CN103044181A - Method for preparing octylene-1 by ethylene tetramerization reaction - Google Patents
Method for preparing octylene-1 by ethylene tetramerization reaction Download PDFInfo
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Abstract
The invention relates to a method for preparing octylene-1 by ethylene tetramerization reaction. The catalyst is composed of components (a), (b), (c) and/or (d) in a mol ratio of 1:(0.5-100):(0.1-5000):(0-500), wherein the component (a) is 1,2-bis(N(P(phenyl2)2)-benzene, 1,4-bis(N(P(phenyl)2)2)-benzene or N(CH2CH2N(P(phenyl)2)2)3; the component (b) is CrCl3(THF)3, chromium isooctoate or chromium acetylacetone; the component (c) is the product of reacting an alkyl aluminum compound or aluminoxane compound with a modifier containing at least two heteroatoms; and the component (d) is ortho-trichloromethylfluorobenzene, ortho-trifluoromethylchlorobenzene, ortho-trichloromethylchlorobenzene, ortho-trifluoromethylchlorobenzene, or 2 or 6-dichloro-trichloromethylbenzene. The mass percentage of the C8 linear alpha-olefin in the product is greater than 60%.
Description
Technical field
The present invention relates to the method that a kind of ethene four poly-reactions prepare octene-1.
Background technology
The senior linear alpha-alkenes such as decylene-1, octene-1 and hexene-1 obtain by ethylene oligomerization reaction.But in the ethylene oligomerization technology of routine, generally can contain multiple high alpha-olefin in the product, meet Schulz-Flory distribution or Poisson and distribute.Disclose a kind of nickel catalyst such as US Patent No. 6184428, it comprises 2-diphenylphosphine phenylformic acid as chelating ligand, as the NiCl of nickel precursor
26H
2O and as the Tetraphenyl sodium borate of catalyst activator.Also disclose in this patent documentation, in the ethylene oligomerization reaction of using this nickel catalyst, the selectivity of octene-1 is 19%.SHOP technique (US 3676523, US 3635937) is used similar catalyst system, and the content of octene-1 accounts for 11% in the oligomerization product.Other typical ethylene oligomerization technique, in the ethylene oligomerization technique such as the Chevron technique (DE1443927) of Gulf Oil Corporation, ethyl corporation (BP/Amoco, US3906053), the content of octene-1 is generally 13～25%.The chromium-based catalysts system is used for ethylene trimerization and prepares hexene-1, has also realized suitability for industrialized production (US5550305), but the content of its principal product hexene-1 is generally all greater than 90%, and the content of octene-1 is (＜3%) seldom.
Fe-series catalyst (J.Am.Chem.Soc., 1998, the 120:7143 of the report such as Brookhart; Chem.Commun.1998,849; WO 99/02472) be used for ethylene oligomerization, the oligomerization product that obtains also is wide distribution, and the content of its octene-1 is lower (＜20%) also.
A lot of patents and bibliographical information have been arranged transition metal and aromatic ring ligand binding is formed for the method for alkene trimerization, four poly-or catalyzer that polymerization is used, such as WO 03/053890A1, WO03/053891, WO 03/054038, WO 04/056479A1, WO 04/056477A1, WO04/056480A1, WO 04/056478A1, US 2005187418A1, WO 05/123884A2 and WO 05/123633A1 etc.Recently the ethene four poly-three-way catalyst systems of report can high selectivity octene-1 (WO 2004/056478A1), and the content of octene-1 reaches 60% in its purpose product.Patent documentation WO 04/056479, US20090118117, US7906681, US7829749, US7511183, US7381857, US7297832 disclose by make ethene four gather to prepare the method for octene-1 with chromium-based catalysts, wherein said chromium-based catalysts contains and has phosphorus and nitrogen as heteroatomic heteroatom ligand, such as (phenyl)
2PN (sec.-propyl) P (phenyl)
2Deng.Patent CN101720253, CN101606605, CN101600722, CN101351424, CN101291734, CN1993180A, CN1741850A and CN1741849A etc. disclose the method that alkene four gathers, described catalyst system all comprises heteroatom ligand, transistion metal compound and promotor, and other described promotor is mainly aluminum alkyls, alkylaluminoxane and boron compound etc.Disclose in above-mentioned ethene four poly-technology and can surpass 70% octene-1 by ethene four being gathered prepare selectivity, wherein said chromium-based catalysts contains and has phosphorus and nitrogen as heteroatomic heteroatom ligand.
