CN109265309A - A kind of method that polyethylene wax generates in ethene suppressing oligomerisation reaction - Google Patents
A kind of method that polyethylene wax generates in ethene suppressing oligomerisation reaction Download PDFInfo
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- CN109265309A CN109265309A CN201810923408.4A CN201810923408A CN109265309A CN 109265309 A CN109265309 A CN 109265309A CN 201810923408 A CN201810923408 A CN 201810923408A CN 109265309 A CN109265309 A CN 109265309A
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- C07—ORGANIC CHEMISTRY
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- C07C7/20—Use of additives, e.g. for stabilisation
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- C—CHEMISTRY; METALLURGY
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
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Abstract
The invention discloses the methods that polyethylene wax in a kind of ethene suppressing oligomerisation reaction generates, it include: that co-catalyst, major catalyst and polyethylene wax inhibitor are pre-mixed or are added separately in the oligomerisation reaction device containing reaction medium, control suitable reaction temperature, vinyl monomer is introduced to reaction pressure, ethylene oligomerization is carried out and prepares higher linear alpha olefins.The polyethylene wax inhibitor is selected from level-one aromatic amine compounds (Ar-NH2) one of or it is a variety of.The present invention can be while effectively inhibiting polyethylene wax to generate, and the yield for improving liquid phase alpha-olefin is conducive to the safe and stable operation of device so that the content of polyethylene wax in ethylene oligomerization reaction product be greatly reduced to obtain higher economic benefit.
Description
Technical field
The present invention relates to ethylene oligomerizations to prepare higher linear alpha olefins field more particularly to a kind of ethene suppressing oligomerisation reaction
The method of process generation by-product polyethylene wax.
Background technique
Linear alpha-alkene refers to double bond in the C of molecular end4Or more linear alkene, be that a kind of demand is huge heavy
Want petrochemical materials.Wherein, C4~C24Linear alpha-alkene wash preparing low density polyethylene (LDPE), high density polyethylene (HDPE), top grade
Many fields such as agent, higher alcohol, advanced PAO lubricating oil, surfactant and oil dope are washed to have a wide range of applications.Mesh
Before, ethylene oligomerization method is production of linear alpha-olefins, especially C4~C24Linear alpha-alkene it is main and most promising
Method.
1998, Brookhart and the place Gibson seminar independently reported using diimine pyridine as ligand
Iron, cobalt series catalyst.Such catalyst has the high catalytic activity for the metallocene catalyst that can match in excellence or beauty, and passes through modified ligand bone
The structure of frame or aromatic ring substituents can meet Schulz-Flory with efficient catalytic ethylene oligomerization, gained linear alpha-alkene product
Distribution, and linear selectivity >=95%, have boundless application prospect.Therefore, such catalyst is just rapid once reporting
Research and development hot spot as ethylene oligomerization field.However, its be catalyzed ethylene oligomerization product be often distributed it is very wide, predominantly
Carbon number is in C4~C30+Even carbon alpha-olefin and weight average molecular weight produced in the even higher wax-like polyethylene of 1000-10000
Product.Due to containing the more polyethylene wax insoluble in solvent in product, the viscous kettle problem of reaction kettle becomes very serious.In material
In transmission process, this part polyethylene wax is also easy to blocking pipeline, causes unnecessary parking and maintenance.In addition, a large amount of poly-
The presence of ethylene waxes also gives subsequent product separation to increase energy consumption and cost.Therefore the problem of by-product polyethylene wax, has become neat
The major obstacle of poly- reaction industry.
Aiming at the problem that a large amount of by-product polyethylene waxes in oligomerization, Chinese patent CN 96110306.X and United States Patent (USP)
US 5523508 is disclosed through cyclic part lighter products come the heavy oligomer in dissolution reactor, to eliminate wax precipitation
Method.But in fact, lighter products are limited to the solvability of heavy oligomer, the precipitation of wax cannot be completely eliminated.And
For Fe-series catalyst, the polyethylene wax molecular weight of by-product is higher, it is difficult to is completely dissolved by this method.The U.S.
6555723 B2 of patent US 2002019575 A1 and US discloses Fe-series catalyst in continuous operation, reduces co-catalyst
The method that the ratio of alkyl aluminum carries out reaction to reduce polyethylene wax generation.However, such method is to significantly reduce catalysis
Activity is cost, and the effect for reducing polyethylene wax is very limited, is difficult to carry out actual industrial application.In addition, being matched by changing
Body structure, people have carried out a large amount of exploratory developments to the catalyst that Novel Ligands are coordinated, however new catalyst system is often led to
Activity is greatly reduced or product is distributed (the primary product C that kicks the beam4Equal low-carbon alkenes), it is as a result unsatisfactory.
