CN109701652A - A kind of carbon monoxide-olefin polymeric and its application - Google Patents
A kind of carbon monoxide-olefin polymeric and its application Download PDFInfo
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Abstract
The present invention relates to a kind of ethylene oligomerization carbon monoxide-olefin polymerics, including ligand compound, transistion metal compound shown in Formulas I and containing the alkane solution of aluminum cocatalyst；
Description
Technical field
The present invention relates to a kind of carbon monoxide-olefin polymerics for ethylene oligomerization reaction.The invention further relates to one kind for being catalyzed
Application of the agent composition in ethylene oligomerization technique.
Background technique
Ethylene oligomerization is one of most important reaction in olefinic polymerization industry.It, can will be cheap small by oligomerisation reaction
Molecular olefine is transformed into high value-added product.Ethylene oligomerization product-linear alpha-alkene (LAO) is important and organises
Work raw material.Such as LAO C4-C8 is mainly used in production high-quality polyethylene as important Organic Ingredients and chemical intermediate
(PE) field.PE can be significantly improved by the linear low density polyethylene (LLDPE) of 1- hexene or the production of 1- octene and ethylene copolymer
Properties, can especially significantly improve mechanical performance, optical property and the tear strength and impact strength of polyethylene,
Product is very suitable for the fields such as the agricultural mulch films such as packaging film and greenhouse, canopy room.LAO C10-C30 can be used as preparing daily cleaning
Agent, flotation agent, emulsifier, the emollient component of refrigeration machine and bore liquid emollient component, plasticizer, various additives, low viscosity are closed
At oil, polymer and copolymer, petroleum and oil product additive, senior alkylamines, advanced organo-aluminum compound, advanced alkane virtue
The pure and mild fatty acid of base hydrocarbon, higher aliphatic, epoxides and additive of heat carrier etc..On the basis LAO C20-C30
On can also composite adhesives, sealant and coating.In recent years, with the continuous development of polyolefin industry, world wide is interior to α-
The demand rapid development of alkene.Wherein most alpha-olefins is prepared by ethylene oligomerization.
Since 1970s, the research of transient metal complex catalysis in olefine polymerization and oligomerisation is gradually by science
The attention of family, people start to make great efforts research raw catelyst and improve existing catalyst, improve the activity and catalysate of catalyst
Selectivity.In numerous explorations, study that earliest, with fastest developing speed, compare concentration is nickel cation type catalyst system, such as
Early reported United States Patent (USP) has US3686351 and US3676523, and Shell Co. Ltd's SHOP work based on the patented technology
Skill.It is related to O-P bridging type ligand in Shell Co. Ltd's SHOP technique, but contains virose organophosphorous groups in the catalyst,
And synthesis step is complicated, stability is poor.The many such as O-O, P-N, P-P and N-N type coordination Raney nickel were developed again later
Patent, such as JP11060627, WO9923096, WO991550, CN1401666, CN1769270 etc..However, being obtained by above-mentioned patent
The relatively complicated disadvantage of the generally existing preparation method of catalyst obtained.Other catalyst there are also chromium system, zirconium and aluminium system etc.,
Brookhart group (Brookhart, M et al., J.Am.Chem.Soc., 1998,120,7143-7144；WO99/02472,
1999), Gibson group (Gibson, V.C. et al., Chem.Commun., 1998,849-850；Chem.Eur.J.,2000,
It 2221-2231) finds that some Fe (II) and the trident pyridinimine complex of Co (II) can be catalyzed ethylene oligomerization respectively, not only urges
The catalytic activity of agent is very high, and the selectivity of alpha-olefin is also very high.
Olefinic polymerization especially metallocene catalysis field generally uses aluminum alkoxide such as methylaluminoxane (MAO) or modified first
Base aikyiaiurnirsoxan beta (MMAO) is used as co-catalyst, and MAO price is higher by tens times than the price of other alkyl aluminums, becomes for a long time
Restrict the main bottleneck of the field industrialization.In addition, MAO is very difficult to dissolve in alkane solvents, therefore commercially available MAO is general
In the reaction product so as to cause aromatic hydrocarbons residual cause catalyst activity low for arene solutions such as toluene, also seriously affect product
Quality.And it is copolymerized grade a- alkene and is used to prepare during polyethylene often its arene content of considered critical.
