CN104511311B - A kind of ethylene trimer of high selectivity, four poly- catalyst systems and its application method - Google Patents
A kind of ethylene trimer of high selectivity, four poly- catalyst systems and its application method Download PDFInfo
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Abstract
The present invention provides a kind of ethylene trimer of high selectivity, four poly- catalyst systems and its application method, and the catalyst system includes three parts：（1）A kind of chromium compound；（2）A kind of part, its general structure is：(Ph2)P‑N(R1)‑P(Ph2), wherein R1It is phenyl, the alkyl or cycloalkyl of synthesis；（3）A kind of activator or co-catalyst.The catalyst system is improved to original PNP chromium-based catalysts, improves the common selectivity of 1 hexene and 1 octene, reduces wax-like product, and maintain activity higher.
Description
Technical field
The present invention relates to be used for the poly- positive-negative-positive chromium-based catalysts of ethene high selectivity trimerization four and its preparation ethene is catalyzed with it
Trimerization, four poly- methods.
Background technology
Linear alpha-olefins (1inear α-olefins, LAOs) refer to C4And C4More than linear alkene, its series of products is
Important basic organic chemical industry raw material, is preparing High performance polyolefin, high-grade detergent, higher alcohol, senior lubricant, surface work
The property field such as agent and oil dope has a wide range of applications.Wherein C6-C8Alpha-olefin be mainly used as comonomer and produce property high
Energy polyolefin, consumption is maximum, and appreciation potential is maximum, is the product that the country is most badly in need of at present.
Polyethylene is a class in industry and daily life using macromolecular material widely.Due to abundant raw material,
It is cheap, shaping, high comprehensive performance, therefore yield maximum are easily worked, using quite varied.But it is in machining
There is certain defect in the aspects such as performance, heat resistance, flexibility, the transparency, to improve these performances of polyethylene, 70 years last century
In generation, produces ethene and C4-C10Alpha-olefin copolymer new type resin, LLDPE (LLDPE).Linea low density
Polyethylene has good tensile strength, impact strength and environmental stress crack resistance, is referred to as " third generation polyethylene ".Mesh
Preceding 1- butylene is the LLDPE comonomers for generally using, but 1- butylene is improving LLDPE tearing toughness and breakdown strength etc.
Aspect of performance is far away from 1- hexenes and 1- octenes.So to produce high-quality LLDPE depends on 1- hexenes and 1- octene techniques
Development.
The method of industrial production LAOs is broadly divided into two kinds：A kind of is traditional super distributed mode of production, is mainly led to
Cross non-selective oligomerisation, cyclenes hydrocarbon isomerization, dehydration of alcohols, wax cracking or coal cracking etc. and obtain alpha-olefin, this mode is given birth to
The alpha-olefin of product needs to obtain the product that purity reaches copolymerization requirement by separation and Extraction again, but the amount of production is fewer, and
And cost is higher；Another way is selective oligomerization, mainly directly by dimerization, the trimerization and four of ethene high selectivity
It is poly- to respectively obtain 1- butylene, 1- hexenes and 1- octenes.The latter has atom utilization and preferable economic benefit very high, more
Meet the requirement of Modern Green Chemistry.
At present, Chevron Phillips companies deliver patent US5198563, and realize work in Qatar in 2003
Industry trimerization produces 1- hexenes.And the consor of ethylene selectivity four, into 1- octenes, Sasol companies delivered patent in 2004
WO2004/056478, and it has been reported that the consor of ethylene selectivity four will be industrialized into 1- octenes in 2013.
In recent years, the successive appearance of the report for gathering with ethene high selectivity trimerization four, develops high-selective ethylene oligomerisation
Catalyst, particularly chromium system catalyst for ethylene tetramerization have become the focus of current research.The master of chromium system catalyst for ethylene tetramerization
Catalyst is chromium source（Chromium trichloride, chromium acetylacetonate etc.）Obtained with bluk recombination with positive-negative-positive, in the relatively-stationary condition in chromium source
Under, adjusting the structure of positive-negative-positive part becomes the inevitable means for changing major catalyst structure and regulation catalytic performance, and produces therewith
The PNP parts of a series of new are given birth to.In these researchs, it is to the substitution on N atoms in PNP to have substantial portion of work
Base is modified, and research is found by changing substitution base, can produce obvious influence to the common selectivity of 1- hexenes/1- octenes.
The high selectivity catalyst for oligomerization reported can obtain nearly 90% common selectivity at present, but this be not met by it is industrialized
It is required that, therefore, still need to the further new positive-negative-positive catalyst of exploitation design.
The content of the invention
It is an object of the invention to provide a kind of ethylene trimer of high selectivity, four poly- catalyst systems and its catalysis ethene
Trimerization, four poly- methods, the catalyst system are improved to original PNP chromium-based catalysts, improve 1- hexenes and 1- is pungent
The common selectivity of alkene, reduces wax-like product, and maintain activity higher.