Disclosed ethene four poly-catalyzer and method have one or more lower column defects usually in science and patent documentation up to now: 1. product hexene-1 or octene-1 selectivity are low; 2. product purity low, the high carbon number product of part long-chain arranged; 3. form polymkeric substance, this causes reactor plugs, is difficult to continuous long-term operation; 4. poor catalyst activity, promotor cost are high; 5. severe reaction conditions, need high pressure, cause input, maintenance and energy cost high; 6. responsive to the promotor qualitative change.
Summary of the invention
The object of the present invention is to provide a kind of ethene four poly-reactions to prepare the method for octene-1; The catalyst system of four components that the used catalyzer of present method is comprised of heteroatomic part (a), transistion metal compound (b), organometallic compound activator (c) by containing at least two heteroatomic compound modifier modifications and promotor (d); Catalyst system possesses the performance that highly selective prepares octene-1.
Described a kind of ethene four poly-reactions of the present invention prepare the method for octene-1, ethene four poly-reactions are to carry out in the inert solvent, selectable solvent comprises alkane, aromatic hydrocarbons, halohydrocarbon, alkene, and typical solvent comprises benzene,toluene,xylene, isopropyl benzene, normal heptane, normal hexane, methylcyclohexane, hexanaphthene, 1-hexene, 1-octene, ionic liquid.
The temperature of ethene four poly-reactions is carried out preferred 50 ℃～150 ℃ in 0 ℃～200 ℃.The pressure of ethene four poly-reactions carries out under the pressure of 0.1MPa～20MPa, preferred 1.0MPa～10MPa.The concentration of catalyzer is from 0.01 μ mol metal/L～1000 μ mol metal/L in the reaction system, preferred 0.1 μ mol metal/L～10 μ mol metal/L.
The catalyst composition that is used for ethylene oligomerization is by containing heteroatomic part (a), transistion metal compound (b), the organometallic compound activator (c) by containing at least two heteroatomic compound modified dose of modifications, the catalyst system of three or four components that promotor (d) forms;
The described heteroatomic part (a) that contains is to meet the compound shown in the following general formula (I):
Wherein, group A and D are identical or different, are selected from the group that contains phosphorus, nitrogen, sulphur atom; B is a linking group or single atom, is selected from C, N, P atom; Or be selected from alkyl and derivative, aryl and derivative thereof; R
5Be selected from the alkyl of hydrogen, straight or branched; Or be selected from monocycle and polyaromatic and derivative thereof; Or be selected from halogen atom; R
1, R
2, R
3, R
4Be selected from phenyl, substituted-phenyl and derivative thereof; Describedly contain heteroatomic part (a), or contain two or more structural unit shown in the general formula (I) connects formation by group or chemical bond compounds that meet;
Said transistion metal compound (b) is the compound of chromium, molybdenum, tungsten, titanium, tantalum, vanadium, zirconium, iron, nickel or palladium;
Said organometallic compound activator (c) is alkylaluminium cpd or aluminium alkoxide compound and contains at least two interactional products of heteroatomic properties-correcting agent, or two or more aluminum alkylss or aikyiaiurnirsoxan beta and the interactional product of two or more properties-correcting agent;
It is described that to contain at least two heteroatomic properties-correcting agent are [Ph
3C] [Al{OC (CF
3)
3}
4], Ph
2C (Me) OAlMe
2, B (C
6F5)
3, phenylo boric acid, methyl-boron-dihydroxide, two valeryl two boron, BF
3, BCl
3, BBr
3Or BCl
3
Described promotor (d) is aromatic hydrocarbons or the haloarene compounds that halogenated alkane or a kind of haloalkyl that contains at least an alkyl that is replaced at alpha-position by at least two halogen atoms on aromatic ring replace;
In the described catalyst composition, the component that comprises (a), (b), (c) and mol ratio (d) are (a): (b): (c): (d)=1: 0.5～100: 0.1～5000: 0～500; Four components with (a), (b), (c), (d) form are pre-mixed; Or can join directly that to carry out original position in the reaction system synthetic; Described catalyst component is used for ethylene oligomerization, and reaction is carried out in the inert solvent, can be selected from alkane, aromatic hydrocarbons, alkene, ionic liquid; 0 ℃～200 ℃ of the temperature of reaction, reaction pressure 0.1MPa～20MPa makes the ethylene oligomerization product.
