w/ M n=28.0, T m=123.6.
Embodiment 38,
Add the vinyl polymerization of depressing and use 300 milliliters of stainless steel polymeric kettles that are equipped with mechanical stirring oar and temperature-control device.Polymeric kettle is vacuumized and be heated to 100 ° of C, and continue two hours heat-up time.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (30 ° of C) of imagination.Add 50mL toluene then successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyzer (Fe3), 2.33mL promotor (MMAO, the n-heptane solution of 1.93mol/L) (Fe=1500), residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, add acidic alcohol, in the baking oven of 60 ° of C, be dried to constant weight behind the filtration washing, obtain the 4.72g polymkeric substance, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 3.14 * 10 6G of PEmol -1(M) h -1, polymkeric substance M w=19.2Kgmol -1, M w/ M n=12.8, T m=123.2.
Embodiment 39/
Add the vinyl polymerization of depressing and use 300 milliliters of stainless steel polymeric kettles that are equipped with mechanical stirring oar and temperature-control device.Polymeric kettle is vacuumized and be heated to 100 ° of C, and continue two hours heat-up time.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (30 ° of C) of imagination.Add 50mL toluene then successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyzer (Fe3), 3.10mL promotor (MMAO, the n-heptane solution of 1.93mol/L) (Al/Fe=2000), residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, add acidic alcohol, in the baking oven of 60 ° of C, be dried to constant weight behind the filtration washing, obtain the 6.49g polymkeric substance, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 4.33 * 10 6G of PEmol -1(M) h -1, polymkeric substance M w=13.0Kgmol -1, M w/ M n=9.3, T m=123.5.
Embodiment 40,
Add the vinyl polymerization of depressing and use 300 milliliters of stainless steel polymeric kettles that are equipped with mechanical stirring oar and temperature-control device.Polymeric kettle is vacuumized and be heated to 100 ° of C, and continue two hours heat-up time.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (30 ° of C) of imagination.Add 50mL toluene then successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyzer (Fe3), 3.89mL promotor (MMAO, the n-heptane solution of 1.93mol/L) Al/Fe=2500), residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, add acidic alcohol, in the baking oven of 60 ° of C, be dried to constant weight behind the filtration washing, obtain the 6.00g polymkeric substance, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 4.00 * 10 6G ofPEmol -1(M) h -1, polymkeric substance M w=8.1Kgmol -1, M w/ M n=5.7, T m=120.5.
Embodiment 41,
Add the vinyl polymerization of depressing and use 300 milliliters of stainless steel polymeric kettles that are equipped with mechanical stirring oar and temperature-control device.Polymeric kettle is vacuumized and be heated to 100 ° of C, and continue two hours heat-up time.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (40 ° of C) of imagination.Add 50mL toluene then successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyzer (Fe3), 3.10mL promotor (MMAO, the n-heptane solution of 1.93mol/L) (Al/Fe=2000), residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, add acidic alcohol, in the baking oven of 60 ° of C, be dried to constant weight behind the filtration washing, obtain the 7.04g polymkeric substance, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 4.69 * 10 6G of PEmol -1(M) h -1, polymkeric substance M w=17.4Kgmol -1, M w/ M n=9.1, T m=123.1.
Embodiment 42,
Add the vinyl polymerization of depressing and use 300 milliliters of stainless steel polymeric kettles that are equipped with mechanical stirring oar and temperature-control device.Polymeric kettle is vacuumized and be heated to 100 ° of C, and continue two hours heat-up time.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (50 ° of C) of imagination.Add 50mL toluene then successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyzer (Fe3), 3.10mL promotor (MMAO, the n-heptane solution of 1.93mol/L) (Al/Fe=2000), residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, add acidic alcohol, in the baking oven of 60 ° of C, be dried to constant weight behind the filtration washing, obtain the 22.3g polymkeric substance, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 14.8 * 10 6G ofPEmol -1(M) h -1, polymkeric substance M w=32.7Kgmol -1, M w/ M n=8.9, T m=128.2.
Embodiment 43,
Add the vinyl polymerization of depressing and use 300 milliliters of stainless steel polymeric kettles that are equipped with mechanical stirring oar and temperature-control device.Polymeric kettle is vacuumized and be heated to 100 ° of C, and continue two hours heat-up time.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (60 ° of C) of imagination.Add 50mL toluene then successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyzer (Fe3), 3.10mL promotor (MMAO, the n-heptane solution of 1.93mol/L) (Al/Fe=2000), residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, add acidic alcohol, in the baking oven of 60 ° of C, be dried to constant weight behind the filtration washing, obtain the 18.9g polymkeric substance, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 12.6 * 10 6G ofPEmol -1(M) h -1, polymkeric substance M w=29.9Kgmol -1, M w/ M n=8.9, T m=127.7.
