CN102407159B - Trimerisation And Oligomerisation Of Olefins Using A Chromium Based Catalyst - Google Patents
Trimerisation And Oligomerisation Of Olefins Using A Chromium Based Catalyst Download PDFInfo
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- CN102407159B CN102407159B CN201110225810.3A CN201110225810A CN102407159B CN 102407159 B CN102407159 B CN 102407159B CN 201110225810 A CN201110225810 A CN 201110225810A CN 102407159 B CN102407159 B CN 102407159B
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Abstract
The invention provides a mixed heteroatomic ligand for an oligomerisation of olefins catalyst, which ligand includes at least three heteroatoms, of which at least one heteroatom is nitrogen and at least two heteroatoms are not the same. The invention also provides a multidentate mixed heteroatomic ligand for an oligomerisation of olefins catalyst, which ligand includes at least three heteroatoms. At least one heteroatom may be nitrogen and at least 2 heteroatoms may not be the same.
Description
The divisional application that the application is the applying date is on December 19th, 2002, application number is 02825515.1 (corresponding international application no is PCT/ZA02/00217), denomination of invention is the application for a patent for invention of " olefin oligomerisation and the trimerization that use chromium-based catalysts ".
Technical field
The present invention relates to a kind of part and a kind of catalyst system, more specifically, relate to a kind of catalyst system and the method for olefin oligomerisation or trimerization.
Background technology
People carry out alkene to use chrome catalysts, and mainly the oligomerization of alpha-olefin gives and studies widely.More specifically, multiple chrome catalysts has been developed and for the trimerization of alkene.About this point, it is very important that ethylene trimer generates 1-hexene, because 1-hexene is except being used as specific chemical substance, it is also widely used in polymerization technique as monomer or comonomer.Such as, and the trimerization product obtained from long-chain olefin can be used as synthetic lubricant fluid (such as, poly alpha olefin/PAOs) well, and other various application, the component of drilling mud, and be used as the raw material of cleaning agent and plasticizer.
The chromium base ethylene trimer method of prior art comprises:
A) a kind of by making alkene and catalyst exposure, make the method for alkene generation trimerization reaction, the organo-aluminum compound that this catalyst contains chromium compound, is hydrolyzed with the water of specified quantitative, and the product (No. 4668838th, United States Patent (USP)) of electron donor ligand being selected from alkyl isonitrile, amine and ether;
B) a kind of ethylene trimer generates the method for 1-hexene, the method comprises and being contacted with the catalyst system of stabilisation by ethene, described catalyst system comprises chromium source, compound containing pyrroles, metal alkyl and aromatic compound (No. 0668105th, European patent);
C) a kind of method preparing alpha-olefin oligomer, it comprises by making described alpha-olefin and chromium-based catalyst systems react, carry out the oligomerization of alpha-olefin in a solvent, described catalyst system comprises at least one chromium compound, a kind of amine or metal amide, and a kind of combination of alkyl aluminum compound, chromium compound and alkyl aluminum compound do not contact with each other in advance (No. 5750817th, United States Patent (USP));
D) ethene oligomerization prepares a method for 1-butylene and/or 1-hexene, and wherein catalyst composition is by being R by least one chromium compound, at least one general formula
nal (R ' O)
3-naryloxy group aluminium compound and at least one other aryloxy group aluminium compound be obtained by mixing, wherein R is the alkyl radical containing the linear of 1-30 carbon atom or branching, R ' O is the aryloxy group free radical containing 6-80 carbon atom, n be selected from one of 0,1 and 2 integer; Other aryloxy group aluminium compound is selected from three (alkyl) aluminium compound, chlorination hydrocarbyl aluminium compound or bromination hydrocarbyl aluminium compound (No. 6031145th, United States Patent (USP));
E) a kind of method making ethene generation trimerization generate 1-hexene, described method comprises the many dentates phosphine, arsenic and/or the antimony complex that use and contain aikyiaiurnirsoxan beta and chromic salts, ethene is reacted and generates 1-hexene (No. 5811618th, United States Patent (USP)).
Summary of the invention
Below in conjunction with Summary of drawings the present invention.
In the accompanying drawings:
Fig. 1 represents the X-ray crystal structure of alchlor (two-(2-diphenyl phosphine-ethyl)-amine),
Fig. 2 represents the schematic diagram (flow chart) according to a detailed description of the invention of olefin oligomerisation process of the present invention.
The present invention has recognized the need to a kind of catalyst system, and it can be conducive to highly selective and produce 1-hexene, avoids producing a large amount of polyethylene common property things simultaneously.But this catalyst system also can be used in oligomerization or the trimerization, particularly alpha-olefin of other alkene.
In this, from prior art (such as No. 537609th, European patent), the chrome catalysts comprising multidentate amine coordination chromic salts compound and aikyiaiurnirsoxan beta or alkyl aluminum compound generally in optionally three polyethylene without remarkable result.This is demonstrated experimentally, as described in Example 1.
The present invention relates generally to how to pass through to use the chrome catalysts system comprised with the multidentate ligand of at least one amine functional group to meet the needs optionally using ethylene making 1-hexene at least in part.