It is undoubted, the demand to the new catalyst of excellent combination property is remained in olefin(e) oligomerization field.?
Attention is placed on how to obtain the superior co-catalyst of cost more low performance, to develop with high activity and selectivity
Ethylene oligomerisation catalyst is worth paying close attention in the industry.
Summary of the invention
Present inventor is when studying ethylene oligomerisation catalyst, it was found that a kind of carbon monoxide-olefin polymeric.By the catalysis
For agent composition for being catalyzed ethylene oligomerization reaction, especially ethylene trimer and four poly- reactions, active high and selectivity is high
Advantage.
According to an aspect of the invention, there is provided a kind of carbon monoxide-olefin polymeric, including ligand compound shown in Formulas I,
Transistion metal compound and alkane solution containing aluminum cocatalyst；
R and R ' are identical or different in formula, are each independently selected from hydrogen, alkyl, alkoxy, naphthenic base and halogen；N be greater than
Or the integer equal to 1；
The preparation method of the alkane solution containing aluminum cocatalyst includes:
Step a: water is reacted with the arene solution of alkyl aluminum；Wherein, the general formula of the alkyl aluminum is R1R2R3Al,
R1、R2And R3It is identical or different, independently selected from C1-C20Alkyl；
Step b: the solution obtained after reacting in step a is reacted with the arene solution of aikyiaiurnirsoxan beta；The aikyiaiurnirsoxan beta
In alkyl and R1、R2And R3It is different；
Step c: after the solution obtained after reacting in step b is reacted with water, aromatic hydrocarbons is removed, alkane is added, obtains
Alkane solution containing aluminum cocatalyst.
Catalyst according to the invention composition, prepare it is simple, at low cost, can effectively catalyze ethylene oligomerization reaction,
Especially ethylene trimer and four poly- reactions, active high and selective high advantage.
Catalyst according to the invention composition, preparation method include: first passing through method comprising the following steps preparation
Alkane solution containing aluminum cocatalyst:
Step a: water is reacted with the arene solution of alkyl aluminum；Wherein, the general formula of the alkyl aluminum is R1R2R3Al,
R1、R2And R3It is identical or different, independently selected from C1-C20Alkyl；
Step b: the solution obtained after reacting in step a is reacted with the arene solution of aikyiaiurnirsoxan beta；The aikyiaiurnirsoxan beta
In alkyl and R1、R2And R3It is different；
Step c: after the solution obtained after reacting in step b is reacted with water, aromatic hydrocarbons is removed, alkane is added, obtains
Alkane solution containing aluminum cocatalyst；
Then the alkane solution containing aluminum cocatalyst described in it will prepare, with ligand compound shown in the Formulas I
And the transistion metal compound is mixed, or is mixed when in use.
Some preferred embodiments according to the present invention, in the general formula of the alkyl aluminum, R1、R2And R3It is identical or different, solely
On the spot it is selected from C1-C10Alkyl.In some preferred embodiments, R1、R2And R3It is identical, selected from methyl, ethyl, n-propyl, different
One of propyl, butyl, isobutyl group, tert-butyl and n-pentyl.
Some preferred embodiments according to the present invention, the aikyiaiurnirsoxan beta is in methylaluminoxane and ethylaluminoxane
It is at least one.
Some preferred embodiments according to the present invention, the step a include adding water to triisobutyl at low temperature
It in aluminium arene solution, is stirred to react after a certain period of time, temperature rising reflux, it is spare to be then down to room temperature.Preferably, the step a packet
It including, the arene solution of the water and alkyl aluminum is at -20 DEG C to 10 DEG C, and such as -20 DEG C to 0 DEG C, as reacted 0.1h at -10 DEG C to 0 DEG C
To 1h, then heating reflux reaction 0.1h to 1h.Water and the alkyl in some preferred embodiments, in the step a
The molar ratio of aluminium is (0.5-1): 1.