Applicant was once disclosed in Chinese patent CN 104961618A with phenols and other phenolic hydroxy group aromatic compounds
Object is as polyethylene wax inhibitor, the method for adjusting the distribution of iron series oligomerization catalysis system product.This method significant effect, Neng Gou
While effectively polyethylene wax being inhibited to generate, the yield of liquid phase alpha-olefin is significantly improved, so that ethylene oligomerization reaction be greatly reduced
The content of polyethylene wax in product is conducive to the safe and stable operation of device to obtain higher economic benefit.However, this method
Generally requiring could at biggish phenolic inhibitors dosage (molar ratio >=0.7 of the aluminium in institute's phenolic hydroxy group and co-catalyst)
Reach preferable polyethylene wax inhibitory effect, this will lead to accumulation of the inhibitor in final product, improve separation costs.
Therefore, the present invention will further preferably more suitable efficient polyethylene wax inhibitor, substantially eliminating polyethylene
While wax generates, the dosage of inhibitor is reduced.The problem is solved, can effectively prevent or reduce the viscous wall of reactor and pipeline is stifled
Plug reduces the frequency of parking and clear kettle, improves product quality, more effectively, economically productive target product, brings huge warp
Ji benefit.
Summary of the invention
The present invention is directed to further preferred polyethylene wax inhibitor, and provide in a kind of efficient ethene suppressing oligomerisation reaction and gather
The method that ethylene waxes generate.It include: by polyethylene wax inhibitor, co-catalyst premixing or to be added separately to containing reaction medium
Oligomerisation reaction device in pre-reaction, major catalyst is then added, controls suitable reaction temperature, introduces vinyl monomer to reaction pressure
Power carries out oligomerisation and prepares higher linear alpha olefins.
The polyethylene wax inhibitor is selected from aniline, single or multiple substituted aniline, polyamino benzene, single or multiple substituted connection
The level-ones aromatic amine compounds such as aniline, condensed ring arylamine (Ar-NH2) one of or it is a variety of.The single or multiple substituted benzene
Amine, benzidine, the single or multiple substituent group in condensed ring arylamine are alkyl, alkoxy, aryl, aryloxy group, halogen, nitro, hydroxyl, carboxylic
One of groups such as base, sulfydryl, ketone group, aldehyde radical, ester group, sulfonic group, amide groups are a variety of.
The polyethylene wax inhibitor can be further selected from aniline, containing C1~C10Alkyl benzene amine contains C1~C10Alkoxy
Aniline, containing phenylaniline, containing phenoxybenzamine, Fluoroaniline, chloro aminobenzen, bromoaniline, iodo aniline, nitroaniline, contain
C1~C10The aniline of alkyl and halogenic substituent contains C1~C10The aniline of alkyl and nitro (or other common groups), phenylenediamine,
One of level-ones aromatic amines such as benzidine, condensed ring arylamine are a variety of.It specifically may be selected from but not limited to aniline, para-totuidine, neighbour
Toluidines, 2,4- dimethylaniline, 2,6- dimethylaniline, 2- ethyl aniline, 4- ethyl aniline, 2,4- diethylaniline, 2,
6- diethylaniline, 2- isopropyl aniline, 4- isopropyl aniline, 2,4- diisopropyl aniline, 2,6- diisopropyl aniline, uncle 2-
Butylaniline, 4- tert-butyl aniline, 2,4- di-tert-butyl aniline, 2,6- di-tert-butyl aniline, 2,4,6- tri-tert aniline, 4-
Methyl -2,6- di-tert-butyl aniline, 2- aminoanisole, 3- aminoanisole, 4- aminoanisole, 2- fluoroaniline, 3- fluorobenzene
Amine, 4- fluoroaniline, 2,4 difluorobenzene amine, 2,6- difluoroaniline, 3,5- difluoroaniline, 2,4,6- trifluoromethyl aniline, perfluor aniline, 3-
Fluoro- 4- tert-butyl aniline, the fluoro- 4- tert-butyl aniline of 2-, the fluoro- 4- chloroaniline of 2-, the fluoro- 4- bromaniline of 2-, the fluoro- 4- Iodoaniline of 2-,
The fluoro- 4- methylaniline of 2-, 2- bromaniline, 3- bromaniline, 4- bromaniline, the bromo- 4- tert-butyl aniline of 3-, 2- chloroaniline, 3- chlorobenzene
The chloro- 4- tert-butyl aniline of amine, 4- chloroaniline, 3-, 2- nitroaniline, 3- nitroaniline, 4- nitroaniline, the bromo- 4- nitre of 2,6- bis-
Base aniline, naphthalidine, 2- naphthylamines, benzidine, 2- mercaptoaniline, 4- mercaptoaniline, 2- 5-trifluoromethylaniline, 3- trifluoromethylbenzene
Amine, 4- 5-trifluoromethylaniline, o-phenylenediamine, m-phenylene diamine (MPD), p-phenylenediamine, 2- carboxyanilino, 3- carboxyanilino, 4- carboxyl benzene
Amine, 2- phenylaniline, 3- phenylaniline, 4- phenylaniline, 4- perfluorophenyl aniline, 4- phenoxybenzamine, 4- perfluor phenoxy group
One of aniline, diamino-diphenyl ether are a variety of.