Embodiment 44,
Add the vinyl polymerization of depressing and use 300 milliliters of stainless steel polymeric kettles that are equipped with mechanical stirring oar and temperature-control device.Polymeric kettle is vacuumized and be heated to 100 ° of C, and continue two hours heat-up time.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (70 ° of C) of imagination.Add 50mL toluene then successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyzer (Fe3), 3.10mL promotor (MMAO, the n-heptane solution of 1.93mol/L) (Al/Fe=2000), residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, add acidic alcohol, in the baking oven of 60 ° of C, be dried to constant weight behind the filtration washing, obtain the 17.3g polymkeric substance, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 11.5 * 10 6G ofPEmol -1(M) h -1, polymkeric substance M w=15.1Kgmol -1, M w/ M n=4.5, T m=127.2.
Embodiment 45,
Add the vinyl polymerization of depressing and use 300 milliliters of stainless steel polymeric kettles that are equipped with mechanical stirring oar and temperature-control device.Polymeric kettle is vacuumized and be heated to 100 ° of C, and continue two hours heat-up time.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (50 ° of C) of imagination.Add 50mL toluene then successively, 20mL is dissolved with the 3 μ mol catalyzer (toluene solution of Fe1,3.10mL promotor (MMAO, the n-heptane solution of 1.93mol/L) (Al/Fe=2000), residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, add acidic alcohol, in the baking oven of 60 ° of C, be dried to constant weight behind the filtration washing, obtain the 22.5g polymkeric substance, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 14.8 * 10 6G of PEmol -1(M) h -1, polymkeric substance M w=11.7Kgmol -1, M w/ M n=4.0, T m=126.3.
Embodiment 46,
Add the vinyl polymerization of depressing and use 300 milliliters of stainless steel polymeric kettles that are equipped with mechanical stirring oar and temperature-control device.Polymeric kettle is vacuumized and be heated to 100 ° of C, and continue two hours heat-up time.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (50 ° of C) of imagination.Add 50mL toluene then successively, 20mL is dissolved with the 3 μ mol catalyzer (toluene solution of Fe2,3.10mL promotor (MMAO, the n-heptane solution of 1.93mol/L) (Al/Fe=2000), residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, add acidic alcohol, in the baking oven of 60 ° of C, be dried to constant weight behind the filtration washing, obtain the 14.7g polymkeric substance, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 9.81 * 10 6G of PEmol -1(M) h -1, polymkeric substance M w=12.9Kgmol -1, M w/ M n=5.1, T m=125.2.
Embodiment 47,
Add the vinyl polymerization of depressing and use 300 milliliters of stainless steel polymeric kettles that are equipped with mechanical stirring oar and temperature-control device.Polymeric kettle is vacuumized and be heated to 100 ° of C, and continue two hours heat-up time.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (50 ° of C) of imagination.Add 50mL toluene then successively, 20mL is dissolved with the 3 μ mol catalyzer (toluene solution of Fe4,3.10mL promotor (MMAO, the n-heptane solution of 1.93mol/L) (Al/Fe=2000), residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, add acidic alcohol, in the baking oven of 60 ° of C, be dried to constant weight behind the filtration washing, obtain the 23.0g polymkeric substance, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 15.4 * 10 6G of PEmol -1(M) h -1, polymkeric substance M w=14.8Kgmol -1, M w/ M n=6.0, T m=127.4.
Embodiment 48,
Add the vinyl polymerization of depressing and use 300 milliliters of stainless steel polymeric kettles that are equipped with mechanical stirring oar and temperature-control device.Polymeric kettle is vacuumized and be heated to 100 ° of C, and continue two hours heat-up time.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (50 ° of C) of imagination.Add 50mL toluene then successively, 20mL is dissolved with the 3 μ mol catalyzer (toluene solution of Fe5,3.10mL promotor (MMAO, the n-heptane solution of 1.93mol/L) (Al/Fe=2000), residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, add acidic alcohol, in the baking oven of 60 ° of C, be dried to constant weight behind the filtration washing, obtain the 20.3g polymkeric substance, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 13.5 * 10 6G of PEmol -1(M) h -1, polymkeric substance M w=12.8Kgmol -1, M w/ M n=5.8, T m=126.7.
Embodiment 49,
Add the vinyl polymerization of depressing and use 300 milliliters of stainless steel polymeric kettles that are equipped with mechanical stirring oar and temperature-control device.Polymeric kettle is vacuumized and be heated to 100 ° of C, and continue two hours heat-up time.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (50 ° of C) of imagination.Add 50mL toluene then successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyzer (Fe3), 3.10mL promotor (MMAO, the n-heptane solution of 1.93mol/L) (Al/Fe=2000), residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (15min), the ethylene pressure in the still is discharged, add acidic alcohol, in the baking oven of 60 ° of C, be dried to constant weight behind the filtration washing, obtain the 18.0g polymkeric substance, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 24.0 * 10 6G of PEmol -1(M) h -1, polymkeric substance M w=9.8Kgmol -1, M w/ M n=2.7, T m=127.5.
