CN101348502B - 2-benzimidazole-1,10-phenanthroline transient metal complex, and preparation and use thereof - Google Patents

2-benzimidazole-1,10-phenanthroline transient metal complex, and preparation and use thereof Download PDF

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CN101348502B
CN101348502B CN2007101192812A CN200710119281A CN101348502B CN 101348502 B CN101348502 B CN 101348502B CN 2007101192812 A CN2007101192812 A CN 2007101192812A CN 200710119281 A CN200710119281 A CN 200710119281A CN 101348502 B CN101348502 B CN 101348502B
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title complex
reaction
phenanthroline
benzoglyoxaline
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CN101348502A (en
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孙文华
张民
张树
郝鹏
介素云
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Institute of Chemistry CAS
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Abstract

The invention discloses a 2-benzimidazole1, 10-phenanthrolines transition metal complex and a preparation method thereof and an application thereof. The structure formula of the 2-benzimidazole1, 10-phenanthrolines transition metal complex of the invention is shown as the formula(I), wherein R<1> is hydrogen or methyl, R<2>is hydrogen, methyl, ethyl, isopropyl or benzyl, M is transition metal, and X is halogen; under the synergic action of catalyst accelerato, the transition metal complex of the invention can better catalyze the ethylene oligomerization, and has the advantages of small catalyst accelerato consumption, high catalytic activity and good selectivity for ethylene oligomerization reaction, so that the transition metal complex has broad application prospect.

Description

2-benzoglyoxaline-1,10-phenanthroline transient metal complex and preparation method thereof and application
Technical field
The present invention relates to a kind of 2-benzoglyoxaline-1,10-phenanthroline transient metal complex and preparation method thereof, and the application of this title complex in the catalyzed ethylene oligomerisation.
Background technology
Ethylene oligomerization is a kind of method of industrially producing alpha-alkene.And alpha-olefin is the important source material of preparation sanitising agent, fluidizer, fine chemicals and production of linear new LDPE (film grade) comonomer.The method of the linear alpha-olefin of the previous main industrial production of order is to use SHOP type catalyzer, its structure be shown below (Angew.Chem., Int.Ed.Engl.1978,17,466-467; Angew.Chem., Int.Ed.Engl.1983,22,503; J.Chem.Soc., Chem.Commun.1994,2203-2204):
Figure S071B9281220070813D000011
1998, Brookhart and Gibson reported the title complex of pyridine diimine Fe (II) and Co (II) when being equal to, by regulating the substituting group on the phenyl ring, catalyzed ethylene oligomerisation or polymerization well, its structure (J.Am.Chem.Soc., 1998 as follows, 120,4049-4050; Chem.Commun.1998,849-850):
Figure S071B9281220070813D000012
The contriver is devoted to the research of ethylene oligomerization and polymerizing catalyst and Catalytic processes in the past in the several years always, researched and developed the ethylene oligomerization catalyst of multiclass nickel complex: Chinese patent ZL00121033.5, July 17 2000 applying date, Granted publication day 2003.1.8; Chinese patent application number 01118455.8, the May 31 calendar year 2001 applying date; Chinese patent ZL01120214.9, the applying date: July 6 calendar year 2001, Granted publication day 2004.7.7; Chinese patent application number 01120554.7, the July 20 calendar year 2001 applying date; Chinese patent ZL02118523.9, April 26 2002 applying date, Granted publication day 2004.12.22; Chinese patent ZL02123213.X, June 12 2002 applying date, Granted publication day 2003.11.19; Chinese patent application number 03137727.0, June 23 2003 applying date; Chinese patent application 03148378.X, July 2 2003 applying date; Chinese patent application number 03154463.0, October 8 2003 applying date; Chinese patent application number October 29 2004 200410086284.7 applying date; Chinese patent application number December 30 2004 200410081711.2 applying date.Meanwhile, study and invented iron complex ethylene oligomerization and polymerizing catalyst: Chinese patent ZL 00 1 32106.4, December 13 2000 applying date, January 28 2004 Granted publication day; Chinese patent ZL 01 1 18568.6, the June 4 calendar year 2001 applying date, December 3 2003 Granted publication day; Chinese patent ZL 01 1 20553.9, the July 20 calendar year 2001 applying date, September 1 2004 Granted publication day; Chinese patent application 01124240.X, the August 17 calendar year 2001 applying date; Chinese patent application numbers 200410086374.6, October 27 2004 applying date, Chinese patent application numbers 200510066427.2, April 22 2005 applying date; Chinese patent application numbers 200610165446.5, December 20 2006 applying date.In the research of these catalyzer, how to obtain the core content that more highly active ethylene oligomerization and polymerizing catalyst become research, also be to advance industrialized key as early as possible.
Summary of the invention
The objective of the invention is the invention provides a kind of the have active 2-benzoglyoxaline-1 of good ethylene oligomerization catalysis, 10-phenanthroline transient metal complex and preparation method thereof.
2-benzoglyoxaline-1 provided by the present invention, the 10-phenanthroline transient metal complex, structure is suc as formula shown in the I,
(formula I)
Wherein, R 1Be hydrogen or methyl; R 2Be hydrogen, methyl, ethyl, sec.-propyl or benzyl; M is selected from transition metal; X is a halogen.
Preferably, M is iron, cobalt or nickel; X is Cl or Br.
This 2-benzoglyoxaline-1, the preparation method of 10-phenanthroline transient metal complex comprises the steps:
1) with 2,9-dimethyl-1,10-phenanthroline or 2-carboxyl-1,10-phenanthroline and O-Phenylene Diamine react, and obtain the phenanthroline part;
2) with gained phenanthroline part in acetonitrile with K 2CO 3The reaction deprotonation is finished the N-alkylated reaction with alkyl iodide for thing or benzyl bromine reaction again, preparation phenanthroline ligand derivatives;
3), obtain described 2-benzoglyoxaline-1, the 10-phenanthroline transient metal complex with phenanthroline ligand derivatives and transition metal reactant salt.
Common, transition metal salt has NiCl 26H 2O, (DME) NiBr 2, FeCl 24H 2O, anhydrous CoCl 2Deng.
Another object of the present invention provides the purposes of transition metal complex of the present invention.
Transition metal complex of the present invention has the activity of good catalyzed ethylene oligomerisation, the oligomerisation reaction of energy catalyzed ethylene, and simultaneously, selectivity is better, and main catalyzed ethylene carries out dimerization and trimerization reaction, and wherein major product is a 1-butylene.Therefore, use transition metal complex of the present invention and come the catalyzed ethylene oligomerisation reaction, also belong to protection scope of the present invention.
When carrying out the ethylene oligomerization reaction, catalyzer also is added with promotor, and promotor is selected from one or more in aikyiaiurnirsoxan beta, alkylaluminium cpd and the chlorination aluminum alkyls.Preferably, aikyiaiurnirsoxan beta is methylaluminoxane, modified methylaluminoxane, ethyl aikyiaiurnirsoxan beta or isobutyl aluminium alkoxide; Aluminum alkyls is trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum or tri-n-octylaluminium; The chlorination aluminum alkyls is diethylaluminum chloride or ethylaluminium dichloride.
In above-mentioned oligomerisation reaction, the mol ratio Al/M of metallic aluminium and catalyst center metal M is 200-1000 in the promotor, and polymerization temperature is 20-80 ℃, and polymerization pressure is 0.1-3Mpa.Preferably, the Al/M mol ratio is 300-1000, and polymerization temperature is 20-40 ℃, and polymerization pressure is 3.0Mpa.
Under the promotor synergy, 2-benzoglyoxaline-1 of the present invention, the catalyzed ethylene oligomerisation preferably of 10-phenanthroline late transition metal complex, have following advantage: 1) consumption of promotor is few.The mol ratio Al/M of metallic aluminium and catalyst center metal M is 300 o'clock in promotor, just can reach suitable activity.Consider the price that promotor is relatively costly, this advantage can be saved cost greatly, is beneficial to this system and moves towards the industrialization.2) catalytic activity height.Under the less prerequisite of promotor consumption, this system can reach very high activity, reaches 10 7Gmol -1(M) h -1This order of magnitude; 3) selectivity for the ethylene oligomerization reaction is good.Reach 10 in activity 7Gmol -1(M) h -1Under the prerequisite of the order of magnitude, the alpha-butylene selectivity that its catalyzed ethylene dimerization/trimerization reaction produces reaches more than 70%; Reach 10 in activity 6Gmol -1(M) h -1Under the prerequisite of the order of magnitude, the alpha-butylene selectivity can reach more than 90% especially in its product.Find simultaneously, under triethyl aluminum, the situation of methylaluminoxane as promotor, equally can the catalyzed ethylene oligomerisation reaction; And during catalyst system catalyzed ethylene oligomerisation of the present invention, the selectivity of the linear alpha-butylene of catalytic activity and gained changes adjustable with catalyzer and catalytic condition, be with a wide range of applications.
Description of drawings
Fig. 1 is the crystalline structure figure of title complex 1;
Fig. 2 is the crystalline structure figure of title complex 3;
Fig. 3 is the crystalline structure figure of title complex 6;
Fig. 4 is the crystalline structure figure of title complex 15;
Fig. 5 is the crystalline structure figure of title complex 21;
Fig. 6 is the crystalline structure figure of title complex 36;
Fig. 7 is the crystalline structure figure of title complex 39.
Embodiment
2-benzoglyoxaline-1 provided by the present invention, 10-phenanthroline iron (II), cobalt (II) and the serial title complex of nickel (II) can synthesize according to following synthetic route:
Figure S071B9281220070813D000041
Concrete preparation process is as follows:
One, part synthetic general method
Work as R 1When being different replacement situation with R, the synthetic of part slightly had any different:
1) with 2 of 1:1.2 mole, 9-dimethyl-1,10-phenanthroline (R 1Be methyl with R) and O-Phenylene Diamine uniform mixing, the industrial sulphur that adds the 1:5 mole was made oxygenant, 170 ℃ of following stirring reactions 8 hours.Purify through column chromatography, promptly get the phenanthroline part; Be dissolved in the acetonitrile again with after the salt of wormwood of 5 times of molar equivalents mixes, back flow reaction made the part dehydrogenation in 8 hours, added methyl iodide, iodoethane, 2-iodopropane, the benzyl bromine of 1.5 times of molar equivalents then respectively, continued reaction 8 hours.Reaction is finished after column chromatography is purified, and promptly gets the part of wanting.
2) with 2-carboxyl-1,10-phenanthroline (R 1Be H, R is COOH, after the preparation method sees (Organometallics, 2006,25,666-677)) and O-Phenylene Diamine mixes by the 1:1.2 molar ratio, adds 10 times of normal polyphosphoric acid, reacts under microwave irradiation.Reaction is finished after column chromatography is purified, and promptly gets the phenanthroline part.Be dissolved in the acetonitrile again with after the salt of wormwood of 5 times of molar equivalents mixes, back flow reaction made the part dehydrogenation in 8 hours, added methyl iodide, iodoethane, 2-iodopropane, the benzyl bromine of 1.5 times of molar equivalents then respectively, continued reaction 8 hours.Reaction is finished after column chromatography is purified, and promptly gets the part of wanting.
Two, title complex synthetic general method
1, nickel complex is synthetic
When room temperature, with part and NiCl 26H 2O is dissolved in respectively in the ethanol, and the two mixing was then stirred after 8 hours, promptly had yellow or green precipitate thing to separate out, and reaction solution is concentrated, cools off, filters, and promptly gets the title complex of its nickelous chloride after the drying.
The synthetic operation of its nickelous bromide title complex is slightly different: under the room temperature, take by weighing (DME) NiBr under the nitrogen protection fast 2Medicine.Use the Schlenk technology, 1/1 normal 2-benzoglyoxaline-1 will be housed, 10-phenanthroline part and (DME) NiBr with biexhaust pipe 2The exsiccant nitrogen replacement is drained and used to air in the reaction flask of solid medicine, three times so repeatedly.Under nitrogen protection, add about 10 milliliters of exsiccant methylene dichloride, stirring reaction 8 hours with syringe.After reaction is finished, as seen there are yellow or green title complex to separate out.Behind the concentration of reaction solution, filter, be drying to obtain title complex a little.
2, other title complexs is synthetic
Other metals, synthetic similar as the synthetic and above-mentioned nickelous chloride title complex of Co title complex, reaction needed is selected anhydrous CoCl for use 2The synthetic method that can adopt similar above-mentioned synthetic bromination nickel complex of Fe title complex, reaction needed is selected FeCl for use 24H 2O.