Therefore, according to a first aspect of the invention, provide a kind of mixing heteroatom ligand of the catalyst for olefin oligomerisation, described part comprises at least three hetero atoms, and wherein at least one hetero atom is nitrogen, and at least two hetero atoms are not identical.
Described part can be the multidentate mixed heteroatomic part for alkene catalyst for trimerization, and this part is at least containing three hetero atoms.
At least one hetero atom can be nitrogen, and at least two hetero atoms can not be identical.
Except nitrogen, described part at least can contain a phosphorus heteroatoms.
Described part can be selected, make non-carbon hetero atom directly and the hetero atom bonding of other any non-carbon.
Usually, described part can not comprise sulfur heteroatom.
" multidentate mixed heteroatomic " represents the part of donor atom containing more than one non-carbon, wherein has a donor atom different from other donor atoms, and the transition-metal coordination in all donor atoms and catalyst system.Applicant finds, all non-carbon donor atoms and transition-metal coordination, therefore, but part preferably not necessarily, need between donor atom, have a bridging atom, for providing necessary distance between donor atom, and in order to the coordination of all atoms, allow part to take necessary spatial orientation, this is very important for catalyst activity.Fig. 1 illustrates the molecular structure of the compound formed by an example (two-(2-diphenyl phosphine-ethyl)-amine) of chromium trichloride and described multidentate mixed heteroatomic part, and it is obtained by X-ray crystal structure.Bond length selected in this molecular structure and bond angle are shown in Table 1.
Table 1: the selected bond length of chromium trichloride (two-(2-diphenyl phosphine-ethyl)-amine) and bond angle
As can be seen from Figure 1, this specific multidentate mixed heteroatomic part has warp-wise arrangement in the composite, thus forms the Cr-P key (see table 1) that two have almost equal bond length.Only have when to there is at least one bridging atom between donor atom, this warp-wise arrangement of part is only possible.Can expect, the size at the P-Cr-N chelating angle of formation is also very close.
Therefore, also can select multidentate mixed heteroatomic part, make non-carbon hetero atom directly and the hetero atom bonding of other any non-carbon.
Multidentate mixed heteroatomic part can limit with following general formula:
R
1a (R
2bR
3r
4) (R
5cR
6r
7), wherein R
1, R
3, R
4, R
6and R
7can be hydrogen or be independently selected from following group: alkyl, aryl, aryloxy group, halogen, nitro, alkoxy carbonyl group, carbonyl oxygen base, alkoxyl, amino carbonyl, carbonylamino, dialkyl amido, or their derivative, or by aryl that these substituting groups replace; R
2and R
5c
1to about C
15alkyl, they can be the same or different; At least A, B or C are nitrogen, and remaining A, B and C are nitrogen or phosphorus independently.The part of these multidentate mixed heteroatomic bases can according to document or according to such as A.A.Danopoulos, A.R.Wills and P.G. Edwards, Polyhedron (polyhedron), the method synthesis that 1990,9,2413-2418 adopts.
The instantiation of multidentate mixed heteroatomic ylidene ligands comprises: two-(2-diethyl phosphino--ethyl)-amine, two-(diethyl phosphino--methyl)-amine, two-(2-diethyl phosphino--phenyl)-amine, N-methyl two-(2-diethyl phosphino--ethyl)-amine, two-(2-diphenylphosphino-ethyl)-amine, (2-diethyl phosphino--ethyl) (3-diethyl phosphino--propyl group)-amine, two-(2-dicyclohexylphosphontetrafluoroborate-ethyl)-amine, N-benzyl two-(2-diethyl phosphino--ethyl)-amine, N-methyl-(2-diethyl phosphino--ethyl) (3-diethyl phosphino--propyl group)-amine, (2-diethyl phosphino--ethyl) (2-Diethylamino-ethyl)-amine, N-methyl-(2-diethyl phosphino--ethyl) (2-Diethylamino-ethyl)-amine and two-(2-Diethylamino-ethyl) ethyl phosphine.
Suitable multidentate mixed heteroatomic part is two-(2-diethyl phosphine-ethyl)-amine and derivative thereof.
Modification is carried out to multidentate mixed heteroatomic part, is connected on polymer chain (molecular weight=1000 or higher), to such an extent as to the transition metal composite generated is solvable when heating up, but soluble 25 DEG C time.Use the method can reclaim compound for recycling from reactant mixture, and the method is for other catalyst, as D.E.Berbreiter etc., J.Am.Chem.Soc. (JACS), described in 1987,109,177-179.Similarly, can by multidentate mixed heteroatomic part being fixed on silicon, silica gel, polysiloxanes or aluminium skeleton these being fixed of transition metal composite, as C.Yuanyin etc., Chinese J.React.Pol. (Chinese reactive polymeric thing magazine), 1992, such for fixing platinum complexes described in 1 (2), 152-159.
According to another aspect of the present invention, a kind of catalyst system of olefin oligomerisation is provided.