Embodiment 50,
Add the vinyl polymerization of depressing and use 300 milliliters of stainless steel polymeric kettles that are equipped with mechanical stirring oar and temperature-control device.Polymeric kettle is vacuumized and be heated to 100 ° of C, and continue two hours heat-up time.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (50 ° of C) of imagination.Add 50mL toluene then successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyzer (Fe3), 3.10mL promotor (MMAO, the n-heptane solution of 1.93mol/L) (Al/Fe=2000), residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (40min), the ethylene pressure in the still is discharged, add acidic alcohol, in the baking oven of 60 ° of C, be dried to constant weight behind the filtration washing, obtain the 28.0g polymkeric substance, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 12.5 * 10 6G of PEmol -1(M) h -1, polymkeric substance M w=46.2Kgmol -1, M w/ M n=11.1, T m=128.9.
Embodiment 51,
Add the vinyl polymerization of depressing and use 300 milliliters of stainless steel polymeric kettles that are equipped with mechanical stirring oar and temperature-control device.Polymeric kettle is vacuumized and be heated to 100 ° of C, and continue two hours heat-up time.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (50 ° of C) of imagination.Add 50mL toluene then successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyzer (Co4), 1.03mL promotor MAO (1.46mol/L toluene solution) (Al/Co=500), residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, add acidic alcohol, in the baking oven of 60 ° of C, be dried to constant weight behind the filtration washing, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 9.29 * 10 6G ofPEmol -1(M) h -1, polymkeric substance M w=1124gmol -1, M w/ M n=1.7, T m=102.2
Embodiment 52,
The vinyl polymerization of depressing uses 300 milliliters of stainless steel polymeric kettles that are equipped with mechanical stirring oar and temperature-control device.Polymeric kettle is vacuumized and be heated to 100 ° of C, and continue two hours heat-up time.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (50 ° of C) of imagination.Add 50mL toluene then successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyzer (Co4), 1.54mL promotor MAO (1.46mol/L toluene solution) (Al/Co=750), residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, add acidic alcohol, in the baking oven of 60 ° of C, be dried to constant weight behind the filtration washing, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 12.63 * 10 6G ofPEmol -1(M) h -1, polymkeric substance M w=1000gmol -1, M w/ M n=1.5, T m=101.4 ° of C.
Embodiment 53,
Add the vinyl polymerization of depressing and use 300 milliliters of stainless steel polymeric kettles that are equipped with mechanical stirring oar and temperature-control device.Polymeric kettle is vacuumized and be heated to 100 ° of C, and continue two hours heat-up time.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (50 ° of C) of imagination.Add 50mL toluene then successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyzer (Co4), 2.05mL promotor MAO (1.46mol/L toluene solution) (Al/Co=1000), residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, add acidic alcohol, in the baking oven of 60 ° of C, be dried to constant weight behind the filtration washing, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 14.76 * 10 6G ofPEmol -1(M) h -1, polymkeric substance M w=949gmol -1, M w/ M n=1.5, T m=99.6 ° of C.
Embodiment 54,
Add the vinyl polymerization of depressing and use 300 milliliters of stainless steel polymeric kettles that are equipped with mechanical stirring oar and temperature-control device.Polymeric kettle is vacuumized and be heated to 100 ° of C, and continue two hours heat-up time.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (50 ° of C) of imagination.Add 50mL toluene then successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyzer (Co4), 2.57mL promotor MAO (1.46mol/L toluene solution) (Al/Co=1250), residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, add acidic alcohol, in the baking oven of 60 ° of C, be dried to constant weight behind the filtration washing, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 13.29 * 10 6G ofPEmol -1(M) h -1, polymkeric substance M w=998gmol -1, M w/ M n=1.6T m=100.9 ° of C.
Embodiment 55,
Add the vinyl polymerization of depressing and use 300 milliliters of stainless steel polymeric kettles that are equipped with mechanical stirring oar and temperature-control device.Polymeric kettle is vacuumized and be heated to 100 ° of C, and continue two hours heat-up time.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (50 ° of C) of imagination.Add 50mL toluene then successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyzer (Co4), 3.08mL promotor MAO (1.46mol/L toluene solution) (Al/Co=1500), residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, add acidic alcohol, in the baking oven of 60 ° of C, be dried to constant weight behind the filtration washing, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 12.00 * 10 6G ofPEmol -1(M) h -1, polymkeric substance M w=1029gmol -1, M w/ M n=1.5, T m=102.3 ° of C.
Embodiment 56,
Add the vinyl polymerization of depressing and use 300 milliliters of stainless steel polymeric kettles that are equipped with mechanical stirring oar and temperature-control device.Polymeric kettle is vacuumized and be heated to 100 ° of C, and continue two hours heat-up time.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (30 ° of C) of imagination.Add 50mL toluene then successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyzer (Co4), 2.05mL promotor MAO (1.46mol/L toluene solution) (Al/Co=1000), residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, add acidic alcohol, in the baking oven of 60 ° of C, be dried to constant weight behind the filtration washing, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 6.72 * 10 6G ofPEmol -1(M) h -1, polymkeric substance M w=1219gmol -1, M w/ M n=1.6, T m=100.9 ° of C.
