CN100372609C - Catalyst for oligomerization of ethylene, its preparing method and use - Google Patents

Catalyst for oligomerization of ethylene, its preparing method and use Download PDF

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CN100372609C
CN100372609C CNB2005100664272A CN200510066427A CN100372609C CN 100372609 C CN100372609 C CN 100372609C CN B2005100664272 A CNB2005100664272 A CN B2005100664272A CN 200510066427 A CN200510066427 A CN 200510066427A CN 100372609 C CN100372609 C CN 100372609C
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toluene
phenanthroline
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mao
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CN1850339A (en
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孙文华
介素云
张树
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Institute of Chemistry CAS
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Abstract

The present invention relates to a catalyst for ethylene oligomerization and polymerization, which is 2-imino-1, 10-phenanthroline coordinated chloride of Fe<2+>, Co<2+> and Ni<2+>. The present invention also discloses a preparation method of the catalyst and an application. Under the action of a cocatalyst, namely methylaluminoxane, the catalyst has the good performance of ethylene oligomerization and polymerization catalysis, wherein an iron (2) complex expresses very high oligomerization and polymerization activity to ethene and reaches 10<7>g mol Fe<-1>h<-1>; an oligomerization product comprises C4, C6, C8, C10, C12, C14, C16, C18, C20, C22, etc., and the selectivity of alpha-olefin is up to more than 99.5%; polymers are low molecular weight polyolefin and waxy polyolefin. When alkyl aluminum chloride comprises trimethylaluminium, triethylaluminum, triisobutylaluminium, trin-hexylaluminum, trin-octylaluminum, diethylaluminum chloride and ethylaluminum dichloride as the cocatalyst, a catalytic system can also realize oligomerization and polymerization catalytic catalysis to the ethene. The present invention respectively measures the dependency relationship of the catalyst influencing the ethylene oligomerization and the polymerization activity and catalytic condition changes.

Description

A kind of catalyst and preparation method and purposes that is used for ethylene oligomerization and polymerization
Technical field
The present invention relates to the late transition metal complex catalyst of a class ethylene oligomerization and polymerization, promptly contain iron (II), cobalt (II) and nickel (II) composition catalyst, its preparation method and the purposes that is used for catalyzed ethylene oligomerisation and polymerization of three tooth N^N^N dentates.
Background technology
Ethylene oligomerization can the large-scale production linear alkene, its product is important organic chemical industry's intermediate, has multiple different performance and purposes, for example can be used as washing agent, plasticizer, comonomer of syntholube and preparation LLDPE (LLDPE) or the like.Since the seventies, the research of transient metal complex homogeneous catalysis ethylene oligomerization is subject to people's attention, shell (Shell) company has found shell higher olefins preparation technology the earliest, it is SHOP (Shell Higher Olefin Process) technical process, relevant patent: US Patent3686351,19720711 and US Pantent3676523,19720822, this is an O-P bridging type coordination Raney nickel, and the ethylene oligomerization catalysis activity is approximately 10 5Gmol -1(Ni) h -1, 99% is linear alpha-olefins in this technology products therefrom, wherein alpha-olefin accounts for 98%, and suitability for industrialized production and extensive use.
Figure C20051006642700051
Yet people make great efforts to improve when having catalyst, make great efforts the research new catalyst, simplify the synthetic and preparation technology of catalyst, the catalytic activity of raising catalyst and the selectivity of catalysate.Having developed multiple in recent years again is the post-transition metal catalyst system of dentate with hetero atoms such as O, N, P, wherein the nitrogen-atoms catalyst of making the coordination tooth is subjected to people's extensive attention, as recent patent: Jpn.Kokai Tokkyo Koho JP11060627, A22Mar1999Heisei; PCT Int.Appl.WO9923096 A1 14 May 1999; PCT Int.Appl.WO9951550 A1 14 Oct 1999.
Ethylene oligomerization is observed identical reaction mechanism with polymerization, thereby ethylene oligomerization and polymerization are the products of two class different in kinds of catalyzed ethylene reaction.Half of macromolecular material use amount is vistanex, olefin resin is compared with other resin material has fine environment harmony, be used to the material that emphasis is promoted in developed country's automobile industry, the world production amount in 2003 has just reached 8,330 ten thousand tons; Wherein polyethylene is a synthetic resin with fastest developing speed, that output is maximum, purposes is extremely wide, reaches 5,110 ten thousand tons then.Industrialized polyethylene catalysts has Ziegler-Natta type catalyst (DE Pat889229 (1953); IT Pat545332 (1956) and IT Pat536899 (1955); Chem.Rev., 2000,100,1169 and this special issue pertinent literature), Phillips type catalyst (Belg.Pat.530617 (1955); Chem.Rev.1996,96,3327) and metallocene type catalyst (W.Kaminsky, Metalorganic Catalystsfor Synthesis and Polymerization, Berlin:Springer, 1999), and the efficient ethylene oligomerization and the polymerization catalyst of the late transition metal metal compounding material type of development in recent years.Nineteen ninety-five, Brookhart etc. have reported the complex of a class alpha-diimine Ni (II), can high activity ground polymerising ethylene, its structure be shown below (J.Am.Chem.Soc., 1995,117,6414-6415):
Figure C20051006642700061
1998, Brookhart and Gibson etc. reported the complex of pyridine diimine Fe (II) and Co (II) again simultaneously, by regulating the substituting group on the phenyl ring, oligomerisation or polymerising ethylene well, its structure (J.Am.Chem.Soc., 1998 as shown below, 120,4049-4050; Chem.Commun.1998,849-850):
Figure C20051006642700062
R 1＝Me，i-Pr
M＝Fe，Co R 2＝H，Me，i-Pr
R＝H，Me R 3＝H，Me
The applicant is devoted to the research of ethylene oligomerization and polymerization catalyst and Catalytic processes in the past in the several years always, researched and developed the ethylene oligomerisation catalyst of multiclass nickel complex type: 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 ZL 01 1 20214.9, 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 ZL 02 1 18523.9, April 26 2002 applying date, Granted publication day 2004.12.22; Chinese patent ZL 02 1 23213.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 polymerization catalyst: Chinese patent ZL00132106.4, December 13 2000 applying date, January 28 2004 Granted publication day; Chinese patent ZL01118568.6, 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 number October 27 2004 200410086374.6 applying date.In the research of these catalyst, how to obtain the core content that more highly active ethylene oligomerization and polymerization catalyst become research, also be to advance industrialized key as early as possible.
Summary of the invention
The object of the present invention is to provide a kind of after-trasition metal coordination catalyst that is used for ethylene oligomerization and polymerization;
Another purpose of the present invention provides above-mentioned Preparation of catalysts method;
For achieving the above object, the N^N^N dentate that contains provided by the invention, 2-imido grpup-1, the 10-phenanthroline, iron (II), cobalt (II) and nickel (II) complex ethylene oligomerization and polymerization catalyst, three metalloids have all showed and have better arrived good catalytic activity, and wherein iron (II) complex shows high oligomerisation and polymerization activity to ethene, reaches 10 7G mol -1(Fe) h -1), oligomerization product comprises C 4, C 6, C 8, C 10, C 12, C 14, C 16, C 18, C 20And C 22, be expected to be applied in that ethylene oligomerization is industrial up to more than 99.5% Deng, the selectivity of alpha-olefin; Meanwhile, catalyst shows high polymerization activity, obtains relatively low polyolefin of molecular weight and polyolefin waxy body, and the basis of catalyst is provided for related industries production and technique research and development.
Ethylene oligomerization after-trasition metal coordination catalyst involved in the present invention, i.e. chlorination 2-imido grpup-1,10-phenanthroline iron (II), cobalt (II) and nickel (II) complex, general structure is:
Figure C20051006642700081
Wherein:
M is a late transition metal, preferred Fe (II), Co (II) and Ni (II);
R 1-R 5Be selected from hydrogen independently of one another, alkyl, halogen, alkoxyl and nitro; Preferably be selected from hydrogen independently of one another, methyl, ethyl, isopropyl, fluorine, chlorine, bromine, methoxyl group, ethyoxyl and nitro; R preferably is selected from 1-naphthyl and diphenyl methyl independently of one another.
For the present invention, preferred chlorination 2-imido grpup-1,10-phenanthroline iron (II), cobalt (II) and nickel (II) complex are substituting group M, R and the R in the structural formula 1-R 5Be complex 1-63 as described below:
1：M＝Fe，R 1＝Me，R 2＝R 3＝R 4＝R 5＝H；2：M＝Fe，R 2＝Me，R 1＝R 3＝R 4＝R 5＝H；
3：M＝Fe，R 3＝Me，R 1＝R 2＝R 4＝R 5＝H；4：M＝Fe，R 1＝R 2＝Me，R 3＝R 4＝R 5＝H；
5：M＝Fe，R 1＝R 3＝Me，R 2＝R 4＝R 5＝H；6：M＝Fe，R 1＝R 4＝Me，R 2＝R 3＝R 5＝H；
7：M＝Fe，R 1＝R 5＝Me，R 2＝R 3＝R 4＝H；8：M＝Fe，R 2＝R 3＝Me，R 1＝R 4＝R 5＝H；
9：M＝Fe，R 2＝R 4＝Me，R 1＝R 3＝R 5＝H；10：M＝Fe，R 1＝R 3＝R 5＝Me，R 2＝R 4＝H；
11：M＝Fe，R 1＝R 5＝Me，R 3＝Br，R 2＝R 4＝H；12：M＝Fe，R 1＝Et，R 2＝R 3＝R 4＝R 5＝H；
13：M＝Fe，R 1＝Et，R 5＝Me，R 2＝R 3＝R 4＝H；14：M＝Fe，R 1＝R 5＝Et，R 2＝R 3＝R 4＝H；
15：M＝Fe，R 1＝iPr，R 2＝R 3＝R 4＝R 5＝H；16：M＝Fe，R 1＝R 5＝iPr，R 2＝R 3＝R 4＝H；
17：M＝Fe，R 1＝F，R 2＝R 3＝R 4＝R 5＝H；18：M＝Fe，R 1＝F，R 3＝Me，R 2＝R 4＝R 5＝H；
19：M＝Fe，R 1＝F，R 4＝Me，R 2＝R 3＝R 5＝H；20：M＝Fe，R 1＝R 3＝F，R 2＝R 4＝R 5＝H；
21：M＝Fe，R 1＝R 4＝F，R 2＝R 3＝R 5＝H；22：M＝Fe，R 1＝R 5＝F，R 2＝R 3＝R 4＝H；
23：M＝Fe，R 2＝R 3＝F，R 1＝R 4＝R 5＝H；24：M＝Fe，R 1＝R 2＝R 3＝F，R 4＝R 5＝H；
25：M＝Fe，R 1＝R 3＝R 4＝F，R 2＝R 5＝H；26：M＝Fe，R 1＝R 3＝R 5＝F，R 2＝R 4＝H；
27：M＝Fe，R 1＝R 2＝R 3＝R 4＝R 5＝F；28：M＝Fe，R 1＝CI，R 2＝R 3＝R 4＝R 5＝H；
29：M＝Fe，R 2＝Cl，R 1＝R 3＝R 4＝R 5＝H；30：M＝Fe，R 1＝R 5＝Cl，R 2＝R 3＝R 4＝H；
31：M＝Fe，R 1＝R 2＝R 3＝Cl，R 4＝R 5＝H；32：M＝Fe，R 1＝R 3＝R 4＝Cl，R 2＝R 5＝H；
33：M＝Fe，R 1＝R 3＝R 5＝Cl，R 2＝R 4＝H；34：M＝Fe，R 1＝Br，R 2＝R 3＝R 4＝R 5＝H；
35：M＝Fe，R 1＝Br，R 3＝Me，R 2＝R 4＝R 5＝H；36：M＝Fe，R 1＝Br，R 3＝F，R 2＝R 4＝R 5＝H；
37：M＝Fe，R 1＝F，R 3＝Br，R 2＝R 4＝R 5＝H；38：M＝Fe，R 1＝R 3＝Br，R 2＝R 4＝R 5＝H；
39：M＝Fe，R 1＝R 5＝Br，R 2＝R 3＝R 4＝H；40：M＝Fe，R 1＝R 5＝Br，R 3＝Me，R 2＝R 4＝H；
41：M＝Fe，R 1＝R 5＝Br，R 3＝Cl，R 2＝R 4＝H；42：M＝Fe，R 1＝R 3＝R 5＝Br，R 2＝R 4＝H；
43：M＝Fe，R 1＝Br，R 3＝F，R 5＝Cl，R 2＝R 4＝H；44：M＝Fe，R 1＝Br，R 3＝Cl，R 5＝F，R 2＝R 4＝H；
45：M＝Fe，R 1＝Br，R 3＝R 5＝F，R 2＝R 4＝H；46：M＝Fe，R 2＝NO 2，R 1＝R 3＝R 4＝R 5＝H；
47：M＝Fe，R 3＝NO 2，R 1＝R 2＝R 4＝R 5＝H；48：M＝Fe，R 3＝OMe，R 1＝R 2＝R 4＝R 5＝H；
49：M＝Fe，R 1＝Me，R 2＝OMe，R 3＝R 4＝R 5＝H；50：M＝Fe，R 3＝OEt，R 1＝R 2＝R 4＝R 5＝H；
51：M＝Fe，R＝1-naphthyl；52：M＝Fe，R＝CH(Ph) 2
53：M＝Co，R 1＝R 5＝Me，R 2＝R 3＝R 4＝H；54：M＝Co，R 1＝R 3＝R 5＝Me，R 2＝R 4＝H；
55：M＝Co，R 1＝R 5＝Et，R 2＝R 3＝R 4＝H；56：M＝Co，R 1＝R 5＝iPr，R 2＝R 3＝R 4＝H；
57：M＝Co，R 1＝R 5＝F，R 2＝R 3＝R 4＝H；58：M＝Co，R 1＝R 5＝Cl，R 2＝R 3＝R 4＝H；
59：M＝Co，R 1＝R 5＝Br，R 2＝R 3＝R 4＝H；60：M＝Ni，R 1＝R 5＝Me，R 2＝R 3＝R 4＝H；
61：M＝Ni，R 1＝R 3＝R 5＝Me，R 2＝R 4＝H；62：M＝Ni，R 1＝R 5＝Et，R 2＝R 3＝R 4＝H；
63：M＝Ni，R 1＝R 5＝iPr，R 2＝R 3＝R 4＝H。
The present invention also provides a kind of above-mentioned chlorination 2-imido grpup-1, the preparation method of 10-phenanthroline iron (II), cobalt (II) and the serial complex of nickel (II), and it comprises:
(1) with 2-acetyl group-1, the aniline reaction Synthetic 2-imido grpup-1 of 10-phenanthroline and replacement, 10-phenanthroline part;
(2) with the 2-imido grpup-1 that obtains in the step 1,10-phenanthroline part respectively with FeCl 24H 2O, CoCl 2And NiCl 26H 2The O reaction can obtain complex.
The reaction equation of complex preparation of the present invention can be represented with formula 1:
Figure C20051006642700101
Formula 1
1：M＝Fe，R 1＝Me，R 2＝R 3＝R 4＝R 5＝H；2：M＝Fe，R 2＝Me，R 1＝R 3＝R 4＝R 5＝H；
3：M＝Fe，R 3＝Me，R 1＝R 2＝R 4＝R 5＝H；4：M＝Fe，R 1＝R 2＝Me，R 3＝R 4＝R 5＝H；
5：M＝Fe，R 1＝R 3＝Me，R 2＝R 4＝R 5＝H；6：M＝Fe，R 1＝R 4＝Me，R 2＝R 3＝R 5＝H；
7：M＝Fe，R 1＝R 5＝Me，R 2＝R 3＝R 4＝H；8：M＝Fe，R 2＝R 3＝Me，R 1＝R 4＝R 5＝H；
9：M＝Fe，R 2＝R 4＝Me，R 1＝R 3＝R 5＝H；10：M＝Fe，R 1＝R 3＝R 5＝Me，R 2＝R 4＝H；
11：M＝Fe，R 1＝R 5＝Me，R 3＝Br，R 2＝R 4＝H；12：M＝Fe，R 1＝Et，R 2＝R 3＝R 4＝R 5＝H；
13：M＝Fe，R 1＝Et，R 5＝Me，R 2＝R 3＝R 4＝H；14：M＝Fe，R 1＝R 5＝Et，R 2＝R 3＝R 4＝H；
15：M＝Fe，R 1＝iPr，R 2＝R 3＝R 4＝R 5＝H；16：M＝Fe，R 1＝R 5＝iPr，R 2＝R 3＝R 4＝H；
17：M＝Fe，R 1＝F，R 2＝R 3＝R 4＝R 5＝H；18：M＝Fe，R 1＝F，R 3＝Me，R 2＝R 4＝R 5＝H；
19：M＝Fe，R 1＝F，R 4＝Me，R 2＝R 3＝R 5＝H；20：M＝Fe，R 1＝R 3＝F，R 2＝R 4＝R 5＝H；
21：M＝Fe，R 1＝R 4＝F，R 2＝R 3＝R 5＝H；22：M＝Fe，R 1＝R 5＝F，R 2＝R 3＝R 4＝H；
23：M＝Fe，R 2＝R 3＝F，R 1＝R 4＝R 5＝H；24：M＝Fe，R 1＝R 2＝R 3＝F，R 4＝R 5＝H；
25：M＝Fe，R 1＝R 3＝R 4＝F，R 2＝R 5＝H；26：M＝Fe，R 1＝R 3＝R 5＝F，R 2＝R 4＝H；
27：M＝Fe，R 1＝R 2＝R 3＝R 4＝R 5＝F；28：M＝Fe，R 1＝Cl，R 2＝R 3＝R 4＝R 5＝H；
29：M＝Fe，R 2＝Cl，R 1＝R 3＝R 4＝R 5＝H；30：M＝Fe，R 1＝R 5＝Cl，R 2＝R 3＝R 4＝H；
31：M＝Fe，R 1＝R 2＝R 3＝Cl，R 4＝R 5＝H；32：M＝Fe，R 1＝R 3＝R 4＝Cl，R 2＝R 5＝H；
33：M＝Fe，R 1＝R 3＝R 5＝Cl，R 2＝R 4＝H；34：M＝Fe，R 1＝Br，R 2＝R 3＝R 4＝R 5＝H；
35：M＝Fe，R 1＝Br，R 3＝Me，R 2＝R 4＝R 5＝H；36：M＝Fe，R 1＝Br，R 3＝F，R 2＝R 4＝R 5＝H；
37：M＝Fe，R 1＝F，R 3＝Br，R 2＝R 4＝R 5＝H；38：M＝Fe，R 1＝R 3＝Br，R 2＝R 4＝R 5＝H；
39：M＝Fe，R 1＝R 5＝Br，R 2＝R 3＝R 4＝H；40：M＝Fe，R 1＝R 5＝Br，R 3＝Me，R 2＝R 4＝H；
41：M＝Fe，R 1＝R 5＝Br，R 3＝Cl，R 2＝R 4＝H；42：M＝Fe，R 1＝R 3＝R 5＝Br，R 2＝R 4＝H；
43：M＝Fe，R 1＝Br，R 3＝F，R 5＝Cl，R 2＝R 4＝H；44：M＝Fe，R 1＝Br，R 3＝Cl，R 5＝F，R 2＝R 4＝H；
45：M＝Fe，R 1＝Br，R 3＝R 5＝F，R 2＝R 4＝H；46：M＝Fe，R 2＝NO 2，R 1＝R 3＝R 4＝R 5＝H；
47：M＝Fe，R 3＝NO 2，R 1＝R 2＝R 4＝R 5＝H；48：M＝Fe，R 3＝OMe，R 1＝R 2＝R 4＝R 5＝H；
49：M＝Fe，R 1＝Me，R 2＝OMe，R 3＝R 4＝R 5＝H；50：M＝Fe，R 3＝OEt，R 1＝R 2＝R 4＝R 5＝H；
51：M＝Fe，R＝1-naphthyl；52：M＝Fe，R＝CH(Ph) 2
53：M＝Co，R 1＝R 5＝Me，R 2＝R 3＝R 4＝H；54：M＝Co，R 1＝R 3＝R 5＝Me，R 2＝R 4＝H；
55：M＝Co，R 1＝R 5＝Et，R 2＝R 3＝R 4＝H；56：M＝Co，R 1＝R 5＝iPr，R 2＝R 3＝R 4＝H；
57：M＝Co，R 1＝R 5＝F，R 2＝R 3＝R 4＝H；58：M＝Co，R 1＝R 5＝Cl，R 2＝R 3＝R 4＝H；
59：M＝Co，R 1＝R 5＝Br，R 2＝R 3＝R 4＝H；60：M＝Ni，R 1＝R 5＝Me，R 2＝R 3＝R 4＝H；
61：M＝Ni，R 1＝R 3＝R 5＝Me，R 2＝R 4＝H；62：M＝Ni，R 1＝R 5＝Et，R 2＝R 3＝R 4＝H；
63：M＝Ni，R 1＝R 5＝iPr，R 2＝R 3＝R 4＝H。
Concrete preparation process is as follows:
One, the synthetic conventional method of part
1) 2-acetyl group-1; the aniline that 10-phenanthroline and alkyl replace is catalyst backflow 1-2 days with the p-methyl benzenesulfonic acid in ethanol, and reactant liquor concentrates back parlkaline aluminium oxide pillar, with petrol ether/ethyl acetate (4: 1) drip washing; second flow point is a product, and removing desolvates obtains yellow solid.
2) 2-acetyl group-1; the aniline that 10-phenanthroline and fluorine, methoxyl group and nitro replace is catalyst with the p-methyl benzenesulfonic acid and adds molecular sieve or anhydrous sodium sulfate is made dehydrating agent reflux in toluene 1 day; remove solvent toluene parlkaline aluminium oxide pillar after the filtration; with petrol ether/ethyl acetate (4: 1) drip washing; second flow point is a product, and removing desolvates obtains yellow solid.
3) 2-acetyl group-1; the aniline that 10-phenanthroline and chlorine, bromine replace is made catalyst with p-methyl benzenesulfonic acid; adopt ethyl orthosilicate to make solvent and dehydrating agent; under 140-150 ℃, added thermal response 1 day; ethyl orthosilicate is removed in decompression, and parlkaline aluminium oxide pillar is used petrol ether/ethyl acetate (4: 1) drip washing then; second flow point is a product, and removing desolvates obtains yellow solid.
Above-mentioned all synthetic 2-imido grpups-1,10-phenanthroline part have all obtained confirmation by nuclear-magnetism, infrared and elementary analysis.
Two, iron (II), cobalt (II), the synthetic conventional method of nickel (II) complex
With FeCl 24H 2O, CoCl 2Or NiCl 26H 2The ethanolic solution of O in molar ratio 1: 1-1: 1.2 are added drop-wise to 2-imido grpup-1, and in the solution of 10-phenanthroline part, stirring at room is separated out precipitation, filter with ether washing back drying and just obtain 2-imido grpup-1,10-phenanthroline complex.All by the sign of elementary analysis and infrared spectrum, the result of sign provides in respective embodiments complex 1-63.In addition, tested the crystal structure of complex 10,14,16,30,55,60 with the method for X-ray single crystal diffraction, crystal structure provides in formula 2, formula 3, formula 4, formula 5, formula 6 and formula 7 respectively.
Figure C20051006642700121
The crystal structure of formula 2. complexs 10
Figure C20051006642700122
The crystal structure of formula 3. complexs 14
Figure C20051006642700123
The crystal structure of formula 4. complexs 16
Figure C20051006642700131
The crystal structure of formula 5. complexs 30
Figure C20051006642700132
The crystal structure of formula 6. complexs 55
Figure C20051006642700133
The crystal structure of formula 7. complexs 60
With 2-imido grpup-1 provided by the invention, the catalyst of 10-phenanthroline series complex is as active component, and the carbon monoxide-olefin polymeric that is used for co-catalyst (the being activator) composition of major catalyst activation can be used for ethylene oligomerization and polymerisation.Described major catalyst is aforesaid 2-imido grpup-1 of the present invention, 10-phenanthroline iron (II), cobalt (II), the serial complex of nickel (II).
Can use aikyiaiurnirsoxan beta as co-catalyst, the example of aikyiaiurnirsoxan beta comprises MAO (MAO), modified methylaluminoxane (MMAO), ethyl aikyiaiurnirsoxan beta and isobutyl aluminium alkoxide.Aikyiaiurnirsoxan beta can produce by the hydrolysis of various trialkyl aluminium compounds.MMAO can produce by the hydrolysis of trimethyl aluminium and more senior trialkylaluminium such as triisobutyl aluminium.
Other activator that is suitable as in the carbon monoxide-olefin polymeric of the present invention is an alkyl aluminum compound, as trialkylaluminium and chlorination alkyl aluminum.The example of these activators comprises trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, tri-n-octylaluminium, diethylaluminum chloride, ethylaluminium dichloride etc.The preferred aikyiaiurnirsoxan beta of using, as MAO (MAO) as activator.
Specific embodiment
Embodiment one
1. the preparation of part: 2-acetyl group-1; 10-phenanthroline (2-aminotoluene contracts): 2-acetyl group-1; 10-phenanthroline (0.4445g; 2mmol) and 2-aminotoluene (0.2981g; 2.8mmol) add the 40mg p-methyl benzenesulfonic acid and make catalyst and add the 2g4A molecular sieve to make dehydrating agent; 30ml reflux in toluene 1 day; remove solvent toluene after the filtration; residue supports with the carrene dissolving; parlkaline aluminium oxide pillar, with petrol ether/ethyl acetate (4: 1) drip washing, second flow point is a product; removing desolvates obtains yellow solid 0.141g, and productive rate is 23%.FT-IR(KBr?disc，cm -1)：2988，2908，1635，1595，1551，1485，1456，1389，1363，1320，1283，1227，1189，1114，1079，1042，850，829，789，746，657。 1H?NMR(300MHz，CDCl 3)：δ9.25(d，J＝4.5Hz，1H)；8.70(dd，J＝8.4Hz，1H)；8.35(dd，J＝8.7Hz，1H)；8.30(d，J＝8.1Hz，1H)；7.88(s，2H)；7.68(m，1H)；7.24(d，J＝4.2Hz，1H)；7.20(dd，J＝5.7Hz，1H)；7.06(t，J＝7.5Hz，1H)；6.74(d，J＝7.8Hz，1H)；2.65(s，3H，CH 3)；2.17(s，3H，PhCH 3)。Elementary analysis (C 21H 17N 3) theoretical value (%): C81.00, H5.50, N13.49; Experiment value (%): C80.89, H5.94, N13.57.
2. the preparation of catalyst 1: iron (II) (1) is closed in chlorination [2-acetyl group-1,10-phenanthroline (2-aminotoluene contracts)]: with 5mlFeCl 24H 2O (48mg; 0.24mmol) ethanol solution be added drop-wise to 5ml2-acetyl group-1; 10-phenanthroline (2-aminotoluene contracts) part (62.3mg; 0.2mmol) ethanol solution in; stirring at room 6 hours; separate out precipitation, filter with ether washing back drying and obtain blackish green powder solid, productive rate is 85%.FT-IR(KBr?disc，cm -1)：3053，2916，1605，1576，1503，1442，1397，1337，1300，1248，1202，1148，1097，850，740，656。Elementary analysis (C 21H 19Cl 2FeN 3): C57.57, H3.91, N9.59; Experiment value (%): C57.24, H3.94, N9.56.
3. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of continuous drying 6hrs 2Gas displacement 3 times.Add 2.2mg (5 μ mol) catalyst 1 and then vacuumize and with ethene displacement 3 times.Toluene with syringe injection 30ml adds 1.7ml MAO (MAO) (toluene solution of 1.46mol/l) again, makes Al/Fe=500.Under 20 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the watery hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 3.54 * 10 4G mol -1(Fe) h -1, oligomer content is respectively: C 486%, C 614%.Remaining mixture does not obtain polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment two
1. the preparation of part: 2-acetyl group-1; 10-phenanthroline (the 3-methylaniline contracts): 2-acetyl group-1; 10-phenanthroline (0.444g; 2mmol) with 3-methylaniline (0.2978g; 2.8mmol) add the 40mg p-methyl benzenesulfonic acid and make catalyst and add the 2g molecular sieve to make dehydrating agent; 30ml reflux in toluene 1 day; remove solvent toluene after the filtration; residue supports with the carrene dissolving; parlkaline aluminium oxide pillar, with petrol ether/ethyl acetate (4: 1) drip washing, second flow point is a product; removing desolvates obtains yellow solid, and productive rate is 22%.FT-IR(KBr?disc，cm -1)：3046，2916，2908，1636，1591，1551，1485，1456，1389，1363，1319，1284，1190，1115，1079，829，745，658。 1H?NMR(300MHz，CDCl 3)：δ9.25(s，1H)；8.62(d，J＝8.4Hz，1H)；8.35(d，J＝8.7Hz，1H)；8.31(d，J＝8.7Hz，1H)；7.88(s，2H)；7.68(m，1H)；7.31(d，J＝7.8Hz，1H)；6.96(d，J＝7.2Hz，1H)；6.70(m，2H)；2.72(s，3H，CH 3)；2.40(s，3H，PhCH 3)。Elementary analysis (C 21H 17N 3) theoretical value (%): C81.00, H5.50, N13.49; Experiment value (%): C80.56, H5.35, N12.99.
2. the preparation of catalyst 2: iron (II) (2) is closed in chlorination [2-acetyl group-1,10-phenanthroline (the 3-methylaniline contracts)]: with 5mlFeCl 24H 2O (47.6mg; 0.24mmol) ethanol solution be added drop-wise to 5ml2-acetyl group-1; 10-phenanthroline (the 3-methylaniline contracts) part (62.3mg; 0.2mmol) ethanol solution in; stirring at room 6 hours; separate out precipitation, filter with ether washing back drying and obtain blackish green powder solid, productive rate is 61%.FT-IR(KBr?disc，cm -1)：3056，1605，1581，1503，1441，1398，1337，1300，1246，1148，1097，851，742，658。Elementary analysis (C 21H 19Cl 2FeN 3): C57.57, H3.91, N9.59; Experiment value (%): C57.19, H4.06, N9.23.
3. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of continuous drying 6hrs 2Gas displacement 3 times.Add 2.2mg (5 μ mol) catalyst 2 and then vacuumize and with ethene displacement 3 times.Toluene with syringe injection 30ml adds 1.7ml MAO (MAO) (toluene solution of 1.46mol/l) again, makes Al/Fe=500.Under 20 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the watery hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 3.45 * 10 4G mol -1(Fe) h -1, oligomer content is respectively: C 4100%.Remaining mixture does not obtain polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment three
1. the preparation of part: 2-acetyl group-1; 10-phenanthroline (the 4-methylaniline contracts): 2-acetyl group-1; 10-phenanthroline (0.4445g; 2mmol) with 4-methylaniline (0.2980g; 2.8mmol) add the 40mg p-methyl benzenesulfonic acid and make catalyst and add the 2g molecular sieve to make dehydrating agent; 30ml reflux in toluene 1 day; remove solvent toluene after the filtration; residue supports with the carrene dissolving; parlkaline aluminium oxide pillar, with petrol ether/ethyl acetate (4: 1) drip washing, second flow point is a product; removing desolvates obtains yellow solid, and productive rate is 10%.FT-IR(KBr?disc，cm -1)：2918，1636，1591，1552，1485，1390，1321，1283，1187，1115，1080，850，746，657。 1H?NMR(300MHz，CDCl 3)：δ9.26(d，J＝4.5Hz，1H)；8.70(dd，J＝8.4Hz，1H)；8.36(dd，J＝8.7Hz，1H)；8.31(d，J＝8.1Hz，1H)；7.89(s，2H)；7.68(m，1H)；7.24(d，J＝4.2Hz，2H)；7.12(d，J＝4.2Hz，2H)；2.67(s，3H，CH 3)；2.36(s，3H，PhCH 3)。Elementary analysis (C 21H 17N 3) theoretical value (%): C81.00, H5.50, N13.49; Experiment value (%): C80.59, H5.85, N12.99.
2. the preparation of catalyst 3: iron (II) (3) is closed in chlorination [2-acetyl group-1,10-phenanthroline (the 4-methylaniline contracts)]: with 5mlFeCl 24H 2O (48.0mg; 0.24mmol) ethanol solution be added drop-wise to 5ml2-acetyl group-1; 10-phenanthroline (the 4-methylaniline contracts) part (62.3mg; 0.2mmol) ethanol solution in; stirring at room 3 hours; separate out precipitation, filter with ether washing back drying and obtain blackish green powder solid, productive rate is 79%.FT-IR(KBr?disc，cm -1)：3051，2915，1604，1591，1503，1442，1398，1338，1248，1150，1097，852，740，658。Elementary analysis (C 21H 19Cl 2FeN 3): C57.57, H3.91, N9.59; Experiment value (%): C57.18, H3.99, N9.47.
3. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of continuous drying 6hrs 2Gas displacement 3 times.Add 2.2mg (5 μ mol) catalyst 3 and then vacuumize and with ethene displacement 3 times.Toluene with syringe injection 30ml adds 1.7ml MAO (MAO) (toluene solution of 1.46mol/l) again, makes Al/Fe=500.Under 20 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the watery hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 2.98 * 10 4G mol -1(Fe) h -1, oligomer content is respectively: C 4100%.Remaining mixture does not obtain polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment four
1. the preparation of part: 2-acetyl group-1; the 10-phenanthroline (contracts 2; the 3-dimethylaniline): 2-acetyl group-1; 10-phenanthroline (0.4445g; 2mmol) with 2; 3-dimethylaniline (0.3175g; 2.6mmol) add the 40mg p-methyl benzenesulfonic acid and make catalyst and add the 2g molecular sieve to make dehydrating agent, 30ml reflux in toluene 1 day, remove solvent toluene after the filtration; residue supports with the carrene dissolving; parlkaline aluminium oxide pillar, with petrol ether/ethyl acetate (4: 1) drip washing, second flow point is a product; removing desolvates obtains yellow solid, and productive rate is 29%.FT-IR(KBr?disc，cm -1)：3046，2917，1634，1591，1551，1492，1442，1361，1284，1115，998，850，739，657。 1H?NMR(300MHz，CDCl 3)：δ9.25(t，J＝2.3Hz，1H)；8.70(dd，J＝8.4Hz，1H)；8.36(dd，J＝8.4Hz，1H)；8.31(d，J＝7.5Hz，1H)；7.88(s，2H)；7.67(m，1H)；7.15-6.76(m，3H)；2.65(s，3H，CH 3)；2.33(s，3H，PhCH 3)；2.15(s，3H，PhCH 3)。Elementary analysis (C 22H 19N 3) theoretical value (%): C81.20, H5.89, N12.91; Experiment value (%): C80.88, H5.93, N12.81.
2. the preparation of catalyst 4: iron (II) (4) is closed in chlorination [2-acetyl group-1,10-phenanthroline (contracting 2, the 3-dimethylaniline)]: with 5mlFeCl 24H 2O (48.0mg; 0.24mmol) ethanol solution be added drop-wise to 5ml2-acetyl group-1; the 10-phenanthroline (contracts 2; the 3-dimethylaniline) part (65.1mg; 0.2mmol) ethanol solution in, stirring at room 6 hours is separated out precipitation; filtration obtains blackish green powder solid with ether washing back drying, and productive rate is 72%.FT-IR(KBr?disc，cm -1)：3045，2912，1605，1587，1513，1407，1291，1161，1114，857，741，658。Elementary analysis (C 22H 19Cl 2FeN 3): C58.44, H4.24, N9.29; Experiment value (%): C57.96, H4.63, N8.87.
3. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of continuous drying 6hrs 2Gas displacement 3 times.Add 2.3mg (5 μ mol) catalyst 4 and then vacuumize and with ethene displacement 3 times.Toluene with syringe injection 30ml adds 1.7ml MAO (MAO) (toluene solution of 1.46mol/l) again, makes Al/Fe=500.Under 20 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the watery hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 2.89 * 10 4G mol -1(Fe) h -1, oligomer content is respectively: C 493%, C 67%.Remaining mixture does not obtain polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment five
1. the preparation of part: 2-acetyl group-1; the 10-phenanthroline (contracts 2; the 4-dimethylaniline): 2-acetyl group-1; 10-phenanthroline (0.4445g; 2mmol) with 2; 4-dimethylaniline (0.3175g; 2.6mmol) add the 40mg p-methyl benzenesulfonic acid and make catalyst and add the 2g molecular sieve to make dehydrating agent, 30ml reflux in toluene 1 day, remove solvent toluene after the filtration; residue supports with the carrene dissolving; parlkaline aluminium oxide pillar, with petrol ether/ethyl acetate (4: 1) drip washing, second flow point is a product; removing desolvates obtains yellow solid 0.148g, and productive rate is 23%.FT-IR(KBr?disc，cm -1)：3034，2918，2860，1636，1585，1550，1441，1389，1359，1318，1262，1114，884，743，659。1H?NMR(300MHz，CDCl 3)：δ9.25(d，J＝4.5Hz，1H)；8.69(dd，J＝8.4Hz，1H)；8.35(dd，J＝8.7Hz，1H)；8.30(d，J＝8.1Hz，1H)；7.89(s，2H)；7.68(m，1H)；7.16(d，J＝4.2Hz，1H)；6.89(m，2H)；2.67(s，3H，CH 3)；2.36(s，3H，PhCH 3)，2.17(s，3H，PhCH 3)。Elementary analysis (C 22H 19N 3) theoretical value (%): C81.20, H5.89, N12.91; Experiment value (%): C81.01, H5.98, N12.75.
2. the preparation of catalyst 5: iron (II) (5) is closed in chlorination [2-acetyl group-1,10-phenanthroline (contracting 2, the 4-dimethylaniline)]: with 5mlFeCl 24H 2O (48.0mg; 0.24mmol) ethanol solution be added drop-wise to 5ml2-acetyl group-1; the 10-phenanthroline (contracts 2; the 4-dimethylaniline) part (65.1mg; 0.2mmol) ethanol solution in, stirring at room 6 hours is separated out precipitation; filtration obtains blackish green powder solid with ether washing back drying, and productive rate is 85%.FT-IR(KBr?disc，cm -1)：3038，2918，1608，1585，1513，1410，1286，1221，1161，1115，857，740，658。Elementary analysis (C 22H 19Cl 2FeN 3): C58.44, H4.24, N9.29; Experiment value (%): C58.09, H4.62, N8.92.
3. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of continuous drying 6hrs 2Gas displacement 3 times.Add 2.3mg (5 μ mol) catalyst 5 and then vacuumize and with ethene displacement 3 times.Toluene with syringe injection 30ml adds 1.7ml MAO (MAO) (toluene solution of 1.46mol/l) again, makes Al/Fe=500.Under 20 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the watery hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 4.30 * 10 4G mol -1(Fe) h -1, oligomer content is respectively: C 4100%.Remaining mixture does not obtain polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment six
1. the preparation of part: 2-acetyl group-1; the 10-phenanthroline (contracts 2; the 5-dimethylaniline): 2-acetyl group-1; 10-phenanthroline (0.4445g; 2mmol) with 2; 5-dimethylaniline (0.3175g; 2.6mmol) add the 40mg p-methyl benzenesulfonic acid and make catalyst and add the 2g molecular sieve to make dehydrating agent, 30ml reflux in toluene 1 day, remove solvent toluene after the filtration; residue supports with the carrene dissolving; parlkaline aluminium oxide pillar, with petrol ether/ethyl acetate (4: 1) drip washing, second flow point is a product; removing desolvates obtains yellow solid 0.195g, and productive rate is 30%.FT-IR(KBr?disc，cm -1)：3042，3015，2968，2917，1634，1611，1551，1492，1446，1361，1322，1283，1249，1115，1079，998，879，846，808，772，733，657。 1H?NMR(300MHz，CDCl 3)：δ9.25(t，J＝2.3Hz，1H)；8.69(dd，J＝8.4Hz，1H)；8.35(dd，J＝8.4Hz，1H)；8.30(d，J＝7.5Hz，1H)；7.88(s，2H)；7.67(m，1H)；7.14(d，J＝7.8Hz，1H)；687(d，J＝7.5Hz，1H)；6.55(s，1H)；2.65(s，3H，CH 3)；2.35(s，3H，PhCH 3)；2.11(s，3H，PhCH 3)。Elementary analysis (C 22H 19N 3) theoretical value (%): C81.20, H5.89, N12.91; Experiment value (%): C80.78, H6.21, N12.83.
2. the preparation of catalyst 6: iron (II) (6) is closed in chlorination [2-acetyl group-1,10-phenanthroline (contracting 2, the 5-dimethylaniline)]: with 5mlFeCl 24H 2O (48.0mg; 0.24mmol) ethanol solution be added drop-wise to 5ml2-acetyl group-1; the 10-phenanthroline (contracts 2; the 5-dimethylaniline) part (65.1mg; 0.2mmol) ethanol solution in, stirring at room 9 hours is separated out precipitation; filtration obtains blackish green powder solid with ether washing back drying, and productive rate is 75%.FT-IR(KBr?disc，cm -1)：3056，2915，1606，1575，1503，1442，1397，1337，1300，1246，1202，1148，1097，850，738，655。Elementary analysis (C 22H 19Cl 2FeN 3): C58.44, H4.24, N9.29; Experiment value (%): C58.13, H4.56, N9.12.
3. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of continuous drying 6hrs 2Gas displacement 3 times.Add 2.3mg (5 μ mol) catalyst 6 and then vacuumize and with ethene displacement 3 times.Toluene with syringe injection 30ml adds 1.7ml MAO (MAO) (toluene solution of 1.46mol/l) again, makes Al/Fe=500.Under 20 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the watery hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 1.72 * 10 5G mol -1(Fe) h -1, oligomer content is respectively: C 437%, C 615%, C 832%, C 106%, C 124%, C 14-C 205%.Remaining mixture does not obtain polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment seven
1. the preparation of catalyst 6 is with embodiment six.
2. (1MPa) ethylene oligomerization pressurizes: the toluene solution of 1000ml toluene and 3.3ml MAO (MAO) (1.54mol/l in toluene) and 10ml catalyst 6 (10.0 μ mol) is joined in the stainless steel autoclave of 2000-ml.Mechanical agitation begins, and keeps 350 rev/mins, when polymerization temperature reaches 40 ℃, charges into ethene in reactor, and polymerisation begins.Under 40 ℃, keep the ethylene pressure of 1MPa, stirring reaction 1h.With syringe take out spiece with in 5% the watery hydrochloric acid with laggard promoting the circulation of qi chromatogram (GC) analysis mutually: the oligomerisation activity is 2.92 * 10 7G mol -1(Fe) h -1, oligomer content is respectively: C 415.7%, C 620.5%, C 814.1%, C 1014.4%, C 1210.9%, C 14-C 2824.6%.Remaining mixture obtains the white wax shaped polymer with the ethanolic solution neutralization of 5% hcl acidifying, and polymerization activity is 4.0 * 10 6G mol -1(Fe) h -1
Embodiment eight
1. the preparation of part: 2-acetyl group-1,10-phenanthroline (contracting 2, the 6-dimethylaniline): 2-acetyl group-1; 10-phenanthroline (0.4445g; 2mmol) with 2, (0.3175g 2.6mmol) adds the 40mg p-methyl benzenesulfonic acid and makes catalyst the 6-dimethylaniline; in the 10ml absolute ethyl alcohol, refluxed 2 days under the nitrogen protection; concentrate back residue parlkaline aluminium oxide pillar, with petrol ether/ethyl acetate (4: 1) drip washing, second flow point is a product; removing desolvates obtains yellow solid 0.32g, and productive rate is 49%.Fusing point is 170-172 ℃.FT-IR(KBr?disc，cm -1)：3435(br)，2933(m)，1645(s)，1469(m)，1367(m)，1117(m)，866(m)，777(m)。 1H?NMR(300MHz，CDCl 3)：δ9.24(t，J＝2.1Hz，1H)；8.80(dd，J＝8.7Hz，1H)；8.34(dd，J＝8.4Hz，1H)；8.27(d，J＝7.8Hz，1H)；7.85(s，2H)；7.65(m，1H)；7.10(d，J＝7.5Hz，2H)；6.96(t，J＝7.5Hz，1H)；2.56(s，3H，CH 3)；2.08(s，6H，CH 3)。Elementary analysis (C 22H 19N 3) theoretical value (%): C81.20, H5.89, N12.91; Experiment value (%): C80.99, H5.94, N12.87.
2. the preparation of catalyst 7: iron (II) (7) is closed in chlorination [2-acetyl group-1,10-phenanthroline (contracting 2, the 6-dimethylaniline)]: with 5mlFeCl 24H 2O (48.0mg; 0.24mmol) ethanol solution be added drop-wise to 5ml2-acetyl group-1; the 10-phenanthroline (contracts 2; the 6-dimethylaniline) part (65.1mg; 0.2mmol) ethanol solution in, stirring at room 6 hours is separated out precipitation; filtration obtains black-and-blue powder solid with ether washing back drying, and productive rate is 96%.FT-IR(KBr?disc，cm -1)：3436，3047，1612，1512，1406，1287，1209，864，790。Elementary analysis (C 22H 19Cl 2FeN 3): C58.44, H4.24, N9.29; Experiment value (%): C58.51, H4.49, N9.07.
3. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of continuous drying 6hrs 2Gas displacement 3 times.Add 2.3mg (5 μ mol) catalyst 7 and then vacuumize and with ethene displacement 3 times.Toluene with syringe injection 30ml adds 1.7ml MAO (MAO) (toluene solution of 1.46mol/l) again, makes Al/Fe=500.Under 40 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 60min.With syringe take out spiece with in 5% the watery hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 9.5 * 10 4G mol -1(Fe) h -1, oligomer content is respectively: C 411%, C 618%, C 813%, C 1013%, C 1211%, C 14-C 2634%.Remaining mixture does not obtain polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment nine
1. the preparation of catalyst 7 is with embodiment eight.
2. (1MPa) ethylene oligomerization pressurizes: the toluene solution of 1000ml toluene and 3.3ml MAO (MAO) (1.54mol/l in toluene) and 10ml catalyst 7 (18.0 μ mol) is joined in the stainless steel autoclave of 2000-ml.Mechanical agitation begins, and keeps 350 rev/mins, when polymerization temperature reaches 40 ℃, charges into ethene in reactor, and polymerisation begins.Under 40 ℃, keep the ethylene pressure of 1MPa, stirring reaction 1h.With syringe take out spiece with in 5% the watery hydrochloric acid with laggard promoting the circulation of qi chromatogram (GC) analysis mutually: the oligomerisation activity is 1.16 * 10 7G mol -1(Fe) h -1, oligomer content is respectively: C 48%, C 618%, C 1017%, C 1215%, C 14-C 2425%.Remaining mixture obtains the white wax shaped polymer with the ethanolic solution neutralization of 5% hcl acidifying, and polymerization activity is 3.23 * 10 6G mol -1(Fe) h -1
Embodiment ten
1. the preparation of catalyst 7 is with embodiment eight.
2. (1MPa) ethylene oligomerization pressurizes: the toluene solution of toluene and 1.4ml MAO (MAO) (1.46mol/lin toluene) and 6ml catalyst 7 (2.0 μ mol) is joined in the stainless steel autoclave of 250-ml, making cumulative volume is 100ml, Al/Fe=1000.When polymerization temperature reaches 40 ℃, in reactor, charge into ethene, keep the ethylene pressure of 1MPa, stirring reaction 1h.With syringe take out spiece with in 5% the watery hydrochloric acid with laggard promoting the circulation of qi chromatogram (GC) analysis mutually: the oligomerisation activity is 3.89 * 10 7G mol -1(Fe) h -1, oligomer content is respectively: C 418.9%, C 622.9%, C 817%, C 1014.5%, C 1211.4%, C 14, 8.9, C 16-C 2423.5%.Remaining mixture obtains the white wax shaped polymer with the ethanolic solution neutralization of 5% hcl acidifying, and polymerization activity is 1.02 * 10 7G mol -1(Fe) h -1
Embodiment 11
1. the preparation of part: 2-acetyl group-1; the 10-phenanthroline (contracts 3; the 4-dimethylaniline): 2-acetyl group-1; 10-phenanthroline (0.4445g; 2mmol) with 3; 4-dimethylaniline (0.3175g; 2.6mmol) add the 40mg p-methyl benzenesulfonic acid and make catalyst and add the 2g molecular sieve to make dehydrating agent, 30ml reflux in toluene 1 day, remove solvent toluene after the filtration; residue supports with the carrene dissolving; parlkaline aluminium oxide pillar, with petrol ether/ethyl acetate (4: 1) drip washing, second flow point is a product; removing desolvates obtains yellow solid, and productive rate is 26%.FT-IR(KBr?disc，cm -1)：2918，1637，1591，1553，1485，1389，1364，1320，1283，1187，1115，1042，851，741。 1H?NMR(300MHz，CDCl 3)：δ9.25(d，J＝4.5Hz，1H)；8.70(dd，J＝8.4Hz，1H)；8.35(dd，J＝8.7Hz，1H)；8.30(d，J＝8.1Hz，1H)；7.88(s，2H)；7.68(m，1H)；7.06(s，1H)；6.94(m，2H)；2.67(s，3H，CH 3)；2.35(s，3H，PhCH 3)，2.19(s，3H，PhCH 3)。Elementary analysis (C 22H 19N 3) theoretical value (%): C81.20, H5.89, N12.91; Experiment value (%): C80.78, H6.12, N12.63.
2. the preparation of catalyst 8: iron (II) (8) is closed in chlorination [2-acetyl group-1,10-phenanthroline (contracting 3, the 4-dimethylaniline)]: with 5mlFeCl 24H 2O (48.0mg; 0.24mmol) ethanol solution be added drop-wise to 5ml2-acetyl group-1; the 10-phenanthroline (contracts 3; the 4-dimethylaniline) part (65.1mg; 0.2mmol) ethanol solution in, stirring at room 9 hours is separated out precipitation; filtration obtains blackish green powder solid with ether washing back drying, and productive rate is 76%.FT-IR(KBr?disc，cm -1)：3046，2916，1603，1591，1514，1382，1286，1221，1161，1114，857，741。Elementary analysis (C 22H 19Cl 2FeN 3): C58.44, H4.24, N9.29; Experiment value (%): C58.05, H4.58, N9.15.
3. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of continuous drying 6hrs 2Gas displacement 3 times.Add 2.3mg (5 μ mol) catalyst 8 and then vacuumize and with ethene displacement 3 times.Toluene with syringe injection 30ml adds 1.7ml MAO (MAO) (toluene solution of 1.46mol/l) again, makes Al/Fe=500.Under 20 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the watery hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 2.83 * 10 4G mol -1(Fe) h -1, oligomer content is respectively: C 4100%.Remaining mixture does not obtain polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 12
1. the preparation of part: 2-acetyl group-1; the 10-phenanthroline (contracts 3; the 5-dimethylaniline): 2-acetyl group-1; 10-phenanthroline (0.4445g; 2mmol) with 3; 5-dimethylaniline (0.3175g; 2.6mmol) add the 40mg p-methyl benzenesulfonic acid and make catalyst and add the 2g molecular sieve to make dehydrating agent, 30ml reflux in toluene 1 day, remove solvent toluene after the filtration; residue supports with the carrene dissolving; parlkaline aluminium oxide pillar, with petrol ether/ethyl acetate (4: 1) drip washing, second flow point is a product; removing desolvates obtains yellow solid 0.148g, and productive rate is 23%.FT-IR(KBr?disc，cm -1)：3053，2908，1635，1592，1551，1485，1389，1363，1320，1283，1189，1114，1042，850，746，657。 1H?NMR(300MHz，CDCl 3)：δ9.25(d，J＝4.5Hz，1H)；8.70(dd，J＝8.4Hz，1H)；8.35(dd，J＝8.7Hz，1H)；8.30(d，J＝8.1Hz，1H)；7.88(s，2H)；7.68(m，1H)；7.14(s，2H)；7.02(s，1H)；2.67(s，3H，CH 3)；2.31(s，6H，PhCH 3)。Elementary analysis (C 22H 19N 3) theoretical value (%): C81.20, H5.89, N12.91; Experiment value (%): C80.83, H6.15, N12.69.
2. the preparation of catalyst 9: iron (II) (9) is closed in chlorination [2-acetyl group-1,10-phenanthroline (contracting 3, the 5-dimethylaniline)]: with 5mlFeCl 24H 2O (48.0mg; 0.24mmol) ethanol solution be added drop-wise to 5ml2-acetyl group-1; the 10-phenanthroline (contracts 3; the 5-dimethylaniline) part (65.1mg; 0.2mmol) ethanol solution in, stirring at room 9 hours is separated out precipitation; filtration obtains blackish green powder solid with ether washing back drying, and productive rate is 85%.FT-IR(KBr?disc，cm -1)：3039，2918，1604，1513，1407，1286，1221，1161，1115，857，741。Elementary analysis (C 22H 19Cl 2FeN 3): C58.44, H4.24, N9.29; Experiment value (%): C58.08, H4.71, N9.03.
3. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of continuous drying 6hrs 2Gas displacement 3 times.Add 2.3mg (5 μ mol) catalyst 9 and then vacuumize and with ethene displacement 3 times.Toluene with syringe injection 30ml adds 1.7ml MAO (MAO) (toluene solution of 1.46mol/l) again, makes Al/Fe=500.Under 20 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the watery hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 3.68 * 10 4G mol -1(Fe) h -1, oligomer content is respectively: C 496%, C 64%.Remaining mixture does not obtain polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 13
1. the preparation of part: 2-acetyl group-1; the 10-phenanthroline (contracts 2; 4; the 6-trimethylaniline): 2-acetyl group-1; 10-phenanthroline (0.4445g; 2mmol) with 2; 4, (0.3345g 2.4mmol) adds the 40mg p-methyl benzenesulfonic acid and makes catalyst the 6-trimethylaniline; in the 10ml absolute ethyl alcohol, refluxed 2 days under the nitrogen protection; concentrate back residue parlkaline aluminium oxide pillar, with petrol ether/ethyl acetate (4: 1) drip washing, second flow point is a product; removing desolvates obtains yellow solid 0.54g, and productive rate is 80%.Fusing point is 146-148 ℃.FT-IR(KBr?disc，cm -1)：2937，1634，1551，1480，1364，1216，1115，863。 1H?NMR(400MHz，CDCl 3)：δ9.25(dd，J＝4.4Hz，1H)；8.80(d，J＝8.4Hz，1H)；8.35(d，J＝8.4Hz，1H)；8.30(dd，J＝8.0Hz，1H)；7.88(s，2H)；7.68(q，J＝4.4Hz，1H)；6.93(s，2H)；2.56(s，3H，CH 3)；2.32(s，3H，CH 3)；2.05(s，6H，CH 3)。Elementary analysis (C 23H 21N 3) theoretical value (%): C81.38, H6.24, N12.38; Experiment value (%): C81.42, H6.26, N12.14.
2. the preparation of catalyst 10: iron (II) (10) is closed in chlorination [2-acetyl group-1,10-phenanthroline (contracting 2,4, the 6-trimethylaniline)]: with 5mlFeCl 24H 2O (48.0mg; 0.24mmol) ethanol solution be added drop-wise to 5ml2-acetyl group-1; the 10-phenanthroline (contracts 2; 4, the 6-trimethylaniline) (67.9mg is in ethanol solution 0.2mmol) for part; stirring at room 9 hours; separate out precipitation, filter with ether washing back drying and obtain black-and-blue powder solid, productive rate is 64%.FT-IR(KBr?disc，cm -1)：2912，1606，1513，1407，1286，1221，1161，857，741。Elementary analysis (C 23H 21Cl 2FeN 30.5C 2H 6O) theoretical value (%): C58.92, H4.94, N8.59; Experiment value (%): C58.24, H4.94, N8.56.
3. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of continuous drying 6hrs 2Gas displacement 3 times.Add 2.5mg (5 μ mol) catalyst 10 and then vacuumize and with ethene displacement 3 times.Toluene with syringe injection 30ml adds 1.7ml MAO (MAO) (toluene solution of 1.46mol/l) again, makes Al/Fe=500.Under 40 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 60min.With syringe take out spiece with in 5% the watery hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 3.40 * 10 5G mol -1(Fe) h -1, oligomer content is respectively: C 410%, C 614%, C 812%, C 1012%, C 1213%, C 14-C 2439%.Remaining mixture does not obtain polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 14
1. the preparation of catalyst 10 is with embodiment 12.
2. (1MPa) ethylene oligomerization pressurizes: the toluene solution of 1000ml toluene and 3.3ml MAO (MAO) (1.54mol/l in toluene) and 10ml catalyst 10 (19.0 μ mol) is joined in the stainless steel autoclave of 2000-ml.Mechanical agitation begins, and keeps 350 rev/mins, when polymerization temperature reaches 40 ℃, charges into ethene in reactor, and polymerisation begins.Under 40 ℃, keep the ethylene pressure of 1MPa, stirring reaction 1h.With syringe take out spiece with in 5% the watery hydrochloric acid with laggard promoting the circulation of qi chromatogram (GC) analysis mutually: the oligomerisation activity is 8.20 * 10 6G mol -1(Fe) h -1, oligomer content is respectively: C 49%, C 619%, C 817%, C 1016%, C 1214%, C 14-C 2625%.Remaining mixture obtains the white wax shaped polymer with the ethanolic solution neutralization of 5% hcl acidifying, and polymerization activity is 1.38 * 10 6G mol -1(Fe) h -1
Embodiment 15
1. the preparation of catalyst 10 is with embodiment 12.
2. (1MPa) ethylene oligomerization pressurizes: the toluene solution of toluene and 1.4ml MAO (MAO) (1.46mol/lin toluene) and 6ml catalyst 10 (2.0 μ mol) is joined in the stainless steel autoclave of 250-ml, making cumulative volume is 100ml, Al/Fe=1000.When polymerization temperature reaches 40 ℃, in reactor, charge into ethene, keep the ethylene pressure of 1MPa, stirring reaction 1h.With syringe take out spiece with in 5% the watery hydrochloric acid with laggard promoting the circulation of qi chromatogram (GC) analysis mutually: the oligomerisation activity is 1.24 * 10 7G mol -1(Fe) h -1, oligomer content is respectively: C 417.5%, C 619.0%, C 1015.2%, C 1213.3%, C 14, 11.1%, C 16-C 2824.0%.Remaining mixture obtains the white wax shaped polymer with the ethanolic solution neutralization of 5% hcl acidifying, and polymerization activity is 1.38 * 10 7G mol -1(Fe) h -1
Embodiment 16
1. the preparation of part: 2-acetyl group-1; (the 10-phenanthroline contracts 4-bromo-2; the 6-dimethylaniline): 2-acetyl group-1; 10-phenanthroline (0.4445g; 2mmol) with 4-bromo-2; 6-dimethylaniline (0.50g; 2.5mmol) add the 40mg p-methyl benzenesulfonic acid and make catalyst and add the 2g molecular sieve to make dehydrating agent, 30ml reflux in toluene 1 day, remove solvent toluene after the filtration; residue supports with the carrene dissolving; parlkaline aluminium oxide pillar, with petrol ether/ethyl acetate (4: 1) drip washing, second flow point is a product; removing desolvates obtains yellow solid 0.526g, and productive rate is 65%.FT-IR(KBr?disc，cm -1)：3036，2969，2913，1641，1584，1550，1462，1397，1366，1323，1284，1201，1113，1077，997，880，853，780，743，710，661。 1H?NMR(300MHz，CDCl 3)：δ9.25(dd.，J＝4.2Hz，1H)；8.76(d，J＝8.4Hz，1H)；8.37(d，J＝8.4Hz，1H)；8.31(d，J＝7.8Hz，1H)；7.89(s，2H)；7.68(dd，J＝7.8Hz，1H)；7.25(d，J＝5.7Hz，2H)；2.55(s，3H，CH 3)；2.05(s，6H，PhCH 3)。Elementary analysis (C 22H 18BrN 3) theoretical value (%): C65.36, H4.49, N10.39; Experiment value (%): C64.97, H4.49, N10.39.
2. the preparation of catalyst 11: iron (II) (11) is closed in chlorination [2-acetyl group-1,10-phenanthroline (the 4-bromo-2 that contracts, 6-dimethylaniline)]: with 5mlFeCl 24H 2O (48.0mg; 0.24mmol) ethanol solution be added drop-wise to 5ml2-acetyl group-1; (the 10-phenanthroline contracts 4-bromo-2; the 6-dimethylaniline) part (80.9mg; 0.2mmol) ethanol solution in, stirring at room 6 hours is separated out precipitation; filtration obtains the purplish grey powder solid with ether washing back drying, and productive rate is 91%.FT-IR(KBr?disc，cm -1)：3047，2952，2911，1618，1580，1515，1494，1466，1436，1406，1372，1286，1206，854，796，738，657。Elementary analysis (C 22H 18BrCl 2FeN 3): C49.76, H3.42, N7.91; Experiment value (%): C49.89, H3.53, N7.83.
3. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of continuous drying 6hrs 2Gas displacement 3 times.Add 2.7mg (5 μ mol) catalyst 11 and then vacuumize and with ethene displacement 3 times.Toluene with syringe injection 30ml adds 1.7ml MAO (MAO) (toluene solution of 1.46mol/l) again, makes Al/Fe=500.Under 20 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the watery hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 1.73 * 10 5G mol -1(Fe) h -1, oligomer content is respectively: C 414%, C 637%, C 813%, C 1011%, C 1210%, C 14-C 2015%.Remaining mixture obtains a small amount of wax, filtration, washing, dry 0.02g with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 17
1. the preparation of catalyst 11 is with embodiment 16.
2. (1MPa) ethylene oligomerization pressurizes: the toluene solution of 1000ml toluene and 3.3ml MAO (MAO) (1.54mol/l in toluene) and 10ml catalyst 11 (10.0 μ mol) is joined in the 2000-ml stainless steel autoclave.Mechanical agitation begins, and keeps 350 rev/mins, when polymerization temperature reaches 40 ℃, charges into ethene in reactor, and polymerisation begins.Under 40 ℃, keep the ethylene pressure of 1MPa, stirring reaction 1h.With syringe take out spiece with in 5% the watery hydrochloric acid with laggard promoting the circulation of qi chromatogram (GC) analysis mutually: the oligomerisation activity is 4.60 * 10 7G mol -1(Fe) h -1, oligomer content is respectively: C 428.9%, C 632.8%, C 813.0%, C 109.9%, C 125.8%, C 14-C 269.7%.Remaining mixture obtains the white wax oily polymer with the ethanolic solution neutralization of 5% hcl acidifying, and polymerization activity is 3.96 * 10 7G mol -1(Fe) h -1
Embodiment 18
1. the preparation of catalyst 11 is with embodiment 16.
2. (1MPa) ethylene oligomerization pressurizes: the toluene solution of toluene and 1.4ml MAO (MAO) (1.46mol/lin toluene) and 6ml catalyst 11 (2.0 μ mol) is joined in the stainless steel autoclave of 250-ml, making cumulative volume is 100ml, Al/Fe=1000.When polymerization temperature reaches 40 ℃, in reactor, charge into ethene, keep the ethylene pressure of 1MPa, stirring reaction 1h.With syringe take out spiece with in 5% the watery hydrochloric acid with laggard promoting the circulation of qi chromatogram (GC) analysis mutually: the oligomerisation activity is 4.82 * 10 7G mol -1(Fe) h -1, oligomer content is respectively: C 415.1%, C 624.6%, C 1014.0%, C 1211.7%, C 14, 9.1%, C 16-C 3025.5%.Remaining mixture obtains the white wax shaped polymer with the ethanolic solution neutralization of 5% hcl acidifying, and polymerization activity is 1.74 * 10 7G mol -1(Fe) h -1
Embodiment 19
1. the preparation of part: 2-acetyl group-1; 10-phenanthroline (the 2-MEA contracts): 2-acetyl group-1; 10-phenanthroline (0.4445g; 2mmol) with 2-MEA (0.33g; 2.7mmol) add the 40mg p-methyl benzenesulfonic acid and make catalyst and add the 2g molecular sieve to make dehydrating agent; 30ml reflux in toluene 1 day; remove solvent toluene after the filtration; residue supports with the carrene dissolving; parlkaline aluminium oxide pillar, with petrol ether/ethyl acetate (4: 1) drip washing, second flow point is a product; removing desolvates obtains yellow solid 0.15g, and productive rate is 23%.FT-IR(KBr?disc，cm -1)：2961，2928，2869，1633，1592，1551，1484，1446，1416，1390，1363，1321，1283，1241，1221，1186，1113，1079，1050，850，821，788，770，752，658。 1H?NMR(300MHz，CDCl 3)：δ9.25(t，J＝2.3Hz，1H)；8.70(d，J＝8.4Hz，1H)；8.35(d，J＝8.4Hz，1H)；8.30(d，J＝7.5Hz，1H)；7.87(s，2H)；7.67(m，1H)；7.29(d，J＝7.8Hz，1H)；7.22(dd，J＝7.2Hz，1H)；7.14(t，J＝7.2Hz，1H)；6.72(d，J＝8.1Hz，1H)；2.68(s，3H，CH 3)；2.56(m，2H，CH 2CH 3)；1.18(t，J＝7.5Hz，3H，CH 2CH 3)。Elementary analysis (C 22H 19N 3) theoretical value (%): C81.20, H5.89, N12.91; Experiment value (%): C80.95, H5.82, N12.71.
2. the preparation of catalyst 12: iron (II) (12) is closed in chlorination [2-acetyl group-1,10-phenanthroline (the 2-MEA contracts)]: with 5mlFeCl 24H 2O (48.0mg; 0.24mmol) ethanol solution be added drop-wise to 5ml2-acetyl group-1; 10-phenanthroline (the 2-MEA contracts) part (65.1mg; 0.2mmol) ethanol solution in; stirring at room 9 hours; separate out precipitation, filter with ether washing back drying and obtain black-and-blue powder solid, productive rate is 82%.FT-IR(KBr?disc，cm -1)：3482，3059，2966，2934，2876，1608，1579，1513，1484，1447，1405，1370，1337，1286，1223，1147，858，786，742，657。Elementary analysis (C 22H 19Cl 2FeN 3): C58.44, H4.24, N9.29; Experiment value (%): C58.21, H4.59, N9.07.
3. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of continuous drying 6hrs 2Gas displacement 3 times.Add 2.5mg (5 μ mol) catalyst 12 and then vacuumize and with ethene displacement 3 times.Toluene with syringe injection 30ml adds 1.7ml MAO (MAO) (toluene solution of 1.46mol/l) again, makes Al/Fe=500.Under 20 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the watery hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 4.70 * 10 4G mol -1(Fe) h -1, oligomer content is respectively: C 4100%.Remaining mixture does not obtain polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 20
1. the preparation of catalyst 12 is with embodiment 19.
2. (1MPa) ethylene oligomerization pressurizes: the toluene solution of toluene and 1.4ml MAO (MAO) (1.46mol/lin toluene) and 6ml catalyst 12 (2.0 μ mol) is joined in the stainless steel autoclave of 250-ml, making cumulative volume is 100ml, Al/Fe=1000.When polymerization temperature reaches 40 ℃, in reactor, charge into ethene, keep the ethylene pressure of 1MPa, stirring reaction 1h.With syringe take out spiece with in 5% the watery hydrochloric acid with laggard promoting the circulation of qi chromatogram (GC) analysis mutually: the oligomerisation activity is 1.78 * 10 7G mol -1(Fe) h -1, oligomer content is respectively: C 422.6%, C 643.4%, C 1013.9%, C 1211.5%, C 14, 2.4%, C 16-C 181.2%.Remaining mixture obtains traces of polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 21
1. the preparation of part: 2-acetyl group-1; 10-phenanthroline (2-ethyl-6-methylaniline contracts): 2-acetyl group-1; 10-phenanthroline (0.4445g; 2mmol) with 2-ethyl-6-methylaniline (0.34g; 2.5mmol) add the 40mg p-methyl benzenesulfonic acid and make catalyst and add the 2g molecular sieve to make dehydrating agent; 30ml reflux in toluene 1 day; remove solvent toluene after the filtration; residue supports with the carrene dissolving; parlkaline aluminium oxide pillar, with petrol ether/ethyl acetate (4: 1) drip washing, second flow point is a product; removing desolvates obtains yellow solid 0.28g, and productive rate is 56%.FT-IR(KBr?disc，cm -1)：3059，3014，2966，2930，2870，1636，1587，1551，1490，1456，1417，1389，1362，1322，1283，1248，1202，1137，1115，887，864，821，782，743，661。 1H?NMR(300MHz，CDCl 3)：δ9.25(d，J＝3.9Hz，1H)；8.80(d，J＝8.4Hz，1H)；8.35(d，J＝8.4Hz，1H)；8.29(d，J＝7.8Hz，1H)；7.89(s，2H)；7.67(dd，J＝8.1Hz，1H)；7.12(t，J＝7.5Hz，2H)；7.02(t，J＝7.5Hz，1H)；2.58(s，3H，CH 3)；2.45(m，2H，CH 2CH 3)；2.08(s，3H，PhCH 3)；1.17(t，J＝7.5Hz，3H，CH 2CH 3)。Elementary analysis (C 23H 21N 3) theoretical value (%): C81.38, H6.24, N12.38; Experiment value (%): C81.30, H6.27, N12.11.
2. the preparation of catalyst 13: iron (II) (13) is closed in chlorination [2-acetyl group-1,10-phenanthroline (2-ethyl-6-methylaniline contracts)]: with 5mlFeCl 24H 2O (48.0mg; 0.24mmol) ethanol solution be added drop-wise to 5ml2-acetyl group-1; 10-phenanthroline (2-ethyl-6-methylaniline contracts) part (67.9mg; 0.2mmol) ethanol solution in; stirring at room 9 hours; separate out precipitation, filter with ether washing back drying and obtain black-and-blue powder solid, productive rate is 88%.FT-IR(KBr?disc，cm -1)：3446，2974，1912，1609，1581，1509，1489，1456，1403，1372，1339，1285，1203，1143，1095，1046，991，895，862，836，783，741，656。Elementary analysis (C 23H 21Cl 2FeN 3): C59.26, H4.54, N9.01; Experiment value (%): C58.87, H4.85, N8.59.
3. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of continuous drying 6hrs 2Gas displacement 3 times.Add 2.3mg (5 μ mol) catalyst 13 and then vacuumize and with ethene displacement 3 times.Toluene with syringe injection 30ml adds 1.7ml MAO (MAO) (toluene solution of 1.46mol/l) again, makes Al/Fe=500.Under 20 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the watery hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 3.50 * 10 4G mol -1(Fe) h -1, oligomer content is respectively: C 479%, C 65%, C 105%, C 12-C 1811%.Remaining mixture does not obtain polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 22
1. the preparation of catalyst 13 is with embodiment 21.
2. (1MPa) ethylene oligomerization pressurizes: the toluene solution of toluene and 1.4ml MAO (MAO) (1.46mol/lin toluene) and 6ml catalyst 13 (2.0 μ mol) is joined in the stainless steel autoclave of 250-ml, making cumulative volume is 100ml, Al/Fe=1000.When polymerization temperature reaches 40 ℃, in reactor, charge into ethene, keep the ethylene pressure of 1MPa, stirring reaction 1h.With syringe take out spiece with in 5% the watery hydrochloric acid with laggard promoting the circulation of qi chromatogram (GC) analysis mutually: the oligomerisation activity is 9.37 * 10 6G mol -1(Fe) h -1, oligomer content is respectively: C 423.3%, C 621.5%, C 105.3%, C 1212.7%, C 14, 9.2%, C 16-C 2612.2%.Remaining mixture obtains the white wax shaped polymer with the ethanolic solution neutralization of 5% hcl acidifying, and polymerization activity is 5.24 * 10 6G mol -1(Fe) h -1
Embodiment 23
1. the preparation of part: 2-acetyl group-1,10-phenanthroline (contracting 2, the 6-diethylaniline): 2-acetyl group-1; 10-phenanthroline (0.4445g; 2mmol) with 2, (0.3655g 2.4mmol) adds the 40mg p-methyl benzenesulfonic acid and makes catalyst the 6-diethylaniline; in the 10ml absolute ethyl alcohol, refluxed 2 days under the nitrogen protection; concentrate back residue parlkaline aluminium oxide pillar, with petrol ether/ethyl acetate (4: 1) drip washing, second flow point is a product; removing desolvates obtains yellow solid 0.48g, and productive rate is 68%.Fusing point is 188-190 ℃.FT-IR(KBr?disc，cm -1)：3424(br)，2966(s)，1639(s)，1453(m)，1363(m)，1116(m)，867(m)，782(m)。 1H?NMR(300MHz，CDCl 3)：δ9.25(dd，J＝3.0Hz，1H)；8.80(d，J＝8.3Hz，1H)；8.35(d，J＝8.3Hz，1H)；8.27(dd，J＝7.8Hz，1H)；7.86(s，2H)；7.66(m，1H)；7.15(d，J＝7.6Hz，2H)；6.96(t，J＝7.5Hz，1H)；2.58(s，3H，CH 3)；2.43(m，4H，CH 2)，1.16(t，6H，CH 3)。Elementary analysis (C 24H 23N 3) theoretical value (%): C81.55, H6.56, N11.89; Experiment value (%): C80.88, H6.59, N11.78.
2. the system of catalyst 14 respectively: iron (II) (14) is closed in chlorination [2-acetyl group-1,10-phenanthroline (contracting 2, the 6-diethylaniline)]: with 5mlFeCl 24H 2O (48.0mg; 0.24mmol) ethanol solution be added drop-wise to 5ml2-acetyl group-1; the 10-phenanthroline (contracts 2; the 6-diethylaniline) part (73.8mg; 0.2mmol) ethanol solution in, stirring at room 9 hours is separated out precipitation; filtration obtains black-and-blue powder solid with ether washing back drying, and productive rate is 96%.FT-IR(KBr?disc，cm -1)：3436(br)，3047(m)，1612(s)，1512(m)，1406(s)，1287(s)，1209(s)，864(s)，790(m)。Elementary analysis (C 22H 19Cl 2FeN 3) theoretical value (%): C58.44, H4.24, N9.29; Experiment value (%): C58.51, H4.49, N9.07.
3. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of continuous drying 6hrs 2Gas displacement 3 times.Add 2.3mg (5 μ mol) catalyst 14 and then vacuumize and with ethene displacement 3 times.Toluene with syringe injection 30ml adds 1.7ml MAO (MAO) (toluene solution of 1.46mol/l) again, makes Al/Fe=500.Under 40 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 60min.With syringe take out spiece with in 5% the watery hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 8.1 * 10 4G mol -1(Fe) h -1, oligomer content is respectively: C 49%, C 620%, C 811%, C 1014%, C 1212%, C 14-C 2634%.Remaining mixture does not obtain polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 24
1. the preparation of catalyst 14 is with embodiment 23.
2. (1MPa) ethylene oligomerization pressurizes: the toluene solution of 1000ml toluene and 3.3ml MAO (MAO) (1.54mol/l in toluene) and 10ml catalyst 14 (9.8 μ mol) is joined in the 2000-ml stainless steel autoclave.Mechanical agitation begins, and keeps 350 rev/mins, when polymerization temperature reaches 40 ℃, charges into ethene in reactor, and polymerisation begins.Under 40 ℃, keep the ethylene pressure of 1MPa, stirring reaction 1h.With syringe take out spiece with in 5% the watery hydrochloric acid with laggard promoting the circulation of qi chromatogram (GC) analysis mutually: the oligomerisation activity is 6.10 * 10 7G mol -1(Fe) h -1, oligomer content is respectively: C 412%, C 619%, C 816%, C 1016%, C 1214%, C 14-C 2423%.Remaining mixture obtains the white wax oily polymer with the ethanolic solution neutralization of 5% hcl acidifying, and polymerization activity is 1.84 * 10 6G mol -1(Fe) h -1
Embodiment 25
1. the preparation of catalyst 14 is with embodiment 23.
2. (1MPa) ethylene oligomerization pressurizes: the toluene solution of toluene and 0.3ml MAO (MAO) (1.46mol/lin toluene) and 6ml catalyst 14 (2.0 μ mol) is joined in the stainless steel autoclave of 250-ml, making cumulative volume is 100ml, Al/Fe=200.When polymerization temperature reaches 40 ℃, in reactor, charge into ethene, keep the ethylene pressure of 1MPa, stirring reaction 1h.With syringe take out spiece with in 5% the watery hydrochloric acid with laggard promoting the circulation of qi chromatogram (GC) analysis mutually: the oligomerisation activity is 1.20 * 10 6G mol -1(Fe) h -1, oligomer content is respectively: C 437.1%, C 619.4%, C 1012.8%, C 129.9%, C 14, 7.8%, C 16-C 2413.0%.Remaining mixture obtains the white wax shaped polymer with the ethanolic solution neutralization of 5% hcl acidifying, and polymerization activity is 1.01 * 10 5G mol -1(Fe) h -1
Embodiment 26
1. the preparation of catalyst 14 is with embodiment 23.
2. (1MPa) ethylene oligomerization pressurizes: the toluene solution of toluene and 0.7ml MAO (MAO) (1.46mol/lin toluene) and 6ml catalyst 14 (2.0 μ mol) is joined in the stainless steel autoclave of 250-ml, making cumulative volume is 100ml, Al/Fe=500.When polymerization temperature reaches 40 ℃, in reactor, charge into ethene, keep the ethylene pressure of 1MPa, stirring reaction 1h.With syringe take out spiece with in 5% the watery hydrochloric acid with laggard promoting the circulation of qi chromatogram (GC) analysis mutually: the oligomerisation activity is 2.12 * 10 7G mol -1(Fe) h -1, oligomer content is respectively: C 427.0%, C 623.9%, C 1015.8%, C 1212.2%, C 14, 9.1%, C 16-C 2612.2%.Remaining mixture obtains the white wax shaped polymer with the ethanolic solution neutralization of 5% hcl acidifying, and polymerization activity is 1.56 * 10 5G mol -1(Fe) h -1
Embodiment 27
1. the preparation of catalyst 14 is with embodiment 23.
2. (1MPa) ethylene oligomerization pressurizes: the toluene solution of toluene and 1.4ml MAO (MAO) (1.46mol/lin toluene) and 6ml catalyst 14 (2.0 μ mol) is joined in the stainless steel autoclave of 250-ml, making cumulative volume is 100ml, Al/Fe=1000.When polymerization temperature reaches 40 ℃, in reactor, charge into ethene, keep the ethylene pressure of 1MPa, stirring reaction 1h.With syringe take out spiece with in 5% the watery hydrochloric acid with laggard promoting the circulation of qi chromatogram (GC) analysis mutually: the oligomerisation activity is 4.91 * 10 7G mol -1(Fe) h -1, oligomer content is respectively: C 414.8%, C 622.8%, C 813.0%, C 1014.3%, C 1210.8%, C 14, 7.8%, C 16-C 2616.5%.Remaining mixture obtains the white wax shaped polymer with the ethanolic solution neutralization of 5% hcl acidifying, and polymerization activity is 1.46 * 10 6G mol -1(Fe) h -1
Embodiment 28
1. the preparation of catalyst 14 is with embodiment 23.
2. (1MPa) ethylene oligomerization pressurizes: the toluene solution of toluene and 2.1ml MAO (MAO) (1.46mol/lin toluene) and 6ml catalyst 14 (2.0 μ mol) is joined in the stainless steel autoclave of 250-ml, making cumulative volume is 100ml, Al/Fe=1500.When polymerization temperature reaches 40 ℃, in reactor, charge into ethene, keep the ethylene pressure of 1MPa, stirring reaction 1h.With syringe take out spiece with in 5% the watery hydrochloric acid with laggard promoting the circulation of qi chromatogram (GC) analysis mutually: the oligomerisation activity is 2.55 * 10 7G mol -1(Fe) h -1, oligomer content is respectively: C 423.0%, C 625.1%, C 87.8%, C 1013.7%, C 1210.1%, C 14, 7.3%, C 16-C 2813.01%.Remaining mixture obtains the white wax shaped polymer with the ethanolic solution neutralization of 5% hcl acidifying, and polymerization activity is 9.13 * 10 5Gmol -1(Fe) h -1
Embodiment 29
1. the preparation of catalyst 14 is with embodiment 23.
2. (1MPa) ethylene oligomerization pressurizes: the toluene solution of toluene and 2.8ml MAO (MAO) (1.46mol/lin toluene) and 6ml catalyst 14 (2.0 μ mol) is joined in the stainless steel autoclave of 250-ml, making cumulative volume is 100ml, Al/Fe=2000.When polymerization temperature reaches 40 ℃, in reactor, charge into ethene, keep the ethylene pressure of 1MPa, stirring reaction 1h.With syringe take out spiece with in 5% the watery hydrochloric acid with laggard promoting the circulation of qi chromatogram (GC) analysis mutually: the oligomerisation activity is 7.50 * 10 6G mol -1(Fe) h -1, oligomer content is respectively: C 433.5%, C 621.3%, C 1013.6%, C 1210.6%, C 14, 7.9%, C 16-C 2413.1%.Remaining mixture obtains the white wax shaped polymer with the ethanolic solution neutralization of 5% hcl acidifying, and polymerization activity is 1.25 * 10 5G mol -1(Fe) h -1
Embodiment 30
1. the preparation of catalyst 14 is with embodiment 23.
2. (1MPa) ethylene oligomerization pressurizes: the toluene solution of toluene and 1.4ml MAO (MAO) (1.46mol/lin toluene) and 6ml catalyst 14 (2.0 μ mol) is joined in the stainless steel autoclave of 250-ml, making cumulative volume is 100ml, Al/Fe=1000.When polymerization temperature reaches 20 ℃, in reactor, charge into ethene, keep the ethylene pressure of 1MPa, stirring reaction 1h.With syringe take out spiece with in 5% the watery hydrochloric acid with laggard promoting the circulation of qi chromatogram (GC) analysis mutually: the oligomerisation activity is 1.64 * 10 7G mol -1(Fe) h -1, oligomer content is respectively: C 430.9%, C 623.2%, C 819.0%, C 1011.7%, C 127.2%, C 14, 4.1%, C 16-C 203.8%.Remaining mixture obtains the white wax shaped polymer with the ethanolic solution neutralization of 5% hcl acidifying, and polymerization activity is 1.01 * 10 6G mol -1(Fe) h -1
Embodiment 31
1. the preparation of catalyst 14 is with embodiment 23.
2. (1MPa) ethylene oligomerization pressurizes: the toluene solution of toluene and 1.4ml MAO (MAO) (1.46mol/lin toluene) and 6ml catalyst 14 (2.0 μ mol) is joined in the stainless steel autoclave of 250-ml, making cumulative volume is 100ml, Al/Fe=1000.When polymerization temperature reaches 30 ℃, in reactor, charge into ethene, keep the ethylene pressure of 1MPa, stirring reaction 1h.With syringe take out spiece with in 5% the watery hydrochloric acid with laggard promoting the circulation of qi chromatogram (GC) analysis mutually: the oligomerisation activity is 2.14 * 10 7G mol -1(Fe) h -1, oligomer content is respectively: C 426.5%, C 622.3%, C 816.4%, C 1012.5%, C 128.7%, C 14, 5.6%, C 16-C 268.0%.Remaining mixture obtains the white wax shaped polymer with the ethanolic solution neutralization of 5% hcl acidifying, and polymerization activity is 2.63 * 10 6G mol -1(Fe) h -1
Embodiment 32
1. the preparation of catalyst 14 is with embodiment 23.
2. (1MPa) ethylene oligomerization pressurizes: the toluene solution of toluene and 1.4ml MAO (MAO) (1.46mol/lin toluene) and 6ml catalyst 14 (2.0 μ mol) is joined in the stainless steel autoclave of 250-ml, making cumulative volume is 100ml, Al/Fe=1000.When polymerization temperature reaches 50 ℃, in reactor, charge into ethene, keep the ethylene pressure of 1MPa, stirring reaction 1h.With syringe take out spiece with in 5% the watery hydrochloric acid with laggard promoting the circulation of qi chromatogram (GC) analysis mutually: the oligomerisation activity is 3.55 * 10 7G mol -1(Fe) h -1, oligomer content is respectively: C 415.6%, C 625.0%, C 815.4%, C 1013.7%, C 129.9%, C 14, 7.0%, C 16-C 2813.4%.Remaining mixture obtains the white wax shaped polymer with the ethanolic solution neutralization of 5% hcl acidifying, and polymerization activity is 5.87 * 10 6G mol -1(Fe) h -1
Embodiment 33
1. the preparation of catalyst 14 is with embodiment 23.
2. (1MPa) ethylene oligomerization pressurizes: the toluene solution of toluene and 1.4ml MAO (MAO) (1.46mol/lin toluene) and 6ml catalyst 14 (2.0 μ mol) is joined in the stainless steel autoclave of 250-ml, making cumulative volume is 100ml, Al/Fe=1000.When polymerization temperature reaches 60 ℃, in reactor, charge into ethene, keep the ethylene pressure of 1MPa, stirring reaction 1h.With syringe take out spiece with in 5% the watery hydrochloric acid with laggard promoting the circulation of qi chromatogram (GC) analysis mutually: the oligomerisation activity is 1.44 * 10 7G mol -1(Fe) h -1, oligomer content is respectively: C 428.0%, C 626.3%, C 819.3%, C 1011.9%, C 127.0%, C 14, 3.6%, C 16-C 244.0%.Remaining mixture obtains the white wax shaped polymer with the ethanolic solution neutralization of 5% hcl acidifying, and polymerization activity is 4.88 * 10 5G mol -1(Fe) h -1
Embodiment 34
1. the preparation of catalyst 14 is with embodiment 23.
2. (1MPa) ethylene oligomerization pressurizes: the toluene solution of 1000ml toluene and 5.0ml triethyl aluminum (TEA) (1.0mol/l in hexane) and 10ml catalyst 14 (10 μ mol) is joined in the 2000-ml stainless steel autoclave.Mechanical agitation begins, and keeps 350 rev/mins, when polymerization temperature reaches 40 ℃, charges into ethene in reactor, and polymerisation begins.Under 40 ℃, keep the ethylene pressure of 1MPa, stirring reaction 1h.With syringe take out spiece with in 5% the watery hydrochloric acid with laggard promoting the circulation of qi chromatogram (GC) analysis mutually: the oligomerisation activity is 2.71 * 10 5G mol -1(Fe) h -1, oligomer content is respectively: C 439.3%, C 629.3%, C 8-C 2231.4%.Remaining mixture does not obtain polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 35
1. the preparation of catalyst 14 is with embodiment 23.
2. (1MPa) ethylene oligomerization pressurizes: the toluene solution of 1000ml toluene and 5.0ml triisobutyl aluminium (TIBA) (1.0mol/l in hexane) and 10ml catalyst 14 (10 μ mol) is joined in the 2000-ml stainless steel autoclave.Mechanical agitation begins, and keeps 350 rev/mins, when polymerization temperature reaches 40 ℃, charges into ethene in reactor, and polymerisation begins.Under 40 ℃, keep the ethylene pressure of 1MPa, stirring reaction 1h.With syringe take out spiece with in 5% the watery hydrochloric acid with laggard promoting the circulation of qi chromatogram (GC) analysis mutually: the oligomerisation activity is 4.03 * 10 5G mol -1(Fe) h -1, oligomer content is respectively: C 473.0%, C 614.2%, C 8-C 2012.8%.Remaining mixture does not obtain polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 36
1. the preparation of catalyst 14 is with embodiment 23.
2. (1MPa) ethylene oligomerization pressurizes: with 1000ml toluene and 2.5ml diethylaluminum chloride (Et 2AlCl) toluene solution of (2.0mol/l in hexane) and 10ml catalyst 14 (10 μ mol) joins in the 2000-ml stainless steel autoclave.Mechanical agitation begins, and keeps 350 rev/mins, when polymerization temperature reaches 40 ℃, charges into ethene in reactor, and polymerisation begins.Under 40 ℃, keep the ethylene pressure of 1MPa, stirring reaction 1h.With syringe take out spiece with in 5% the watery hydrochloric acid with laggard promoting the circulation of qi chromatogram (GC) analysis mutually: the oligomerisation activity is 6.24 * 10 5G mol -1(Fe) h -1, oligomer content is respectively: C 468.2%, C 614.1%, C 8-C 2017.7%.Remaining mixture does not obtain polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 37
1. the preparation of part: 2-acetyl group-1; 10-phenanthroline (the 2-isopropyl aniline contracts): 2-acetyl group-1; 10-phenanthroline (0.4445g; 2mmol) with 2-isopropyl aniline (0.35g; 2.5mmol) add the 40mg p-methyl benzenesulfonic acid and make catalyst and add the 2g anhydrous sodium sulfate to make dehydrating agent; 30ml reflux in toluene 1 day; remove solvent toluene after the filtration; residue supports with the carrene dissolving; parlkaline aluminium oxide pillar, with petrol ether/ethyl acetate (4: 1) drip washing, second flow point is a product; removing desolvates obtains yellow solid 0.27g, and productive rate is 40%.Fusing point is 125-126 ℃.FT-IR(KBr?disc，cm -1)：2958，2926，2866，1630，1591，1551，1483，1446，1417，1388，1362，1313，1279，1223，1188，1115，1082，1032，849，783，754，659。 1H?NMR(300MHz，CDCl 3)：δ9.25(t，J＝2.4Hz，1H)；8.71(d，J＝8.4Hz，1H)；8.35(d，J＝8.4Hz，1H)；8.30(d，J＝7.5Hz，1H)；7.87(s，2H)；7.67(m，1H)；7.36(d，J＝8.1Hz，1H)；7.23(m，1H)；7.14(t，J＝7.2Hz，1H)；6.70(d，J＝7.5Hz，1H)；3.08(sept，J＝6.6Hz，1H，CH(CH 3) 2)；2.70(s，3H，CH 3)；1.21(d，J＝6.6Hz，6H，CH(CH 3) 2)。Elementary analysis (C 23H 21N 3) theoretical value (%): C81.38, H6.24, N12.38; Experiment value (%): C81.10, H6.40, N12.20.
2. the preparation of catalyst 15: iron (II) (15) is closed in chlorination [2-acetyl group-1,10-phenanthroline (the 2-isopropyl aniline contracts)]: with 5mlFeCl 24H 2O (48.0mg; 0.24mmol) ethanol solution be added drop-wise to 5ml2-acetyl group-1; 10-phenanthroline (the 2-isopropyl aniline contracts) part (67.9mg; 0.2mmol) ethanol solution in; stirring at room 9 hours; separate out precipitation, filter with ether washing back drying and obtain the dusty blue powder solid, productive rate is 75%.FT-IR(KBr?disc，cm -1)：3447，3060，2962，2922，2869，1610，1578，1514，1486，1445，1406，1371，1286，1228，1195，1145，1089，1033，858，835，790，756，741，656。Elementary analysis (C 23H 21Cl 2FeN 3): C59.26, H4.54, N9.01; Experiment value (%): C58.46, H4.63, N8.87.
3. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of continuous drying 6hrs 2Gas displacement 3 times.Add 2.3mg (5 μ mol) catalyst 15 and then vacuumize and with ethene displacement 3 times.Toluene with syringe injection 30ml adds 1.7ml MAO (MAO) (toluene solution of 1.46mol/l) again, makes Al/Fe=500.Under 20 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 60min.With syringe take out spiece with in 5% the watery hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 5.18 * 10 5G mol -1(Fe) h -1, oligomer content is respectively: C 454%, C 639%, C 8-C 147%.Remaining mixture does not obtain polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 38
1. the preparation of catalyst 15 is with embodiment 37.
2. (1MPa) ethylene oligomerization pressurizes: the toluene solution of 1000ml toluene and 3.5ml MAO (MAO) (1.46mol/l in toluene) and 10ml catalyst 15 (10.0 μ mol) is joined in the 2000-ml stainless steel autoclave.Mechanical agitation begins, and keeps 350 rev/mins, when polymerization temperature reaches 40 ℃, charges into ethene in reactor, and polymerisation begins.Under 40 ℃, keep the ethylene pressure of 1MPa, stirring reaction 1h.With syringe take out spiece with in 5% the watery hydrochloric acid with laggard promoting the circulation of qi chromatogram (GC) analysis mutually: the oligomerisation activity is 3.79 * 10 7G mol -1(Fe) h -1, oligomer content is respectively: C 445.1%, C 641.3%, C 87.3%, C 104.0%, C 121.4%, C 14-C 200.8%.Remaining mixture does not obtain polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 39
1. the preparation of catalyst 15 is with embodiment 37.
2. (1MPa) ethylene oligomerization pressurizes: the toluene solution of toluene and 1.4ml MAO (MAO) (1.46mol/lin toluene) and 6ml catalyst 15 (2.0 μ mol) is joined in the stainless steel autoclave of 250-ml, making cumulative volume is 100ml, Al/Fe=1000.When polymerization temperature reaches 40 ℃, in reactor, charge into ethene, keep the ethylene pressure of 1MPa, stirring reaction 1h.With syringe take out spiece with in 5% the watery hydrochloric acid with laggard promoting the circulation of qi chromatogram (GC) analysis mutually: the oligomerisation activity is 1.89 * 10 7G mol -1(Fe) h -1, oligomer content is respectively: C 434.9%, C 646.5%, C 89.9%, C 105.7%, C 121.9%, C 14-C 241.1%.Remaining mixture obtains the white wax shaped polymer with the ethanolic solution neutralization of 5% hcl acidifying, and polymerization activity is 3.30 * 10 4G mol -1(Fe) h -1
Embodiment 40
1. the preparation of part: 2-acetyl group-1; the 10-phenanthroline (contracts 2; the 6-diisopropyl aniline): 2-acetyl group-1; 10-phenanthroline (0.4445g; 2mmol) with 2; 6-diisopropyl aniline (0.4255g; 2.4mmol) add the 40mg p-methyl benzenesulfonic acid and make catalyst; in the 10ml absolute ethyl alcohol, refluxed 2 days under the nitrogen protection; concentrate back residue parlkaline aluminium oxide pillar, with petrol ether/ethyl acetate (4: 1) drip washing, second flow point is a product; removing desolvates obtains yellow solid 0.55g, and productive rate is 72%.Fusing point is 196-198 ℃.FT-IR(KBr?disc，cm -1)：3434，2961，1646，1459，1115，861，772。 1H?NMR(300MHz，CDCl 3)：δ9.25(d，J＝2.7Hz，1H)；8.82(d，J＝8.7Hz，1H)；8.33(m，2H)；7.85(s，2H)；7.65(m，1H)；7.17(m，3H)；2.86(hept，J＝6.6Hz，2H，CH)，2.60(s，3H，CH 3)；1.17(d，12H，CH 3)。Elementary analysis (C 26H 27N 3) theoretical value (%): C81.85, H7.13, N11.01; Experiment value (%): C81.82, H7.25, N10.71.
2. the preparation of catalyst 16: iron (II) (16) is closed in chlorination [2-acetyl group-1,10-phenanthroline (contracting 2, the 6-diisopropyl aniline)]: with 5mlFeCl 24H 2O (48.0mg; 0.24mmol) ethanol solution be added drop-wise to 5ml2-acetyl group-1; the 10-phenanthroline (contracts 2; the 6-diisopropyl aniline) part (76.3mg; 0.2mmol) ethanol solution in, stirring at room 9 hours is separated out precipitation; filtration obtains black-and-blue powder solid with ether washing back drying, and productive rate is 63%.FT-IR(KBr?disc，cm -1)：3440，2967，1605，1407，1289，850，789。Elementary analysis (C 26H 27Cl 2FeN 3) theoretical value (%): C61.44, H5.35, N8.27; Experiment value (%): C61.44, H5.58, N8.05.
3. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of continuous drying 6hrs 2Gas displacement 3 times.Add 2.6mg (5 μ mol) catalyst 16 and then vacuumize and with ethene displacement 3 times.Toluene with syringe injection 30ml adds 1.7ml MAO (MAO) (toluene solution of 1.46mol/l) again, makes Al/Fe=500.Under 40 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 60min.With syringe take out spiece with in 5% the watery hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 8.2 * 10 4G mol -1(Fe) h -1, oligomer content is respectively: C 422%, C 633%, C 813%, C 1012%, C 128%, C 14-C 2412%.Remaining mixture does not obtain polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 41
1. the preparation of catalyst 16 is with embodiment 40.
2. (1MPa) ethylene oligomerization pressurizes: the toluene solution of 1000ml toluene and 3.3ml MAO (MAO) (1.54mol/l in toluene) and 10ml catalyst 16 (14 μ mol) is joined in the 2000-ml stainless steel autoclave.Mechanical agitation begins, and keeps 350 rev/mins, when polymerization temperature reaches 40 ℃, charges into ethene in reactor, and polymerisation begins.Under 40 ℃, keep the ethylene pressure of 1MPa, stirring reaction 1h.With syringe take out spiece with in 5% the watery hydrochloric acid with laggard promoting the circulation of qi chromatogram (GC) analysis mutually: the oligomerisation activity is 8.98 * 10 6G mol -1(Fe) h -1, oligomer content is respectively: C 417%, C 626%, C 819%, C 1014%, C 1211%, C 14-C 2213%.Remaining mixture obtains the white wax oily polymer with the ethanolic solution neutralization of 5% hcl acidifying, and polymerization activity is 4.3 * 10 5G mol -1(Fe) h -1
Embodiment 42
1. the preparation of catalyst 16 is with embodiment 40.
2. (1MPa) ethylene oligomerization pressurizes: the toluene solution of toluene and 1.4ml MAO (MAO) (1.46mol/lin toluene) and 6ml catalyst 15 (2.0 μ mol) is joined in the stainless steel autoclave of 250-ml, making cumulative volume is 100ml, Al/Fe=1000.When polymerization temperature reaches 40 ℃, in reactor, charge into ethene, keep the ethylene pressure of 1MPa, stirring reaction 1h.With syringe take out spiece with in 5% the watery hydrochloric acid with laggard promoting the circulation of qi chromatogram (GC) analysis mutually: the oligomerisation activity is 9.42 * 10 6G mol -1(Fe) h -1, oligomer content is respectively: C 433.5%, C 633.9%, C 1014.1%, C 128.6%, C 145.0%, C 16-C 221.1%.Remaining mixture obtains the white wax shaped polymer with the ethanolic solution neutralization of 5% hcl acidifying, and polymerization activity is 2.10 * 10 4G mol -1(Fe) h -1
Embodiment 43
1. the preparation of part: 2-acetyl group-1; 10-phenanthroline (the 2-fluoroaniline contracts): 2-acetyl group-1; 10-phenanthroline (0.4445g; 2mmol) with 2-fluoroaniline (0.284g; 2.5mmol) add the 40mg p-methyl benzenesulfonic acid and make catalyst and add the 2g molecular sieve to make dehydrating agent; 30ml reflux in toluene 1 day; remove solvent toluene after the filtration; residue supports with the carrene dissolving; parlkaline aluminium oxide pillar, with petrol ether/ethyl acetate (4: 1) drip washing, second flow point is a product; removing desolvates obtains yellow solid 0.202g, and productive rate is 32%.FT-IR(KBr?disc，cm -1)：3055，2972，1638，1611，1552，1486，1451，1419，1365，1320，1238，1194，1117，1031，888，852，776，749，658。 1H?NMR(300MHz，CDCl 3)：δ9.24(d，J＝4.2Hz，1H)；8.65(d，J＝8.4Hz，1H)；8.34(d，J＝8.4Hz，1H)；8.29(d，J＝7.8Hz，1H)；7.86(s，2H)；7.66(dd，J＝7.8Hz，1H)；7.19-6.93(m，4H)；2.72(s，3H，CH 3)。Elementary analysis (C 20H 14FN 3) theoretical value (%): C76.18, H4.47, N13.33; Experiment value (%): C76.35, H4.68, N13.32.