Describe catalyst system in detail and contain following component:
(1) at least a being selected from contained heteroatomic part (a) shown in the general formula (I)
In the formula, group A and D are identical or different, be selected to contain phosphorus, arsenic, antimony, bismuth, nitrogen, sulphur atom group, or single atom; B is a linking group, is selected from alkyl, substituted hydrocarbon radical and contains heteroatomic substituted hydrocarbon radical, and such as methylene radical, dimethylated methylene base, 1,2-ethane, 1,2-phenylene, 1,2-propane, 1, the adjacent diphenol, 1 of 2-, 2-dimethylhydrazine; Or single atom, ion, such as boron, silicon, phosphorus, nitrogen, sulphur.B or do not have makes A be connected chemical bond with D and directly connects; R
5Be selected from alkyl, alkenyl, cycloalkyl, aryl, arylalkyl, alkylaryl or the fused ring aryl of hydrogen, halogen, straight or branched, or contain heteroatomic group, as contain the group of N, siliceous group and their derivative; R
5Preferably sec.-propyl, the tertiary butyl, cyclohexyl, aryl and their derivative.
R
1, R
2, R
3, R
4Be phenmethyl, phenyl, tolyl, xylyl, 2,4,6-trimethylphenyl, 3,5-dimethylbenzene methyl, two phenyl, naphthyl, anthryl, methoxyl group, oxyethyl group, phenoxy group, tolyloxy, dimethylamino, the first and second amino, sulfur phenenyl, pyridyl, sulphur ethyl, sulphur phenoxy group, trimethyl silicon based, methyl, ethyl, vinyl, propyl group, butyl, propenyl, proyl, cyclopentyl, cyclohexyl, ferrocenyl, tetrahydrofuran base etc.Preferred R
1, R
2, R
3, R
4Be phenyl, substituted-phenyl, xylyl, two phenyl, naphthyl, sulfur phenenyl and ethyl.
(2) a kind of transistion metal compound (b)
Selectable transistion metal compound has the compound of chromium, molybdenum, tungsten, titanium, tantalum, vanadium, zirconium, iron, nickel, palladium etc.Preferably chromium, zirconium, titanium compound, best is chromium cpd.Selectable chromium cpd comprises general formula CrR
n mThose shown compounds, R in the formula
nBe organic negative ion or neutral molecule, R
nIn usually contain 1～10 carbon atom, n is 0～6 integer, the valence state of chromium is 0～6 valency.Concrete R
nGroup is as being organism or its group that contains carboxyl, beta-diketon base and alkyl.Consider that from the angle that is easy to dissolve with easy handling chromium cpd preferably comprises chromium acetate, isocaprylic acid chromium, n-caprylic acid chromium, chromium acetylacetonate, diisoamyl diene chromium, dibenzene-chromium, CrCl
3(THF)
3, (phenyl) tricarbonyl chromium, Chromium hexacarbonyl a kind of and or multiple mixture.Best chromium cpd is CrCl
3(THF)
3, isocaprylic acid chromium, chromium acetylacetonate.