The technical scheme is that：
A kind of ethylene trimer of high selectivity, four poly- catalyst systems, it is characterised in that：Including three parts：
（i）A kind of chromium compound；
（ii）A kind of part, its general structure is：(Ph2)P-N(R1)-P(Ph2),
Wherein R1It is phenyl, the alkyl or cycloalkyl of synthesis；
（iii）A kind of activator or co-catalyst.
According to the catalyst system that the present invention is provided, it is preferred that the chromium compound is selected from organic salt, the nothing of trivalent chromium
Machine salt, co-ordination complex or metal-organic complex.
According to the catalyst system that the present invention is provided, it is preferred that the chromium compound is selected from Cr (acac)3、CrCl3
(THF)3, 2 ethyl hexanoic acid chromium (III), sad chromium (III), chromium carbonyl,（Benzene）One kind in tricarbonyl chromium.
According to the catalyst system that the present invention is provided, it is preferred that the R in the ligand structure formula1Group is selected from（It is different
Propyl group isobutyl group）Methyl,（Double isopropyls）Methyl,（Isopropylcyclohexyl）Methyl,（Isobutyl butylcyclohexyl）Methyl,（Cyclopenta
Cyclohexyl）Methyl,（1,2,5- trimethyls）Cyclohexyl, 1- phenylcyclohexyls, 1- naphthyls cyclohexyl, trityl group, 1- naphthyls
One or more in isobutyl group, 1- propyloxy phenyls base, 1- cyclohexylcyclohexyls.
The improvement for essentially consisting in part of the invention, the part is PNP parts, with below formula：
Wherein, 1- hexenes and 1- Octenes selectivities part higher such as following formula are generated for ethylene oligomerization,
New PNP parts of the present invention, it is preferred that wherein, R1During for alkyl, the part as listed by following formula：
New PNP parts of the present invention, it is preferred that wherein, R1During for arylcyloalkanes, match somebody with somebody as listed by following formula
Body：
According to the catalyst system that the present invention is provided, it is preferred that the activator or co-catalyst be selected from triethyl aluminum,
Trimethyl aluminium, triisopropylaluminiuand, triisobutyl aluminium, the aluminium of triethyl group tri-chlorination two, the aluminium of triethyl group tri-chlorination two, diethyl chlorination
One or more in aluminium, ethylaluminum dichloride, MAO and modified methylaluminoxane.
According to the catalyst system that the present invention is provided, it is preferred that also include a kind of solvent in the catalyst system.
According to the catalyst system that the present invention is provided, it is preferred that the solvent is selected from aromatic hydrocarbon, straight chain or ring-shaped fat
One kind in hydrocarbon, ether.
According to the catalyst system that the present invention is provided, it is preferred that the solvent is linear alkene.
According to the present invention provide catalyst system, it is preferred that the solvent be selected from benzene, toluene, ethylbenzene, isopropylbenzene,
One kind in dimethylbenzene, hexane, octane, hexamethylene, methyl cyclopentane, hexene, heptene, Anaesthetie Ether and tetrahydrofuran.
According to the catalyst system that the present invention is provided, it is preferred that the chromium concn is 0.01-100mmol/L.
According to the catalyst system that the present invention is provided, it is further preferred that, the chromium concn is 0.1-10mmol/L.
According to the catalyst system that the present invention is provided, it is preferred that the part is 0.01- with the mol ratio of chromium
100mol/mol。
According to the catalyst system that the present invention is provided, it is further preferred that, the part is 0.8- with the mol ratio of chromium
3.0mol/mol。
According to the catalyst system that the present invention is provided, it is preferred that the co-catalyst is 1- with the mol ratio of chromium
5000mol/mol。
According to the catalyst system that the present invention is provided, it is further preferred that, the co-catalyst is with the mol ratio of chromium
10-1000mol/mol。
The ethylene trimer for also providing described high selectivity of the invention, four poly- catalyst systems catalysis ethylene trimers, four gather
Application method, it is characterised in that comprise the following steps：
（1）In 300mL autoclaves, nitrogen displacement is first carried out to autoclave, then carry out ethylene gas displacement；Then to height
Solvent is injected in pressure kettle, and is stirred under ethylene gas atmosphere, heating；
（2）Above-mentioned activator or co-catalyst, part and chromium compound are injected in autoclave, stirring, to reactor
In be passed through ethylene gas and adjust pressure in kettle, oligomerisation reaction starts；
（3）After oligomerisation reaction 10min to 20h, ethylene gas are closed, and reaction system are quickly cooled to -20-40 DEG C,
Product deionized water split-phase, obtains organic phase for 1- hexenes and 1- octenes.
