CN102731578B - 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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CN102731578B
CN102731578B CN201210189480.1A CN201210189480A CN102731578B CN 102731578 B CN102731578 B CN 102731578B CN 201210189480 A CN201210189480 A CN 201210189480A CN 102731578 B CN102731578 B CN 102731578B
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toluene
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ethene
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CN102731578A (en
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孙文华
张文娟
柴文斌
孔少亮
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Institute of Chemistry CAS
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Abstract

The invention discloses a 2,8-diimine-5,6,7 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)-5,6,7-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-5,6,7 hydro quinoline compound is obtained; (2) the 2,8-diimine-5,6,7 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-5,6,7-tri-hydrogen quinoline transition metal complex and preparation method thereof and application
Technical field
The present invention relates to a kind of 2,8-diimine-5,6,7-tri-hydrogen quinoline transition metal complex and preparation method thereof and application, be specially the application in catalyzed ethylene polymerization.
Background technology
Polyolefine mainly comprises polyethylene, polypropylene and poly 1-butene etc., and as the maximum product of amount, it accounts for the half of macromolecular material.And due to the material property that it is excellent, polyolefine material is widely used in all respects of producing and living.Wherein polyethylene is with fastest developing speed, that output is maximum, purposes is extremely wide synthetic resins material.And polyethylene comprises many types, wherein polyethylene be molecular weight larger more than hundreds of thousands of, be polyethylene, 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, close to High molecular weight polyethylene, obtaining because of its excellent winter hardiness, thermotolerance, chemical resistant properties and wear resistance should general application.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, remain the chromium in transition metal, vanadium, zirconium, the large metal of titanium four compound be Primary Catalysts, be aided with promotor and carrier composition catalyst system that Primary Catalysts and polyreaction adapt.And our nearest result of study shows, no matter late transition metal catalyst is preparing high density polyethylene(HDPE) or polyethylene wax has potential huge potentiality.
First in 1998, the title complex of pyridine diimine iron (II) and cobalt (II) is reported when Brookhart and Gibson is equal to, by regulating the substituting group on phenyl ring, can oligomerisation or polymerising ethylene well, its structure is such as formula (J.Am.Chem.Soc. shown in A, 1998,120,4049-4050; Chem.Commun.1998,849-850):
Afterwards, round pyridine diimine iron cobalt complex catalyst, people have carried out a large amount of research work, and improve catalyst structure.From the initial imitation to pyridine diimine iron cobalt complex catalyst model, the model of independently design and development new catalyst till now, the seminar at contriver place successfully develops a series of late transition metal catalyst model in the past 13 years.
2005, this seminar developed the composition catalyst (formula B) of 2-amido-1,10-phenanthroline iron and cobalt, and such catalyzer not only shows the activity 8.95 × 10 of high catalyzed ethylene oligomerisation 7gmol -1(Fe) h -1, have very high selectivity to alpha-olefin, oligomerization product distribution is approximate meets Schluz-Flory rule (Organometallics2006,25,666-677, Chinese Patent Application No. 200510066427.2 applying date: on April 22nd, 2005 simultaneously; Authorized announcement date: on March 5th, 2008; Authorization Notice No.: CN100372609C).This type of catalyst activity can compare favourably with classical pyridine diimine iron catalyst.
Afterwards, this seminar develops again 2-benzoglyoxaline-6-amido pyridine iron and cobalt complex catalyst (formula C), such catalyzer can highly active catalytic ethylene oligomerization and polymerization activity (Organometallics 2007,26,2720-2734, Chinese Patent Application No. 200610165446.5 applying date: on December 20th, 2006).Iron (II) title complex shows very high oligomerisation and polymerization activity to ethene, reaches 10 7g mol Fe -1h -1.Oligomerization 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 alpha-olefin is up to more than 99%; Polymkeric substance is low molecular weight polyethylene and polyethylene wax.
In above result of study, these catalyst systems highly actively can obtain high density polyethylene(HDPE), or containing some polyethylene waxs in product.In the research and development of catalyzer, exploitation high reactivity and be convenient to the core content that industrialized ethylene oligomerization and polymerizing catalyst always are Study of Novel Catalyst, although there is a various difficult problem to need to solve, but along with to the more deep research and development of new catalyst, be all can obtain more accumulation on knowwhy or design experiences.
Summary of the invention
The object of this invention is to provide a kind of 2,8-diimine-5,6,7-tri-hydrogen quinoline transition metal complex and preparation method thereof and application.
2,8-diimine-5,6,7-tri-hydrogen quinoline transition metal complexes provided by the present invention, its structural formula such as formula shown in I,
In 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 transition metal.
In 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.
Present invention also offers the preparation method of above-mentioned transition metal complex, comprise the steps:
(1) substituted aniline shown in 2-aldehyde radical shown in formula II (ketone)-5,6,7-hydrogenation-8-quinolinone and formula III carries out being obtained by reacting 2,8-diimine-5,6,7-tri-hydrogen quinoline compound under catalyzer existent condition;
The structural formula of described 2,8-diimine-5,6,7-tri-hydrogen quinoline compounds is for shown in formula IV and/or formula V;
In above 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) described 2,8-diimine-5,6,7-tri-hydrogen quinoline compound and MCl 2react and obtain product; M is transition metal.
In above-mentioned preparation method, in step (1), described catalyzer can be tosic acid; The solvent of described reaction can be propyl carbinol; The temperature of described reaction can be 110 ~ 125 DEG C, and specifically can be 110 DEG C or 125 DEG C, the time can be 6h ~ 20h, specifically can be 6h or 20h.
In above-mentioned preparation method, when in formula III, R 2, R 3, R 4, R 5and R 6when being selected from fluorine or chlorine independently of one another, described catalyzer can be tosic acid, and described solvent can be tetraethoxy, and the temperature of described reaction can be 140 ~ 150 DEG C, and the time can be 1 ~ 2 day.
In above-mentioned preparation method, in step (2), MCl 2with described 2,8-diimine-5,6, the molfraction ratio of 7-tri-hydrogen 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 described reaction can be 20 ~ 25 DEG C, and the time can be 4 ~ 18h, is preferably 4h, 10h or 18h.
The present invention still further provides a kind of catalyst composition, and it is made up of above-mentioned transition metal complex and promotor, and described promotor is selected from one or more in aikyiaiurnirsoxan beta, alkylaluminium cpd and chlorination aluminum alkyls.
In above-mentioned catalyst composition, described aikyiaiurnirsoxan beta specifically can be the methylaluminoxane (MMAO) of methylaluminoxane (MAO) or the modification of tertiary butyl aluminium; Described aluminum compound specifically can be trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum or tri-n-octylaluminium; Described chlorination aluminum alkyls specifically can be diethylaluminum chloride or ethylaluminium dichloride;
In above-mentioned catalyst composition, aluminium in described promotor can be (100 ~ 10000) with the molfraction ratio of the central metal M in described transition metal complex: 1, specifically can be (500 ~ 2500): 1,500:1,750:1,1000:1,1250:1,1500:1,1750:1,2000:1 or 2500:1.
Invention still further provides above-mentioned transition metal complex and the application of above-mentioned catalyst composition in catalyzed ethylene polymerization reaction; When catalyzed ethylene polymerization, polymerization temperature can be 20 ~ 100 DEG C, specifically can be 30 DEG C, 40 DEG C, 50 DEG C, 60 DEG C, 70 DEG C or 80 DEG C; Pressure can be 0.1 ~ 1.0MPa, specifically can be 0.5MPa or 1.0MPa.
The present invention has designed and synthesized containing N^N^N dentate 2,8 – diimines-5,6,7-tri-hydrogen quinoline transition metal complex, this metal complexes is used for catalyzed ethylene polymerization reaction, and gained polyethylene 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 prospects for commercial application widely.
Accompanying drawing explanation
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
The experimental technique used in following embodiment if no special instructions, is ordinary method.
Material used in following embodiment, reagent etc., if no special instructions, all can obtain from commercial channels.
In following embodiment, the synthesis of title complex is carried out according to following equation:
Preferably, title complex Fe1-Fe8 and Co1-Co8 of situation can be replaced 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 6iPr,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 6iPr,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=R 6=Me,16.M=Co,R 1=Et,R 2=R 6=Me,R 3=R 4=R 5=H.
The synthesis of embodiment 1,2,8-(2,6-dimethyl benzene imines)-5,6,7-tri-hydrogen quinoline (L1/L1 ') part
Raw material 2,8-5 is dropped into, 6 in 100ml two-mouth bottle, 7-hydrogenated quinoline diketone (0.189g, 0.1mmol) and 2,6-xylidine (0.302g, 0.25mmol)] and tosic acid 0.015g, backflow in propyl carbinol (30ml), after 6 hours are carried out in reaction, reaction solution concentrates, silica gel column chromatography (PE:EA=50:1, v/v), after being separated, 0.174g yellow solid is obtained, yield 44.2%.
Nuclear-magnetism shows there are two kinds of isomer, and wherein eneamines isomer is primary product, L1:L1 '=0.19:1 (detected by 1h NMR) .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.
The synthesis of embodiment 2,2,8-(2,6-diethylbenzene imines)-5,6,7-tri-hydrogen quinoline (L2/L2 ') part
Raw material 2,8-5 is dropped into, 6 in 100ml two-mouth bottle, 7--hydrogenated quinoline diketone (0.189g, 0.1mmol) and 2,6-Diethyl Aniline (0.373g, 0.25mmol) and tosic acid 0.015g, backflow in propyl carbinol (30ml), after 6 hours are carried out in reaction, reaction solution concentrates, silica gel column chromatography (PE:EA=50:1, v/v), after being separated, 0.24g yellow solid is obtained, yield 53%.
Nuclear-magnetism shows there are two kinds of isomer, and wherein eneamines isomer is primary product, L2:L2 '=0.33:1 (detected by 1h NMR) .Mp:138-139 DEG 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.for C 31H 37N 3:C,82.44,H,8.26,N,9.30;Found:C,82.44,H,8.32,N,9.15.
The synthesis of embodiment 3,2,8-(2,6-diisopropyl benzene imines)-5,6,7-tri-hydrogen quinoline (L3/L3 ') part
Raw material 2,8-5 is dropped into, 6 in 100ml two-mouth bottle, 7-hydrogenated quinoline diketone (0.189g, 0.1mmol) and 2,6-isopropyl aniline (0.443g, 0.25mmol) and tosic acid 0.015g, backflow in propyl carbinol (30ml), temperature is 110 DEG C, after 20 hours are carried out in reaction, reaction solution concentrates, after silica gel column chromatography (PE:EA=50:1, v/v) is separated, obtain 0.309g yellow solid, yield 61.0%.
Nuclear-magnetism shows there are two kinds of isomer, and wherein eneamines isomer is primary product.L3:L3’=0.3:1(detected by 1H NMR).Mp:183-184℃.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).
The synthesis of embodiment 4,2,8-(2,4,6-Three methyl Benzene imines)-5,6,7-tri-hydrogen quinoline (L4/L4 ') part
Raw material 2,8-5 is dropped into, 6 in 100ml two-mouth bottle, 7-hydrogenated quinoline diketone (0.189g, 0.1mmol) and 2,4,6-trimethylaniline (0.338g (2.5eq)] and tosic acid 0.015g, backflow in propyl carbinol (30ml), temperature is 125 DEG C, after 6 hours are carried out in reaction, reaction solution concentrates, after silica gel column chromatography (PE:EA=50:1, v/v) is separated, obtain 0.181g yellow solid, yield 43.0%.
Nuclear-magnetism shows there are two kinds of isomer, and wherein eneamines isomer is primary product.L4:L4’=0.15:1(detected by 1H NMR).FT-IR(KBr,cm -1):3366(ν 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.
The synthesis of embodiment 5,2,8-(2,6-diethyl-4-methylbenzene imines)-5,6,7-tri-hydrogen quinoline (L5/L5 ') part
Raw material 2,8-5 is dropped into, 6 in 100ml two-mouth bottle, 7-hydrogenated quinoline diketone (0.189g, 0.1mmol) and 2,6-diethyl-4-monomethylaniline (0.408g, 0.25mmol) and tosic acid 0.015g, backflow in propyl carbinol (30ml), after 6 hours are carried out in reaction, reaction solution concentrates, silica gel column chromatography (PE:EA=50:1, v/v), after being separated, 0.234g yellow solid is obtained, yield 47.0%.