2. the preparation of catalyst 17: iron (II) (17) is closed in chlorination [2-acetyl group-1,10-phenanthroline (the 2-fluoroaniline contracts)]: with 5mlFeCl 24H 2O (48.0mg; 0.24mmol) ethanol solution be added drop-wise to 5ml2-acetyl group-1; 10-phenanthroline (the 2-fluoroaniline contracts) part (63.1mg; 0.2mmol) ethanol solution in; stirring at room 9 hours; separate out precipitation, filter with ether washing back drying and obtain blackish green powder solid, productive rate is 99%.FT-IR(KBr?disc，cm -1)：3060，2918，1610，1579，1514，1486，1406，1371，1286，1228，1145，1089，1033，858，741，656。Elementary analysis (C 20H 14Cl 2FFeN 3): C54.34, H3.19, N9.50; Experiment value (%): C54.24, H3.36, N9.41.
3. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of continuous drying 6hrs 2Gas displacement 3 times.Add 2.2mg (5 μ mol) catalyst 17 and then vacuumize and with ethene displacement 3 times.Toluene with syringe injection 30ml adds 1.7ml MAO (MAO) (toluene solution of 1.46mol/l) again, makes Al/Fe=500.Under 20 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the watery hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 2.18 * 10 5G mol -1(Fe) h -1, oligomer content is respectively: C 4100%.Remaining mixture does not obtain polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 44
1. the preparation of catalyst 17 is with embodiment 43.
2. pressurization (1MPa) ethylene oligomerization: the 250-ml stainless steel still that mechanical agitation and thermocouple will be housed vacuumizes and with nitrogen replacement 3 times, replaces 2 times with ethene again.Behind the cool to room temperature, add the toluene solution of toluene and 1.7ml MAO (MAO) (1.46mol/l in toluene) and 10ml catalyst 17 (5.0 μ mol), the cumulative volume of toluene is 150ml, Al/Fe=500.The pressure of ethene is increased to 10 atmospheric pressure, at 40 ℃ of following vigorous stirring 1h.With syringe take out spiece with in 5% the watery hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 2.98 * 10 5G mol -1(Fe) h -1, oligomer content is respectively: C 493%, C 67%.Remaining mixture does not obtain polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 45
1. the preparation of part: 2-acetyl group-1; 10-phenanthroline (2-fluoro-4-methylaniline contracts): 2-acetyl group-1; 10-phenanthroline (0.4445g; 2mmol) with 2-fluoro-4-methylaniline (0.32g; 2.5mmol) add the 40mg p-methyl benzenesulfonic acid and make catalyst and add the 2g molecular sieve to make dehydrating agent; 30ml reflux in toluene 1 day; remove solvent toluene after the filtration; residue supports with the carrene dissolving; parlkaline aluminium oxide pillar, with petrol ether/ethyl acetate (4: 1) drip washing, second flow point is a product; removing desolvates obtains yellow solid 0.132g, and productive rate is 20%.FT-IR(KBr?disc，cm -1)：3042，2996，2927，1641，1588，1552，1498，1451，1416，1389，1365，1319，1275，1252，1214，1117，1081，934，885，853，827，765，741，659。 1H?NMR(300MHz，CDCl 3)：δ9.24(s，1H)；8.63(d，J＝7.8Hz，1H)；8.30(m，2H)；7.85(s，2H)；7.67(dd，J＝7.8Hz，1H)；7.00-6.83(m，3H)；2.73(s，3H，CH 3)，2.37(s，3H，PhCH 3)。Elementary analysis (C 21H 16FN 3) theoretical value (%): C76.58, H4.90, N12.76; Experiment value (%): C76.00, H4.90, N12.45.
2. the preparation of catalyst 18: iron (II) (18) is closed in chlorination [2-acetyl group-1,10-phenanthroline (2-fluoro-4-methylaniline contracts)]: with 5mlFeCl 24H 2O (48.0mg; 0.24mmol) ethanol solution be added drop-wise to 5ml2-acetyl group-1; 10-phenanthroline (2-fluoro-4-methylaniline contracts) part (65.9mg; 0.2mmol) ethanol solution in; stirring at room 9 hours; separate out precipitation, filter with ether washing back drying and obtain blackish green powder solid, productive rate is 66%.FT-IR(KBr?disc，cm -1)：3060，2962，2922，1608，1581，1487，1446，1406，1372，1228，1195，1145，1033，858，742，657。Elementary analysis (C 21H 16Cl 2FFeN 3): C55.30, H3.54, N9.21; Experiment value (%): C54.96, H3.94, N8.87.
3. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of continuous drying 6hrs 2Gas displacement 3 times.Add 2.3mg (5 μ mol) catalyst 18 and then vacuumize and with ethene displacement 3 times.Toluene with syringe injection 30ml adds 1.7ml MAO (MAO) (toluene solution of 1.46mol/l) again, makes Al/Fe=500.Under 20 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 360min.With syringe take out spiece with in 5% the watery hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 5.28 * 10 3G mol -1(Fe) h -1, oligomer content is respectively: C 491%, C 69%.Remaining mixture does not obtain polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 46
1. the preparation of catalyst 18 is with embodiment 45.
2. pressurization (1MPa) ethylene oligomerization: the 250-ml stainless steel still that mechanical agitation and thermocouple will be housed vacuumizes and with nitrogen replacement 3 times, replaces 2 times with ethene again.Behind the cool to room temperature, add the toluene solution of toluene and 1.7ml MAO (MAO) (1.46mol/l in toluene) and 10ml catalyst 18 (5.0 μ mol), the cumulative volume of toluene is 150ml, Al/Fe=500.The pressure of ethene is increased to 10 atmospheric pressure, at 40 ℃ of following vigorous stirring 1h.With syringe take out spiece with in 5% the watery hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 1.35 * 10 5G mol -1(Fe) h -1, oligomer content is respectively: C 4100%.Remaining mixture does not obtain polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 47
1. the preparation of part: 2-acetyl group-1; 10-phenanthroline (2-fluoro-5-methylaniline contracts): 2-acetyl group-1; 10-phenanthroline (0.4445g; 2mmol) with 2-fluoro-5-methylaniline (0.32g; 2.5mmol) add the 40mg p-methyl benzenesulfonic acid and make catalyst and add the 2g molecular sieve to make dehydrating agent; 30ml reflux in toluene 1 day; remove solvent toluene after the filtration; residue supports with the carrene dissolving; parlkaline aluminium oxide pillar, with petrol ether/ethyl acetate (4: 1) drip washing, second flow point is a product; removing desolvates obtains yellow solid 0.1g, and productive rate is 15%.FT-IR(KBr?disc，cm -1)：3045，2980，1637，1551，1495，1458，1390，1365，1319，1257，1202，1117，924，852，814，774，748，658。 1H?NMR(300MHz，CDCl 3)：δ9.25(d，J＝3.3Hz，1H)；8.65(d，J＝8.4Hz，1H)；8.35(d，J＝8.4Hz，1H)；8.30(d，J＝8.4Hz，1H)；7.87(s，2H)；7.68(dd，J＝7.8Hz，1H)；7.08-6.76(m，3H)；2.73(s，3H，CH3)，2.36(s，3H，PhCH 3)。Elementary analysis (C 21H 16FN 3) theoretical value (%): C76.58, H4.90, N12.76; Experiment value (%): C76.53, H4.98, N12.63.
2. the preparation of catalyst 19: iron (II) (19) is closed in chlorination [2-acetyl group-1,10-phenanthroline (2-fluoro-5-methylaniline contracts)]: with 5mlFeCl 24H 2O (48.0mg; 0.24mmol) ethanol solution be added drop-wise to 5ml2-acetyl group-1; 10-phenanthroline (2-fluoro-5-methylaniline contracts) part (65.9mg; 0.2mmol) ethanol solution in; stirring at room 9hrs; separate out precipitation, filter with ether washing back drying and obtain blackish green powder solid, productive rate is 58%.FT-IR(KBr?disc，cm -1)：3051，2918，1605，1582，1487，1446，1371，1286，1114，1035，859，742，658。Elementary analysis (C 21H 16Cl 2FFeN 3): C55.30, H3.54, N9.21; Experiment value (%): C55.02, H3.76, N9.01.
3. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of continuous drying 6hrs 2Gas displacement 3 times.Add 2.3mg (5 μ mol) catalyst 19 and then vacuumize and with ethene displacement 3 times.Toluene with syringe injection 30ml adds 1.7ml MAO (MAO) (toluene solution of 1.46mol/l) again, makes Al/Fe=500.Under 20 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the watery hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 9.09 * 10 3G mol -1(Fe) h -1, oligomer content is respectively: C 495%, C 65%.Remaining mixture does not obtain polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 48
1. the preparation of catalyst 19 is with embodiment 47.
2. pressurization (1MPa) ethylene oligomerization: the 250-ml stainless steel still that mechanical agitation and thermocouple will be housed vacuumizes and with nitrogen replacement 3 times, replaces 2 times with ethene again.Behind the cool to room temperature, add the toluene solution of toluene and 1.7ml MAO (MAO) (1.46mol/l in toluene) and 10ml catalyst 19 (5.0 μ mol), the cumulative volume of toluene is 150ml, Al/Fe=500.The pressure of ethene is increased to 10 atmospheric pressure, at 40 ℃ of following vigorous stirring ih.With syringe take out spiece with in 5% the watery hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 5.49 * 10 4G mol -1(Fe) h -1, oligomer content is respectively: C 4100%.Remaining mixture does not obtain polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 49
1. the preparation of part: 2-acetyl group-1; the 10-phenanthroline (contracts 2; the 4-difluoroaniline): 2-acetyl group-1; 10-phenanthroline (0.4445g; 2mmol) with 2; 4-difluoroaniline (0.33g; 2.5mmol) add the 40mg p-methyl benzenesulfonic acid and make catalyst and add the 2g molecular sieve to make dehydrating agent, 30ml reflux in toluene 1 day, remove solvent toluene after the filtration; residue supports with the carrene dissolving; parlkaline aluminium oxide pillar, with petrol ether/ethyl acetate (4: 1) drip washing, second flow point is a product; removing desolvates obtains yellow solid 0.28g, and productive rate is 42%.FT-IR(KBr?disc，cm -1)：3045，2962，1639，1592，1555，1495，1421，1391，1365，1321，1254，1197，1140，1118，959，887，849，766，715，658。 1HNMR(300MHz，CDCl 3)：δ9.25(d，J＝4.2Hz，1H)；8.63(d，J＝8.4Hz，1H)；8.35(d，J＝8.7Hz，1H)；8.30(dd，J＝7.5Hz，1H)；7.88(s，2H)；7.68(dd，J＝8.1Hz，1H)；6.98-6.89(m，3H)；2.73(s，3H，CH 3)。Elementary analysis (C 20H 13F 2N 3) theoretical value (%): C72.06, H3.93, N12.61; Experiment value (%): C71.85, H4.13, N12.46.
2. the preparation of catalyst 20: iron (II) (20) is closed in chlorination [2-acetyl group-1,10-phenanthroline (contracting 2, the 4-difluoroaniline)]: with 5mlFeCl 24H 2O (48.0mg; 0.24mmol) ethanol solution be added drop-wise to 5ml2-acetyl group-1; the 10-phenanthroline (contracts 2; the 4-difluoroaniline) part (66.7mg; 0.2mmol) ethanol solution in, stirring at room 9 hours is separated out precipitation; filtration obtains blackish green powder solid with ether washing back drying, and productive rate is 75%.FT-IR(KBr?disc，cm -1)：3404，3072，1973，1607，1541，1497，1429，1398，1340，1299，1271，1207，1144，1097，964，850，738，656。Elementary analysis (C 20H 13Cl 2F 2FeN 3): C52.21, H2.85, N9.13; Experiment value (%): C51.90, H3.02, N8.96.
3. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of continuous drying 6hrs 2Gas displacement 3 times.Add 2.3mg (5 μ mol) catalyst 20 and then vacuumize and with ethene displacement 3 times.Toluene with syringe injection 30ml adds 1.7ml MAO (MAO) (toluene solution of 1.46mol/l) again, makes Al/Fe=500.Under 20 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the watery hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 1.08 * 10 5G mol -1(Fe) h -1, oligomer content is respectively: C 4100%.Remaining mixture does not obtain polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 50
1. the preparation of catalyst 20 is with embodiment 49.
2. pressurization (1MPa) ethylene oligomerization: the 250-ml stainless steel still that mechanical agitation and thermocouple will be housed vacuumizes and with nitrogen replacement 3 times, replaces 2 times with ethene again.Behind the cool to room temperature, add the toluene solution of toluene and 1.7ml MAO (MAO) (1.46mol/l in toluene) and 10ml catalyst 20 (5.0 μ mol), the cumulative volume of toluene is 150ml, Al/Fe=500.The pressure of ethene is increased to 10 atmospheric pressure, at 40 ℃ of following vigorous stirring 1h.With syringe take out spiece with in 5% the watery hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 8.17 * 10 4G mol -1(Fe) h -1, oligomer content is respectively: C 481.2%, C 616.8%.Remaining mixture does not obtain polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 51
1. the preparation of part: 2-acetyl group-1; the 10-phenanthroline (contracts 2; the 5-difluoroaniline): 2-acetyl group-1; 10-phenanthroline (0.4445g; 2mmol) with 2; 5-difluoroaniline (0.33g; 2.5mmol) add the 40mg p-methyl benzenesulfonic acid and make catalyst and add the 2g molecular sieve to make dehydrating agent, 30ml reflux in toluene 1 day, remove solvent toluene after the filtration; residue supports with the carrene dissolving; parlkaline aluminium oxide pillar, with petrol ether/ethyl acetate (4: 1) drip washing, second flow point is a product; removing desolvates obtains yellow solid 0.307g, and productive rate is 46%.FT-IR(KBr?disc，cm -1)：3049，2967，1640，1593，1553，1491，1417，1391，1365，1322，1272，1245，1191，1146，1119，1099，989，934，855，805，766，659。 1H?NMR(300MHz，CDCl 3)：δ9.25(dd，J＝4.2Hz，1H)；8.62(d，J＝8.7Hz，1H)；8.35(d，J＝8.1Hz，1H)；8.30(dd，J＝7.8Hz，1H)；7.87(s，2H)；7.68(dd，J＝8.1Hz，1H)；7.11(m，1H)；6.81(m，1H)；6.70(m，1H)；2.75(s，3H，CH 3)。Elementary analysis (C 20H 13F 2N 3) theoretical value (%): C72.06, H3.93, N12.61; Experiment value (%): C71.69, H4.15, N12.53.
2. the preparation of catalyst 21: iron (II) (21) is closed in chlorination [2-acetyl group-1,10-phenanthroline (contracting 2, the 5-difluoroaniline)]: with 5mlFeCl 24H 2O (48.0mg; 0.24mmol) ethanol solution be added drop-wise to 5ml2-acetyl group-1; the 10-phenanthroline (contracts 2; the 5-difluoroaniline) part (66.7mg; 0.2mmol) ethanol solution in, stirring at room 9 hours is separated out precipitation; filtration obtains blackish green powder solid with ether washing back drying, and productive rate is 88%.FT-IR(KBr?disc，cm -1)：3416，3056，2906，1621，1604，1580，1496，1442，1397，1374，1339，1307，1250，1202，1172，1103，951，855，828，765，740，655。Elementary analysis (C 20H 13Cl 2F 2FeN 3): C52.21, H2.85, N9.13; Experiment value (%): C51.71, H3.08, N8.87.
3. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of continuous drying 6hrs 2Gas displacement 3 times.Add 2.3mg (5 μ mol) catalyst 21 and then vacuumize and with ethene displacement 3 times.Toluene with syringe injection 30ml adds 1.7ml MAO (MAO) (toluene solution of 1.46mol/l) again, makes Al/Fe=500.Under 20 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the watery hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 3.23 * 10 4G mol -1(Fe) h -1, oligomer content is respectively: C 454%, C 646%.Remaining mixture does not obtain polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 52
1. the preparation of catalyst 21 is with embodiment 51.
2. pressurization (1MPa) ethylene oligomerization: the 250-ml stainless steel still that mechanical agitation and thermocouple will be housed vacuumizes and with nitrogen replacement 3 times, replaces 2 times with ethene again.Behind the cool to room temperature, add the toluene solution of toluene and 1.7ml MAO (MAO) (1.46mol/l in toluene) and 10ml catalyst 21 (5.0 μ mol), the cumulative volume of toluene is 150ml, Al/Fe=500.The pressure of ethene is increased to 10 atmospheric pressure, at 40 ℃ of following vigorous stirring 1h.With syringe take out spiece with in 5% the watery hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 1.14 * 10 5G mol -1(Fe) h -1, oligomer content is respectively: C 476.6%, C 610.6%, C 102.5%, C 123.3%, C 14-C 206.9%.Remaining mixture does not obtain polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 53
1. the preparation of part: 2-acetyl group-1; the 10-phenanthroline (contracts 2; the 6-difluoroaniline): 2-acetyl group-1; 10-phenanthroline (0.4445g; 2mmol) with 2; 6-difluoroaniline (0.33g; 2.5mmol) add the 40mg p-methyl benzenesulfonic acid and make catalyst and add the 2g molecular sieve to make dehydrating agent, 30ml reflux in toluene 1 day, remove solvent toluene after the filtration; residue supports with the carrene dissolving; parlkaline aluminium oxide pillar, with petrol ether/ethyl acetate (4: 1) drip washing, second flow point is a product; removing desolvates obtains yellow solid 0.36g, and productive rate is 54%.FT-IR(KBr?disc，cm -1)：3429，3015，1637，1585，1556，1473，1421，1391，1368，1322，1277，1237，1121，1066，1027，999，888，852，821，766，744，697，658。 1H?NMR(300MHz，CDCl 3)：δ9.25(dd，J＝4.2Hz，1H)；8.70(d，J＝8.4Hz，1H)；8.36(d，J＝8.7Hz，1H)；8.30(dd，J＝8.7Hz，1H)；7.88(s，2H)；7.68(dd，J＝7.8Hz，1H)；7.11-6.97(m，3H)；2.76(s，3H，CH 3)。Elementary analysis (C 20H 13F 2N 3) theoretical value (%): C72.06, H3.93, N12.61; Experiment value (%): C71.89, H3.90, N12.87.
2. the preparation of catalyst 22: iron (II) (22) is closed in chlorination [2-acetyl group-1,10-phenanthroline (contracting 2, the 6-difluoroaniline)]: with 5mlFeCl 24H 2O (48.0mg; 0.24mmol) ethanol solution be added drop-wise to 5ml2-acetyl group-1; the 10-phenanthroline (contracts 2; the 6-difluoroaniline) part (66.7mg; 0.2mmol) ethanol solution in, stirring at room 9 hours is separated out precipitation; filtration obtains blackish green powder solid with ether washing back drying, and productive rate is 87%.FT-IR(KBr?disc，cm -1)：3392，3048，2898，1606，1585，1544，1510，1471，1441，1396，1339，1303，1284，1241，1219，1149，1099，1005，853，791，738，708，657。Elementary analysis (C 20H 13Cl 2F 2FeN 3): C52.21, H2.85, N9.13; Experiment value (%): C52.32, H3.43, N8.13.
3. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of continuous drying 6hrs 2Gas displacement 3 times.Add 2.3mg (5 μ mol) catalyst 22 and then vacuumize and with ethene displacement 3 times.Toluene with syringe injection 30ml adds 1.7ml MAO (MAO) (toluene solution of 1.46mol/l) again, makes Al/Fe=500.Under 20 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the watery hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 1.10 * 10 5G mol -1(Fe) h -1, oligomer content is respectively: C 451%, C 622%, C 89%, C 108%, C 125%, C 14-C 205%.Remaining mixture does not obtain polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 54
1. the preparation of catalyst 22 is with embodiment 53.
2. (1MPa) ethylene oligomerization pressurizes: the toluene solution of 1000ml toluene and 3.5ml MAO (MAO) (1.46mol/l in toluene) and 10ml catalyst 22 (10 μ mol) is joined in the 2000-ml stainless steel autoclave.Mechanical agitation begins, and keeps 350 rev/mins, when polymerization temperature reaches 40 ℃, charges into ethene in reactor, and polymerisation begins.Under 40 ℃, keep the ethylene pressure of 1MPa, stirring reaction 1h.With syringe take out spiece with in 5% the watery hydrochloric acid with laggard promoting the circulation of qi chromatogram (GC) analysis mutually: the oligomerisation activity is 1.62 * 10 7G mol -1(Fe) h -1, oligomer content is respectively: C 428.7%, C 638.6%, C 815.5%, C 109.1%, C 124.6%, C 14-C 223.6%.Remaining mixture obtains small amount of polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 55
1. the preparation of catalyst 22 is with embodiment 53.
2. (1MPa) ethylene oligomerization pressurizes: the toluene solution of toluene and 1.4ml MAO (MAO) (1.46mol/lin toluene) and 6ml catalyst 22 (2.0 μ mol) is joined in the stainless steel autoclave of 250-ml, making cumulative volume is 100ml, Al/Fe=1000.When polymerization temperature reaches 40 ℃, in reactor, charge into ethene, keep the ethylene pressure of 1MPa, stirring reaction 1h.With syringe take out spiece with in 5% the watery hydrochloric acid with laggard promoting the circulation of qi chromatogram (GC) analysis mutually: the oligomerisation activity is 2.37 * 10 7G mol -1(Fe) h -1, oligomer content is respectively: C 420.4%, C 642.1%, C 816.5%, C 1012.0%, C 125.1%, C 14, 2.2%, C 16-C 241.7%.Remaining mixture obtains traces of polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 56
1. the preparation of part: 2-acetyl group-1; the 10-phenanthroline (contracts 3; the 4-difluoroaniline): 2-acetyl group-1; 10-phenanthroline (0.4445g; 2mmol) with 3; 4-difluoroaniline (0.33g; 2.5mmol) add the 40mg p-methyl benzenesulfonic acid and make catalyst and add the 2g molecular sieve to make dehydrating agent, 30ml reflux in toluene 1 day, remove solvent toluene after the filtration; residue supports with the carrene dissolving; parlkaline aluminium oxide pillar, with petrol ether/ethyl acetate (4: 1) drip washing, second flow point is a product; removing desolvates obtains yellow solid 0.08g, and productive rate is 12%.FT-IR(KBr?disc，cm -1)：2994，1634，1601，1556，1512，1420，1393，1367，1289，1208，1142，1116，985，938，855，778，660。 1H?NMR(300MHz，CDCl 3)：δ9.24(dd，J＝4.2Hz，1H)；8.57(d，J＝8.7Hz，1H)；8.35(d，J＝8.7Hz，1H)；8.30(dd，J＝8.7Hz，1H)；7.88(s，2H)；7.68(dd，J＝7.8Hz，1H)；7.24-7.15(m，1H)；6.78-6.71(m，1H)；6.62-6.59(m，1H)；2.73(s，3H，CH 3)。Elementary analysis (C 20H 13F 2N 3) theoretical value (%): C72.06, H3.93, N12.61; Experiment value (%): C71.83, H4.26, N12.83.
2. the preparation of catalyst 23: iron (II) (23) is closed in chlorination [2-acetyl group-1,10-phenanthroline (contracting 3, the 4-difluoroaniline)]: with 5mlFeCl 24H 2O (48.0mg; 0.24mmol) ethanol solution be added drop-wise to 5ml2-acetyl group-1; the 10-phenanthroline (contracts 3; the 4-difluoroaniline) part (66.7mg; 0.2mmol) ethanol solution in, stirring at room 9 hours is separated out precipitation; filtration obtains blackish green powder solid with ether washing back drying, and productive rate is 70%.FT-IR(KBr?disc，cm -1)：3048，2898，1603，1585，1545，1511，1472，1396，303，1284，1243，1149，1099，853，738，657。Elementary analysis (C 20H 13Cl 2F 2FeN 3): C52.21, H2.85, N9.13; Experiment value (%): C58.02, H3.12, N9.01.
3. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of continuous drying 6hrs 2Gas displacement 3 times.Add 2.3mg (5 μ mol) catalyst 23 and then vacuumize and with ethene displacement 3 times.Toluene with syringe injection 30ml adds 1.7ml MAO (MAO) (toluene solution of 1.46mol/l) again, makes Al/Fe=500.Under 20 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the watery hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 2.11 * 10 4G mol -1(Fe) h -1, oligomer content is respectively: C 494%, C 66%.Remaining mixture does not obtain polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 57
1. the preparation of part: 2-acetyl group-1; the 10-phenanthroline (contracts 2; 3; the 4-trifluoromethyl aniline): 2-acetyl group-1; (0.4445g is 2mmol) with 2,3 for the 10-phenanthroline; 4-trifluoromethyl aniline (0.368g; 2.5mmol) add the 40mg p-methyl benzenesulfonic acid and make catalyst and add the 2g molecular sieve to make dehydrating agent, 30ml reflux in toluene 1 day, remove solvent toluene after the filtration; residue supports with the carrene dissolving; parlkaline aluminium oxide pillar, with petrol ether/ethyl acetate (4: 1) drip washing, second flow point is a product; removing desolvates obtains yellow solid 0.26g, and productive rate is 37%.Fusing point is 211-212 ℃.FT-IR(KBr?disc，cm -1)：3036，2968，1643，1605，1591，1554，1503，1477，1369，1306，1252，1168，1117，1051，993，946，857，823，744，659。 1H?NMR(300MHz，CDCl 3)：δ9.26(d，J＝3.3Hz，1H)；8.62(d，J＝8.4Hz，1H)；8.37(d，J＝8.4Hz，1H)；8.31(d，J＝8.1Hz，1H)；7.89(s，2H)；7.69(dd，J＝7.8Hz，1H)；7.02(m，1H)；6.68(m，1H)；2.75(s，3H，CH 3)。Elementary analysis (C 20H 12F 3N 3) theoretical value (%): C68.37, H3.44, N11.96; Experiment value (%): C67.87, H3.52, N11.82.
2. the preparation of catalyst 24: iron (II) (24) is closed in chlorination [2-acetyl group-1,10-phenanthroline (contracting 2,3, the 4-trifluoromethyl aniline)]: with 5mlFeCl 24H 2O (48.0mg; 0.24mmol) ethanol solution be added drop-wise to 5ml2-acetyl group-1; the 10-phenanthroline (contracts 2; 3, the 4-trifluoromethyl aniline) (70.3mg is in ethanol solution 0.2mmol) for part; stirring at room 9 hours; separate out precipitation, filter with ether washing back drying and obtain blackish green powder solid, productive rate is 92%.FT-IR(KBr?disc，cm -1)：3046，2916，1612，1581，1504，1477，1369，1286，1158，1029，857，741，658。Elementary analysis (C 20H 12Cl 2F 3FeN 3): C50.25, H2.53, N8.79; Experiment value (%): C49.92, H2.83, N8.56.
3. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of continuous drying 6hrs 2Gas displacement 3 times.Add 2.4mg (5 μ mol) catalyst 24 and then vacuumize and with ethene displacement 3 times.Toluene with syringe injection 30ml adds 1.7ml MAO (MAO) (toluene solution of 1.46mol/l) again, makes Al/Fe=500.Under 20 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the watery hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 1.81 * 10 4G mol -1(Fe) h -1, oligomer content is respectively: C 497%, C 63%.Remaining mixture does not obtain polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 58
1. the preparation of part: 2-acetyl group-1; the 10-phenanthroline (contracts 2; 4; the 5-trifluoromethyl aniline): 2-acetyl group-1; (0.4445g is 2mmol) with 2,4 for the 10-phenanthroline; 5-trifluoromethyl aniline (0.368g; 2.5mmol) add the 40mg p-methyl benzenesulfonic acid and make catalyst and add the 2g molecular sieve to make dehydrating agent, 30ml reflux in toluene 1 day, remove solvent toluene after the filtration; residue supports with the carrene dissolving; parlkaline aluminium oxide pillar, with petrol ether/ethyl acetate (4: 1) drip washing, second flow point is a product; removing desolvates obtains yellow solid, and productive rate is 28%.Fusing point is 191-192 ℃.FT-IR(KBr?disc，cm -1)：3016，2987，1636，1510，1415，1366，1205，1163，1118，848，742，662。 1H?NMR(300MHz，CDCl 3)：δ9.26(d，J＝3.3Hz，1H)；8.61(d，J＝8.4Hz，1H)；8.37(d，J＝8.4Hz，1H)；8.31(d，J＝8.1Hz，1H)；7.89(s，2H)；7.69(dd，J＝7.8Hz，1H)；7.06(m，1H)；6.84(m，1H)；2.75(s，3H，CH 3)。Elementary analysis (C 20H 12F 3N 3) theoretical value (%): C68.37, H3.44, N11.96; Experiment value (%): C67.80, H3.56, N11.91.
2. the preparation of catalyst 25: iron (II) (25) is closed in chlorination [2-acetyl group-1,10-phenanthroline (contracting 2,4, the 5-trifluoromethyl aniline)]: with 5mlFeCl 24H 2O (48.0mg; 0.24mmol) ethanol solution be added drop-wise to 5ml2-acetyl group-1; the 10-phenanthroline (contracts 2; 4, the 5-trifluoromethyl aniline) (70.3mg is in ethanol solution 0.2mmol) for part; stirring at room 9 hours; separate out precipitation, filter with ether washing back drying and obtain blackish green powder solid, productive rate is 80%.FT-IR(KBr?disc，cm -1)：3036，2916，1611，1511，1412，1366，1206，1163，1115，848，741，658。Elementary analysis (C 20H 12Cl 2F 3FeN 3): C50.25, H2.53, N8.79; Experiment value (%): C49.73, H2.76, N8.51.
3. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of continuous drying 6hrs 2Gas displacement 3 times.Add 2.4mg (5 μ mol) catalyst 25 and then vacuumize and with ethene displacement 3 times.Toluene with syringe injection 30ml adds 1.7ml MAO (MAO) (toluene solution of 1.46mol/l) again, makes Al/Fe=500.Under 20 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the watery hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 4.66 * 10 4G mol -1(Fe) h -1, oligomer content is respectively: C 4100%.Remaining mixture does not obtain polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 59
1. the preparation of part: 2-acetyl group-1; the 10-phenanthroline (contracts 2; 4; the 6-trifluoromethyl aniline): 2-acetyl group-1; (0.4445g is 2mmol) with 2,4 for the 10-phenanthroline; 6-trifluoromethyl aniline (0.368g; 2.5mmol) add the 40mg p-methyl benzenesulfonic acid and make catalyst and add the 2g molecular sieve to make dehydrating agent, 30ml reflux in toluene 1 day, remove solvent toluene after the filtration; residue supports with the carrene dissolving; parlkaline aluminium oxide pillar, with petrol ether/ethyl acetate (4: 1) drip washing, second flow point is a product; removing desolvates obtains yellow solid 0.281g, and productive rate is 40%.FT-IR(KBr?disc，cm -1)：3102，3033，1629，1595，1553，1492，1444，1391，1368，1320，1284，1216，1119，1080，1036，998，856，804，778，728，659。 1H?NMR(300MHz，CDCl 3)：δ9.25(dd，J＝4.2Hz，1H)；8.67(d，J＝8.4Hz，1H)；8.36(d，J＝8.4Hz，1H)；8.30(dd，J＝8.4Hz，1H)；7.87(s，2H)；7.68(dd，J＝7.8Hz，1H)；6.81(m，2H)；2.76(s，3H，CH 3)。Elementary analysis (C 20H 12F 3N 3) theoretical value (%): C68.37, H3.44, N11.96; Experiment value (%): C67.70, H3.61, N11.37.
2. the preparation of catalyst 26: iron (II) (26) is closed in chlorination [2-acetyl group-1,10-phenanthroline (contracting 2,4, the 6-trifluoromethyl aniline)]: with 5mlFeCl 24H 2O (48.0mg; 0.24mmol) ethanol solution be added drop-wise to 5ml2-acetyl group-1; the 10-phenanthroline (contracts 2; 4, the 6-trifluoromethyl aniline) (70.3mg is in ethanol solution 0.2mmol) for part; stirring at room 9 hours; separate out precipitation, filter with ether washing back drying and obtain blackish green powder solid, productive rate is 84%.FT-IR(KBr?disc，cm -1)：3400，3056，1600，1578，1492，1447，1398，1125，1046，999，849。Elementary analysis (C 20H 12Cl 2F 3FeN 3): C50.25, H2.53, N8.79; Experiment value (%): C49.86, H2.54, N8.61.
3. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of continuous drying 6hrs 2Gas displacement 3 times.Add 2.4mg (5 μ mol) catalyst 26 and then vacuumize and with ethene displacement 3 times.Toluene with syringe injection 30ml adds 1.7ml MAO (MAO) (toluene solution of 1.46mol/l) again, makes Al/Fe=500.Under 20 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the watery hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 1.58 * 10 4G mol -1(Fe) h -1, oligomer content is respectively: C 494%, C 66%.Remaining mixture does not obtain polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 60
1. the preparation of catalyst 26 is with embodiment 59.