Term " oligomerization " typically refers to the identical reaction of the monomeric unit of oligomeric products.But this term also comprises common oligomerization, wherein the mixture of alkene is used as reaction reagent, generates containing the product more than a kind of monomeric unit (that is, different alkene).This altogether oligomerization often produces the oligomer with alkyl-and/or aryl-side chain with peculiar property, as C.Pelecchia etc., Macromolecules (large molecule), described in 2000,33,2807-2814.
Hydrocarbon conversion catalyst system can comprise mixing heteroatom ligand as above and transition metal.
Described transition metal can be chromium.
Described catalyst system can comprise the mixing heteroatomic coordination complex of chromium and the combination of aikyiaiurnirsoxan beta.
According to the present invention, when described chromium coordination complex mixes with aikyiaiurnirsoxan beta, can catalyzed ethylene generation trimerization, this chromium coordination complex can represent with general formula LCrXn suitably, and wherein X represents anion, can be the same or different, n is the integer of 0-5, and L is mixing heteroatom ligand.
Prepare the chromium precursor used in coordination complex and can be selected from organic or inorganic chromium compound, wherein the oxidation state of chromium atom is from 0 to 6.
Prepare the chromic salts used in chromium coordination complex and can be selected from chromium acetylacetonate (III), chromium acetate (III), 2,2,6,6-dipivaloylmethane acid chromium (III), three (2 ethyl hexanoic acid) chromium (III), chromium chloride (III), chromium acetate (II), chromium chloride (II), chromic nitrate (II) and chromium sulfate (III).
Or, organometallic compounds can be used, such as chromium trichloride three-oxolane compound, (benzyl) tricarbonyl chromium, chromium carbonyl and analog thereof preparing in chromium coordination complex.
The aikyiaiurnirsoxan beta used in catalyst system can use prior art to pass through to make water or hydrous matter and trialkyl aluminium compound react obtained.Preferred aikyiaiurnirsoxan beta uses trialkylaluminium to obtain, such as trimethyl aluminium, triethyl aluminum, tri-propyl aluminum, tri-butyl aluminum, triisobutyl aluminium, three hexyl aluminium and analogs thereof.The mixture of different aikyiaiurnirsoxan beta also can be used in catalyst system.In these aikyiaiurnirsoxan beta, more preferred aikyiaiurnirsoxan beta is obtained by trimethyl aluminium and/or tetraethyl lead.Described aikyiaiurnirsoxan beta must be used to obtain catalytic activity.
Except aikyiaiurnirsoxan beta or its mixture, described catalyst system can also comprise trialkylaluminium, and its content is 0.01-100 moles/mole aikyiaiurnirsoxan beta.But it should be noted that aikyiaiurnirsoxan beta usually also containing a considerable amount of corresponding trialkyl aluminium compound, the latter uses in the preparation of aikyiaiurnirsoxan beta.There are these trialkyl aluminium compounds in aikyiaiurnirsoxan beta to cause because of the latter's incomplete hydrolysis in water.Any amount of trialkyl aluminium compound mentioned in the present invention refers to the amount except alkyl aluminum compound contained in aikyiaiurnirsoxan beta.
The applicant has found that trialkylaluminium can protect aikyiaiurnirsoxan beta as noxious material scavenger, and catalytic activity can be caused in some cases to increase.
Aikyiaiurnirsoxan beta can form a part for alumoxane mixture.Applicant finds, the MAO of such as required at least partially costliness can replace with cheap ethylaluminoxane, and the mixture obtained shows (if not having to increase) identical catalytic activity.
Aikyiaiurnirsoxan beta or its mixture are preferably selected from MAO or ethylaluminoxane.
Combine chromium coordination complex and aikyiaiurnirsoxan beta in proportion, make the mol ratio of Al/Cr be about 1: 1 to 10000: 1.
The catalyst system that hydrocarbon transforms can be the catalyst system of alpha-olefin trimerization or ethylene trimer.
Other catalyst systems that hydrocarbon conversion catalyst system of the present invention and can also be suitable for olefinic polymerization combinationally use.In this case, the oligomerization of catalyst system and trimerization product can be introduced in the polymer or other chemical products with desired properties.Such as G.C.Bazan, Z.J.A.Komon, Am.Chem.Soc., 2000,121,1830 and C.Pelecchia etc., Macromolecules, 2000,33, describe the thinking using dual catalyst system to prepare polyethylene and ethylene copolymers in 2807-2814, wherein a kind of catalyst system is used for oligomerization, the another kind of polymerization being used for alkene.
Described catalyst system can be the catalyst system of alpha-olefin trimerization or ethylene trimer.
The multidentate mixed heteroatomic coordination complex of chromic salts can add in reactant mixture, or in-situ preparation.Known literature method can be used for displacement (ex-situ) preparation of this chromic salts coordination complex.The example of this method is stated in the following documents: R.D
and G.K.
angew.Chem.Int.Ed.Engl. (the international English edition of applied chemistry), 1994,33 (18), 1877-1878; R.D etc.,
angew.Chem.Int.Ed., 2000,39 (23), 4337-4339, and P.Wasserscheid etc., Adv.Synth.Catal. (high synthesis and catalysis), 2001,343 (8), 814-818.