Preferably, 2-benzoglyoxaline-1 of the present invention, 10-phenanthroline iron (II), cobalt (II) and nickel (II) title complex are M, the substituent R in the structural formula 1And R 2Be title complex 1-40 as described below:
1：M＝Ni，R 1＝Me，R 2＝H，X＝Cl； 2：M＝Ni，R 1＝Me，R 2＝Me，X＝Cl；
3：M＝Ni，R 1＝Me，R 2＝Et，X＝Cl； 4：M＝Ni，R 1＝Me，R 2＝ iPr，X＝Cl；
5：M＝Ni，R 1＝Me，R 2＝Bn，X＝Cl； 6：M＝Ni，R 1＝H，R 2＝H，X＝Cl；
7：M＝Ni，R 1＝H，R 2＝Me，X＝Cl； 8：M＝Ni，R 1＝H，R 2＝Et，X＝Cl；
9：M＝Ni，R 1＝H，R 2＝ iPr，X＝Cl； 10：M＝Ni，R 1＝H，R 2＝Bn，X＝Cl；
11：M＝Ni，R 1＝Me，R 2＝H，X＝Br； 12：M＝Ni，R 1＝Me，R 2＝Me，X＝Br；
13：M＝Ni，R 1＝Me，R 2＝Et，X＝Br； 14：M＝Ni，R 1＝Me，R 2＝ iPr，X＝Br；
15：M＝Ni，R 1＝Me，R 2＝Bn，X＝Br； 16：M＝Ni，R 1＝H，R 2＝H，X＝Br；
17：M＝Ni，R 1＝H，R 2＝Me，X＝Br； 18：M＝Ni，R 1＝H，R 2＝Et，X＝Br；
19：M＝Ni，R 1＝H，R 2＝ iPr，X＝Br； 20：M＝Ni，R 1＝H，R 2＝Bn，X＝Br；
21：M＝Fe，R 1＝Me，R 2＝H，X＝Cl； 22：M＝Fe，R 1＝Me，R 2＝Me，X＝Cl；
23：M＝Fe，R 1＝Me，R 2＝Et，X＝Cl； 24：M＝Fe，R 1＝Me，R 2＝ iPr，X＝Cl；
25：M＝Fe，R 1＝Me，R 2＝Bn，X＝Cl； 26：M＝Fe，R 1＝H，R 2＝H，X＝Cl；
27：M＝Fe，R 1＝H，R 2＝Me，X＝Cl； 28：?M＝Fe，R 1＝H，R 2＝Et，X＝Cl；
29：M＝Fe，R 1＝H，R2＝ iPr，X＝Cl； 30：M＝Fe，R1＝H，R 2＝Bn，X＝Cl；
31：M＝Co，R 1＝Me，R 2＝H，X＝Cl； 32：M＝Co，R 1＝Me，R 2＝Me，X＝Cl；
33：M＝Co，R 1＝Me，R 2＝Et，X＝Cl； 34：M＝Co，R 1＝Me，R 2＝ iPr，X＝Cl；
35：M＝Co，R 1＝Me，R 2＝Bn，X＝Cl； 36：M＝Co，R 1＝H，R 2＝H，X＝Cl；
37：M＝Co，R 1＝H，R 2＝Me，X＝Cl； 38：M＝Co，R 1＝H，R 2＝Et，X＝Cl；
39：M＝Co，R 1＝H，R 2＝ iPr，X＝Cl； 40：M＝Co，R 1＝H，R 2＝Bn，X＝Cl；
Here, the Me represent methylidene, Et represents ethyl, iPr represents sec.-propyl, and Bn represents benzyl.
With 2-benzoglyoxaline-1 provided by the invention, 10-phenanthroline late transition metal complex can be used for the ethylene oligomerization reaction as active ingredient; And, in this catalyst system, also can add in right amount and be used for Primary Catalysts activatory promotor (being activator).
Be suitable for as promotor aikyiaiurnirsoxan beta, alkylaluminium cpd, chlorination aluminum alkyls etc. are arranged, the example of aikyiaiurnirsoxan beta comprises methylaluminoxane (MAO), modified methylaluminoxane (MMAO), ethyl aikyiaiurnirsoxan beta and isobutyl aluminium alkoxide.Aikyiaiurnirsoxan beta can produce by the hydrolytic action of various trialkyl aluminium compounds, and MMAO can produce by the hydrolytic action of trimethyl aluminium and more senior trialkylaluminium such as triisobutyl aluminium.Alkylaluminium cpd comprises trialkylaluminium, as trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, tri-n-octylaluminium etc.; The example of chlorination aluminum alkyls comprises diethylaluminum chloride, ethylaluminium dichloride etc.Preferably, use aikyiaiurnirsoxan beta can make the active high of catalyst system as promotor, as methylaluminoxane (MAO) as activator.
Below with specific embodiment the present invention is described.
Embodiment 1, preparation 2-(1H-benzoglyoxaline)-9-methyl isophthalic acid, 10-phenanthroline [ligand 1]
In the 250ml flask, add 2,9-methyl isophthalic acid, 10-phenanthroline 1.004 grams (4.80mmol), O-Phenylene Diamine 0.58 gram (5.36mmol), industrial sulphur 6.00 grams (24.00mmol).Mix the back at 8 hours (tail gas H of 170 ℃ of following stirring reactions 2S need absorb with dense potassium hydroxide solution, and reaction is preferably in the stink cupboard to be carried out).After reaction is finished, add about 200mL methyl alcohol while hot, the methods such as stirring, ultrasonic wave that make full use of make the resultant of reaction dissolving.The methanol solution filtration under diminished pressure is removed part sulphur, add loaded by silica gel in the filtrate.Silica gel column chromatography is done eluent drip washing with trichloromethane-ethyl acetate-methyl alcohol of 20:20:1, and the 4th component is a product.Decompression concentrates leacheate, be placed in the refrigerator 0 ℃ freezing 10 hours down, promptly get white product crystal 0.60 and restrain productive rate 42%.
FT-IR(KBr?disc，cm -1)：3419，3051，2950，1620，1590，1466，1435，1337，1189，1065，889，768，743；
1H?NMR(400MHz，CDCl 3)：δ＝13.60(s，1H，NH)；8.58(d， 1J＝8.4Hz，1H，Phen)；8.18(d， 1J＝8.4Hz，1H，Phen)；8.06(d， 1J＝8.4Hz，1H，Phen)；7.82(d， 1J＝6.0Hz，1H，Phen)；7.66(s，2H，Phen)；7.49(d， 1J＝6.0Hz，1H，benzimidazole)；7.36(d， 1J＝8.4Hz，1H，benzimidazole)；7.24(dd， 1J＝6.0Hz，2H，benzimidazole)；2.80(s，3H，CH 3)ppm.
13C?NMR(75MHz，CDCl 3)：δ＝157.9，151.9，150.6，147.2，143.7，143.5，135.8，135.6，127.7，126.0，125.5，124.5，123.0，119.8，111.9，23.5ppm.
Ultimate analysis: C 20H 14N 4Theoretical value (%): C, 77.06; H, 4.39; N, 18.55; Experimental value (%): C, 77.40; H, 4.55; N, 18.05.
Embodiment 2, preparation 2-(1-methyl isophthalic acid H-benzoglyoxaline)-9-methyl isophthalic acid, 10-phenanthroline [part 2]
With 0.25 gram (0.80mmol) 2-(1H-benzoglyoxaline)-9-methyl isophthalic acid, 10-phenanthroline part is dissolved in 50 milliliters of acetonitriles, adds the salt of wormwood of 0.50 gram (3.62mmol) again.With this mixing solutions reflux 8 hours, be cooled to room temperature then earlier, add the methyl iodide of 0.07mL (1.12mmol) again.Stirring reaction is 8 hours under the room temperature, and decompression was spin-dried for acetonitrile after question response was finished.Add 50mL deionized water dissolving post reaction mixture, divide three extractions with trichloromethane again.Merge organic phase, behind anhydrous magnesium sulfate drying, use loaded by silica gel.Silica gel column chromatography is eluent drip washing with the triethylamine, and the 3rd component is a product.The evaporated under reduced pressure solvent promptly gets white powder product 0.12 gram, productive rate 46%.
FT-IR (KBr disc, cm -1): 2919,1614,1588,1438,1414,1326,1258,1096,855,728; 1H NMR (400MHz, CDCl 3): δ=8.77 (d, 1J=8.4Hz, 1H, Phen); 8.38 (d, 1J=8.4Hz, 1H, Phen); 8.17 (d, 1J=8.4Hz, 1H, Phen); 7.89 (d, 1J=8.0Hz, 1H, Phen); 7.83 (d, 1J=8.8Hz, 1H, Phen); 7.79 (d, 1J=8.8Hz, 1H, Phen); 7.55 (t, 1J=7.2Hz, 2H, benzimidazole); 7.40 (t, 1J=7.2Hz, 1H, benzimidazole); 7.35 (t, 1J=7.2Hz, 1H, benzimidazole); 4.78 (s, 3H, CH 3); 2.94 (s, 3H, CH3) ppm. 13C NMR (75MHz, CDCl 3): δ=159.5,150.4,150.1,145.7,145.0,142.8,137.8,136.7,136.3,127.2,127.0,125.3,123.7,123.4,122.7,120.2,110.2,33.2,26.0ppm. ultimate analysis: C 21H 16N 4Theoretical value (%): C, 77.45; H, 5.23; N, 17.32; Experimental value (%): C, 77.76; H, 4.97; N, 17.27.
Embodiment 3, preparation 2-(1-ethyl-1H-benzoglyoxaline)-9-methyl isophthalic acid, 10-phenanthroline [part 3]
Experimental procedure is with embodiment 2, with identical mixing solutions reflux 8 hours, is cooled to room temperature then earlier, adds the iodoethane of 0.09mL (1.12mmol) again.60 ℃ of following stirring reactions 8 hours, last handling process was identical with embodiment 2.Get pink solid 0.15 gram, productive rate 60%.
FT-IR (KBr disc, cm -1): 2962,1615,1588,1488,1416,1329,1264,1097,849,731. 1HNMR (400MHz, CDCl 3): δ=8.75 (d, 1J=8.4Hz, 1H, Phen); 8.37 (d, 1J=8.4Hz, 1H, Phen); 8.16 (d, 1J=8.4Hz, 1H, Phen); 7.90 (d, 1J=8.0Hz, 1H, Phen); 7.83 (d, 1J=8.8Hz, 1H, Phen), 7.79 (d, 1J=8.8Hz, 1H, Phen); 7.55 (t, 1J=7.2Hz, 2H, benzimidazole); 7.39 (t, 1J=7.2Hz, 1H, benzimidazole); 7.34 (t, 1J=7.2Hz, 1H, benzimidazole); 5.34 (q, 1J=7.2Hz, 2H, CH 2CH 3); 2.92 (s, 3H, CH 3); 1.77 (t, 1J=7.2Hz, 3H, CH 2CH 3) ppm. 13CNMR (75MHz, CDCl 3): δ=159.5,150.2,150.0,145.9,145.3,143.1,136.8,136.6,136.1,128.4,127.2,127.0,125.3,123.6,123.3,122.6,120.3,110.3,41.4,25.8,15.8ppm. ultimate analysis: C 22H 18N 4Theoretical value (%): C, 77.81; H, 5.66; N, 16.53; Experimental value (%): C, 78.08; H, 5.36; N, 16.56.
Embodiment 4, preparation 2-(1-sec.-propyl-1H-benzoglyoxaline)-9-methyl isophthalic acid, 10-phenanthroline [part 4]
Experimental procedure is with embodiment 2, with identical mixing solutions reflux 8 hours, is cooled to room temperature then earlier, adds the 2-iodopropane of 0.11mL (1.12mmol) again.Back flow reaction 8 hours, last handling process is identical with embodiment 2.Get yellow crystals 0.11 gram, productive rate 43%.
FT-IR (KBr disc, cm -1): 2967,1617,1588,1493,1419,1404,1387,1132,855,740. 1HNMR (300MHz, CDCl 3): δ=8.63 (d, 1J=8.4Hz, 1H, Phen); 8.36 (d, 1J=8.4Hz, 1H, Phen); 8.12 (d, 1J=8.1Hz, 1H, Phen); 7.91 (d, 1J=8.4Hz, 1H, Phen); 7.77 (m, 3H); 7.51 (d, 1J=8.4Hz, 1H, benzimidazole); 7.33 (m, 2H, benzimidazole); 6.67 (sept, 1J=6.6Hz, 1H, CH (CH 3) 2); 2.90 (s, 3H, CH 3); 1.90 (d, 1J=6.6Hz, 6H, CH (CH 3) 2) ppm. 13C NMR (75MHz, CDCl 3): δ=158.6,145.0,149.5,144.9,144.1,142.8,135.9,135.3,134.3,127.4,126.4,126.1,124.4,123.2,122.8,122.1,121.4,119.8,112.3,48.7,25.0,20.9ppm. ultimate analysis: C 23H 20N 4Theoretical value (%): C, 77.98; H, 6.03; N, 15.99; Experimental value (%): C, 78.38; H, 5.72; N, 15.90.
Embodiment 5, preparation 2-(1-benzyl-1H-benzoglyoxaline)-9-methyl isophthalic acid, 10-phenanthroline [part 5]
Experimental procedure is with embodiment 2, with identical mixing solutions reflux 8 hours, is cooled to room temperature then earlier, adds the benzyl bromine of 0.13mL (1.12mmol) again.Back flow reaction 8 hours, last handling process is identical with embodiment 2, gets ivory buff powder 0.14 gram, productive rate 55%.
FT-IR (KBr disc, cm -1): 3038,3004,1616,1587,1495,1442,1414,1329,864,740,720. 1H NMR (400MHz, CDCl 3): δ=8.77 (d, 1J=8.4Hz, 1H, Phen); 8.36 (d, 1J=8.4Hz, 1H, Phen); 8.17 (d, 1J=8.0Hz, 1H, Phen); 7.94 (dd, 1J=6.0Hz, 1H, Phen); 7.80 (dd, 1J=8.4Hz, 2H, Phen); 7.55 (d, 1J=8.0Hz, 2H, benzimidazole); 7.37 (dd, 1J=6.0Hz, 2H, benzimidazole); 7.31 (d, 1J=6.0Hz, 2H, Ph); 7.13 (m, 3H, Ph); 6.90 (s, 2H, CH 2); 2.89 (s, 3H, CH 3) ppm. 13C NMR (75MHz, CDCl 3): δ=163.6,158.5,149.1,145.2,143.9,143.6,143.2,142.0,137.2,136.4,135.7,135.2,127.4,126.2,124.3,122.7,122.3,121.9,119.4,110.0,48.1,24.8ppm. ultimate analysis: C 27H 20N 4Theoretical value: C, 80.53; H, 5.23; N, 14.24; Experimental value: C, 80.98; H, 5.03; N, 13.99.