Embodiment 57,
Add the vinyl polymerization of depressing and use 300 milliliters of stainless steel polymeric kettles that are equipped with mechanical stirring oar and temperature-control device.Polymeric kettle is vacuumized and be heated to 100 ° of C, and continue two hours heat-up time.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (40 ° of C) of imagination.Add 50mL toluene then successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyzer (Co4),, 2.05mL promotor MAO (1.46mol/L toluene solution) (Al/Co=1000), residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, add acidic alcohol, in the baking oven of 60 ° of C, be dried to constant weight behind the filtration washing, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 7.66 * 10 6G ofPEmol -1(M) h -1, polymkeric substance M w=960gmol -1, M w/ M n=1.6, T m=100.3 ° of C.
Embodiment 58,
Add the vinyl polymerization of depressing and use 300 milliliters of stainless steel polymeric kettles that are equipped with mechanical stirring oar and temperature-control device.Polymeric kettle is vacuumized and be heated to 100 ° of C, and continue two hours heat-up time.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (60 ° of C) of imagination.Add 50mL toluene then successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyzer (Co4),, 2.05mL promotor MAO (1.46mol/L toluene solution) (Al/Co=1000), residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, add acidic alcohol, in the baking oven of 60 ° of C, be dried to constant weight behind the filtration washing, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 16.37 * 10 6G ofPEmol -1(M) h -1, polymkeric substance M w=910gmol -1, M w/ M n=1.5, T m=99.6 ° of C.
Embodiment 59,
Add the vinyl polymerization of depressing and use 300 milliliters of stainless steel polymeric kettles that are equipped with mechanical stirring oar and temperature-control device.Polymeric kettle is vacuumized and be heated to 100 ° of C, and continue two hours heat-up time.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (70 ° of C) of imagination.Add 50mL toluene then successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyzer (Co4), 2.05mL promotor MAO (1.46mol/L toluene solution) (Al/Co=1000), residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, add acidic alcohol, in the baking oven of 60 ° of C, be dried to constant weight behind the filtration washing, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 15.60 * 10 6G ofPEmol -1(M) h -1, polymkeric substance M w=880gmol -1, M w/ M n=1.6, T m=99.0 ° of C.
Embodiment 60,
Add the vinyl polymerization of depressing and use 300 milliliters of stainless steel polymeric kettles that are equipped with mechanical stirring oar and temperature-control device.Polymeric kettle is vacuumized and be heated to 100 ° of C, and continue two hours heat-up time.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (60 ° of C) of imagination.Add 50mL toluene then successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyzer (Co4), 2.05mL promotor MAO (1.46mol/L toluene solution) (Al/Co=1000), residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (5min), the ethylene pressure in the still is discharged, add acidic alcohol, in the baking oven of 60 ° of C, be dried to constant weight behind the filtration washing, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 4.83 * 10 6G ofPEmol -1(M) h -1, polymkeric substance M w=891gmol -1, M w/ M n=1.5, T m=100.5 ° of C.
Embodiment 61,
Add the vinyl polymerization of depressing and use 300 milliliters of stainless steel polymeric kettles that are equipped with mechanical stirring oar and temperature-control device.Polymeric kettle is vacuumized and be heated to 100 ° of C, and continue two hours heat-up time.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (60 ° of C) of imagination.Add 50mL toluene then successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyzer (Co4), 2.05mL promotor MAO (1.46mol/L toluene solution) (Al/Co=1000), residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (10min), the ethylene pressure in the still is discharged, add acidic alcohol, in the baking oven of 60 ° of C, be dried to constant weight behind the filtration washing, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 10.13 * 10 6G ofPEmol -1(M) h -1, polymkeric substance M w=896gmol -1, M w/ M n=1.5, T m=99.8 ° of C
Embodiment 62,
Add the vinyl polymerization of depressing and use 300 milliliters of stainless steel polymeric kettles that are equipped with mechanical stirring oar and temperature-control device.Polymeric kettle is vacuumized and be heated to 100 ° of C, and continue two hours heat-up time.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (60 ° of C) of imagination.Add 50mL toluene then successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyzer (Co4), 2.05mL promotor MAO (1.46mol/L toluene solution) (Al/Co=1000), residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (60min), the ethylene pressure in the still is discharged, add acidic alcohol, in the baking oven of 60 ° of C, be dried to constant weight behind the filtration washing, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 18.43 * 10 6G ofPEmol -1(M) h -1, polymkeric substance M w=1016gmol -1, M w/ M n=1.5, T m=99.8 ° of C
Embodiment 63,
Add the vinyl polymerization of depressing and use 300 milliliters of stainless steel polymeric kettles that are equipped with mechanical stirring oar and temperature-control device.Polymeric kettle is vacuumized and be heated to 100 ° of C, and continue two hours heat-up time.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (60 ° of C) of imagination.Add 50mL toluene then successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyzer (Co4), 2.05mL promotor MAO (1.46mol/L toluene solution) (Al/Co=1000), residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (5atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, add acidic alcohol, in the baking oven of 60 ° of C, be dried to constant weight behind the filtration washing, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 8.20 * 10 6G ofPEmol -1(M) h -1, polymkeric substance M w=914gmol -1, M w/ M n=1.4, T m=100.5 ° of C.
