CN109701647A - 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 carbon monoxide-olefin polymeric, including major catalyst chlorination 2 shown in formula (I), 8- diacetyl quinoline contracting amine closes iron (II) complex and the alkane solution containing aluminum cocatalyst；Each variable-definition wherein in formula is as follows: R1~R5It is each independently selected from hydrogen, C1~C6Alkyl, halogen, C1~C6Alkoxy and nitro.The invention further relates to the applications of the carbon monoxide-olefin polymeric.Carbon monoxide-olefin polymeric of the invention has very high activity；Meanwhile it avoiding in the polymerization using aromatic solvent, available high-quality product.
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-C8As important Organic Ingredients and chemical intermediate, it is mainly used in production high-quality polyethylene
(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-C30It 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..In LAOC20-C30On the basis of
It can also composite adhesives, sealant and coating.In recent years, with the continuous development of polyolefin industry, world wide is interior to α-alkene
The demand rapid development of hydrocarbon.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 product quality is seriously affected for arene solutions such as toluene.And it is copolymerized grade alpha-olefin
It 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
Agent composition is for being catalyzed ethylene oligomerization reaction, active high and selective high advantage.
According to an aspect of the invention, there is provided a kind of carbon monoxide-olefin polymeric, including major catalyst chlorination shown in Formulas I
2,8- diacetyl quinoline contracting amine closes iron (II) complex and the alkane solution containing aluminum cocatalyst；
Each variable-definition wherein in formula is as follows:
R1~R5It is each independently selected from hydrogen, C1~C6Alkyl, halogen, C1~C6Alkoxy and nitro.
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 R1’R2’R3’
Al, R1’、R2' and R3' 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’、R2' and R3' 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 is carried out with complex shown in the Formulas I
Mixing, or mixed when in use.
Catalyst according to the invention composition, prepare it is simple, at low cost, can effectively catalyze ethylene oligomerization reaction,
Advantage active high and that selectivity is high.
Some preferred embodiments according to the present invention, in the general formula of the alkyl aluminum, R1’、R2' and R3' identical or not
Together, independently selected from C1-C10Alkyl.In some preferred embodiments, R1’、R2' and R3' it is identical, selected from methyl, ethyl,
One of n-propyl, isopropyl, 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,
Trimethylbenzene and by halogen, nitro or alkyl-substituted phenyl derivatives.
In the present invention, term " alkane " refers to the hydrocarbon of saturation classes, as pentane, n-hexane, normal heptane,
At least one of pentamethylene, hexamethylene and hexahydrotoluene etc..
In the present invention, term " C1~C6Alkyl " refers to that the saturation containing 1~6 carbon atom is direct-connected or branched hydrocarbyl.
As C1~C6Alkyl, it can be mentioned that methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, tert-butyl, just
Amyl, sec-amyl, n-hexyl and Sec-Hexyl；Particularly preferred methyl, ethyl and isopropyl.
In the present invention, term " C1~C6Alkoxy " refers to above-mentioned C1~C6Alkyl connect to obtain with an oxygen atom
Group.As C1~C6Alkoxy, it can be mentioned that methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, isobutyl
Oxygroup, sec-butoxy, tert-butoxy, n-pentyloxy, secondary amoxy, positive hexyloxy and secondary hexyloxy；Particularly preferred methoxyl group and
Ethyoxyl.
In the present invention, term " halogen " refers to fluorine, chlorine, bromine and iodine, particularly preferred fluorine, chlorine and bromine.
Some preferred embodiments according to the present invention, the R1’、R2' and R3' identical, it is isobutyl group, it is described to be helped containing aluminium
After catalyst hydrolysis, iso-butane content is higher than 75wt%, preferably 78wt-94wt% in the gas-phase product that measures through gas-chromatography.
Some preferred embodiments according to the present invention, the preparation method containing aluminum cocatalyst 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.
Some preferred embodiments according to the present invention, the molar ratio of aluminium and iron in major catalyst is in the co-catalyst
(30-900): 1, preferably (30-500): 1, more preferably (50-300): 1.That is, the iron relative to 1mol closes object, it is described
Amount containing aluminum cocatalyst is 30-900mol, preferably 30-500mol, more preferably 50-300mol.
According to the present invention, co-catalyst solubility in alkane is good, the catalyst combination with iron complex composition
Object activity is high.
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 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.
According to the present invention, organic solvent used, such as alkane are carrying out Non-aqueous processing using preceding；The nothing of organic solvent
Processing method generally in the art can be used in method for treating water.
