CN1651142A - Catalyst component used for ethylene oligomerization, preparing process and application thereof - Google Patents
Catalyst component used for ethylene oligomerization, preparing process and application thereof Download PDFInfo
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Abstract
A catalyst for the oligomerization of ethene and its preparing process are disclosed. Its advantages are high catalytic activity, long service life and low cost.
Description
Technical field
The present invention relates to a kind of olefin(e) oligomerization that is used for, particularly relate to catalytic component, preparation method and application thereof that alkene four gathers.
Technical background
As everyone knows, linear alpha-alkenes such as octene-1, hexene-1 are important chemical product and intermediate, are widely used in fields such as polyethylene comonomer, plasticizer alcohol, essence and flavoring agent, synthetic lubricant fluid and oil dope.Octene-1, hexene-1 are used as comonomer can obviously improve poly density, improves mechanical performances such as its tear-proof and hot strength.When being used as plasticizer alcohol, can make low-temperature pliability, processability, the outdoor weather resistance of polyethylene products better, be particularly useful for making cable and wire, auto parts machinery or decoration etc.
Be worth although octene-1 has important use in chemical industry, also do not have the technology of ethene four poly-high selectivity synthesizing octenes-1 at present.The carbon number distribution of the product that traditional ethylene oligomerization technology obtains meets Schulz-Flory and distributes, and this distribution makes the content of octene-1 in the oligomerization product can not be too high.For example US6184428 discloses a kind of Raney nickel, and the employing boron compound is a co-catalyst, can the catalyzed ethylene oligomerisation obtains the mixture of linear alpha-alkene, and wherein the content of octene-1 accounts for 19%.SHOP technology (US3676523, US3635937) is used similar catalyst system and catalyzing, and the content of octene-1 accounts for 11% in the oligomerization product.Other typical ethylene oligomerization technology, (BP/Amoco, in ethylene oligomerization technology US3906053), the content of octene-1 is generally 13～25% as Chevron technology (DE1443927), the ethyl corporation of Gulf Oil Corporation.The chromium-based catalysts system is used for ethylene trimer 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 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, the content of its octene-1 also lower (＜20%).
Recently the ethene four poly-three-way catalyst systems of report can high selectivity synthesizing octene-1 (WO2004/056478A1), and the content of octene-1 reaches 60% in its purpose product.Four-way catalyst system of the present invention under the same conditions, the content of octene-1 is better than WO2004/056478A1 in the purpose product.
Summary of the invention
The objective of the invention is to remedy the deficiencies in the prior art part, and the preparation of a kind of catalyst system and catalyzing that comprises three or four components that heteroatomic part (a), transistion metal compound (b), organo-metallic compound activator (c) and promoter (d) forms, catalyst system and catalyzing is provided and is used for olefin(e) oligomerization, highly-selective preparation octene-1 particularly.
The object of the invention can realize by following measure: be used for the catalytic component of ethylene oligomerization, comprising a kind of catalyst system and catalyzing, described heteroatomic part (a) that contains that contains heteroatomic part (a), a kind of transistion metal compound (b), a kind of organo-metallic compound activator (c) and a kind of containing/do not contain three or four components that promoter (d) is formed is to meet the compound shown in the following general formula (I):
Wherein, group A and D are preferably identical or different, can be selected from the group that contains phosphorus, nitrogen, sulphur atom; B is preferably a linking group or single atom, can be selected from C, N, P atom; Also can be selected from alkyl and derivative thereof, aryl and derivative thereof; R
5Preferably can be selected from the alkyl of hydrogen, straight or branched; Also can be selected from monocycle and polyaromatic and derivative thereof; Also can be selected from halogen atom; R
1, R
2, R
3, R