Embodiment 64,
The vinyl polymerization of depressing uses 300 milliliters of stainless steel polymeric kettles that are equipped with mechanical stirring oar and temperature-control device.Polymeric kettle is vacuumized and be heated to 100 ° of C, and continue two hours heat-up time.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (60 ° of C) of imagination.Add 50mL toluene then successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyzer (Co1), 2.05mL promotor MAO (1.46mol/L toluene solution) (Al/Co=1000), residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (5atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, add acidic alcohol, in the baking oven of 60 ° of C, be dried to constant weight behind the filtration washing, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 16.29 * 10 6G ofPEmol -1(M) h -1, polymkeric substance M w=827gmol -1, M w/ M n=1.6, T m=99.0 ° of C.
Embodiment 65,
Add the vinyl polymerization of depressing and use 300 milliliters of stainless steel polymeric kettles that are equipped with mechanical stirring oar and temperature-control device.Polymeric kettle is vacuumized and be heated to 100 ° of C, and continue two hours heat-up time.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (60 ° of C) of imagination.Add 50mL toluene then successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyzer (Co2), 2.05mL promotor MAO (1.46mol/L toluene solution) (Al/Co=1000), residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (5atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, add acidic alcohol, in the baking oven of 60 ° of C, be dried to constant weight behind the filtration washing, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 13.37 * 10 6G ofPEmol -1(M) h -1, polymkeric substance M w=1955gmol -1, M w/ M n=1.9, T m=117.4 ° of C.
Embodiment 66,
Add the vinyl polymerization of depressing and use 300 milliliters of stainless steel polymeric kettles that are equipped with mechanical stirring oar and temperature-control device.Polymeric kettle is vacuumized and be heated to 100 ° of C, and continue two hours heat-up time.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (60 ° of C) of imagination.Add 50mL toluene then successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyzer (Co3), 2.05mL promotor MAO (1.46mol/L toluene solution) (Al/Co=1000), residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (5atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, add acidic alcohol, in the baking oven of 60 ° of C, be dried to constant weight behind the filtration washing, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 6.70 * 10 6G ofPEmol -1(M) h -1, polymkeric substance M w=10189gmol -1, M w/ M n=2.0, T m=128.9 ° of C.
Embodiment 67,
Add the vinyl polymerization of depressing and use 300 milliliters of stainless steel polymeric kettles that are equipped with mechanical stirring oar and temperature-control device.Polymeric kettle is vacuumized and be heated to 100 ° of C, and continue two hours heat-up time.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (60 ° of C) of imagination.Add 50mL toluene then successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyzer (Co5), 2.05mL promotor MAO (1.46mol/L toluene solution) (Al/Co=1000), residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (5atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, add acidic alcohol, in the baking oven of 60 ° of C, be dried to constant weight behind the filtration washing, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 16.21 * 10 6G ofPEmol -1(M) h -1, polymkeric substance M w=2009gmol -1, M w/ M n=1.9, T m=117.6 ° of C.
Embodiment 68,
Add the vinyl polymerization of depressing and use 300 milliliters of stainless steel polymeric kettles that are equipped with mechanical stirring oar and temperature-control device.Polymeric kettle is vacuumized and be heated to 100 ° of C, and continue two hours heat-up time.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (50 ° of C) of imagination.Add 50mL toluene then successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyzer (Co4), 1.55mL promotor (MMAO, the n-heptane solution of 1.93mol/L) (Al/Co=1000), residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, add acidic alcohol, in the baking oven of 60 ° of C, be dried to constant weight behind the filtration washing, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 9.35 * 10 6G of PEmol -1(M) h -1, polymkeric substance M w=1031gmol -1, M w/ M n=1.5, T m=102.0 ° of C.
Embodiment 69,
Polymeric kettle is vacuumized and be heated to 100 ° of C, and continue two hours heat-up time.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (50 ° of C) of imagination.Add 50mL toluene then successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyzer (Co4), 1.94mL promotor (MMAO, the n-heptane solution of 1.93mol/L) (Al/Co=1250), residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, add acidic alcohol, in the baking oven of 60 ° of C, be dried to constant weight behind the filtration washing, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 10.05 * 10 6G ofPEmol -1(M) h -1, polymkeric substance M w=1064gmol -1, M w/ M n=1.5, T m=101.6 ° of C.