The catalyst of catalyst system may reside in the solution of atent solvent.This atent solvent comprises any saturated aliphatic hydrocarbon and undersaturated aliphatic hydrocarbon, and aromatic hydrocarbon and halogenated hydrocarbons.Aliphatic saturated hydrocarbon and each molecule of unsaturated aliphatic hydrocarbon can have the carbon atom of arbitrary number, but due to commercial availability and final use, usually containing being no more than 20 carbon atoms.Preferred solvent includes, but are not limited to benzene,toluene,xylene, ethylo benzene, 1,3,5-trimethylbenzene, heptane, nonane, cyclohexane, hexahydrotoluene, 1-hexene, chlorobenzene, methyl phenyl ethers anisole and analog thereof.
In order to obtain active catalyst, each component of catalyst system of the present invention can when presence or absence solvent, simultaneously or with any sequential combination together.The mixing of catalytic component can be carried out under the arbitrary temp between 0 DEG C-150 DEG C.When mixed catalyst component, temperature seems to have no significant effect catalyst performance.Usually when mixed catalyst component, the existence of alkene provides protective effect, and the performance of catalyst can be caused to improve.
Combine chromium coordination complex and aikyiaiurnirsoxan beta in proportion, make the mol ratio of Al/Cr be about 1: 1 to 10000: 1, preferably 1: 1 to 1000: 1.
Also can by by described catalyst system or its each component load at heterogeneous surface as on tripoli, alumina, silicon-alum clay, magnesia, zirconia or its analog, to catalyst system or its each being fixed of component.The method is also convenient to reclaim catalyst from reactant mixture, for recycling.This thinking is by T.Monoi and Y.Sasaki, J.Mol.Cat.A:Chem.. (Journal of Molecular Catalysis A: chemistry), and the another kind of chromium base catalyst of ethylene trimerization disclosed in 1987,109,177-179 successfully confirms.In some cases, heterogeneous surface (carrier) can also be used as catalytic component, such as, when this carrier contains aikyiaiurnirsoxan beta functional group or when this carrier can play the chemical action similar to aikyiaiurnirsoxan beta, and such as IOLA
tM(commercial goods from Davison Catalysts).
According to a further aspect in the invention, provide a kind of method of olefin oligomerisation, under the method is included in the pressure of atmospheric pressure to 100 bar gauge pressure, at the temperature of 0 DEG C to 200 DEG C, make the step that alkene contacts with above-mentioned catalyst system.
Method of the present invention can be implemented in atent solvent.Any atent solvent do not reacted with tetraalkyl aluminium and aluminium alkoxide compound can use.These atent solvents comprise any aliphatic saturated hydrocarbon and unsaturated aliphatic hydrocarbon, and aromatic hydrocarbon and halogenated hydrocarbons.Preferred solvent comprises, but is not limited to, benzene,toluene,xylene, heptane, cyclohexane, 1-hexene and analog thereof.The consumption of solvent is not very crucial, usually accounts for the 50-99.9wt% of initial reaction mixture.But, due to the concentration of catalyst in initial reaction mixture lower time (being generally 0.001-0.1mmol Cr/100ml reactant mixture) catalyst productivity ratio tend to higher, therefore the concentration of selecting catalyst, makes the productivity ratio of catalyst and selectively reaches maximum.
Described catalyst dissolution is in atent solvent.
Described method is included in the step that reactant mixture situ generates multidentate mixed heteroatomic chromium complexes.
The inventive method can be clung to table pressure at atmospheric pressure to 100 and be implemented.Usually, the inventive method can be implemented under any pressure within the scope of this, but, actual reaction pressure should be selected, make the productivity ratio of catalyst and selectively reach maximum.Particularly preferably the pressure of ethene is in the scope that 30-60 clings to.
The inventive method can be implemented at the temperature of 0 DEG C-200 DEG C.Usually, the inventive method can be implemented under any temperature within the scope of this, but, the same with selecting the pressure of ethene, actual reaction pressure should be selected, make the productivity ratio of catalyst and selectively reach maximum.Particularly preferably 80 DEG C-120 DEG C.
Preferably, alkene 30 to 50 bar gauge pressures pressure under and contact with catalyst system at the temperature of 80 DEG C to 100 DEG C.
Described method can be implemented under the existence of oxidant as oxygen or its analog.
Implement under the arbitrary temp of described method usually within the scope of this, but the same with selecting the pressure of ethene, actual reaction pressure should be selected, make the productivity ratio of catalyst and selectively reach maximum.Particularly preferably 80 DEG C-120 DEG C.
Described method can be implemented under the existence of oxidant as oxygen or its analog.About this on the one hand, found to use the olefinic reactants containing a small amount of oxygen (1-2000 part/1,000,000 part), such as ethene, can improve the performance of catalyst system and the selective of product.
Although these catalyst, its each component, reagent, solvent and product normally use in acyclic mode, all these raw materials can both and in fact preferably recycle to a certain extent, to reduce production cost.