Some preferred embodiments according to the present invention, the step b include, by the product and methyl alumina in step a
Alkane arene solution mixes, then heating reflux reaction, then is cooled to room temperature spare.Preferably, the solution obtained after step a reaction
Arene solution with aikyiaiurnirsoxan beta is preferably mixed at room temperature at 5 DEG C to 40 DEG C, is heated to reflux 0.1h later to 1h.Some
In preferred embodiment, the molar ratio of aikyiaiurnirsoxan beta and the alkyl aluminum in the step b is (0.1-3): 1, preferably (0.5-
1):1。
Some preferred embodiments according to the present invention, the step c include being added water in step b at low temperature
Arene solution in, be stirred to react after a certain period of time, be then heated to reflux, then be down to room temperature；Preferably, after being reacted in step b
Obtained solution and water reacts 0.1h to 1h at -20 DEG C to 10 DEG C, preferably -10 DEG C to 0 DEG C, is then heated to reflux 0.1h extremely
1h.In some preferred embodiments, the molar ratio of water and the aikyiaiurnirsoxan beta in the step c is (0.1-0.3): 1.
According to the present invention, the temperature of mentioned reflux is the boiling temperature of aromatic solvent.
In the present invention, term " aromatic hydrocarbons " refers to the hydrocarbon containing benzene ring structure, as benzene,toluene,xylene,
Naphthalene and by halogen, nitro or alkyl-substituted phenyl derivatives.
In the present invention, term " alkane " refers to the hydrocarbon of saturation classes, such as pentane, hexane, heptane, ring penta
At least one of alkane, hexamethylene and hexahydrotoluene etc..
Some preferred embodiments according to the present invention, the R1-R3It is identical, it is isobutyl group, the water containing aluminum cocatalyst
Xie Hou, iso-butane content is higher than 75wt%, preferably 78wt-94wt% in the gas-phase product measured through gas-chromatography.
Some preferred embodiments according to the present invention, the preparation method containing aluminum cocatalyst specifically include:
A. it adds water in triisobutyl aluminium arene solution, is stirred to react after a certain period of time, temperature rising reflux at low temperature,
Then it is spare to be down to room temperature；
B. the product in step a is mixed, then heating reflux reaction with methylaluminoxane arene solution, then is down to room temperature
It is spare afterwards；
C. it is added water in the arene solution in step b at low temperature, is stirred to react after a certain period of time, then heats back
Stream, then it is down to room temperature, which is removed under reduced pressure aromatic hydrocarbons, is then added after alkane to get the alkane containing aluminum cocatalyst is arrived
Solution.Triisobutyl aluminium is used in step a, uses methylaluminoxane in step b, after what is obtained hydrolyzes containing aluminum cocatalyst, warp
Gas chromatographic detection, iso-butane content is higher than 75wt%, such as 78-94wt% in gas-phase product, remaining is methane.
In a preferred embodiment of the present invention, the transistion metal compound is selected from chromium compound, molybdenum compound, iron
At least one of compound, titanium compound, zirconium compounds and nickel compound, preferably chromium acetylacetonate, isooctyl acid chromium, three
At least one of (tetrahydrofuran) chromium trichloride or two (tetrahydrofuran) chromium dichlorides.
A preferred embodiment according to the present invention, ligand compound shown in the Formulas I can be selected commonly used in the art
Meeting formula I structure ligand compound.Wherein, alkyl includes linear or branched alkyl group, such as C1-C20Straight chained alkyl or C1-C10
Straight chained alkyl, C3-C20Branched alkyl or C3-C10Branched alkyl；Naphthenic base such as C3-C20Naphthenic base etc..Alkoxy such as C1-
C20Alkoxy or C1-C10Alkoxy.
In a preferred embodiment of the present invention, the R and R ' are selected from methyl, ethyl, n-propyl, isopropyl, positive fourth
Base, isobutyl group, cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, suberyl and halogen；Wherein, halogen is preferably selected from chlorine or bromine.
In a preferred embodiment of the present invention, the n is selected from 1~10, is preferably selected from 1~3.
Some preferred embodiments of carbon monoxide-olefin polymeric according to the present invention, relative to 1 mole of the ligand
Compound, the amount of the transistion metal compound are 0.1-10 moles, preferably 0.25-2 moles, more preferable 0.5-2 moles；It is described
Amount containing aluminum cocatalyst is 1-1000 moles, preferably 10-700 moles, more preferably 100-200 moles.
According to the present invention, co-catalyst solubility in alkane is good, the catalyst group formed with ligand, metal salt
It is high to close object activity.