Embodiment 6, preparation 2-(1H-benzoglyoxaline)-1,10-phenanthroline [part 6]
With 1.12 gram (5.00mmol) 2-carboxyls-1,10-phenanthroline and 0.58 gram (5.40mmol) O-Phenylene Diamine mix, and add 7.00 gram polyphosphoric acid then, in microwave irradiation (450W) reaction down.Take the mode of intermittent irradiation, shone 2 minutes at every turn, shone once concurrent irradiation 3 times in about one minute at interval.To just react cancellation reaction in the about 300mL frozen water of the liquid impouring of finishing while hot, add NaHCO then 3, adjust about the pH value to 9 of solution.Insolubles in the filtration under diminished pressure aqueous solution is dissolved in this insolubles in the ethanol, supports.Silica gel column chromatography is made one section eluent with ethyl acetate-methyl alcohol of 10:1, goes out the less impurity of polarity, makes two sections eluents with ethyl acetate-methyl alcohol of 1:1 again, goes out product.The evaporated under reduced pressure solvent gets white crystal 0.36 gram, productive rate 26%.
FT-IR (KBr disc, cm -1): 3399,3059,1619,1587,1502,1431,1315,1275,856,740. 1HNMR (400MHz, CDCl 3): δ=13.43 (s, 1H, NH); 9.06 (dd, 1J=4.4Hz, 1H, Phen); 8.74 (d, 1J=8.4Hz, 1H, Phen); 8.35 (d, 1J=8.4Hz, 1H, Phen); 8.24 (dd, 1J=8.0Hz, 1H, Phen); 7.88 (t, 1J=6.4Hz, 1H, benzimidazole); 7.82 (dd, 1J=8.8Hz, 2H, Phen); 7.64 (dd, 1J=8.0Hz, 1H, Phen); 7.57 (m, 1H, benzimidazole); 7.30 (m, 2H, benzimidazole) ppm. 13CNMR (75MHz, CDCl 3): δ=151.3,149.0,148.4,145.2,144.8,144.2,136.6,136.5,134.7,128.8,128.5,126.4,123.6,123.0,122.0,120.9,119.6,111.6ppm. ultimate analysis: C 19H 12N 4Theoretical value: C, 77.38; H, 3.83; N, 18.79; Experimental value: C, 77.01; H, 4.08; N, 18.91.
Embodiment 7, preparation 2-(1-methyl isophthalic acid H-benzoglyoxaline)-1,10-phenanthroline [part 7]
Experimental procedure is with embodiment 2, methyl iodide and 2-(1H-benzoglyoxaline)-1, and the reaction of 10-phenanthroline part obtains the white powder solid, productive rate 51%.
FT-IR (KBr disc, cm -1): 2936,1617,1590,1496,1463,1439,1414,1259,1100,855,736. 1H NMR (300MHz, CDCl3): δ=9.23 (d, 1J=3.9Hz, 1H, Phen); 8.77 (d, 1J=8.4Hz, 1H, Phen); 8.42 (d, 1J=8.4Hz, 1H, Phen); 8.31 (d, 1J=8.0Hz, 1H, Phen); 7.88 (m, 3H); 7.70 (dd, 1J=7.8Hz, 1H, Phen); 7.55 (d, 1J=7.4Hz, 1H, benzimidazole); 7.41 (t, 1J=7.2Hz, 1H, benzimidazole); 7.36 (t, 1J=7.2Hz, 1H, benzimidazole); 4.72 (s, 3H, CH 3) ppm. 13C NMR (75MHz, CDCl 3): δ=149.4,149.2,145.1,144.3,144.0,141.6,138.0,136.4,135.6,134.9,127.9,126.1,125.2,122.7,122.4,122.0,121.5,119.0,109.0,29.7ppm. ultimate analysis: C 20H 14N 4Theoretical value: C, 77.18; H, 4.88; N, 17.94; Experimental value: C, 77.40; H, 4.55; N, 18.05.
Embodiment 8,2-(1-ethyl-1H-benzoglyoxaline)-1,10-phenanthroline [part 8]
Experimental procedure is with embodiment 3, iodoethane and 2-(1H-benzoglyoxaline)-1, and the reaction of 10-phenanthroline part obtains the light yellow solid product, productive rate 62%.
FT-IR (KBr disc, cm -1): 3038,2961,1614,1588,1555,1461,1418,1379,1328,1290,1105,845,734. 1H NMR (400MHz, CDCl 3): δ=9.22 (d, 1J=4.0Hz, 1H, Phen); 8.76 (d, 1J=8.4Hz, 1H, Phen); 8.42 (d, 1J=8.4Hz, 1H, Phen); 8.30 (d, 1J=8.0Hz, 1H, Phen); 7.91 (d, 1J=7.6Hz, 1H, benzimidazole); 7.88 (s, 2H, Phen); 7.68 (dd, 1J=8.0Hz, 1H, Phen); 7.57 (d, 1J=8.0Hz, 1H, benzimidazole); 7.40 (t, 1J=7.2Hz, 1H, benzimidazole); 7.36 (t, 1J=7.2Hz, 1H, benzimidazole); 5.38 (q, 1J=7.2Hz, 2H, CH 2CH 3); 1.61 (t, 1J=7.2Hz, 3H, CH 2CH 3) ppm. 13C NMR (75MHz, CDCl 3): δ=149.3,149.1,148.7,145.3,144.2,141.8,137.5,135.4,134.7,127.8,126.1,125.1,122.4,122.3,121.9,121.3,119.0,109.0,39.8,14.3ppm. ultimate analysis: C 21H 16N 4Theoretical value: C, 77.76; H, 4.97; N, 17.27; Experimental value: C, 77.48; H, 4.78; N, 17.64.
Embodiment 9, preparation 2-(1-sec.-propyl-1H-benzoglyoxaline)-1,10-phenanthroline [part 9]
Experimental procedure is with embodiment 4, different propane of 2-iodine and 2-(1H-benzoglyoxaline)-1, and the reaction of 10-phenanthroline part obtains the light brown solid phase prod, productive rate 32%.
FT-IR (KBr disc, cm -1): 2973,1617,1586,1495,1457,1422,1336,1282,1254,1136,862,744. 1H NMR (300MHz, CDCl 3): δ=9.18 (d, 1J=3.3Hz, 1H, Phen); 8.60 (d, 1J=8.4Hz, 1H, Phen); 8.41 (d, 1J=8.4Hz, 1H, Phen); 8.27 (d, 1J=8.0Hz, 1H, Phen); 7.90 (d, 1J=5.4Hz, 1H, benzimidazole); 7.86 (s, 2H, Phen); 7.76 (d, 1J=6.0Hz, 1H, benzimidazole); 7.65 (dd, 1J=7.2Hz, 1H, Phen); 7.32 (m, 2H, benzimidazole); 6.45 (sept, 1J=6.9Hz, 1H, CH (CH 3) 2); (1.86 d, 6H, CH (CH3) 2) ppm. 13C NMR (75MHz, CDCl 3): δ=149.7,149.5,149.4,145.2,144.1,142.5,135.6,134.7,133.8,127.8,127.0,126.2,125.1,123.2,122.0,121.7,121.0,119.5,111.9,48.2,20.5ppm. ultimate analysis: C 22H 18N 4Theoretical value: C, 78.08; H, 5.36; N, 16.56; Experimental value: C, 78.44; H, 4.93; N, 16.63.
Embodiment 10, preparation 2-(1-benzyl-1H-benzoglyoxaline)-1,10-phenanthroline [ligand 1 0]
Experimental procedure is with embodiment 5, benzyl bromine and 2-(1H-benzoglyoxaline)-1, and the reaction of 10-phenanthroline part obtains the light brown solid phase prod, productive rate 47%.
FT-IR (KBr disc, cm -1): 2928,1605,1588,1496,1434,1351,1259,1163,1078,857,735. 1H NMR (300MHz, CDCl 3): δ=9.13 (d, 1J=3.2Hz, 1H, Phen); 8.65 (d, 1J=8.4Hz, 1H, Phen); 8.27 (d, 1J=8.4Hz, 1H, Phen); 8.18 (d, 1J=7.2Hz, 1H, Phen); 7.84 (t, 1J=6.0Hz, 1H, benzimidazole); 7.74 (s, 2H, Phen); 7.58 (dd, 1J=8.0Hz, 1H, Phen); 7.47 (t, 1J=6.0Hz, 1H, benzimidazole); 7.28 (t, 1J=3.2Hz, 2H, benzimidazole); 7.22 (s, 1H, Phen); 7.12 (d, 1J=3.2Hz, 2H, Ph); 6.99 (m, 3H, Ph); 6.71 (s, 2H, CH2) ppm. 13C NMR (75MHz, CDCl 3): δ=149.4,149.2,148.9,145.3,141.9,137.0,136.2,135.7,134.9,128.0,127.3,126.3,126.1,125.2,122.9,122.6,122.1,121.8,119.3,109.8,47.9ppm. ultimate analysis: C 26H 18N 4Theoretical value: C, 80.81; H, 4.69; N, 14.50; Experimental value: C, 81.13; H, 4.82; N, 14.05.
Nickelous chloride (II) [title complex 1] is closed in embodiment 11, preparation [2-(1H-benzoglyoxaline)-9-methyl isophthalic acid, 10-phenanthroline]
Under the room temperature, with 1.05 gram (3.2mmol) 2-(1H-benzoglyoxaline)-9-methyl isophthalic acids, 10-phenanthroline part is dissolved in the 10mL ethanol, again with the NiCl of identical molar equivalent 26H 2O also is dissolved in the ethanol, and two solution are mixed.Stirring down, reaction promptly had the green precipitate thing to separate out after 8 hours.Pressure reducing and steaming partial solvent concentrated solution filters with the glass sand core funnel then, leach thing with exsiccant ether flushing three times after, collect and leach thing.To leach thing and put into oven drying, take out, obtain title complex 1.13 grams of desired green, productive rate 87% through 8 hours.
FT-IR (KBr disc, cm -1): 3254,1624,1588,1504,1429,1321,863,747; Ultimate analysis: C 20H 14N 4NiCl 2H 2O theoretical value: C, 52.19; H, 3.17; N, 12.66; Experimental value: C, 52.45; H, 3.52; N, 12.23.
Its crystalline structure as shown in Figure 1.
Nickelous chloride (II) [title complex 2] is closed in embodiment 12, preparation [2-(1-methyl isophthalic acid H-benzoglyoxaline)-9-methyl isophthalic acid, 10-phenanthroline]
Experimental procedure is with embodiment 11,2-(1-methyl isophthalic acid H-benzoglyoxaline)-9-methyl isophthalic acid, 10-phenanthroline and NiCl 26H 2The O reaction obtains green title complex 2, and productive rate is 82%.
FT-IR (KBr disc, cm -1): 1622,1589,1504,1486,1464,862,745. ultimate analysis: C 21H 16N 4NiCl 2Theoretical value: C, 55.14; H, 3.07; N, 12.55; Experimental value: C, 55.56; H, 3.55; N, 12.34.
Nickelous chloride (II) [title complex 3] is closed in embodiment 13, preparation [2-(1-ethyl-1H-benzoglyoxaline)-9-methyl isophthalic acid, 10-phenanthroline]
Experimental procedure is with embodiment 11,2-(1-ethyl-1H-benzoglyoxaline)-9-methyl isophthalic acid, 10-phenanthroline and NiCl 26H 2The O reaction obtains green title complex 3, and productive rate is 86%.
FT-IR (KBr disc, cm -1): 3333,1621,1585,1491,1441,1334,862,746. ultimate analysis: C 22H 18N 4NiCl 2Theoretical value: C, 56.14; H, 3.47; N, 11.65; Experimental value: C, 56.46; H, 3.88; N, 11.97.
Its crystalline structure as shown in Figure 2.
Nickelous chloride (II) [title complex 4] is closed in embodiment 14, preparation [2-(1-sec.-propyl-1H-benzoglyoxaline)-9-methyl isophthalic acid, 10-o-phenanthroline]
Experimental procedure is with embodiment 11,2-(1-sec.-propyl-1H-benzoglyoxaline)-9-methyl isophthalic acid, 10-phenanthroline and NiCl 26H 2The O reaction obtains green title complex 4, and productive rate is 91%.
FT-IR (KBr disc, cm -1): 3371,2973,1622,1586,1517,1446,1334,1161,865,747. ultimate analyses: C 23H 20N 4NiCl 2Theoretical value: C, 57.62; H, 4.46; N, 11.33; Experimental value: C, 57.31; H, 4.18; N, 11.62.
Nickelous chloride (II) [title complex 5] is closed in embodiment 15, preparation [2-(1-benzyl-1H-benzoglyoxaline)-9-methyl isophthalic acid, 10-phenanthroline]
Experimental procedure is with embodiment 11,2-(1-benzyl-1H-benzoglyoxaline)-9-methyl isophthalic acid, 10-phenanthroline and NiCl 26H 2The O reaction obtains green title complex 5, and productive rate is 90%.
FT-IR (KBr disc, cm -1): 3056,1619,1586,1522,1481,1447,1426,1334,857,746. ultimate analyses: C 27H 20N 4NiCl 2Theoretical value: C, 61.04; H, 3.57; N, 10.65; Experimental value: C, 61.18; H, 3.80; N, 10.57.
Nickelous chloride (II) [title complex 6] is closed in embodiment 16, preparation [2-(1H-benzoglyoxaline)-1,10-phenanthroline]
Experimental procedure is with embodiment 11,2-(1H-benzoglyoxaline)-1,10-phenanthroline and NiCl 26H 2The O reaction obtains green title complex 6, and productive rate is 84%.
FT-IR (KBr disc, cm -1): 3273,3046,1614,1581,1512,1446,1321,859,742,706. ultimate analyses: C 19H 12N 4NiCl 2Theoretical value: C, 53.13; H, 2.51; N, 13.50; Experimental value: C, 53.58; H, 2.84; N, 13.15.
Its crystalline structure as shown in Figure 3.
Nickelous chloride (II) [title complex 7] is closed in embodiment 17, preparation [2-(1-methyl isophthalic acid H-benzoglyoxaline)-1,10-phenanthroline]
Experimental procedure is with embodiment 11,2-(1-methyl isophthalic acid H-benzoglyoxaline)-1,10-phenanthroline and NiCl 26H 2The O reaction obtains green title complex 7, and productive rate is 88%.