4Preferably can be selected from phenyl, substituted-phenyl and derivative thereof; The described heteroatomic part (a) that contains also can be to contain construction unit shown in two or more general molecular formula (I) connects formation by group or chemical bond noval chemical compound; Said transistion metal compound (b) is the compound of chromium, molybdenum, tungsten, titanium, tantalum, vanadium, zirconium, iron, nickel, palladium; Said organo-metallic compound activator (c) is alkyl aluminum compound, aluminium alkoxide compound, organoboron compound, organic salt, inorganic acid and inorganic salts, also can be one or more the mixture in them; Described promoter (d) is a kind of aromatic hydrocarbons or haloarene compounds that contains at least two halogen atoms of a quilt in the haloalkyl replacement of the alkyl of alpha-position replacement on aromatic ring at least; In the described catalyst, the component (a) and (b) that comprise, (c) and mol ratio (d) are (a): (b): (c): (d)=1: 0.5～100: 0.1～5000: 0～500; Three or four components with (a) and (b), (c), (d) form are pre-mixed; Or can join directly that to carry out original position in the reaction system synthetic; Described catalytic component is used for ethylene oligomerization, is reflected in the inert solvent to carry out, and 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 the product that catalyst system and catalyzing contains following component in detail:
(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, can be selected to contain phosphorus, arsenic, antimony, bismuth, nitrogen, the equiatomic group of sulphur, and also can be single atom; B is a linking group, can be selected from alkyl, substituted hydrocarbon radical and contain heteroatomic substituted hydrocarbon radical, and as methylene, dimethylated methylene base, 1,2-ethane, 1,2-phenylene, 1,2-propane, 1, the adjacent diphenol, 1 of 2-, 2-dimethylhydrazine; Also can be single atom, ion, as boron, silicon, phosphorus, nitrogen, sulphur etc.B can not have yet, and A directly directly is connected by chemical bond with D; R
5Can be selected from alkyl, alkenyl, cycloalkyl, aryl, aryl alkyl, alkylaryl or the fused ring aryl of hydrogen, halogen, straight or branched, also can be to contain heteroatomic group, as contain the group of N, siliceous group and their derivative; R
5Preferably isopropyl, the tert-butyl group, cyclohexyl, aryl and their derivative.
R
1, R
2, R
3, R
4Can be benzyl, phenyl, tolyl, xylyl, 2,4,6-trimethylphenyl, 3,5-dimethylbenzene methyl, two phenyl, naphthyl, anthryl, methoxyl group, ethyoxyl, phenoxy group, toloxyl, dimethylamino, first and second amino, sulfur phenenyl, pyridine radicals, sulphur ethyl, sulphur phenoxy group, trimethyl silicon based, methyl, ethyl, vinyl, propyl group, butyl, acrylic, propinyl, cyclopenta, 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.Preferably chromium, zirconium, titanium compound, best is chromium compound.Selectable chromium compound comprises general formula CrR
n mThose shown compounds, R in the formula
nBe organic negative ion or neutral molecule, R
nIn contain 1～10 carbon atom usually, n is 0～6 integer, the valence state of chromium is 0～6 valency.Concrete R
nGroup is as being organic matter or its group that contains carboxyl, beta-diketon base and alkyl.Consider that from the angle that is easy to dissolve chromium compound preferably comprises chromic acetate, isooctyl acid chromium, caprylic acid chromium, chromium acetylacetonate, diisoamyl diene chromium, dibenzene-chromium, CrCl with easy operating
3(THF)
3, (phenyl) tricarbonyl chromium, chromium carbonyl a kind of and or multiple mixture.Best chromium compound is CrCl
3(THF)
3, isooctyl acid chromium, chromium acetylacetonate.
(3) a kind of organo-metallic compound activating agent (c)
Selectable organo-metallic compound comprises alkyl aluminum compound, aluminium alkoxide compound, organoboron compound, organic salt, inorganic acid and inorganic salts.Particularly be selected from various trialkylaluminiums and aluminium alkoxide compound, as aikyiaiurnirsoxan beta of triethyl aluminum, triisobutyl aluminium, three n-butylaluminum, tri-n-hexyl aluminum, tri-n-octylaluminium, MAO, ethyl aikyiaiurnirsoxan beta, isobutyl aluminium alkoxide and modification etc.Also can use aluminum alkyl halide, alkyl aluminum hydride or alkylaluminium sesquichloride, as AlEt
2Cl and Al
2Et
3Cl
3, also can be and above-mentioned one or more alkyl aluminums mentioned or the mixture of aikyiaiurnirsoxan beta.Organic salt activator such as lithium methide, methyl-magnesium-bromide etc.; Inorganic acid and inorganic salts activator such as tetrafluoro boric acid etherate, tetrafluoroborate, hexafluoro antimonate etc.Organoboron compound comprises boroxin, sodium borohydride, boron triethyl, three (pentafluorophenyl group) boron, tri butyl boron hydrochlorate etc.