2. (1MPa) ethylene oligomerization pressurizes: the toluene solution of toluene and 1.4ml MAO (MAO) (1.46mol/lin toluene) and 6ml catalyst 26 (2.0 μ mol) is joined in the stainless steel autoclave of 250-ml, making cumulative volume is 100ml, Al/Fe=1000.When polymerization temperature reaches 40 ℃, in reactor, charge into ethene, keep the ethylene pressure of 1MPa, stirring reaction 1h.With syringe take out spiece with in 5% the watery hydrochloric acid with laggard promoting the circulation of qi chromatogram (GC) analysis mutually: the oligomerisation activity is 1.08 * 10 6G mol -1(Fe) h -1, oligomer content is respectively: C 494%, C 66%.Remaining mixture does not obtain polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 61
1. the preparation of part: 2-acetyl group-1, the 10-phenanthroline (contracts 2,3; 4; 5,6-phenyl-pentafluoride amine): 2-acetyl group-1,10-phenanthroline (0.4445g; 2mmol) with 2; 3,4,5; 6-phenyl-pentafluoride amine (0.458g; 2.5mmol) add the 40mg p-methyl benzenesulfonic acid and make catalyst and add the 2g molecular sieve to make dehydrating agent, 30ml reflux in toluene 1 day, remove solvent toluene after the filtration; residue supports with the carrene dissolving; parlkaline aluminium oxide pillar, with petrol ether/ethyl acetate (4: 1) drip washing, second flow point is a product; removing desolvates obtains yellow solid, and productive rate is 37%.FT-IR(KBr?disc，cm -1)：3046，1632，1555，1517，1498，1368，1323，1282，1118，1008，987，938，850，779。 1H?NMR(300MHz，CDCl 3)：δ9.24(dd，J＝4.2Hz，1H)；8.63(d，J＝8.4Hz，1H)；8.35(d，J＝8.4Hz，1H)；8.29(dd，J＝8.4Hz，1H)；7.87(s，2H)；7.68(dd，J＝7.8Hz，1H)；2.83(s，3H，CH 3)。Elementary analysis (C 20H 10F 5N 3) theoretical value (%): C62.02, H2.60, N10.85; Experiment value (%): C61.73, H2.86, N10.69.
2. the preparation of catalyst 27: iron (II) (27) is closed in chlorination [2-acetyl group-1,10-phenanthroline (contracting 2,3,4,5,6-phenyl-pentafluoride amine)]: with 5mlFeCl 24H 2O (48.0mg; 0.24mmol) ethanol solution be added drop-wise to 5ml2-acetyl group-1, the 10-phenanthroline (contracts 2,3; 4; 5,6-phenyl-pentafluoride amine) (77.5mg is in ethanol solution 0.2mmol) for part; stirring at room 9 hours; separate out precipitation, filter with ether washing back drying and obtain blackish green powder solid, productive rate is 74%.FT-IR(KBr?disc，cm -1)：3393，3060，1607，1513，1396，1027，994，858。Elementary analysis (C 20H 10Cl 2F 5FeN 3): C46.73, H1.96, N8.17; Experiment value (%): C46.45, H2.13, N8.09.
3. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of continuous drying 6hrs 2Gas displacement 3 times.Add 2.6mg (5 μ mol) catalyst 27 and then vacuumize and with ethene displacement 3 times.Toluene with syringe injection 30ml adds 1.7ml MAO (MAO) (toluene solution of 1.46mol/l) again, makes Al/Fe=500.Under 20 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the watery hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 2.09 * 10 4G mol -1(Fe) h -1, oligomer content is respectively: C 4100%.Remaining mixture does not obtain polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 62
1. the preparation of catalyst 27 is with embodiment 61.
2. (1MPa) ethylene oligomerization pressurizes: the toluene solution of toluene and 1.4ml MAO (MAO) (1.46mol/lin toluene) and 6ml catalyst 27 (2.0 μ mol) is joined in the stainless steel autoclave of 250-ml, making cumulative volume is 100ml, Al/Fe=1000.When polymerization temperature reaches 40 ℃, in reactor, charge into ethene, keep the ethylene pressure of 1MPa, stirring reaction 1h.With syringe take out spiece with in 5% the watery hydrochloric acid with laggard promoting the circulation of qi chromatogram (GC) analysis mutually: the oligomerisation activity is 1.78 * 10 7G mol -1(Fe) h -1, oligomer content is respectively: C 452.2%, C 640.6%, C 10-C 207.2%.Remaining mixture obtains traces of polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 63
1. the preparation of part: 2-acetyl group-1; 10-phenanthroline (the 2-chloroaniline contracts): 2-acetyl group-1; 10-phenanthroline (0.4445g; 2mmol) with 2-chloroaniline (0.3189g; 2.5mmol) add the 40mg p-methyl benzenesulfonic acid and make catalyst and add the 2g molecular sieve to make dehydrating agent; 30ml reflux in toluene 1 day; remove solvent toluene after the filtration; residue supports with the carrene dissolving; parlkaline aluminium oxide pillar, with petrol ether/ethyl acetate (4: 1) drip washing, second flow point is a product; removing desolvates obtains yellow solid 0.338g, and productive rate is 51%.FT-IR(KBr?disc，cm -1)：3046，2981，1642，1585，1552，1472，1465，1392，1363，1319，1260，1220，1114，1056，1028，885，853，775，744，682。 1HNMR(300MHz，CDCl 3)：δ9.24(d，J＝3.3Hz，1H)；8.68(dd，J＝8.4Hz，1H)；8.35(dd，J＝8.1Hz，1H)；8.29(d，J＝8.1Hz，1H)；7.86(s，2H)；7.67(m，1H)；7.46(d，J＝7.8Hz，1H)；7.29(t，J＝7.5Hz，1H)；7.08(t，J＝7.5Hz，1H)；6.87(d，J＝7.5Hz，1H)；2.68(s，3H，CH 3)。Elementary analysis (C 20H 14ClN 3) theoretical value (%): C72.40, H4.25, N12.66; Experiment value (%): C71.96, H4.27, N12.49.
2. the preparation of catalyst 28: iron (II) (28) is closed in chlorination [2-acetyl group-1,10-phenanthroline (the 2-chloroaniline contracts)]: with 5mlFeCl 24H 2O (48.0mg; 0.24mmol) ethanol solution be added drop-wise to 5ml2-acetyl group-1; 10-phenanthroline (the 2-chloroaniline contracts) part (66.3mg; 0.2mmol) ethanol solution in; stirring at room 9 hours; separate out precipitation, filter with ether washing back drying and obtain blackish green powder solid, productive rate is 80%.FT-IR(KBr?disc，cm -1)：3045，2962，2916，1609，1581，1515，1486，1445，1406，1372，1286，1195，1145，1089，1033，858，791，742，656。Elementary analysis (C 20H 14Cl 3FeN 3): C52.39, H3.08, N9.16; Experiment value (%): C52.03, H3.28, N8.94.
3. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of continuous drying 6hrs 2Gas displacement 3 times.Add 2.3mg (5 μ mol) catalyst 28 and then vacuumize and with ethene displacement 3 times.Toluene with syringe injection 30ml adds 1.7ml MAO (MAO) (toluene solution of 1.46mol/l) again, makes Al/Fe=500.Under 20 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the watery hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 2.18 * 10 4G mol -1(Fe) h -1, oligomer content is respectively: C 4100%.Remaining mixture does not obtain polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 64
1. the preparation of catalyst 28 is with embodiment 63.
2. (1MPa) ethylene oligomerization pressurizes: the toluene solution of toluene and 1.4ml MAO (MAO) (1.46mol/lin toluene) and 6ml catalyst 28 (2.0 μ mol) is joined in the stainless steel autoclave of 250-ml, making cumulative volume is 100ml, Al/Fe=1000.When polymerization temperature reaches 40 ℃, in reactor, charge into ethene, keep the ethylene pressure of 1MPa, stirring reaction 1h.With syringe take out spiece with in 5% the watery hydrochloric acid with laggard promoting the circulation of qi chromatogram (GC) analysis mutually: the oligomerisation activity is 9.83 * 10 5G mol -1(Fe) h -1, oligomer content is respectively: C 474.9%, C 6-C 1825.1%.Remaining mixture obtains traces of polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 65
1. the preparation of part: 2-acetyl group-1; 10-phenanthroline (the 3-chloroaniline contracts): 2-acetyl group-1; 10-phenanthroline (0.4445g; 2mmol) with 3-chloroaniline (0.3189g; 2.5mmol) add the 40mg p-methyl benzenesulfonic acid and make catalyst and add the 2g molecular sieve to make dehydrating agent; 30ml reflux in toluene 1 day; remove solvent toluene after the filtration; residue supports with the carrene dissolving; parlkaline aluminium oxide pillar, with petrol ether/ethyl acetate (4: 1) drip washing, second flow point is a product; removing desolvates obtains yellow solid, and productive rate is 31%.FT-IR(KBr?disc，cm -1)：3250，3051，1634，1591，1557，1487，1394，1319，1271，853，762，683。 1H?NMR(300MHz，CDCl 3)：δ9.24(d，J＝3.3Hz，1H)；8.56(d，J＝8.4Hz，1H)；8.31(d，J＝8.1Hz，1H)；8.27(d，J＝8.1Hz，1H)；7.84(s，2H)；7.66(m，1H)；7.28(t，J＝7.8Hz，1H)；7.10(d，J＝7.5Hz，1H)；7.01(t，J＝7.8Hz，1H)；6.89(s，1H)；2.69(s，3H，CH 3)。Elementary analysis (C 20H 14ClN 3) theoretical value (%): C72.40, H4.25, N12.66; Experiment value (%): C71.96, H4.27, N12.49.
2. the preparation of catalyst 29: iron (II) (29) is closed in chlorination [2-acetyl group-1,10-phenanthroline (the 3-chloroaniline contracts)]: with 5mlFeCl 24H 2O (48.0mg; 0.24mmol) ethanol solution be added drop-wise to 5ml2-acetyl group-1; 10-phenanthroline (the 3-chloroaniline contracts) part (66.3mg; 0.2mmol) ethanol solution in; stirring at room 9 hours; separate out precipitation, filter with ether washing back drying and obtain blackish green powder solid, productive rate is 80%.FT-IR(KBr?disc，cm -1)：3381，3054，1619，1585，1507，1396，1338，1147，1097，854，730，689。Elementary analysis (C 20H 14Cl 3FeN 3): C52.39, H3.08, N9.16; Experiment value (%): C52.03, H3.34, N8.97.
3. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of continuous drying 6hrs 2Gas displacement 3 times.Add 2.3mg (5 μ mol) catalyst 29 and then vacuumize and with ethene displacement 3 times.Toluene with syringe injection 30ml adds 1.7ml MAO (MAO) (toluene solution of 1.46mol/l) again, makes Al/Fe=500.Under 20 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the watery hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 3.01 * 10 4G mol -1(Fe) h -1, oligomer content is respectively: C 492%, C 68%.Remaining mixture does not obtain polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 66
1. the preparation of catalyst 29 is with embodiment 65.
2. pressurization (1MPa) ethylene oligomerization: the 250-ml stainless steel still that mechanical agitation and thermocouple will be housed vacuumizes and with nitrogen replacement 3 times, replaces 2 times with ethene again.Behind the cool to room temperature, add the toluene solution of toluene and 1.7ml MAO (MAO) (1.46mol/l in toluene) and 10ml catalyst 29 (5.0 μ mol), the cumulative volume of toluene is 150ml, Al/Fe=500.The pressure of ethene is increased to 10 atmospheric pressure, at 40 ℃ of following vigorous stirring 1h.With syringe take out spiece with in 5% the watery hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 1.14 * 10 6G mol -1(Fe) h -1, oligomer content is respectively: C 454.2%, C 636.0%, C 83.7%, C 104.0%, C 121.4%, C 14-C 180.8%.Remaining mixture does not obtain polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 67
1. the preparation of part: 2-acetyl group-1; the 10-phenanthroline (contracts 2; the 6-dichloroaniline): 2-acetyl group-1; 10-phenanthroline (0.4445g; 2mmol) with 2; (0.4133g 2.5mmol) adds the 40mg p-methyl benzenesulfonic acid and makes catalyst the 6-dichloroaniline, reacts 1 day down in 140-150 ℃ in the 5ml ethyl orthosilicate; and tell the ethanol of generation with oil water separator; ethyl orthosilicate is removed in decompression, and residue supports parlkaline aluminium oxide pillar with the carrene dissolving; with petrol ether/ethyl acetate (4: 1) drip washing; second flow point is a product, and removing desolvates obtains yellow solid 0.231g, and productive rate is 32%.Fusing point is 184-185 ℃.FT-IR(KBrdisc，cm -1)：2966，2926，1641，1629，1585，1554，1489，1448，1432，1390，1367，1324，1285，1260，1223，1119，1079，854，782，761，738，658。 1H?NMR(300MHz，CDCl 3)：δ9.26(d，J＝4.2Hz，1H)；8.78(d，J＝8.4Hz，1H)；8.38(d，J＝8.4Hz，1H)；8.31(d，J＝7.8Hz，1H)；7.89(s，2H)；7.69(dd，J＝8.1Hz，1H)；7.39(d，J＝8.1Hz，2H)；7.02(t，J＝8.1Hz，1H)；2.68(s，3H，CH 3)。Elementary analysis (C 20H 13Cl 2N 3) theoretical value (%): C65.59, H3.58, N11.47; Experiment value (%): C65.29, H3.70, N11.28.
2. the preparation of catalyst 30: iron (II) (30) is closed in chlorination [2-acetyl group-1,10-phenanthroline (contracting 2, the 6-dichloroaniline)]: with 5mlFeCl 24H 2O (48.0mg; 0.24mmol) ethanol solution be added drop-wise to 5ml2-acetyl group-1; the 10-phenanthroline (contracts 2; the 6-dichloroaniline) part (74.3mg; 0.2mmol) ethanol solution in, stirring at room 9 hours is separated out precipitation; filtration obtains the purplish grey powder solid with ether washing back drying, and productive rate is 99%.FT-IR(KBr?disc，cm -1)：3447，3066，2992，2911，1614，1580，1561，1516，1495，1439，1407，1376，1332，1286，1231，1209，1160，1150，1090，859，832，788，749，684，657。Elementary analysis (C 20H 13Cl 4FeN 3Et 2O): C50.83, H4.09, N7.41; Experiment value (%): C50.86, H3.75, N7.49.
3. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of continuous drying 6hrs 2Gas displacement 3 times.Add 2.5mg (5 μ mol) catalyst 30 and then vacuumize and with ethene displacement 3 times.Toluene with syringe injection 30ml adds 1.7ml MAO (MAO) (toluene solution of 1.46mol/l) again, makes Al/Fe=500.Under 20 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the watery hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 2.82 * 10 4G mol -1(Fe) h -1, oligomer content is respectively: C 4100%.Remaining mixture does not obtain polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 68
1. the preparation of catalyst 30 is with embodiment 67.
2. (1MPa) ethylene oligomerization pressurizes: the toluene solution of 1000ml toluene and 3.5ml MAO (MAO) (1.46mol/l in toluene) and 10ml catalyst 30 (10 μ mol) is joined in the 2000-ml stainless steel autoclave.Mechanical agitation begins, and keeps 350 rev/mins, when polymerization temperature reaches 40 ℃, charges into ethene in reactor, and polymerisation begins.Under 40 ℃, keep the ethylene pressure of 1MPa, stirring reaction 1h.With syringe take out spiece with in 5% the watery hydrochloric acid with laggard promoting the circulation of qi chromatogram (GC) analysis mutually: the oligomerisation activity is 9.75 * 10 6G mol -1(Fe) h -1, oligomer content is respectively: C 420.3%, C 626.1%, C 817.0%, C 1013.2%, C 128.7%, C 14-C 266.6%.Remaining mixture obtains the white wax shaped polymer with the ethanolic solution neutralization of 5% hcl acidifying, and polymerization activity is 2.12 * 10 5G mol -1(Fe) h -1
Embodiment 69
1. the preparation of catalyst 30 is with embodiment 67.
2. (1MPa) ethylene oligomerization pressurizes: the toluene solution of toluene and 1.4ml MAO (MAO) (1.46mol/lin toluene) and 6ml catalyst 30 (2.0 μ mol) is joined in the stainless steel autoclave of 250-ml, making cumulative volume is 100ml, Al/Fe=1000.When polymerization temperature reaches 40 ℃, in reactor, charge into ethene, keep the ethylene pressure of 1MPa, stirring reaction 1h.With syringe take out spiece with in 5% the watery hydrochloric acid with laggard promoting the circulation of qi chromatogram (GC) analysis mutually: the oligomerisation activity is 3.51 * 10 7G mol -1(Fe) h -1, oligomer content is respectively: C 415.1%, C 630.2%, C 89.1%, C 1017.6%, C 1211.9%, C 147.2%, C 16-C 288.9%.Remaining mixture obtains traces of polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 70
1. the preparation of part: 2-acetyl group-1; the 10-phenanthroline (contracts 2; 3; the 4-trichloroaniline): 2-acetyl group-1, (0.4445g is 2mmol) with 2 for the 10-phenanthroline; 3; (0.5012g 2.5mmol) adds the 40mg p-methyl benzenesulfonic acid and makes catalyst the 4-trichloroaniline, reacts 1 day down in 140-150 ℃ in the 5ml ethyl orthosilicate; and tell the ethanol of generation with oil water separator; ethyl orthosilicate is removed in decompression, and residue supports parlkaline aluminium oxide pillar with the carrene dissolving; with petrol ether/ethyl acetate (4: 1) drip washing; second flow point is a product, and removing desolvates obtains yellow solid, and productive rate is 15%.FT-IR(KBr?disc，cm -1)：3042，1638，1585，1568，1552，1489，1439，1365，1236，1116，1079，907，853，821，779，742。 1H?NMR(300MHz，CDCl 3)：δ9.24(dd，J＝3.3Hz，1H)；8.64(d，J＝6.3Hz，1H)；8.36(d，J＝6.3Hz，1H)；8.30(d，J＝6.0Hz，1H)；7.87(s，2H)；7.68(dd，J＝6.0Hz，1H)；7.41(d，J＝6.6Hz，1H)；6.75(d，J＝6.3Hz，1H)；2.69(s，3H，CH 3。Elementary analysis (C 20H 12Cl 3N 3) theoretical value (%): C59.95, H3.02, N10.49; Experiment value (%): C59.85, H3.00, N10.31.
2. the preparation of catalyst 31: iron (II) (31) is closed in chlorination [2-acetyl group-1,10-phenanthroline (contracting 2,3, the 4-trichloroaniline)]: with 5mlFeCl 24H 2O (48.0mg; 0.24mmol) ethanol solution be added drop-wise to 5ml2-acetyl group-1; the 10-phenanthroline (contracts 2; 3, the 4-trichloroaniline) (80.1mg is in ethanol solution 0.2mmol) for part; stirring at room 9 hours; separate out precipitation, filter with ether washing back drying and obtain the dusty blue powder solid, productive rate is 99%.FT-IR(KBr?disc，cm -1)：3447，3051，1862，1614，1578，1512，1441，1404，1368，1285，1241，1150，1057，878，833，784，743，658。Elementary analysis (C 20H 12Cl 5FeN 3): C45.54, H2.29, N7.97; Experiment value (%): C45.16, H2.41, N7.76.
3. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of continuous drying 6hrs 2Gas displacement 3 times.Add 2.6mg (5 μ mol) catalyst 31 and then vacuumize and with ethene displacement 3 times.Toluene with syringe injection 30ml adds 1.7ml MAO (MAO) (toluene solution of 1.46mol/l) again, makes Al/Fe=500.Under 20 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the watery hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 5.62 * 10 4G mol -1(Fe) h -1, oligomer content is respectively: C 492%, C 68%.Remaining mixture does not obtain polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 71
1. the preparation of part: 2-acetyl group-1; the 10-phenanthroline (contracts 2; 4; the 5-trichloroaniline): 2-acetyl group-1, (0.4445g is 2mmol) with 2 for the 10-phenanthroline; 4; (0.5012g 2.5mmol) adds the 40mg p-methyl benzenesulfonic acid and makes catalyst the 5-trichloroaniline, reacts 1 day down in 140-150 ℃ in the 5ml ethyl orthosilicate; and tell the ethanol of generation with oil water separator; ethyl orthosilicate is removed in decompression, and residue supports parlkaline aluminium oxide pillar with the carrene dissolving; with petrol ether/ethyl acetate (4: 1) drip washing; second flow point is a product, and removing desolvates obtains yellow solid, and productive rate is 19%.FT-IR(KBr?disc，cm -1)：3078，3046，1634，1586，1553，1489，1456，1368，1341，1323，1285，1224，1115，1073，981，888，849，765，738，657。 1H?NMR(300MHz，CDCl 3)：δ9.26(s，1H)；8.63(d，J＝8.4Hz，1H)；8.37(d，J＝8.4Hz，1H)；8.31(d，J＝7.8Hz，1H)；7.89(s，2H)；7.69(m，1H)；7.58(s，1H)；7.01(s，1H)；2.72(s，3H，CH 3)。Elementary analysis (C 20H 12Cl 3N 3) theoretical value (%): C59.95, H3.02, N10.49; Experiment value (%): C60.09, H3.04, N10.27.
2. the preparation of catalyst 32: iron (II) (32) is closed in chlorination [2-acetyl group-1,10-phenanthroline (contracting 2,4, the 5-trichloroaniline)]: with 5mlFeCl 24H 2O (48.0mg; 0.24mmol) ethanol solution be added drop-wise to 5ml2-acetyl group-1; the 10-phenanthroline (contracts 2; 4, the 5-trichloroaniline) (80.1mg is in ethanol solution 0.2mmol) for part; stirring at room 12 hours; separate out precipitation, filter with ether washing back drying and obtain the celadon powder solid, productive rate is 45%.FT-IR(KBr?disc，cm -1)：3059，1613，1578，1513，1455，1403，1344，1286，1151，1080，859，740。Elementary analysis (C 20H 12Cl 5FeN 3): C45.54, H2.29, N7.97; Experiment value (%): C45.12, H2.58, N7.85.
3. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of continuous drying 6hrs 2Gas displacement 3 times.Add 2.6mg (5 μ mol) catalyst 32 and then vacuumize and with ethene displacement 3 times.Toluene with syringe injection 30ml adds 1.7ml MAO (MAO) (toluene solution of 1.46mol/l) again, makes Al/Fe=500.Under 20 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the watery hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 2.39 * 10 4G mol -1(Fe) h -1, oligomer content is respectively: C 4100%.Remaining mixture does not obtain polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 72
1. the preparation of catalyst 32 is with embodiment 71.
2. pressurization (1MPa) ethylene oligomerization: the 250-ml stainless steel still that mechanical agitation and thermocouple will be housed vacuumizes and with nitrogen replacement 3 times, replaces 2 times with ethene again.Behind the cool to room temperature, add the toluene solution of toluene and 1.7ml MAO (MAO) (1.46mol/l in toluene) and 10ml catalyst 32 (5.0 μ mol), the cumulative volume of toluene is 150ml, Al/Fe=500.The pressure of ethene is increased to 10 atmospheric pressure, at 40 ℃ of following vigorous stirring 1h.With syringe take out spiece with in 5% the watery hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 1.28 * 10 5G mol -1(Fe) h -1, oligomer content is respectively: C 418.7%, C 671.7%, C 84.9%, C 102.0%, C 120.9%, C 14-C 161.7%.Remaining mixture does not obtain polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 73
1. the preparation of part: 2-acetyl group-1; the 10-phenanthroline (contracts 2; 4; the 6-trichloroaniline): 2-acetyl group-1, (0.4445g is 2mmol) with 2 for the 10-phenanthroline; 4; (0.5012g 2.5mmol) adds the 40mg p-methyl benzenesulfonic acid and makes catalyst the 6-trichloroaniline, reacts 1 day down in 140-150 ℃ in the 5ml ethyl orthosilicate; and tell the ethanol of generation with oil water separator; ethyl orthosilicate is removed in decompression, and residue supports parlkaline aluminium oxide pillar with the carrene dissolving; with petrol ether/ethyl acetate (4: 1) drip washing; second flow point is a product, and removing desolvates obtains yellow solid 012g, and productive rate is 15%.FT-IR(KBr?disc，cm -1)：3049，1643，1587，1543，1490，1450，1430，1362，1322，1285，1229，1135，1114，854，798，706。 1H?NMR(300MHz，CDCl 3)：δ9.26(d，J＝4.2Hz，1H)；8.74(d，J＝8.4Hz，1H)；8.38(d，J＝8.4Hz，1H)；8.31(dd，J＝7.8Hz，1H)；7.89(s，2H)；7.69(dd，J＝7.8Hz，1H)；7.41(s，2H)；2.67(s，3H，CH 3)。Elementary analysis (C 20H 12Cl 3N 3) theoretical value (%): C59.95, H3.02, N10.49; Experiment value (%): C59.65, H3.07, N10.20.
2. the preparation of catalyst 33: iron (II) (33) is closed in chlorination [2-acetyl group-1,10-phenanthroline (contracting 2,4, the 6-trichloroaniline)]: with 5mlFeCl 24H 2O (48.0mg; 0.24mmol) ethanol solution be added drop-wise to 5ml2-acetyl group-1; the 10-phenanthroline (contracts 2; 4, the 6-trichloroaniline) (80.1mg is in ethanol solution 0.2mmol) for part; stirring at room 9 hours; separate out precipitation, filter with ether washing back drying and obtain the purplish grey powder solid, productive rate is 75%.FT-IR(KBr?disc，cm -1)：3466，3061，2910，1613，1578，1548，1514，1491，1438，1405，1375，1286，1232，1152，859，799，739，656。Elementary analysis (C 20H 12Cl 5FeN 3): C45.54, H2.29, N7.97; Experiment value (%): C45.31, H2.41, N7.86.
3. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of continuous drying 6hrs 2Gas displacement 3 times.Add 2.6mg (5 μ mol) catalyst 33 and then vacuumize and with ethene displacement 3 times.Toluene with syringe injection 30ml adds 1.7ml MAO (MAO) (toluene solution of 1.46mol/l) again, makes Al/Fe=500.Under 20 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the watery hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 2.75 * 10 4G mol -1(Fe) h -1, oligomer content is respectively: C 498%, C 62%.Remaining mixture does not obtain polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 74
1. the preparation of catalyst 33 is with embodiment 73.
2. (1MPa) ethylene oligomerization pressurizes: the toluene solution of 1000ml toluene and 3.5ml MAO (MAO) (1.46mol/l in toluene) and 10ml catalyst 33 (10 μ mol) is joined in the 2000-ml stainless steel autoclave.Mechanical agitation begins, and keeps 350 rev/mins, when polymerization temperature reaches 40 ℃, charges into ethene in reactor, and polymerisation begins.Under 40 ℃, keep the ethylene pressure of 1MPa, stirring reaction 1h.With syringe take out spiece with in 5% the watery hydrochloric acid with laggard promoting the circulation of qi chromatogram (GC) analysis mutually: the oligomerisation activity is 9.65 * 10 6G mol -1(Fe) h -1, oligomer content is respectively: C 420.0%, C 633.0%, C 815.1%, C 1011.7%, C 127.9%, C 14-C 2412.3%.Remaining mixture obtains the white wax shaped polymer with the ethanolic solution neutralization of 5% hcl acidifying, and polymerization activity is 7.3 * 10 4G mol -1(Fe) h -1
Embodiment 75
1. the preparation of catalyst 33 is with embodiment 73.
2. (1MPa) ethylene oligomerization pressurizes: the toluene solution of toluene and 1.4ml MAO (MAO) (1.46mol/lin toluene) and 6ml catalyst 33 (2.0 μ mol) is joined in the stainless steel autoclave of 250-ml, making cumulative volume is 100ml, Al/Fe=1000.When polymerization temperature reaches 40 ℃, in reactor, charge into ethene, keep the ethylene pressure of 1MPa, stirring reaction 1h.With syringe take out spiece with in 5% the watery hydrochloric acid with laggard promoting the circulation of qi chromatogram (GC) analysis mutually: the oligomerisation activity is 4.46 * 10 7G mol -1(Fe) h -1, oligomer content is respectively: C 422.1%, C 625.3%, C 817.6%, C 1012.9%, C 128.2%, C 145.6%, C 16-C268.4%.Remaining mixture obtains the white wax shaped polymer with the ethanolic solution neutralization of 5% hcl acidifying, and polymerization activity is 6.41 * 10 6G mol -1(Fe) h -1
Embodiment 76
1. the preparation of part: 2-acetyl group-1; 10-phenanthroline (the 2-bromaniline contracts): 2-acetyl group-1; 10-phenanthroline (0.4445g; 2mmol) with 2-bromaniline (0.430g; 2.5mmol) add the 40mg p-methyl benzenesulfonic acid and make catalyst and add the 2g molecular sieve to make dehydrating agent; 30ml reflux in toluene 1 day; remove solvent toluene after the filtration; residue supports with the carrene dissolving; parlkaline aluminium oxide pillar, with petrol ether/ethyl acetate (4: 1) drip washing, second flow point is a product; removing desolvates obtains yellow solid 0.30g, and productive rate is 40%.FT-IR(KBr?disc，cm -1)：3045，2994，1643，1584，1552，1489，1462，1393，1363，1320，1276，1221，1115，1078，1023，886，853，818，776，745，659。 1H?NMR(300MHz，CDCl 3)：δ9.24(d，J＝4.1Hz，1H)；8.70(dd，J＝8.4Hz，1H)；8.36(dd，J＝8.4Hz，1H)；8.29(d，J＝7.8Hz，1H)；7.87(s，2H)；7.68(d，J＝4.5Hz，1H)；7.65(d，J＝9.0Hz，1H)；7.34(t，J＝7.5Hz，1H)；7.01(t，J＝7.5Hz，1H)；6.86(d，J＝7.8Hz，1H)；2.67(s，3H，CH 3)。Elementary analysis (C 20H 14BrN 3) theoretical value (%): C63.84, H3.75, N11.17; Experiment value (%): C63.84, H3.76, N11.09.
2. the preparation of catalyst 34: iron (II) (34) is closed in chlorination [2-acetyl group-1,10-phenanthroline (the 2-bromaniline contracts)]: with 5mlFeCl 24H 2O (48.0mg; 0.24mmol) ethanol solution be added drop-wise to 5ml2-acetyl group-1; 10-phenanthroline (the 2-bromaniline contracts) part (75.3mg; 0.2mmol) ethanol solution in; stirring at room 9 hours; separate out precipitation, filter with ether washing back drying and obtain the darkviolet powder solid, productive rate is 98%.FT-IR(KBr?disc，cm -1)：3468，3059，2910，1612，1580，1514，1464，1426，1406，1373，1287，1223，1149，1027，862，834，789，762，739，657。Elementary analysis (C 20H 14BrCl 2FeN 3): C47.76, H2.81, N8.35; Experiment value (%): C47.45, H2.98, N8.27.
3. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of continuous drying 6hrs 2Gas displacement 3 times.Add 2.5mg (5 μ mol) catalyst 34 and then vacuumize and with ethene displacement 3 times.Toluene with syringe injection 30ml adds 1.7ml MAO (MAO) (toluene solution of 1.46mol/l) again, makes Al/Fe=500.Under 20 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the watery hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 1.86 * 10 4G mol -1(Fe) h -1, oligomer content is respectively: C 493%, C 67%.Remaining mixture does not obtain polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 77
1. the preparation of catalyst 34 is with embodiment 76.
2. (1MPa) ethylene oligomerization pressurizes: the toluene solution of toluene and 1.4ml MAO (MAO) (1.46mol/lin toluene) and 6ml catalyst 34 (2.0 μ mol) is joined in the stainless steel autoclave of 250-ml, making cumulative volume is 100ml, Al/Fe=1000.When polymerization temperature reaches 40 ℃, in reactor, charge into ethene, keep the ethylene pressure of 1MPa, stirring reaction 1h.With syringe take out spiece with in 5% the watery hydrochloric acid with laggard promoting the circulation of qi chromatogram (GC) analysis mutually: the oligomerisation activity is 2.61 * 10 7G mol -1(Fe) h -1, oligomer content is respectively: C 438.2%, C 643.5%, C 84.3%, C 107.3%, C 123.4%, C 141.7%, C 16-C 241.7%.Remaining mixture obtains traces of polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 78
1. the preparation of part: 2-acetyl group-1; 10-phenanthroline (2-bromo-4-methylaniline contracts): 2-acetyl group-1; 10-phenanthroline (0.4445g; 2mmol) with 2-bromo-4-methylaniline (0.4651g; 2.5mmol) add the 40mg p-methyl benzenesulfonic acid and make catalyst and add the 2g molecular sieve to make dehydrating agent; 30ml reflux in toluene 1 day; remove solvent toluene after the filtration; residue supports with the carrene dissolving; parlkaline aluminium oxide pillar, with petrol ether/ethyl acetate (4: 1) drip washing, second flow point is a product; removing desolvates obtains yellow solid, and productive rate is 30%.FT-IR(KBr?disc，cm -1)：3204，2917，1641，1556，1506，1361，1313，1271，1117，853，818，739，657。 1H?NMR(300MHz，CDCl 3)：δ9.26(s，1H)；8.70(d，J＝8.4Hz，1H)；8.36(d，J＝8.4Hz，1H)；8.30(d，J＝7.8Hz，1H)；7.87(s，2H)；7.68(m，1H)；7.49(s，1H)；7.15(d，J＝7.5Hz，1H)；6.76(t，J＝7.8Hz，1H)；2.68(s，3H，CH3)，2.36(s，3H，PhCH 3)。Elementary analysis (C 21H 16BrN 3) theoretical value (%): C64.63, H4.13, N10.77; Experiment value (%): C64.64, H4.22, N10.48.
