CN109701644A - 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 trimer carbon monoxide-olefin polymeric, including ligand compound shown in formula (I), transistion metal compound, contain aluminum cocatalyst；R in formula1Independently selected from alkyl, aryl, alkyl derivative or aryl derivatives；R2For C1~C15Alkylene.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 avoiding in the polymerization using aromatic solvent, the toxicity of production process is greatly reduced, the harm to environment is reduced, high-quality product can also be obtained.
Description
Technical field
The present invention relates to a kind of carbon monoxide-olefin polymerics for ethylene oligomerization reaction.The invention further relates to a kind of catalyst groups
Close application of the object in ethylene trimer technique.
Background technique
Olefin(e) oligomerization is carried out using chromium-based catalysts, the oligomerisation of mainly alpha-olefin has obtained extensive research.It is more quasi-
It really says, has developed many chromium-based catalysts, and prepare alpha-olefin for olefin(e) oligomerization.Wherein, 1- is made in ethylene trimer
Hexene and ethylene tetramerization have more special meaning in terms of 1- octene is made.By the LLDPE resin of 1- alkene, 1- octene copolymer
Compared with the copolymer of 1- butylene, tensile strength, impact strength, tear resistance and durable performance are all obvious excellent, special
It Shi Yu not agricultural mulch films such as packaging film and greenhouse, canopy room etc..In terms of alpha-olefin is as comonomer, 1- hexene and 1- octene
1- butylene is substituted gradually to produce high performance PE product.
The production method of alpha-olefin mainly has wax destructive distillation method, ethylene oligomerization method, extraction separation method, fatty alcohol dehydriding, interior
Olefin isomerization method etc..Wherein, with high purity, selectivity is good, raw material availability is high because the alpha-olefin of its production has for ethylene oligomerization method
The features such as one of important channel as alpha-olefin production.
After John R.Briggs in J.Chem.Soc., Chem.Commun., 1989,674-675 pages, it was recently reported that with
After phase ternary chromium-based catalysts selectively prepare the approach of 1- hexene to be catalyzed ethylene trimer, 1- hexene production technology has obtained length
The development of foot.In order to more rationally utilize petroleum, people are being dedicated to developing efficient catalyst for oligomerization always, it is expected that obtaining
High-purity high alpha-olefin.In numerous explorations, heteroatom ligand and chromium sub-group compound are acted on, and for its olefin(e) oligomerization at
For the new research hotspot in the field.Disclosed in CN1606539A a kind of multiple tooth dentate phosphine containing aikyiaiurnirsoxan beta and chromic salts,
The complex of arsenic and/or antimony, and be used in ethylene oligomerization reaction process；WO2003053890 reports a kind of new
Sulphur nitrogen heteroatom ligand is used for olefin oligomerization, and olefin oligomerization occurs under the action of chromium compound and alkylaluminoxane, should
Carbon monoxide-olefin polymeric has the characteristics that catalytic activity is high, product 1- hexene purity is high.However, the catalyst obtained by above-mentioned patent
Generally existing disadvantage expensive, product cost is higher.
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
For arene solutions such as toluene, in the reaction product so as to cause aromatic hydrocarbons residual, or even catalyst performance living is influenced, also serious shadow
Ring 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 being catalyzed ethylene oligomerization reaction, especially ethylene trimer reacts agent composition, active high and selective 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；
In formula: R1Independently selected from alkyl, aryl, alkyl derivative or aryl derivatives；R2For C1~C15Alkylene,
Preferably C2~C10Alkylidene.
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 reacts, 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 5min at -10 DEG C to 0 DEG C
H to 60min, then heating reflux reaction 5min h to 60min.In some preferred embodiments, water in the step a with
The molar ratio of the alkyl aluminum 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 5min h to 60min at -20 DEG C to 10 DEG C, preferably -10 DEG C to 0 DEG C, is then heated to reflux
5min h to 60min.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 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.
A preferred embodiment according to the present invention, R1Independently selected from C1-C10Alkyl and phenyl；R2For C2~C10
Alkylidene.The alkyl includes straight chained alkyl and branched alkyl；Alkylidene includes straight-chain alkyl-sub and branched alkylidene.
A preferred embodiment according to the present invention, the transistion metal compound are selected from chromium, molybdenum, iron, titanium, zirconium or nickel
At least one of compound, preferably chromium acetylacetonate, isooctyl acid chromium, three (tetrahydrofuran) chromium trichlorides or two (tetrahydros
At least one of furans) chromium dichloride.
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 1-1500 moles, preferably 10-800 moles, more preferably 100-260 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 another above-mentioned carbon monoxide-olefin polymeric, packet are additionally provided
Include progress ethylene oligomerization such as trimerization reaction in the presence of above-mentioned carbon monoxide-olefin polymeric.In some preferred examples, having
Solvent preferably carries out ethylene trimer reaction in alkane.The condition of reaction is as follows: temperature is 0-200 DEG C, preferably 0-100
℃；Ethylene pressure is 1-20.0MPa, preferably 2.0-7.0MPa.In general, catalyst activity is as reaction pressure increases
And it increases.