(4) a kind of promoter (d)
Can add or not add promoter in the catalyst of the present invention, but add the selectivity that can improve activity of such catalysts and purpose product 1-octene after the promoter.Preferred concrete promoter 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 fluoromethane benzene, ortho position three chloro fluoromethane benzene, ortho position three bromo fluoromethane benzene, ortho position two fluoro fluoromethane 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 methyl bromide benzene, ortho position three chloro methyl bromide benzene, ortho position three bromo methyl bromide benzene, ortho position dichloro-methyl bromobenzene, ortho position dichloro-methyl bromobenzene, ortho position two bromo methyl bromide 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, 2,6-dibromo benzal chloride, 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 promoter is: ortho position three chloro fluoromethane 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-diisopropyl 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 chlorinated diphenyl base phosphorus (A3).A3 and aminated compounds react and obtain containing heteroatomic part (a).
Containing heteroatomic part (a) in the catalyst 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 organo-metallic compound activator (c) in the catalyst is preferably from 1: 1～1000: 1, more preferably from 1: 1～200: 1.
Halogen-containing promoter can add or not add, but can improve the selectivity of activity of such catalysts and purpose product 1-octene after adding.Containing heteroatomic part (a) in the catalyst can be from 1: 0～1: 500 with the mol ratio of promoter.
(I) the heteroatomic part described in also can be one or more unit as (I) formula structure, combines by group, chemical bond or intermolecular force etc.As obtain the compound of bridging, dendroid and star, also can be the polymer that is incorporated into the producing high-molecular that forms on the macromolecular chain.More typically but be not be used to limit of the present invention, as 1, the two (N (P (phenyl) of 2-
2)
2)-benzene, 1, the two (N (P (phenyl) of 4-
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 promoter, can pass through liquid phase reactor, as under the effect of solvent, reacting selectable solvent such as toluene, benzene and derivative thereof etc.; Also can pass through solid phase reaction; Also can generate catalyst 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 promoter.The process of this reaction also is ageing (pre-complexing) process of catalyst.
Ethene four poly-reactions are mainly carried out in the inert solvent.Selectable solvent comprises alkane, aromatic hydrocarbons, halogenated hydrocarbons, alkene etc.Typical solvent includes, but are not limited to benzene,toluene,xylene, isopropylbenzene, normal heptane, n-hexane, hexahydrotoluene, cyclohexane, 1-hexene, 1-octene, ionic liquid etc.
Preparation of catalysts is that one or more that contain heteroatomic part (a), transistion metal compound (b), organo-metallic compound activator (c), promoter (d) are pre-mixed; Also can join directly that to carry out original position in the reaction system synthetic containing heteroatomic part (a), transistion metal compound (b), organo-metallic compound activator (c), promoter (d);
The temperature of ethene four poly-reactions can be carried out preferred 50 ℃～150 ℃ in 0 ℃～200 ℃.The pressure of ethene four poly-reactions can carry out under the pressure of 0.1MPa～20MPa, preferred 1.0MPa～10MPa.Catalyst concentration can be 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.
Four-way catalyst system of the present invention is used for ethylene oligomerization, particularly ethene four is poly-, compared with prior art have following advantage: catalyst activity height, purpose product octene-1 selectivity height, catalyst synthesize characteristics such as simple, that cost is low, catalyst life is long, C in the product
6～C
8Quality percentage composition＞90% of linear alpha-alkene, C
8Quality percentage composition＞60% of linear alpha-alkene.
Description of drawings
Fig. 1 is the structural formula of embodiment 1 (a), 2 (a), 3 (a), 4 (a), 5 (a), 10 (a), 11 (a), 12 (a)
The specific embodiment
Enumerate 12 embodiment and 1 Comparative Examples below, the present invention is further specified, rather than be used for limiting the scope of the invention.
Embodiment 1
1, preparation (diphenyl) phosphorus nitrogen (isopropyl) phosphorus (diphenyl) part (C
27H
27NP
2)
(1) preparation N, N-diisopropyl dichlor-phosphoryl amine
Through N
2Fully add toluene (100mL) in the 250mL reactor that the band of displacement stirs, add PCl through processed
3(21.87mL 0.25mol), and cools to-20 ℃.(70mL 0.5mol), stirs and rises to room temperature after 3 hours and continued to react 2 hours again, filters then, dry product 38.1g (0.19mol, 74%) to add diisopropylamine under the room temperature while stirring lentamente.