2. the preparation of catalyst 35: iron (II) (35) is closed in chlorination [2-acetyl group-1,10-phenanthroline (2-bromo-4-methylaniline contracts)]: with 5mlFeCl 24H 2O (48.0mg; 0.24mmol) ethanol solution be added drop-wise to 5ml2-acetyl group-1; 10-phenanthroline (2-bromo-4-methylaniline contracts) part (78.1mg; 0.2mmol) ethanol solution in; stirring at room 9 hours; separate out precipitation, filter with ether washing back drying and obtain blackish green powder solid, productive rate is 50%.FT-IR(KBr?disc，cm -1)：3436，3016，2922，1612，1579，1514，1487，1445，1406，1286，1228，1195，1145，1089，858，790，756，742，658。Elementary analysis (C 21H 16BrCl 2FeN 3): C48.78, H3.12, N8.13; Experiment value (%): C48.36, H3.48, N8.06.
3. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of continuous drying 6hrs 2Gas displacement 3 times.Add 2.6mg (5 μ mol) catalyst 35 and then vacuumize and with ethene displacement 3 times.Toluene with syringe injection 30ml adds 1.7ml MAO (MAO) (toluene solution of 1.46mol/l) again, makes Al/Fe=500.Under 20 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the watery hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 3.95 * 10 4G mol -1(Fe) h -1, oligomer content is respectively: C 4100%.Remaining mixture does not obtain polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 79
1. the preparation of catalyst 35 is with embodiment 78.
2. (1MPa) ethylene oligomerization pressurizes: the toluene solution of toluene and 1.4ml MAO (MAO) (1.46mol/lin toluene) and 6ml catalyst 35 (2.0 μ mol) is joined in the stainless steel autoclave of 250-ml, making cumulative volume is 100ml, Al/Fe=1000.When polymerization temperature reaches 40 ℃, in reactor, charge into ethene, keep the ethylene pressure of 1MPa, stirring reaction 1h.With syringe take out spiece with in 5% the watery hydrochloric acid with laggard promoting the circulation of qi chromatogram (GC) analysis mutually: the oligomerisation activity is 2.86 * 10 7G mol -1(Fe) h -1, oligomer content is respectively: C 420.7%, C 632.3%, C 819.4%, C 1012.1%, C 127.4%, C 144.4%, C 16-C 183.7%.Remaining mixture obtains traces of polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 80
1. the preparation of part: 2-acetyl group-1; 10-phenanthroline (2-bromo-4-fluoroaniline contracts): 2-acetyl group-1; 10-phenanthroline (0.4445g; 2mmol) with 2-bromo-4-fluoroaniline (0.475g; 2.5mmol) add the 40mg p-methyl benzenesulfonic acid and make catalyst and add the 2g molecular sieve to make dehydrating agent; 30ml reflux in toluene 1 day; remove solvent toluene after the filtration; residue supports with the carrene dissolving; parlkaline aluminium oxide pillar, with petrol ether/ethyl acetate (4: 1) drip washing, second flow point is a product; removing desolvates obtains yellow solid 0.308g, and productive rate is 39%.FT-IR(KBr?disc，cm -1)：3045，1641，1589，1554，1479，1396，1366，1321，1253，1234，1193，1118，1078，854，825，763，740，654。 1HNMR(300MHz，CDCl 3)：δ9.25(dd，J＝4.2Hz，1H)；8.63(d，J＝8.4Hz，1H)；8.36(d，J＝8.1Hz，1H)；8.29(dd，J＝7.5Hz，1H)；7.88(s，2H)；7.69(q，J＝4.5Hz，1H)；7.34(t，J＝7.5Hz，2H)；6.86(t，J＝8.7Hz，1H)；2.72(s，3H，CH 3)。Elementary analysis (C 20H 13BrFN 3) theoretical value (%): C60.93, H3.32, N10.66; Experiment value (%): C61.08, H3.41, N10.26.
2. the preparation of catalyst 36: iron (II) (36) is closed in chlorination [2-acetyl group-1,10-phenanthroline (2-bromo-4-fluoroaniline contracts)]: with 5mlFeCl 24H 2O (48.0mg; 0.24mmol) ethanol solution be added drop-wise to 5ml2-acetyl group-1; 10-phenanthroline (2-bromo-4-fluoroaniline contracts) part (78.9mg; 0.2mmol) ethanol solution in; stirring at room 12 hours; separate out precipitation, filter with ether washing back drying and obtain blackish green powder solid, productive rate is 84%.FT-IR(KBr?disc，cm -1)：3421，3051，2970，2909，1605，1576，1511，1481，1442，1399，1341，1305，1205，852，813，739，658。Elementary analysis (C 20H 13BrCl 2FFeN 3): C46.11, H2.52, N8.07; Experiment value (%): C45.73, H2.86, N7.91.
3. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of continuous drying 6hrs 2Gas displacement 3 times.Add 2.6mg (5 μ mol) catalyst 36 and then vacuumize and with ethene displacement 3 times.Toluene with syringe injection 30ml adds 1.7ml MAO (MAO) (toluene solution of 1.46mol/l) again, makes Al/Fe=500.Under 20 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the watery hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 3.36 * 10 4G mol -1(Fe) h -1, oligomer content is respectively: C 454%, C 646%.Remaining mixture does not obtain polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 81
1. the preparation of catalyst 36 is with embodiment 80.
2. (1MPa) ethylene oligomerization pressurizes: the toluene solution of toluene and 1.4ml MAO (MAO) (1.46mol/lin toluene) and 6ml catalyst 36 (2.0 μ mol) is joined in the stainless steel autoclave of 250-ml, making cumulative volume is 100ml, Al/Fe=1000.When polymerization temperature reaches 40 ℃, in reactor, charge into ethene, keep the ethylene pressure of 1MPa, stirring reaction 1h.With syringe take out spiece with in 5% the watery hydrochloric acid with laggard promoting the circulation of qi chromatogram (GC) analysis mutually: the oligomerisation activity is 5.85 * 10 5G mol -1(Fe) h -1, oligomer content is respectively: C 477.6%, C 6-C 1822.4%.Remaining mixture does not obtain polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 82
1. the preparation of part: 2-acetyl group-1; 10-phenanthroline (4-bromo-2-fluoroaniline contracts): 2-acetyl group-1; 10-phenanthroline (0.4445g; 2mmol) with 4-bromo-2-fluoroaniline (0.475g; 2.5mmol) add the 40mg p-methyl benzenesulfonic acid and make catalyst and add the 2g molecular sieve to make dehydrating agent; 30ml reflux in toluene 1 day; remove solvent toluene after the filtration; residue supports with the carrene dissolving; parlkaline aluminium oxide pillar, with petrol ether/ethyl acetate (4: 1) drip washing, second flow point is a product; removing desolvates obtains yellow solid 0.245g, and productive rate is 31%.FT-IR(KBr?disc，cm -1)：3064，1633，1586，1553，1474，1394，1367，1322，1286，1251，1187，1114，1080，1036，860，822，776，714，661。 1H?NMR(300MHz，CDCl 3)：δ9.24(dd，J＝4.2Hz，1H)；8.68(d，J＝8.4Hz，1H)；8.36(d，J＝8.4Hz，1H)；8.25(dd，J＝8.1Hz，1H)；7.87(s，2H)；7.68(q，J＝4.5Hz，1H)；7.41(dd，J＝7.8Hz，1H)；7.09(m，1H)；6.82(dd，J＝8.7Hz，1H)；2.68(s，3H，CH 3)。Elementary analysis (C 20H 13BrFN 3) theoretical value (%): C60.93, H3.32, N10.66; Experiment value (%): C60.53, H3.34, N10.28.
2. the preparation of catalyst 37: iron (II) (37) is closed in chlorination [2-acetyl group-1,10-phenanthroline (4-bromo-2-fluoroaniline contracts)]: with 5mlFeCl 24H 2O (48.0mg; 0.24mmol) ethanol solution be added drop-wise to 5ml2-acetyl group-1; 10-phenanthroline (4-bromo-2-fluoroaniline contracts) part (78.9mg; 0.2mmol) ethanol solution in; stirring at room 9 hours; separate out precipitation, filter with ether washing back drying and obtain blackish green powder solid, productive rate is 74%.FT-IR(KBr?disc，cm -1)：3430，3072，2915，1595，1510，1476，1441，1397，1337，1305，1256，1196，1038，848，809，654。Elementary analysis (C 20H 13BrCl 2FFeN 3): C46.11, H2.52, N8.07; Experiment value (%): C45.69, H2.94, N7.93.
3. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of continuous drying 6hrs 2Gas displacement 3 times.Add 2.6mg (5 μ mol) catalyst 37 and then vacuumize and with ethene displacement 3 times.Toluene with syringe injection 30ml adds 1.7ml MAO (MAO) (toluene solution of 1.46mol/l) again, makes Al/Fe=500.Under 20 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the watery hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 4.35 * 10 4G mol -1(Fe) h -1, oligomer content is respectively: C 475%, C 625%.Remaining mixture does not obtain polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 83
1. the preparation of catalyst 37 is with embodiment 82.
2. pressurization (1MPa) ethylene oligomerization: the 250-ml stainless steel still that mechanical agitation and thermocouple will be housed vacuumizes and with nitrogen replacement 3 times, replaces 2 times with ethene again.Behind the cool to room temperature, add the toluene solution of toluene and 1.7ml MAO (MAO) (1.46mol/l in toluene) and 10ml catalyst 37 (5.0 μ mol), the cumulative volume of toluene is 150ml, Al/Fe=500.The pressure of ethene is increased to 10 atmospheric pressure, at 40 ℃ of following vigorous stirring 1h.With syringe take out spiece with in 5% the watery hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 8.11 * 10 4G mol -1(Fe) h -1, oligomer content is respectively: C 479.3%, C 6-C 1620.7%.Remaining mixture does not obtain polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 84
1. the preparation of part: 2-acetyl group-1; the 10-phenanthroline (contracts 2; the 4-dibromo aniline): 2-acetyl group-1; 10-phenanthroline (0.4445g; 2mmol) with 2; 4-dibromo aniline (0.6273g; 2.5mmol) add the 40mg p-methyl benzenesulfonic acid and make catalyst and add the 2g molecular sieve to make dehydrating agent, 30ml reflux in toluene 1 day, remove solvent toluene after the filtration; residue supports with the carrene dissolving; parlkaline aluminium oxide pillar, with petrol ether/ethyl acetate (4: 1) drip washing, second flow point is a product; removing desolvates obtains yellow solid 0.41g, and productive rate is 45%.FT-IR(KBr?disc，cm -1)：3419，3054，1636，1587，1551，1488，1458，1391，1365，1319，1284，1253，1219，1116，1077，1042，859，831，742，686。 1HNMR(300MHz，CDCl 3)：δ9.25(dd，J＝4.2Hz，1H)；8.67(d，J＝8.1Hz，1H)；8.37(d，J＝8.4Hz，1H)；8.31(dd，J＝8.1Hz，1H)；7.88(s，2H)；7.80(s，1H)；7.68(q，J＝4.2Hz，1H)；7.47(dd，J＝8.4Hz，1H)；6.74(d，J＝8.4Hz，1H)；2.68(s，3H，CH 3)。Elementary analysis (C 20H 13Br 2N 3) theoretical value (%): C52.78, H2.88, N9.23; Experiment value (%): C52.71, H2.97, N9.25.
2. the preparation of catalyst 38: iron (II) (38) is closed in chlorination [2-acetyl group-1,10-phenanthroline (contracting 2, the 4-dibromo aniline)]: with 5mlFeCl 24H 2O (48.0mg; 0.24mmol) ethanol solution be added drop-wise to 5ml2-acetyl group-1; the 10-phenanthroline (contracts 2; the 4-dibromo aniline) part (91.0mg; 0.2mmol) ethanol solution in, stirring at room 9 hours is separated out precipitation; filtration obtains blackish green powder solid with ether washing back drying, and productive rate is 62%.FT-IR(KBr?disc，cm -1)：3410，3067，2913，1605，1573，1510，1458，1396，1371，1338，1302，1218，1148，1083，1044，996，850，759，655。Elementary analysis (C 20H 13Br 2Cl 2FeN 3): C41.28, H2.25, N7.22; Experiment value (%): C40.82, H2.58, N7.03.
3. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of continuous drying 6hrs 2Gas displacement 3 times.Add 2.9mg (5 μ mol) catalyst 38 and then vacuumize and with ethene displacement 3 times.Toluene with syringe injection 30ml adds 1.7ml MAO (MAO) (toluene solution of 1.46mol/l) again, makes Al/Fe=500.Under 20 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the watery hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 1.55 * 10 4G mol -1(Fe) h -1, oligomer content is respectively: C 468%, C 632%.Remaining mixture does not obtain polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 85
1. the preparation of catalyst 38 is with embodiment 84.
2. (1MPa) ethylene oligomerization pressurizes: the toluene solution of toluene and 1.4ml MAO (MAO) (1.46mol/lin toluene) and 6ml catalyst 38 (2.0 μ mol) is joined in the stainless steel autoclave of 250-ml, making cumulative volume is 100ml, Al/Fe=1000.When polymerization temperature reaches 40 ℃, in reactor, charge into ethene, keep the ethylene pressure of 1MPa, stirring reaction 1h.With syringe take out spiece with in 5% the watery hydrochloric acid with laggard promoting the circulation of qi chromatogram (GC) analysis mutually: the oligomerisation activity is 2.23 * 10 7G mol -1(Fe) h -1, oligomer content is respectively: C 442.8%, C 639.4%, C 108.8%, C 124.7%, C 142.4%, C 16-C 181.8%.Remaining mixture obtains the white wax shaped polymer with the ethanolic solution neutralization of 5% hcl acidifying, and polymerization activity is 1.24 * 10 5G mol -1(Fe) h -1
Embodiment 86
1. the preparation of part: 2-acetyl group-1; the 10-phenanthroline (contracts 2; the 6-dibromo aniline): 2-acetyl group-1; 10-phenanthroline (0.4445g; 2mmol) with 2; (0.6273g 2.5mmol) adds the 40mg p-methyl benzenesulfonic acid and makes catalyst the 6-dibromo aniline, reacts 1 day down in 140-150 ℃ in the 5ml ethyl orthosilicate; and tell the ethanol of generation with oil water separator; ethyl orthosilicate is removed in decompression, and residue supports parlkaline aluminium oxide pillar with the carrene dissolving; with petrol ether/ethyl acetate (4: 1) drip washing; second flow point is a product, and removing desolvates obtains yellow solid 0.2g, and productive rate is 22%.Fusing point is 170-171 ℃.FT-IR(KBrdisc，cm -1)：3011，2966，1639，1625，1587，1550，1503，1489，1448，1426，1391，1365，1323，1284，1263，1220，1194，1137，1118，1080，889，855，818，775，759，739，725，658。 1H?NMR(300MHz，CDCl 3)：δ9.26(d，J＝4.2Hz，1H)；8.81(d，J＝8.4Hz，1H)；8.39(d，J＝8.4Hz，1H)；8.31(d，J＝8.1Hz，1H)；7.89(s，2H)；7.69(d，J＝8.1Hz，1H)；7.60(d，J＝8.1Hz，2H)；6.88(t，J＝8.1Hz，1H)；2.67(s，3H，CH 3)。Elementary analysis (C 20H 13Br 2N 3) theoretical value (%): C52.78, H2.88, N9.23; Experiment value (%): C52.78, H2.92, N9.16.
2. the preparation of catalyst 39: iron (II) (39) is closed in chlorination [2-acetyl group-1,10-phenanthroline (contracting 2, the 6-dibromo aniline)]: with 5mlFeCl 24H 2O (48.0mg; 0.24mmol) ethanol solution be added drop-wise to 5ml2-acetyl group-1; the 10-phenanthroline (contracts 2; the 6-dibromo aniline) part (91.0mg; 0.2mmol) ethanol solution in, stirring at room 9 hours is separated out precipitation; filtration obtains the purplish grey powder solid with ether washing back drying, and productive rate is 90%.FT-IR(KBr?disc，cm -1)：3462，3059，2969，2909，1614，1578，1551，1515，1493，1432，1406，1376，1331，1286，1266，1231，1204，1150，863，833，784，732，658。Elementary analysis (C 20H 13Br 2Cl 2FeN 3): C41.28, H2.25, N7.22; Experiment value (%): C41.07, H2.46, N7.15.
3. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of continuous drying 6hrs 2Gas displacement 3 times.Add 2.9mg (5 μ mol) catalyst 39 and then vacuumize and with ethene displacement 3 times.Toluene with syringe injection 30ml adds 1.7ml MAO (MAO) (toluene solution of 1.46mol/l) again, makes Al/Fe=500.Under 20 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the watery hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 4.2 * 10 4G mol -1(Fe) h -1, oligomer content is respectively: C 4100%.Remaining mixture does not obtain polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 87
1. the preparation of catalyst 39 is with embodiment 86.
2. (1MPa) ethylene oligomerization pressurizes: the toluene solution of 1000ml toluene and 3.5ml MAO (MAO) (1.46mol/l in toluene) and 10ml catalyst 39 (10 μ mol) is joined in the 2000-ml stainless steel autoclave.Mechanical agitation begins, and keeps 350 rev/mins, when polymerization temperature reaches 40 ℃, charges into ethene in reactor, and polymerisation begins.Under 40 ℃, keep the ethylene pressure of 1MPa, stirring reaction 1h.With syringe take out spiece with in 5% the watery hydrochloric acid with laggard promoting the circulation of qi chromatogram (GC) analysis mutually: the oligomerisation activity is 1.86 * 10 7G mol -1(Fe) h -1, oligomer content is respectively: C 434.1%, C 629.0%, C 812.9%, C 109.0%, C 125.4%, C 14-C 269.7%.Remaining mixture obtains the white wax shaped polymer with the ethanolic solution neutralization of 5% hcl acidifying, and polymerization activity is 2.26 * 10 5G mol -1(Fe) h -1
Embodiment 88
1. the preparation of catalyst 39 is with embodiment 86.
2. (1MPa) ethylene oligomerization pressurizes: the toluene solution of toluene and 1.4ml MAO (MAO) (1.46mol/lin toluene) and 6ml catalyst 38 (2.0 μ mol) is joined in the stainless steel autoclave of 250-ml, making cumulative volume is 100ml, Al/Fe=1000.When polymerization temperature reaches 40 ℃, in reactor, charge into ethene, keep the ethylene pressure of 1MPa, stirring reaction 1h.With syringe take out spiece with in 5% the watery hydrochloric acid with laggard promoting the circulation of qi chromatogram (GC) analysis mutually: the oligomerisation activity is 4.06 * 10 7G mol -1(Fe) h -1, oligomer content is respectively: C 412.7%, C 623.7%, C 812.9%, C 1014.7%, C 1210.6%, C 147.6%, C 16-C 3217.8%.Remaining mixture obtains the white wax shaped polymer with the ethanolic solution neutralization of 5% hcl acidifying, and polymerization activity is 6.55 * 10 6G mol -1(Fe) h -1
Embodiment 89
1. the preparation of part: 2-acetyl group-1; the 10-phenanthroline (contracts 2; 6-two bromo-4-methylanilines): 2-acetyl group-1; 10-phenanthroline (0.4445g; 2mmol) with 2; (0.6775g 2.5mmol) adds the 40mg p-methyl benzenesulfonic acid and makes catalyst 6-two bromo-4-methylanilines, reacts 1 day down in 140-150 ℃ in the 5ml ethyl orthosilicate; and tell the ethanol of generation with oil water separator; ethyl orthosilicate is removed in decompression, and residue supports parlkaline aluminium oxide pillar with the carrene dissolving; with petrol ether/ethyl acetate (4: 1) drip washing; second flow point is a product, and removing desolvates obtains yellow solid 0.351g, and productive rate is 37%.Fusing point is 213-214 ℃.FT-IR(KBr?disc，cm -1)：2966，2921，1628，1585，1551，1486，1449，1388，1363，1319，1284，1229，1195，1116，1079，853，775，740，658。 1H?NMR(300MHz，CDCl 3)：δ9.26(dd，J＝4.2Hz，1H)；8.80(d，J＝8.4Hz，1H)；8.38(d，J＝8.4Hz，1H)；8.31(dd，J＝7.5Hz，1H)；7.89(s，2H)；7.68(d，J＝8.1Hz，1H)；7.43(s，2H)；2.66(s，3H，CH 3)；2.18(s，3H，PhCH 3)。Elementary analysis (C 21H 15Br 2N 3) theoretical value (%): C53.76, H3.22, N8.96; Experiment value (%): C53.95, H3.49, N8.80.
2. the preparation of catalyst 40: iron (II) (40) is closed in chlorination [2-acetyl group-1,10-phenanthroline (contracting 2,6-two bromo-4-methylanilines)]: with 5mlFeCl 24H 2O (48.0mg; 0.24mmol) ethanol solution be added drop-wise to 5ml2-acetyl group-1; the 10-phenanthroline (contracts 2; 6-two bromo-4-methylanilines) part (93.8mg; 0.2mmol) ethanol solution in, stirring at room 9 hours is separated out precipitation; filtration obtains the purplish grey powder solid with ether washing back drying, and productive rate is 77%.FT-IR(KBr?disc，cm -1)：3469，3057，2911，1611，1579，1537，1515，1492，1449，1407，1376，1333，1287，1235，1149，860，744，658。Elementary analysis (C 21H 15Br 2Cl 2FeN 3): C42.33, H2.54, N7.05; Experiment value (%): C41.76, H2.68, N6.77.
3. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of continuous drying 6hrs 2Gas displacement 3 times.Add 3.0mg (5 μ mol) catalyst 40 and then vacuumize and with ethene displacement 3 times.Toluene with syringe injection 30ml adds 1.7ml MAO (MAO) (toluene solution of 1.46mol/l) again, makes Al/Fe=500.Under 20 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the watery hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 4.05 * 10 4G mol -1(Fe) h -1, oligomer content is respectively: C 4100%.Remaining mixture does not obtain polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 90
1. the preparation of catalyst 40 is with embodiment 89.
2. (1MPa) ethylene oligomerization pressurizes: the toluene solution of toluene and 1.4ml MAO (MAO) (1.46mol/lin toluene) and 6ml catalyst 40 (2.0 μ mol) is joined in the stainless steel autoclave of 250-ml, making cumulative volume is 100ml, Al/Fe=1000.When polymerization temperature reaches 40 ℃, in reactor, charge into ethene, keep the ethylene pressure of 1MPa, stirring reaction 1h.With syringe take out spiece with in 5% the watery hydrochloric acid with laggard promoting the circulation of qi chromatogram (GC) analysis mutually: the oligomerisation activity is 3.89 * 10 7G mol -1(Fe) h -1, oligomer content is respectively: C 48.8%, C 620.1%, C 1015.8%, C 1213.2%, C 1411.3%, C 16-C 2830.8%.Remaining mixture obtains the white wax shaped polymer with the ethanolic solution neutralization of 5% hcl acidifying, and polymerization activity is 2.41 * 10 7G mol -1(Fe) h -1
Embodiment 91
1. the preparation of part: 2-acetyl group-1; the 10-phenanthroline (contracts 2; 6-two bromo-4-chloroanilines): 2-acetyl group-1; 10-phenanthroline (0.4445g; 2mmol) with 2; (0.7135g 2.5mmol) adds the 40mg p-methyl benzenesulfonic acid and makes catalyst 6-two bromo-4-chloroanilines, reacts 1 day down in 140-150 ℃ in the 5ml ethyl orthosilicate; and tell the ethanol of generation with oil water separator; ethyl orthosilicate is removed in decompression, and residue supports parlkaline aluminium oxide pillar with the carrene dissolving; with petrol ether/ethyl acetate (4: 1) drip washing; second flow point is a product, and removing desolvates obtains yellow solid 0.217g, and productive rate is 22%.Fusing point is 214-215 ℃.FT-IR(KBr?disc，cm -1)：3070，3045，2987，1656，1619，1587，1552，1531，1491，1450，1439，1425，1390，1365，1322，1285，1229，1190，1137，1117，1081，858，821，773，742，699，659。 1H?NMR(300MHz，CDCl 3)：δ9.25(d，J＝3.3Hz，1H)；8.77(d，J＝8.4Hz，1H)；8.38(d，J＝8.4Hz，1H)；8.31(d，J＝7.8Hz，1H)；7.89(s，2H)；7.69(dd，J＝7.8Hz，1H)；7.62(s，2H)；2.66(s，3H，CH 3)。Elementary analysis (C 20H 12Br 2ClN 3) theoretical value (%): C49.06, H2.47, N8.58; Experiment value (%): C49.17, H2.49, N8.43.
2. the preparation of catalyst 41: iron (II) (41) is closed in chlorination [2-acetyl group-1,10-phenanthroline (contracting 2,6-two bromo-4-chloroanilines)]: with 5mlFeCl 24H 2O (48.0mg; 0.24mmol) ethanol solution be added drop-wise to 5ml2-acetyl group-1; the 10-phenanthroline (contracts 2; 6-two bromo-4-chloroanilines) part (98.2mg; 0.2mmol) ethanol solution in, stirring at room 9 hours is separated out precipitation; filtration obtains the purplish grey powder solid with ether washing back drying, and productive rate is 95%.FT-IR(KBr?disc，cm -1)：3449，3050，2910，1613，1572，1539，1512，1491，1433，1407，1372，1288，1263，1232，1155，1138，875，858，842，792，747，732，699，658。Elementary analysis (C 20H 12Br 2Cl 3FeN 3): C38.97, H1.96, N6.82; Experiment value (%): C39.34, H2.60, N6.14.
3. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of continuous drying 6hrs 2Gas displacement 3 times.Add 3.1mg (5 μ mol) catalyst 41 and then vacuumize and with ethene displacement 3 times.Toluene with syringe injection 30ml adds 1.7ml MAO (MAO) (toluene solution of 1.46mol/l) again, makes Al/Fe=500.Under 20 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the watery hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 2.76 * 10 4G mol -1(Fe) h -1, oligomer content is respectively: C 479%, C 68%, C 8-C 1813%.Remaining mixture obtains traces of polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 92
1. the preparation of catalyst 41 is with embodiment 91.
2. (1MPa) ethylene oligomerization pressurizes: the toluene solution of toluene and 1.4ml MAO (MAO) (1.46mol/lin toluene) and 6ml catalyst 41 (2.0 μ mol) is joined in the stainless steel autoclave of 250-ml, making cumulative volume is 100ml, Al/Fe=1000.When polymerization temperature reaches 40 ℃, in reactor, charge into ethene, keep the ethylene pressure of 1MPa, stirring reaction 1h.With syringe take out spiece with in 5% the watery hydrochloric acid with laggard promoting the circulation of qi chromatogram (GC) analysis mutually: the oligomerisation activity is 1.96 * 10 7G mol -1(Fe) h -1, oligomer content is respectively: C 422.3%, C 631.9%, C 814.0%, C 1013.1%, C 127.1%, C 144.1%, C 16-C 267.5%.Remaining mixture obtains the white wax shaped polymer with the ethanolic solution neutralization of 5% hcl acidifying, and polymerization activity is 1.46 * 10 6G mol -1(Fe) h -1
Embodiment 93
1. the preparation of part: 2-acetyl group-1; the 10-phenanthroline (contracts 2; 4; the 6-tribromaniline): 2-acetyl group-1, (0.4445g is 2mmol) with 2 for the 10-phenanthroline; 4; (0.8150g 2.4mmol) adds the 40mg p-methyl benzenesulfonic acid and makes catalyst the 6-tribromaniline, reacts 1 day down in 140-150 ℃ in the 5ml ethyl orthosilicate; and tell the ethanol of generation with oil water separator; ethyl orthosilicate is removed in decompression, and residue supports parlkaline aluminium oxide pillar with the carrene dissolving; with petrol ether/ethyl acetate (4: 1) drip washing; second flow point is a product, and removing desolvates obtains yellow solid 0.23g, and productive rate is 22%.Fusing point is 206-207 ℃.FT-IR(KBr?disc，cm -1)：3066，1644，1586，1551，1529，1489，1450，1421，1393，1363，1323，1286，1225，1192，1136，1114，1079，887，854，829，775，741，681，658。 1H?NMR(300MHz，CDCl 3)：δ9.25(d，J＝3.3Hz，1H)；8.77(d，J＝8.4Hz，1H)；8.38(d，J＝8.4Hz，1H)；8.30(d，J＝7.8Hz，1H)；7.88(s，2H)；7.75(s，2H)；7.68(dd，J＝7.8Hz，1H)；2.66(s，3H，CH 3)。Elementary analysis (C 20H 12Br 3N 3) theoretical value (%): C44.98, H2.26, N7.87; Experiment value (%): C45.16, H2.32, N7.94.
2. the preparation of catalyst 42: iron (II) (42) is closed in chlorination [2-acetyl group-1,10-phenanthroline (contracting 2,4, the 6-tribromaniline)]: with 5mlFeCl 24H 2O (48.0mg; 0.24mmol) ethanol solution be added drop-wise to 5ml2-acetyl group-1; the 10-phenanthroline (contracts 2; 4, the 6-tribromaniline) (106.8mg is in ethanol solution 0.2mmol) for part; stirring at room 9 hours; separate out precipitation, filter with ether washing back drying and obtain the purplish grey powder solid, productive rate is 75%.FT-IR(KBr?disc，cm -1)：3450，3050，2910，1613，1581，1562，1538，1512，1491，1430，1408，1369，1288，1155，1138，876，856，789，746，732，692，658。Elementary analysis (C 20H 12Br 3Cl 2FeN 3): C36.35, H1.83, N6.36; Experiment value (%): C35.47, H2.11, N6.31.
3. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of continuous drying 6hrs 2Gas displacement 3 times.Add 3.3mg (5 μ mol) catalyst 42 and then vacuumize and with ethene displacement 3 times.Toluene with syringe injection 30ml adds 1.7ml MAO (MAO) (toluene solution of 1.46mol/l) again, makes Al/Fe=500.Under 20 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the watery hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 1.79 * 10 4G mol -1(Fe) h -1, oligomer content is respectively: C 494%, C 66%.Remaining mixture does not obtain polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 94
1. the preparation of catalyst 42 is with embodiment 93.
2. (1MPa) ethylene oligomerization pressurizes: the toluene solution of 1000ml toluene and 3.5ml MAO (MAO) (1.46mol/l in toluene) and 10ml catalyst 42 (10 μ mol) is joined in the 2000-ml stainless steel autoclave.Mechanical agitation begins, and keeps 350 rev/mins, when polymerization temperature reaches 40 ℃, charges into ethene in reactor, and polymerisation begins.Under 40 ℃, keep the ethylene pressure of 1MPa, stirring reaction 1h.With syringe take out spiece with in 5% the watery hydrochloric acid with laggard promoting the circulation of qi chromatogram (GC) analysis mutually: the oligomerisation activity is 7.86 * 10 6G mol -1(Fe) h -1, oligomer content is respectively: C 426.9%, C 633.5%, C 816.0%, C 108.2%, C 125.4%, C 14-C 249.1%.Remaining mixture obtains the white wax shaped polymer with the ethanolic solution neutralization of 5% hcl acidifying, and polymerization activity is 1.15 * 10 5G mol -1(Fe) h -1
Embodiment 95
1. the preparation of catalyst 42 is with embodiment 94.