According to another aspect of the present invention, the application method of above-mentioned carbon monoxide-olefin polymeric is additionally provided, including upper
In the presence of the carbon monoxide-olefin polymeric stated, ethylene oligomerization reaction is carried out.In some preferred examples, in organic solvent, more excellent
It is selected in progress ethylene oligomerization reaction in alkane.In ethylene oligomerization reaction, reaction temperature is 0-200 DEG C, preferably 0-100
℃；Ethylene pressure is 0.1-20.0MPa, preferably 0.5-5.0MPa.
According to another aspect of the present invention, the application method of another above-mentioned carbon monoxide-olefin polymeric, packet are additionally provided
It includes and carries out ethylene trimer and/or four poly- reactions in the presence of above-mentioned carbon monoxide-olefin polymeric.In some preferred examples,
Organic solvent preferably carries out ethylene trimer and/or four poly- reactions in alkane.The condition of reaction is as follows: temperature is 0-200 DEG C,
Preferably 0-100 DEG C；Ethylene pressure is 0.1-20.0MPa, preferably 0.5-5.0MPa.
According to the present invention, the carbon monoxide-olefin polymeric when in use, is added after each component in composition being mixed
In reactor, each component in composition can also be added separately in reactor.
It according to the present invention, can be to avoid using aromatic hydrocarbons when the carbon monoxide-olefin polymeric of the application reacts in alkane
Solvent, and remained in product without aromatic hydrocarbons, product quality is high, and the 'alpha '-olefin monomers of high-quality can be provided for chemical industry.
Carbon monoxide-olefin polymeric provided by the invention comprising the co-catalyst can carry out effectively being catalyzed ethylene oligomerization anti-
It answers, especially ethylene trimer and/or four poly- reactions, catalyst activity can be more than 5 × 106g/(gCr·h)；The sorting of 1- octene group
Selecting property reaches 75%, 1- hexene component selection about 20%.Has the characteristics that high activity, highly selective.Therefore, according to the present invention
Carbon monoxide-olefin polymeric, have preferable prospects for commercial application and economic value.
It is anti-that carbon monoxide-olefin polymeric provided by the invention comprising the co-catalyst carries out ethylene oligomerization in organic solvent
It answers, solvent used is carrying out Non-aqueous processing using preceding；The Non-aqueous processing method of organic solvent can be used generally in the art
Processing method.
Specific embodiment
The following example is only used for that the present invention is described in detail, it will be appreciated that the scope of the present invention is not limited to
These embodiments.
In the present invention, aluminium content test uses inductive coupling plasma emission spectrum (ICP Optima8300, U.S. PE
Company) it is detected.
In the present invention, gas-chromatography is detected using 5890 chromatograph of Hewlett-Packard.Chromatographic column: Agilent HP-Al/KCL,
Column length 50m, internal diameter 0.320mm；Column temperature: 100 DEG C, constant temperature 10 minutes, 10 DEG C/min of heating rate was warming up to 160 DEG C, constant temperature 10
Minute, 250 DEG C of injector temperature, 250 DEG C of detector temperature；Carrier gas: nitrogen, fid detector.
Ligand used in the present invention can refer to document (CN102909071B) self-control.
Embodiment 1
Under nitrogen protection, slowly 7mmol water droplet is added in 10mmol triisobutyl aluminium (1M toluene solution) under ice bath,
After being stirred to react 0.5 hour, temperature rising reflux 1 hour, it is spare to be then down to room temperature；Taking 10mmol methylaluminoxane, (1M toluene is molten
Liquid), it is added in above-mentioned solution, is then heated to reflux 1 hour, then be down to room temperature；2mmol water is slowly added under ice bath
State in mixed liquor, after being stirred to react 0.5 hour, be heated to reflux 1 hour, then be down to room temperature, decompression abstraction toluene solvant, then plus
Enter methyl cyclohexane alkane solvents, mixed liquor total volume is 20mL to get co-catalyst A (1M, hexahydrotoluene solution) is arrived.
Product analysis: taking quantitative co-catalyst A, and being slowly added to excessive water makes its decomposition, and liquid phase component is tested aluminium with ICP and contained
Amount is 3.4wt%；Gaseous component tests iso-butane content 89wt%, methane content 11wt%.