FT-IR (KBr disc, cm -1): 3273,1621,1577,1530,1510,1460,1418,1335,854,743,706. ultimate analysis: C 20H 14N 4NiCl 2Theoretical value: C, 54.11; H, 3.59; N, 12.47; Experimental value: C, 54.60; H, 3.21; N, 12.73.
Nickelous chloride (II) [title complex 8] is closed in embodiment 18, preparation [2-(1-ethyl-1H-benzoglyoxaline)-1,10-phenanthroline]
Experimental procedure is with embodiment 11,2-(1-ethyl-1H-benzoglyoxaline)-1,10-phenanthroline and NiCl 26H 2The O reaction obtains green title complex 8, and productive rate is 85%.FT-IR (KBr disc, cm -1): 3340,1621,1607,1579,1526,1482,1442,1334,853,745. ultimate analyses: C 21H 16N 4NiCl 2Theoretical value: C, 55.17; H, 3.88; N, 12.11; Experimental value: C, 55.56; H, 3.55; N, 12.34.
Nickelous chloride (II) [title complex 9] is closed in embodiment 19, preparation [2-(1-sec.-propyl-1H-benzoglyoxaline)-1,10-phenanthroline]
Experimental procedure is with embodiment 11,2-(1-sec.-propyl-1H-benzoglyoxaline)-1,10-phenanthroline and NiCl 26H 2The O reaction obtains green title complex 9, and productive rate is 89%.
FT-IR (KBr disc, cm -1): 2976,1620,1577,1522,1440,1334,857,746. ultimate analysis: C 22H 18N 4NiCl 2Theoretical value: C, 56.09; H, 3.51; N, 12.32; Experimental value: C, 56.46; H, 3.88; N, 11.97.
Nickelous chloride (II) [title complex 10] is closed in embodiment 20, preparation [2-(1-benzyl-1H-benzoglyoxaline)-1,10-phenanthroline]
Experimental procedure is with embodiment 11,2-(1-benzyl-1H-benzoglyoxaline)-1,10-phenanthroline and NiCl 26H 2The O reaction obtains green title complex 10, and productive rate is 90%.
FT-IR (KBr disc, cm -1): 3055,1621,1605,1577,1523,1467,1436,1333,857,739. ultimate analyses: C 26H 18N 4NiCl 2Theoretical value: C, 60.14; H, 3.13; N, 10.59; Experimental value: C, 60.51; H, 3.52; N, 10.86.
Nickelous bromide (II) [title complex 11] is closed in embodiment 21, preparation [2-(1H-benzoglyoxaline)-9-methyl isophthalic acid, 10-phenanthroline]
With 1.11 gram (3.57mmol) 2-(1H-benzoglyoxaline)-9-methyl isophthalic acids, (DME) NiBr of 10-phenanthroline part and identical molar equivalent 2Mix being placed in the single port Schlenk bottle of a 50mL, vacuumize back inflated with nitrogen displaced air, three times so repeatedly.Under nitrogen protection, with exsiccant CH 2Cl 2(20mL) squeeze in the Schlenk bottle enclosed system reaction 8 hours with syringe.The reaction solution solvent is concentrated into about 3mL, filters, obtain green title complex 11, productive rate 79% with the glass sand core funnel.
FT-IR (KBr disc, cm -1): 3373,1624,1588,1504,1446,1321,1147,864,745. ultimate analyses: C 20H 14N 4Br 2Ni theoretical value: C, 45.66; H, 2.74; N, 10.35; Experimental value: C, 45.42; H, 2.67; N, 10.59.
Nickelous bromide (II) [title complex 12] is closed in embodiment 22, preparation [2-(1-methyl isophthalic acid H-benzoglyoxaline)-9-methyl isophthalic acid, 10-phenanthroline]
Experimentation is with embodiment 21,2-(1-methyl isophthalic acid H-benzoglyoxaline)-9-methyl isophthalic acid, (DME) NiBr of 10-phenanthroline part and identical molar equivalent 2Reaction obtains green title complex 12, productive rate 77%.
FT-IR (KBr disc, cm -1): 2963,1622,1587,1486,1461,1261,1097,1024,861,801,741. ultimate analysis: C 21H 16N 4Br 2Ni theoretical value: C, 46.24; H, 2.65; N, 10.77; Experimental value: C, 46.46; H, 2.97; N, 10.32.
Nickelous bromide (II) [title complex 13] is closed in embodiment 23, preparation [2-(1-ethyl-1H-benzoglyoxaline)-9-methyl isophthalic acid, 10-phenanthroline]
Experimentation is with embodiment 21,2-(1-ethyl-1H-benzoglyoxaline)-9-methyl isophthalic acid, (DME) NiBr of 10-phenanthroline part and identical molar equivalent 2Reaction obtains green title complex 13, productive rate 80%.
FT-IR (KBr disc, cm -1): 3333,1622,1586,1486,1446,1335,1200,1155,860,744. ultimate analyses: C 22H 18N 4Br 2Ni0.5H 2O theoretical value: C, 47.06; H, 3.68; N, 10.33; Experimental value: C, 46.69; H, 3.38; N, 9.90.
Nickelous bromide (II) [title complex 14] is closed in embodiment 24, preparation [2-(1-sec.-propyl-1H-benzoglyoxaline)-9-methyl isophthalic acid, 10-phenanthroline]
Experimentation is with embodiment 21,2-(1-sec.-propyl-1H-benzoglyoxaline)-9-methyl isophthalic acid, (DME) NiBr of 10-phenanthroline part and identical molar equivalent 2Reaction obtains green title complex 14, productive rate 82%.
FT-IR (KBr disc, cm -1): 2971,1622,1587,1516,1457,1334,1160,861,752. ultimate analyses: C 23H 20N 4Br 2Ni theoretical value: C, 48.67; H, 3.98; N, 9.41; Experimental value: C, 48.39; H, 3.53; N, 9.81.
Nickelous bromide (II) [title complex 15] is closed in embodiment 25, preparation [2-(1-benzyl-1H-benzoglyoxaline)-9-methyl isophthalic acid, 10-phenanthroline]
Experimentation is with embodiment 21,2-(1-benzyl-1H-benzoglyoxaline)-9-methyl isophthalic acid, (DME) NiBr of 10-phenanthroline part and identical molar equivalent 2Reaction obtains green title complex 15, productive rate 73%.
FT-IR (KBr disc, cm -1): 3044,1624,1589,1482,1448,1333,1151,859,731. ultimate analyses: C 27H 20N 4Br 2Ni theoretical value: C, 52.78; H, 3.64; N, 9.50; Experimental value: C, 52.39; H, 3.26; N, 9.05.
Its crystalline structure as shown in Figure 4.
Nickelous bromide (II) [title complex 16] is closed in embodiment 26, preparation [2-(1H-benzoglyoxaline)-1,10-phenanthroline]
Experimentation is with embodiment 21,2-(1H-benzoglyoxaline)-1, (DME) NiBr of 10-phenanthroline part and identical molar equivalent 2Reaction obtains green title complex 16, productive rate 70%.
FT-IR (KBr disc, cm -1): 3363,1623,1580,1514,1446,1320,1144,980,858,743. ultimate analyses: C 19H 12N 4Br 2Ni theoretical value: C, 44.02; H, 2.59; N, 10.51; Experimental value: C, 44.33; H, 2.35; N, 10.88.
Nickelous bromide (II) [title complex 17] is closed in embodiment 27, preparation [2-(1-methyl isophthalic acid H-benzoglyoxaline)-1,10-phenanthroline]
Experimentation is with embodiment 21,2-(1-methyl isophthalic acid H-benzoglyoxaline)-1, (DME) NiBr of 10-phenanthroline part and identical molar equivalent 2Reaction obtains green title complex 17, productive rate 73%.
FT-IR (KBr disc, cm -1): 3310,1621,1576,1531,1511,1480,1460,1418,1335,1132,1043,854,742,706. ultimate analyses: C 20H 14N 4Br 2Ni theoretical value: C, 44.97; H, 2.28; N, 10.11; Experimental value: C, 45.42; H, 2.67; N, 10.59.
Nickelous bromide (II) [title complex 18] is closed in embodiment 28, preparation [2-(1-ethyl-1H-benzoglyoxaline)-1,10-phenanthroline]
Experimentation is with embodiment 21,2-(1-ethyl-1H-benzoglyoxaline)-1, (DME) NiBr of 10-phenanthroline part and identical molar equivalent 2Reaction obtains green title complex 18, productive rate 71%.
FT-IR (KBr disc, cm -1): 3369,1620,1607,1577,1525,1481,1441,1334,858,743. ultimate analyses: C 21H 16N 4Br 2Ni theoretical value: C, 46.95; H, 2.52; N, 10.78; Experimental value: C, 46.46; H, 2.97; N, 10.32.
Nickelous bromide (II) [title complex 19] is closed in embodiment 29, preparation [2-(1-sec.-propyl-1H-benzoglyoxaline)-1,10-phenanthroline]
Experimentation is with embodiment 21,2-(1-sec.-propyl-1H-benzoglyoxaline)-1, (DME) NiBr of 10-phenanthroline part and identical molar equivalent 2Reaction obtains green title complex 19, productive rate 81%.
FT-IR(KBr?disc，cm -1)：
3351,1622,1580,1521,1441,1335,857,746. ultimate analysis: C 22H 18N 4Br 2Ni theoretical value: C, 46.99; H, 3.57; N, 10.48; Experimental value: C, 47.45; H, 3.26; N, 10.06.
Nickelous bromide (II) [title complex 20] is closed in embodiment 30, preparation [2-(1-benzyl-1H-benzoglyoxaline)-1,10-phenanthroline]
Experimentation is with embodiment 21,2-(1-benzyl-1H-benzoglyoxaline)-1, (DME) NiBr of 10-phenanthroline part and identical molar equivalent 2Reaction obtains green title complex 20, productive rate 77%.
FT-IR (KBr disc, cm -1): 3374,1621,1606,1576,1524,1438,1334,854,737,697. ultimate analyses: C 26H 18N 4Br 2Ni theoretical value: C, 51.27; H, 3.34; N, 9.58; Experimental value: C, 51.62; H, 3.00; N, 9.26.
Iron(ic) chloride (II) [title complex 21] is closed in embodiment 31, preparation [2-(1H-benzoglyoxaline)-9-methyl isophthalic acid, 10-phenanthroline]
With 1.06 gram (3.0mmol) 2-(1H-benzoglyoxaline)-9-methyl isophthalic acids, the FeCl of 10-phenanthroline part and identical molar equivalent 24H 2O adds in the 100mL Schlenk bottle after mixing, and vacuumizes the back with air remaining in the nitrogen replacement bottle, three times so repeatedly, the air in the bottle is eliminated fully.Under nitrogen protection, add about 20mL dehydrated alcohol, stirring reaction 8 hours with syringe.With a glass sand core funnel with the reaction solution filtration under diminished pressure, leach thing with anhydrous diethyl ether flushing three times after, take out and leach thing, be placed in the baking oven dry 8 hours, obtain brown title complex 210.89 grams, productive rate 80%.
FT-IR (KBr disc, cm -1): 3417,1599,1586,1544,1507,1488,1396,881,766,703. ultimate analyses: C 20H 14N 4Cl 2Fe theoretical value: C, 54.96; H, 3.23; N, 12.82; Experimental value: C, 54.66; H, 3.00; N, 12.46.
Its crystalline structure as shown in Figure 5.
Iron(ic) chloride (II) [title complex 22] is closed in embodiment 32, preparation [2-(1-methyl isophthalic acid H-benzoglyoxaline)-9-methyl isophthalic acid, 10-phenanthroline]
Experimentation is with embodiment 31, with 2-(1-methyl isophthalic acid H-benzoglyoxaline)-9-methyl isophthalic acid, and the FeCl of 10-phenanthroline part and identical molar equivalent 24H 2After the O reaction, obtain yellow title complex 22, productive rate 70%.
FT-IR (KBr disc, cm -1): 3409,1588,1580,1540,1501,1482,1390,879,761,701. ultimate analyses: C 21H 16N 4Cl 2Fe theoretical value: C, 55.91; H, 3.57; N, 12.42; Experimental value: C, 55.66; H, 3.40; N, 12.11.
Iron(ic) chloride (II) [title complex 23] is closed in embodiment 33, preparation [2-(1-ethyl-1H-benzoglyoxaline)-9-methyl isophthalic acid, 10-phenanthroline]
Experimentation is with embodiment 31, with 2-(1-ethyl-1H-benzoglyoxaline)-9-methyl isophthalic acid, and the FeCl of 10-phenanthroline part and identical molar equivalent 2.4H 2After the O reaction, obtain yellow title complex 23, productive rate 72%.
FT-IR (KBr disc, cm -1): 3402,1584,1577,1543,1507,1480,1384,874,760,698. ultimate analyses: C 22H 18N 4Cl 2Fe theoretical value: C, 56.81; H, 3.90; N, 12.04; Experimental value: C, 56.62; H, 3.77; N, 12.11.
Iron(ic) chloride (II) [title complex 24] is closed in embodiment 34, preparation [2-(1-sec.-propyl-1H-benzoglyoxaline)-9-methyl isophthalic acid, 10-phenanthroline]
Experimentation is with embodiment 31, with 2-(1-sec.-propyl-1H-benzoglyoxaline)-9-methyl isophthalic acid, and the FeCl of 10-phenanthroline part and identical molar equivalent 24H 2After the O reaction, obtain green title complex 24, productive rate 73%.
FT-IR (KBr disc, cm -1): 3400,1580,1574,1541,1501,1485,1380,872,755,691. ultimate analyses: C 23H 20N 4Cl 2Fe theoretical value: C, 57.65; H, 4.21; N, 11.69; Experimental value: C, 57.62; H, 3.97; N, 11.51.