Catalysis ethylene trimer, the four poly- oligomerizations provided according to the present invention, it is preferred that the structure of the part is led to
Formula is：(Ph2)P-N(R1)-P(Ph2), wherein R1Group is selected from（Isopropyl butyl）Methyl,（Double isopropyls）Methyl,（Isopropyl
Butylcyclohexyl）Methyl,（Isobutyl butylcyclohexyl）Methyl,（Cyclopentyl cyclohexyl）Methyl,（1,2,5- methyl）Cyclohexyl, 1- phenyl
In cyclohexyl, 1- naphthyls cyclohexyl, trityl group, 1- naphthyls isobutyl group, 1- propyloxy phenyls base, 1- cyclohexylcyclohexyls one
Plant or several.
Catalysis ethylene trimer, the four poly- oligomerizations provided according to the present invention, it is preferred that the chromium compound is selected from
The organic salt of trivalent chromium, inorganic salts, co-ordination complex or metal-organic complex.
Catalysis ethylene trimer, the four poly- oligomerizations provided according to the present invention, it is preferred that the chromium compound is selected from
Cr(acac)3、CrCl3(THF)3, 2 ethyl hexanoic acid chromium (III), sad chromium (III), chromium carbonyl,（Benzene）In tricarbonyl chromium
It is a kind of.
Catalysis ethylene trimer, the four poly- oligomerizations provided according to the present invention, it is preferred that the activator or help is urged
Agent is selected from triethyl aluminum, trimethyl aluminium, triisopropylaluminiuand, triisobutyl aluminium, the aluminium of triethyl group tri-chlorination two, diethyl chlorination
One or more in aluminium, ethylaluminum dichloride, MAO and modified methylaluminoxane.
Catalysis ethylene trimer, the four poly- oligomerizations provided according to the present invention, it is preferred that the solvent is selected from fragrance
One kind in hydrocarbon, straight chain or cyclic aliphatic hydrocarbon, ether.
Catalysis ethylene trimer, the four poly- oligomerizations provided according to the present invention, it is preferred that the solvent is straight chain alkene
Hydrocarbon.
Catalysis ethylene trimer, the four poly- oligomerizations provided according to the present invention, it is preferred that the solvent be selected from benzene,
Toluene, ethylbenzene, isopropylbenzene, dimethylbenzene, hexane, octane, hexamethylene, methyl cyclopentane, hexene, heptene, Anaesthetie Ether and tetrahydrochysene
One kind in furans.
Catalysis ethylene trimer, the four poly- oligomerizations provided according to the present invention, it is preferred that the chromium concn is
0.01-100mmol/L。
Catalysis ethylene trimer, the four poly- oligomerizations provided according to the present invention, it is further preferred that, the chromium concn
It is 0.1-10mmol/L.
Catalysis ethylene trimer, the four poly- oligomerizations provided according to the present invention, it is preferred that the part rubs with chromium
You are than being 0.01-100mol/mol.
Catalysis ethylene trimer, the four poly- oligomerizations provided according to the present invention, it is further preferred that, the part with
The mol ratio of chromium is 0.8-3.0mol/mol.
Catalysis ethylene trimer, the four poly- oligomerizations provided according to the present invention, it is preferred that the co-catalyst and chromium
Mol ratio be 1-5000mol/mol.
Catalysis ethylene trimer, the four poly- oligomerizations provided according to the present invention, it is further preferred that, the co-catalysis
Agent is 10-1000mol/mol with the mol ratio of chromium.
Catalysis ethylene trimer, the four poly- oligomerizations provided according to the present invention, it is preferred that the pressure of the oligomerisation reaction
Power is 0.1-20MPa.
Catalysis ethylene trimer, the four poly- oligomerizations provided according to the present invention, it is further preferred that, the oligomerisation is anti-
The pressure answered is 2.0-6.5MPa.
Catalysis ethylene trimer, the four poly- oligomerizations provided according to the present invention, it is preferred that the oligomerisation reaction temperature
It is 10-200 DEG C.
Catalysis ethylene trimer, the four poly- oligomerizations provided according to the present invention, it is further preferred that, the oligomerisation is anti-
It is 20-100 DEG C to answer temperature.
Catalysis ethylene trimer, the four poly- oligomerizations provided according to the present invention, it is preferred that the oligomerisation reaction time
For 10min to 20h.
Catalysis ethylene trimer, the four poly- oligomerizations provided according to the present invention, it is further preferred that, the oligomerisation is anti-
It is 0.5h to 4h between seasonable.
According to the preparation method of part of the present invention：At 0 DEG C, by chloro diphenylphosphine and corresponding phenyl, alkyl or ring
Alkylamine is according to 2:1 mol ratio is stirred in adding dichloromethane solution, and after stirring 40min, continuation is stirred at normal temperatures
Overnight.The amine hydrochlorate produced in reaction is filtered to remove, product is obtained after recrystallization.