Embodiment 70,
Polymeric kettle is vacuumized and be heated to 100 ° of C, and continue two hours heat-up time.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (50 ° of C) of imagination.Add 50mL toluene then successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyzer (Co4), 2.33mL promotor (MMAO, the n-heptane solution of 1.93mol/L) (Al/Co=1500), residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, add acidic alcohol, in the baking oven of 60 ° of C, be dried to constant weight behind the filtration washing, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 11.52 * 10 6G ofPEmol -1(M) h -1, polymkeric substance M w=1056gmol -1, M w/ M n=1.6, T m=99.5 ° of C.
Embodiment 71,
Polymeric kettle is vacuumized and be heated to 100 ° of C, and continue two hours heat-up time.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (50 ° of C) of imagination.Add 50mL toluene then successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyzer (Co4), 2.72mL promotor (MMAO, the n-heptane solution of 1.93mol/L) (Al/Co=1750), residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, add acidic alcohol, in the baking oven of 60 ° of C, be dried to constant weight behind the filtration washing, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 11.05 * 10 6G ofPEmol -1(M) h -1, polymkeric substance M w=1088gmol -1, M w/ M n=1.6, T m=100.8 ° of C.
Embodiment 72,
Polymeric kettle is vacuumized and be heated to 100 ° of C, and continue two hours heat-up time.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (30 ° of C) of imagination.Add 50mL toluene then successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyzer (Co4), 2.33mL promotor (MMAO, the n-heptane solution of 1.93mol/L) (Al/Co=1500), residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, add acidic alcohol, in the baking oven of 60 ° of C, be dried to constant weight behind the filtration washing, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 5.89 * 10 6G ofPEmol -1(M) h -1, T m=100.4 ° of C
Embodiment 73,
Polymeric kettle is vacuumized and be heated to 100 ° of C, and continue two hours heat-up time.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (40 ° of C) of imagination.Add 50mL toluene then successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyzer (Co4), 2.33mL promotor (MMAO, the n-heptane solution of 1.93mol/L) (Al/Co=1500), residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, add acidic alcohol, in the baking oven of 60 ° of C, be dried to constant weight behind the filtration washing, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 8.68 * 10 6G ofPEmol -1(M) h -1, polymkeric substance M w=927Kgmol -1, M w/ M n=1.6, T m=99.4 ° of C.
Embodiment 74,
Polymeric kettle is vacuumized and be heated to 100 ° of C, and continue two hours heat-up time.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (60 ° of C) of imagination.Add 50mL toluene then successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyzer (Co4), 2.33mL promotor (MMAO, the n-heptane solution of 1.93mol/L) (Al/Co=1500), residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, add acidic alcohol, in the baking oven of 60 ° of C, be dried to constant weight behind the filtration washing, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 13.21 * 10 6G ofPEmol -1(M) h -1, polymkeric substance M w=951gmol -1, M w/ M n=1.5, T m=98.7 ° of C.
Embodiment 75,
Polymeric kettle is vacuumized and be heated to 100 ° of C, and continue two hours heat-up time.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (70 ° of C) of imagination.Add 50mL toluene then successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyzer (Co4), 2.33mL promotor (MMAO, the n-heptane solution of 1.93mol/L) (Al/Co=1500), residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, add acidic alcohol, in the baking oven of 60 ° of C, be dried to constant weight behind the filtration washing, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 4.92 * 10 6G ofPEmol -1(M) h -1, polymkeric substance M w=950gmol -1, M w/ M n=1.5, T m=100.3 ° of C.
Embodiment 76,
Polymeric kettle is vacuumized and be heated to 100 ° of C, and continue two hours heat-up time.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (60 ° of C) of imagination.Add 50mL toluene then successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyzer (Co1), 2.33mL promotor (MMAO, the n-heptane solution of 1.93mol/L) (Al/Co=1500), residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, add acidic alcohol, in the baking oven of 60 ° of C, be dried to constant weight behind the filtration washing, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 8.83 * 10 6G ofPEmol -1(M) h -1, polymkeric substance M w=996gmol -1, M w/ M n=1.5, T m=100.4 ° of C.
Embodiment 77,
Polymeric kettle is vacuumized and be heated to 100 ° of C, and continue two hours heat-up time.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (60 ° of C) of imagination.Add 50mL toluene then successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyzer (Co2), 2.33mL promotor (MMAO, the n-heptane solution of 1.93mol/L) (Al/Co=1500), residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, add acidic alcohol, in the baking oven of 60 ° of C, be dried to constant weight behind the filtration washing, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 5.72 * 10 6G ofPEmol -1(M) h -1, polymkeric substance M w=2162gmol -1, M w/ M n=1.9, T m=118.4 ° of C.