The co-catalyst is selected from one of alkylaluminoxane, modified alkylaluminoxanes or a variety of；It preferably is selected from C1~
C10Alkylaluminoxane, modified C1~C10One of alkylaluminoxane is a variety of；Specifically optional methylaluminoxane (MAO), alkane
The modified methylaluminoxane of base (such as ethyl or isobutyl group modified methylaluminoxane (MMAO-Et or MMAO-iBu)), aluminium ethide
Oxygen alkane (EAO), isobutyl aluminium alkoxide (iBAO), one of ethyl isobutyl base aikyiaiurnirsoxan beta (EBAO) or a variety of；Further preferably
One of MAO, MMAO or a variety of.MAO and MMAO is more effective co-catalyst for iron, cobalt series catalyst.
Contained amino (- NH in the polyethylene wax inhibitor2) with co-catalyst in aluminium molar ratio be 0.01~1:
1, preferably 0.1~1:1；The polyethylene wax inhibitor can interact with each catalyst component in reaction system, promote
The liquid phase olefin product of low molecular weight is obtained into β-H transfer reaction.
Various organic solvents commonly used in the art can be selected in the reaction medium, such as aromatic hydrocarbon, halogenated aromatic, fat
One of hydrocarbon, halogenated aliphatic hydrocarbon are a variety of；It is preferred that C6~C18Aromatic hydrocarbon, halogenated C6~C18Aromatic hydrocarbon, C1~C18Aliphatic hydrocarbon, halogen
For C1~C18One of aliphatic hydrocarbon is a variety of；Specifically optional benzene,toluene,xylene, chlorobenzene, ethylbenzene, chlorotoluene, pentane,
One of isopentane, hexane, hexamethylene, heptane, octane, nonane, chloromethanes, chloroethanes are a variety of, and C also can be selected6~C18
One of linear alpha-alkene or a variety of；One of further preferred n-hexane, hexamethylene, normal heptane, toluene are a variety of.
Above-mentioned solvent is more commonly used in this field, is the good solvent of catalyst, and price is more cheap.
The reaction temperature is 0~130 DEG C, further preferably 30~100 DEG C.
The reaction pressure is 0.1~10MPa, further preferably 0.1~3MPa.
The reaction time is 1~180min, further preferably 30~90min.
The oligomerisation reaction device is selected from stirring one or both of complete mixing flow reaction kettle or plug flow reactor.
The major catalyst in iron series, cobalt system, chromium system, titanium system, zirconium, nickel system, palladium system, vanadium series catalyst one
Kind is a variety of；One of rear transition Fe-series catalyst being further preferably coordinated with two teeth or tridentate ligand is a variety of, adopts
The Fe-series catalyst reacted with the ethylene oligomerization of the prior art, may be selected from but not limited to following three teeth as shown in formula a~h
The complex of class ligand and organoiron compound, iron halide or ferrous halide composition.
Each substituent group is defined as follows (various only to take the substituent group indicated) in the three tooth class ligand a~h:
R1With R1 ’It is identical or different, it is each independently selected from C1~C4Alkyl, C6~C12Aromatic radical, C1~C6Ester
Base, C1~C6Alkyl replace amido, H, halogen (F, Cl, Br, I), nitro or cyano；
R2With R2' identical or different, it is each independently selected from H, halogen (F, Cl, Br, I), C1~C4Alkyl or C1~C6
The amido that alkyl replaces；
R6With R6' identical or different, it is each independently selected from H, halogen (F, Cl, Br, I), C1~C4Alkyl or C1~C6
The amido that alkyl replaces；
R3、R4、R5、R3’、R4' and R5' identical or different, it is each independently selected from C1~C4Alkyl, C6~C12Virtue
Perfume base, C1~C6Alkoxy, C1~C6Ester group, C1~C6Alkyl replace amido, H, halogen (F, Cl, Br, I), nitro
Or cyano；
R7、R8、R9、R7’、R8' and R9' identical or different, it is each independently selected from C1~C4Alkyl, C6~C12Virtue
Perfume base, C1~C6Alkoxy, C1~C6Ester group, C1~C6Alkyl replace amido, H, halogen (F, Cl, Br, I), nitro
Or cyano.