Iron(ic) chloride (II) [title complex 25] is closed in embodiment 35, preparation [2-(1-benzyl-1H-benzoglyoxaline)-9-methyl isophthalic acid, 10-phenanthroline]
Experimentation is with embodiment 31, with 2-(1-benzyl-1H-benzoglyoxaline)-9-methyl isophthalic acid, and the FeCl of 10-phenanthroline part and identical molar equivalent 24H 2After the O reaction, obtain green title complex 25, productive rate 66%.
FT-IR (KBr disc, cm -1): 3405,1582,1570,1540,1506,1477,1375,866,748,682. ultimate analyses: C 27H 20N 4Cl 2Fe theoretical value: C, 61.51; H, 3.82; N, 10.63; Experimental value: C, 61.62; H, 3.92; N, 10.51.
Iron(ic) chloride (II) [title complex 26] is closed in embodiment 36, preparation [2-(1H-benzoglyoxaline)-1,10-o-phenanthroline]
Experimentation is with embodiment 31, with 2-(1H-benzoglyoxaline)-1, and the FeCl of 10-phenanthroline part and identical molar equivalent 24H 2After the O reaction, obtain green title complex 26, productive rate 69%.
FT-IR (KBr disc, cm -1): 3411,1590,1582,1546,1513,1485,1388,875,757,699. ultimate analyses: C 19H 12N 4Cl 2Fe theoretical value: C, 53.94; H, 2.86; N, 13.24; Experimental value: C, 53.69; H, 3.02; N, 13.59.
Iron(ic) chloride (II) [title complex 27] is closed in embodiment 37, preparation [2-(1-methyl isophthalic acid H-benzoglyoxaline)-1,10-phenanthroline]
Experimentation is with embodiment 31, with 2-(1-methyl isophthalic acid H-benzoglyoxaline)-1, and the FeCl of 10-phenanthroline part and identical molar equivalent 24H 2After the O reaction, obtain green title complex 27, productive rate 70%.
FT-IR (KBr disc, cm -1): 3413,1592,1586,1549,1515,1488,1389,877,759,701. ultimate analyses: C 20H 14N 4Cl 2Fe theoretical value: C, 54.96; H, 3.23; N, 12.82; Experimental value: C, 54.69; H, 3.09; N, 12.58.
Iron(ic) chloride (II) [title complex 28] is closed in embodiment 38, preparation [2-(1-ethyl-1H-benzoglyoxaline)-1,10-phenanthroline]
Experimentation is with embodiment 31, with 2-(1-ethyl-1H-benzoglyoxaline)-1, and the FeCl of 10-phenanthroline part and identical molar equivalent 24H 2After the O reaction, obtain green title complex 28, productive rate 70%.
FT-IR (KBr disc, cm -1): 3410,1590,1580,1541,1511,1481,1381,871,753,702. ultimate analyses: C 21H 16N 4Cl 2Fe theoretical value: C, 55.91; H, 3.57; N, 12.42; Experimental value: C, 55.69; H, 3.19; N, 12.55.
Iron(ic) chloride (II) [title complex 29] is closed in embodiment 39, preparation [2-(1-sec.-propyl-1H-benzoglyoxaline)-1,10-phenanthroline]
Experimentation is with embodiment 31, with 2-(1-sec.-propyl-1H-benzoglyoxaline)-1, and the FeCl of 10-o-phenanthroline part and identical molar equivalent 24H 2After the O reaction, obtain green title complex 29, productive rate 71%.
FT-IR (KBr disc, cm -1): 3408,1588,1577,1536,1504,1471,1375,866,745,699. ultimate analyses: C 22H 18N 4Cl 2Fe theoretical value: C, 56.81; H, 3.90; N, 12.04; Experimental value: C, 56.62; H, 3.77; N, 12.43.
Iron(ic) chloride (II) [title complex 30] is closed in embodiment 40, preparation [2-(1-benzyl-1H-benzoglyoxaline)-1,10-phenanthroline]
Experimentation is with embodiment 31, with 2-(1-benzyl-1H-benzoglyoxaline)-1, and the FeCl of 10-phenanthroline part and identical molar equivalent 2.4H 2After the O reaction, obtain blue title complex 30, productive rate 62%.
FT-IR (KBr disc, cm -1): 3419,1596,1589,1548,1517,1488,1386,879,755,710. ultimate analyses: C 26H 18N 4Cl 2Fe theoretical value: C, 60.85; H, 3.54; N, 10.92; Experimental value: C, 60.60; H, 3.71; N, 10.43.
Cobalt chloride (II) [title complex 31] is closed in embodiment 41, preparation [2-(1H-benzoglyoxaline)-9-methyl isophthalic acid, 10-phenanthroline]
With 1.11 gram 2-(1H-benzoglyoxaline)-9-methyl isophthalic acids, 10-phenanthroline part is dissolved in about 15mL CH 2Cl 2In, take by weighing the anhydrous CoCl of identical molar equivalent 2, also it is dissolved in about 15mLCH 2Cl 2In, both are mixed stirring reaction 8 hours.Concentration of reaction solution filters with the glass sand core funnel to the 5mL, with anhydrous diethyl ether flushing three times, will leach thing and transfer in the baking oven again, places 8 hours, obtains green title complex 31, productive rate 84%.
FT-IR (KBr disc, cm -1): 3399,1572,1563,1524,1498,1455,1361,852,733,680. ultimate analyses: C 20H 14N 4Cl 2Co theoretical value: C, 54.57; H, 3.21; N, 12.73; Experimental value: C, 54.62; H, 3.61; N, 12.55.
Cobalt chloride (II) [title complex 32] is closed in embodiment 42, preparation [2-(1-methyl isophthalic acid H-benzoglyoxaline)-9-methyl isophthalic acid, 10-phenanthroline]
With 2-(1-methyl isophthalic acid H-benzoglyoxaline)-9-methyl isophthalic acid, the anhydrous CoCl of 10-phenanthroline part and identical molar equivalent 2Stirring reaction 8 hours obtains green title complex 32, productive rate 88%.
FT-IR (KBr disc, cm -1): 3391,1570,1560,1518,1492,1451,1355,844,726,673. ultimate analyses: C 21H 16N 4Cl 2Co theoretical value: C, 55.53; H, 3.55; N, 12.33; Experimental value: C, 55.66; H, 3.68; N, 12.65.
Cobalt chloride (II) [title complex 33] is closed in embodiment 43, preparation [2-(1-ethyl-1H-benzoglyoxaline)-9-methyl isophthalic acid, 10-phenanthroline]
With 2-(1-ethyl-1H-benzoglyoxaline)-9-methyl isophthalic acid, the anhydrous CoCl of 10-phenanthroline part and identical molar equivalent 2Stirring reaction 8 hours obtains green title complex 33, productive rate 84%.
FT-IR (KBr disc, cm -1): 3390,1573,1562,1513,1490,1453,1351,842,723,671. ultimate analyses: C 22H 18N 4Cl 2Co theoretical value: C, 56.43; H, 3.87; N, 11.97; Experimental value: C, 55.66; H, 3.68; N, 11.62.
Cobalt chloride (II) [title complex 34] is closed in embodiment 44, preparation [2-(1-sec.-propyl-1H-benzoglyoxaline)-9-methyl isophthalic acid, 10-phenanthroline]
With 2-(1-sec.-propyl-1H-benzoglyoxaline)-9-methyl isophthalic acid, the anhydrous CoCl2 stirring reaction of 10-phenanthroline part and identical molar equivalent 8 hours obtains green title complex 34, productive rate 82%.
FT-IR (KBr disc, cm -1): 3386,1569,1561,1507,1482,1443,1347,833,716,659. ultimate analyses: C 23H 20N 4Cl 2Co theoretical value: C, 57.28; H, 4.18; N, 11.62; Experimental value: C, 55.66; H, 3.68; N, 12.65.
Cobalt chloride (II) [title complex 35] is closed in embodiment 45, preparation [2-(1-benzyl-1H-benzoglyoxaline)-9-methyl isophthalic acid, 10-phenanthroline]
With 2-(1-benzyl-1H-benzoglyoxaline)-9-methyl isophthalic acid, the anhydrous CoCl of 10-phenanthroline part and identical molar equivalent 2Stirring reaction 8 hours obtains green title complex 35, productive rate 83%.
FT-IR (KBr disc, cm -1): 3381,1562,1560,1502,1483,1441,1343,831,710,652. ultimate analyses: C 27H 20N 4Cl 2Co theoretical value: C, 61.15; H, 3.80; N, 10.56; Experimental value: C, 61.62; H, 3.69; N, 10.61.
Cobalt chloride (II) [title complex 36] is closed in embodiment 46, preparation [2-(1H-benzoglyoxaline)-1,10-phenanthroline]
With 2-(1H-benzoglyoxaline)-1, the anhydrous CoCl of 10-o-phenanthroline part and identical molar equivalent 2Stirring reaction 8 hours obtains green title complex 36, productive rate 89%.
FT-IR (KBr disc, cm -1): 3394,1575,1570,1513,1494,1453,1358,846,729,677. ultimate analyses: C 19H 12N 4Cl 2Co theoretical value: C, 53.55; H, 2.84; N, 13.15; Experimental value: C, 53.76; H, 2.61; N, 13.49.
Its crystalline structure as shown in Figure 6.
Cobalt chloride (II) [title complex 37] is closed in embodiment 47, preparation [2-(1-methyl isophthalic acid H-benzoglyoxaline)-1,10-o-phenanthroline]
With 2-(1-methyl isophthalic acid H-benzoglyoxaline)-1, the anhydrous CoCl of 10-o-phenanthroline part and identical molar equivalent 2Stirring reaction 8 hours obtains green title complex 37, productive rate 84%.
FT-IR (KBr disc, cm -1): 3392,1571,1566,1508,1491,1450,1351,841,723,671. ultimate analyses: C 20H 14N 4Cl 2Co theoretical value: C, 54.57; H, 3.21; N, 12.73; Experimental value: C, 54.79; H, 3.63; N, 12.43.
Cobalt chloride (II) [title complex 38] is closed in embodiment 48, preparation [2-(1-ethyl-1H-benzoglyoxaline)-1,10-phenanthroline]
With 2-(1-ethyl-1H-benzoglyoxaline)-1, the anhydrous CoCl of 10-phenanthroline part and identical molar equivalent 2Stirring reaction 8 hours obtains green title complex 38, productive rate 87%.
FT-IR (KBr disc, cm -1): 3389,1568,1560,1501,1487,1447,1348,832,719,658. ultimate analyses: C 21H 16N 4Cl 2Co theoretical value: C, 55.53; H, 3.55; N, 12.33; Experimental value: C, 55.79; H, 3.68; N, 12.19.
Cobalt chloride (II) [title complex 39] is closed in embodiment 49, preparation [2-(1-sec.-propyl-1H-benzoglyoxaline)-1,10-phenanthroline]
With 2-(1-sec.-propyl-1H-benzoglyoxaline)-1, the anhydrous CoCl of 10-phenanthroline part and identical molar equivalent 2Stirring reaction 8 hours obtains green title complex 38, productive rate 80%.
FT-IR (KBr disc, cm -1): 3383,1562,1557,1497,1479,1440,1341,830,712,651. ultimate analyses: C 22H 18N 4Cl 2Co theoretical value: C, 56.43; H, 3.87; N, 11.97; Experimental value: C, 56.77; H, 3.61; N, 12.14.
Its crystalline structure as shown in Figure 7.
Cobalt chloride (II) [title complex 40] is closed in embodiment 50, preparation [2-(1-benzyl-1H-benzoglyoxaline)-1,10-phenanthroline]
With 2-(1-benzyl-1H-benzoglyoxaline)-1, the anhydrous CoCl of 10-phenanthroline part and identical molar equivalent 2Stirring reaction 8 hours obtains green title complex 38, productive rate 81%.
FT-IR (KBr disc, cm -1): 3380,1561,1555,1492,1473,1433,1336,824,701,644. ultimate analyses: C 26H 18N 4Cl 2Co theoretical value: C, 60.49; H, 3.51; N, 10.85; Experimental value: C, 60.71; H, 3.76; N, 10.44.
Embodiment 51, [title complex 1] catalyzed ethylene oligomerisation
Use a 250mL stainless steel polymeric kettle that is equipped with mechanical stirring oar and temperature-control device.Polymeric kettle is vacuumized and be heated to 80 ℃, and continue two hours heat-up time.Replacing in advance under the condition of nitrogen in the still with ethene, allowing polymeric kettle slowly cool to 20 ℃.Wash still three times with toluene, add the toluene solution 99mL that contains 3.5mg (5 μ mol) title complex 1 then successively, with Et 2AlCI is promotor (solution 1.3mL, Al/Ni=300)), and makes the cumulative volume of the two remain on 100mL.With still sealing, logical ethene and the constant pressure of keeping ethene are at 3.0MPa.Behind reaction 20min under 20 ℃, the ethylene pressure in the still is discharged, collect the sub-fraction polymeric solution simultaneously.This polymer fluid sample is stopped polymerization with the ethanolic soln of 5% hydrochloric acid, analyze the composition and the distribution of ethylene oligomer in the polymer fluid sample with gas chromatograph.Through gas chromatographic analysis, reaction product mainly is dimer (92.3%) and a spot of tripolymer (7.7%) of ethene, and the oligomerisation activity is 2.33 * 10 6Gmol -1(Ni) h -1, wherein the content of alpha-butylene reaches 90.5%.Remaining mixture does not obtain polymkeric substance with the ethanolic soln neutralization of 5% hcl acidifying.
Embodiment 52, [title complex 2] catalyzed ethylene oligomerisation
Catalyst system therefor is a title complex 2, and promotor is Et 2AlCl, polymerization process and other reaction conditions are with embodiment 51.Through stratographic analysis, reaction product mainly is dimer (93.4%) and a spot of tripolymer (6.6%) of ethene, and the oligomerisation activity is 1.06 * 10 6Gmol -1(Ni) h -1, wherein the content of alpha-butylene reaches 85.7%.