Embodiment 78,
Polymeric kettle is vacuumized and be heated to 100 ° of C, and continue two hours heat-up time.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (60 ° of C) of imagination.Add 50mL toluene then successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyzer (Co3), 2.33mL promotor (MMAO, the n-heptane solution of 1.93mol/L) (Al/Co=1500), residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, add acidic alcohol, in the baking oven of 60 ° of C, be dried to constant weight behind the filtration washing, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 3.41 * 10 6G of PEmol -1(M) h -1, polymkeric substance M w=8096gmol -1, M w/ M n=3.2, T m=129.1 ° of C.
Embodiment 79,
Polymeric kettle is vacuumized and be heated to 100 ° of C, and continue two hours heat-up time.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (60 ° of C) of imagination.Add 50mL toluene then successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyzer (Co5), 2.33mL promotor (MMAO, the n-heptane solution of 1.93mol/L) (Al/Co=1500), residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, add acidic alcohol, in the baking oven of 60 ° of C, be dried to constant weight behind the filtration washing, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 7.81 * 10 6G ofPEmol -1(M) h -1, polymkeric substance M w=2052gmol -1, M w/ M n=1.9, T m=119.0 ° of C.
Embodiment 80,
Add the vinyl polymerization of depressing and use 300 milliliters of stainless steel polymeric kettles that are equipped with mechanical stirring oar and temperature-control device.Polymeric kettle is vacuumized and be heated to 100 ° of C, and continue two hours heat-up time.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (50 ° of C) of imagination.Add 50mL toluene then successively, 20mL is dissolved with the 3 μ mol catalyzer (toluene solution of Fe6,3.10mL promotor (MMAO, the n-heptane solution of 1.93mol/L) (Al/Fe=2000), residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, add acidic alcohol, in the baking oven of 60 ° of C, be dried to constant weight behind the filtration washing, obtain the 11.5g polymkeric substance, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 7.8 * 10 6G of PEmol -1(M) h -1, polymkeric substance M w=23.8Kgmol -1, M w/ M n=4.0, T m=127.4.
Embodiment 81,
Add the vinyl polymerization of depressing and use 300 milliliters of stainless steel polymeric kettles that are equipped with mechanical stirring oar and temperature-control device.Polymeric kettle is vacuumized and be heated to 100 ° of C, and continue two hours heat-up time.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (50 ° of C) of imagination.Add 50mL toluene then successively, 20mL is dissolved with the 3 μ mol catalyzer (toluene solution of Fe7,3.10mL promotor (MMAO, the n-heptane solution of 1.93mol/L) (Al/Fe=2000), residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, add acidic alcohol, in the baking oven of 60 ° of C, be dried to constant weight behind the filtration washing, obtain the 20.0g polymkeric substance, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 13.4 * 10 6G of PEmol -1(M) h -1, polymkeric substance M w=20Kgmol -1, M w/ M n=8.4, T m=124.4.
Embodiment 82,
Add the vinyl polymerization of depressing and use 300 milliliters of stainless steel polymeric kettles that are equipped with mechanical stirring oar and temperature-control device.Polymeric kettle is vacuumized and be heated to 100 ° of C, and continue two hours heat-up time.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (50 ° of C) of imagination.Add 50mL toluene then successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyzer (Fe8), 3.10mL promotor (MMAO, the n-heptane solution of 1.93mol/L) (Al/Fe=2000), residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, add acidic alcohol, in the baking oven of 60 ° of C, be dried to constant weight behind the filtration washing, obtain the 8.0g polymkeric substance, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 5.3 * 10 6G of PEmol -1(M) h -1, polymkeric substance M w=40.8Kgmol -1, M w/ M n=2.0, T m=127.4.
Embodiment 83,
Add the vinyl polymerization of depressing and use 300 milliliters of stainless steel polymeric kettles that are equipped with mechanical stirring oar and temperature-control device.Polymeric kettle is vacuumized and be heated to 100 ° of C, and continue two hours heat-up time.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (60 ° of C) of imagination.Add 50mL toluene then successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyzer (Co6), 2.05mL promotor MAO (1.46mol/L toluene solution) (Al/Co=1000), residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (5atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, add acidic alcohol, in the baking oven of 60 ° of C, be dried to constant weight behind the filtration washing, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 3.70 * 10 6G ofPEmol -1(M) h -1, polymkeric substance M w=5400gmol -1, M w/ M n=1.8, T m=124.9 ° of C.
Embodiment 84,
Add the vinyl polymerization of depressing and use 300 milliliters of stainless steel polymeric kettles that are equipped with mechanical stirring oar and temperature-control device.Polymeric kettle is vacuumized and be heated to 100 ° of C, and continue two hours heat-up time.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (60 ° of C) of imagination.Add 50mL toluene then successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyzer (Co7), 2.05mL promotor MAO (1.46mol/L toluene solution) (Al/Co=1000), residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (5atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, add acidic alcohol, in the baking oven of 60 ° of C, be dried to constant weight behind the filtration washing, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 23.21 * 10 6G ofPEmol -1(M) h -1, polymkeric substance M w=2002gmol -1, M w/ M n=1.6, T m=110.6 ° of C.