2. (1MPa) ethylene oligomerization pressurizes: the toluene solution of toluene and 1.4ml MAO (MAO) (1.46mol/lin toluene) and 6ml catalyst 42 (2.0 μ mol) is joined in the stainless steel autoclave of 250-ml, making cumulative volume is 100ml, Al/Fe=1000.When polymerization temperature reaches 40 ℃, in reactor, charge into ethene, keep the ethylene pressure of 1MPa, stirring reaction 1h.With syringe take out spiece with in 5% the watery hydrochloric acid with laggard promoting the circulation of qi chromatogram (GC) analysis mutually: the oligomerisation activity is 2.22 * 10 7G mol -1(Fe) h -1, oligomer content is respectively: C 415.3%, C 628.3%, C 1015.5%, C 1211.6%, C 148.7%, C 16-C 3020.6%.Remaining mixture obtains the white wax shaped polymer with the ethanolic solution neutralization of 5% hcl acidifying, and polymerization activity is 6.41 * 10 6G mol -1(Fe) h -1
Embodiment 96
1. the preparation of part: 2-acetyl group-1; 10-phenanthroline (2-bromo-6-chloro-4-fluoroaniline contracts): 2-acetyl group-1; 10-phenanthroline (0.4445g; 2mmol) with 2-bromo-6-chloro-4-fluoroaniline (0.5215g; 2.3mmol) add the 40mg p-methyl benzenesulfonic acid and make catalyst; in the 5ml ethyl orthosilicate, reacted 1 day down in 140-150 ℃; and tell the ethanol of generation with oil water separator; ethyl orthosilicate is removed in decompression, and residue supports parlkaline aluminium oxide pillar with the carrene dissolving; with petrol ether/ethyl acetate (4: 1) drip washing; second flow point is a product, and removing desolvates obtains yellow solid 0.332g, and productive rate is 39%.Fusing point is 197-198 ℃.FT-IR(KBr?disc，cm -1)：3076，2986，1657，1586，1562，1491，1440，1389，1362，1319，1284，1252，1195，1137，1115，928，858772，658。 1H?NMR(300MHz，CDCl 3)：δ9.25(d，J＝3.3Hz，1H)；8.76(d，J＝8.4Hz，1H)；8.37(d，J＝8.4Hz，1H)；8.30(d，J＝7.8Hz，1H)；7.88(s，2H)；7.68(dd，J＝7.8Hz，1H)；7.35(d，J＝6.9Hz，1H)；7.23(d，J＝8.1Hz，1H)；2.66(s，3H，CH 3)。Elementary analysis (C 20H 12BrClFN 3) theoretical value (%): C56.04, H2.82, N9.80; Experiment value (%): C55.66, H2.84, N9.58.
2. the preparation of catalyst 43: iron (II) (43) is closed in chlorination [2-acetyl group-1,10-phenanthroline (2-bromo-6-chloro-4-fluoroaniline contracts)]: with 5mlFeCl 24H 2O (48.0mg; 0.24mmol) ethanol solution be added drop-wise to 5ml2-acetyl group-1; 10-phenanthroline (2-bromo-6-chloro-4-fluoroaniline contracts) part (86.1mg; 0.2mmol) ethanol solution in; stirring at room 9 hours; separate out precipitation, filter with ether washing back drying and obtain the purplish grey powder solid, productive rate is 99%.FT-IR(KBr?disc，cm -1)：3482，3059，2969，2908，1612，1589，1470，1515，1493，1448，1407，1286，1200，936，861，779，734，657。Elementary analysis (C 20H 12BrCl 3FFeN 3): C43.25, H2.18, N7.57; Experiment value (%): C43.01, H2.36, N7.39.
3. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of continuous drying 6hrs 2Gas displacement 3 times.Add 2.8mg (5 μ mol) catalyst 43 and then vacuumize and with ethene displacement 3 times.Toluene with syringe injection 30ml adds 1.7ml MAO (MAO) (toluene solution of 1.46mol/l) again, makes Al/Fe=500.Under 20 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the watery hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 1.34 * 10 5G mol -1(Fe) h -1, oligomer content is respectively: C 435%, C 618%, C 83%, C 1011%, C 129%, C 148%, C 16-C 24, 16%.Remaining mixture obtains small amount of polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 97
1. the preparation of catalyst 43 is with embodiment 96.
2. (1MPa) ethylene oligomerization pressurizes: the toluene solution of toluene and 1.4ml MAO (MAO) (1.46mol/lin toluene) and 6ml catalyst 43 (2.0 μ mol) is joined in the stainless steel autoclave of 250-ml, making cumulative volume is 100ml, Al/Fe=1000.When polymerization temperature reaches 40 ℃, in reactor, charge into ethene, keep the ethylene pressure of 1MPa, stirring reaction 1h.With syringe take out spiece with in 5% the watery hydrochloric acid with laggard promoting the circulation of qi chromatogram (GC) analysis mutually: the oligomerisation activity is 2.71 * 10 7G mol -1(Fe) h -1, oligomer content is respectively: C 426.7%, C 635.5%, C 817.1%, C 1010.2%, C 125.3%, C 14-C 185.2%.Remaining mixture obtains the white wax shaped polymer with the ethanolic solution neutralization of 5% hcl acidifying, and polymerization activity is 1.55 * 10 5G mol -1(Fe) h -1
Embodiment 98
1. the preparation of part: 2-acetyl group-1; 10-phenanthroline (2-bromo-4-chloro-6-fluoroaniline contracts): 2-acetyl group-1; 10-phenanthroline (0.4445g; 2mmol) with 2-bromo-4-chloro-6-fluoroaniline (0.5719g; 2.5mmol) add the 40mg p-methyl benzenesulfonic acid and make catalyst; in the 5ml ethyl orthosilicate, reacted 1 day down in 140-150 ℃; and tell the ethanol of generation with oil water separator; ethyl orthosilicate is removed in decompression, and residue supports parlkaline aluminium oxide pillar with the carrene dissolving; with petrol ether/ethyl acetate (4: 1) drip washing; second flow point is a product, and removing desolvates obtains yellow solid 0.313g, and productive rate is 43%.Fusing point is 117-118 ℃.FT-IR(KBr?disc，cm -1)：3061，2919，1639，1587，1554，1504，1490，1455，1418，1401，1392，1372，1323，1286，1266，1246，1212，1170，1136，1118，1080，921，887，857，822，775，762，742，710，659，625。 1H?NMR(300MHz，CDCl 3)：δ9.25(d，J＝3.3Hz，1H)；8.71(d，J＝7.5Hz，1H)；8.36(d，J＝7.8Hz，1H)；8.30(d，J＝7.2Hz，1H)；7.87(s，2H)；7.68(s，1H)；7.48(s，1H)；7.18(d，J＝8.1Hz，1H)；2.70(s，3H，CH 3)。Elementary analysis (C 20H 12BrClFN 3) theoretical value (%): C56.04, H2.82, N9.80; Experiment value (%): C55.68, H2.83, N9.71.
2. the preparation of catalyst 44: iron (II) (44) is closed in chlorination [2-acetyl group-1,10-phenanthroline (2-bromo-4-chloro-6-fluoroaniline contracts)]: with 5mlFeCl 24H 2O (48.0mg; 0.24mmol) ethanol solution be added drop-wise to 5ml2-acetyl group-1; 10-phenanthroline (2-bromo-4-chloro-6-fluoroaniline contracts) part (86.1mg; 0.2mmol) ethanol solution in; stirring at room 9 hours; separate out precipitation, filter with ether washing back drying and obtain the purplish grey powder solid, productive rate is 71%.FT-IR(KBr?disc，cm -1)：3459，3060，1612，1562，1513，1454，1405，1287，1216，928，860，791，740，657。Elementary analysis (C 20H 12BrCl 3FFeN 3): C43.25, H2.18, N7.57; Experiment value (%): C42.86, H2.41, N7.48.
3. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of continuous drying 6hrs 2Gas displacement 3 times.Add 2.8mg (5 μ mol) catalyst 44 and then vacuumize and with ethene displacement 3 times.Toluene with syringe injection 30ml adds 1.7ml MAO (MAO) (toluene solution of 1.46mol/l) again, makes Al/Fe=500.Under 20 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the watery hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 5.12 * 10 4G mol -1(Fe) h -1, oligomer content is respectively: C 481%, C 65%, C 18-C 2214%.Remaining mixture does not obtain polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 99
1. the preparation of catalyst 44 is with embodiment 98.
2. (1MPa) ethylene oligomerization pressurizes: the toluene solution of toluene and 1.4ml MAO (MAO) (1.46mol/lin toluene) and 6ml catalyst 44 (2.0 μ mol) is joined in the stainless steel autoclave of 250-ml, making cumulative volume is 100ml, Al/Fe=1000.When polymerization temperature reaches 40 ℃, in reactor, charge into ethene, keep the ethylene pressure of 1MPa, stirring reaction 1h.With syringe take out spiece with in 5% the watery hydrochloric acid with laggard promoting the circulation of qi chromatogram (GC) analysis mutually: the oligomerisation activity is 2.64 * 10 7G mol -1(Fe) h -1, oligomer content is respectively: C 441.3%, C 624.7%, C 823.0%, C 105.9%, C 122.7%, C 14-C 222.5%.Remaining mixture obtains the white wax shaped polymer with the ethanolic solution neutralization of 5% hcl acidifying, and polymerization activity is 1.44 * 10 5G mol -1(Fe) h -1
Embodiment 100
1. the preparation of part: 2-acetyl group-1; (the 10-phenanthroline contracts 2-bromo-4; the 6-difluoroaniline): 2-acetyl group-1; 10-phenanthroline (0.4445g; 2mmol) with 2-bromo-4; (0.520g 2.5mmol) adds the 40mg p-methyl benzenesulfonic acid and makes catalyst the 6-difluoroaniline, reacts 1 day down in 140-150 ℃ in the 5ml ethyl orthosilicate; and tell the ethanol of generation with oil water separator; ethyl orthosilicate is removed in decompression, and residue supports parlkaline aluminium oxide pillar with the carrene dissolving; with petrol ether/ethyl acetate (4: 1) drip washing; second flow point is a product, and removing desolvates obtains yellow solid 0.331g, and productive rate is 40%.FT-IR(KBr?disc，cm -1)：3079，2976，1631，1603，1583，1553，1489，1464，1419，1366，1324，1290，1206，1164，1109，992，851，724，659。 1H?NMR(300MHz，CDCl 3)：δ9.25(d，J＝3.3Hz，1H)；8.71(d，J＝7.5Hz，1H)；8.37(d，J＝7.8Hz，1H)；8.30(d，J＝7.2Hz，1H)；7.88(s，2H)；7.68(s，1H)；7.48(s，1H)；7.18(d，J＝8.1Hz，1H)；2.69(s，3H，CH 3)。Elementary analysis (C 20H 12BrF 2N 3) theoretical value (%): C58.27, H2.93, N10.19; Experiment value (%): C57.92, H3.15, N10.06.
2. the preparation of catalyst 45: iron (II) (45) is closed in chlorination [2-acetyl group-1,10-phenanthroline (the 2-bromo-4 that contracts, 6-difluoroaniline)]: with 5mlFeCl 24H 2O (48.0mg; 0.24mmol) ethanol solution be added drop-wise to 5ml2-acetyl group-1; (the 10-phenanthroline contracts 2-bromo-4; the 6-difluoroaniline) part (82.5mg; 0.2mmol) ethanol solution in, stirring at room 9 hours is separated out precipitation; filtration obtains blackish green powder solid with ether washing back drying, and productive rate is 44%.FT-IR(KBr?disc，cm -1)：3456，2916，1609，1581，1538，1492，1430，1410，1369，1289，1156，876，789，741，658。Elementary analysis (C 20H 12BrCl 2F 2FeN 3): C44.57, H2.24, N7.80; Experiment value (%): C44.21, H2.45, N7.56.
3. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of continuous drying 6hrs 2Gas displacement 3 times.Add 2.7mg (5 μ mol) catalyst 45 and then vacuumize and with ethene displacement 3 times.Toluene with syringe injection 30ml adds 1.7ml MAO (MAO) (toluene solution of 1.46mol/l) again, makes Al/Fe=500.Under 20 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the watery hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 3.06 * 10 4G mol -1(Fe) h -1, oligomer content is respectively: C 4100%.Remaining mixture does not obtain polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 101
1. the preparation of catalyst 45 is with embodiment 100.
2. (1MPa) ethylene oligomerization pressurizes: the toluene solution of toluene and 1.4ml MAO (MAO) (1.46mol/lin toluene) and 6ml catalyst 45 (2.0 μ mol) is joined in the stainless steel autoclave of 250-ml, making cumulative volume is 100ml, Al/Fe=1000.When polymerization temperature reaches 40 ℃, in reactor, charge into ethene, keep the ethylene pressure of 1MPa, stirring reaction 1h.With syringe take out spiece with in 5% the watery hydrochloric acid with laggard promoting the circulation of qi chromatogram (GC) analysis mutually: the oligomerisation activity is 1.03 * 10 6G mol -1(Fe) h -1, oligomer content is respectively: C 447.8%, C 611.9%, C 8-C 2040.3%.Remaining mixture obtains the white wax shaped polymer with the ethanolic solution neutralization of 5% hcl acidifying, and polymerization activity is 1.22 * 10 5G mol -1(Fe) h -1
Embodiment 102
1. the preparation of part: 2-acetyl group-1; 10-phenanthroline (the 3-nitroaniline contracts): 2-acetyl group-1; 10-phenanthroline (0.4445g; 2mmol) with 3-nitroaniline (0.3453g; 2.5mmol) add the 40mg p-methyl benzenesulfonic acid and make catalyst and add the 2g molecular sieve to make dehydrating agent; 30ml reflux in toluene 1 day; remove solvent toluene after the filtration; residue supports with the carrene dissolving; parlkaline aluminium oxide pillar, with petrol ether/ethyl acetate (4: 1) drip washing, second flow point is a product; removing desolvates obtains yellow solid, and productive rate is 15%.FT-IR(KBr?disc，cm -1)：3046，2916，1635，1581，1554，1489，1416，1366，1324，1290，1206，1116，993，851，742，658。 1H?NMR(300MHz，CDCl 3)：δ9.26(s，1H)；8.60(d，J＝8.1Hz，1H)；8.39(d，J＝8.1Hz，1H)；8.32(d，J＝7.8Hz，1H)；8.03(d，J＝7.5Hz，1H)；7.90(s，2H)；7.86(s，1H)；7.71(m，1H)；7.58(t，J＝7.5Hz，1H)；7.21(d，J＝7.5Hz，1H)；2.74(s，3H，CH 3)。Elementary analysis (C 20H 14N 4O 2) theoretical value (%): C70.17, H4.12, N16.37; Experiment value (%): C69.93, H4.32, N16.15.
2. the preparation of catalyst 46: iron (II) (46) is closed in chlorination [2-acetyl group-1,10-phenanthroline (the 3-nitroaniline contracts)]: with 5mlFeCl 24H 2O (48.0mg; 0.24mmol) ethanol solution be added drop-wise to 5ml2-acetyl group-1; 10-phenanthroline (the 3-nitroaniline contracts) part (68.5mg; 0.2mmol) ethanol solution in; stirring at room 9 hours; separate out precipitation, filter with ether washing back drying and obtain blackish green powder solid, productive rate is 57%.FT-IR(KBr?disc，cm -1)：3456，2936，1609，1581，1538，1492，1430，1369，1289，1156，876，789，741，658。Elementary analysis (C 20H 14Cl 2FeN 4O 2): C51.21, H3.01, N11.94; Experiment value (%): C50.87, H3.39, N11.82.
3. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of continuous drying 6hrs 2Gas displacement 3 times.Add 2.4mg (5 μ mol) catalyst 46 and then vacuumize and with ethene displacement 3 times.Toluene with syringe injection 30ml adds 1.7ml MAO (MAO) (toluene solution of 1.46mol/l) again, makes Al/Fe=500.Under 20 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the watery hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 5.28 * 10 4G mol -1(Fe) h -1, oligomer content is respectively: C 462%, C 615%, C 86%, C 105%, C 124%, C 14-C 228%.Remaining mixture does not obtain polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 103
1. the preparation of catalyst 46 is with embodiment 102.
2. pressurization (1MPa) ethylene oligomerization: the 250-ml stainless steel still that mechanical agitation and thermocouple will be housed vacuumizes and with nitrogen replacement 3 times, replaces 2 times with ethene again.Behind the cool to room temperature, add the toluene solution of toluene and 1.7ml MAO (MAO) (1.46mol/l in toluene) and 10ml catalyst 46 (5.0 μ mol), the cumulative volume of toluene is 150ml, Al/Fe=500.The pressure of ethene is increased to 10 atmospheric pressure, at 40 ℃ of following vigorous stirring 1h.With syringe take out spiece with in 5% the watery hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 2.97 * 10 6G mol -1(Fe) h -1, oligomer content is respectively: C 444.2%, C 627.2%, C 84.4%, C 105.5%, C 123.0%, C 14-C 244.1%.Remaining mixture obtains small amount of polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 104
1. the preparation of part: 2-acetyl group-1; 10-phenanthroline (the 4-nitroaniline contracts): 2-acetyl group-1; 10-phenanthroline (0.4445g; 2mmol) with 3-nitroaniline (0.3453g; 2.5mmol) add the 40mg p-methyl benzenesulfonic acid and make catalyst and add the 2g molecular sieve to make dehydrating agent; 30ml reflux in toluene 1 day; remove solvent toluene after the filtration; residue supports with the carrene dissolving; parlkaline aluminium oxide pillar, with petrol ether/ethyl acetate (4: 1) drip washing, second flow point is a product; removing desolvates obtains yellow solid, and productive rate is 20%.FT-IR(KBr?disc，cm -1)：3484，3364，3223，1634，1589，1507，1482，1472，1344，1302，1113，860，843，754。 1H?NMR(300MHz，CDCl 3)：δ9.25(s，1H)；8.61(d，J＝8.1Hz，1H)；8.39(d，J＝8.1Hz，1H)；8.32(d，J＝7.8Hz，1H)；8.03(d，J＝7.5Hz，2H)；7.90(s，2H)；7.58(m，1H)；7.21(d，J＝7.5Hz，2H)；2.73(s，3H，CH 3)。Elementary analysis (C 20H 14N 4O 2) theoretical value (%): C70.17, H4.12, N16.37; Experiment value (%): C69.79, H4.56, N16.03.
2. the preparation of catalyst 47: iron (II) (47) is closed in chlorination [2-acetyl group-1,10-phenanthroline (the 4-nitroaniline contracts)]: with 5mlFeCl 24H 2O (48.0mg; 0.24mmol) ethanol solution be added drop-wise to 5ml2-acetyl group-1; 10-phenanthroline (the 4-nitroaniline contracts) part (68.5mg; 0.2mmol) ethanol solution in; stirring at room 9 hours; separate out precipitation, filter with ether washing back drying and obtain blackish green powder solid, productive rate is 42%.FT-IR(KBr?disc，cm -1)：3062，1607，1593，1518，1397，1345，1286，1224，855。Elementary analysis (C 20H 14Cl 2FeN 4O 2): C51.21, H3.01, N11.94; Experiment value (%): C51.03, H3.19, N11.75.
3. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of continuous drying 6hrs 2Gas displacement 3 times.Add 2.4mg (5 μ mol) catalyst 47 and then vacuumize and with ethene displacement 3 times.Toluene with syringe injection 30ml adds 1.7ml MAO (MAO) (toluene solution of 1.46mol/l) again, makes Al/Fe=500.Under 20 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the watery hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 6.06 * 10 4G mol -1(Fe) h -1, oligomer content is respectively: C 469%, C 615%, C 8-C 2016%.Remaining mixture does not obtain polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 105
1. the preparation of catalyst 47 is with embodiment 104.
2. pressurization (1MPa) ethylene oligomerization: the 250-ml stainless steel still that mechanical agitation and thermocouple will be housed vacuumizes and with nitrogen replacement 3 times, replaces 2 times with ethene again.Behind the cool to room temperature, add the toluene solution of toluene and 1.7ml MAO (MAO) (1.46mol/l in toluene) and 10ml catalyst 47 (5.0 μ mol), the cumulative volume of toluene is 150ml, Al/Fe=500.The pressure of ethene is increased to 10 atmospheric pressure, at 40 ℃ of following vigorous stirring 1h.With syringe take out spiece with in 5% the watery hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 7.14 * 10 6G mol -1(Fe) h -1, oligomer content is respectively: C 436.9%, C 639.7%, C 814.0%, C 105.7%, C 122.2%, C 14-C 181.2%.Remaining mixture does not obtain polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 106
1. the preparation of part: 2-acetyl group-1; 10-phenanthroline (the 4-aminoanisole contracts): 2-acetyl group-1; 10-phenanthroline (0.4445g; 2mmol) with 4-aminoanisole (0.3079g; 2.5mmol) add the 40mg p-methyl benzenesulfonic acid and make catalyst and add the 2g molecular sieve to make dehydrating agent; 30ml reflux in toluene 1 day; remove solvent toluene after the filtration; residue supports with the carrene dissolving; parlkaline aluminium oxide pillar, with petrol ether/ethyl acetate (4: 1) drip washing, second flow point is a product; removing desolvates obtains yellow solid 0.11g, and productive rate is 17%.FT-IR(KBr?disc，cm -1)：3034，2928，2833，1635，1602，1581，1553，1491，1364，1283，1254，1213，1163，1118，1049，859，741，659。 1H?NMR(300MHz，CDCl 3)：δ9.25(dd.，J＝4.2Hz，1H)；8.63(d，J＝8.4Hz，1H)；8.34(d，J＝8.4Hz，1H)；8.30(d，J＝8.1Hz，1H)；7.87(s，2H)；7.68(dd，J＝8.1Hz，1H)；6.98(d，J＝8.7Hz，2H)；6.89(d，J＝8.7Hz，2H)；3.86(s，3H，OCH 3)；2.76(s，3H，CH 3)。Elementary analysis (C 21H 17N 3O) theoretical value (%): C77.04, H5.23, N12.84; Experiment value (%): C76.83, H5.38, N12.79.
2. the preparation of catalyst 48: iron (II) (48) is closed in chlorination [2-acetyl group-1,10-phenanthroline (the 4-aminoanisole contracts)]: with 5mlFeCl 24H 2O (48.0mg; 0.24mmol) ethanol solution be added drop-wise to 5ml2-acetyl group-1; 10-phenanthroline (the 4-aminoanisole contracts) part (65.5mg; 0.2mmol) ethanol solution in; stirring at room 9 hours; separate out precipitation, filter with ether washing back drying and obtain blackish green powder solid, productive rate is 85%.FT-IR(KBr?disc，cm -1)：3058，2919，1611，1581，1552，1492，1364，1283，1213，1164，1118，1049，858，741，659。Elementary analysis (C 21H 17Cl 2FeN 3O): C55.54, H3.77, N9.25; Experiment value (%): C55.32, H3.87, N9.06.
3. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of continuous drying 6hrs 2Gas displacement 3 times.Add 2.3mg (5 μ mol) catalyst 48 and then vacuumize and with ethene displacement 3 times.Toluene with syringe injection 30ml adds 1.7ml MAO (MAO) (toluene solution of 1.46mol/l) again, makes Al/Fe=500.Under 20 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the watery hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 4.47 * 10 4G mol -1(Fe) h -1, oligomer content is respectively: C 4100%.Remaining mixture does not obtain polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 107
1. the preparation of part: 2-acetyl group-1; 10-phenanthroline (2-methyl-4-aminoanisole contracts): 2-acetyl group-1; 10-phenanthroline (0.4445g; 2mmol) with 2-methyl-4-aminoanisole (0.343g; 2.5mmol) add the 40mg p-methyl benzenesulfonic acid and make catalyst and add the 2g molecular sieve to make dehydrating agent; 30ml reflux in toluene 1 day; remove solvent toluene after the filtration; residue supports with the carrene dissolving; parlkaline aluminium oxide pillar, with petrol ether/ethyl acetate (4: 1) drip washing, second flow point is a product; removing desolvates obtains yellow solid, and productive rate is 21%.FT-IR(KBr?disc，cm -1)：2993，2833，1633，1609，1586，1552，1492，1364，1283，1253，1212，1163，1117，1049，858，743，663。 1H?NMR(300MHz，CDCl 3)：δ9.25(dd.，J＝4.2Hz，1H)；8.69(d，J＝8.4Hz，1H)；8.34(d，J＝8.4Hz，1H)；8.31(d，J＝8.1Hz，1H)；7.87(s，2H)；7.67(dd，J＝8.1Hz，1H)；6.84(s，1H)；6.80(d，J＝8.4Hz，1H)；6.68(d，J＝8.4Hz，1H)；3.83(s，3H，OCH 3)；2.67(s，3H，CH 3)；2.18(s，3H，PhCH 3)。Elementary analysis (C 22H 19N 3O) theoretical value (%): C77.40, H5.61, N12.31; Experiment value (%): C77.06, H5.76, N12.17.
2. the preparation of catalyst 49: iron (II) (49) is closed in chlorination [2-acetyl group-1,10-phenanthroline (2-methyl-4-aminoanisole contracts)]: with 5mlFeCl 24H 2O (48.0mg; 0.24mmol) ethanol solution be added drop-wise to 5ml2-acetyl group-1; 10-phenanthroline (2-methyl-4-aminoanisole contracts) part (65.5mg; 0.2mmol) ethanol solution in; stirring at room 9 hours; separate out precipitation, filter with ether washing back drying and obtain blackish green powder solid, productive rate 67%.FT-IR(KBr?disc，cm -1)：3453，2919，1609，1582，1552，1491，1364，1283，1213，1164，1115，858，741，658。Elementary analysis (C 21H 17Cl 2FeN 3O): C55.54, H3.77, N9.25; Experiment value (%): C55.19, H3.89, N9.13.
3. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of continuous drying 6hrs 2Gas displacement 3 times.Add 2.3mg (5 μ mol) catalyst 49 and then vacuumize and with ethene displacement 3 times.Toluene with syringe injection 30ml adds 1.7ml MAO (MAO) (toluene solution of 1.46mol/l) again, makes Al/Fe=500.Under 20 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the watery hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 5.96 * 10 4G mol -1(Fe) h -1, oligomer content is respectively: C 4100%.Remaining mixture does not obtain polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 108
1. the preparation of catalyst 49 is with embodiment 107.
2. pressurization (1MPa) ethylene oligomerization: the 250-ml stainless steel still that mechanical agitation and thermocouple will be housed vacuumizes and with nitrogen replacement 3 times, replaces 2 times with ethene again.Behind the cool to room temperature, add the toluene solution of toluene and 1.7ml MAO (MAO) (1.46mol/l in toluene) and 10ml catalyst 49 (5.0 μ mol), the cumulative volume of toluene is 150ml, Al/Fe=500.The pressure of ethene is increased to 10 atmospheric pressure, at 40 ℃ of following vigorous stirring 1h.With syringe take out spiece with in 5% the watery hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 4.70 * 10 5G mol -1(Fe) h -1, oligomer content is respectively: C 464.5%, C 614.1%, C 8-C 2221.4%.Remaining mixture does not obtain polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 109
1. the preparation of part: 2-acetyl group-1; 10-phenanthroline (the 4-phenetidine contracts): 2-acetyl group-1; 10-phenanthroline (0.4445g; 2mmol) with 4-phenetidine (0.3427g; 2.5mmol) add the 40mg p-methyl benzenesulfonic acid and make catalyst and add the 2g molecular sieve to make dehydrating agent; 30ml reflux in toluene 1 day; remove solvent toluene after the filtration; residue supports with the carrene dissolving; parlkaline aluminium oxide pillar, with petrol ether/ethyl acetate (4: 1) drip washing, second flow point is a product; removing desolvates obtains yellow solid, and productive rate is 21%.FT-IR(KBr?disc，cm -1)：3056，2918，1636，1589，1553，1492，1364，1284，1254，1213，1164，1117，1049，858，741，658。 1H?NMR(300MHz，CDCl 3)：δ9.25(dd.，J＝4.2Hz，1H)；8.63(d，J＝8.4Hz，1H)；8.35(d，J＝8.4Hz，1H)；8.30(d，J＝8.1Hz，1H)；7.87(s，2H)；7.68(dd，J＝8.1Hz，1H)；7.12(d，J＝8.7Hz，2H)；6.89(d，J＝8.7Hz，2H)；3.98(q，2H，OCH 2)；2.76(s，3H，CH 3)；1.36(t，3H，OCH 2CH 3)。Elementary analysis (C 22H 19N 3O) theoretical value (%): C77.40, H5.61, N12.31; Experiment value (%): C77.06, H5.82, N12.19.
2. the preparation of catalyst 50: iron (II) (50) is closed in chlorination [2-acetyl group-1,10-phenanthroline (the 4-phenetidine contracts)]: with 5mlFeCl 24H 2O (48.0mg; 0.24mmol) ethanol solution be added drop-wise to 5ml2-acetyl group-1; 10-phenanthroline (the 4-phenetidine contracts) part (68.3mg; 0.2mmol) ethanol solution in; stirring at room 9 hours; separate out precipitation, filter with ether washing back drying and obtain blackish green powder solid, productive rate is 83%.FT-IR(KBr?disc，cm -1)：3046，2919，1608，1589，1552，1491，1364，1284，1212，1164，1118，1049，859，741，658。Elementary analysis (C 22H 19Cl 2FeN 3O): C56.44, H4.09, N8.98; Experiment value (%): C56.32, H4.18, N9.01.
3. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of continuous drying 6hrs 2Gas displacement 3 times.Add 2.4mg (5 μ mol) catalyst 50 and then vacuumize and with ethene displacement 3 times.Toluene with syringe injection 30ml adds 1.7ml MAO (MAO) (toluene solution of 1.46mol/l) again, makes Al/Fe=500.Under 20 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the watery hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 5.12 * 10 4G mol -1(Fe) h -1, oligomer content is respectively: C 4100%.Remaining mixture does not obtain polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 110
1. the preparation of part: 2-acetyl group-1; 10-phenanthroline (naphthalidine contracts): 2-acetyl group-1; 10-phenanthroline (0.4445g; 2mmol) and naphthalidine (0.358g; 2.5mmol) add the 40mg p-methyl benzenesulfonic acid and make catalyst and add the 2g molecular sieve to make dehydrating agent; 30ml reflux in toluene 1 day; remove solvent toluene after the filtration; residue supports with the carrene dissolving; parlkaline aluminium oxide pillar, with petrol ether/ethyl acetate (4: 1) drip washing, second flow point is a product; removing desolvates obtains yellow solid, and productive rate is 72%.FT-IR(KBr?disc，cm -1)：3224，3043，1635，1578，1494，1388，1368，1257，1116，1084，857，780，741。 1H?NMR(300MHz，CDCl 3)：δ9.25(d.，J＝4.2Hz，1H)；8.83(d，J＝8.4Hz，1H)；8.41(d，J＝8.4Hz，1H)；8.32(d，J＝8.1Hz，1H)；7.90(s，2H)；7.83(m，2H)；7.54-7.40(m，4H)；7.30(d，J＝6.9Hz，1H)；6.89(d，J＝7.2Hz，1H)；2.70(s，3H，CH 3)。Elementary analysis (C 24H 17N 3) theoretical value (%): C82.97, H4.93, N12.10; Experiment value (%): C82.68, H5.21, N11.89.
2. the preparation of catalyst 51: iron (II) (51) is closed in chlorination [2-acetyl group-1,10-phenanthroline (naphthalidine contracts)]: with 5mlFeCl 24H 2O (48.0mg; 0.24mmol) ethanol solution be added drop-wise to 5ml2-acetyl group-1; 10-phenanthroline (naphthalidine contracts) part (69.5mg; 0.2mmol) ethanol solution in; stirring at room 9 hours; separate out precipitation, filter with ether washing back drying and obtain blackish green powder solid, productive rate is 60%.FT-IR(KBr?disc，cm -1)：3224，3046，1610，1579，1492，1388，1369，1257，1117，1084，857，780，741。Elementary analysis (C 24H 17Cl 2FeN 3): C60.79, H3.61, N8.86; Experiment value (%): C60.71, H3.82, N8.73.
3. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of continuous drying 6hrs 2Gas displacement 3 times.Add 2.4mg (5 μ mol) catalyst 51 and then vacuumize and with ethene displacement 3 times.Toluene with syringe injection 30ml adds 1.7ml MAO (MAO) (toluene solution of 1.46mol/l) again, makes Al/Fe=500.Under 20 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the watery hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 2.57 * 10 4G mol -1(Fe) h -1, oligomer content is respectively: C 4100%.Remaining mixture does not obtain polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 111
1. the preparation of catalyst 51 is with embodiment 110.
2. pressurization (1MPa) ethylene oligomerization: the 250-ml stainless steel still that mechanical agitation and thermocouple will be housed vacuumizes and with nitrogen replacement 3 times, replaces 2 times with ethene again.Behind the cool to room temperature, add the toluene solution of toluene and 1.7ml MAO (MAO) (1.46mol/l in toluene) and 10ml catalyst 51 (5.0 μ mol), the cumulative volume of toluene is 150ml, Al/Fe=500.The pressure of ethene is increased to 10 atmospheric pressure, at 40 ℃ of following vigorous stirring 1h.With syringe take out spiece with in 5% the watery hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 1.23 * 10 5G mol -1(Fe) h -1, oligomer content is respectively: C 472.4%, C 64.5%, C 8-C 1623.1%.Remaining mixture does not obtain polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 112
1. the preparation of part: 2-acetyl group-1; 10-phenanthroline (the diphenyl methylamine contracts): 2-acetyl group-1; 10-phenanthroline (0.4445g; 2mmol) with diphenyl methylamine (0.458g; 2.5mmol) add the 40mg p-methyl benzenesulfonic acid and make catalyst and add the 2g molecular sieve to make dehydrating agent; 30ml reflux in toluene 1 day; remove solvent toluene after the filtration; residue supports with the carrene dissolving; parlkaline aluminium oxide pillar, with petrol ether/ethyl acetate (4: 1) drip washing, second flow point is a product; removing desolvates obtains yellow solid, and productive rate is 39%.FT-IR(KBr?disc，cm -1)：3046，1634，1581，1492，1388，1369，1258，1119，1084，857，780，741。 1H?NMR(300MHz，CDCl 3)：δ9.21(d.，J＝4.2Hz，1H)；8.73(d，J＝8.4Hz，1H)；8.27(m，2H)；7.83(s，2H)；7.63(dd，J＝3.9Hz，1H)；7.51(d，J＝7.5Hz，4H)；7.34(d，J＝7.5Hz，4H)；7.25-7.20(m，2H)；6.04(s，1H)；2.82(s，3H，CH 3)。Elementary analysis (C 27H 21N 3) theoretical value (%): C83.69, H5.46, N10.84; Experiment value (%): C83.33, H5.53, N10.71.