Nuclear-magnetism shows there are two kinds of isomer, and wherein eneamines isomer is primary product.L5:L5’=0.23:1.Mp:98-99℃.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。
The synthesis of embodiment 6,2,8-(2,6-dichlorobenzene imines)-5,6,7-tri-hydrogen quinoline (L6) part
Raw material 2,8-5 is dropped into, 6 in 100ml two-mouth bottle, 7-hydrogenated quinoline diketone (0.189g, 0.1mmol) and 2,6-DCA (0.405,0.25mmol) and tosic acid 0.015g, backflow in propyl carbinol (30ml), after 6 hours are carried out in reaction, reaction solution concentrates, silica gel column chromatography (PE:EA=50:1, v/v), after being separated, 0.144g yellow solid is obtained, yield 30.2%.
Nuclear-magnetism shows there are two kinds of isomer, and wherein eneamines isomer is primary product.L6:L6’=0.26:FT-IR(KBr,cm -1):3359(ν 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) synthesis of quinoline 8-amino (L7/L7 ') part
Raw material 2-aldehyde radical-8 ketone-5,6,7-hydrogenated quinoline (0.175g is dropped in 100ml two-mouth bottle, 1mmol) He 2,6-xylidine (0.302g, 2.5mmol) and tosic acid 0.015g, backflow in propyl carbinol (30ml), after 6 hours are carried out in reaction, reaction solution concentrates, after silica gel column chromatography (PE:EA=50:1, v/v) is separated, obtain 0.222g yellow solid, yield 58.2%.
Nuclear-magnetism shows there are two kinds of isomer, and wherein eneamines isomer is primary product.L7:L7’=0.23:1.Mp:98-99℃.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.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.
The synthesis of embodiment 8,2,8-(2,6-dimethylimino)-5,6,7-tri-hydrogen quinoline (L8) part
Raw material 2-propionyl-8-5 is dropped into, 6,7-hydrogenated quinoline ketone (0.203g in 100ml two-mouth bottle; 1mmol) He 2; 6-xylidine (0.302g, 0.25mmol) and tosic acid 0.015g, backflow in propyl carbinol (30ml); after 6 hours are carried out in reaction; reaction solution concentrates, after silica gel column chromatography (PE:EA=50:1, v/v) is separated; obtain 0.10g yellow solid, yield 25.2%.
Nuclear-magnetism shows there are two kinds of isomer, and wherein eneamines isomer is primary product.L8:L8’=0.15:1.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.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). 13C NMR(100MHz;CDCl 3):169.1,152.9,145.2,141.5,138.9,135.5,135.0,133.9,132.2,131.2,130.1,127.2,126.7,126.6,99.3,24.7,24.6,24.5,24.3,21.4,20.9,16.9,15.2,13.8,10.9.
The preparation of embodiment 9, title complex Fe1
By the FeCl of ligand L 1/L1 ' (0.15g, 0.38mmol) and 1 equivalent 24H 2o (0.070g, 0.35mmol) be placed in Schlenk pipe, after vacuum nitrogen filling gas three times, add the dehydrated alcohol that 5ml is degassed, stirred at ambient temperature reacts 10 hours, adds anhydrous diethyl ether, has and precipitates generation in a large number, by sedimentation and filtration and with anhydrous diethyl ether washing, obtain powder (0.16g, 76.2%) after drying.
Its characterization data is as follows: FT-IR (KBr, cm -1): 2951,2914,2324,1621,1586,1468,1428,1369,1264,1242,1195,1092,1038,923,835,766.Anal.Calcd.for C 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 as shown in Figure 1.
The preparation of embodiment 10, title complex Fe2
By the FeCl of ligand L 2/L2 ' (0.158g, 0.38mmol) and 1 equivalent 24H 2o (0.070g, 0.35mmol) be placed in Schlenk pipe, after vacuum nitrogen filling gas three times, add the dehydrated alcohol that 5ml is degassed, stirred at ambient temperature reacts 4 hours, adds anhydrous diethyl ether, has and precipitates generation in a large number, by sedimentation and filtration and with anhydrous diethyl ether washing, obtain powder (0.144g, 71.4%) after drying.
Its characterization data is as follows: FT-IR (KBr, cm -1): 2967,2940,2874,2359,1608,1578,1551,1446,1421,1372,1270,1246,1188,1111,1039,867,808,777.Anal.Calcd.for C 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 as shown in Figure 2.
The preparation of embodiment 11, title complex Fe3
By the FeCl of ligand L 3/L3 ' (0.192g, 0.38mmol) and 1.2 equivalents 24H 2o (0.084g, 0.42mmol) be placed in Schlenk pipe, after vacuum nitrogen filling gas three times, add the dehydrated alcohol that 5ml is degassed, stirred at ambient temperature reacts 18 hours, adds anhydrous diethyl ether, has and precipitates generation in a large number, by sedimentation and filtration and with anhydrous diethyl ether washing, obtain blue powder (0.131g, 59.1%) after drying.
Its characterization data is as follows: FT-IR (KBr, cm -1): 2964,1864,2360,2341,1602,1577,1554,1461,1441,1364,1324,1270,1247,1186,1103,1042,924,831,801,777.Anal.Calcd.for C 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
By the FeCl of ligand L 4/L4 ' (0.15g, 0.38mmol) and 1 equivalent 24H 2o (0.070g, 0.35mmol) be placed in Schlenk pipe, after vacuum nitrogen filling gas three times, add the dehydrated alcohol that 5ml is degassed, stirred at ambient temperature reacts 10 hours, adds anhydrous diethyl ether, has and precipitates generation in a large number, by sedimentation and filtration and with anhydrous diethyl ether washing, obtain blue powder (0.106g, 55.5%) after drying.
Its characterization data is as follows: FT-IR (KBr, cm -1): 2948,2913,1359,1618,1581,1479,1416,1368,1278,1230,1153,1036,906,862,829,761.Anal.Calcd.for C 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
By the FeCl of ligand L 5/L5 ' (0.182g, 0.38mmol) and 0.67 equivalent 24H 2o (0.047g, 0.23mmol) be placed in Schlenk pipe, after vacuum nitrogen filling gas three times, add the dehydrated alcohol that 5ml is degassed, stirred at ambient temperature reacts 10 hours, adds anhydrous diethyl ether, has and precipitates generation in a large number, by sedimentation and filtration and with anhydrous diethyl ether washing, obtain blue powder (0.121g, 57.1%) after drying.
Its characterization data is as follows: FT-IR (KBr, cm -1): 2963,2926,2865,2359,1612,1577,1455,1419,1371,1268,1250,1206,1153,1036,857,829,796,760.Anal.Calcd.for C 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
By the FeCl of ligand L 6/L6 ' (0.181g, 0.38mmol) and 1 equivalent 24H 2o (0.070g, 0.35mmol) be placed in Schlenk pipe, after vacuum nitrogen filling gas three times, add the dehydrated alcohol that 5ml is degassed, stirred at ambient temperature reacts 10 hours, adds anhydrous diethyl ether, has and precipitates generation in a large number, by sedimentation and filtration and with anhydrous diethyl ether washing, obtain blue powder (0.120g, 57.1%) after drying.
Its characterization data is as follows: FT-IR (KBr, cm -1): 2963,2926,2865,2359,1612,1577,1455,1419,1371,1268,1250,1206,1153,1036,857,829,796,760.Anal.Calcd.for C 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
By the FeCl of ligand L 7/L7 ' (0.145g, 0.38mmol) and 1 equivalent 24H 2o (0.070g, 0.35mmol) be placed in Schlenk pipe, after vacuum nitrogen filling gas three times, add the dehydrated alcohol that 5ml is degassed, stirred at ambient temperature reacts 10 hours, adds anhydrous diethyl ether, has and precipitates generation in a large number, by sedimentation and filtration and with anhydrous diethyl ether washing, obtain blue powder (0.107g, 60.1%) after drying.
Its characterization data is as follows: FT-IR (KBr, cm -1): 2963,2926,2865,2359,1612,1577,1455,1419,1371,1268,1250,1206,1153,1036,857,829,796,760.Anal.Calcd.for C 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
By the FeCl of ligand L 8/L8 ' (0.156g, 0.38mmol) and 1 equivalent 24H 2o (0.070g, 0.35mmol) be placed in Schlenk pipe, after vacuum nitrogen filling gas three times, add the dehydrated alcohol that 5ml is degassed, stirred at ambient temperature reacts 10 hours, adds anhydrous diethyl ether, has and precipitates generation in a large number, by sedimentation and filtration and with anhydrous diethyl ether washing, obtain blue powder (0.122g, 65.1%) after drying.
Its characterization data is as follows: FT-IR (KBr, cm -1): 2963,2926,2865,2359,1612,1577,1455,1419,1371,1268,1250,1206,1153,1036,857,829,796,760.Anal.Calcd.for C 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
By the CoCl of ligand L 1/L1 ' (0.15g, 0.38mmol) and 1 equivalent 2(0.045g, 0.35mmol) be placed in Schlenk pipe, after vacuum nitrogen filling gas three times, add the dehydrated alcohol that 5ml is degassed, stirred at ambient temperature reacts 10 hours, adds anhydrous diethyl ether, have and precipitate generation in a large number, by sedimentation and filtration and with anhydrous diethyl ether washing, obtain powder, (0.126g, 68.5%) after drying.
Its characterization data is as follows: 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 as shown in Figure 3.
The preparation of embodiment 18, title complex Co2
By the CoCl of ligand L 2/L2 ' (0.158g, 0.38mmol) and 1 equivalent 2(0.045g, 0.35mmol) be placed in Schlenk pipe, after vacuum nitrogen filling gas three times, add the dehydrated alcohol that 5ml is degassed, stirred at ambient temperature reacts 10 hours, adds anhydrous diethyl ether, has and precipitates generation in a large number, by sedimentation and filtration and with anhydrous diethyl ether washing, obtain powder (0.132g, 65.0%) after drying.
Its characterization data is as follows: 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 as shown in Figure 4.
The preparation of embodiment 19, title complex Co3
By the CoCl of ligand L 3/L3 ' (0.192g, 0.38mmol) and 1 equivalent 2(0.045g, 0.35mmol) be placed in Schlenk pipe, after vacuum nitrogen filling gas three times, add the dehydrated alcohol that 5ml is degassed, stirred at ambient temperature reacts 10 hours, adds anhydrous diethyl ether, has and precipitates generation in a large number, by sedimentation and filtration and with anhydrous diethyl ether washing, obtain powder (0.130g, 58.5%) after drying.
Its characterization data is as follows: 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
By the CoCl of ligand L 4/L4 ' (0.15g, 0.38mmol) and 1 equivalent 2(0.045g, 0.35mmol) be placed in Schlenk pipe, after vacuum nitrogen filling gas three times, add the dehydrated alcohol that 5ml is degassed, stirred at ambient temperature reacts 10 hours, adds anhydrous diethyl ether, has and precipitates generation in a large number, by sedimentation and filtration and with anhydrous diethyl ether washing, obtain powder (0.165g, 85.6%) after drying.
Its characterization data is as follows: 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
By the CoCl of ligand L 5/L5 ' (0.182g, 0.38mmol) and 1 equivalent 2(0.045g, 0.35mmol) be placed in Schlenk pipe, after vacuum nitrogen filling gas three times, add the dehydrated alcohol that 5ml is degassed, stirred at ambient temperature reacts 10 hours, adds anhydrous diethyl ether, has and precipitates generation in a large number, by sedimentation and filtration and with anhydrous diethyl ether washing, obtain yellow powder (0.169g, 79.1%) after drying.
Its characterization data is as follows: 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 as shown in Figure 5.