(2) preparation phenyl-magnesium-bromide lattice reagent
Through N
2Add through the THF of processed (100mL) in the 250mL reactor of the band stirring of fully replacing, and the magnesium powder (9.11g, 0.375mol), ice bath cooling and slow dropping bromobenzene (11.775g, 0.075mol).After 2 hours, add hot reflux continuation reaction and obtained lattice reagent in 2 hours.
(3) preparation diphenyl phosphorus chloride
Through N
2Fully add through the THF of processed (100mL) in the 250mL reactor that the band of displacement stirs, add N, N-diisopropyl phosphorus dichloride acid amides (6.64mL 36mmol), is cooled to 0 ℃, slowly add phenyl-magnesium-bromide lattice reagent (6.52g, 36mmol).Rose to room temperature reaction 12 hours.Reactant mixture dilutes with cyclohexane then, and with dry HCl gas bubbling 1 hour, filters, and drying obtains chlorinated diphenyl base phosphorus.
(4) preparation (diphenyl) phosphorus nitrogen (isopropyl) phosphorus (diphenyl)
Through N
2Fully add carrene (20mL) in the 100mL reactor that the band of displacement stirs through processed, triethylamine (3.75mL), diphenyl phosphorus chloride (1.326mL 7.2mol), is 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 of catalysts
Through N
2Fully add toluene (10mL) in the 100mL reactor that the band of displacement stirs through processed, 1.4mol/L MAO (MAO) toluene solution (7.0mL, 9.9mmol), (diphenyl) phosphorus nitrogen (isopropyl) phosphorus (diphenyl) is (67.8 μ mol) (29mg), CrCl
3(THF)
3(12mg, 33 μ mol), standby behind the room temperature reaction 5min.
3, ethylene oligomerization
The autoclave of 500mL is heated to and vacuumizes 2 hours, charges into ethene through nitrogen replacement for several times, cools to predetermined temperature, adds toluene (200mL) and above-mentioned catalyst through processed.Carrying out oligomerisation reaction under 40 ℃, the pressure of 2.4MPa, with ice bath cooling, release, is 10% acidifying ethanol cessation reaction with mass fraction behind the reaction 30min.Obtain oligomerization product 11.4g, catalyst activity is 7.13 * 10
5G oligomer/mol Cr.h.The distribution of oligomerization product sees Table 1.
Embodiment 2
With embodiment 1.R
5Group is a cyclohexyl.Obtain oligomerization product 18.3g, catalyst activity is 1.14 * 10
6G oligomer/mol Cr.h.The distribution of oligomerization product sees Table 1.
Embodiment 3
With embodiment 1.Difference is R
5Group is a fluorenyl.Obtain oligomerization product 16.6g, catalyst activity is 1.03 * 10
6G oligomer/mol Cr.h.The distribution of oligomerization product sees Table 1.
Embodiment 4
1, preparation 1, the two (N (P (phenyl) of 4-
2)
2)-benzene part (C
54H
44N
2P
4)
(1), (2), (3) are with embodiment 1.
(4) preparation 1, the two (N (P (phenyl) of 4-
2)
2)-benzene
Through N
2Fully add carrene (20mL) in the 100mL reactor that the band of displacement stirs through processed, triethylamine (3.75mL), diphenyl phosphorus chloride (1.326mL 7.2mmol), is cooled to 0 ℃, slowly adds 1, and the 4-phenylenediamine (0.19g, 1.8mmol).Rise to room temperature behind the stirring reaction 30min and continue reaction 12 hours.Filtration, drying obtain product (0.8g, 52.3%).
2, Preparation of catalysts
Through N
2Fully add toluene (10mL) in the 100mL reactor that the band of displacement stirs through processed, and the MAO toluene solution of 1.4mol/L (7mL, 9.9mol), preparation 1, the two (N (P (phenyl) of 4-
2)
2)-benzene (27mg, 67.8 μ mol), CrCl
3(THF)
3(12mg, 33 μ mol), standby behind the room temperature reaction 5min.