2. the preparation of catalyst 52: iron (II) (52) is closed in chlorination [2-acetyl group-1,10-phenanthroline (the diphenyl methylamine contracts)]: with 5mlFeCl 24H 2O (48.0mg; 0.24mmol) ethanol solution be added drop-wise to 5ml2-acetyl group-1; 10-phenanthroline (the diphenyl methylamine contracts) part (77.5mg; 0.2mmol) ethanol solution in; stirring at room 9 hours; separate out precipitation, filter with ether washing back drying and obtain blackish green powder solid, productive rate is 85%.FT-IR(KBr?disc，cm -1)：3056，1608，1581，1491，1389，1369，1258，1118，1084，858，741。Elementary analysis (C 27H 21Cl 2FeN 3): C63.06, H4.12, N8.17; Experiment value (%): C62.91, H4.23, N8.13.
3. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of continuous drying 6hrs 2Gas displacement 3 times.Add 2.6mg (5 μ mol) catalyst 52 and then vacuumize and with ethene displacement 3 times.Toluene with syringe injection 30ml adds 1.7ml MAO (MAO) (toluene solution of 1.46mol/l) again, makes Al/Fe=500.Under 20 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 30min.With syringe take out spiece with in 5% the watery hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 2.47 * 10 4G mol -1(Fe) h -1, oligomer content is respectively: C 4100%.Remaining mixture does not obtain polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 113
1. the preparation of part is with embodiment eight.
2. the preparation of catalyst 53: cobalt (II) (53) is closed in chlorination [2-acetyl group-1,10-phenanthroline (contracting 2, the 6-dimethylaniline)]: with 5mlCoCl 2(31.2mg; 0.24mmol) ethanol solution be added drop-wise to 5ml2-acetyl group-1; the 10-phenanthroline (contracts 2; the 6-dimethylaniline) part (65.1mg; 0.2mmol) ethanol solution in, stirring at room 9 hours is separated out precipitation; filtration obtains brown solid with ether washing back drying, and productive rate is 86%.FT-IR(KBr?disc，cm -1)：3435，3049，1612，1511，1406，1287，1211，864(s)，790。Elementary analysis (C 22H 19Cl 2CoN 3) theoretical value (%): C58.04, H4.21, N9.23; Experiment value (%): C58.02, H4.31, N8.95.
3. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of continuous drying 6hrs 2Gas displacement 3 times.Add 2.3mg (5 μ mol) catalyst 53 and then vacuumize and with ethene displacement 3 times.Toluene with syringe injection 30ml adds 1.7ml MAO (MAO) (toluene solution of 1.46mol/l) again, makes Al/Co=500.Under 40 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 60min.With syringe take out spiece with in 5% the watery hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 7.2 * 10 4G mol -1(Co) h -1, oligomer content is respectively: C 496%, C 66%.Remaining mixture does not obtain polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 114
1. the preparation of catalyst 53 is with embodiment 113.
2. pressurization (1MPa) ethylene oligomerization: the 250-ml stainless steel still that mechanical agitation and thermocouple will be housed vacuumizes and with nitrogen replacement 3 times, replaces 2 times with ethene again.Behind the cool to room temperature, add the toluene solution of toluene and 1.7ml MAO (MAO) (1.46mol/l in toluene) and 10ml catalyst 53 (5.0 μ mol), the cumulative volume of toluene is 150ml, Al/Co=500.The pressure of ethene is increased to 10 atmospheric pressure, at 40 ℃ of following vigorous stirring 1h.With syringe take out spiece with in 5% the watery hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 1.40 * 10 6G mol -1(Co) h -1, oligomer content is respectively: C 4100%.Remaining mixture does not obtain polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 115
1. the preparation of part is with embodiment 13.
2. the preparation of catalyst 54: cobalt (II) (54) is closed in chlorination [2-acetyl group-1,10-phenanthroline (contracting 2,4, the 6-trimethylaniline)]: with 5mlCoCl 2(31.2mg; 0.24mmol) ethanol solution be added drop-wise to 5ml2-acetyl group-1; the 10-phenanthroline (contracts 2; 4, the 6-trimethylaniline) (67.9mg is in ethanol solution 0.2mmol) for part; stirring at room 9 hours; separate out precipitation, filter with ether washing back drying and obtain brown solid, productive rate is 60%.FT-IR(KBr?disc，cm -1)：3438，2910，1611，1541，1488，1404，1286，1222，1118，860，651。Elementary analysis (C 23H 21Cl 2CoN 3) theoretical value (%): C58.87, H4.51, N8.95; Experiment value (%): C58.51, H4.41, N, 8.83.
3. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of continuous drying 6hrs 2Gas displacement 3 times.Add 2.3mg (5 μ mol) catalyst 54 and then vacuumize and with ethene displacement 3 times.Toluene with syringe injection 30ml adds 1.7ml MAO (MAO) (toluene solution of 1.46mol/l) again, makes Al/Co=500.Under 40 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 60min.With syringe take out spiece with in 5% the watery hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 9.6 * 10 3G mol -1(Co) h -1, oligomer content is respectively: C 4100%.Remaining mixture does not obtain polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 116
1. the preparation of catalyst 54 is with embodiment 115.
2. pressurization (1MPa) ethylene oligomerization: the 250-ml stainless steel still that mechanical agitation and thermocouple will be housed vacuumizes and with nitrogen replacement 3 times, replaces 2 times with ethene again.Behind the cool to room temperature, add the toluene solution of toluene and 1.7ml MAO (MAO) (1.46mol/l in toluene) and 10ml catalyst 54 (5.0 μ mol), the cumulative volume of toluene is 150ml, Al/Co=500.The pressure of ethene is increased to 10 atmospheric pressure, at 40 ℃ of following vigorous stirring 1h.With syringe take out spiece with in 5% the watery hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 1.55 * 10 5G mol -1(Co) h -1, oligomer content is respectively: C 4100%.Remaining mixture does not obtain polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 117
1. the preparation of part is with embodiment 23.
2. the preparation of catalyst 55: cobalt (II) (55) is closed in chlorination [2-acetyl group-1,10-phenanthroline (contracting 2, the 6-diethylaniline)]: with 5mlCoCl 2(31.2mg; 0.24mmol) ethanol solution be added drop-wise to 5ml2-acetyl group-1; the 10-phenanthroline (contracts 2; the 6-diethylaniline) part (70.7mg; 0.2mmol) ethanol solution in, stirring at room 9 hours is separated out precipitation; filtration obtains brown solid with ether washing back drying, and productive rate is 58%.FT-IR(KBr?disc，cm -1)：3448，2964，1611，1513，1407，1286，873，785。Elementary analysis (C 24H 23Cl 2CoN 3) theoretical value (%): C59.64, H4.80, N8.69; Experiment value (%): C59.69, H4.86, N8.62.
3. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of continuous drying 6hrs 2Gas displacement 3 times.Add 2.4mg (5 μ mol) catalyst 55 and then vacuumize and with ethene displacement 3 times.Toluene with syringe injection 30ml adds 1.7ml MAO (MAO) (toluene solution of 1.46mol/l) again, makes Al/Co=500.Under 40 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 60min.With syringe take out spiece with in 5% the watery hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 4.8 * 10 4G mol -1(Co) h -1, oligomer content is respectively: C 4100%.Remaining mixture does not obtain polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 118
1. the preparation of catalyst 55 is with embodiment 117.
2. pressurization (1MPa) ethylene oligomerization: the 250-ml stainless steel still that mechanical agitation and thermocouple will be housed vacuumizes and with nitrogen replacement 3 times, replaces 2 times with ethene again.Behind the cool to room temperature, add the toluene solution of toluene and 1.7ml MAO (MAO) (1.46mol/l in toluene) and 10ml catalyst 55 (5.0 μ mol), the cumulative volume of toluene is 150ml, Al/Co=500.The pressure of ethene is increased to 10 atmospheric pressure, at 40 ℃ of following vigorous stirring 1h.With syringe take out spiece with in 5% the watery hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 1.87 * 10 6G mol -1(Co) h -1, oligomer content is respectively: C 4100%.Remaining mixture does not obtain polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 119
1. the preparation of part is with embodiment 40.
2. the preparation of catalyst 56: cobalt (II) (56) is closed in chlorination [2-acetyl group-1,10-phenanthroline (contracting 2, the 6-diisopropyl aniline)]: with 5mlCoCl 2(31.2mg; 0.24mmol) ethanol solution be added drop-wise to 5ml2-acetyl group-1; the 10-phenanthroline (contracts 2; the 6-diisopropyl aniline) part (76.3mg; 0.2mmol) ethanol solution in, stirring at room 9 hours is separated out precipitation; filtration obtains brown solid with ether washing back drying, and productive rate is 76%.FT-IR(KBr?disc，cm -1)：3435，2967，1609，1410，1287，850，789。Elementary analysis (C 26H 27Cl 2CoN 3) theoretical value (%): C61.07, H5.32, N8.22; Experiment value (%): C60.86, H5.49, N7.83.
3. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of continuous drying 6hrs 2Gas displacement 3 times.Add 2.6mg (5 μ mol) catalyst 56 and then vacuumize and with ethene displacement 3 times.Toluene with syringe injection 30ml adds 1.7ml MAO (MAO) (toluene solution of 1.46mol/l) again, makes Al/Co=500.Under 40 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 60min.With syringe take out spiece with in 5% the watery hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 4.3 * 10 4G mol -1(Co) h -1, oligomer content is respectively: C 4100%.Remaining mixture does not obtain polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 120
1. the preparation of catalyst 56 is with embodiment 119.
2. pressurization (1MPa) ethylene oligomerization: the 250-ml stainless steel still that mechanical agitation and thermocouple will be housed vacuumizes and with nitrogen replacement 3 times, replaces 2 times with ethene again.Behind the cool to room temperature, add the toluene solution of toluene and 1.7ml MAO (MAO) (1.46mol/l in toluene) and 10ml catalyst 56 (5.0 μ mol), the cumulative volume of toluene is 150ml, Al/Co=500.The pressure of ethene is increased to 10 atmospheric pressure, at 40 ℃ of following vigorous stirring 1h.With syringe take out spiece with in 5% the watery hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 1.67 * 10 6G mol -1(Co) h -1, oligomer content is respectively: C 4100%.Remaining mixture does not obtain polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 121
1. the preparation of part is with embodiment 53.
2. the preparation of catalyst 57: cobalt (II) (57) is closed in chlorination [2-acetyl group-1,10-phenanthroline (contracting 2, the 6-difluoroaniline)]: with 5mlCoCl 2(31.2mg; 0.24mmol) ethanol solution be added drop-wise to 5ml2-acetyl group-1; the 10-phenanthroline (contracts 2; the 6-difluoroaniline) part (66.7mg; 0.2mmol) ethanol solution in, stirring at room 9 hours is separated out precipitation; filtration obtains the yellowish-brown solid with ether washing back drying, and productive rate is 85%.FT-IR(KBr?disc，cm -1)：3435，2967，2916，1605，1578，1410，1287，1118，850，789，740，659。Elementary analysis (C 20H 13Cl 2CoF 2N 3) theoretical value (%): C51.86, H2.83, N9.07; Experiment value (%): C51.76, H2.94, N8.95.
3. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of continuous drying 6hrs 2Gas displacement 3 times.Add 2.3mg (5 μ mol) catalyst 57 and then vacuumize and with ethene displacement 3 times.Toluene with syringe injection 30ml adds 1.7ml MAO (MAO) (toluene solution of 1.46mol/l) again, makes Al/Co=500.Under 40 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 60min.With syringe take out spiece with in 5% the watery hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 1.30 * 10 5G mol -1(Co) h -1, oligomer content is respectively: C 4100%.Remaining mixture does not obtain polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 122
1. the preparation of part is with embodiment 67.
2. the preparation of catalyst 58: chlorination [2-acetyl group-1; the 10-phenanthroline (contracts 2; the 6-dichloroaniline)] close cobalt (II) (58): with 5mlCoCl2 (31.2mg, ethanol solution 0.24mmol) is added drop-wise to 5ml2-acetyl group-1, the 10-phenanthroline (contracts 2; the 6-diisopropyl aniline) part (73.2mg; 0.2mmol) ethanol solution in, stirring at room 9 hours is separated out precipitation; filtration obtains the yellow green solid with ether washing back drying, and productive rate is 81%.FT-IR(KBr?disc，cm -1)：3043，2919，1610，1591，1487，1410，1287，1119，850，789，740。Elementary analysis (C 20H 13Cl 4CoN 3) theoretical value (%): C48.42, H2.64, N8.47; Experiment value (%): C48.12, H2.83, N8.31.
3. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of continuous drying 6hrs 2Gas displacement 3 times.Add 2.5mg (5 μ mol) catalyst 58 and then vacuumize and with ethene displacement 3 times.Toluene with syringe injection 30ml adds 1.7ml MAO (MAO) (toluene solution of 1.46mol/l) again, makes Al/Co=500.Under 40 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 60min.With syringe take out spiece with in 5% the watery hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 1.35 * 10 5G mol -1(Co) h -1, oligomer content is respectively: C 4100%.Remaining mixture does not obtain polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 123
1. the preparation of part is with embodiment 86.
2. the preparation of catalyst 59: cobalt (II) (59) is closed in chlorination [2-acetyl group-1,10-phenanthroline (contracting 2, the 6-dibromo aniline)]: with 5mlCoCl 2(31.2mg; 0.24mmol) ethanol solution be added drop-wise to 5ml2-acetyl group-1; the 10-phenanthroline (contracts 2; the 6-dibromo aniline) part (91.0mg; 0.2mmol) ethanol solution in, stirring at room 9 hours is separated out precipitation; filtration obtains the yellow green solid with ether washing back drying, and productive rate is 86%.FT-IR(KBr?disc，cm -1)：3435，2968，2918，1610，1581，1410，1286，1119，851，789，740。Elementary analysis (C 20H 13Br 2Cl 2CoN 3) theoretical value (%): C41.06, H2.24, N7.18; Experiment value (%): C40.86, H2.49, N7.13.
3. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of continuous drying 6hrs 2Gas displacement 3 times.Add 2.7mg (5 μ mol) catalyst 59 and then vacuumize and with ethene displacement 3 times.Toluene with syringe injection 30ml adds 1.7ml MAO (MAO) (toluene solution of 1.46mol/l) again, makes Al/Co=500.Under 40 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 60min.With syringe take out spiece with in 5% the watery hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 2.65 * 10 5G mol -1(Co) h -1, oligomer content is respectively: C 4100%.Remaining mixture does not obtain polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 124
1. the preparation of part is with embodiment eight.
2. the preparation of catalyst 60: nickel (II) (60) is closed in chlorination [2-acetyl group-1,10-phenanthroline (contracting 2, the 6-dimethylaniline)]: with 5mlNiCl 26H 2O (57.0mg; 0.24mmol) ethanol solution be added drop-wise to 5ml2-acetyl group-1; the 10-phenanthroline (contracts 2; the 6-dimethylaniline) part (65.1mg; 0.2mmol) ethanol solution in, stirring at room 9 hours is separated out precipitation; filtration obtains the yellowish-brown solid with ether washing back drying, and productive rate is 81%.FT-IR(KBr?disc，cm -1)：3427，3050，1612，1511，1408，1288，1212，865，772。Elementary analysis (C 22H 19Cl 2N 3Ni) theoretical value (%): C58.07, H4.21, N9.24; Experiment value (%): C57.75, H4.22, N8.92.
3. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of continuous drying 6hrs 2Gas displacement 3 times.Add 2.3mg (5 μ mol) catalyst 60 and then vacuumize and with ethene displacement 3 times.Toluene with syringe injection 30ml adds 1.7ml MAO (MAO) (toluene solution of 1.46mol/l) again, makes Al/Ni=500.Under 40 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 60min.With syringe take out spiece with in 5% the watery hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 3.0 * 10 2G mol -1(Ni) h -1, oligomer content is respectively: C 4100%.Remaining mixture does not obtain polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 125
1. the preparation of catalyst 60 is with embodiment 124.
2. pressurization (1MPa) ethylene oligomerization: the 250-ml stainless steel still that mechanical agitation and thermocouple will be housed vacuumizes and with nitrogen replacement 3 times, replaces 2 times with ethene again.Behind the cool to room temperature, add the toluene solution of toluene and 1.7ml MAO (MAO) (1.46mol/l in toluene) and 10ml catalyst 60 (5.0 μ mol), the cumulative volume of toluene is 150ml, Al/Ni=500.The pressure of ethene is increased to 10 atmospheric pressure, at 40 ℃ of following vigorous stirring 1h.With syringe take out spiece with in 5% the watery hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 1.59 * 10 5G mol -1(Ni) h -1, oligomer content is respectively: C 4100%.Remaining mixture does not obtain polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 126
1. the preparation of part is with embodiment 13.
2. the preparation of catalyst 61: nickel (II) (61) is closed in chlorination [2-acetyl group-1,10-phenanthroline (contracting 2,4, the 6-trimethylaniline)]: with 5mlNiCl 26H 2O (57.0mg; 0.24mmol) ethanol solution be added drop-wise to 5ml2-acetyl group-1; the 10-phenanthroline (contracts 2; 4, the 6-trimethylaniline) (67.9mg is in ethanol solution 0.2mmol) for part; stirring at room 9 hours; separate out precipitation, filter with ether washing back drying and obtain the orange colour solid, productive rate is 47%.FT-IR(KBr?disc，cm -1)：3046，2918，1608，1514，1409，1285，1212，1164，856，742。Elementary analysis (C 23H 21Cl 2N 3NiC 2H 6O) theoretical value (%): C58.29, H5.28, N8.16; Experiment value (%): C57.88, H5.04, N8.00.
3. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of continuous drying 6hrs 2Gas displacement 3 times.Add 2.3mg (5 μ mol) catalyst 61 and then vacuumize and with ethene displacement 3 times.Toluene with syringe injection 30ml adds 1.7ml MAO (MAO) (toluene solution of 1.46mol/l) again, makes Al/Ni=500.Under 40 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 60min.With syringe take out spiece with in 5% the watery hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 8.0 * 10 2G mol -1(Ni) h -1, oligomer content is respectively: C 4100%.Remaining mixture does not obtain polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 127
1. the preparation of catalyst 61 is with embodiment 126.
2. pressurization (1MPa) ethylene oligomerization: the 250-ml stainless steel still that mechanical agitation and thermocouple will be housed vacuumizes and with nitrogen replacement 3 times, replaces 2 times with ethene again.Behind the cool to room temperature, add the toluene solution of toluene and 1.7ml MAO (MAO) (1.46mol/l in toluene) and 10ml catalyst 61 (5.0 μ mol), the cumulative volume of toluene is 150ml, Al/Ni=500.The pressure of ethene is increased to 10 atmospheric pressure, at 40 ℃ of following vigorous stirring 1h.With syringe take out spiece with in 5% the watery hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 8.51 * 10 4G mol -1(Ni) h -1, oligomer content is respectively: C 4100%.Remaining mixture does not obtain polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 128
1. the preparation of part is with embodiment 23.
2. the preparation of catalyst 62: nickel (II) (62) is closed in chlorination [2-acetyl group-1,10-phenanthroline (contracting 2, the 6-diethylaniline)]: with 5mlNiCl 26H 2O (57.0mg; 0.24mmol) ethanol solution be added drop-wise to 5ml2-acetyl group-1; the 10-phenanthroline (contracts 2; the 6-diethylaniline) part (70.7mg; 0.2mmol) ethanol solution in, stirring at room 9 hours is separated out precipitation; filtration obtains the yellowish-brown solid with ether washing back drying, and productive rate is 65%.FT-IR(KBr?disc，cm -1)：3429，2964，1609，1512，1409，1287，874，787。Elementary analysis (C 24H 23Cl 2N 3Ni) theoretical value (%): C59.67, H4.80, N8.70; Experiment value (%): C59.64, H4.82, N8.53.
3. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of continuous drying 6hrs 2Gas displacement 3 times.Add 2.4mg (5 μ mol) catalyst 62 and then vacuumize and with ethene displacement 3 times.Toluene with syringe injection 30ml adds 1.7ml MAO (MAO) (toluene solution of 1.46mol/l) again, makes Al/Ni=500.Under 40 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 60min.With syringe take out spiece with in 5% the watery hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 4.0 * 10 3G mol -1(Ni) h -1, oligomer content is respectively: C 4100%.Remaining mixture does not obtain polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 129
1. the preparation of catalyst 62 is with embodiment 128.
2. pressurization (1MPa) ethylene oligomerization: the 250-ml stainless steel still that mechanical agitation and thermocouple will be housed vacuumizes and with nitrogen replacement 3 times, replaces 2 times with ethene again.Behind the cool to room temperature, add the toluene solution of toluene and 1.7ml MAO (MAO) (1.46mol/l in toluene) and 10ml catalyst 62 (5.0 μ mol), the cumulative volume of toluene is 150ml, Al/Ni=500.The pressure of ethene is increased to 10 atmospheric pressure, at 40 ℃ of following vigorous stirring 1h.With syringe take out spiece with in 5% the watery hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 1.22 * 10 5G mol -1(Ni) h -1, oligomer content is respectively: C 4100%.Remaining mixture does not obtain polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 130
1. the preparation of part is with embodiment 40.
2. the preparation of catalyst 63: nickel (II) (63) is closed in chlorination [2-acetyl group-1,10-phenanthroline (contracting 2, the 6-diisopropyl aniline)]: with 5mlNiCl 26H 2O (57.0mg; 0.24mmol) ethanol solution be added drop-wise to 5ml2-acetyl group-1; the 10-phenanthroline (contracts 2; the 6-diisopropyl aniline) part (76.3mg; 0.2mmol) ethanol solution in, stirring at room 9 hours is separated out precipitation; filtration obtains brown solid with ether washing back drying, and productive rate is 90%.FT-IR(KBr?disc，cm -1)：3414，2967，1608，1411，1288，850，790。Elementary analysis (C 26H 27Cl 2N 3Ni) theoretical value (%): C61.10, H5.32, N8.22; Experiment value (%): C60.91, H5.44, N7.88.
3. normal pressure ethylene oligomerization: the 250ml three neck round-bottomed flasks that magnetic stick will be housed vacuumize and use N while hot at 130 ℃ of continuous drying 6hrs 2Gas displacement 3 times.Add 2.6mg (5 μ mol) catalyst 63 and then vacuumize and with ethene displacement 3 times.Toluene with syringe injection 30ml adds 1.7ml MAO (MAO) (toluene solution of 1.46mol/l) again, makes Al/Ni=500.Under 40 ℃, keep the ethylene pressure of 1atm, vigorous stirring reaction 60min.With syringe take out spiece with in 5% the watery hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 2.0 * 10 3G mol -1(Ni) h -1, oligomer content is respectively: C 4100%.Remaining mixture does not obtain polymer with the ethanolic solution neutralization of 5% hcl acidifying.
Embodiment 131
1. the preparation of catalyst 63 is with embodiment 130.
2. pressurization (1MPa) ethylene oligomerization: the 250-ml stainless steel still that mechanical agitation and thermocouple will be housed vacuumizes and with nitrogen replacement 3 times, replaces 2 times with ethene again.Behind the cool to room temperature, add the toluene solution of toluene and 1.7ml MAO (MAO) (1.46mol/l in toluene) and 10ml catalyst 63 (5.0 μ mol), the cumulative volume of toluene is 150ml, Al/Ni=500.The pressure of ethene is increased to 10 atmospheric pressure, at 40 ℃ of following vigorous stirring 1h.With syringe take out spiece with in 5% the watery hydrochloric acid and after carry out the GC analysis: the oligomerisation activity is 2.30 * 10 5G mol -1(Ni) h -1, oligomer content is respectively: C 4100%.Remaining mixture does not obtain polymer with the ethanolic solution neutralization of 5% hcl acidifying.

Claims (8)

1. catalyst that is used for ethylene oligomerization and polymerization, for have as shown in the formula chlorination 2-imido grpup-1,10-phenanthroline iron (II), cobalt (II) or nickel (II) complex:
Figure C2005100664270002C1
Or
Figure C2005100664270002C2
Wherein:
M is Fe (II), Co (II) or Ni (II);
R 1-R 5Be selected from hydrogen independently of one another, alkyl, halogen, alkoxyl and nitro
R is selected from 1-naphthyl and diphenyl methyl independently of one another.
2. according to the catalyst of claim 1, R wherein 1-R 5Be selected from hydrogen independently of one another, methyl, ethyl, isopropyl, fluorine, chlorine, bromine, methoxyl group, ethyoxyl and nitro.
3. according to the catalyst of claim 1, wherein M, R, R 1-R 5Be selected from:
1：M＝Fe，R 1＝Me，R 2＝R 3＝R 4＝R 5＝H；2：M＝Fe，R 2＝Me，R 1＝R 3＝R 4＝R 5＝H；
3：M＝Fe，R 3＝Me，R 1＝R 2＝R 4＝R 5＝H；4：M＝Fe，R 1＝R 2＝Me，R 3＝R 4＝R 5＝H；
5：M＝Fe，R 1＝R 3＝Me，R 2＝R 4＝R 5＝H；6：M＝Fe，R 1＝R 4＝Me，R 2＝R 3＝R 5＝H；
7：M＝Fe，R 1＝R 5＝Me，R 2＝R 3＝R 4＝H；8：M＝Fe，R 2＝R 3＝Me，R 1＝R 4＝R 5＝H；
9：M＝Fe，R 2＝R 4＝Me，R 1＝R 3＝R 5＝H；10：M＝Fe，R 1＝R 3＝R 5＝Me，R 2＝R 4＝H；
11：M＝Fe，R 1＝R 5＝Me，R 3＝Br，R 2＝R 4＝H；12：M＝Fe，R 1＝Et，R 2＝R 3＝R 4＝R 5＝H；
13：M＝Fe，R 1＝Et，R 5＝Me，R 2＝R 3＝R 4＝H；14：M＝Fe，R 1＝R 5＝Et，R 2＝R 3＝R 4＝H；
15：M＝Fe，R 1＝iPr，R 2＝R 3＝R 4＝R 5＝H；16：M＝Fe，R 1＝R 5＝iPr，R 2＝R 3＝R 4＝H；
17：M＝Fe，R 1＝F，R 2＝R 3＝R 4＝R 5＝H；18：M＝Fe，R 1＝F，R 3＝Me，R 2＝R 4＝R 5＝H；
19：M＝Fe，R 1＝F，R 4＝Me，R 2＝R 3＝R 5＝H；20：M＝Fe，R 1＝R 3＝F，R 2＝R 4＝R 5＝H；
21：M＝Fe，R 1＝R 4＝F，R 2＝R 3＝R 5＝H；22：M＝Fe，R 1＝R 5＝F，R 2＝R 3＝R 4＝H；
23：M＝Fe，R 2＝R 3＝F，R 1＝R 4＝R 5＝H；24：M＝Fe，R 1＝R 2＝R 3＝F，R 4＝R 5＝H；
25：M＝Fe，R 1＝R 3＝R 4＝F，R 2＝R 5＝H；26：M＝Fe，R 1＝R 3＝R 5＝F，R 2＝R 4＝H；
27：M＝Fe，R 1＝R 2＝R 3＝R 4＝R 5＝F；28：M＝Fe，R 1＝Cl，R 2＝R 3＝R 4＝R 5＝H；
29：M＝Fe，R 2＝Cl，R 1＝R 3＝R 4＝R 5＝H；30：M＝Fe，R 1＝R 5＝Cl，R 2＝R 3＝R 4＝H；
31：M＝Fe，R 1＝R 2＝R 3＝Cl，R 4＝R 5＝H；32：M＝Fe，R 1＝R 3＝R 4＝Cl，R 2＝R 5＝H；
33：M＝Fe，R 1＝R 3＝R 5＝Cl，R 2＝R 4＝H；34：M＝Fe，R 1＝Br，R 2＝R 3＝R 4＝R 5＝H；
35：M＝Fe，R 1＝Br，R 3＝Me，R 2＝R 4＝R 5＝H；36：M＝Fe，R 1＝Br，R 3＝F，R 2＝R 4＝R 5＝H；
37：M＝Fe，R 1＝F，R 3＝Br，R 2＝R 4＝R 5＝H；38：M＝Fe，R 1＝R 3＝Br，R 2＝R 4＝R 5＝H；
39：M＝Fe，R 1＝R 5＝Br，R 2＝R 3＝R 4＝H；40：M＝Fe，R 1＝R 5＝Br，R 3＝Me，R 2＝R 4＝H；
41：M＝Fe，R 1＝R 5＝Br，R 3＝Cl，R 2＝R 4＝H；42：M＝Fe，R 1＝R 3＝R 5＝Br，R 2＝R 4＝H；
43：M＝Fe，R 1＝Br，R 3＝F，R 5＝Cl，R 2＝R 4＝H；4：M＝Fe，R 1＝Br，R 3＝Cl，R 5＝F，R 2＝R 4＝H；
45：M＝Fe，R 1＝Br，R 3＝R 5＝F，R 2＝R 4＝H；46：M＝Fe，R 2＝NO 2，R 1＝R 3＝R 4＝R 5＝H；
47：M＝Fe，R 3＝NO 2，R 1＝R 2＝R 4＝R 5＝H；48：M＝Fe，R 3＝OMe，R 1＝R 2＝R 4＝R 5＝H；
49：M＝Fe，R 1＝Me，R 2＝OMe，R 3＝R 4＝R 5＝H；50：M＝Fe，R 3＝OEt，R 1＝R 2＝R 4＝R 5＝H；
51：M＝Fe，R＝1-naphthyl；52：M＝Fe，R＝CH(Ph) 2
53：M＝Co，R 1＝R 5＝Me，R 2＝R 3＝R 4＝H；54：M＝Co，R 1＝R 3＝R 5＝Me，R 2＝R 4＝H；
55：M＝Co，R 1＝R 5＝Et，R 2＝R 3＝R 4＝H；56：M＝Co，R 1＝R 5＝iPr，R 2＝R 3＝R 4＝H；
57：M＝Co，R 1＝R 5＝F，R 2＝R 3＝R 4＝H；58：M＝Co，R 1＝R 5＝Cl，R 2＝R 3＝R 4＝H；
59：M＝Co，R 1＝R 5＝Br，R 2＝R 3＝R 4＝H；60：M＝Ni，R 1＝R 5＝Me，R 2＝R 3＝R 4＝H；
61：M＝Ni，R 1＝R 3＝R 5＝Me，R 2＝R 4＝H；62：M＝Ni，R 1＝R 5＝Et，R 2＝R 3＝R 4＝H；
Or 63:M=Ni, R 1=R 5=iPr, R 2=R 3=R 4=H.
4. the described Preparation of catalysts method of claim 1 the steps include:
A) with 2-acetyl group-1, aniline reaction Synthetic 2-the imido grpup-1 of 10-phenanthroline and replacement, 10-phenanthroline part: 2-acetyl group-1, the aniline of 10-phenanthroline and different replacements is by 1: 1.2-1: 1.4 molar ratio, with the p-methyl benzenesulfonic acid is that condensation catalyst is respectively in ethanol or reflux in toluene, perhaps in silester, under 140-150 ℃, add thermal response 1-2 days, after products therefrom removes and desolvates, at alkali alumina is chromatography on the carrier packed column, adopt benzinum: ethyl acetate=4: 1 is eluent, obtain 2-imido grpup-1, the pure component of 10-phenanthroline boils off solvent and obtains yellow solid;
B) the 2-imido grpup-1 that obtains with step a, 10-phenanthroline part respectively with FeCl 24H 2O, CoCl 2Or NiCl 26H 2The O reaction can obtain complex: with FeCl 24H 2O, CoCl 2Or NiCl 26H 2The ethanolic solution of O in molar ratio 1: 1-1: 1.2 are added drop-wise to 2-imido grpup-1, in the solution of 10-phenanthroline part, and stirring at room reaction 3 to 12 hours, the sedimentation and filtration of generation also obtains 2-imido grpup-1,10-phenanthroline metal complex with ether washing back drying.
5. according to the preparation method of claim 4, wherein the aniline of different substituents is selected different solvents and dehydrating agent for use in step a.
6. the purposes of the described catalyst of claim 1 in catalyzed ethylene oligomerisation and polymerisation, this catalyst is with the chlorination 2-imido grpup-1 in the claim 1,10-phenanthroline iron (II), cobalt (II) or nickel (II) complex are major catalyst, and co-catalyst is selected from aikyiaiurnirsoxan beta, alkyl aluminum compound and chlorination alkyl aluminum.
7. according to the purposes of claim 6, wherein said aikyiaiurnirsoxan beta is a MAO.
8. according to the purposes of claim 6, wherein said alkyl aluminum and chlorination alkyl aluminum comprise trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, tri-n-octylaluminium, diethylaluminum chloride, ethylaluminium dichloride.
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