The preparation of embodiment 22, title complex Co6
By the CoCl of ligand L 6/L6 ' (0.181g, 0.38mmol) and 1 equivalent 2(0.045g, 0.35mmol) be placed in Schlenk pipe, after vacuum nitrogen filling gas three times, add the dehydrated alcohol that 5ml is degassed, stirred at ambient temperature reacts 10 hours, adds anhydrous diethyl ether, has and precipitates generation in a large number, by sedimentation and filtration and with anhydrous diethyl ether washing, obtain yellow powder (0.168g, 79.5%) after drying.
Its characterization data is as follows: 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
By the CoCl of ligand L 7/L7 ' (0.145g, 0.38mmol) and 1 equivalent 2(0.045g, 0.35mmol) be placed in Schlenk pipe, after vacuum nitrogen filling gas three times, add the dehydrated alcohol that 5ml is degassed, stirred at ambient temperature reacts 10 hours, adds anhydrous diethyl ether, has and precipitates generation in a large number, by sedimentation and filtration and with anhydrous diethyl ether washing, obtain yellow powder (0.143g, 80%) after drying.
Its characterization data is as follows: 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
By the CoCl of ligand L 8/L8 ' (0.156g, 0.38mmol) and 1 equivalent 2(0.045g, 0.35mmol) be placed in Schlenk pipe, after vacuum nitrogen filling gas three times, add the dehydrated alcohol that 5ml is degassed, stirred at ambient temperature reacts 10 hours, adds anhydrous diethyl ether, has and precipitates generation in a large number, by sedimentation and filtration and with anhydrous diethyl ether washing, obtain yellow powder (0.123g, 65.5%) after drying.
Its characterization data is as follows: 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 is the embodiment utilizing the title complex of above-mentioned preparation to carry out catalyzed ethylene polymerization.
Embodiment 25,
The vinyl polymerization adding pressure uses the 300 milliliters of stainless steel polymeric kettles being equipped with mechanical stirring oar and temperature-control device.Vacuumized by polymeric kettle and be heated to 100 DEG C, heat-up time continues two hours.Under the condition of replacing nitrogen in still in advance with ethene, polymeric kettle is allowed to slowly cool to the polymerization temperature (30 DEG C) of imagination.Then 50mL toluene is added successively, 20mL is dissolved with the toluene solution of 3 μm of ol catalyzer (Fe3), 2.05mL promotor (MAO, 1.46mol/L toluene solution) (Al/Fe=1000), residual toluene (making toluene total amount be 100 milliliters).Closed by still, logical ethene also maintains the constant pressure (10atm) of ethene.After reaching in polyreaction the time (30min) preset, by the ethylene pressure release in still, add acidic alcohol, after filtration washing, in the baking oven of 60 DEG C, be dried to constant weight, obtain 2.45g polymkeric substance, according to the Production rate polymerization activity of polymkeric substance.Polymerization activity: 1.63 × 10 6g of PEmol -1(M) h -1, polymkeric substance M w=203.4Kgmol -1, M w/ M n=3.4, T m=135.5.
Embodiment 26,
The vinyl polymerization adding pressure uses the 300 milliliters of stainless steel polymeric kettles being equipped with mechanical stirring oar and temperature-control device.Vacuumized by polymeric kettle and be heated to 100 DEG C, heat-up time continues two hours.Under the condition of replacing nitrogen in still in advance with ethene, polymeric kettle is allowed to slowly cool to the polymerization temperature (30 DEG C) of imagination.Then 50mL toluene is added successively, 20mL is dissolved with the toluene solution of 3 μm of ol catalyzer (Fe3), 3.08mL promotor (MAO, 1.46mol/L toluene solution) (Al/Fe=1500), residual toluene (making toluene total amount be 100 milliliters).Closed by still, logical ethene also maintains the constant pressure (10atm) of ethene.After reaching in polyreaction the time (30min) preset, by the ethylene pressure release in still, add acidic alcohol, after filtration washing, in the baking oven of 60 DEG C, be dried to constant weight, obtain 3.12g polymkeric substance, according to the Production rate polymerization activity of polymkeric substance.Polymerization activity: 2.08 × 10 6g of PEmol -1(M) h -1, polymkeric substance M w=132.9Kgmol -1, M w/ M n=8.5, T m=133.3.
Embodiment 27,
The vinyl polymerization adding pressure uses the 300 milliliters of stainless steel polymeric kettles being equipped with mechanical stirring oar and temperature-control device.Vacuumized by polymeric kettle and be heated to 100 DEG C, heat-up time continues two hours.Under the condition of replacing nitrogen in still in advance with ethene, polymeric kettle is allowed to slowly cool to the polymerization temperature (30 DEG C) of imagination.Then 50mL toluene is added successively, 20mL is dissolved with the toluene solution of 3 μm of ol catalyzer (Fe3), 4.10mL promotor (MAO, 1.46mol/L toluene solution) (Al/Fe=2000), residual toluene (making toluene total amount be 100 milliliters).Closed by still, logical ethene also maintains the constant pressure (10atm) of ethene.After reaching in polyreaction the time (30min) preset, by the ethylene pressure release in still, add acidic alcohol, after filtration washing, in the baking oven of 60 DEG C, be dried to constant weight, obtain 4.90g polymkeric substance, according to the Production rate polymerization activity of polymkeric substance.Polymerization activity: 3.27 × 10 6g of PEmol -1(M) h -1, polymkeric substance M w=174.5Kgmol -1, M w/ M n=32.5, T m=130.6.
Embodiment 28,
The vinyl polymerization adding pressure uses the 300 milliliters of stainless steel polymeric kettles being equipped with mechanical stirring oar and temperature-control device.Vacuumized by polymeric kettle and be heated to 100 DEG C, heat-up time continues two hours.Under the condition of replacing nitrogen in still in advance with ethene, polymeric kettle is allowed to slowly cool to the polymerization temperature (30 DEG C) of imagination.Then 50mL toluene is added successively, 20mL is dissolved with the toluene solution of 3 μm of ol catalyzer (Fe3), 5.14mL promotor (MAO, 1.46mol/L toluene solution) (Al/Fe=2500), residual toluene (making toluene total amount be 100 milliliters).Closed by still, logical ethene also maintains the constant pressure (10atm) of ethene.After reaching in polyreaction the time (30min) preset, by the ethylene pressure release in still, add acidic alcohol, after filtration washing, in the baking oven of 60 DEG C, be dried to constant weight, obtain 3.79g polymkeric substance, according to the Production rate polymerization activity 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,
The vinyl polymerization adding pressure uses the 300 milliliters of stainless steel polymeric kettles being equipped with mechanical stirring oar and temperature-control device.Vacuumized by polymeric kettle and be heated to 100 DEG C, heat-up time continues two hours.Under the condition of replacing nitrogen in still in advance with ethene, polymeric kettle is allowed to slowly cool to the polymerization temperature (40 DEG C) of imagination.Then 50mL toluene is added successively, 20mL is dissolved with the toluene solution of 3 μm of ol catalyzer (Fe3), 4.10mL promotor MAO (1.46mol/L toluene solution) (Al/Fe=2000), residual toluene (making toluene total amount be 100 milliliters).Closed by still, logical ethene also maintains the constant pressure (10atm) of ethene.After reaching in polyreaction the time (30min) preset, by the ethylene pressure release in still, add acidic alcohol, after filtration washing, in the baking oven of 60 DEG C, be dried to constant weight, obtain 5.95g polymkeric substance, according to the Production rate polymerization activity of polymkeric substance.Polymerization activity: 3.97 × 10 6g of PEmol -1(M) h -1, polymkeric substance M w=77.0Kgmol -1, M w/ M n=23.5, T m=128.
Embodiment 30,
The vinyl polymerization adding pressure uses the 300 milliliters of stainless steel polymeric kettles being equipped with mechanical stirring oar and temperature-control device.Vacuumized by polymeric kettle and be heated to 100 DEG C, heat-up time continues two hours.Under the condition of replacing nitrogen in still in advance with ethene, polymeric kettle is allowed to slowly cool to the polymerization temperature (50 DEG C) of imagination.Then 50mL toluene is added successively, 20mL is dissolved with the toluene solution of 3 μm of ol catalyzer (Fe3), 4.10mL promotor MAO (1.46mol/L toluene solution) (Al/Fe=2000), residual toluene (making toluene total amount be 100 milliliters).Closed by still, logical ethene also maintains the constant pressure (10atm) of ethene.After reaching in polyreaction the time (30min) preset, by the ethylene pressure release in still, add acidic alcohol, after filtration washing, in the baking oven of 60 DEG C, be dried to constant weight, obtain 13.2g polymkeric substance, according to the Production rate polymerization activity of polymkeric substance.Polymerization activity: 8.80 × 10 6g of PEmol -1(M) h -1, polymkeric substance M w=121.6Kgmol -1, M w/ M n=13.9, T m=130.7.
Embodiment 31,
The vinyl polymerization adding pressure uses the 300 milliliters of stainless steel polymeric kettles being equipped with mechanical stirring oar and temperature-control device.Vacuumized by polymeric kettle and be heated to 100 DEG C, heat-up time continues two hours.Under the condition of replacing nitrogen in still in advance with ethene, polymeric kettle is allowed to slowly cool to the polymerization temperature (60 DEG C) of imagination.Then 50mL toluene is added successively, 20mL is dissolved with the toluene solution of 3 μm of ol catalyzer (Fe3), 4.10mL promotor MAO (1.46mol/L toluene solution) (Al/Fe=2000), residual toluene (making toluene total amount be 100 milliliters).Closed by still, logical ethene also maintains the constant pressure (10atm) of ethene.After reaching in polyreaction the time (30min) preset, by the ethylene pressure release in still, add acidic alcohol, after filtration washing, in the baking oven of 60 DEG C, be dried to constant weight, obtain 11.0g polymkeric substance, according to the Production rate polymerization activity of polymkeric substance.Polymerization activity: 7.34 × 10 6g of PEmol -1(M) h -1, polymkeric substance M w=13.3Kgmol -1, M w/ M n=2.8, T m=128.1.
Embodiment 32,
The vinyl polymerization adding pressure uses the 300 milliliters of stainless steel polymeric kettles being equipped with mechanical stirring oar and temperature-control device.Vacuumized by polymeric kettle and be heated to 100 DEG C, heat-up time continues two hours.Under the condition of replacing nitrogen in still in advance with ethene, polymeric kettle is allowed to slowly cool to the polymerization temperature (80 DEG C) of imagination.Then 50mL toluene is added successively, 20mL is dissolved with the toluene solution of 3 μm of ol catalyzer (Fe3), 4.10mL promotor MAO (1.46mol/L toluene solution) (Al/Fe=2000), residual toluene (making toluene total amount be 100 milliliters).Closed by still, logical ethene also maintains the constant pressure (10atm) of ethene.After reaching in polyreaction the time (30min) preset, by the ethylene pressure release in still, add acidic alcohol, after filtration washing, in the baking oven of 60 DEG C, be dried to constant weight, obtain 10.2g polymkeric substance, according to the Production rate polymerization activity of polymkeric substance.Polymerization activity: 6.81 × 10 6g of PEmol -1(M) h -1, polymkeric substance M w=18.5Kgmol -1, M w/ M n=4.3, T m=127.6.
Embodiment 33,
The vinyl polymerization adding pressure uses the 300 milliliters of stainless steel polymeric kettles being equipped with mechanical stirring oar and temperature-control device.Vacuumized by polymeric kettle and be heated to 100 DEG C, heat-up time continues two hours.Under the condition of replacing nitrogen in still in advance with ethene, polymeric kettle is allowed to slowly cool to the polymerization temperature (50 DEG C) of imagination.Then 50mL toluene is added successively, 20mL is dissolved with the toluene solution of 3 μm of ol catalyzer (Fe1), 4.10mL promotor MAO (1.46mol/L toluene solution) (Al/Fe=2000), residual toluene (making toluene total amount be 100 milliliters).Closed by still, logical ethene also maintains the constant pressure (10atm) of ethene.After reaching in polyreaction the time (30min) preset, by the ethylene pressure release in still, add acidic alcohol, after filtration washing, in the baking oven of 60 DEG C, be dried to constant weight, obtain 8.41g polymkeric substance, according to the Production rate polymerization activity of polymkeric substance.Polymerization activity: 5.61 × 10 6g of PEmol -1(M) h -1, polymkeric substance M w=22.8Kgmol -1, M w/ M n=4.7, T m=128.7.