Another equivalent technical scheme of the invention is：
Present invention is mainly used for ethene high selectivity trimerization and four poly- reactions, 1- hexenes and 1- butylene, its catalyst are generated
Composition mainly includes following components：
（1）A kind of chromium compound
（2）A kind of part, its general structure is：(Ph2)P-N(R1)-P(Ph2)
Wherein R1It is the alkyl, phenyl or the cycloalkyl that synthesize, concrete structure is referring to accompanying drawing.
（3）A kind of activator or co-catalyst
（4）A kind of organic solvent
Wherein, chromium compound may be selected the organic salt or inorganic salts, co-ordination complex and Organometallic complex of Cr (III)
Thing.Optimal selection is chromium acetylacetonate Cr (acac)3, tetrahydrofuran chromium chloride CrCl3(THF)3, 2 ethyl hexanoic acid chromium (III)；
R in part1Group is mainly alkyl, phenyl or cycloalkyl, and concrete structure is shown in structure above.
Activator or co-catalyst are mainly alkyl aluminum class, and triethyl aluminum, trimethyl aluminium, triisopropylaluminiuand, three may be selected
Aluminium isobutyl, the aluminium of triethyl group tri-chlorination two, the aluminium of triethyl group tri-chlorination two, diethyl aluminum chloride, ethylaluminum dichloride, methyl alumina
Alkane or its mixture etc., optimal selection are modified methylaluminoxane MMAO or MAO MAO.
In addition, present invention also offers the experimental technique that the catalyst system is used for ethylene oligomerization.
Solvent toluene can be replaced with other solvents, and the solvent of catalyst system is selected from aromatic hydrocarbon（Benzene, ethylbenzene, isopropylbenzene,
Dimethylbenzene etc.）；Aliphatic hydrocarbon（Straight chain and ring-type, such as hexane, octane, hexamethylene, methyl cyclopentane）；Linear alkene, such as hexene,
Heptene etc.；Ether, such as Anaesthetie Ether or tetrahydrofuran, preferably toluene.
In the polymerization process of body series, chromium concn is 0.01-100mmol/L, and 0.1-10mmol/ is preferably in the system
L；Part is 0.01-100mol/mol, preferably 0.8-3.0mol/mol with the mol ratio of Cr；The mol ratio of co-catalyst and Cr
It is 1-5000mol/mol, body series are preferably 10-1000mol/mol.
Likewise, the polymerization that the present invention is provided is applied to the oligomerisation reaction under various pressure, and it is 0.1-20MPa, it is excellent
It is selected in 2.0-6.5MPa；Temperature is 10-200 DEG C, and preferable temperature is 20-100 DEG C；And this programme be applicable to it is continuous, semicontinuous,
Or the method for interval；Mean residence time is 10min-20h, preferably 0.5h-4h.
The beneficial effects of the invention are as follows：
It is the ethylene trimer of high selectivity that the present invention is provided, four poly- catalyst systems and its catalysis ethylene trimer, four poly-
Method, the catalyst system is improved to original PNP chromium-based catalysts, improves the common selection of 1- hexenes and 1- octenes
Property, wax-like product is reduced, and maintain activity higher.
Specific embodiment
Embodiment 1
1 prepares part 5
At 0 DEG C, by chloro diphenylphosphine with it is corresponding（Isopropylcyclohexyl）Methyl amine is according to 2:1 mol ratio adds dichloro
It is stirred in dichloromethane, after stirring 40min, continuation is stirred overnight at normal temperatures.It is filtered to remove the amine salt produced in reaction
Hydrochlorate.Product is obtained after recrystallization, yield is 81%.
2 ethylene oligomerizations react
Ethylene oligomerization reaction is carried out in 300mL autoclaves.Before oligomerisation starts, reactor is carried out nitrogen displacement three times and
Ethene is replaced twice.Then solvent toluene is added in autoclave, and is stirred under ethene atmosphere, and be heated to design temperature.
By the MAO of scheduled volume, part and CrCl3(THF)3In addition autoclave, and stir 1min.Ethene is passed through in a kettle. and is adjusted
Pressure reaches setting value in section kettle, and reaction starts.After reaction 30min, ethylene gas are closed, and reaction system is quickly cooled to
20℃.Wherein, MAO, part and CrCl3(THF)3Molar ratio is 300:3:1, reaction condition is 60 DEG C, 4.5MPa, anti-every time
It is 2.5 μm of ol Cr that should measure.Product deionized water split-phase, then organic facies analysis.End reaction the results are shown in Table 1.
Embodiment 2
1 prepares part 7
At 0 DEG C, by chloro diphenylphosphine with it is corresponding（Isobutyl butylcyclohexyl）Methyl amine is according to 2:1 mol ratio adds dichloro
It is stirred in dichloromethane, after stirring 40min, continuation is stirred overnight at normal temperatures.It is filtered to remove the amine salt produced in reaction
Hydrochlorate.Product is obtained after recrystallization, yield is 76%.