(3) a kind of organometallic compound promoting agent (c)
Selectable organometallic compound activator (c) is alkylaluminium cpd or aluminium alkoxide compound and contains at least two interactional products of heteroatomic properties-correcting agent, also can be two or more aluminum alkylss or aikyiaiurnirsoxan beta and the interactional product of two or more properties-correcting agent; Particularly be selected from various trialkylaluminiums and aluminium alkoxide compound, such as aikyiaiurnirsoxan beta of triethyl aluminum, triisobutyl aluminium, three n-butylaluminum, tri-n-hexyl aluminum, tri-n-octylaluminium, methylaluminoxane, ethylaluminoxane, isobutyl aluminium alkoxide and modification etc.Or use aluminum alkyl halide, alkyl aluminum hydride or alkylaluminium sesquichloride, such as AlEt
2Cl and Al
2Et
3Cl
3, or with above-mentioned one or more aluminum alkylss of mentioning or the mixture of aikyiaiurnirsoxan beta.At least contain two heteroatomic properties-correcting agent such as Tetrafluoroboric acid etherate, a tetrafluoro borate, hexafluoro antimonate, boroxin, three (pentafluorophenyl group) boron, the tri butyl boron hydrochlorate, tributyl borate, boric acid three isopropyl junket, trityl four (pentafluorophenyl group) borate, 3,5-dimethylphenyl ammonium four (pentafluorophenyl group) borate, diethyl phenyl ammonium four (pentafluorophenyl group) borate, methyldiphenyl base ammonium four (pentafluorophenyl group) borate, ethyl phenylbenzene ammonium four (pentafluorophenyl group) borate, [Ph
3C] [Al{OC (CF
3)
3}
4], Ph
2C (Me) OAlMe
2, phenylo boric acid, methyl-boron-dihydroxide, two valeryl two boron, BF
3, BCl
3, BBr
3Or BCl
3
(4) a kind of promotor (d)
Promotor can be added or not add in the catalyzer of the present invention, but the activity of catalyzer and the selectivity of purpose product octene-1 can be improved after adding promotor.Preferred promotor of using comprises halogen-containing organic compound, but is not limited to following compounds:
Three fluoro methylbenzene, three chloro methylbenzene, three bromo methylbenzene, ortho position three fluoro methyl fluoride benzene, ortho position three chloro methyl fluoride benzene, ortho position three bromo methyl fluoride benzene, ortho position two fluoro methyl fluoride benzene, ortho position dichloro-methyl fluorobenzene, ortho position two bromo methyl chloride benzene, ortho position three fluoro methyl chloride benzene, ortho position three chloro methyl chloride benzene, ortho position three bromo methyl chloride benzene, ortho position two fluoro methyl chloride benzene, ortho position dichloro-methyl chlorobenzene, ortho position two bromo methyl chloride benzene, ortho position three fluoro monobromomethane benzene, ortho position three chloro monobromomethane benzene, ortho position three bromo monobromomethane benzene, ortho position dichloro-methyl bromobenzene, ortho position dichloro-methyl bromobenzene, ortho position two bromo monobromomethane benzene, 2,6-dichloro three fluoro methylbenzene, 2,6-dichloro three chloro methylbenzene, 2,6-dichloro three bromo methylbenzene, 2,6-dichloro two fluoro methylbenzene, 2,6-dichloro benzal chloride, 2,6-dichloro two bromo methylbenzene, 2,6-difluoro two fluoro methylbenzene, 2,6-difluoro three chloro methylbenzene, 2,6-difluoro three bromo methylbenzene, 2,6-difluoro benzal chloride, 2,5-difluoro two bromo methylbenzene, 2,6-dibromo three fluoro methylbenzene, 2,6-dibromo three chloro methylbenzene, 2,6-dibromo two fluoro methylbenzene, 2, the 6-Dibromo-dichloro is for methylbenzene, 2-fluoro-6-chloro-three fluoro methylbenzene, 2-fluoro-6-chloro-three chloro methylbenzene, 2-chloro-6-chloro-benzal chloride, 2-fluoro-6-chloro-two fluoro methylbenzene, 2-fluoro-6-chloro-three bromo methylbenzene, 2-fluoro-6-bromo-three fluoro methylbenzene, 2-chloro-6-bromo-three chloro methylbenzene, 2-chloro-6-bromo-two fluoro methylbenzene, 2-chloro-6-bromo-benzal chloride, 2-chloro-6-bromo-three fluoro methylbenzene, 2-chloro-6-bromo-three chloro methylbenzene, 2-fluoro-6-bromo-two fluoro methylbenzene, 2-fluoro-6-bromo-benzal chloride, wherein more effective promotor is: ortho position three chloro methyl fluoride benzene, ortho position three fluoro methyl chloride benzene, ortho position three chloro methyl chloride benzene, ortho position three fluoro methyl chloride benzene, 2,6-, two chloro-trichlorines are for methylbenzene.