Embodiment 34,
The vinyl polymerization adding pressure uses the 300 milliliters of stainless steel polymeric kettles being equipped with mechanical stirring oar and temperature-control device.Vacuumized by polymeric kettle and be heated to 100 DEG C, heat-up time continues two hours.Under the condition of replacing nitrogen in still in advance with ethene, polymeric kettle is allowed to slowly cool to the polymerization temperature (50 DEG C) of imagination.Then 50mL toluene is added successively, 20mL is dissolved with the toluene solution of 3 μm of ol catalyzer (Fe2), 4.10mL promotor MAO (1.46mol/L toluene solution) (Al/Fe=2000), residual toluene (making toluene total amount be 100 milliliters).Closed by still, logical ethene also maintains the constant pressure (10atm) of ethene.After reaching in polyreaction the time (30min) preset, by the ethylene pressure release in still, add acidic alcohol, after filtration washing, in the baking oven of 60 DEG C, be dried to constant weight, obtain 23.4g polymkeric substance, according to the Production rate polymerization activity of polymkeric substance.Polymerization activity: 15.6 × 10 6g of PEmol -1(M) h -1, polymkeric substance M w=22.7Kgmol -1, M w/ M n=6.3, T m=129.9.
Embodiment 35,
The vinyl polymerization adding pressure uses the 300 milliliters of stainless steel polymeric kettles being equipped with mechanical stirring oar and temperature-control device.Vacuumized by polymeric kettle and be heated to 100 DEG C, heat-up time continues two hours.Under the condition of replacing nitrogen in still in advance with ethene, polymeric kettle is allowed to slowly cool to the polymerization temperature (50 DEG C) of imagination.Then 50mL toluene is added successively, 20mL is dissolved with the toluene solution of 3 μm of ol catalyzer (Fe4), 4.10mL promotor MAO (1.46mol/L toluene solution) (Al/Fe=2000), residual toluene (making toluene total amount be 100 milliliters).Closed by still, logical ethene also maintains the constant pressure (10atm) of ethene.After reaching in polyreaction the time (30min) preset, by the ethylene pressure release in still, add acidic alcohol, after filtration washing, in the baking oven of 60 DEG C, be dried to constant weight, obtain 8.34g polymkeric substance, according to the Production rate polymerization activity of polymkeric substance.Polymerization activity: 5.56 × 10 6g of PEmol -1(M) h -1, polymkeric substance M w=31.5Kgmol -1, M w/ M n=7.2, T m=128.6.
Embodiment 36,
The vinyl polymerization adding pressure uses the 300 milliliters of stainless steel polymeric kettles being equipped with mechanical stirring oar and temperature-control device.Vacuumized by polymeric kettle and be heated to 100 DEG C, heat-up time continues two hours.Under the condition of replacing nitrogen in still in advance with ethene, polymeric kettle is allowed to slowly cool to the polymerization temperature (50 DEG C) of imagination.Then 50mL toluene is added successively, 20mL is dissolved with the toluene solution of 3 μm of ol catalyzer (Fe5), 4.10mL promotor MAO (1.46mol/L toluene solution) (Al/Fe=2000), residual toluene (making toluene total amount be 100 milliliters).Closed by still, logical ethene also maintains the constant pressure (10atm) of ethene.After reaching in polyreaction the time (30min) preset, by the ethylene pressure release in still, add acidic alcohol, after filtration washing, in the baking oven of 60 DEG C, be dried to constant weight, obtain 12.4g polymkeric substance, according to the Production rate polymerization activity of polymkeric substance.Polymerization activity: 8.25 × 10 6g of PEmol -1(M) h -1, polymkeric substance M w=29.7Kgmol -1, M w/ M n=5.3, T m=129.8.
Embodiment 37,
The vinyl polymerization adding pressure uses the 300 milliliters of stainless steel polymeric kettles being equipped with mechanical stirring oar and temperature-control device.Vacuumized by polymeric kettle and be heated to 100 DEG C, heat-up time continues two hours.Under the condition of replacing nitrogen in still in advance with ethene, polymeric kettle is allowed to slowly cool to the polymerization temperature (30 DEG C) of imagination.Then 50mL toluene is added successively, 20mL is dissolved with the toluene solution of 3 μm of ol catalyzer (Fe3), 1.55mL promotor (MMAO, the n-heptane solution of 1.93mol/L) (Al/Fe=1000), residual toluene (making toluene total amount be 100 milliliters).Closed by still, logical ethene also maintains the constant pressure (10atm) of ethene.After reaching in polyreaction the time (30min) preset, by the ethylene pressure release in still, add acidic alcohol, after filtration washing, in the baking oven of 60 DEG C, be dried to constant weight, obtain 2.91g polymkeric substance, according to the Production rate polymerization activity of polymkeric substance.Polymerization activity: 1.94 × 10 6g of PEmol -1(M) h -1, polymkeric substance M w=37.8Kgmol -1, M w/ M n=28.0, T m=123.6.
Embodiment 38,
The vinyl polymerization adding pressure uses the 300 milliliters of stainless steel polymeric kettles being equipped with mechanical stirring oar and temperature-control device.Vacuumized by polymeric kettle and be heated to 100 DEG C, heat-up time continues two hours.Under the condition of replacing nitrogen in still in advance with ethene, polymeric kettle is allowed to slowly cool to the polymerization temperature (30 DEG C) of imagination.Then 50mL toluene is added successively, 20mL is dissolved with the toluene solution of 3 μm of ol catalyzer (Fe3), 2.33mL promotor (n-heptane solution of MMAO, 1.93mol/L) (/Fe=1500), residual toluene (making toluene total amount be 100 milliliters).Closed by still, logical ethene also maintains the constant pressure (10atm) of ethene.After reaching in polyreaction the time (30min) preset, by the ethylene pressure release in still, add acidic alcohol, after filtration washing, in the baking oven of 60 DEG C, be dried to constant weight, obtain 4.72g polymkeric substance, according to the Production rate polymerization activity 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/
The vinyl polymerization adding pressure uses the 300 milliliters of stainless steel polymeric kettles being equipped with mechanical stirring oar and temperature-control device.Vacuumized by polymeric kettle and be heated to 100 DEG C, heat-up time continues two hours.Under the condition of replacing nitrogen in still in advance with ethene, polymeric kettle is allowed to slowly cool to the polymerization temperature (30 DEG C) of imagination.Then 50mL toluene is added successively, 20mL is dissolved with the toluene solution of 3 μm of ol catalyzer (Fe3), 3.10mL promotor (MMAO, the n-heptane solution of 1.93mol/L) (Al/Fe=2000), residual toluene (making toluene total amount be 100 milliliters).Closed by still, logical ethene also maintains the constant pressure (10atm) of ethene.After reaching in polyreaction the time (30min) preset, by the ethylene pressure release in still, add acidic alcohol, after filtration washing, in the baking oven of 60 DEG C, be dried to constant weight, obtain 6.49g polymkeric substance, according to the Production rate polymerization activity 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,
The vinyl polymerization adding pressure uses the 300 milliliters of stainless steel polymeric kettles being equipped with mechanical stirring oar and temperature-control device.Vacuumized by polymeric kettle and be heated to 100 DEG C, heat-up time continues two hours.Under the condition of replacing nitrogen in still in advance with ethene, polymeric kettle is allowed to slowly cool to the polymerization temperature (30 DEG C) of imagination.Then 50mL toluene is added successively, 20mL is dissolved with the toluene solution of 3 μm of ol catalyzer (Fe3), 3.89mL promotor (n-heptane solution of MMAO, 1.93mol/L) Al/Fe=2500), residual toluene (making toluene total amount be 100 milliliters).Closed by still, logical ethene also maintains the constant pressure (10atm) of ethene.After reaching in polyreaction the time (30min) preset, by the ethylene pressure release in still, add acidic alcohol, after filtration washing, in the baking oven of 60 DEG C, be dried to constant weight, obtain 6.00g polymkeric substance, according to the Production rate polymerization activity of polymkeric substance.Polymerization activity: 4.00 × 10 6g of PEmol -1(M) h -1, polymkeric substance M w=8.1Kgmol -1, M w/ M n=5.7, T m=120.5.
Embodiment 41,
The vinyl polymerization adding pressure uses the 300 milliliters of stainless steel polymeric kettles being equipped with mechanical stirring oar and temperature-control device.Vacuumized by polymeric kettle and be heated to 100 DEG C, heat-up time continues two hours.Under the condition of replacing nitrogen in still in advance with ethene, polymeric kettle is allowed to slowly cool to the polymerization temperature (40 DEG C) of imagination.Then 50mL toluene is added successively, 20mL is dissolved with the toluene solution of 3 μm of ol catalyzer (Fe3), 3.10mL promotor (MMAO, the n-heptane solution of 1.93mol/L) (Al/Fe=2000), residual toluene (making toluene total amount be 100 milliliters).Closed by still, logical ethene also maintains the constant pressure (10atm) of ethene.After reaching in polyreaction the time (30min) preset, by the ethylene pressure release in still, add acidic alcohol, after filtration washing, in the baking oven of 60 DEG C, be dried to constant weight, obtain 7.04g polymkeric substance, according to the Production rate polymerization activity 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,
The vinyl polymerization adding pressure uses the 300 milliliters of stainless steel polymeric kettles being equipped with mechanical stirring oar and temperature-control device.Vacuumized by polymeric kettle and be heated to 100 DEG C, heat-up time continues two hours.Under the condition of replacing nitrogen in still in advance with ethene, polymeric kettle is allowed to slowly cool to the polymerization temperature (50 DEG C) of imagination.Then add 50mL toluene successively, 20mL is dissolved with 3 μthe toluene solution of mol catalyzer (Fe3), 3.10mL promotor (n-heptane solution of MMAO, 1.93mol/L) (Al/Fe=2000), residual toluene (making toluene total amount be 100 milliliters).Closed by still, logical ethene also maintains the constant pressure (10atm) of ethene.After reaching in polyreaction the time (30min) preset, by the ethylene pressure release in still, add acidic alcohol, after filtration washing, in the baking oven of 60 DEG C, be dried to constant weight, obtain 22.3g polymkeric substance, according to the Production rate polymerization activity of polymkeric substance.Polymerization activity: 14.8 × 10 6g of PEmol -1(M) h -1, polymkeric substance M w=32.7Kgmol -1, M w/ M n=8.9, T m=128.2.
Embodiment 43,
The vinyl polymerization adding pressure uses the 300 milliliters of stainless steel polymeric kettles being equipped with mechanical stirring oar and temperature-control device.Vacuumized by polymeric kettle and be heated to 100 DEG C, heat-up time continues two hours.Under the condition of replacing nitrogen in still in advance with ethene, polymeric kettle is allowed to slowly cool to the polymerization temperature (60 DEG C) of imagination.Then 50mL toluene is added successively, 20mL is dissolved with the toluene solution of 3 μm of ol catalyzer (Fe3), 3.10mL promotor (MMAO, the n-heptane solution of 1.93mol/L) (Al/Fe=2000), residual toluene (making toluene total amount be 100 milliliters).Closed by still, logical ethene also maintains the constant pressure (10atm) of ethene.After reaching in polyreaction the time (30min) preset, by the ethylene pressure release in still, add acidic alcohol, after filtration washing, in the baking oven of 60 DEG C, be dried to constant weight, obtain 18.9g polymkeric substance, according to the Production rate polymerization activity of polymkeric substance.Polymerization activity: 12.6 × 10 6g of PEmol -1(M) h -1, polymkeric substance M w=29.9Kgmol -1, M w/ M n=8.9, T m=127.7.