The Fe-series catalyst is further preferably the bis (imino) pyridines ligand as shown in formula a and organoiron compound network
The catalyst system being combined into, wherein the molar ratio of organoiron compound and bis (imino) pyridines ligand shown in formula a is 0.1~10:
1；
The organoiron compound is selected from the compound that following formula indicates:
Wherein, S1With S2It is identical or different, it is each independently selected from C1~C4Alkyl, C1~C4Halohydrocarbyl, C6~
C12Aromatic radical, C1~C6Ester group, C1~C6Alkyl replace amido, H, halogen (F, Cl, Br, I), nitro or cyano；Into
The preferred C of one step1~C4Alkyl, C1~C4Halohydrocarbyl and halogen；N is 2 or 3.
The bis (imino) pyridines ligand of structure shown in formula a, can be prepared using preparation method generally in the art；General ginseng
Examine article " highly active Fe cobalt ethylene rolymerization catalyst " (High active iron of Small B L, Brookhart et al.
and cobalt catalyst for the polymerization of ethylene.Journal of American
Chemical Society, 1998,120 (16): 4049-4050) in record bis (imino) pyridines ligand preparation method,
It is double to can refer to the pyridine recorded in the Chinese patent ZL 01113195.0 of entitled " a method of synthesis three tooth imine ligands "
The preparation method of imines ligand.
Alternatively, the Fe-series catalyst preferably is selected from pyridine diimine iron complex shown in formula a ':
In formula a ', M is ferrous iron or ferric iron；
X1With X2It is identical or different, it is each independently selected from Cl, Br, I or C1~C4Alkyl.
The pyridyl di-imine iron complex of structure shown in formula a ' is also prepared using method generally in the art, generally
It " is prepared linearly with high activity and the highly selective ethylene oligomerization that is used for reference to the article of Small B L, Brookhart et al.
The iron catalyst of alpha-olefin " (Iron-based catalysts with exceptionally high activities and
selectivities for oligomerization of ethylene to linearα-olefins,Journal of
American Chemical Society, 1998,120 (28): 7143-7144) in record complex preparation method,
It can refer to the Chinese patent of entitled " a kind of iron catalyst composition series of ethylene oligomerization and the preparation method of alpha-olefin "
The preparation method for the complex recorded in ZL01109134.7.
The major catalyst, with the densimeter of central metal iron, concentration in the reaction system is 1 × 10-7~1 ×
10-4mol/L；Further preferably 1 × 10-6~1 × 10-4mol/L。
In the reaction system, the molar ratio of metal is 20~3000:1 in the aluminium and major catalyst in co-catalyst；
To reduce co-catalyst cost, further preferably 20~1500:1.
The oligomerization product is by C4~C30+Linear alpha-alkene and a certain amount of polyethylene wax composition mixture,
Linear selectivity >=95% meets Schulz-Flory distribution, and the K value of characterization product distribution is 0.35~0.85 (K=chain growth
Rate/(rate of chain growth+chain tra nsfer rate)=Cn+2Molal quantity/CnMolal quantity, n is positive integer).
It is deeply ground in the mechanism of the ethylene oligomerization process by-product polyethylene wax or high polymer that are catalyzed to Fe-series catalyst
It is found after studying carefully, Fe-series catalyst has the characteristics that dynamics model.Unreacted three are typically contained in co-catalyst MAO used
Aluminium methyl, under the activation of the co-catalyst, Fe-series catalyst will form two different activated centres, i.e., activate shape by MAO
At cationic iron complex and anion [Me-MAO]-The ion pair active specy 1 of composition, and shape is activated by trimethyl aluminium
At electroneutral active specy 2.1 stability of active specy is high, but huge anion [Me-MAO]-Iron will be centrally formed aobvious
The steric hindrance and screen effect of work are unfavorable for its induction β-H and shift to form alpha-olefin, therefore it is a certain amount of to polymerize ethylene synthesis
High polymer.The iron immediate vicinity steric hindrance of active specy 2 is smaller, and product is based on alpha-olefin.Two kinds of activated centres all have compared with
High reactivity.However, active specy 2 is unstable, it is easy inactivation.Alkyl aluminum present in co-catalyst can be further substituted with
With the iron center of ligands in active specy 2, aluminum complex is formed.The complex does not have catalytic activity, this is active matter
One of the main reason for 2 inactivation of kind.