Embodiment 2
Under nitrogen protection, slowly 5mmol water droplet is added in 10mmol triisobutyl aluminium (1M toluene solution) under ice bath,
After being stirred to react 0.5 hour, temperature rising reflux 1 hour, it is spare to be then down to room temperature；Taking 10mmol methylaluminoxane, (1M toluene is molten
Liquid), it is added in above-mentioned solution, is then heated to reflux 1 hour, then be down to room temperature；2mmol water is slowly added under ice bath
State in mixed liquor, after being stirred to react 0.5 hour, be heated to reflux 1 hour, then be down to room temperature, decompression abstraction toluene solvant, then plus
Enter methyl cyclohexane alkane solvents, mixed liquor total volume is 20mL to get cocatalyst B (1M, hexahydrotoluene solution) is arrived.
Product analysis: taking quantitative (with embodiment 1) cocatalyst B, and being slowly added to excessive water makes its decomposition, and liquid phase component is used
It is 3.4wt% that ICP, which tests aluminium content,；Gaseous component tests iso-butane content 90wt%, methane content 10wt%.
Embodiment 3
Under nitrogen protection, 10mmol water droplet is slowly added to 10mmol triisobutyl aluminium (1M toluene solution) under ice bath
In, after being stirred to react 0.5 hour, temperature rising reflux 1 hour, it is spare to be then down to room temperature；Take 10mmol methylaluminoxane (1M toluene
Solution), it is added in above-mentioned solution, is then heated to reflux 1 hour, then be down to room temperature；2mmol water is slowly added under ice bath
It in above-mentioned mixed liquor, after being stirred to react 0.5 hour, is heated to reflux 1 hour, then be down to room temperature, decompression abstraction toluene solvant, then
Be added methyl cyclohexane alkane solvents, mixed liquor total volume be 20mL to get arrive co-catalyst C (1M, hexahydrotoluene solution).
Product analysis: taking quantitative (with embodiment 1) co-catalyst C, and being slowly added to excessive water makes its decomposition, and liquid phase component is used
It is 3.4wt% that ICP, which tests aluminium content,；Gaseous component tests iso-butane content 78wt%, methane content 22wt%.
Embodiment 4
Under nitrogen protection, slowly 7mmol water droplet is added in 10mmol triisobutyl aluminium (1M toluene solution) under ice bath,
After being stirred to react 0.5 hour, temperature rising reflux 1 hour, it is spare to be then down to room temperature；Taking 10mmol methylaluminoxane, (1M toluene is molten
Liquid), it is added in above-mentioned solution, is then heated to reflux 1 hour, then be down to room temperature；3mmol water is slowly added under ice bath
State in mixed liquor, after being stirred to react 0.5 hour, be heated to reflux 1 hour, then be down to room temperature, decompression abstraction toluene solvant, then plus
Enter methyl cyclohexane alkane solvents, mixed liquor total volume is 20mL to get co-catalyst D (1M, hexahydrotoluene solution) is arrived.
Product analysis: taking quantitative (with embodiment 1) co-catalyst D, and being slowly added to excessive water makes its decomposition, and liquid phase component is used
It is 3.4wt% that ICP, which tests aluminium content,；Gaseous component tests iso-butane content 91wt%, methane content 9wt%.
Embodiment 5
Under nitrogen protection, slowly 7mmol water droplet is added in 10mmol triisobutyl aluminium (1M toluene solution) under ice bath,
After being stirred to react 0.5 hour, temperature rising reflux 1 hour, it is spare to be then down to room temperature；Taking 10mmol methylaluminoxane, (1M toluene is molten
Liquid), it is added in above-mentioned solution, is then heated to reflux 1 hour, then be down to room temperature；1mmol water is slowly added under ice bath
State in mixed liquor, after being stirred to react 0.5 hour, be heated to reflux 1 hour, then be down to room temperature, decompression abstraction toluene solvant, then plus
Enter methyl cyclohexane alkane solvents, mixed liquor total volume is 20mL to get co-catalyst E (1M, hexahydrotoluene solution) is arrived.
Product analysis: taking quantitative (with embodiment 1) co-catalyst E, and being slowly added to excessive water makes its decomposition, and liquid phase component is used
It is 3.4wt% that ICP, which tests aluminium content,；Gaseous component tests iso-butane content 87wt%, methane content 13wt%.