3, ethylene oligomerization
With embodiment 1.Obtain oligomerization product 15.0g, catalyst activity is 9.34 * 10
5G oligomer/mol Cr.h.The distribution of oligomerization product sees Table 1.
Embodiment 5
1, preparation 1, the two (N (P (phenyl) of 2-
2)
2)-ethane part (C
50H
44N
2P
4)
With embodiment 4.Different heres are that two linking groups between the construction unit are ethylidene.Obtain oligomerization product 19.2g, catalyst activity is 1.2 * 10
6G oligomer/mol Cr.h.The distribution of oligomerization product sees Table 1.
Embodiment 6
With embodiment 1.Difference is that catalytic component is (a) and (b), (c), (d) four kinds of catalyst components.Wherein (d) is three chloro methylbenzene, and addition is 0.2mmol.Obtain oligomerization product 12.4g, catalyst activity is 7.69 * 10
5G oligomer/mol Cr.h.
Embodiment 7
With embodiment 1.Difference is that (a) and (b), (c) three kinds of catalyst components original position in polymerization process is synthetic.Obtain oligomerization product 11.8g, catalyst activity is 7.34 * 10
5G oligomer/molCr.h.The distribution of oligomerization product sees Table 1.
Embodiment 8
With embodiment 1.Difference is that reaction pressure is 4.2MPa.Obtain oligomerization product 19.2g, catalyst activity is 1.2 * 10
6G oligomer/mol Cr.h.The distribution of oligomerization product sees Table 1.The distribution of oligomerization product sees Table 1.
Embodiment 9
With embodiment 1.Difference is that reaction temperature is 80 ℃.Obtain oligomerization product 26.8g, catalyst activity is 1.67 * 10
6G oligomer/mol Cr.h.The distribution of oligomerization product sees Table 1.
Embodiment 10
1, preparation (4-methoxybenzene)
2Phosphorus nitrogen (isopropyl) phosphorus (4-methoxybenzene)
2Part (C
31H
35NO
4P
2)
(1) with embodiment 1.
(2) preparation 4-methoxyphenyl magnesium bromide lattice reagent
Through N
2Add through the THF of processed (100mL) in the 250mL reactor of the band stirring of fully replacing, and the magnesium powder (9.11g, 0.375mol), ice bath cooling and slow dropping 4-methoxyl group bromobenzene (9.39ml, 0.075mol).After 2 hours, add hot reflux continuation reaction and obtained lattice reagent in 2 hours.
(3) two (tetramethoxy phenyl) phosphorus chloride of preparation
With embodiment 1.
(4) two (4-methoxyphenyl) phosphorus nitrogen (isopropyl) phosphorus of preparation two (4-methoxyphenyl)
Through N
2Fully add carrene (20mL) in the 100mL reactor that the band of displacement stirs through processed, triethylamine (3.75mL), diphenyl phosphorus chloride (1.326mL 7.2mol), is 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 of catalysts
Through N
2Fully add toluene (10mL) in the 100mL reactor that the band of displacement stirs, (tetramethoxy benzene) through processed
2Phosphorus nitrogen (isopropyl) phosphorus (tetramethoxy benzene)
2(30mg, 67.8 μ mol), chromium acetylacetonate (0.033mmol), MAO (toluene solution of 1.4mol/L) 7mL (9.9mmol), promoter three chloro methylbenzene 0.2mmol, standby behind the room temperature reaction 5min.
3, ethylene oligomerization
The autoclave of 500mL is heated to and vacuumizes 2 hours, charges into ethene through nitrogen replacement for several times, cools to predetermined temperature, adds toluene (80mL) and above-mentioned catalyst through processed.Carrying out oligomerisation reaction under 65 ℃, the pressure of 3.0MPa, with ice bath cooling, release, is 10% acidifying ethanol cessation reaction with mass fraction behind the reaction 30min.Obtain oligomerization product 20.5g, catalyst activity is 1.22 * 10
6G oligomer/mol Cr.h.The distribution of oligomerization product sees Table 1.
Embodiment 11
1, preparation (4-methylbenzene)
2Phosphorus nitrogen (isopropyl) phosphorus (4-methylbenzene)
2Part
With embodiment 10, difference is R
1, R
2, R
3, R
4Be the 4-methylbenzene.Obtain oligomerization product 19.5g, catalyst activity is 1.21 * 10
6G oligomer/mol Cr.h.The distribution of oligomerization product sees Table 1.