Therefore, ethylene oligomerization process is adjusted using polyethylene wax inhibitor of the invention, it can effectively be tied
It closes on the surface MAO and hinders it too close to iron center, to reduce the steric hindrance of iron immediate vicinity, it is made to be unfavorable for high polymer
It generates.Meanwhile inhibitor can also be reacted with the trimethyl aluminium in MAO, reduce the formation of active specy 2, to obtain more
The high active specy 1 of stability.This can hinder trimethyl aluminium to be further substituted with iron to be centrally generated inactive aluminium cooperation simultaneously
Object, it is suppressed that the inactivation of active specy.Under the collective effect of these factors, the high polymer content in ethylene oligomerization drops significantly
It is low, and the yield of alpha-olefin improves.Compare phenolic inhibitors disclosed in Chinese patent CN104961618A (Ar-OH), this
Invention level-one aromatic amine inhibitor (Ar-NH used2) each active group (- NH2) active hydrogen containing there are two, it can be same
When reacted with two molecule trimethyl aluminiums, this makes its interaction with co-catalyst MAO more more efficient than phenolic inhibitors, can be
Reach better regulating effect under relatively lower dosage.The technical program is to disclosed in Chinese patent CN 104961618A
One kind of scheme is efficiently modified, principle simple possible, it is easy to accomplish.
The present invention has the advantage that
1) present invention is adjusted ethylene oligomerization process using polyethylene wax inhibitor, can be effective under less dosage
Ground inhibits high poly- activated centre to generate polymer, to make the yield of the polyethylene wax in oligomerization insoluble in solvent greatly
It reduces, or even close disappearance；
2) the polyethylene wax inhibitor that uses of the present invention is simultaneously for being also a kind of activator for liquid phase alpha-olefin, can be with
The inactivation for effectively inhibiting oligomeric activated centre improves its reactivity, makes the output increased of alpha-olefin；
3) the present invention be directed to the solutions that the problem of a large amount of by-product polyethylene waxes of ethylene oligomerization process or polyethylene is proposed
Scheme, simple possible, it is easy to accomplish, preferable economic benefit is easy to get in actual industrial production.
Specific embodiment
Technical solution of the present invention is described in further detail with comparative example combined with specific embodiments below, but cannot
It is limited the scope of the invention with this.It is i.e. all according to made by scope of the present invention patent variation and modification, should still belong in hair
In the range of bright patent covers.
Embodiment 1
Under nitrogen protection, by { 2,6- bis--[(the 2-aminotoluene base ethyls) of bis (imino) pyridines ligand L shown in formula a
Pyridine] } with after frerrous chloride 1:1 cooperation in molar ratio, obtain catalyst shown in formula a '.It is made into 4 × 10-6The main reminder of mol/mL
Agent toluene suspension.Co-catalyst methylaluminoxane (MAO) is the toluene solution of 10wt%, and substance withdrawl syndrome is about
1.5mol/L.Polyethylene wax inhibitor is aniline.
Catalyst LFeCl2Structural formula:
The oligomerisation reaction device of 250ml is heated to 90 DEG C or more, vacuumizes baking 2h, is replaced therebetween with high pure nitrogen more
It is secondary.Temperature of reaction kettle is then adjusted to 50 DEG C of reaction temperature by collet cooling water circulation, 50mL toluene is added and is situated between as reaction
Matter.The concentration of the Fe-series catalyst in reaction medium is set as 4 × 10-5Mol/L, with [Al]: the molar ratio of [Fe]=1000 adds
Enter a certain amount of co-catalyst MAO, and with [- NH2]: a certain amount of polyethylene wax inhibitor is added in the molar ratio of [Al]=0.3
Aniline is stirred to react.Ethylene pressure regulating valve is opened, be passed through ethylene rapidly and guarantees that reaction pressure is 0.1MPa, when oligomerisation reaction
Between be 30min.
Products therefrom is reacted after gas-liquid-solid separates, and polyethylene wax drying weighing obtains 0.043g；Liquid phase alpha-olefin product is logical
Crossing gas chromatograph-mass spectrometer (GC-MS), (temperature program of gas-chromatography is as follows: 50 DEG C of initial temperature, 5min is kept, then with 20
DEG C/min is warming up to 350 DEG C, then keep 10min.) analyzed.It is analyzed, obtains 3.12g；Polyethylene wax is in gross product
Content is 1.4wt%.
Embodiment 2
With [- NH2]: a certain amount of polyethylene wax inhibitor aniline is added in the molar ratio of [Al]=0.5, other operations are the same as real
Apply example 1.Products therefrom is reacted after gas-liquid-solid separates, and polyethylene wax drying weighing obtains 0.02g；Liquid phase alpha-olefin product is through color
Spectrum analysis obtains 3.85g；Content of the polyethylene wax in gross product is 0.5wt%.
Embodiment 3
With [- NH2]: a certain amount of polyethylene wax inhibitor aniline is added in the molar ratio of [Al]=0.7, other operations are the same as real
Apply example 1.Products therefrom is reacted after gas-liquid-solid separates, no polyethylene wax；Liquid phase alpha-olefin product obtains 3.56g through chromatography；
Content of the polyethylene wax in gross product is 0.