Embodiment 85,
Add the vinyl polymerization of depressing and use 300 milliliters of stainless steel polymeric kettles that are equipped with mechanical stirring oar and temperature-control device.Polymeric kettle is vacuumized and be heated to 100 ° of C, and continue two hours heat-up time.Replacing in advance under the condition of nitrogen in the still with ethene, letting polymeric kettle slowly cool to the polymerization temperature (50 ° of C) of imagination.Add 50mL toluene then successively, 20mL is dissolved with the toluene solution of 3 μ mol catalyzer (Co8), 2.05mL promotor (MMAO, the n-heptane solution of 1.93mol/L) (Al/Fe=1000), residual toluene (making that the toluene total amount is 100 milliliters).With still sealing, logical ethene is also kept the constant pressure (10atm) of ethene.After polyreaction reaches the predefined time (30min), the ethylene pressure in the still is discharged, add acidic alcohol, in the baking oven of 60 ° of C, be dried to constant weight behind the filtration washing, calculate polymerization activity according to the output of polymkeric substance.Polymerization activity: 10.4 * 10 6G ofPEmol -1(M) h -1, polymkeric substance M w=7000gmol -1, M w/ M n=1.8, T m=126.4.

Claims (10)

1.2 8-diimine-4,5,6 hydrogenated quinoline class transition metal complexes, its structural formula be suc as formula shown in the I,
Figure FDA00001741759400011
The formula I
In the formula I, R 1Be selected from hydrogen, methyl, ethyl and propyl group, R 2, R 3, R 4, R 5And R 6Be selected from hydrogen, alkyl, nitro and halogen independently of one another; M is a transition metal.
2. transition metal complex according to claim 1 is characterized in that: R 1Be selected from hydrogen, methyl and ethyl; R 2, R 3, R 4, R 5And R 6Be selected from hydrogen, methyl, ethyl, sec.-propyl, fluorine, chlorine, bromine and nitro independently of one another; M is Fe or Co.
3. the preparation method of claim 1 or 2 said transition metal complexes comprises the steps:
(1) 2-aldehyde radical shown in the formula II (ketone)-4,5, substituted aniline shown in 6-hydrogenation-8-quinolinone and the formula III react under the condition that catalyzer exists and obtain 2,8-diimine-4,5,6-hydrogenated quinoline compound;
Said 2,8-diimine-4,5, the structural formula of 6-hydrogenated quinoline compound is suc as formula shown in IV and/or the formula V;
Figure FDA00001741759400012
Formula II formula III
Figure FDA00001741759400013
Formula IV formula V
In the following formula, R 1Be selected from hydrogen, methyl, ethyl and propyl group, R 2, R 3, R 4, R 5And R 6Be selected from hydrogen, alkyl, nitro and halogen independently of one another;
(2) said 2,8-diimine-4,5,6-hydrogenated quinoline compound and MCl 2Reaction promptly gets product; M is a transition metal.
4. method according to claim 3 is characterized in that: in the step (1), said catalyzer is a tosic acid; The solvent of said reaction is a propyl carbinol; The temperature of said reaction is 110 ~ 125 ° of C, and the time is 6h ~ 20h.
5. method according to claim 3 is characterized in that: in the formula III, and R 2, R 3, R 4, R 5And R 6When being selected from fluorine or chlorine independently of one another, catalyzer is a tosic acid described in the step (1), and said solvent is a tetraethoxy, and the temperature of said reaction is 140 ~ 150 ° of C, and the time is 1 ~ 2 day.
6. according to arbitrary described method among the claim 3-5, it is characterized in that: in the step (2), MCl 2With said 2,8-diimine-4,5, the molfraction of 6-hydrogenated quinoline compound is than being (1 ~ 1.5): (1 ~ 1.2), the temperature of said reaction are 20 ~ 25 ° of C, and the time is 4 ~ 18h.
7. catalyst composition is made up of claim 1 or 2 said transition metal complexes and promotor, and said promotor is selected from one or more in aikyiaiurnirsoxan beta, alkylaluminium cpd and the chlorination aluminum alkyls.
8. compsn according to claim 7 is characterized in that: said aikyiaiurnirsoxan beta is the MAO of MAO or the modification of tertiary butyl aluminium; Said aluminum compound is trimethylaluminium, triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum or tri-n-octylaluminium; Said chlorination aluminum alkyls is diethylaluminum chloride or ethylaluminium dichloride; The molfraction of central metal M in aluminium in the said promotor and the said transition metal complex is than being (100 ~ 10000): 1.
9. claim 1 or 2 said transition metal complexes and claim 7 or the 8 said catalyst compositions application in the catalyzed ethylene polymerization reaction.
10. application according to claim 9 is characterized in that: the temperature of said ethylene polymerization is 20 ~ 100 ° of C, and pressure is 0.1 ~ 1.0MPa.
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