2 ethylene oligomerizations react
Ethylene oligomerization reaction is carried out in 300mL autoclaves.Before oligomerisation starts, nitrogen displacement and ethene are carried out to reactor
Displacement, keeps the water oxygen value in kettle relatively low.Then solvent toluene is added in autoclave, and is stirred under ethene atmosphere, and added
Heat arrives design temperature.By the MAO of scheduled volume, part and Cr (acac)3In addition autoclave, and stir 1min.In a kettle.
It is passed through ethene and adjusts pressure in kettle and reach setting value, reaction starts.After reaction 10min, ethylene gas are closed, and by reactant
System is quickly cooled to 20 DEG C.Wherein, MAO, part and Cr (acac)3Molar ratio is 300:3:1, reaction condition be 10 DEG C,
2MPa, each reacting dose is 2.5 μm of ol Cr.Product deionized water split-phase, then organic facies analysis.End reaction
The results are shown in Table 1.
Embodiment 3
1 prepares ligand 17
At 0 DEG C, by chloro diphenylphosphine with it is corresponding（1,2,5- trimethyls）Cyclo-hexylamine is according to 2:1 mol ratio adds two
It is stirred in chloromethanes solution, after stirring 40min, continuation is stirred overnight at normal temperatures.It is filtered to remove the amine produced in reaction
Hydrochloride.Product is obtained after recrystallization, yield is 70%.
2 ethylene oligomerizations react
Ethylene oligomerization reaction is carried out in 300mL autoclaves.Before oligomerisation starts, nitrogen displacement and ethene are carried out to reactor
Displacement, keeps the water oxygen value in kettle relatively low.Then solvent toluene is added in autoclave, and is stirred under ethene atmosphere, and added
Heat arrives design temperature.During the MAO of scheduled volume, part and 2 ethyl hexanoic acid chromium (III) added into autoclave, and 1min is stirred.
Ethene is passed through in reactor and pressure in kettle is adjusted and reaches setting value, reaction starts.After reaction 1h, ethylene gas are closed, and will
Reaction system is quickly cooled to 20 DEG C.Wherein, MAO, part and 2 ethyl hexanoic acid chromium (III) molar ratio are 300:3:1, reaction
Condition is 30 DEG C, 2.5MPa, and each reacting dose is 2.5 μm of ol Cr.Product deionized water split-phase, then obtains organic phase
Analysis.End reaction the results are shown in Table 1.
Embodiment 4
1 prepares part 22
At 0 DEG C, by chloro diphenylphosphine with it is corresponding（Cyclopentyl cyclohexyl）Methyl amine is according to 2:1 mol ratio adds dichloro
It is stirred in dichloromethane, after stirring 40min, continuation is stirred overnight at normal temperatures, is filtered to remove the amine salt produced in reaction
Hydrochlorate.Product is obtained after recrystallization, yield is 83%.
2 ethylene oligomerizations react
Ethylene oligomerization reaction is carried out in 300mL autoclaves.Before oligomerisation starts, nitrogen displacement and ethene are carried out to reactor
Displacement, keeps the water oxygen value in kettle relatively low.Then solvent toluene is added in autoclave, and is stirred under ethene atmosphere, and added
Heat arrives design temperature.During the MAO of scheduled volume, part and chromium carbonyl added into autoclave, and 1min is stirred.Lead in a kettle.
Enter ethene and adjust pressure in kettle and reach setting value, reaction starts.After reaction 2h, ethylene gas are closed, and reaction system is fast
Speed is cooled to 20 DEG C.Wherein, MAO, part and chromium carbonyl molar ratio are 300:3:1, reaction condition be 90 DEG C, 3.0MPa,
Each reacting dose is 2.5 μm of ol Cr.Product deionized water split-phase, then organic facies analysis.End reaction result is shown in
Table 1.
Embodiment 5
1 prepares part 27
At 0 DEG C, by chloro diphenylphosphine with it is corresponding（Isopropyl butyl）Methyl amine is according to 2:1 mol ratio adds dichloro
It is stirred in dichloromethane, after stirring 40min, continuation is stirred overnight at normal temperatures, is filtered to remove the amine salt produced in reaction
Hydrochlorate, obtains product after recrystallization, yield is 83%.