Embodiment 53, [title complex 2] catalyzed ethylene oligomerisation
Catalyst system therefor is title complex 2 and 20 normal triphenylphosphines, and promotor is Et 2AlCl, polymerization process and other reaction conditions are with embodiment 51.Through stratographic analysis, reaction product mainly is dimer (92.5%) and a spot of tripolymer (7.5%) of ethene, and the oligomerisation activity is 3.78 * 10 7Gmol -1(Ni) h -1, wherein the content of alpha-butylene reaches 19.5%.
Embodiment 54, [title complex 3] catalyzed ethylene oligomerisation
Catalyst system therefor is a title complex 3, and promotor is Et2AlCl, and polymerization process and other reaction conditions are with embodiment 51.Through stratographic analysis, reaction product mainly is dimer (95.9%) and a spot of tripolymer (4.1%) of ethene, and the oligomerisation activity is 9.7 * 10 5Gmol -1(Ni) h -1, wherein the content of alpha-butylene reaches 86.2%.
Embodiment 55, [title complex 4] catalyzed ethylene oligomerisation
Catalyst system therefor is a title complex 4, and promotor is Et 2AlCl, polymerization process and other reaction conditions are with embodiment 51.Through stratographic analysis, polymerisate mainly is dimer (97.1%) and a spot of tripolymer (2.9%) of ethene, and polymerization activity is 9.1 * 10 5Gmol -1(Ni) h -1, wherein the content of alpha-butylene reaches 83.6%.
Embodiment 56, [title complex 5] catalyzed ethylene oligomerisation
Catalyst system therefor is a title complex 5, and promotor is Et 2AlCl, polymerization process and other reaction conditions are with embodiment 51.Through stratographic analysis, reaction product mainly is dimer (95.0%) and a spot of tripolymer (5.0%) of ethene, and the oligomerisation activity is 1.22 * 10 6Gmol -1(Ni) h -1, wherein the content of alpha-butylene reaches 84.2%.
Embodiment 57, [title complex 6] catalyzed ethylene oligomerisation
Catalyst system therefor is a title complex 6, and promotor is Et 2AlCl, polymerization process and other reaction conditions are with embodiment 51.Through stratographic analysis, reaction product mainly is dimer (90.1%) and a spot of tripolymer (9.9%) of ethene, and the oligomerisation activity is 1.27 * 10 7Gmol -1(Ni) h -1, wherein the content of alpha-butylene reaches 72.6%.
Embodiment 58, [title complex 6] catalyzed ethylene oligomerisation
Catalyst system therefor is a title complex 6, and promotor changes AlEt into 3(Al/Ni=1000), polymerization process and other reaction conditions are with embodiment 51.Through stratographic analysis, reaction product mainly is dimer (91.9%) and a spot of tripolymer (8.1%) of ethene, and the oligomerisation activity is 1.22 * 10 6Gmol -1(Ni) h -1, wherein the content of alpha-butylene reaches 61.2%.
Embodiment 59, [title complex 6] catalyzed ethylene oligomerisation
Catalyst system therefor is a title complex 6, and used promotor changes MAO (Al/Ni=1000) into, and polymerization process and other reaction conditions are with embodiment 51.Through stratographic analysis, reaction product mainly is dimer (93.7%) and a spot of tripolymer (6.3%) of ethene, and the oligomerisation activity is 9.2 * 10 5Gmol -1(Ni) h -1, wherein the content of alpha-butylene reaches 54.4%.
Embodiment 60, [title complex 6] catalyzed ethylene oligomerisation
Catalyst system therefor is a title complex 6, and used promotor changes MMAO (Al/Ni=1000) into, and polymerization process and other reaction conditions are with embodiment 51.Through stratographic analysis, reaction product mainly is dimer (93.0%) and a spot of tripolymer (7.0%) of ethene, and the oligomerisation activity is 1.13 * 10 6Gmol -1(Ni) h -1, wherein the content of alpha-butylene reaches 59.1%.
Embodiment 61, [title complex 6] catalyzed ethylene oligomerisation
Catalyst system therefor is a title complex 6, and used promotor is diethylaluminum chloride (Al/Ni=200), and polymerization process and other reaction conditions are with embodiment 51.Through stratographic analysis, reaction product mainly is dimer (93.2%) and a spot of tripolymer (6.8%) of ethene, and the oligomerisation activity is 8.81 * 10 6Gmol -1(Ni) h -1, wherein the content of alpha-butylene reaches 77.5%.
Embodiment 62, [title complex 6] catalyzed ethylene oligomerisation
Catalyst system therefor is a title complex 6, and used promotor is diethylaluminum chloride (Al/Ni=500), and polymerization process and other reaction conditions are with embodiment 51.Through stratographic analysis, reaction product mainly is dimer (91.3%) and a spot of tripolymer (8.7%) of ethene, and the oligomerisation activity is 9.97 * 10 6Gmol -1(Ni) h -1, wherein the content of alpha-butylene reaches 70.2%.
Embodiment 63, [title complex 6] catalyzed ethylene oligomerisation
Catalyst system therefor is a title complex 6, and used promotor is diethylaluminum chloride (Al/Ni=800), and polymerization process and other reaction conditions are with embodiment 51.Through stratographic analysis, reaction product mainly is dimer (89.4%) and a spot of tripolymer (10.6%) of ethene, and the oligomerisation activity is 9.73 * 10 6Gmol -1(Ni) h -1, wherein the content of alpha-butylene reaches 68.7%.
Embodiment 64, [title complex 6] catalyzed ethylene oligomerisation
Catalyst system therefor is a title complex 6, and used promotor is diethylaluminum chloride (Al/Ni=1000), and polymerization process and other reaction conditions are with embodiment 51.Through stratographic analysis, reaction product mainly is dimer (89.9%) and a spot of tripolymer (10.1%) of ethene, and the oligomerisation activity is 8.80 * 10 6Gmol -1(Ni) h -1, wherein the content of alpha-butylene reaches 66.0%.
Embodiment 65, [title complex 6] catalyzed ethylene oligomerisation
Catalyst system therefor is a title complex 6, and used promotor is diethylaluminum chloride (Al/Ni=300), and the temperature of reaction that is adopted is 40 ℃, and polymerization process and other reaction conditions are with embodiment 51.Through stratographic analysis, reaction product mainly is dimer (89.1%) and a spot of tripolymer (10.9%) of ethene, and the oligomerisation activity is 1.01 * 10 7Gmol -1(Ni) h -1, wherein the content of alpha-butylene reaches 46.1%.
Embodiment 66, [title complex 6] catalyzed ethylene oligomerisation
Catalyst system therefor is a title complex 6, and used promotor is diethylaluminum chloride (Al/Ni=300), and the temperature of reaction that is adopted is 60 ℃, and polymerization process and other reaction conditions are with embodiment 51.Through stratographic analysis, reaction product mainly is dimer (94.0%) and a spot of tripolymer (6.0%) of ethene, and the oligomerisation activity is 1.51 * 10 6Gmol -1(Ni) h -1, wherein the content of alpha-butylene reaches 40.8%.
Embodiment 67, [title complex 6] catalyzed ethylene oligomerisation
Catalyst system therefor is a title complex 6, and used promotor is diethylaluminum chloride (Al/Ni=300), and the temperature of reaction that is adopted is 80 ℃, and polymerization process and other reaction conditions are with embodiment 51.Through stratographic analysis, reaction product mainly is dimer (93.8%) and a spot of tripolymer (6.2%) of ethene, and the oligomerisation activity is 5.2 * 10 5Gmol -1(Ni) h -1, wherein the content of alpha-butylene reaches 20.1%.
Embodiment 68, [title complex 6] catalyzed ethylene oligomerisation
Catalyst system therefor is a title complex 6, and used promotor is diethylaluminum chloride (Al/Ni=300), and the ethylene pressure that is adopted is 2.0MPa, and polymerization process and other reaction conditions are with embodiment 51.Through stratographic analysis, reaction product mainly is dimer (90.5%) and a spot of tripolymer (9.5%) of ethene, and the oligomerisation activity is 3.55 * 10 6Gmol -1(Ni) h -1, wherein the content of alpha-butylene reaches 61.4%.
Embodiment 69, [title complex 6] catalyzed ethylene oligomerisation
Catalyst system therefor is a title complex 6, and used promotor is diethylaluminum chloride (Al/Ni=300), and the ethylene pressure that is adopted is 1.0MPa, and polymerization process and other reaction conditions are with embodiment 51.Through stratographic analysis, reaction product mainly is dimer (91.6%) and a spot of tripolymer (8.4%) of ethene, and the oligomerisation activity is 2.16 * 10 6Gmol -1(Ni) h -1, wherein the content of alpha-butylene reaches 54.1%.
Embodiment 70, [title complex 6] catalyzed ethylene oligomerisation
Catalyst system therefor is a title complex 6, and used promotor is diethylaluminum chloride (Al/Ni=300), and the reaction times of being adopted is 30min, and polymerization process and other reaction conditions are with embodiment 51.Through stratographic analysis, reaction product mainly is dimer (91.0%) and a spot of tripolymer (9.0%) of ethene, and the oligomerisation activity is 9.84 * 10 6Gmol -1(Ni) h -1, wherein the content of alpha-butylene reaches 70.5%.
Embodiment 71, [title complex 6] catalyzed ethylene oligomerisation
Catalyst system therefor is a title complex 6, and used promotor is diethylaluminum chloride (Al/Ni=300), and the reaction times of being adopted is 40min, and polymerization process and other reaction conditions are with embodiment 51.Through stratographic analysis, reaction product mainly is dimer (96.5%) and a spot of tripolymer (3.5%) of ethene, and the oligomerisation activity is 8.25 * 10 6Gmol -1(Ni) h -1, wherein the content of alpha-butylene reaches 68.3%.
Embodiment 72, [title complex 6] catalyzed ethylene oligomerisation
Catalyst system therefor is a title complex 6, and used promotor is diethylaluminum chloride (Al/Ni=300), and the reaction times of being adopted is 60min, and polymerization process and other reaction conditions are with embodiment 51.Through stratographic analysis, reaction product mainly is dimer (90.3%) and a spot of tripolymer (9.7%) of ethene, and the oligomerisation activity is 6.17 * 10 6Gmol -1(Ni) h -1, wherein the content of alpha-butylene reaches 64.2%.
Embodiment 73, [title complex 6] catalyzed ethylene oligomerisation
The catalyzer that is adopted is title complex 6 and 20 times of normal triphenylphosphines, and used promotor is diethylaluminum chloride (Al/Ni=300), and polymerization process and other reaction conditions are with embodiment 51.Through stratographic analysis, reaction product mainly is dimer (88.4%) and a spot of tripolymer (11.6%) of ethene, and the oligomerisation activity is 3.21 * 10 7Gmol -1(Ni) h -1, wherein the content of alpha-butylene reaches 20.8%.
Embodiment 74, [title complex 7] catalyzed ethylene oligomerisation
Catalyst system therefor is a title complex 7, used promotor is diethylaluminum chloride (Al/Ni=300), polymerization process and other reaction conditions are with embodiment 51, through stratographic analysis, reaction product mainly is dimer (96.6%) and a spot of tripolymer (3.4%) of ethene, and the oligomerisation activity is 2.77 * 10 6Gmol -1(Ni) h -1, wherein the content of alpha-butylene reaches 70.8%.
Embodiment 75, [title complex 7] catalyzed ethylene oligomerisation
The catalyzer that is adopted is 7 and 20 times of normal triphenylphosphines, and used promotor is diethylaluminum chloride (Al/Ni=300), and polymerization process and other reaction conditions are with embodiment 51.Through stratographic analysis, reaction product mainly is dimer (91.8%) and a spot of tripolymer (8.2%) of ethene, and the oligomerisation activity is 3.95 * 10 7Gmol -1(Ni) h -1, wherein the content of alpha-butylene reaches 12.1%.
Embodiment 76, [title complex 8] catalyzed ethylene oligomerisation
Catalyst system therefor is a title complex 8, and used promotor is diethylaluminum chloride (Al/Ni=300), and polymerization process and other reaction conditions are with embodiment 51.Through stratographic analysis, reaction product mainly is dimer (96.2%) and a spot of tripolymer (3.8%) of ethene, and the oligomerisation activity is 4.03 * 10 6Gmol -1(Ni) h -1, wherein the content of alpha-butylene reaches 66.4%.
Embodiment 77, [title complex 9] catalyzed ethylene oligomerisation
Catalyst system therefor is a title complex 9, and used promotor is diethylaluminum chloride (Al/Ni=300), and polymerization process and other reaction conditions are with embodiment 51.Through stratographic analysis, reaction product mainly is dimer (92.9%) and a spot of tripolymer (7.1%) of ethene, and the oligomerisation activity is 4.21 * 10 6Gmol -1(Ni) h -1, wherein the content of alpha-butylene reaches 67.9%.
Embodiment 78, [title complex 10] catalyzed ethylene oligomerisation
Catalyst system therefor is a title complex 10, and used promotor is diethylaluminum chloride (Al/Ni=300), and polymerization process and other reaction conditions are with embodiment 51.Through stratographic analysis, reaction product mainly is dimer (95.7%) and a spot of tripolymer (4.3%) of ethene, and the oligomerisation activity is 2.00 * 10 6Gmol -1(Ni) h -1, wherein the content of alpha-butylene reaches 70.3%.
Embodiment 79, [title complex 11] catalyzed ethylene oligomerisation
Catalyst system therefor is a title complex 11, and used promotor is diethylaluminum chloride (Al/Ni=300), and polymerization process and other reaction conditions are with embodiment 51.Through stratographic analysis, reaction product mainly is dimer (91.1%) and a spot of tripolymer (8.9%) of ethene, and the oligomerisation activity is 2.52 * 10 6Gmol -1(Ni) h -1, wherein the content of alpha-butylene reaches 89.2%.