Embodiment 6
Under nitrogen protection, slowly 7mmol water droplet is added in 10mmol triisobutyl aluminium (1M toluene solution) under ice bath,
After being stirred to react 0.5 hour, temperature rising reflux 1 hour, it is spare to be then down to room temperature；Taking 5mmol methylaluminoxane, (1M toluene is molten
Liquid), it is added in above-mentioned solution, is then heated to reflux 1 hour, then be down to room temperature；1mmol water is slowly added under ice bath
State in mixed liquor, after being stirred to react 0.5 hour, be heated to reflux 1 hour, then be down to room temperature, decompression abstraction toluene solvant, then plus
Enter methyl cyclohexane alkane solvents, mixed liquor total volume is 15mL to get co-catalyst F (1M, hexahydrotoluene solution) is arrived.
Product analysis: taking quantitative (with embodiment 1) co-catalyst F, and being slowly added to excessive water makes its decomposition, and liquid phase component is used
It is 3.4wt% that ICP, which tests aluminium content,；Gaseous component tests iso-butane content 94wt%, methane content 6wt%.
Embodiment 7 (Polymerization Example)
Ethylene oligomerization reaction uses stainless steel polymeric kettle.Autoclave is heated to 80 DEG C, nitrogen displacement number is used after vacuumizing
It is secondary, it is down to room temperature, is then charged with ethylene displacement for several times.Then hexahydrotoluene is added at 40 DEG C, while 2.5 μm of ol second are added
Acyl acetone chromium and 5 μm of ol ligand Ls1(such as Formulas I, wherein R=R '=H, n=1) and 750 μm of ol co-catalyst A, the totality of mixed liquor
Product is 100mL, and wherein the molar ratio of chromium, ligand compound and co-catalyst is 1:2:300, controls reaction pressure 2MPa, is passed through
Ethylene carries out ethylene oligomerization reaction.
After the reaction was completed, system is cooled to room temperature, and gaseous products are collected in aerometer measuring tank, and liquid-phase product is collected
In conical flask, 1mL ethyl alcohol is added as terminator, terminates ethylene oligomerization reaction.Gas-chromatography is carried out after liquid phase gauging of products
Analysis.Reaction result is shown in Table 1.
Embodiment 8 (Polymerization Example)
With embodiment 7, the difference is that co-catalyst A is changed to cocatalyst B；Reaction result is shown in Table 1.
Embodiment 9 (Polymerization Example)
With embodiment 7, the difference is that co-catalyst A is changed to co-catalyst C；Reaction result is shown in Table 1.
Embodiment 10 (Polymerization Example)
With embodiment 7, the difference is that co-catalyst A is changed to co-catalyst D；Reaction result is shown in Table 1.
Embodiment 11 (Polymerization Example)
With embodiment 7, the difference is that co-catalyst A is changed to co-catalyst E；Reaction result is shown in Table 1.
Embodiment 12 (Polymerization Example)
With embodiment 7, the difference is that co-catalyst A is changed to co-catalyst F；Reaction result is shown in Table 1.
Embodiment 13 (Polymerization Example)
With embodiment 7, the difference is that reaction pressure is changed to 5MPa by 2MPa；Reaction result is shown in Table 1.
Embodiment 14 (Polymerization Example)
With embodiment 7, the difference is that ligand is changed to L2(such as Formulas I, wherein R=R '=H, n=2)；Reaction result
It is shown in Table 1.
Embodiment 15 (Polymerization Example)
With embodiment 7, the difference is that ligand is changed to L3(such as Formulas I, wherein R=R '=H, n=3)；Reaction result
It is shown in Table 1.
Embodiment 16 (Polymerization Example)
With embodiment 7, the difference is that ligand is changed to L4(such as Formulas I, wherein R=2-CH3, R '=H, n=1)；Reaction
It the results are shown in Table 1.
Embodiment 17 (Polymerization Example)
With embodiment 7, the difference is that ligand is changed to L5(such as Formulas I, wherein R=2-OCH3, R '=H, n=1)；Instead
1 should be the results are shown in Table.
Embodiment 18 (Polymerization Example)
With embodiment 7, the difference is that ligand is changed to L6(such as Formulas I, wherein R=3-Cl, R '=H, n=1)；Reaction
It the results are shown in Table 1.
Comparative example 1 (Polymerization Example)
With embodiment 7, the difference is that co-catalyst A is changed to triethyl aluminum；Reaction result is shown in Table 1.