Embodiment 4
Using the major catalyst and co-catalyst in embodiment 1, with [- NH2]: the molar ratio of [Al]=0.3 is added certain
The polyethylene wax inhibitor para-totuidine of amount, other operations are the same as embodiment 1.Products therefrom is reacted after gas-liquid-solid separates, poly- second
The drying weighing of alkene wax, obtains 0.017g；Liquid phase alpha-olefin product obtains 3.17g through chromatography；Polyethylene wax containing in gross product
Amount is 0.5wt%.
Embodiment 5
Using the major catalyst and co-catalyst in embodiment 1, with [- NH2]: the molar ratio of [Al]=0.5 is added certain
The polyethylene wax inhibitor para-totuidine of amount, other operations are the same as embodiment 1.Products therefrom is reacted after gas-liquid-solid separates, poly- second
The drying weighing of alkene wax, obtains 0.006g；Liquid phase alpha-olefin product obtains 2.54g through chromatography；Polyethylene wax containing in gross product
Amount is 0.2wt%.
Embodiment 6
Using the major catalyst and co-catalyst in embodiment 1, with [- NH2]: the molar ratio of [Al]=0.7 is added certain
The polyethylene wax inhibitor para-totuidine of amount, other operations are the same as embodiment 1.Products therefrom is reacted after gas-liquid-solid separates, without poly-
Ethylene waxes；Liquid phase alpha-olefin product obtains 2.93g through chromatography；Content of the polyethylene wax in gross product is 0.
Embodiment 7
Using the major catalyst and co-catalyst in embodiment 1, with [- NH2]: the molar ratio of [Al]=0.3 is added certain
The polyethylene wax inhibitor 2- fluoroaniline of amount, other operations are the same as embodiment 1.Products therefrom is reacted after gas-liquid-solid separates, poly- second
The drying weighing of alkene wax, obtains 0.032g；Liquid phase alpha-olefin product obtains 2.73g through chromatography；Polyethylene wax containing in gross product
Amount is 1.2wt%.
Embodiment 8
Using the major catalyst and co-catalyst in embodiment 1, with [- NH2]: the molar ratio of [Al]=0.5 is added certain
The polyethylene wax inhibitor 2- fluoroaniline of amount, other operations are the same as embodiment 1.Products therefrom is reacted after gas-liquid-solid separates, poly- second
The drying weighing of alkene wax, obtains 0.013g；Liquid phase alpha-olefin product obtains 2.51g through chromatography；Polyethylene wax containing in gross product
Amount is 0.5wt%.
Embodiment 9
Using the major catalyst and co-catalyst in embodiment 1, with [- NH2]: the molar ratio of [Al]=0.7 is added certain
The polyethylene wax inhibitor 2- fluoroaniline of amount, other operations are the same as embodiment 1.Products therefrom is reacted after gas-liquid-solid separates, poly- second
The drying weighing of alkene wax, obtains 0.007g；Liquid phase alpha-olefin product obtains 2.44g through chromatography；Polyethylene wax containing in gross product
Amount is 0.3wt%.
Embodiment 10
Using the major catalyst and co-catalyst in embodiment 1, with [- NH2]: the molar ratio of [Al]=0.3 is added certain
The polyethylene wax inhibitor 2 of amount, 4- difluoroaniline, other operations are the same as embodiment 1.Products therefrom is reacted after gas-liquid-solid separates,
Polyethylene wax drying weighing, obtains 0.125g；Liquid phase alpha-olefin product obtains 3.33g through chromatography；Polyethylene wax is in gross product
Content be 3.6wt%.
Embodiment 11
Using the major catalyst and co-catalyst in embodiment 1, with [- NH2]: the molar ratio of [Al]=0.5 is added certain
The polyethylene wax inhibitor 2 of amount, 4- difluoroaniline, other operations are the same as embodiment 1.Products therefrom is reacted after gas-liquid-solid separates,
Polyethylene wax drying weighing, obtains 0.063g；Liquid phase alpha-olefin product obtains 3.24g through chromatography；Polyethylene wax is in gross product
Content be 1.9wt%.
Embodiment 12
Using the major catalyst and co-catalyst in embodiment 1, with [- NH2]: the molar ratio of [Al]=0.7 is added certain
The polyethylene wax inhibitor 2 of amount, 4- difluoroaniline, other operations are the same as embodiment 1.Products therefrom is reacted after gas-liquid-solid separates,
Polyethylene wax drying weighing, obtains 0.018g；Liquid phase alpha-olefin product obtains 3.21g through chromatography；Polyethylene wax is in gross product
Content be 0.6wt%.
Embodiment 13
Using the major catalyst and co-catalyst in embodiment 1, with [- NH2]: the molar ratio of [Al]=0.3 is added certain
The polyethylene wax inhibitor perfluor aniline of amount, other operations are the same as embodiment 1.Products therefrom is reacted after gas-liquid-solid separates, poly- second
The drying weighing of alkene wax, obtains 0.10g；Liquid phase alpha-olefin product obtains 2.47g through chromatography；Content of the polyethylene wax in gross product
For 3.9wt%.