Embodiment 12
1, preparation (4-chlorobenzene)
2Phosphorus nitrogen (isopropyl) phosphorus (4-chlorobenzene)
2Part
With embodiment 10, difference is R
1, R
2, R
3, R
4Be the 4-chlorphenyl.Obtain oligomerization product 22.4g, catalyst activity is 1.43 * 10
6G oligomer/mol Cr.h.The distribution of oligomerization product sees Table 1.
Comparative Examples 1
With embodiment 10, difference is that catalyst is (a) and (b), (c) three components.Obtain oligomerization product 19.3g, catalyst activity is 1.17 * 10
6G oligomer/mol Cr.h.The distribution of oligomerization product sees Table 1.
The experiment condition and the catalyst activity of embodiment 1～12 and Comparative Examples 1 see Table 2.
The contrast of table 1 oligomerization product carbon number distribution
Product carbon number distribution embodiment 1 embodiment 2 embodiment 3 embodiment 4 embodiment 5 embodiment 6 embodiment 7 embodiment 8 embodiment 9 embodiment 10 embodiment 11 embodiment 12 Comparative Examples 1
C
4(wt％ 0.81 0.61 0.73 0.45 0.01 0.691 0.73 0.41 0.92 0.81 0.96 0.69 3.2
C
6(wt％) 22.77 20.82 18.31 19.4 33.81 21.65 21.82 31.12 23.4 19.81 21.32 19.38 26.0
C
8(wt％) 72.7 73.38 75.25 71.24 61.98 70.3 72.38 63.33 67.24 65.98 71.3 68.52 50.1
C
10(wt％) 1.44 1.6 1.96 2.05 1.36 2.31 1.49 2.36 2.12 3.36 1.31 2.49 4.2
C
12(wt％) 1.1 1.14 1.59 1.69 1.86 1.97 1.04 1.79 1.48 4.86 1.97 2.43
C
14(wt％) 0.33 0.57 0.44 0.52 0.85 1.29 0.75 0.85 1.01 2.85 1.29 1.75
C
16(wt％) 0.39 0.76 0.63 0.96 0.07 0.56 0.66 0.07 0.96 1.07 0.56 1.66
C
18(wt％) 0.26 0.69 0.48 0.95 0.03 0.99 0.69 0.03 0.95 1.03 0.99 1.69
C
20(wt％) 0.23 0.33 0.31 0.83 0.03 0.23 0.33 0.03 0.83 0.22 0.3 1.28
C
22(wt％) -- 0.11 0.16 0.62 0.01 -- 0.11 0.01 0.62 0.01 -- 0.11 C
12 +：16
C
24(wt％) -- -- 0.09 0.47 -- -- -- -- 0.47 -- -- -- ％
C
26(wt％) -- -- 0.04 0.35 -- -- -- -- -- -- --
C
28(wt％) -- -- -- 0.27 -- -- -- -- -- -- --
C
30(wt％) -- -- -- 0.13 -- -- -- -- -- -- --
C
32(wt％) -- -- -- 0.08 -- -- -- -- -- -- --
-- -- -- -- -- -- -- -- --
1-C
6 =Selectivity
-
76.87 76.91 75.9 74.74 88.55 73.21 74.99 83.07 72.33 80.1 75.26 74.12
a(wt％)
1-C
8 =Selectivity
93.5
99.07 97.82 98.67 97.9 99.54 98.7 97.28 98.44 98.91 98.9 99.04 98.8
b(wt％)
aBe meant C
6Middle 1-C
6 =Percentage composition.
bBe meant C
8Middle 1-C
8 =Percentage composition.