Containing the synthetic of heteroatomic part (a) can carry out by the following method: at first by PCl
3And Diisopropylamine (PCl
3With the mol ratio of Diisopropylamine be 1: 2～1: 10) react and obtain product N, N-di-isopropyl phosphorus dichloride acid amides (A1).Magnesium powder and bromobenzene (mol ratio of magnesium powder and bromobenzene is 10: 1～1: 1) react and obtain lattice reagent phenyl-magnesium-bromide (A2).A1 and A2 react the product that obtains and react with dry HCl gas and obtain diphenyl antimony chloride base phosphorus (A3).A3 and aminated compounds react and obtain containing heteroatomic part (a).
Containing heteroatomic part (a) in the catalyzer can be from 1: 0.5～100 with the mol ratio of transistion metal compound (b).
The mol ratio 1: 0.1～1: 5000 that contains heteroatomic part (a) and organometallic compound activator (c) in the catalyzer is preferably from 1: 1～1: 1000, more preferably from 1: 1～1: 100.
Containing heteroatomic part (a) in the catalyzer can be from 1: 0～1: 500 with the mol ratio of promotor.
(I) the heteroatomic part described in, also can be one or more such as the unit of (I) formula structure, combine by group, chemical bond or Intermolecular Forces etc.As obtain the compound of bridging, dendroid and star, also can be the polymkeric substance that is incorporated into the high molecular that forms on the macromolecular chain.More typically but be not of the present invention be used to limiting, such as the two (N (P (phenyl) of 1,2-
2)
2)-benzene, Isosorbide-5-Nitrae-two (N (P (phenyl)
2)
2)-benzene, N (CH
2CH
2N (P (phenyl)
2)
2)
3Deng.
The reactive mode of the heteroatomic part (I), transistion metal compound, metal organic activator and organic compound promotor, can pass through liquid phase reaction, as under the effect of solvent, reacting selectable solvent such as toluene, benzene and its derivative etc.; Also can pass through solid state reaction; Also can generate catalyzer by in the oligomerisation reaction process, carrying out reaction in－situ.Reaction described here can be the reaction between a kind of, two kinds, three kinds and the four kinds of compounds of above-mentioned heteroatomic part, transistion metal compound, metal organic activator and organic compound promotor.The process of this reaction also is ageing (pre-complexing) process of catalyzer.
The preparation of catalyzer is containing heteroatomic part (a), transistion metal compound (b), being pre-mixed through containing at least two heteroatomic compound modified organometallic compound activators (c), promotor (d); Also can be containing heteroatomic part (a), transistion metal compound (b), joining directly through containing at least two heteroatomic compound modified organometallic compound activators (c), promotor (d) that to carry out original position in the reaction system synthetic;
Four-way catalyst system of the present invention is used for ethylene oligomerization, particularly ethene four is poly-, compared with prior art has following advantage: the characteristics such as the promotor consumption is few, catalyst activity is high, purpose product octene-1 selectivity high, catalyzer is synthetic simply, cost is low, catalyst life is long, C in the product
6～C
8The quality percentage composition of linear alpha-alkene＞90%, C
8The quality percentage composition of linear alpha-alkene＞60%.
Embodiment
The below enumerates 10 embodiment and 1 Comparative Examples, and the present invention is further specified.
Embodiment 1
1, preparation (phenylbenzene) phosphorus nitrogen (sec.-propyl) phosphorus (phenylbenzene) part (C
27H
27NP
2)
(1) preparation N, N-di-isopropyl dichlor-phosphoryl amine
Through N
2Add the toluene (100mL) through processed in the 250mL reactor that fully band of displacement stirs, add PCl
3(21.87mL, 0.25mol), and cool to-20 ℃.Add lentamente while stirring Diisopropylamine (70mL, 0.5mol) under the room temperature, stir and rise to room temperature after 3 hours and continued again to react 2 hours, then filter, dry product 38.1g (0.19mol, 74%).
(2) preparation phenyl-magnesium-bromide lattice reagent
Through N
2Add through the THF of processed (100mL) in the 250mL reactor that fully band of displacement stirs, magnesium powder (9.11g, 0.375mol), the ice bath cooling also slowly drips bromobenzene (11.775g, 0.075mol).After 2 hours, reflux continues reaction and obtained lattice reagent in 2 hours.