Described technique comprises the combination of following equipment: a) reactor, b) olefin reactant and catalyst system are passed into the feeding line of reactor, from reactor, c) discharge the drainage conduit of oligomeric products by least one, and d) at least one is separated the separator of the oligomerization product needed, wherein catalyst system comprises multidentate mixed heteroatomic coordination complex and the aikyiaiurnirsoxan beta of chromic salts.
Fig. 2 is the schematic diagram (flow chart) of a detailed description of the invention of olefin oligomerisation technique, uses three separators to come reaction product isolated, solvent and used catalyst (refuse).Although this figure describes a specific embodiment of the present invention for the purpose of description, it is such that the present invention should not be construed as that this figure limits, and this figure attempts to contain all changes under spirit and scope of the invention and improvement.
Implementing various complementary pump essential to the invention, valve, heater, cooler and other conventional apparatus is known by those of skill in the art of the present invention.In order to clear, in Fig. 2, eliminate additional equipment.
Description below about this flow chart provides a kind of method operating present invention process, and attempts to set forth the present invention further." the reactor effluent " that use in description refers to and includes, but are not limited to unreacted alkene, catalyst system, oligomeric products and common property thing by all components can discharged from oligomerization device." refuse " refers to that molecular weight is higher than the reaction common property thing of required oligomerization product, polymerizate and used catalyst system." product " refers to the product that olefin oligomerisation reacts.
Alkene and, selectively, oxygen or air, sent in oligomerization device 1 by feeding line 7/8.Feeding line 5/6 by catalyst system and, selectively, solvent, sends in oligomerization device 1.Reactor effluent is discharged from reactor 1 by pipeline 9.It should be noted that pipeline 6,8 and 9 can be arranged on any position on reactor 1.Under content in pipeline 9,15,16,17 and 19 preferably remains on higher temperature, precipitate to prevent undesirable polymer particle.The operation of formation to this technique of these particles is unfavorable.
Reactor effluent is introduced in separator 2 by pipeline 9, and unreacted alkene and product and high boiling solvent, product and used catalyst system are separated by separator.Pipeline 15/16 is selectable detailed description of the invention of the present invention, and it is conducive to reactor effluent and comprises the higher-boiling compound of catalyst system in feeding line 6 Returning reactor 1.The effluent comprising higher-boiling compound and used catalyst system is transported to separator 4 from separator 2 by pipeline 15/17, and solvent is separated by the latter from the every other compound of this effluent.Pipeline 18 is for sending solvent back to separator 2.Pipeline 19 is discharge pipes, and refuse is discharged by it from separator 4.The effluent comprising unreacted alkene and key reaction product is transported to separator 3 from separator 2 by pipeline 10, and unreacted alkene is separated by the latter from key reaction product.
Effluent contained in pipeline 12/14 comprises unreacted alkene and a small amount of extremely lower boiling product, such as 1-butylene, and described pipeline, by sending effluent back to feeding line 6, is convenient to reclaim olefinic reactants.Pipeline 12/14 is discharge pipe, and it comprises unreacted alkene and a small amount of extremely lower boiling product, and the latter is used for preventing the accumulation of extremely lower boiling product.Pipeline 11 is effluent pipelines, and it comprises key reaction product.
In another detailed description of the invention of this technique, reactor and a separator can be combined, so that separated from reactor by these compounds while forming reactions product.When this reaction is the liquid phase reactor of homogeneous phase, the principle of this reaction is commonly referred to be reactive distillation.When catalyst system is insoluble to solvent or product, and be fixed in the reactor to such an extent as to it is not discharged with reactor product, solvent and unreacted alkene time, the catalytic distillation when principle of this technique it has been generally acknowledged that.
Oligomerisation process described herein can be used for carrying out the trimerization of ethene and the technical process of polymerization simultaneously, thus is incorporated in copolymer by trimerization product.United States Patent (USP) the 5th, 786, describe an embodiment of these class methods in 431.
Detailed description of the invention
Below in conjunction with following embodiment, the present invention is described, the scope that described embodiment does not limit the present invention in any way.
In the following embodiments, all processes are all the pre-dry reagent of use, carry out under inert conditions.
Embodiment 1: the reaction of chromium trichloride (pentamethyl-diethylenetriamine)/MAO and ethene
Reaction is carried out in the 75ml stainless steel autoclave being provided with loading hopper, intake valve and magnetic stirring bar.Add in loading hopper and be dissolved with 0.0149g (0.0449mmol) chromium trichloride (pentamethyl-diethylenetriamine) 20ml toluene solution, the bottom to autoclave adds the MAO toluene solution of 9.0ml1.5M.After 20 minutes, by the bottom-heated of autoclave to 100 DEG C, in reactor, be then filled with the ethene of 40 bar pressures, open loading hopper, chromium complexes solution is mixed with MAO solution.Keep constant ethylene pressure 40 bar after 30 minutes, discharge unnecessary ethene carry out cessation reaction by cooling autoclave to 0 DEG C.Collect the gas of release, analyze by gas chromatography (GC).The liquid of autoclave first stops with the hydrochloric acid of 10% with ethanol again, and the nonane adding 1.000ml is marked as in GC.Also with GC, liquid/interior mark mixture is analyzed.Two GC analysis results show, define the oligomer of 0.12g, wherein have 0.0048g (4 quality %) to be hexene.Filter this liquid, obtain 0.12g polyethylene.