The experiment condition of table 2 embodiment 1～12 and Comparative Examples 1 and catalyst activity
Catalyst concn
(a) (b) (c) (d) catalyst activity
Implement
The reaction temperature reaction pressure
R
1～R
4 R
5
(mmol catalyst synthesis mode addition addition addition addition 10
5The g oligomer
Example
(℃) (MPa)
Cr/L) μmol μmol mmol mmol /mol?Cr.h
1 propyloxy phenyl base 40 2.4 10 synthesizes 67.8 32 9.9-7.13 in advance
2 benzyl ring hexyls 40 2.4 10 synthesize 67.8 32 9.9-11.4 in advance
3 phenyl fluorenyls 40 2.4 10 synthesize 67.8 32 9.9-10.3 in advance
4 phenyl bridgings 40 2.4 10 synthesize 67.8 32 9.9-9.34 in advance
5 ethidene bridged linkages 40 2.4 10 synthesize 67.8 32 9.9-12.4 in advance
6 propyloxy phenyl bases 40 2.4 10 synthesize 67.8 32 9.9 0.2 7.69 in advance
7 propyloxy phenyl bases, 40 2.4 10 original positions synthetic 67.8 32 9.9-7.34
8 propyloxy phenyl bases 40 4.2 10 synthesize 67.8 32 9.9-12.0 in advance
9 propyloxy phenyl bases 80 2.4 10 synthesize 67.8 32 9.9-16.7 in advance
The 4-first
10 oxygen benzene isopropyls 65 3.0 10 synthesize 67.8 32 9.9 0.2 12.2 in advance
Base
The 4-first
11 isopropyls 65 3.0 10 synthesize 67.8 32 9.9 0.2 12.1 in advance
Phenyl
4-chlorine
12 isopropyls 65 3.0 10 synthesize 67.8 32 9.9 0.2 14.3 in advance
Phenyl
The 4-first
Contrast
Oxygen benzene isopropyl 65 3.0 10 synthesizes 67.8 32 9.9-11.7 in advance
Example 1
Base
Claims (9)
1, the catalytic component that is used for ethylene oligomerization is characterized in that comprising a kind of catalyst system and catalyzing that contains heteroatomic part (a), a kind of transistion metal compound (b), a kind of organo-metallic compound activator (c) and a kind of containing/do not contain three or four components that promoter (d) is formed.
2,, it is characterized in that the described heteroatomic part (a) that contains is to meet the compound shown in the following general formula (I) according to the catalytic component of claim 1:
Wherein, group A and D, identical or different, can be selected from the group that contains phosphorus, nitrogen, sulphur atom; B is a linking group or single atom, can be selected from C, N, P atom; Also can be selected from alkyl and derivative thereof, aryl and derivative thereof; R
5Can be selected from the alkyl of hydrogen, straight or branched; Also can be selected from monocycle and polyaromatic and derivative thereof; Also can be selected from halogen atom; R
1, R
2, R
3, R
4Can be selected from phenyl, substituted-phenyl and derivative thereof.
3, according to the catalytic component of claim 1, it is characterized in that the described heteroatomic part (a) that contains, also can be to contain construction unit shown in two or more general molecular formula (I) connects formation by group or chemical bond noval chemical compound.
According to the catalytic component of claim 1, it is characterized in that 4, said transistion metal compound (b) is the compound of chromium, molybdenum, tungsten, titanium, tantalum, vanadium, zirconium, iron, nickel, palladium.
According to the catalytic component of claim 1, it is characterized in that 5, said organo-metallic compound activator (c) is alkyl aluminum compound, aluminium alkoxide compound, organoboron compound, organic salt, inorganic acid and inorganic salts.It also can be one or more the mixture in them.
According to the catalytic component of claim 1, it is characterized in that 6, described promoter (d) is a kind of aromatic hydrocarbons or haloarene compounds that contains at least two halogen atoms of a quilt in the haloalkyl replacement of the alkyl of alpha-position replacement on aromatic ring at least.
7,, it is characterized in that in the described catalyst that the component (a) and (b) that comprise, (c) and mol ratio (d) are (a): (b): (c): (d)=1: 0.5～100: 0.1～5000: 0～500 according to the catalytic component of claim 1.
8, a kind of preparation method according to claim 1 catalytic component is characterized in that three or four components of (a) and (b), (c), (d) composition are pre-mixed; Or can join directly that to carry out original position in the reaction system synthetic.
9, a kind ofly be used for ethylene oligomerization, be reflected in the inert solvent and carry out, can be selected from alkane, aromatic hydrocarbons, alkene, ionic liquid according to the described catalytic component of claim 1; 0 ℃～200 ℃ of the temperature of reaction, reaction pressure 0.1MPa～20MPa makes the ethylene oligomerization product.
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