Carbon monoxide-olefin polymeric provided by the invention comprising the co-catalyst can effectively be catalyzed ethylene oligomerization reaction,
The ethylene oligomerization product of acquisition includes C4、C6、C8、C10、C12、C14、C16、C18、C20、C22Deng；The selectivity of alpha-olefin can achieve
96% or more.After ethylene oligomerization reaction terminates, GC analysis is carried out.The result shows that oligomerization activity is up to 107g·mol(Fe
)-1·h-1More than.Therefore, catalyst according to the invention composition has preferable prospects for commercial application and economic value.
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, the gaseous component after hydrolysis 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 minutes, 250 DEG C of injector temperature, 250 DEG C of detector temperature；Carrier gas: nitrogen, fid detector.
In the present invention, oligomerisation reaction product is detected using Agilent 7890A chromatograph.Chromatographic column: Agilent DB-
1, column length 50m, internal diameter 0.250mm；Column temperature: 30 DEG C, constant temperature 3 minutes, 20 DEG C/min of heating rate, 140 DEG C are warming up to, heating speed
25 DEG C/min of rate is warming up to 300 DEG C, constant temperature 16 minutes, 300 DEG C of injector temperature, 300 DEG C of detector temperature；Carrier gas: nitrogen,
Fid detector.
The present invention, which leads to conjunction iron (II) complex of major catalyst chlorination 2,8- diacetyl quinoline contracting amine shown in formula (I), to adopt
It is made with the preparation method of document (Organometallics 2010,29,1168-1173) report.
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 0.5h, then it is spare to be down to room temperature by temperature rising reflux 1h；10mmol methylaluminoxane (1M toluene solution) is taken, is added
Enter into above-mentioned solution, is then heated to reflux 1h, then be down to room temperature；2mmol water is slowly added into above-mentioned mixed liquor under ice bath
In, after being stirred to react 0.5h, it is heated to reflux 1h, then be down to room temperature, then decompression abstraction toluene solvant is added heptane solvent, mixes
Close liquid total volume be 20mL to get arrive co-catalyst A (1M, n-heptane solution).
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 0.5h, then it is spare to be down to room temperature by temperature rising reflux 1h；10mmol methylaluminoxane (1M toluene solution) is taken, is added
Enter into above-mentioned solution, is then heated to reflux 1h, then be down to room temperature；2mmol water is slowly added into above-mentioned mixed liquor under ice bath
In, after being stirred to react 0.5h, it is heated to reflux 1h, then be down to room temperature, then decompression abstraction toluene solvant is added heptane solvent, mixes
Close liquid total volume be 20mL to get arrive cocatalyst B (1M, n-heptane solution).
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 0.5h, then it is spare to be down to room temperature by temperature rising reflux 1h；10mmol methylaluminoxane (1M toluene solution) is taken,
It is added in above-mentioned solution, is then heated to reflux 1h, then be down to room temperature；2mmol water is slowly added into above-mentioned mixing under ice bath
In liquid, after being stirred to react 0.5h, it being heated to reflux 1h, then be down to room temperature, then heptane solvent is added in decompression abstraction toluene solvant,
Mixed liquor total volume be 20mL to get arrive co-catalyst C (1M, n-heptane 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 0.5h, then it is spare to be down to room temperature by temperature rising reflux 1h；10mmol methylaluminoxane (1M toluene solution) is taken, is added
Enter into above-mentioned solution, is then heated to reflux 1h, then be down to room temperature；3mmol water is slowly added into above-mentioned mixed liquor under ice bath
In, after being stirred to react 0.5h, it is heated to reflux 1h, then be down to room temperature, then decompression abstraction toluene solvant is added heptane solvent, mixes
Close liquid total volume be 20mL to get arrive co-catalyst D (1M, n-heptane solution).
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 0.5h, then it is spare to be down to room temperature by temperature rising reflux 1h；10mmol methylaluminoxane (1M toluene solution) is taken, is added
Enter into above-mentioned solution, is then heated to reflux 1h, then be down to room temperature；1mmol water is slowly added into above-mentioned mixed liquor under ice bath
In, after being stirred to react 0.5h, it is heated to reflux 1h, then be down to room temperature, then decompression abstraction toluene solvant is added heptane solvent, mixes
Close liquid total volume be 20mL to get arrive co-catalyst E (1M, n-heptane solution).