Embodiment 44,
The vinyl polymerization adding pressure uses the 300 milliliters of stainless steel polymeric kettles being equipped with mechanical stirring oar and temperature-control device.Vacuumized by polymeric kettle and be heated to 100 DEG C, heat-up time continues two hours.Under the condition of replacing nitrogen in still in advance with ethene, polymeric kettle is allowed to slowly cool to the polymerization temperature (70 DEG C) of imagination.Then 50mL toluene is added successively, 20mL is dissolved with the toluene solution of 3 μm of ol catalyzer (Fe3), 3.10mL promotor (MMAO, the n-heptane solution of 1.93mol/L) (Al/Fe=2000), residual toluene (making toluene total amount be 100 milliliters).Closed by still, logical ethene also maintains the constant pressure (10atm) of ethene.After reaching in polyreaction the time (30min) preset, by the ethylene pressure release in still, add acidic alcohol, after filtration washing, in the baking oven of 60 DEG C, be dried to constant weight, obtain 17.3g polymkeric substance, according to the Production rate polymerization activity of polymkeric substance.Polymerization activity: 11.5 × 10 6g of PEmol -1(M) h -1, polymkeric substance M w=15.1Kgmol -1, M w/ M n=4.5, T m=127.2.
Embodiment 45,
The vinyl polymerization adding pressure uses the 300 milliliters of stainless steel polymeric kettles being equipped with mechanical stirring oar and temperature-control device.Vacuumized by polymeric kettle and be heated to 100 DEG C, heat-up time continues two hours.Under the condition of replacing nitrogen in still in advance with ethene, polymeric kettle is allowed to slowly cool to the polymerization temperature (50 DEG C) of imagination.Then 50mL toluene is added successively, 20mL is dissolved with 3 μm of ol catalyzer (toluene solutions of Fe1,3.10mL promotor (n-heptane solution of MMAO, 1.93mol/L) (Al/Fe=2000), residual toluene (making toluene total amount be 100 milliliters).Closed by still, logical ethene also maintains the constant pressure (10atm) of ethene.After reaching in polyreaction the time (30min) preset, by the ethylene pressure release in still, add acidic alcohol, after filtration washing, in the baking oven of 60 DEG C, be dried to constant weight, obtain 22.5g polymkeric substance, according to the Production rate polymerization activity 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,
The vinyl polymerization adding pressure uses the 300 milliliters of stainless steel polymeric kettles being equipped with mechanical stirring oar and temperature-control device.Vacuumized by polymeric kettle and be heated to 100 DEG C, heat-up time continues two hours.Under the condition of replacing nitrogen in still in advance with ethene, polymeric kettle is allowed to slowly cool to the polymerization temperature (50 DEG C) of imagination.Then 50mL toluene is added successively, 20mL is dissolved with 3 μm of ol catalyzer (toluene solutions of Fe2,3.10mL promotor (n-heptane solution of MMAO, 1.93mol/L) (Al/Fe=2000), residual toluene (making toluene total amount be 100 milliliters).Closed by still, logical ethene also maintains the constant pressure (10atm) of ethene.After reaching in polyreaction the time (30min) preset, by the ethylene pressure release in still, add acidic alcohol, after filtration washing, in the baking oven of 60 DEG C, be dried to constant weight, obtain 14.7g polymkeric substance, according to the Production rate polymerization activity 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,
The vinyl polymerization adding pressure uses the 300 milliliters of stainless steel polymeric kettles being equipped with mechanical stirring oar and temperature-control device.Vacuumized by polymeric kettle and be heated to 100 DEG C, heat-up time continues two hours.Under the condition of replacing nitrogen in still in advance with ethene, polymeric kettle is allowed to slowly cool to the polymerization temperature (50 DEG C) of imagination.Then 50mL toluene is added successively, 20mL is dissolved with 3 μm of ol catalyzer (toluene solutions of Fe4,3.10mL promotor (n-heptane solution of MMAO, 1.93mol/L) (Al/Fe=2000), residual toluene (making toluene total amount be 100 milliliters).Closed by still, logical ethene also maintains the constant pressure (10atm) of ethene.After reaching in polyreaction the time (30min) preset, by the ethylene pressure release in still, add acidic alcohol, after filtration washing, in the baking oven of 60 DEG C, be dried to constant weight, obtain 23.0g polymkeric substance, according to the Production rate polymerization activity 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,
The vinyl polymerization adding pressure uses the 300 milliliters of stainless steel polymeric kettles being equipped with mechanical stirring oar and temperature-control device.Vacuumized by polymeric kettle and be heated to 100 DEG C, heat-up time continues two hours.Under the condition of replacing nitrogen in still in advance with ethene, polymeric kettle is allowed to slowly cool to the polymerization temperature (50 DEG C) of imagination.Then 50mL toluene is added successively, 20mL is dissolved with 3 μm of ol catalyzer (toluene solutions of Fe5,3.10mL promotor (n-heptane solution of MMAO, 1.93mol/L) (Al/Fe=2000), residual toluene (making toluene total amount be 100 milliliters).Closed by still, logical ethene also maintains the constant pressure (10atm) of ethene.After reaching in polyreaction the time (30min) preset, by the ethylene pressure release in still, add acidic alcohol, after filtration washing, in the baking oven of 60 DEG C, be dried to constant weight, obtain 20.3g polymkeric substance, according to the Production rate polymerization activity 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,
The vinyl polymerization adding pressure uses the 300 milliliters of stainless steel polymeric kettles being equipped with mechanical stirring oar and temperature-control device.Vacuumized by polymeric kettle and be heated to 100 DEG C, heat-up time continues two hours.Under the condition of replacing nitrogen in still in advance with ethene, polymeric kettle is allowed to slowly cool to the polymerization temperature (50 DEG C) of imagination.Then 50mL toluene is added successively, 20mL is dissolved with the toluene solution of 3 μm of ol catalyzer (Fe3), 3.10mL promotor (MMAO, the n-heptane solution of 1.93mol/L) (Al/Fe=2000), residual toluene (making toluene total amount be 100 milliliters).Closed by still, logical ethene also maintains the constant pressure (10atm) of ethene.After reaching in polyreaction the time (15min) preset, by the ethylene pressure release in still, add acidic alcohol, after filtration washing, in the baking oven of 60 DEG C, be dried to constant weight, obtain 18.0g polymkeric substance, according to the Production rate polymerization activity 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,
The vinyl polymerization adding pressure uses the 300 milliliters of stainless steel polymeric kettles being equipped with mechanical stirring oar and temperature-control device.Vacuumized by polymeric kettle and be heated to 100 DEG C, heat-up time continues two hours.Under the condition of replacing nitrogen in still in advance with ethene, polymeric kettle is allowed to slowly cool to the polymerization temperature (50 DEG C) of imagination.Then 50mL toluene is added successively, 20mL is dissolved with the toluene solution of 3 μm of ol catalyzer (Fe3), 3.10mL promotor (MMAO, the n-heptane solution of 1.93mol/L) (Al/Fe=2000), residual toluene (making toluene total amount be 100 milliliters).Closed by still, logical ethene also maintains the constant pressure (10atm) of ethene.After reaching in polyreaction the time (40min) preset, by the ethylene pressure release in still, add acidic alcohol, after filtration washing, in the baking oven of 60 DEG C, be dried to constant weight, obtain 28.0g polymkeric substance, according to the Production rate polymerization activity 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,
The vinyl polymerization adding pressure uses the 300 milliliters of stainless steel polymeric kettles being equipped with mechanical stirring oar and temperature-control device.Vacuumized by polymeric kettle and be heated to 100 DEG C, heat-up time continues two hours.Under the condition of replacing nitrogen in still in advance with ethene, polymeric kettle is allowed to slowly cool to the polymerization temperature (50 DEG C) of imagination.Then 50mL toluene is added successively, 20mL is dissolved with the toluene solution of 3 μm of ol catalyzer (Co4), 1.03mL promotor MAO (1.46mol/L toluene solution) (Al/Co=500), residual toluene (making toluene total amount be 100 milliliters).Closed by still, logical ethene also maintains the constant pressure (10atm) of ethene.After reaching in polyreaction the time (30min) preset, by the ethylene pressure release in still, add acidic alcohol, after filtration washing, in the baking oven of 60 DEG C, be dried to constant weight, according to the Production rate polymerization activity of polymkeric substance.Polymerization activity: 9.29 × 10 6g of PEmol -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 pressure uses the 300 milliliters of stainless steel polymeric kettles being equipped with mechanical stirring oar and temperature-control device.Vacuumized by polymeric kettle and be heated to 100 DEG C, heat-up time continues two hours.Under the condition of replacing nitrogen in still in advance with ethene, polymeric kettle is allowed to slowly cool to the polymerization temperature (50 DEG C) of imagination.Then 50mL toluene is added successively, 20mL is dissolved with the toluene solution of 3 μm of ol catalyzer (Co4), 1.54mL promotor MAO (1.46mol/L toluene solution) (Al/Co=750), residual toluene (making toluene total amount be 100 milliliters).Closed by still, logical ethene also maintains the constant pressure (10atm) of ethene.After reaching in polyreaction the time (30min) preset, by the ethylene pressure release in still, add acidic alcohol, after filtration washing, in the baking oven of 60 DEG C, be dried to constant weight, according to the Production rate polymerization activity of polymkeric substance.Polymerization activity: 12.63 × 10 6g of PEmol -1(M) h -1, polymkeric substance M w=1000gmol -1, M w/ M n=1.5, T m=101.4 DEG C.
Embodiment 53,
The vinyl polymerization adding pressure uses the 300 milliliters of stainless steel polymeric kettles being equipped with mechanical stirring oar and temperature-control device.Vacuumized by polymeric kettle and be heated to 100 DEG C, heat-up time continues two hours.Under the condition of replacing nitrogen in still in advance with ethene, polymeric kettle is allowed to slowly cool to the polymerization temperature (50 DEG C) of imagination.Then 50mL toluene is added successively, 20mL is dissolved with the toluene solution of 3 μm of ol catalyzer (Co4), 2.05mL promotor MAO (1.46mol/L toluene solution) (Al/Co=1000), residual toluene (making toluene total amount be 100 milliliters).Closed by still, logical ethene also maintains the constant pressure (10atm) of ethene.After reaching in polyreaction the time (30min) preset, by the ethylene pressure release in still, add acidic alcohol, after filtration washing, in the baking oven of 60 DEG C, be dried to constant weight, according to the Production rate polymerization activity of polymkeric substance.Polymerization activity: 14.76 × 10 6g of PEmol -1(M) h -1, polymkeric substance M w=949gmol -1, M w/ M n=1.5, T m=99.6 DEG C.
Embodiment 54,
The vinyl polymerization adding pressure uses the 300 milliliters of stainless steel polymeric kettles being equipped with mechanical stirring oar and temperature-control device.Vacuumized by polymeric kettle and be heated to 100 DEG C, heat-up time continues two hours.Under the condition of replacing nitrogen in still in advance with ethene, polymeric kettle is allowed to slowly cool to the polymerization temperature (50 DEG C) of imagination.Then 50mL toluene is added successively, 20mL is dissolved with the toluene solution of 3 μm of ol catalyzer (Co4), 2.57mL promotor MAO (1.46mol/L toluene solution) (Al/Co=1250), residual toluene (making toluene total amount be 100 milliliters).Closed by still, logical ethene also maintains the constant pressure (10atm) of ethene.After reaching in polyreaction the time (30min) preset, by the ethylene pressure release in still, add acidic alcohol, after filtration washing, in the baking oven of 60 DEG C, be dried to constant weight, according to the Production rate polymerization activity of polymkeric substance.Polymerization activity: 13.29 × 10 6g of PEmol -1(M) h -1, polymkeric substance M w=998gmol -1, M w/ M n=1.6T m=100.9 DEG C.
Embodiment 55,
The vinyl polymerization adding pressure uses the 300 milliliters of stainless steel polymeric kettles being equipped with mechanical stirring oar and temperature-control device.Vacuumized by polymeric kettle and be heated to 100 DEG C, heat-up time continues two hours.Under the condition of replacing nitrogen in still in advance with ethene, polymeric kettle is allowed to slowly cool to the polymerization temperature (50 DEG C) of imagination.Then 50mL toluene is added successively, 20mL is dissolved with the toluene solution of 3 μm of ol catalyzer (Co4), 3.08mL promotor MAO (1.46mol/L toluene solution) (Al/ Co=1500), residual toluene (making toluene total amount be 100 milliliters).Closed by still, logical ethene also maintains the constant pressure (10atm) of ethene.After reaching in polyreaction the time (30min) preset, by the ethylene pressure release in still, add acidic alcohol, after filtration washing, in the baking oven of 60 DEG C, be dried to constant weight, according to the Production rate polymerization activity of polymkeric substance.Polymerization activity: 12.00 × 10 6g of PEmol -1(M) h -1, polymkeric substance M w=1029gmol -1, M w/ M n=1.5, T m=102.3 DEG C.