Comparative example 2 (Polymerization Example)
With embodiment 7, the difference is that co-catalyst A is changed to methylaluminoxane (1.5M toluene solution)；Reaction knot
Fruit is shown in Table 1.
Comparative example 3 (Polymerization Example)
With embodiment 7, the difference is that solvent methyl hexamethylene is changed to toluene, co-catalyst A is changed to aluminium methyl
Oxygen alkane (commercially available, 1.5M toluene solution)；Reaction result is shown in Table 1.
Comparative example 4 (Polymerization Example)
Equivalent (with embodiment 1) methylaluminoxane (1.5M toluene solution) is taken, solvent is removed in vacuum, residue is white powder
Last shape solid is added hexahydrotoluene, fails to dissolve；It is used for polymerization reaction, condition can not be normal with embodiment 7, reaction
It carries out.Reaction result is shown in Table 1.
Comparative example 5 (Polymerization Example)
With embodiment 7, the difference is that co-catalyst A is changed to modified methylaluminoxane (aluminium content 3.4wt%, heptan
Alkane solution, iso-butane content 63wt%, methane content 37wt%).The modified methylaluminoxane is by commercially available MMAO-3A 7wt% heptan
Alkane solution is diluted and is obtained after heptane is added.Reaction result is shown in Table 1.
Table 1
The selectivity refers to the mass percentage of the component in the product.
As can be seen from Table 1: co-catalyst of the present invention can be dissolved completely in alkane solvent, in the reaction
Catalytic activity with superelevation；Commercially available methylaluminoxane is only dissolve in aromatic solvent, when being used for oligomerisation reaction, no matter
It is alkane solvent or aromatic solvent, catalytic activity is all decreased obviously；What commercially available methylaluminoxane obtained after removing solvent
White powder solid cannot be dissolved in alkane solvent, can not be effective for reaction；The catalysis of commercially available modified methylaluminoxane
Activity is low, and the content of 1- octene product is low.
Any numerical value mentioned in the present invention, if between any minimum and any highest value be there are two
The interval of unit then includes each all values for increasing a unit from minimum to peak.For example, if stating one kind
The value of the state-variables such as the amount of component, or temperature, pressure, time is 50-90, in the present specification it means that specific
List 51-89,52-88 ... and the numerical value such as 69-71 and 70-71.For the value of non-integer, can with due regard to
0.1,0.01,0.001 or 0.0001 is a unit.This is only some special examples indicated.In this application, with similar side
The all possible combinations of formula, the numerical value between cited minimum and peak are considered to have disclosed.
It should be noted that embodiment described above is applied to explain the present invention, do not constitute to of the invention any
Limitation.By referring to above-mentioned exemplary embodiments, invention has been described, it should be appreciated that wherein all words are
Descriptive and explanatory vocabulary, rather than limited vocabulary.It can be according to the rules within the scope of the claims to this
Modification is made in invention, and revises in without departing substantially from scope and spirit of the present invention to the present invention.Although described in it
The present invention relates to specific method, material and embodiments, it is not intended that the present invention is limited to particular case disclosed in it, phase
Instead, the present invention can be extended to other all methods and applications with the same function.
Claims (14)
1. a kind of carbon monoxide-olefin polymeric, including ligand compound, transistion metal compound shown in Formulas I and contain aluminum cocatalyst
Alkane solution；
R and R ' are identical or different in formula, are each independently selected from hydrogen, alkyl, alkoxy, naphthenic base and halogen；N is to be greater than or wait
In 1 integer；
The preparation method of the alkane solution containing aluminum cocatalyst includes:
Step a: water is reacted with the arene solution of alkyl aluminum；Wherein, the general formula of the alkyl aluminum is R1R2R3Al, R1、R2
And R3It is identical or different, independently selected from C1-C20Alkyl；
Step b: the solution obtained after reacting in step a is reacted with the arene solution of aikyiaiurnirsoxan beta；In the aikyiaiurnirsoxan beta
Alkyl and R1、R2And R3It is different；
Step c: after the solution obtained after reacting in step b is reacted with water, aromatic hydrocarbons is removed, alkane is added, is obtained containing aluminium
The alkane solution of co-catalyst.