2 ethylene oligomerizations react
Ethylene oligomerization reaction is carried out in 300mL autoclaves.Before oligomerisation starts, nitrogen displacement and ethene are carried out to reactor
Displacement, keeps the water oxygen value in kettle relatively low, and solvent toluene is then added in autoclave, and is stirred under ethene atmosphere, and adds
Heat arrives design temperature.By the MAO of scheduled volume, part and（Benzene）Tricarbonyl chromium is added in autoclave, and stirs 1min.In reactor
In be passed through ethene and adjust pressure in kettle and reach setting value, reaction starts.After reaction 3h, ethylene gas are closed, and by reactant
System is quickly cooled to 20 DEG C.Wherein, MAO, part and（Benzene）Tricarbonyl chromium molar ratio is 300:3:1, reaction condition is 120
DEG C, 4.0MPa, each reacting dose be 2.5 μm of ol Cr.Product deionized water split-phase, then organic facies analysis.Finally
Reaction result is shown in Table 1.
Embodiment 6
1 prepares part 28
At 0 DEG C, by chloro diphenylphosphine with it is corresponding（Double isopropyls）Methyl amine is according to 2:1 mol ratio adds dichloromethane
It is stirred in solution, after stirring 40min, continuation is stirred overnight at normal temperatures, is filtered to remove the amine hydrochlorate produced in reaction.
Product is obtained after recrystallization, yield is 80%.
2 ethylene oligomerizations react
Ethylene oligomerization reaction is carried out in 300mL autoclaves.Before oligomerisation starts, nitrogen displacement and ethene are carried out to reactor
Displacement, keeps the water oxygen value in kettle relatively low.Then solvent toluene is added in autoclave, and is stirred under ethene atmosphere, and added
Heat arrives design temperature.By the MAO of scheduled volume, part and CrCl3(THF)3In addition autoclave, and stir 1min.In a kettle.
It is passed through ethene and adjusts pressure in kettle and reach setting value, reaction starts.After reaction 4h, ethylene gas are closed, and by reaction system
It is quickly cooled to 20 DEG C.Wherein, MAO, part and CrCl3(THF)3Molar ratio is 300:3:1, reaction condition be 150 DEG C,
5.0MPa, each reacting dose is 2.5 μm of olCr.Product deionized water split-phase, then organic facies analysis.Reaction result
It is shown in Table 1.
Embodiment 7
1 prepares part 35
At 0 DEG C, by chloro diphenylphosphine with it is corresponding（Triphenyl）Methyl amine is according to 2:1 mol ratio adds dichloromethane molten
It is stirred in liquid, after stirring 40min, continuation is stirred overnight at normal temperatures.It is filtered to remove the amine hydrochlorate produced in reaction.Weight
Product is obtained after crystallization, yield is 78%.
2 ethylene oligomerizations react
Ethylene oligomerization reaction is carried out in 300mL autoclaves.Before oligomerisation starts, nitrogen displacement and ethene are carried out to reactor
Displacement, keeps the water oxygen value in kettle relatively low.Then solvent toluene is added in autoclave, and is stirred under ethene atmosphere, and added
Heat arrives design temperature.By the MAO of scheduled volume, part and CrCl3(THF)3Add in autoclave and stir 1min.In a kettle.
It is passed through ethene and adjusts pressure in kettle and reach setting value, reaction starts.After reaction 10h, ethylene gas are closed, and by reaction system
It is quickly cooled to 20 DEG C.Wherein, MAO, part and CrCl3(THF)3Molar ratio is 300:3:1, reaction condition be 180 DEG C,
6.0MPa, each reacting dose is 2.5 μm of olCr, and end reaction the results are shown in Table 1.
Embodiment 8
1 prepares part 38
At 0 DEG C, by chloro diphenylphosphine and 1- naphthyl isobutylamines according to 2:1 mol ratio is added in dichloromethane solution
It is stirred, after stirring 40min, continuation is stirred overnight at normal temperatures.It is filtered to remove the amine hydrochlorate produced in reaction.Recrystallization
After obtain product, yield is 75%.
2 ethylene oligomerizations react
Ethylene oligomerization reaction is carried out in 300mL autoclaves.Before oligomerisation starts, nitrogen displacement and ethene are carried out to reactor
Displacement, keeps the water oxygen value in kettle relatively low.Then solvent toluene is added in autoclave, and is stirred under ethene atmosphere, and added
Heat arrives design temperature.By the MAO of scheduled volume, part and CrCl3(THF)3In addition autoclave, and stir 1min.In a kettle.
It is passed through ethene and adjusts pressure in kettle and reach setting value, reaction starts.After reaction 20h, ethylene gas are closed, and by reaction system
It is quickly cooled to 20 DEG C.Wherein, MAO, part and CrCl3(THF)3Molar ratio is 10:0.8:1, reaction condition is 200 DEG C,
6.5MPa, each reacting dose is 2.5 μm of ol Cr.Product deionized water split-phase, then organic facies analysis.It is final anti-
1 should be the results are shown in Table.
Embodiment 9
1 prepares part 39
At 0 DEG C, by chloro diphenylphosphine and 1- propyloxy phenyl base amine according to 2:1 mol ratio is added in dichloromethane solution
It is stirred, after stirring 40min, continuation is stirred overnight at normal temperatures.It is filtered to remove the amine hydrochlorate produced in reaction.Recrystallization
After obtain product, yield is 81%.