Embodiment 56,
The vinyl polymerization adding pressure uses the 300 milliliters of stainless steel polymeric kettles being equipped with mechanical stirring oar and temperature-control device.Vacuumized by polymeric kettle and be heated to 100 DEG C, heat-up time continues two hours.Under the condition of replacing nitrogen in still in advance with ethene, polymeric kettle is allowed to slowly cool to the polymerization temperature (30 DEG C) of imagination.Then 50mL toluene is added successively, 20mL is dissolved with the toluene solution of 3 μm of ol catalyzer (Co4), 2.05mL promotor MAO (1.46mol/L toluene solution) (Al/Co=1000), residual toluene (making toluene total amount be 100 milliliters).Closed by still, logical ethene also maintains the constant pressure (10atm) of ethene.After reaching in polyreaction the time (30min) preset, by the ethylene pressure release in still, add acidic alcohol, after filtration washing, in the baking oven of 60 DEG C, be dried to constant weight, according to the Production rate polymerization activity of polymkeric substance.Polymerization activity: 6.72 × 10 6g of PEmol -1(M) h -1, polymkeric substance M w=1219gmol -1, M w/ M n=1.6, T m=100.9 DEG C.
Embodiment 57,
The vinyl polymerization adding pressure uses the 300 milliliters of stainless steel polymeric kettles being equipped with mechanical stirring oar and temperature-control device.Vacuumized by polymeric kettle and be heated to 100 DEG C, heat-up time continues two hours.Under the condition of replacing nitrogen in still in advance with ethene, polymeric kettle is allowed to slowly cool to the polymerization temperature (40 DEG C) of imagination.Then 50mL toluene is added successively, 20mL is dissolved with the toluene solution of 3 μm of ol catalyzer (Co4),, 2.05mL promotor MAO (1.46mol/L toluene solution) (Al/Co=1000), residual toluene (making toluene total amount be 100 milliliters).Closed by still, logical ethene also maintains the constant pressure (10atm) of ethene.After reaching in polyreaction the time (30min) preset, by the ethylene pressure release in still, add acidic alcohol, after filtration washing, in the baking oven of 60 DEG C, be dried to constant weight, according to the Production rate polymerization activity of polymkeric substance.Polymerization activity: 7.66 × 10 6g of PEmol -1(M) h -1, polymkeric substance M w=960gmol -1, M w/ M n=1.6, T m=100.3 DEG C.
Embodiment 58,
The vinyl polymerization adding pressure uses the 300 milliliters of stainless steel polymeric kettles being equipped with mechanical stirring oar and temperature-control device.Vacuumized by polymeric kettle and be heated to 100 DEG C, heat-up time continues two hours.Under the condition of replacing nitrogen in still in advance with ethene, polymeric kettle is allowed to slowly cool to the polymerization temperature (60 DEG C) of imagination.Then 50mL toluene is added successively, 20mL is dissolved with the toluene solution of 3 μm of ol catalyzer (Co4),, 2.05mL promotor MAO (1.46mol/L toluene solution) (Al/Co=1000), residual toluene (making toluene total amount be 100 milliliters).Closed by still, logical ethene also maintains the constant pressure (10atm) of ethene.After reaching in polyreaction the time (30min) preset, by the ethylene pressure release in still, add acidic alcohol, after filtration washing, in the baking oven of 60 DEG C, be dried to constant weight, according to the Production rate polymerization activity of polymkeric substance.Polymerization activity: 16.37 × 10 6g of PEmol -1(M) h -1, polymkeric substance M w=910gmol -1, M w/ M n=1.5, T m=99.6 DEG C.
Embodiment 59,
The vinyl polymerization adding pressure uses the 300 milliliters of stainless steel polymeric kettles being equipped with mechanical stirring oar and temperature-control device.Vacuumized by polymeric kettle and be heated to 100 DEG C, heat-up time continues two hours.Under the condition of replacing nitrogen in still in advance with ethene, polymeric kettle is allowed to slowly cool to the polymerization temperature (70 DEG C) of imagination.Then 50mL toluene is added successively, 20mL is dissolved with the toluene solution of 3 μm of ol catalyzer (Co4), 2.05mL promotor MAO (1.46mol/L toluene solution) (Al/Co=1000), residual toluene (making toluene total amount be 100 milliliters).Closed by still, logical ethene also maintains the constant pressure (10atm) of ethene.After reaching in polyreaction the time (30min) preset, by the ethylene pressure release in still, add acidic alcohol, after filtration washing, in the baking oven of 60 DEG C, be dried to constant weight, according to the Production rate polymerization activity of polymkeric substance.Polymerization activity: 15.60 × 10 6g of PEmol -1(M) h -1, polymkeric substance M w=880gmol -1, M w/ M n=1.6, T m=99.0 DEG C.
Embodiment 60,
The vinyl polymerization adding pressure uses the 300 milliliters of stainless steel polymeric kettles being equipped with mechanical stirring oar and temperature-control device.Vacuumized by polymeric kettle and be heated to 100 DEG C, heat-up time continues two hours.Under the condition of replacing nitrogen in still in advance with ethene, polymeric kettle is allowed to slowly cool to the polymerization temperature (60 DEG C) of imagination.Then 50mL toluene is added successively, 20mL is dissolved with the toluene solution of 3 μm of ol catalyzer (Co4), 2.05mL promotor MAO (1.46mol/L toluene solution) (Al/Co=1000), residual toluene (making toluene total amount be 100 milliliters).Closed by still, logical ethene also maintains the constant pressure (10atm) of ethene.After reaching in polyreaction the time (5min) preset, by the ethylene pressure release in still, add acidic alcohol, after filtration washing, in the baking oven of 60 DEG C, be dried to constant weight, according to the Production rate polymerization activity of polymkeric substance.Polymerization activity: 4.83 × 10 6g of PEmol -1(M) h -1, polymkeric substance M w=891gmol -1, M w/ M n=1.5, T m=100.5 DEG C.
Embodiment 61,
The vinyl polymerization adding pressure uses the 300 milliliters of stainless steel polymeric kettles being equipped with mechanical stirring oar and temperature-control device.Vacuumized by polymeric kettle and be heated to 100 DEG C, heat-up time continues two hours.Under the condition of replacing nitrogen in still in advance with ethene, polymeric kettle is allowed to slowly cool to the polymerization temperature (60 DEG C) of imagination.Then 50mL toluene is added successively, 20mL is dissolved with the toluene solution of 3 μm of ol catalyzer (Co4), 2.05mL promotor MAO (1.46mol/L toluene solution) (Al/Co=1000), residual toluene (making toluene total amount be 100 milliliters).Closed by still, logical ethene also maintains the constant pressure (10atm) of ethene.After reaching in polyreaction the time (10min) preset, by the ethylene pressure release in still, add acidic alcohol, after filtration washing, in the baking oven of 60 DEG C, be dried to constant weight, according to the Production rate polymerization activity of polymkeric substance.Polymerization activity: 10.13 × 10 6g of PEmol -1(M) h -1, polymkeric substance M w=896gmol -1, M w/ M n=1.5, T m=99.8 DEG C
Embodiment 62,
The vinyl polymerization adding pressure uses the 300 milliliters of stainless steel polymeric kettles being equipped with mechanical stirring oar and temperature-control device.Vacuumized by polymeric kettle and be heated to 100 DEG C, heat-up time continues two hours.Under the condition of replacing nitrogen in still in advance with ethene, polymeric kettle is allowed to slowly cool to the polymerization temperature (60 DEG C) of imagination.Then 50mL toluene is added successively, 20mL is dissolved with the toluene solution of 3 μm of ol catalyzer (Co4), 2.05mL promotor MAO (1.46mol/L toluene solution) (Al/Co=1000), residual toluene (making toluene total amount be 100 milliliters).Closed by still, logical ethene also maintains the constant pressure (10atm) of ethene.After reaching in polyreaction the time (60min) preset, by the ethylene pressure release in still, add acidic alcohol, after filtration washing, in the baking oven of 60 DEG C, be dried to constant weight, according to the Production rate polymerization activity of polymkeric substance.Polymerization activity: 18.43 × 10 6g of PEmol -1(M) h -1, polymkeric substance M w=1016gmol -1, M w/ M n=1.5, T m=99.8 DEG C
Embodiment 63,
The vinyl polymerization adding pressure uses the 300 milliliters of stainless steel polymeric kettles being equipped with mechanical stirring oar and temperature-control device.Vacuumized by polymeric kettle and be heated to 100 DEG C, heat-up time continues two hours.Under the condition of replacing nitrogen in still in advance with ethene, polymeric kettle is allowed to slowly cool to the polymerization temperature (60 DEG C) of imagination.Then 50mL toluene is added successively, 20mL is dissolved with the toluene solution of 3 μm of ol catalyzer (Co4), 2.05mL promotor MAO (1.46mol/L toluene solution) (Al/Co=1000), residual toluene (making toluene total amount be 100 milliliters).Closed by still, logical ethene also maintains the constant pressure (5atm) of ethene.After reaching in polyreaction the time (30min) preset, by the ethylene pressure release in still, add acidic alcohol, after filtration washing, in the baking oven of 60 DEG C, be dried to constant weight, according to the Production rate polymerization activity of polymkeric substance.Polymerization activity: 8.20 × 10 6g of PEmol -1(M) h -1, polymkeric substance M w=914 gmol -1, M w/ M n=1.4, T m=100.5 DEG C.
Embodiment 64,
The vinyl polymerization of pressure uses the 300 milliliters of stainless steel polymeric kettles being equipped with mechanical stirring oar and temperature-control device.Vacuumized by polymeric kettle and be heated to 100 DEG C, heat-up time continues two hours.Under the condition of replacing nitrogen in still in advance with ethene, polymeric kettle is allowed to slowly cool to the polymerization temperature (60 DEG C) of imagination.Then 50mL toluene is added successively, 20mL is dissolved with the toluene solution of 3 μm of ol catalyzer (Co1), 2.05mL promotor MAO (1.46mol/L toluene solution) (Al/Co=1000), residual toluene (making toluene total amount be 100 milliliters).Closed by still, logical ethene also maintains the constant pressure (5atm) of ethene.After reaching in polyreaction the time (30min) preset, by the ethylene pressure release in still, add acidic alcohol, after filtration washing, in the baking oven of 60 DEG C, be dried to constant weight, according to the Production rate polymerization activity of polymkeric substance.Polymerization activity: 16.29 × 10 6g of PEmol -1(M) h -1, polymkeric substance M w=827gmol -1, M w/ M n=1.6, T m=99.0 DEG C.
Embodiment 65,
The vinyl polymerization adding pressure uses the 300 milliliters of stainless steel polymeric kettles being equipped with mechanical stirring oar and temperature-control device.Vacuumized by polymeric kettle and be heated to 100 DEG C, heat-up time continues two hours.Under the condition of replacing nitrogen in still in advance with ethene, polymeric kettle is allowed to slowly cool to the polymerization temperature (60 DEG C) of imagination.Then 50mL toluene is added successively, 20mL is dissolved with the toluene solution of 3 μm of ol catalyzer (Co2), 2.05mL promotor MAO (1.46mol/L toluene solution) (Al/Co=1000), residual toluene (making toluene total amount be 100 milliliters).Closed by still, logical ethene also maintains the constant pressure (5atm) of ethene.After reaching in polyreaction the time (30min) preset, by the ethylene pressure release in still, add acidic alcohol, after filtration washing, in the baking oven of 60 DEG C, be dried to constant weight, according to the Production rate polymerization activity of polymkeric substance.Polymerization activity: 13.37 × 10 6g of PEmol -1(M) h -1, polymkeric substance M w=1955gmol -1, M w/ M n=1.9, T m=117.4 DEG C.