Embodiment 14
Using the major catalyst and co-catalyst in embodiment 1, with [- NH2]: the molar ratio of [Al]=0.5 is added certain
The polyethylene wax inhibitor perfluor aniline of amount, other operations are the same as embodiment 1.Products therefrom is reacted after gas-liquid-solid separates, poly- second
The drying weighing of alkene wax, obtains 0.075g；Liquid phase alpha-olefin product obtains 2.93g through chromatography；Polyethylene wax containing in gross product
Amount is 2.5wt%.
Embodiment 15
Using the major catalyst and co-catalyst in embodiment 1, with [- NH2]: the molar ratio of [Al]=0.7 is added certain
The polyethylene wax inhibitor perfluor aniline of amount, other operations are the same as embodiment 1.Products therefrom is reacted after gas-liquid-solid separates, poly- second
The drying weighing of alkene wax, obtains 0.028g；Liquid phase alpha-olefin product obtains 2.80g through chromatography；Polyethylene wax containing in gross product
Amount is 1.0wt%.
Comparative example 1
Any polyethylene wax inhibitor is not added, repeats the operation of embodiment 1.
Products therefrom is reacted after gas-liquid-solid separates, and polyethylene wax drying weighing obtains 0.80g；Liquid phase alpha-olefin product warp
Chromatography obtains 1.65g；Content of the polyethylene wax in gross product is 32.7wt%.
Comparative example 2
Using the major catalyst and co-catalyst in embodiment 1, with [- OH]: the molar ratio of [Al]=0.3 is added a certain amount of
Polyethylene wax inhibitor phenol, other operation with embodiment 1.Products therefrom is reacted after gas-liquid-solid separates, and polyethylene wax dries
Dry weighing, obtains 1.28g；Liquid phase alpha-olefin product obtains 3.15g through chromatography；Content of the polyethylene wax in gross product be
28.9wt%.
Comparative example 3
Using the major catalyst and co-catalyst in embodiment 1, with [- OH]: the molar ratio of [Al]=0.7 is added a certain amount of
Polyethylene wax inhibitor phenol, other operation with embodiment 1.Products therefrom is reacted after gas-liquid-solid separates, and polyethylene wax dries
Dry weighing, obtains 0.19g；Liquid phase alpha-olefin product obtains 3.30g through chromatography；Content of the polyethylene wax in gross product be
5.4wt%.
Comparative example 4
Using the major catalyst and co-catalyst in embodiment 1, with [- OH]: the molar ratio of [Al]=0.3 is added a certain amount of
Polyethylene wax inhibitor p-cresol, other operation with embodiment 1.Products therefrom is reacted after gas-liquid-solid separates, polyethylene
Wax drying weighing, obtains 1.15g；Liquid phase alpha-olefin product obtains 2.70g through chromatography；Content of the polyethylene wax in gross product be
29.9wt%.
Comparative example 5
Using the major catalyst and co-catalyst in embodiment 1, with [- OH]: the molar ratio of [Al]=0.7 is added a certain amount of
Polyethylene wax inhibitor p-cresol, other operation with embodiment 1.Products therefrom is reacted after gas-liquid-solid separates, polyethylene
Wax drying weighing, obtains 0.03g；Liquid phase alpha-olefin product obtains 2.25g through chromatography；Content of the polyethylene wax in gross product be
1.3wt%.
1. embodiment of table and the result of comparative example summarize
Can be seen that technical solution provided by the invention from the comparison of above embodiments and comparative example can be efficiently and effectively
It is greatly reduced or even substantially eliminates the by-product polyethylene wax during ethylene oligomerization.Meanwhile fragrance of the present invention
Amine inhibitor is in [- NH2]/[Al] molar ratio be 0.3 when polyethylene wax inhibitory effect have reached even more than patent CN
Effect of the phenolic inhibitors used in 104961618A when [- OH]/[Al] molar ratio is 0.7.Polyethylene wax of the invention
Inhibitor is more efficient, is conducive to reduce its usage amount in practical applications, to reduce its accumulation in final product.
Claims (10)
1. a kind of method that polyethylene wax generates in ethene suppressing oligomerisation reaction, comprising: by co-catalyst, major catalyst and gather
Ethylene waxes inhibitor is pre-mixed or is added separately in the oligomerisation reaction device containing reaction medium, controls suitable reaction temperature,
Vinyl monomer is introduced to reaction pressure, oligomerisation is carried out and prepares higher linear alpha olefins；The polyethylene wax inhibitor is selected from one
Grade aromatic amine compounds (Ar-NH2) one of or it is a variety of.