2 ethylene oligomerizations react
Ethylene oligomerization reaction is carried out in 300mL autoclaves.Before oligomerisation starts, nitrogen displacement is carried out to reactor three times,
With ethene displacement twice.Then solvent methyl pentamethylene is added in autoclave, and is stirred under ethene atmosphere, and be heated to set
Constant temperature degree.By the triisopropylaluminiuand of scheduled volume, part and CrCl3(THF)3In addition autoclave, and stir 1min.In reactor
In be passed through ethene and adjust pressure in kettle and reach setting value, reaction starts.After reaction 30min, ethylene gas are closed, and will reaction
System is quickly cooled to 20 DEG C.Wherein, triisopropylaluminiuand, part and CrCl3(THF)3Molar ratio is 270:1:1, reaction condition
It it is 60 DEG C, 4.5MPa, each reacting dose is 0.1 μm of olCr.Product deionized water split-phase, then organic facies analysis.
End reaction the results are shown in Table 1.
Embodiment 10
1 prepares part 40
At 0 DEG C, by chloro diphenylphosphine and 1- phenylcyclohexylamines according to 2:1 mol ratio is added in dichloromethane solution
It is stirred, after stirring 40min, continuation is stirred overnight at normal temperatures.It is filtered to remove the amine hydrochlorate produced in reaction.Recrystallization
After obtain product, yield is 85%.
2 ethylene oligomerizations react
Ethylene oligomerization reaction is carried out in 300mL autoclaves.Before oligomerisation starts, nitrogen displacement and ethene are carried out to reactor
Displacement, keeps the water oxygen value in kettle relatively low.Then solvents tetrahydrofurane is added in autoclave, and is stirred under ethene atmosphere,
And it is heated to design temperature.By the triethyl group alundum (Al2O3) of scheduled volume, part and CrCl3(THF)3In addition autoclave, and stir
Mix 1min.Ethene being passed through in a kettle. and pressure in kettle is adjusted and reaching setting value, reaction starts.After reaction 30min, second is closed
Alkene gas, and reaction system is quickly cooled to 20 DEG C.Wherein, triethyl group alundum (Al2O3), part and CrCl3(THF)3Mole
Ratio is 400:1.5:1, reaction condition is 60 DEG C, 4.5MPa, and each reacting dose is 5.0 μm of ol Cr.Product deionization
Moisture phase, then organic facies analysis.End reaction the results are shown in Table 1.
Embodiment 11
1 prepares part 44
At 0 DEG C, by chloro diphenylphosphine and 1- naphthyl cyclo-hexylamines according to 2:1 mol ratio is added in dichloromethane solution
It is stirred, after stirring 40min, continuation is stirred overnight at normal temperatures.It is filtered to remove the amine hydrochlorate produced in reaction.Recrystallization
After obtain product, yield is 82%.
2 ethylene oligomerizations react
Ethylene oligomerization reaction is carried out in 300mL autoclaves.Before oligomerisation starts, nitrogen displacement and ethene are carried out to reactor
Displacement, keeps the water oxygen value in kettle relatively low.Then solvent hexamethylene is added in autoclave, and is stirred under ethene atmosphere, and
It is heated to design temperature.By the MMAO of scheduled volume, part and CrCl3(THF)3In addition autoclave, and stir 1min.In reaction
Ethene is passed through in kettle and pressure in kettle is adjusted and reaches setting value, reaction starts.After reaction 30min, ethylene gas are closed, and will be anti-
System is answered to be quickly cooled to 20 DEG C.Wherein, MMAO, part and CrCl3(THF)3Molar ratio is 500:2:1, reaction condition is 60
DEG C, 4.5MPa, each reacting dose is 7.5 μm of ol Cr.Product deionized water split-phase, then organic facies analysis.Finally
Reaction result is shown in Table 1.
Embodiment 12
1 prepares part 47
At 0 DEG C, by chloro diphenylphosphine and 1- cyclohexylcyclohexyl amine according to 2:1 mol ratio adds dichloromethane solution
In be stirred, stirring 40min after, continuation be stirred overnight at normal temperatures.It is filtered to remove the amine hydrochlorate produced in reaction.Tie again
Product is obtained after crystalline substance, yield is 77%.
2 ethylene oligomerizations react
Ethylene oligomerization reaction is carried out in 300mL autoclaves.Before oligomerisation starts, nitrogen displacement and ethene are carried out to reactor
Displacement, keeps the water oxygen value in kettle relatively low.Then solvent octane is added in autoclave, and is stirred under ethene atmosphere, and added
Heat arrives design temperature.By the DMAO of scheduled volume, part and CrCl3(THF)3In addition autoclave, and stir 1min.In reactor
In be passed through ethene and adjust pressure in kettle and reach setting value, reaction starts.After reaction 30min, ethylene gas are closed, and will reaction
System is quickly cooled to 20 DEG C.Wherein, DMAO, part and CrCl3(THF)3Molar ratio is 1000:3:1, reaction condition is 60
DEG C, 4.5MPa, each reacting dose is 10 μm of ol Cr.Product deionized water split-phase, then organic facies analysis.Finally
Reaction result is shown in Table 1.