Embodiment 2: the preparation of chromium trichloride (two-(2-diphenyl phosphine-ethyl)-amine)
By CrCl
3(THF)
3(0.907mmol) be suspended in 6ml THF (oxolane), add the THF solution of 3ml containing two-(2-diphenyl phosphine-ethyl)-amine (0.934mmol).After removing only about half of solvent by vacuum distillation, add 10ml diethyl ether.Solid collected by filtration product, uses 10ml diethyl ether.After vacuum drying, obtain the violet solid of 0.342g chromium trichloride (two-(2-diphenyl phosphine-ethyl)-amine), (based on CrCl
3(THF)
3productive rate be 92%).+ FAB data: m/z 598 [M]+, 563 [M-Cl]+.Elementary analysis: C
28h
29p
2nCl
3the calculated value (experiment value) of Cr: C 56.07 (55.84), N 2.34 (2.14), H 4.87 (5.16).Crystal parameter: DMSO, C
30h
35cl
3crNOP
2s, M=653.92, monoclinic system, a=27.667 (7), b=14.751 (4),
β=100.923 (7) °,
t=293 (2) K, space group C2/c (no.15), Z=8, μ (Mo-K
α)=0.769mm
-1, measure 28626 pips, 6532 characteristic point (R
int=0.0662) be used in all calculating.Final R (F) and wR (F
2) be respectively 0.0521 (I > 2 σ (I)) and 0.1512 (all data).The bond length selected
with bond angle (°): Cr-P12.4660 (12), Cr-P22.4678 (12), Cr-N 2.139 (3), Cr-Cl1 2.2934 (11), Cr-Cl2 2.3081 (11), Cr-Cl3 2.3480 (11), N-Cr-P1 81.08 (8), N-Cr-P2 82.07 (8), P1-Cr-P2 163.10 (4), N-Cr-Cl1 176.74 (8), N-Cr-Cl2 87.59 (8) and N-Cr-Cl3 85.00 (8).
Embodiment 3: the ethylene trimer reaction using chromium trichloride (two-(2-diphenyl phosphine-ethyl)-amine)/MAO
Catalytic action is carried out in the 75ml stainless steel autoclave being provided with loading hopper, intake valve and magnetic stirring bar.In loading hopper, add the 20ml toluene solution being dissolved with 0.0241g (0.0402mmol) chromium trichloride (two-(2-diphenyl phosphine-ethyl)-amine), the bottom to autoclave adds the MAO toluene solution of 3.3ml1.5M.After 20 minutes, by the bottom-heated of autoclave to 100 DEG C, in reactor, be then filled with the ethene of 40 bar pressures, open loading hopper, chromium complexes solution is mixed with MAO solution.Keep constant ethylene pressure 40 bar after 30 minutes, discharge unnecessary ethene carry out cessation reaction by cooling autoclave to 0 DEG C.Collect the gas of release, analyze by gas chromatography (GC).The liquid of autoclave first stops with the hydrochloric acid of 10% with ethanol again, and the nonane adding 1.000ml is marked as in GC.With GC, upper strata organic matter is analyzed, find that it contains other hexene isomers of 0.08g butylene, 4.75g1-hexene and 0.04g.Gas phase contains 0.01g butylene.Filter liquide obtains 0.007g polyethylene.
Embodiment 4: the ethylene trimer reaction using chromium trichloride (two-(2-diphenyl phosphine-ethyl)-amine)/MAO
Repeat the step of embodiment 3, but use the MAO solution of 0.0066g (0.011mmol) chromium trichloride (two-(2-diphenyl phosphine-ethyl)-amine) and 5.0ml1.5M.Be obtained by reacting the common 2.72g product containing 0.28g polyethylene, 2.23g 1-hexene and other hexene isomers of 0.02g.
The preparation of embodiment 5: two-(2-diethyl phosphine-ethyl)-amine
I) preparation of (2-chloroethyl)-trimethyl silyl amine
Two (2-chloroethyl) amine hydrochlorate (50g, 0.28mol) is suspended in triethylamine (500ml), Me
3siCl (171g, 1.58mol) and (CH
3)
2in the mixture of SO (1.25ml).At room temperature stir the mixture that obtains 2 hours, then add hot reflux 16 hours.Be cooled to room temperature, filter white suspension thing, solvent removed in vacuo, in this filtration product, obtains 31.93g colorless oil (productive rate: 53.5%).