Embodiment 80, [title complex 11] catalyzed ethylene oligomerisation
The catalyzer that is adopted is 11 and 20 times of normal triphenylphosphines, and used promotor is diethylaluminum chloride (Al/Ni=300), and polymerization process and other reaction conditions are with embodiment 51.Through stratographic analysis, reaction product mainly is dimer (91.3%) and a spot of tripolymer (8.7%) of ethene, and the oligomerisation activity is 2.67 * 10 7Gmol -1(Ni) h -1, wherein the content of alpha-butylene reaches 26.7%.
Embodiment 81, [title complex 12] catalyzed ethylene oligomerisation
Catalyst system therefor is a title complex 12, and used promotor is diethylaluminum chloride (Al/Ni=300), and polymerization process and other reaction conditions are with embodiment 51.Through stratographic analysis, reaction product mainly is dimer (92.5%) and a spot of tripolymer (7.5%) of ethene, and the oligomerisation activity is 1.27 * 10 6Gmol -1(Ni) h -1, wherein the content of alpha-butylene reaches 82.8%.
Embodiment 82, [title complex 13] catalyzed ethylene oligomerisation
Catalyst system therefor is a title complex 13, and used promotor is diethylaluminum chloride (Al/Ni=300), and polymerization process and other reaction conditions are with embodiment 51.Through stratographic analysis, reaction product mainly is dimer (97.4%) and a spot of tripolymer (2.6%) of ethene, and the oligomerisation activity is 1.14 * 10 6Gmol -1(Ni) h -1, wherein the content of alpha-butylene reaches 80.9%.
Embodiment 83, [title complex 14] catalyzed ethylene oligomerisation
Catalyst system therefor is a title complex 14, and used promotor is diethylaluminum chloride (Al/Ni=300), and polymerization process and other reaction conditions are with embodiment 51.Through stratographic analysis, reaction product mainly is dimer (94.4%) and a spot of tripolymer (5.6%) of ethene, and the oligomerisation activity is 1.02 * 10 6Gmol -1(Ni) h -1, wherein the content of alpha-butylene reaches 86.4%.
Embodiment 84, [title complex 15] catalyzed ethylene oligomerisation
Catalyst system therefor is a title complex 15, and used promotor is diethylaluminum chloride (Al/Ni=300), and polymerization process and other reaction conditions are with embodiment 51.Through stratographic analysis, reaction product mainly is dimer (94.0%) and a spot of tripolymer (6.0%) of ethene, and the oligomerisation activity is 1.50 * 10 6Gmol -1(Ni) h -1, wherein the content of alpha-butylene reaches 81.1%.
Embodiment 85, [title complex 15] catalyzed ethylene oligomerisation
Catalyst system therefor is a title complex 15, and used promotor changes AlEt into 3(Al/Ni=1000), polymerization process and other reaction conditions are with embodiment 51.Through stratographic analysis, reaction product mainly is dimer (91.3%) and a spot of tripolymer (8.7%) of ethene, and the oligomerisation activity is 1.01 * 10 6Gmol -1(Ni) h -1, wherein the content of alpha-butylene reaches 68.4%.
Embodiment 86, [title complex 15] catalyzed ethylene oligomerisation
Catalyst system therefor is a title complex 15, and used promotor changes MAO (Al/Ni=1000) into, and polymerization process and other reaction conditions are with embodiment 51.Through stratographic analysis, reaction product mainly is dimer (93.2%) and a spot of tripolymer (6.8%) of ethene, and the oligomerisation activity is 8.7 * 10 5Gmol -1(Ni) h -1, wherein the content of alpha-butylene reaches 62.3%.
Embodiment 87, [title complex 15] catalyzed ethylene oligomerisation
Catalyst system therefor is a title complex 15, and used promotor changes MMAO (Al/Ni=1000) into, and polymerization process and other reaction conditions are with embodiment 51.Through stratographic analysis, reaction product mainly is dimer (92.4%) and a spot of tripolymer (7.6%) of ethene, and the oligomerisation activity is 9.4 * 10 5Gmol -1(Ni) h -1, wherein the content of alpha-butylene reaches 65.4%.
Embodiment 88, [title complex 15] catalyzed ethylene oligomerisation
Catalyst system therefor is a title complex 15, and used promotor is diethylaluminum chloride (Al/Ni=200), and polymerization process and other reaction conditions are with embodiment 51.Through stratographic analysis, reaction product mainly is dimer (95.5%) and a spot of tripolymer 4.5% of ethene), the oligomerisation activity is 9.0 * 10 5Gmol -1(Ni) h -1, wherein the content of alpha-butylene reaches 85.3%.
Embodiment 89, [title complex 15] catalyzed ethylene oligomerisation
Catalyst system therefor is a title complex 15, and used promotor is diethylaluminum chloride (Al/Ni=500), and polymerization process and other reaction conditions are with embodiment 51.Through stratographic analysis, reaction product mainly is dimer (94.9%) and a spot of tripolymer (5.1%) of ethene, and the oligomerisation activity is 2.03 * 10 6Gmol -1(Ni) h -1, wherein the content of alpha-butylene reaches 75.4%.
Embodiment 90, [title complex 15] catalyzed ethylene oligomerisation
Catalyst system therefor is a title complex 15, and used promotor is diethylaluminum chloride (Al/Ni=800), and polymerization process and other reaction conditions are with embodiment 51.Through stratographic analysis, reaction product mainly is dimer (91.0%) and a spot of tripolymer (9.0%) of ethene, and the oligomerisation activity is 4.0 * 10 6Gmol -1(Ni) h -1, wherein the content of alpha-butylene reaches 74.2%.
Embodiment 91, [title complex 15] catalyzed ethylene oligomerisation
Catalyst system therefor is a title complex 15, and used promotor is diethylaluminum chloride (Al/Ni=1000), and polymerization process and other reaction conditions are with embodiment 51.Through stratographic analysis, reaction product mainly is dimer (90.2%) and a spot of tripolymer (9.8%) of ethene, and the oligomerisation activity is 3.40 * 10 6Gmol -1(Ni) h -1, wherein the content of alpha-butylene reaches 72.5%.
Embodiment 92, [title complex 15] catalyzed ethylene oligomerisation
Catalyst system therefor is a title complex 15, and the promotor that is adopted is that diethylaluminum chloride (Al/Ni=800), temperature of reaction change 40 ℃ into, and polymerization process and other reaction conditions are with embodiment 51.Through stratographic analysis, reaction product mainly is dimer (92.5%) and a spot of tripolymer (7.5%) of ethene, and the oligomerisation activity is 3.60 * 10 6Gmol -1(Ni) h -1, wherein the content of alpha-butylene reaches 50.9%.
Embodiment 93, [title complex 15] catalyzed ethylene oligomerisation
Catalyst system therefor is a title complex 15, and the promotor that is adopted is that diethylaluminum chloride (Al/Ni=800), temperature of reaction change 60 ℃ into, and polymerization process and other reaction conditions are with embodiment 51.Through stratographic analysis, reaction product mainly is dimer (97.1%) and a spot of tripolymer (2.9%) of ethene, and the oligomerisation activity is 8.3 * 10 5Gmol -1(Ni) h -1, wherein the content of alpha-butylene reaches 43.8%.
Embodiment 94, [title complex 15] catalyzed ethylene oligomerisation
Catalyst system therefor is a title complex 15, and the promotor that is adopted is that diethylaluminum chloride (Al/Ni=800), temperature of reaction change 80 ℃ into, and polymerization process and other reaction conditions are with embodiment 51.Through stratographic analysis, reaction product mainly is dimer (96.6%) and a spot of tripolymer (3.4%) of ethene, and the oligomerisation activity is 1.6 * 10 5Gmol -1(Ni) h -1, wherein the content of alpha-butylene reaches 21.4%.
Embodiment 95, [title complex 15] catalyzed ethylene oligomerisation
Catalyst system therefor is a title complex 15, and the promotor that is adopted is that diethylaluminum chloride (Al/Ni=800), ethylene pressure change 2.0MPa into, and polymerization process and other reaction conditions are with embodiment 51.Through stratographic analysis, reaction product mainly is dimer (96.5%) and a spot of tripolymer (3.5%) of ethene, and the oligomerisation activity is 1.03 * 10 6Gmol -1(Ni) h -1, wherein the content of alpha-butylene reaches 70.4%.
Embodiment 96, [title complex 15] catalyzed ethylene oligomerisation
Catalyst system therefor is a title complex 15, and the promotor that is adopted is that diethylaluminum chloride (Al/Ni=800), ethylene pressure change 1.0MPa into, and polymerization process and other reaction conditions are with embodiment 51.Through stratographic analysis, reaction product mainly is dimer (92.9%) and a spot of tripolymer (7.1%) of ethene, and the oligomerisation activity is 7.5 * 10 5Gmol -1(Ni) h -1, wherein the content of alpha-butylene reaches 63.1%.
Embodiment 97, [title complex 15] catalyzed ethylene oligomerisation
Catalyst system therefor is a title complex 15, and the promotor that is adopted is diethylaluminum chloride (Al/Ni=800), reaction times to change 30min into, and polymerization process and other reaction conditions are with embodiment 51.Through stratographic analysis, reaction product mainly is dimer (90.3%) and a spot of tripolymer (9.7%) of ethene, and the oligomerisation activity is 2.67 * 10 6Gmol -1(Ni) h -1, wherein the content of alpha-butylene reaches 73.1%.
Embodiment 98, [title complex 15] catalyzed ethylene oligomerisation
Catalyst system therefor is a title complex 15, and the promotor that is adopted is diethylaluminum chloride (Al/Ni=800), reaction times to change 40min into, and polymerization process and other reaction conditions are with embodiment 51.Through stratographic analysis, reaction product mainly is dimer (94.7%) and a spot of tripolymer (5.3%) of ethene, and the oligomerisation activity is 1.96 * 10 6Gmol -1(Ni) h -1, wherein the content of alpha-butylene reaches 72.5%.
Embodiment 99, [title complex 15] catalyzed ethylene oligomerisation
Catalyst system therefor is a title complex 15, and the promotor that is adopted is diethylaluminum chloride (Al/Ni=800), reaction times to change 60min into, and polymerization process and other reaction conditions are with embodiment 51.Through stratographic analysis, reaction product mainly is dimer (92.2%) and a spot of tripolymer (7.8%) of ethene, and the oligomerisation activity is 1.28 * 10 6Gmol -1(Ni) h -1, wherein the content of alpha-butylene reaches 72.0%.
Embodiment 100, [title complex 16] catalyzed ethylene oligomerisation
Catalyst system therefor is a title complex 16, and the promotor that is adopted is diethylaluminum chloride (Al/Ni=300), and polymerization process and other reaction conditions are with embodiment 51.Through stratographic analysis, reaction product mainly is dimer (90.4%) and a spot of tripolymer (9.6%) of ethene, and the oligomerisation activity is 1.08 * 10 7Gmol -1(Ni) h -1, wherein the content of alpha-butylene reaches 71.3%.
Embodiment 101, [title complex 17] catalyzed ethylene oligomerisation
Catalyst system therefor is a title complex 17, and the promotor that is adopted is diethylaluminum chloride (Al/Ni=300), and polymerization process and other reaction conditions are with embodiment 51.Through stratographic analysis, reaction product mainly is dimer (96.9%) and a spot of tripolymer (3.1%) of ethene, and the oligomerisation activity is 3.28 * 10 6Gmol -1(Ni) h -1, wherein the content of alpha-butylene reaches 68.9%.
Embodiment 102, [title complex 18] catalyzed ethylene oligomerisation
Catalyst system therefor is a title complex 18, and the promotor that is adopted is diethylaluminum chloride (Al/Ni=300), and polymerization process and other reaction conditions are with embodiment 51.Through stratographic analysis, reaction product mainly is dimer (94.6%) and a spot of tripolymer (5.4%) of ethene, and the oligomerisation activity is 4.24 * 10 6Gmol -1(Ni) h -1, wherein the content of alpha-butylene reaches 67.2%.
Embodiment 103, [title complex 19] catalyzed ethylene oligomerisation
Catalyst system therefor is a title complex 19, and the promotor that is adopted is diethylaluminum chloride (Al/Ni=300), and polymerization process and other reaction conditions are with embodiment 51.Through stratographic analysis, reaction product mainly is dimer (95.2%) and a spot of tripolymer (4.8%) of ethene, and the oligomerisation activity is 4.68 * 10 6Gmol -1(Ni) h -1, wherein the content of alpha-butylene reaches 66.1%.
Embodiment 104, [title complex 20] catalyzed ethylene oligomerisation
Catalyst system therefor is a title complex 20, and the promotor that is adopted is diethylaluminum chloride (Al/Ni=300), and polymerization process and other reaction conditions are with embodiment 51.Through stratographic analysis, reaction product mainly is dimer (95.6%) and a spot of tripolymer (4.4%) of ethene, and the oligomerisation activity is 2.16 * 10 6Gmol -1(Ni) h -1, wherein the content of alpha-butylene reaches 69.0%.
Embodiment 105, [title complex 21] catalyzed ethylene oligomerisation
Catalyst system therefor is a title complex 21, and used promotor is that (V=1.61mL, Al/Fe=500), polymerization process and other reaction conditions are with embodiment 51 for MAO.Through stratographic analysis, reaction product mainly is dimer (85.6%) and a spot of tripolymer (14.4%) of ethene, and the oligomerisation activity is 1.74 * 10 6Gmol -1(Fe) h -1, wherein the content of alpha-butylene reaches 89.0%.
Embodiment 106, [title complex 22] catalyzed ethylene oligomerisation
Catalyst system therefor is a title complex 22, and used promotor is that (V=1.61mL, Al/Fe=500), polymerization process and other reaction conditions are with embodiment 51 for MAO.Through stratographic analysis, reaction product mainly is dimer (81.1%) and a spot of tripolymer (18.9%) of ethene, and the oligomerisation activity is 1.02 * 10 6Gmol -1(Fe) h -1, wherein the content of alpha-butylene reaches 81.1%.