Influence of the difference PNP parts of table 1 to ethylene oligomerization reaction selectivity and activity
It is the ethylene trimer of high selectivity that the present invention is provided, four poly- catalyst systems and its catalysis ethylene trimer, four poly-
Method, the catalyst system is improved to original PNP chromium-based catalysts, improves the common selection of 1- hexenes and 1- octenes
Property, wax-like product is reduced, and maintain activity higher.
Claims (9)
1. a kind of ethylene trimer of high selectivity and four poly- catalyst systems, it is characterised in that：Including three parts：
(1) a kind of chromium compound；
(2) a kind of part, its general structure is：(Ph2)P-N(R1)-P(Ph2)；
(3) a kind of co-catalyst；
R in the ligand structure formula1Group is selected from (isopropyl butyl) methyl, (double isopropyls) methyl, (isopropyl basic ring
Hexyl) methyl, (isobutyl butylcyclohexyl) methyl, (cyclopentyl cyclohexyl) methyl, the one kind in (1,2,5- trimethyls) cyclohexyl；
The chromium compound is selected from organic salt, inorganic salts, co-ordination complex or the metal-organic complex of trivalent chromium；
The co-catalyst be selected from triethyl aluminum, trimethyl aluminium, triisopropylaluminiuand, triisobutyl aluminium, the aluminium of triethyl group tri-chlorination two,
One or more in diethyl aluminum chloride, ethylaluminum dichloride, MAO and modified methylaluminoxane.
2. catalyst system according to claim 1, it is characterised in that：The chromium compound is selected from Cr (acac)3、CrCl3
(THF)3、CrCl3, 2 ethyl hexanoic acid chromium (III), sad chromium (III), chromium carbonyl, the one kind in benzene tricarbonyl chromium.
3. catalyst system according to claim 1, it is characterised in that：Also include in the catalyst system a kind of molten
Agent.
4. catalyst system according to claim 3, it is characterised in that：The solvent is selected from aromatic hydrocarbon, straight chain or ring-type
One kind in aliphatic hydrocarbon, linear alkene, ether.
5. the catalyst system according to claim 3 or 4, it is characterised in that：The solvent is selected from benzene, toluene, ethylbenzene, different
One kind in propyl benzene, dimethylbenzene, hexane, octane, hexamethylene, methyl cyclopentane, hexene, heptene, Anaesthetie Ether and tetrahydrofuran.
6. catalyst system according to claim 1, it is characterised in that：The chromium concn of the chromium compound is 0.01-
100mmol/L；The part is 0.01-100mol/mol with the mol ratio of chromium；The co-catalyst is 1- with the mol ratio of chromium
5000mol/mol。
7. the catalyst system described in a kind of any one of claim 1-6 is catalyzed ethylene trimer and four poly- application methods, and it is special
Levy and be, comprise the following steps：
(1) in autoclave, nitrogen displacement is first carried out to autoclave, then carry out ethylene gas displacement；Then noted in autoclave
Enter solvent, and stirred under ethylene gas atmosphere, heating；
(2) in the co-catalyst, part and chromium compound being added into autoclave, stirring, to being passed through ethylene gas in autoclave
And it is 0.1-20MPa to adjust pressure in kettle, oligomerisation reaction starts；The general structure of the part is：(Ph2)P-N(R1)-P
(Ph2), wherein R1Group is selected from (isopropyl butyl) methyl, (double isopropyls) methyl, (isopropylcyclohexyl) methyl, (isobutyl
Butylcyclohexyl) methyl, (cyclopentyl cyclohexyl) methyl, the one kind in (1,2,5- trimethyls) cyclohexyl；
(3) after oligomerisation reaction 10min to 20h, ethylene gas are closed, and reaction system is quickly cooled to -20-40 DEG C, reaction
Product deionized water split-phase, obtains organic phase for 1- hexenes and 1- octenes.
It is 8. according to claim 7 to be catalyzed ethylene trimer and four poly- application methods, it is characterised in that：The chromium compound
Chromium concn be 0.01-100mmol/L；The part is 0.01-100mol/mol with the mol ratio of chromium；The co-catalyst with
The mol ratio of chromium is 1-5000mol/mol.
It is 9. according to claim 7 to be catalyzed ethylene trimer and four poly- application methods, it is characterised in that：The oligomerisation is anti-
It is 10-200 DEG C to answer temperature.
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