Ii) preparation of two (2-diethyl phosphine-ethyl)-amine
At-35 DEG C, stir oxolane (150ml) solution of diethyl phosphine (6.72g, 74.6mmol), add 47ml n-BuLi (1.6M) wherein.Then, at-50 DEG C to LiP (Et)
2tetrahydrofuran solution in dropwise add the tetrahydrofuran solution 40ml of two (2-chloroethyl) trimethyl silyl amine (8.18g, 38.4mmol).Mixture is heated to room temperature, stirs 30 minutes.Then be heated to 60 DEG C, stirring is spent the night, then adds 100ml water, and silicyl is hydrolyzed, and reactant mixture is heated to 60 DEG C, keeps 1 hour, to ensure to remove silicyl completely.By reactant mixture by small-sized MgSO
4bed carries out drying, then with the washing of 60ml diethyl etherate.Except desolventizing, obtain 6.96g bis-(2-diethyl phosphine-ethyl)-amine (productive rate: 73%).
1h-NMR (C
6d
6) δ 1.12 (12H, d of t, CH
2cH
3,=7.2 and 14.1Hz), 1.38 (8H, q, CH
2cH
3, J=7.2), 1.60 (4H, t, (CH
2) P, J=7.2) and 2.84 (4H, q, (CH
2n), J=7.8).
31P-NMR(C
6D
6)δ-26.02。
Embodiment 6: the preparation of chromium trichloride (two (2-diethyl phosphine-ethyl)-amine)
At room temperature the tetrahydrofuran solution of 5ml bis-(2-diethyl phosphine-ethyl)-amine (0.183g, 0.734mmol) is added the CrCl of 10ml
3(THF)
3in the tetrahydrofuran solution of (0.262g, 0.699mmol).Stir this solution 10 minutes, then solvent removed in vacuo, until residue 3ml.Filter this solution, with the washing of extra diethyl etherate, vacuum drying, obtains 0.254g product (productive rate: 89%).Elementary analysis: C
12h
29nP
2cl
3the calculated value (experiment value) of Cr: C 35.36 (35.29), N 3.44 (3.21) and H 7.17 (7.49).
Embodiment 7: the ethylene trimer reaction of chromium trichloride (two (2-diethyl phosphine-ethyl)-amine)
Catalytic action is carried out in the 75ml stainless steel autoclave being provided with loading hopper, intake valve and magnetic stirring bar.In loading hopper, add the 20ml toluene solution being dissolved with 0.0044g (0.0108mmol) chromium trichloride (two-(2-diethyl phosphine-ethyl)-amine), the bottom to autoclave adds the toluene solution of the MAO of 5ml1.5M.After 20 minutes, by the bottom-heated of autoclave to 100 DEG C, in reactor, be then filled with the ethene of 40 bar pressures, open loading hopper, chromium complexes solution is mixed with MAO solution.Keep constant ethylene pressure 40 bar after 30 minutes, discharge unnecessary ethene carry out cessation reaction by cooling autoclave to 0 DEG C.Collect the gas of release, analyze by gas chromatography (GC).The liquid of autoclave first stops with the hydrochloric acid of 10% with ethanol again, and the nonane adding 1.000ml is marked as in GC.Be obtained by reacting other hexene isomers of 0.063g polyethylene, 0.04g butylene, 8.67g 1-hexene and 0.10g.
Embodiment 8: the ethylene trimer reaction using chromium trichloride (two-(2-diethyl phosphine-ethyl)-amine)/MAO
Repeat the step of embodiment 7, but use 0.0048g (0.0118mmol) chromium trichloride (two-(2-diethyl phosphine-ethyl)-amine), react 1 hour at 80 DEG C.Be obtained by reacting 0.045g polyethylene, 0.21g butylene, 12.77g 1-hexene, other hexene isomers of 0.09g and 0.09g decene.
Embodiment 9: the ethylene trimer reaction using chromium trichloride (two-(2-diethyl phosphine-ethyl)-amine)/MAO
Repeat the step of embodiment 7, but use 0.0052g (0.013mmol) chromium trichloride (two-(2-diethyl phosphine-ethyl)-amine), react 1 hour at 50 DEG C.Be obtained by reacting the common 0.54g product containing 0.12g polyethylene, 0.41g 1-hexene and other hexene isomers of 0.01g.
Embodiment 10: the ethylene trimer reaction using chromium trichloride (two-(2-diethyl phosphine-ethyl)-amine)/MAO
Repeat the step of embodiment 7, but use 0.0046g (0.0113mmol) chromium trichloride (two-(2-diethyl phosphine-ethyl)-amine), reaction temperature is 120 DEG C.Be obtained by reacting the common 7.86g product containing 0.16g polyethylene, 7.26g 1-hexene and other hexene isomers of 0.05g.
Embodiment 11: the ethylene trimer reaction using chromium trichloride (two-(2-diethyl phosphine-ethyl)-amine)/MAO
Repeat the step of embodiment 7, but use the MAO toluene solution of 0.020g (0.05mmol) chromium trichloride (two-(2-diethyl phosphine-ethyl)-amine) and 3.3ml1.5M.Be obtained by reacting the common 12.13g product containing 0.24g polyethylene, 11.79g 1-hexene, other hexene isomers of 0.10g.