Embodiment 107, [title complex 23] catalyzed ethylene oligomerisation
Catalyst system therefor is a title complex 23, and used promotor is that (V=1.61mL, Al/Fe=500), polymerization process and other reaction conditions are with embodiment 51 for MAO.Through stratographic analysis, reaction product mainly is dimer (77.9%) and a spot of tripolymer (22.1%) of ethene, and the oligomerisation activity is 1.23 * 10 6Gmol -1(Fe) h -1, wherein the content of alpha-butylene reaches 88.1%.
Embodiment 108, [title complex 24] catalyzed ethylene oligomerisation
Catalyst system therefor is a title complex 24, and used promotor is that (V=1.61mL, Al/Fe=500), polymerization process and other reaction conditions are with embodiment 51 for MAO.Through stratographic analysis, reaction product mainly is dimer (87.1%) and a spot of tripolymer (12.9%) of ethene, and the oligomerisation activity is 1.19 * 10 6Gmol -1(Fe) h -1, wherein the content of alpha-butylene reaches 78.4%.
Embodiment 109, [title complex 25] catalyzed ethylene oligomerisation
Catalyst system therefor is a title complex 25, and used promotor is that (V=1.61mL, Al/Fe=500), polymerization process and other reaction conditions are with embodiment 51 for MAO.Through stratographic analysis, reaction product mainly is dimer (83.3%) and a spot of tripolymer (16.7%) of ethene, and the oligomerisation activity is 1.11 * 10 6Gmol -1(Fe) h -1, wherein the content of alpha-butylene reaches 84.4%.
Embodiment 110, [title complex 26] catalyzed ethylene oligomerisation
Catalyst system therefor is a title complex 26, and used promotor is that (V=1.61mL, Al/Fe=500), polymerization process and other reaction conditions are with embodiment 51 for MAO.Through stratographic analysis, reaction product mainly is dimer (77.2%) and a spot of tripolymer (22.8%) of ethene, and the oligomerisation activity is 4.18 * 10 6Gmol -1(Fe) h -1, wherein the content of alpha-butylene reaches 77.4%.
Embodiment 111, [title complex 27] catalyzed ethylene oligomerisation
Catalyst system therefor is a title complex 27, and used promotor is that (V=1.61mL, Al/Fe=500), polymerization process and other reaction conditions are with embodiment 51 for MAO.Through stratographic analysis, reaction product mainly is dimer (73.3%) and a spot of tripolymer (26.7%) of ethene, and the oligomerisation activity is 3.04 * 10 6Gmol -1(Fe) h -1, wherein the content of alpha-butylene reaches 77.4%.
Embodiment 112, [title complex 28] catalyzed ethylene oligomerisation
Catalyst system therefor is a title complex 28, and used promotor is that (V=1.61mL, Al/Fe=500), polymerization process and other reaction conditions are with embodiment 51 for MAO.Through stratographic analysis, reaction product mainly is dimer (71.0%) and a spot of tripolymer (29.0%) of ethene, and the oligomerisation activity is 2.77 * 10 6Gmol -1(Fe) h -1, wherein the content of alpha-butylene reaches 70.1%.
Embodiment 113, [title complex 29] catalyzed ethylene oligomerisation
Catalyst system therefor is a title complex 29, and used promotor is that (V=1.61mL, Al/Fe=500), polymerization process and other reaction conditions are with embodiment 51 for MAO.Through stratographic analysis, reaction product mainly is dimer (69.4%) and a spot of tripolymer (30.6%) of ethene, and the oligomerisation activity is 2.19 * 10 6Gmol -1(Fe) h -1, wherein the content of alpha-butylene reaches 75.5%.
Embodiment 114, [title complex 30] catalyzed ethylene oligomerisation
Catalyst system therefor is a title complex 30, and used promotor is that (V=1.61mL, Al/Fe=500), polymerization process and other reaction conditions are with embodiment 51 for MAO.Through stratographic analysis, reaction product mainly is dimer (75.5%) and a spot of tripolymer (24.5%) of ethene, and the oligomerisation activity is 3.07 * 10 6Gmol -1(Fe) h -1, wherein the content of alpha-butylene reaches 70.5%.
Embodiment 115, [title complex 31] catalyzed ethylene oligomerisation
Catalyst system therefor is a title complex 31, and used promotor is that (V=2.72mL, Al/Co=1000), polymerization process and other reaction conditions are with embodiment 51 for MMAO.Through stratographic analysis, reaction product mainly is dimer (82.5%) and a spot of tripolymer (17.5%) of ethene, and the oligomerisation activity is 2.88 * 10 6Gmol -1(Co) h -1, wherein the content of alpha-butylene reaches 86.2%.
Embodiment 116, [title complex 32] catalyzed ethylene oligomerisation
Catalyst system therefor is a title complex 32, and used promotor is that (V=2.72mL, Al/Co=1000), polymerization process and other reaction conditions are with embodiment 51 for MMAO.Through stratographic analysis, reaction product mainly is dimer (86.1%) and a spot of tripolymer (13.9%) of ethene, and the oligomerisation activity is 2.45 * 10 6Gmol -1(Co) h -1, wherein the content of alpha-butylene reaches 80.1%.
Embodiment 117, [title complex 33] catalyzed ethylene oligomerisation
Catalyst system therefor is a title complex 33, and used promotor is that (V=2.72mL, Al/Co=1000), polymerization process and other reaction conditions are with embodiment 51 for MMAO.Through stratographic analysis, reaction product mainly is dimer (84.9%) and a spot of tripolymer (15.1%) of ethene, and the oligomerisation activity is 2.04 * 10 6Gmol -1(Co) h -1, wherein the content of alpha-butylene reaches 79.2%.
Embodiment 118, [title complex 34] catalyzed ethylene oligomerisation
Catalyst system therefor is a title complex 34, and used promotor is that (V=2.72mL, Al/Co=1000), polymerization process and other reaction conditions are with embodiment 51 for MMAO.Through stratographic analysis, reaction product mainly is dimer (86.3%) and a spot of tripolymer (13.7%) of ethene, and the oligomerisation activity is 1.98 * 10 6Gmol -1(Co) h -1, wherein the content of alpha-butylene reaches 77.8%.
Embodiment 119, [title complex 35] catalyzed ethylene oligomerisation
Catalyst system therefor is a title complex 35, and used promotor is that (V=2.72mL, Al/Co=1000), polymerization process and other reaction conditions are with embodiment 51 for MMAO.Through stratographic analysis, reaction product mainly is dimer (81.2%) and a spot of tripolymer (18.8%) of ethene, and the oligomerisation activity is 2.56 * 10 6Gmol -1(Co) h -1, wherein the content of alpha-butylene reaches 78.9%.
Embodiment 120, [title complex 36] catalyzed ethylene oligomerisation
Catalyst system therefor is a title complex 36, and used promotor is that (V=2.72mL, Al/Co=1000), polymerization process and other reaction conditions are with embodiment 51 for MMAO.Through stratographic analysis, reaction product mainly is dimer (80.4%) and a spot of tripolymer (19.6%) of ethene, and the oligomerisation activity is 4.78 * 10 6Gmol -1(Co) h -1, wherein the content of alpha-butylene reaches 75.1%.
Embodiment 121, [title complex 37] catalyzed ethylene oligomerisation
Catalyst system therefor is a title complex 37, and used promotor is that (V=2.72mL, Al/Co=1000), polymerization process and other reaction conditions are with embodiment 51 for MMAO.Through stratographic analysis, reaction product mainly is dimer (88.4%) and a spot of tripolymer (11.6%) of ethene, and the oligomerisation activity is 2.75 * 10 6Gmol -1(Co) h -1, wherein the content of alpha-butylene reaches 65.9%.
Embodiment 122, [title complex 38] catalyzed ethylene oligomerisation
Catalyst system therefor is a title complex 38, and used promotor is that (V=2.72mL, Al/Co=1000), polymerization process and other reaction conditions are with embodiment 51 for MMAO.Through stratographic analysis, polymerisate mainly is dimer (85.2%) and a spot of tripolymer (14.8%) of ethene, and polymerization activity is 3.29 * 10 6Gmol -1(Co) h -1, wherein the content of alpha-butylene reaches 69.3%.
Embodiment 123, [title complex 39] catalyzed ethylene oligomerisation
Catalyst system therefor is a title complex 39, and used promotor is that (V=2.72mL, Al/Co=1000), polymerization process and other reaction conditions are with embodiment 51 for MMAO.Through stratographic analysis, reaction product mainly is dimer (84.4%) and a spot of tripolymer (15.6%) of ethene, and the oligomerisation activity is 3.00 * 10 6Gmol -1(Co) h -1, wherein the content of alpha-butylene reaches 65.6%.
Embodiment 124, [title complex 40] catalyzed ethylene oligomerisation
Catalyst system therefor is a title complex 40, and used promotor is that (V=2.72mL, Al/Co=1000), polymerization process and other reaction conditions are with embodiment 51 for MMAO.Through stratographic analysis, reaction product mainly is dimer (81.1%) and a spot of tripolymer (18.9%) of ethene, and the oligomerisation activity is 2.88 * 10 6Gmol -1(Co) h -1, wherein the content of alpha-butylene reaches 62.5%.

Claims (14)

1. the 2-benzoglyoxaline-1 of formula I structure, the 10-phenanthroline transient metal complex,
Figure FSB00000590814800011
(formula I)
Wherein, R 1Be hydrogen or methyl; R 2Be hydrogen, methyl, ethyl, sec.-propyl or benzyl; M is iron or cobalt; X is a halogen.
2. 2-benzoglyoxaline-1 according to claim 1, the 10-phenanthroline transient metal complex is characterized in that: X is Cl or Br.
3. 2-benzoglyoxaline-1 according to claim 2, the 10-phenanthroline transient metal complex is characterized in that: described title complex is M, R 1, R 2, X is selected from the title complex of following any one combination:
M＝Fe，R 1＝Me，R 2＝H，X＝Cl； M＝Fe，R 1＝Me，R 2＝Me，X＝Cl；
M＝Fe，R 1＝Me，R 2＝Et，X＝Cl； M＝Fe，R 1＝Me，R 2＝ iPr，X＝Cl；
M＝Fe，R 1＝Me，R 2＝Bn，X＝Cl； M＝Fe，R 1＝H，R 2＝H，X＝Cl；
M＝Fe，R 1＝H，R 2＝Me，X＝Cl； M＝Fe，R 1＝H，R 2＝Et，X＝Cl；
M＝Fe，R 1＝H，R 2＝ iPr，X＝Cl； M＝Fe，R 1＝H，R 2＝Bn，X＝Cl；
M＝Co，R 1＝Me，R 2＝H，X＝Cl； M＝Co，R 1＝Me，R 2＝Me，X＝Cl；
M＝Co，R 1＝Me，R 2＝Et，X＝Cl； M＝Co，R 1＝Me，R 2＝ iPr，X＝Cl；
M＝Co，R 1＝Me，R 2＝Bn，X＝Cl； M＝Co，R 1＝H，R 2＝H，X＝Cl；
M＝Co，R 1＝H，R 2＝Me，X＝Cl； M＝Co，R 1＝H，R 2＝Et，X＝Cl；
M＝Co，R 1＝H，R 2＝ iPr，X＝Cl； M＝Co，R 1＝H，R 2＝Bn，X＝Cl；
Here, the Me represent methylidene, Et represents ethyl, iPr represents sec.-propyl, and Bn represents benzyl.
4. one kind is carried out the method that ethylene oligomerization reacts, it is characterized in that: catalyst for reaction is the described 2-benzoglyoxaline-1 of claim 1, the 10-phenanthroline transient metal complex, also be added with promotor, described promotor is selected from one or more in aikyiaiurnirsoxan beta, alkylaluminium cpd and the chlorination aluminum alkyls.
5. method according to claim 4 is characterized in that: described aikyiaiurnirsoxan beta is methylaluminoxane, ethyl aikyiaiurnirsoxan beta or isobutyl aluminium alkoxide; Aluminum alkyls is trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum or tri-n-octylaluminium; The chlorination aluminum alkyls is diethylaluminum chloride or ethylaluminium dichloride.
6. according to claim 4 or 5 described methods, it is characterized in that: the mol ratio Al/M of metallic aluminium and catalyst center metal M is 200-1000 in the promotor.
7. method according to claim 6 is characterized in that: the mol ratio Al/M of metallic aluminium and catalyst center metal M is 300-1000 in the described promotor.
8. according to claim 4 or 5 described methods, it is characterized in that: the temperature of oligomerisation reaction is 20-80 ℃, and the pressure of oligomerisation reaction is 1.0-3.0MPa.
9. method according to claim 8 is characterized in that: the temperature of described oligomerisation reaction is 20-40 ℃, and the pressure of oligomerisation reaction is 3.0MPa.
10. one kind is carried out the method that ethylene oligomerization reacts, and it is characterized in that: catalyst for reaction is the described 2-benzoglyoxaline-1 of claim 1, and the 10-phenanthroline transient metal complex also is added with promotor, and described promotor is selected from modified methylaluminoxane.
11. method according to claim 10 is characterized in that: the mol ratio Al/M of metallic aluminium and catalyst center metal M is 200-1000 in the promotor.
12. method according to claim 11 is characterized in that: the mol ratio Al/M of metallic aluminium and catalyst center metal M is 300-1000 in the described promotor.
13. according to arbitrary described method among the claim 10-12, it is characterized in that: the temperature of oligomerisation reaction is 20-80 ℃, the pressure of oligomerisation reaction is 1.0-3.0MPa.
14. method according to claim 13 is characterized in that: the temperature of described oligomerisation reaction is 20-40 ℃, and the pressure of oligomerisation reaction is 3.0MPa.
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