(3) preparation diphenyl phosphorus chloride
Through N
2Add through the THF of processed (100mL) in the 250mL reactor that fully band of displacement stirs, add N, N-di-isopropyl phosphorus dichloride acid amides (6.64mL, 36mmol), be cooled to 0 ℃, slowly add phenyl-magnesium-bromide lattice reagent (6.52g, 36mmol).Rose to room temperature reaction 12 hours.Then reaction mixture dilutes with hexanaphthene, and with dry HCl gas sparging 1 hour, filters, and drying obtains diphenyl antimony chloride base phosphorus.
(4) preparation (phenylbenzene) phosphorus nitrogen (sec.-propyl) phosphorus (phenylbenzene)
Through N
2Add the methylene dichloride (20mL) through processed in the 100mL reactor that fully band of displacement stirs, triethylamine (3.75mL), diphenyl phosphorus chloride (1.326mL, 7.2mol), be cooled to 0 ℃, slowly add Isopropylamine (0.28mL, 3.6mol).Rise to room temperature behind the stirring reaction 30min and continue reaction 12 hours.Filtration, drying obtain product (0.87g, 56.6%).
2, preparation modified active agent
At-78 ℃, under the vigorous stirring, with microsyringe 0.81mL redistilled water (45mmol) slowly is added drop-wise to and contains 6.84mL (50mmol) AlEt
3Toluene (50mL) solution in, after dropwising, make system naturally return to room temperature, continue reaction 12h, namely obtain the toluene solution of EAO.Be added dropwise to the toluene solution 50mL of pentafluorophenyl group boron (10mmol) in the mentioned solution, dropwise rear room temperature and kept 6 hours, obtain the activator of modification.
3, the preparation of catalyzer
Through N
2Add the toluene (10mL) through processed in the 100mL reactor that fully band of displacement stirs, toluene solution (the 20mL of the modified active agent of step 2 preparation, 10mmol), (phenylbenzene) phosphorus nitrogen (sec.-propyl) phosphorus (phenylbenzene) is (67.8 μ mol) (29mg), CrCl
3(THF)
3(12mg, 33 μ mol), for subsequent use behind the room temperature reaction 5min.
4, ethylene oligomerization
The autoclave of 500mL is heated to and vacuumizes 2 hours, is filled with ethene through nitrogen replacement for several times, cools to preset temperature, adds hexanaphthene (200mL) and above-mentioned catalyzer through processed.Carrying out oligomerisation reaction under 45 ℃, the pressure of 5.0MPa, with ice bath cooling, release, is 10% acidifying ethanol termination reaction with massfraction behind the reaction 30min.Obtain oligomerization product 40.75g, catalyst activity is 2.47 * 10
6G oligopolymer/mol Cr.h.The distribution of oligomerization product sees Table 1.
Embodiment 2
1, preparation (phenylbenzene) phosphorus nitrogen (sec.-propyl) phosphorus (phenylbenzene) part (C
27H
27NP
2) with embodiment 1.
2, preparation modified active agent
At-78 ℃, under the vigorous stirring, with microsyringe 0.81mL redistilled water (45mmol) slowly is added drop-wise to and contains 6.84mL (50mmol) AlEt
3Toluene (50mL) solution in, after dropwising, make system naturally return to room temperature, continue reaction 12h, namely obtain the toluene solution of EAO.In mentioned solution, be added dropwise to [Ph
3C] [Al (OC (CF
3)
3)
4] (10mmol) toluene solution 50mL, dropwise rear room temperature and kept 6 hours, obtain the activator of modification.
3, the preparation of catalyzer
With embodiment 1.The modified active agent that adds is modified active agent prepared in the present embodiment.
4, ethylene oligomerization
With embodiment 1.Obtain oligomerization product 6.38g, catalyst activity is 3.87 * 10
5G oligopolymer/mol Cr.h.The distribution of oligomerization product sees Table 1.
Embodiment 3
1, preparation (phenylbenzene) phosphorus nitrogen (sec.-propyl) phosphorus (phenylbenzene) part (C
27H
27NP
2) with embodiment 1.