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 0.5h, then it is spare to be down to room temperature by temperature rising reflux 1h；It takes 5mmol methylaluminoxane (1M toluene solution), is added
Into above-mentioned solution, it is then heated to reflux 1h, then be down to room temperature；1mmol water is slowly added into above-mentioned mixed liquor under ice bath,
After being stirred to react 0.5h, it is heated to reflux 1h, then be down to room temperature, then heptane solvent, mixed liquor is added in decompression abstraction toluene solvant
Total volume be 15mL to get arrive co-catalyst F (1M, n-heptane solution).
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 heptane is added at 40 DEG C, 2.5 μm of ol complex chlorine are successively added
Change 2,8- diacetyl quinoline contracting 2,6- dimethylaniline and closes iron (II) and 500 μm of ol co-catalyst A (in terms of aluminium), mixed liquor
Total volume is that the molar ratio of 100mL, wherein iron complex and co-catalyst are 1:200, controls reaction pressure 1MPa, is passed through second
Alkene carries out ethylene oligomerization reaction.Holding ethylene pressure is 1MPa and reaction temperature is to react 30min at 30 DEG C；(7) stop anti-
It answers, takes out a small amount of reaction product with gas-chromatography and carry out (GC) analysis, analysis the results are 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 3MPa by 1MPa；Reaction result is shown in Table 1.
Embodiment 14 (Polymerization Example)
With embodiment 7, the difference is that iron complex is changed to chlorination 2,8- diacetyl quinoline 2,4,6- trimethyls of contracting
Aniline closes iron (II)；Reaction result is shown in Table 1.
Comparative example 1 (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 2 (Polymerization Example)
With embodiment 7, the difference is that solvent heptane is changed to toluene, co-catalyst A is changed to methylaluminoxane
(1.5M toluene solution)；Reaction result is shown in Table 1.
Comparative example 3 (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 heptane, fails to dissolve.It is used for polymerization reaction, condition can not be normally carried out with embodiment 7, reaction.
Comparative example 4 (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 by commercially available MMAO-3A 7wt%
N-heptane solution is diluted and is obtained after heptane is added.Reaction result is shown in Table 1.
Table 1
As can be seen from Table 1: co-catalyst of the present invention can be dissolved completely in alkane solvent, in the reaction
With very high catalytic activity；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 relatively 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 (11)
1. a kind of carbon monoxide-olefin polymeric, including major catalyst chlorination 2 shown in formula (I), 8- diacetyl quinoline contracting amine closes iron
(II) complex and the alkane solution containing aluminum cocatalyst；
Each variable-definition wherein in formula is as follows:
R1~R5It is each independently selected from hydrogen, C1~C6Alkyl, halogen, C1~C6Alkoxy and nitro；
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 R1’R2’R3' Al,
R1’、R2' and R3' 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’、R2' and R3' 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’、R2' and
R3' identical or different, independently selected from C1-C10Alkyl；It is preferred that R1’、R2' and R3' it is identical, selected from methyl, ethyl, n-propyl,
One of isopropyl, 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 aromatic hydrocarbons include replace or
Unsubstituted aromatic hydrocarbons is preferably selected from one of toluene, dimethylbenzene or nitrobenzene or a variety of.
The alkane is selected from one of pentane, heptane, hexane, hexahydrotoluene, hexamethylene and pentamethylene or a variety of.
8. carbon monoxide-olefin polymeric described in any one of -7 according to claim 1, which is characterized in that the R1’、R2' and R3' phase
It together, is isobutyl group, after the hydrolysis containing aluminum cocatalyst, iso-butane content is higher than in the gas-phase product that measures through gas-chromatography
75wt%, preferably 78wt-94wt%.
9. carbon monoxide-olefin polymeric according to claim 1 to 8, which is characterized in that in the co-catalyst aluminium with
The molar ratio of iron is (30-900): 1, preferably (30-500): 1, more preferably (50-300): 1 in major catalyst.
10. a kind of application method of carbon monoxide-olefin polymeric is included in catalyst group according to claim 1 to 9
In the presence of closing object, ethylene oligomerization reaction is carried out；It is preferred that carrying out ethylene oligomerization reaction in organic solvent, more preferably in alkane.
11. according to the method described in claim 10, it is characterized in that, the ethylene oligomerization reaction in, reaction temperature 0-
200 DEG C, preferably 0-100 DEG C；Ethylene pressure is 0.1-20.0MPa, preferably 0.5-5.0MPa.
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