Claims (15)
1. a catalyst of ethylene trimerization system, it contains: containing the chromium coordination complex of multidentate mixed heteroatomic part;
Wherein, this part comprises three hetero atoms as donor atom, all described donor atoms all with chromium coordination, and described donor atom is not directly and other any donor atom bondings, and described part has general formula R
1a (R
2bR
3r
4) (R
5cR
6r
7),
Wherein, R
1, R
3, R
4, R
6and R
7be hydrogen or be independently selected from following group: alkyl, aryl or the aryl replaced by these substituting groups; R
2and R
5c
1-C
15alkyl, they can be the same or different;
A is nitrogen, and
B and C is phosphorus.
2. catalyst system as claimed in claim 1, wherein said part is selected from two-(2-diethyl phosphine-ethyl)-amine, two-(2-diphenylphosphine-ethyl)-amine, two-(diethyl phosphine-methyl)-amine, two-(2-diethyl phosphine-phenyl)-amine, (2-diethyl phosphine-ethyl) (3-diethyl phosphine-propyl group)-amine and their derivative.
3. catalyst system as claimed in claim 1, this system, except the chromium coordination complex containing mixing heteroatom ligand, also contains aikyiaiurnirsoxan beta.
4. catalyst system as claimed in claim 3, wherein a part for aikyiaiurnirsoxan beta composition alumoxane mixture.
5. catalyst system as claimed in claim 4, wherein chromium coordination complex general formula LCrXn represents, wherein X represents anion, can be the same or different, and n is the integer of 0-5, and L is multidentate mixed heteroatomic part.
6. catalyst system as claimed in claim 1, wherein chromic salts is for the preparation of catalyst system, described chromic salts is selected from chromium acetylacetonate (III), chromium acetate (III), 2,2,6,6-dipivaloylmethane acid chromium (III), three (2 ethyl hexanoic acid) chromium (III), chromium chloride (III), chromium acetate (II), chromium chloride (II), chromic nitrate (II) and chromium sulfate (III).
7. catalyst system as claimed in claim 3, wherein often kind of aikyiaiurnirsoxan beta is all obtained by trialkylaluminium.
8. catalyst system as claimed in claim 3, this system, except containing aikyiaiurnirsoxan beta, also contains trialkylaluminium.
9. catalyst system as claimed in claim 4, this system, except containing alumoxane mixture, also contains trialkylaluminium.
10. catalyst system as claimed in claim 3, wherein aikyiaiurnirsoxan beta is selected from MAO or ethylaluminoxane.
11. catalyst system as claimed in claim 4, wherein alumoxane mixture is selected from MAO or ethylaluminoxane.
The method of 12. 1 kinds of ethylene trimers, under the method is included in the pressure of atmospheric pressure to 100 bar gauge pressure, at the temperature of 0 DEG C to 200 DEG C, makes the step that alkene contacts with catalyst system as claimed in any one of claims 1-9 wherein.
13. methods as claimed in claim 12, wherein alkene 30 to 50 bar gauge pressures pressure under and contact with catalyst system at the temperature of 80 DEG C to 100 DEG C.
14. method as claimed in claim 12, wherein catalyst dissolution is in atent solvent.
15. methods as claimed in claim 13, the method is included in the step that reactant mixture situ generates the chromium coordination complex containing multidentate mixed heteroatomic part.
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| US34256001P | 2001-12-20 | 2001-12-20 | |
| ZA2001/10435 | 2001-12-20 | ||
| US60/342,560 | 2001-12-20 | ||
| ZA200110435 | 2001-12-20 |
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| CNA028255151A Division CN1606539A (en) | 2001-12-20 | 2002-12-19 | Trimerisation and oligomerisation of olefins using a chromium based catalyst |
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| CN102407159B true CN102407159B (en) | 2015-05-20 |
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| CN107235885B (en) * | 2016-03-28 | 2021-11-19 | 中国石油化工股份有限公司 | Ligand compound and preparation method and application thereof |
| CN107597191B (en) * | 2017-07-27 | 2020-01-07 | 天津科技大学 | Catalyst for preparing 1-hexene by ethylene trimerization |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1182729A (en) * | 1996-02-02 | 1998-05-27 | 三菱化学株式会社 | Method for preparing alpha-olfeines low polymer |
| CN1189784A (en) * | 1996-04-30 | 1998-08-05 | 阿莫科公司 | Ruthenium-based catalyst system for olefin metathesis |
| US5811618A (en) * | 1991-10-16 | 1998-09-22 | Amoco Corporation | Ethylene trimerization |
-
2002
- 2002-12-19 ES ES02794480T patent/ES2389649T3/en not_active Expired - Lifetime
- 2002-12-19 CN CN201110225810.3A patent/CN102407159B/en not_active Expired - Lifetime
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5811618A (en) * | 1991-10-16 | 1998-09-22 | Amoco Corporation | Ethylene trimerization |
| CN1182729A (en) * | 1996-02-02 | 1998-05-27 | 三菱化学株式会社 | Method for preparing alpha-olfeines low polymer |
| CN1189784A (en) * | 1996-04-30 | 1998-08-05 | 阿莫科公司 | Ruthenium-based catalyst system for olefin metathesis |
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