2, preparation modified active agent
With embodiment 1.Difference is that two the heteroatomic properties-correcting agent that contain at least that add are the Tetrafluoroboric acid sodium compound.
3, the preparation of catalyzer
With embodiment 1.
4, ethylene oligomerization
With embodiment 1.Obtain oligomerization product 8.5g, catalyst activity is 5.15 * 10
5G oligopolymer/molCr.h.The distribution of oligomerization product sees Table 1.
Embodiment 4
Embodiment 2
1, preparation (phenylbenzene) phosphorus nitrogen (sec.-propyl) phosphorus (phenylbenzene) part (C
27H
27NP
2) with embodiment 1.
2, preparation modified active agent
With embodiment 1.Difference is that two the heteroatomic properties-correcting agent that contain at least that add are the boroxin compound.
3, the preparation of catalyzer
With embodiment 1.
4, ethylene oligomerization
With embodiment 1.Obtain oligomerization product 28.31g, catalyst activity is 1.72 * 10
6G oligopolymer/mol Cr.h.The distribution of oligomerization product sees Table 1.
Embodiment 5
1, preparation (phenylbenzene) phosphorus nitrogen (sec.-propyl) phosphorus (phenylbenzene) part (C
27H
27NP
2) with embodiment 1.
2, preparation modified active agent
With embodiment 1.Difference is that two the heteroatomic properties-correcting agent that contain at least that add are boron trichloride.
3, the preparation of catalyzer
With embodiment 1.
4, ethylene oligomerization
With embodiment 1.Obtain oligomerization product 59.68g, catalyst activity is 3.62 * 10
6G oligopolymer/mol Cr.h.The distribution of oligomerization product sees Table 1.
Embodiment 6
1, preparation (phenylbenzene) phosphorus nitrogen (sec.-propyl) phosphorus (phenylbenzene) part (C
27H
27NP
2) with embodiment 1.
2, preparation modified active agent
With embodiment 1.Difference is that two the heteroatomic properties-correcting agent that contain at least that add are boron trifluoride.
3, the preparation of catalyzer
With embodiment 1.
4, ethylene oligomerization
With embodiment 1.Obtain oligomerization product 65.98g, catalyst activity is 4.0 * 10
6G oligopolymer/mol Cr.h.The distribution of oligomerization product sees Table 1.
Embodiment 7
1, preparation (phenylbenzene) phosphorus nitrogen (sec.-propyl) phosphorus (phenylbenzene) part (C
27H
27NP
2) with embodiment 1.
2, preparation modified active agent
With embodiment 1.Difference is that two the heteroatomic properties-correcting agent that contain at least that add are triethyl borate.
3, the preparation of catalyzer
With embodiment 1.
4, ethylene oligomerization
With embodiment 1.Obtain oligomerization product 8.40g, catalyst activity is 5.0 * 10
5G oligopolymer/molCr.h.The distribution of oligomerization product sees Table 1.
Embodiment 8
1, preparation (phenylbenzene) phosphorus nitrogen (sec.-propyl) phosphorus (phenylbenzene) part (C
27H
27NP
2) with embodiment 1.
2, preparation promoting agent
With embodiment 1.Difference is not add to contain at least two heteroatomic properties-correcting agent.Activator directly uses EAO.
3, the preparation of catalyzer
With embodiment 1.
4, ethylene oligomerization
With embodiment 1.Obtain oligomerization product 6.14g, catalyst activity is 3.72 * 10
5G oligopolymer/mol Cr.h.The distribution of oligomerization product sees Table 1.
Embodiment 9
1, preparation (phenylbenzene) phosphorus nitrogen (sec.-propyl) phosphorus (phenylbenzene) part (C
27H
27NP
2) with embodiment 1.
2, preparation modified active agent
At-78 ℃, under the vigorous stirring, with microsyringe 0.81mL redistilled water (45mmol) slowly is added drop-wise to and contains 6.84mL (50mmol) AlEt
3Toluene (50mL) solution in, after dropwising, make system naturally return to room temperature, continue reaction 12h, namely obtain the toluene solution of EAO.After being added dropwise to the methylaluminoxane of 50mmol in the mentioned solution, drip the toluene solution 50mL of pentafluorophenyl group boron (10mmol), dropwise rear room temperature and kept 6 hours, obtain the activator of modification.