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 carry out effectively being catalyzed ethylene oligomerization anti-
It answers, especially ethylene trimer reacts, and catalyst activity can be more than 3 × 107g/(molCr·h)；C6Component selection > 95%, 1-
Hexene is in C6In account for 99% or more；Other is the alpha-olefins such as a small amount of C4, C8, C10, C12.With high activity, highly selective, and
The features such as heavy polymer is few.Therefore, catalyst according to the invention composition has preferable prospects for commercial application
And economic value.
Specific embodiment
The present invention is described in detail with reference to embodiments, but the present invention is not limited to following embodiments.
Ligand referenced patent ZL201204188829.4 self-control employed in the present invention.
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, gaseous component 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.
Embodiment 1
Under nitrogen protection, 10mmol water droplet is slowly added to 15mmol triisobutyl aluminium (1M toluene solution) under ice bath
In, after being stirred to react 30min, temperature rising reflux 1 hour, it is spare to be then down to room temperature；Taking 15mmol 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
It states in mixed liquor, after being stirred to react 30min, is heated to reflux 1 hour, then be down to room temperature, then decompression abstraction toluene solvant is added
Cyclohexane solvent, mixed liquor total volume be 30mL to get arrive co-catalyst A (1M, cyclohexane 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 30min, 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
It states in mixed liquor, after being stirred to react 30min hours, is heated to reflux 1 hour, then be down to room temperature, decompression abstraction toluene solvant, then
Be added cyclohexane solvent, mixed liquor total volume be 20mL to get arrive cocatalyst B (1M, cyclohexane 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 0.5 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 cyclohexane solvent, mixed liquor total volume be 20mL to get arrive co-catalyst C (1M, cyclohexane 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 cyclohexane solvent, mixed liquor total volume is 20mL to get co-catalyst D (1M, cyclohexane 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 cyclohexane solvent, mixed liquor total volume is 20mL to get co-catalyst E (1M, cyclohexane 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 cyclohexane solvent, mixed liquor total volume is 15mL to get co-catalyst F (1M, cyclohexane 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 hexamethylene is added at 40 DEG C, while 2.5 μm of ol levulinics are added
Ketone chromium and 5 μm of ol ligand (R1SR2)2N ligand (wherein R1For ethyl, R2For ethylidene) and 750 μm of ol co-catalyst A, mixed liquor
Total volume be 100mL, wherein the molar ratio of chromium, ligand compound and co-catalyst be 1:2:240, control reaction pressure
5MPa is passed through ethylene, carries out ethylene trimer 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 2MPa by 4MPa；Reaction result is shown in Table 1.
Embodiment 14 (Polymerization Example)
With embodiment 7, the difference is that R1It is changed to decyl；Reaction result is shown in Table 1.
Embodiment 15 (Polymerization Example)
With embodiment 7, the difference is that R1It is changed to phenyl；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 hexamethylene 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 hexamethylene, 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
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；Commercially available modified methylaluminoxane is used for second
Its catalytic activity is substantially less than carbon monoxide-olefin polymeric of the invention when alkene trimerization reaction.
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 (12)
1. a kind of carbon monoxide-olefin polymeric, including ligand compound, transistion metal compound shown in formula (1), and help and urge containing aluminium
The alkane solution of agent；
In formula, R1Selected from alkyl, aryl, alkyl derivative and aryl derivatives, it is preferably selected from C1-C10Alkyl and phenyl；R2For
C1~C15Alkylene, preferably C2-C10Alkylidene；
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, in the general formula of the alkyl aluminum, R1、R2And R3It 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, butyl, isobutyl
One of base, 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 5~60min at -20 DEG C to 10 DEG C, preferably -10 DEG C to 0 DEG C, is then heated to reflux 5
~60min；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
The solution and water obtained after reacting in step b reacts 5min to 60min at -20 DEG C to 10 DEG C, preferably -10 DEG C to 0 DEG C, then
5min is heated to reflux to 60min；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 alkane be selected from hexane,
One of heptane, hexamethylene, pentamethylene, dodecane, the tetradecane and hexahydrotoluene are a variety of；And/or the aromatic hydrocarbons includes
Substituted or unsubstituted aromatic hydrocarbons is preferably selected from one of toluene, dimethylbenzene or nitrobenzene 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-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
At least one of compound selected from chromium, molybdenum, iron, titanium, zirconium or nickel, preferably chromium acetylacetonate, isooctyl acid chromium, three (tetrahydros
Furans) at least one of chromium trichloride 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 1-1500 moles, preferably 10-800 moles, more preferably 100-260 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 trimer reaction is carried out；It is preferred that it is anti-to carry out ethylene trimer in organic solvent, more preferably in alkane
It answers.
12. according to the method for claim 11, which is characterized in that in ethylene trimer reaction, reaction temperature 0-
200 DEG C, preferably 0-100 DEG C；Ethylene pressure is 0.5-20.0MPa, preferably 2.0-7.0MPa.
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