Embodiment 66,
The vinyl polymerization adding pressure uses the 300 milliliters of stainless steel polymeric kettles being equipped with mechanical stirring oar and temperature-control device.Vacuumized by polymeric kettle and be heated to 100 DEG C, heat-up time continues two hours.Under the condition of replacing nitrogen in still in advance with ethene, polymeric kettle is allowed to slowly cool to the polymerization temperature (60 DEG C) of imagination.Then 50mL toluene is added successively, 20mL is dissolved with the toluene solution of 3 μm of ol catalyzer (Co3), 2.05mL promotor MAO (1.46mol/L toluene solution) (Al/Co=1000), residual toluene (making toluene total amount be 100 milliliters).Closed by still, logical ethene also maintains the constant pressure (5atm) of ethene.After reaching in polyreaction the time (30min) preset, by the ethylene pressure release in still, add acidic alcohol, after filtration washing, in the baking oven of 60 DEG C, be dried to constant weight, according to the Production rate polymerization activity of polymkeric substance.Polymerization activity: 6.70 × 10 6g of PEmol -1(M) h -1, polymkeric substance M w=10189gmol -1, M w/ M n=2.0, T m=128.9 DEG C.
Embodiment 67,
The vinyl polymerization adding pressure uses the 300 milliliters of stainless steel polymeric kettles being equipped with mechanical stirring oar and temperature-control device.Vacuumized by polymeric kettle and be heated to 100 DEG C, heat-up time continues two hours.Under the condition of replacing nitrogen in still in advance with ethene, polymeric kettle is allowed to slowly cool to the polymerization temperature (60 DEG C) of imagination.Then 50mL toluene is added successively, 20mL is dissolved with the toluene solution of 3 μm of ol catalyzer (Co5), 2.05mL promotor MAO (1.46mol/L toluene solution) (Al/Co=1000), residual toluene (making toluene total amount be 100 milliliters).Closed by still, logical ethene also maintains the constant pressure (5atm) of ethene.After reaching in polyreaction the time (30min) preset, by the ethylene pressure release in still, add acidic alcohol, after filtration washing, in the baking oven of 60 DEG C, be dried to constant weight, according to the Production rate polymerization activity of polymkeric substance.Polymerization activity: 16.21 × 10 6g of PEmol -1(M) h -1, polymkeric substance M w=2009gmol -1, M w/ M n=1.9, T m=117.6 DEG C.
Embodiment 68,
The vinyl polymerization adding pressure uses the 300 milliliters of stainless steel polymeric kettles being equipped with mechanical stirring oar and temperature-control device.Vacuumized by polymeric kettle and be heated to 100 DEG C, heat-up time continues two hours.Under the condition of replacing nitrogen in still in advance with ethene, polymeric kettle is allowed to slowly cool to the polymerization temperature (50 DEG C) of imagination.Then 50mL toluene is added successively, 20mL is dissolved with the toluene solution of 3 μm of ol catalyzer (Co4), 1.55mL promotor (MMAO, the n-heptane solution of 1.93mol/L) (Al/Co=1000), residual toluene (making toluene total amount be 100 milliliters).Closed by still, logical ethene also maintains the constant pressure (10atm) of ethene.After reaching in polyreaction the time (30min) preset, by the ethylene pressure release in still, add acidic alcohol, after filtration washing, in the baking oven of 60 DEG C, be dried to constant weight, according to the Production rate polymerization activity 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 DEG C.
Embodiment 69,
Vacuumized by polymeric kettle and be heated to 100 DEG C, heat-up time continues two hours.Under the condition of replacing nitrogen in still in advance with ethene, polymeric kettle is allowed to slowly cool to the polymerization temperature (50 DEG C) of imagination.Then 50mL toluene is added successively, 20mL is dissolved with the toluene solution of 3 μm of ol catalyzer (Co4), 1.94mL promotor (MMAO, the n-heptane solution of 1.93mol/L) (Al/Co=1250), residual toluene (making toluene total amount be 100 milliliters).Closed by still, logical ethene also maintains the constant pressure (10atm) of ethene.After reaching in polyreaction the time (30min) preset, by the ethylene pressure release in still, add acidic alcohol, after filtration washing, in the baking oven of 60 DEG C, be dried to constant weight, according to the Production rate polymerization activity of polymkeric substance.Polymerization activity: 10.05 × 10 6g of PEmol -1(M) h -1, polymkeric substance M w=1064gmol -1, M w/ M n=1.5, T m=101.6 DEG C.
Embodiment 70,
Vacuumized by polymeric kettle and be heated to 100 DEG C, heat-up time continues two hours.Under the condition of replacing nitrogen in still in advance with ethene, polymeric kettle is allowed to slowly cool to the polymerization temperature (50 DEG C) of imagination.Then 50mL toluene is added successively, 20mL is dissolved with the toluene solution of 3 μm of ol catalyzer (Co4), 2.33mL promotor (MMAO, the n-heptane solution of 1.93mol/L) (Al/Co=1500), residual toluene (making toluene total amount be 100 milliliters).Closed by still, logical ethene also maintains the constant pressure (10atm) of ethene.After reaching in polyreaction the time (30min) preset, by the ethylene pressure release in still, add acidic alcohol, after filtration washing, in the baking oven of 60 DEG C, be dried to constant weight, according to the Production rate polymerization activity of polymkeric substance.Polymerization activity: 11.52 × 10 6g of PEmol -1(M) h -1, polymkeric substance M w=1056gmol -1, M w/ M n=1.6, T m=99.5 DEG C.
Embodiment 71,
Vacuumized by polymeric kettle and be heated to 100 DEG C, heat-up time continues two hours.Under the condition of replacing nitrogen in still in advance with ethene, polymeric kettle is allowed to slowly cool to the polymerization temperature (50 DEG C) of imagination.Then 50mL toluene is added successively, 20mL is dissolved with the toluene solution of 3 μm of ol catalyzer (Co4), 2.72mL promotor (MMAO, the n-heptane solution of 1.93mol/L) (Al/Co=1750), residual toluene (making toluene total amount be 100 milliliters).Closed by still, logical ethene also maintains the constant pressure (10atm) of ethene.After reaching in polyreaction the time (30min) preset, by the ethylene pressure release in still, add acidic alcohol, after filtration washing, in the baking oven of 60 DEG C, be dried to constant weight, according to the Production rate polymerization activity of polymkeric substance.Polymerization activity: 11.05 × 10 6g of PEmol -1(M) h -1, polymkeric substance M w=1088gmol -1, M w/ M n=1.6, T m=100.8 DEG C.
Embodiment 72,
Vacuumized by polymeric kettle and be heated to 100 DEG C, heat-up time continues two hours.Under the condition of replacing nitrogen in still in advance with ethene, polymeric kettle is allowed to slowly cool to the polymerization temperature (30 DEG C) of imagination.Then 50mL toluene is added successively, 20mL is dissolved with the toluene solution of 3 μm of ol catalyzer (Co4), 2.33mL promotor (MMAO, the n-heptane solution of 1.93mol/L) (Al/Co=1500), residual toluene (making toluene total amount be 100 milliliters).Closed by still, logical ethene also maintains the constant pressure (10atm) of ethene.After reaching in polyreaction the time (30min) preset, by the ethylene pressure release in still, add acidic alcohol, after filtration washing, in the baking oven of 60 DEG C, be dried to constant weight, according to the Production rate polymerization activity of polymkeric substance.Polymerization activity: 5.89 × 10 6g of PEmol -1(M) h -1, T m=100.4 DEG C
Embodiment 73,
Vacuumized by polymeric kettle and be heated to 100 DEG C, heat-up time continues two hours.Under the condition of replacing nitrogen in still in advance with ethene, polymeric kettle is allowed to slowly cool to the polymerization temperature (40 DEG C) of imagination.Then 50mL toluene is added successively, 20mL is dissolved with the toluene solution of 3 μm of ol catalyzer (Co4), 2.33mL promotor (MMAO, the n-heptane solution of 1.93mol/L) (Al/Co=1500), residual toluene (making toluene total amount be 100 milliliters).Closed by still, logical ethene also maintains the constant pressure (10atm) of ethene.After reaching in polyreaction the time (30min) preset, by the ethylene pressure release in still, add acidic alcohol, after filtration washing, in the baking oven of 60 DEG C, be dried to constant weight, according to the Production rate polymerization activity of polymkeric substance.Polymerization activity: 8.68 × 10 6g of PEmol -1(M) h -1, polymkeric substance M w=927Kgmol -1, M w/ M n=1.6, T m=99.4 DEG C.
Embodiment 74,
Vacuumized by polymeric kettle and be heated to 100 DEG C, heat-up time continues two hours.Under the condition of replacing nitrogen in still in advance with ethene, polymeric kettle is allowed to slowly cool to the polymerization temperature (60 DEG C) of imagination.Then 50mL toluene is added successively, 20mL is dissolved with the toluene solution of 3 μm of ol catalyzer (Co4), 2.33mL promotor (MMAO, the n-heptane solution of 1.93mol/L) (Al/Co=1500), residual toluene (making toluene total amount be 100 milliliters).Closed by still, logical ethene also maintains the constant pressure (10atm) of ethene.After reaching in polyreaction the time (30min) preset, by the ethylene pressure release in still, add acidic alcohol, after filtration washing, in the baking oven of 60 DEG C, be dried to constant weight, according to the Production rate polymerization activity of polymkeric substance.Polymerization activity: 13.21 × 10 6g of PEmol -1(M) h -1, polymkeric substance M w=951gmol -1, M w/ M n=1.5, T m=98.7 DEG C.
Embodiment 75,
Vacuumized by polymeric kettle and be heated to 100 DEG C, heat-up time continues two hours.Under the condition of replacing nitrogen in still in advance with ethene, polymeric kettle is allowed to slowly cool to the polymerization temperature (70 DEG C) of imagination.Then 50mL toluene is added successively, 20mL is dissolved with the toluene solution of 3 μm of ol catalyzer (Co4), 2.33mL promotor (MMAO, the n-heptane solution of 1.93mol/L) (Al/Co=1500), residual toluene (making toluene total amount be 100 milliliters).Closed by still, logical ethene also maintains the constant pressure (10atm) of ethene.After reaching in polyreaction the time (30min) preset, by the ethylene pressure release in still, add acidic alcohol, after filtration washing, in the baking oven of 60 DEG C, be dried to constant weight, according to the Production rate polymerization activity of polymkeric substance.Polymerization activity: 4.92 × 10 6g of PEmol -1(M) h -1, polymkeric substance M w=950gmol -1, M w/ M n=1.5, T m=100.3 DEG C.
Embodiment 76,
Vacuumized by polymeric kettle and be heated to 100 DEG C, heat-up time continues two hours.Under the condition of replacing nitrogen in still in advance with ethene, polymeric kettle is allowed to slowly cool to the polymerization temperature (60 DEG C) of imagination.Then 50mL toluene is added successively, 20mL is dissolved with the toluene solution of 3 μm of ol catalyzer (Co1), 2.33mL promotor (MMAO, the n-heptane solution of 1.93mol/L) (Al/Co=1500), residual toluene (making toluene total amount be 100 milliliters).Closed by still, logical ethene also maintains the constant pressure (10atm) of ethene.After reaching in polyreaction the time (30min) preset, by the ethylene pressure release in still, add acidic alcohol, after filtration washing, in the baking oven of 60 DEG C, be dried to constant weight, according to the Production rate polymerization activity of polymkeric substance.Polymerization activity: 8.83 × 10 6g of PEmol -1(M) h -1, polymkeric substance M w=996gmol -1, M w/ M n=1.5, T m=100.4 DEG C.