2. the method that polyethylene wax generates in ethene suppressing oligomerisation reaction as described in claim 1, which is characterized in that described
Polyethylene wax inhibitor is selected from aniline, single or multiple substituted aniline, polyamino benzene, single or multiple substituted benzidine, condensed ring arylamine
One of or it is a variety of.
3. the method that polyethylene wax generates in suppression ethene suppressing oligomerisation reaction as claimed in claim 2, it is characterised in that described
Single or multiple substituted aniline, benzidine, the single or multiple substituent group in condensed ring arylamine be alkyl, alkoxy, aryl, aryloxy group,
One of groups such as halogen, nitro, hydroxyl, carboxyl, sulfydryl, ketone group, aldehyde radical, ester group, sulfonic group, amide groups are a variety of.
4. the method that polyethylene wax generates in ethene suppressing oligomerisation reaction as claimed in claim 3, which is characterized in that described
The preferably self-contained C of alkyl1~C10Alkyl；The preferably self-contained C of the alkoxy1~C10Alkoxy, the aryl preferably is selected from
Phenyl, the aryloxy group preferably are selected from phenoxy group.
5. the method that polyethylene wax generates in ethene suppressing oligomerisation reaction as described in claim 1, which is characterized in that described
Co-catalyst is selected from one of alkylaluminoxane, modified alkylaluminoxanes or a variety of.
6. the method that polyethylene wax generates in ethene suppressing oligomerisation reaction as claimed in claim 5, which is characterized in that described
Co-catalyst is selected from C1~C10Alkylaluminoxane, modified C1~C10One of alkylaluminoxane is a variety of, and can be further excellent
Selected from one of methylaluminoxane, modified methylaluminoxane or a variety of.
7. the method that polyethylene wax generates in ethene suppressing oligomerisation reaction as described in claim 1, which is characterized in that described
Contained amino (- NH in polyethylene wax inhibitor2) with co-catalyst in aluminium molar ratio be 0.01~1:1.
8. the method that polyethylene wax generates in ethene suppressing oligomerisation reaction as described in claim 1, which is characterized in that described
Major catalyst is selected from one of iron series, cobalt system, chromium system, titanium system, zirconium, nickel system, palladium system, vanadium series catalyst or a variety of.
9. the method that polyethylene wax generates in ethene suppressing oligomerisation reaction as described in claim 1, which is characterized in that described
Major catalyst is selected from one of rear transition Fe-series catalyst being coordinated with two teeth or tridentate ligand or a variety of；The main reminder
Agent, with the densimeter of central metal, concentration in the reaction system is 1 × 10-7~1 × 10-4Mol/L, the co-catalysis
The metalliferous molar ratio of institute is 20~3000:1 in aluminium and major catalyst in agent.
10. the method that polyethylene wax generates in ethene suppressing oligomerisation reaction as described in claim 1, which is characterized in that described
Reaction medium select aromatic hydrocarbon, halogenated aromatic, aliphatic hydrocarbon, one of halogenated aliphatic hydrocarbon or a variety of；The reaction temperature
Degree is 0~130 DEG C；Reaction pressure is 0.1~10MPa；Reaction time is 1~180min.
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| WO2020171730A1 (en) * | 2019-02-22 | 2020-08-27 | Public Joint Stock Company "Sibur Holding" | A method for separating olefin oligomerization products (variants) |
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| US20130211168A1 (en) * | 2012-02-10 | 2013-08-15 | IFP Energies Nouvelles | Catalytic composition and process for oligomerization of olefins using said catalytic composition |
| CN104961618A (en) * | 2015-06-12 | 2015-10-07 | 浙江大学 | Method for inhibiting generation of polyethylene wax in ethylene oligomerization reaction |
| CN105732254A (en) * | 2016-03-18 | 2016-07-06 | 浙江大学 | Method for preparing linear alpha-olefin by ethylene oligomerization |
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| US20130211168A1 (en) * | 2012-02-10 | 2013-08-15 | IFP Energies Nouvelles | Catalytic composition and process for oligomerization of olefins using said catalytic composition |
| CN104961618A (en) * | 2015-06-12 | 2015-10-07 | 浙江大学 | Method for inhibiting generation of polyethylene wax in ethylene oligomerization reaction |
| CN105732254A (en) * | 2016-03-18 | 2016-07-06 | 浙江大学 | Method for preparing linear alpha-olefin by ethylene oligomerization |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2020171730A1 (en) * | 2019-02-22 | 2020-08-27 | Public Joint Stock Company "Sibur Holding" | A method for separating olefin oligomerization products (variants) |
| CN113508102A (en) * | 2019-02-22 | 2021-10-15 | 公共型股份公司希布尔控股 | Process for the separation of olefin oligomerization products (variants) |
| US11912658B2 (en) | 2019-02-22 | 2024-02-27 | Public Joint Stock Company “SIBUR Holding” | Method for separating olefin oligomerization products (variants) |
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