2. carbon monoxide-olefin polymeric according to claim 1, which is characterized in that in the general formula of the alkyl aluminum, R1、R2And R3
It is identical or different, independently selected from C1-C10Alkyl；It is preferred that R1、R2And R3It is identical, it is selected from methyl, ethyl, n-propyl, isopropyl
One of base, butyl, isobutyl group, tert-butyl and n-pentyl.
3. carbon monoxide-olefin polymeric according to claim 1 or 2, which is characterized in that the aikyiaiurnirsoxan beta is selected from methylaluminoxane
At least one of with ethylaluminoxane.
4. carbon monoxide-olefin polymeric according to any one of claim 1-3, which is characterized in that the step a includes, described
The arene solution of water and alkyl aluminum reacts 0.1h to 1h at -20 DEG C to 10 DEG C, preferably -10 DEG C to 0 DEG C, is then heated to reflux
0.1h to 1h；Preferably, the molar ratio of the water in the step a and the alkyl aluminum is (0.5-1): 1.
5. carbon monoxide-olefin polymeric described in any one of -4 according to claim 1, which is characterized in that the step b includes, described
Obtained solution and the arene solution of aikyiaiurnirsoxan beta are preferably mixed, Zhi Houjia at room temperature at 5 DEG C to 40 DEG C after step a reaction
Heat reflux 0.1h to 1h；Preferably, the aikyiaiurnirsoxan beta in the step b and the molar ratio of the alkyl aluminum are (0.1-3): 1, preferably
(0.5-1):1。
6. carbon monoxide-olefin polymeric according to any one of claims 1-5, which is characterized in that the step c includes, described
Obtained solution and water react 0.1h to 1h at -20 DEG C to 10 DEG C, preferably -10 DEG C to 0 DEG C after reacting in step b, then plus
Heat reflux 0.1h to 1h；Preferably, the molar ratio of the water in the step c and the aikyiaiurnirsoxan beta is (0.1-0.3): 1.
7. carbon monoxide-olefin polymeric according to claim 1 to 6, which is characterized in that the R and R ' is selected from hydrogen, first
Base, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, cyclopropyl, cyclobutyl, cyclopenta, cyclohexyl, suberyl and halogen；
And/or n is selected from 1~10, is preferably selected from 1~3.
8. carbon monoxide-olefin polymeric described in any one of -7 according to claim 1, which is characterized in that the R1-R3It is identical, it is different
Butyl, after the hydrolysis containing aluminum cocatalyst, iso-butane content is higher than 75wt% in the gas-phase product that measures through gas-chromatography, excellent
Select 78wt-94wt%.
9. carbon monoxide-olefin polymeric according to claim 1 to 8, which is characterized in that the transistion metal compound
Selected from least one of chromium compound, molybdenum compound, iron compound, titanium compound, zirconium compounds and nickel compound, preferably
At least one of chromium acetylacetonate, isooctyl acid chromium, three (tetrahydrofuran) chromium trichlorides or two (tetrahydrofuran) chromium dichlorides.
10. carbon monoxide-olefin polymeric according to claim 1 to 9, which is characterized in that described in 1 mole
Ligand compound, the amount of the transistion metal compound are 0.1-10 moles, preferably 0.25-2 moles, more preferable 0.5-2 moles；
The amount containing aluminum cocatalyst is 1-1000 moles, preferably 10-700 moles, more preferably 100-200 moles.
11. a kind of application method of carbon monoxide-olefin polymeric, is included in catalyst according to claim 1 to 10
In the presence of composition, ethylene oligomerization reaction is carried out；It is preferred that it is anti-to carry out ethylene oligomerization in organic solvent, more preferably in alkane
It answers.
12. according to the method for claim 11, which is characterized in that in ethylene oligomerization reaction, reaction temperature 0-
200 DEG C, preferably 0-100 DEG C；Ethylene pressure is 0.1-20.0MPa, preferably 0.5-5.0MPa.
13. a kind of application method of carbon monoxide-olefin polymeric, is included in catalyst according to claim 1 to 10
Ethylene trimer and/or four poly- reactions are carried out in the presence of composition, and ethylene is preferably carried out in organic solvent, more preferably in alkane
Trimerization and/or four poly- reactions.
14. according to the method for claim 13, which is characterized in that the condition of reaction is as follows: temperature is 0-200 DEG C, preferably
It is 0-100 DEG C；Ethylene pressure is 0.1-20.0MPa, preferably 0.5-5.0MPa.
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