Embodiment 77,
Vacuumized by polymeric kettle and be heated to 100 DEG C, heat-up time continues two hours.Under the condition of replacing nitrogen in still in advance with ethene, polymeric kettle is allowed to slowly cool to the polymerization temperature (60 DEG C) of imagination.Then 50mL toluene is added successively, 20mL is dissolved with the toluene solution of 3 μm of ol catalyzer (Co2), 2.33mL promotor (MMAO, the n-heptane solution of 1.93mol/L) (Al/Co=1500), residual toluene (making toluene total amount be 100 milliliters).Closed by still, logical ethene also maintains the constant pressure (10atm) of ethene.After reaching in polyreaction the time (30min) preset, by the ethylene pressure release in still, add acidic alcohol, after filtration washing, in the baking oven of 60 DEG C, be dried to constant weight, according to the Production rate polymerization activity of polymkeric substance.Polymerization activity: 5.72 × 10 6g of PEmol -1(M) h -1, polymkeric substance M w=2162gmol -1, M w/ M n=1.9, T m=118.4 DEG C.
Embodiment 78,
Vacuumized by polymeric kettle and be heated to 100 DEG C, heat-up time continues two hours.Under the condition of replacing nitrogen in still in advance with ethene, polymeric kettle is allowed to slowly cool to the polymerization temperature (60 DEG C) of imagination.Then 50mL toluene is added successively, 20mL is dissolved with the toluene solution of 3 μm of ol catalyzer (Co3), 2.33mL promotor (MMAO, the n-heptane solution of 1.93mol/L) (Al/Co=1500), residual toluene (making toluene total amount be 100 milliliters).Closed by still, logical ethene also maintains the constant pressure (10atm) of ethene.After reaching in polyreaction the time (30min) preset, by the ethylene pressure release in still, add acidic alcohol, after filtration washing, in the baking oven of 60 DEG C, be dried to constant weight, according to the Production rate polymerization activity 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 DEG C.
Embodiment 79,
Vacuumized by polymeric kettle and be heated to 100 DEG C, heat-up time continues two hours.Under the condition of replacing nitrogen in still in advance with ethene, polymeric kettle is allowed to slowly cool to the polymerization temperature (60 DEG C) of imagination.Then 50mL toluene is added successively, 20mL is dissolved with the toluene solution of 3 μm of ol catalyzer (Co5), 2.33mL promotor (MMAO, the n-heptane solution of 1.93mol/L) (Al/Co=1500), residual toluene (making toluene total amount be 100 milliliters).Closed by still, logical ethene also maintains the constant pressure (10atm) of ethene.After reaching in polyreaction the time (30min) preset, by the ethylene pressure release in still, add acidic alcohol, after filtration washing, in the baking oven of 60 DEG C, be dried to constant weight, according to the Production rate polymerization activity of polymkeric substance.Polymerization activity: 7.81 × 10 6g of PEmol -1(M) h -1, polymkeric substance M w=2052gmol -1, M w/ M n=1.9, T m=119.0 DEG C.
Embodiment 80,
The vinyl polymerization adding pressure uses the 300 milliliters of stainless steel polymeric kettles being equipped with mechanical stirring oar and temperature-control device.Vacuumized by polymeric kettle and be heated to 100 DEG C, heat-up time continues two hours.Under the condition of replacing nitrogen in still in advance with ethene, polymeric kettle is allowed to slowly cool to the polymerization temperature (50 DEG C) of imagination.Then 50mL toluene is added successively, 20mL is dissolved with 3 μm of ol catalyzer (toluene solutions of Fe6,3.10mL promotor (n-heptane solution of MMAO, 1.93mol/L) (Al/Fe=2000), residual toluene (making toluene total amount be 100 milliliters).Closed by still, logical ethene also maintains the constant pressure (10atm) of ethene.After reaching in polyreaction the time (30min) preset, by the ethylene pressure release in still, add acidic alcohol, after filtration washing, in the baking oven of 60 DEG C, be dried to constant weight, obtain 11.5g polymkeric substance, according to the Production rate polymerization activity 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,
The vinyl polymerization adding pressure uses the 300 milliliters of stainless steel polymeric kettles being equipped with mechanical stirring oar and temperature-control device.Vacuumized by polymeric kettle and be heated to 100 DEG C, heat-up time continues two hours.Under the condition of replacing nitrogen in still in advance with ethene, polymeric kettle is allowed to slowly cool to the polymerization temperature (50 DEG C) of imagination.Then 50mL toluene is added successively, 20mL is dissolved with 3 μm of ol catalyzer (toluene solutions of Fe7,3.10mL promotor (n-heptane solution of MMAO, 1.93mol/L) (Al/Fe=2000), residual toluene (making toluene total amount be 100 milliliters).Closed by still, logical ethene also maintains the constant pressure (10atm) of ethene.After reaching in polyreaction the time (30min) preset, by the ethylene pressure release in still, add acidic alcohol, after filtration washing, in the baking oven of 60 DEG C, be dried to constant weight, obtain 20.0g polymkeric substance, according to the Production rate polymerization activity 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,
The vinyl polymerization adding pressure uses the 300 milliliters of stainless steel polymeric kettles being equipped with mechanical stirring oar and temperature-control device.Vacuumized by polymeric kettle and be heated to 100 DEG C, heat-up time continues two hours.Under the condition of replacing nitrogen in still in advance with ethene, polymeric kettle is allowed to slowly cool to the polymerization temperature (50 DEG C) of imagination.Then 50mL toluene is added successively, 20mL is dissolved with the toluene solution of 3 μm of ol catalyzer (Fe8), 3.10mL promotor (MMAO, the n-heptane solution of 1.93mol/L) (Al/Fe=2000), residual toluene (making toluene total amount be 100 milliliters).Closed by still, logical ethene also maintains the constant pressure (10atm) of ethene.After reaching in polyreaction the time (30min) preset, by the ethylene pressure release in still, add acidic alcohol, after filtration washing, in the baking oven of 60 DEG C, be dried to constant weight, obtain 8.0g polymkeric substance, according to the Production rate polymerization activity 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,
The vinyl polymerization adding pressure uses the 300 milliliters of stainless steel polymeric kettles being equipped with mechanical stirring oar and temperature-control device.Vacuumized by polymeric kettle and be heated to 100 DEG C, heat-up time continues two hours.Under the condition of replacing nitrogen in still in advance with ethene, polymeric kettle is allowed to slowly cool to the polymerization temperature (60 DEG C) of imagination.Then 50mL toluene is added successively, 20mL is dissolved with the toluene solution of 3 μm of ol catalyzer (Co6), 2.05mL promotor MAO (1.46mol/L toluene solution) (Al/Co=1000), residual toluene (making toluene total amount be 100 milliliters).Closed by still, logical ethene also maintains the constant pressure (5atm) of ethene.After reaching in polyreaction the time (30min) preset, by the ethylene pressure release in still, add acidic alcohol, after filtration washing, in the baking oven of 60 DEG C, be dried to constant weight, according to the Production rate polymerization activity of polymkeric substance.Polymerization activity: 3.70 × 10 6g of PEmol -1(M) h -1, polymkeric substance M w=5400gmol -1, M w/ M n=1.8, T m=124.9 DEG C.
Embodiment 84,
The vinyl polymerization adding pressure uses the 300 milliliters of stainless steel polymeric kettles being equipped with mechanical stirring oar and temperature-control device.Vacuumized by polymeric kettle and be heated to 100 DEG C, heat-up time continues two hours.Under the condition of replacing nitrogen in still in advance with ethene, polymeric kettle is allowed to slowly cool to the polymerization temperature (60 DEG C) of imagination.Then 50mL toluene is added successively, 20mL is dissolved with the toluene solution of 3 μm of ol catalyzer (Co7), 2.05mL promotor MAO (1.46mol/L toluene solution) (Al/Co=1000), residual toluene (making toluene total amount be 100 milliliters).Closed by still, logical ethene also maintains the constant pressure (5atm) of ethene.After reaching in polyreaction the time (30min) preset, by the ethylene pressure release in still, add acidic alcohol, after filtration washing, in the baking oven of 60 DEG C, be dried to constant weight, according to the Production rate polymerization activity of polymkeric substance.Polymerization activity: 23.21 × 10 6g of PEmol -1(M) h -1, polymkeric substance M w=2002gmol -1, M w/ M n=1.6, T m=110.6 DEG C.
Embodiment 85,
The vinyl polymerization adding pressure uses the 300 milliliters of stainless steel polymeric kettles being equipped with mechanical stirring oar and temperature-control device.Vacuumized by polymeric kettle and be heated to 100 DEG C, heat-up time continues two hours.Under the condition of replacing nitrogen in still in advance with ethene, polymeric kettle is allowed to slowly cool to the polymerization temperature (50 DEG C) of imagination.Then 50mL toluene is added successively, 20mL is dissolved with the toluene solution of 3 μm of ol catalyzer (Co8), 2.05mL promotor (MMAO, the n-heptane solution of 1.93mol/L) (Al/Fe=1000), residual toluene (making toluene total amount be 100 milliliters).Closed by still, logical ethene also maintains the constant pressure (10atm) of ethene.After reaching in polyreaction the time (30min) preset, by the ethylene pressure release in still, add acidic alcohol, after filtration washing, in the baking oven of 60 DEG C, be dried to constant weight, according to the Production rate polymerization activity of polymkeric substance.Polymerization activity: 10.4 × 10 6g of PEmol -1(M) h -1, polymkeric substance M w=7000gmol -1, M w/ M n=1.8, T m=126.4.

Claims (9)

1.2,8-diimine-5,6,7-tri-hydrogen quinoline transition metal complex, its structural formula such as formula shown in I,
In formula I, R 1be selected from hydrogen, methyl and ethyl; R 2, R 3, R 4, R 5and R 6be selected from hydrogen, methyl, ethyl, sec.-propyl, fluorine, chlorine, bromine and nitro independently of one another; M is Fe or Co.
2. the preparation method of transition metal complex described in claim 1, comprises the steps:
(1) substituted aniline shown in 2-aldehyde radical shown in formula II (ketone)-5,6,7-tri-hydrogen-8-quinolinone and formula III carries out being obtained by reacting 2,8-diimine-5,6,7-tri-hydrogen quinoline compound under catalyzer existent condition;
The structural formula of described 2,8-diimine-5,6,7-tri-hydrogen quinoline compounds is such as formula IV;
In above formula, R 1be selected from hydrogen, methyl and ethyl, R 2, R 3, R 4, R 5and R 6be selected from hydrogen, methyl, ethyl, sec.-propyl, nitro, fluorine, chlorine and bromine independently of one another;
(2) described 2,8-diimine-5,6,7-tri-hydrogen quinoline compound and MCl 2react and obtain product; M is Fe or Co.
3. method according to claim 2, is characterized in that: in step (1), and described catalyzer is tosic acid; The solvent of described reaction is propyl carbinol; The temperature of described reaction is 110 ~ 125 DEG C, and the time is 6h ~ 20h.
4. method according to claim 2, is characterized in that: when in formula III, R 2, R 3, R 4, R 5and R 6when being selected from fluorine or chlorine independently of one another, described in step (1), catalyzer is tosic acid, and solvent is tetraethoxy, and the temperature of described reaction is 140 ~ 150 DEG C, and the time is 1 ~ 2 day.
5. the method according to claim 3 or 4, is characterized in that: in step (2), MCl 2compare for (1 ~ 1.5) with the molfraction of described 2,8-diimine-5,6,7-tri-hydrogen quinoline compounds: (1 ~ 1.2), the temperature of described reaction is 20 ~ 25 DEG C, and the time is 4 ~ 18h.
6. a catalyst composition, is made up of transition metal complex described in claim 1 and promotor, and described promotor is selected from one or more in aikyiaiurnirsoxan beta, alkylaluminium cpd and chlorination aluminum alkyls.
7. composition according to claim 6, is characterized in that: described aikyiaiurnirsoxan beta is the methylaluminoxane of methylaluminoxane or the modification of tertiary butyl aluminium; Described alkylaluminium cpd is trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum or tri-n-octylaluminium; Described chlorination aluminum alkyls is diethylaluminum chloride or ethylaluminium dichloride; Aluminium in described promotor is (100 ~ 10000) with the molfraction ratio of the central metal M in described transition metal complex: 1.
8. the application of catalyst composition described in transition metal complex described in claim 1 or claim 6 or 7 in catalyzed ethylene polymerization reaction.
9. application according to claim 8, is characterized in that: the temperature of described ethylene polymerization is 20 ~ 100 DEG C, and pressure is 0.1 ~ 1.0MPa.
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