3, the preparation of catalyzer
With embodiment 1.
4, ethylene oligomerization
With embodiment 1.Obtain oligomerization product 119.46g, catalyst activity is 7.24 * 10
6G oligopolymer/mol Cr.h.The distribution of oligomerization product sees Table 1.
Embodiment 10
1, preparation (phenylbenzene) phosphorus nitrogen (sec.-propyl) phosphorus (phenylbenzene) part (C
27H
27NP
2) with embodiment 1.
2, preparation modified active agent
With embodiment 10, difference is that the amount of the MAO that adds is 10mmol.
3, the preparation of catalyzer
With embodiment 1.
4, ethylene oligomerization
With embodiment 1.Obtain oligomerization product 82.67g, catalyst activity is 5.01 * 10
6G oligopolymer/mol Cr.h.The distribution of oligomerization product sees Table 1.
Embodiment 11
1, preparation (phenylbenzene) phosphorus nitrogen (sec.-propyl) phosphorus (phenylbenzene) part (C
27H
27NP
2) with embodiment 1.
2, preparation modified active agent
With embodiment 1.
3, the preparation of catalyzer
With embodiment 1.Difference is to add (d) component tetrachloroethane 0.2mmol.
4, ethylene oligomerization
With embodiment 1.Obtain oligomerization product 45.30g, catalyst activity is 2.75 * 10
6G oligopolymer/mol Cr.h.The distribution of oligomerization product sees Table 1.
Embodiment 12
1, preparation (phenylbenzene) phosphorus nitrogen (sec.-propyl) phosphorus (phenylbenzene) part (C
27H
27NP
2) with embodiment 1.
2, preparation modified active agent
With embodiment 1.
3, the preparation of catalyzer
With embodiment 1.Difference is to add (d) component tetrachloroethane 0.5mmol.
4, ethylene oligomerization
With embodiment 1.Obtain oligomerization product 22.31g, catalyst activity is 1.35 * 10
6G oligopolymer/mol Cr.h.The distribution of oligomerization product sees Table 1.
The contrast of table 1 oligomerization product carbon number distribution
aRefer to C
6Middle 1-C
6 =Percentage composition.
bRefer to C
8Middle 1-C
8 =Percentage composition.
The experiment condition of table 2 embodiment 1～10 and catalyst activity
Claims (1)
1. an ethene four gathers the methods that reaction prepares octene-1, it is characterized in that:
Ethene four poly-reactions are to carry out in alkane, aromatic hydrocarbons, halohydrocarbon or alkene solvent;
Temperature of reaction is 0 ℃～200 ℃, and reaction pressure is 0.1MPa～20Mpa, and the concentration of catalyzer is from 0.01 μ mol metal/L～1000 μ mol metal/L;
Catalyzer 1: 0.5 in molar ratio～100: 0.1～5000: 0～500 forms by component (a), (b), (c) and/or (d);
Described component (a) is the two (N (P (phenyl) of 1,2-
2)
2)-benzene, Isosorbide-5-Nitrae-two (N (P (phenyl)
2)
2)-benzene or N (CH
2CH
2N (P (phenyl)
2)
2)
3
Described component (b) is CrCl
3(THF)
3, isocaprylic acid chromium or chromium acetylacetonate;
Described component (c) is alkylaluminium cpd or aluminium alkoxide compound and contains at least two interactional products of heteroatomic properties-correcting agent, or two or more aluminum alkylss or aikyiaiurnirsoxan beta and the interactional product of two or more properties-correcting agent;
It is described that to contain two heteroatomic properties-correcting agent are [Ph
3C] [Al{OC (CF
3)
3}
4], Ph
2C (Me) OAlMe
2, B (C
6F5)
3, phenylo boric acid, methyl-boron-dihydroxide, two valeryl two boron, BF
3, BCl
3, BBr
3Or BCl
3
Described component (d) be ortho position three chloro methyl fluoride benzene, ortho position three fluoro methyl chloride benzene, ortho position three chloro methyl chloride benzene, ortho position three fluoro methyl chloride benzene 2 or 6-two chloro-trichlorines for methylbenzene.
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