CN106582851B - Catalytic component and its catalyst for ethylene selectivity oligomerisation - Google Patents
Catalytic component and its catalyst for ethylene selectivity oligomerisation Download PDFInfo
- Publication number
- CN106582851B CN106582851B CN201610902531.9A CN201610902531A CN106582851B CN 106582851 B CN106582851 B CN 106582851B CN 201610902531 A CN201610902531 A CN 201610902531A CN 106582851 B CN106582851 B CN 106582851B
- Authority
- CN
- China
- Prior art keywords
- compound
- hexane
- catalyst
- phenyl
- diphenylphosphino
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Molecular Biology (AREA)
- General Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention relates to a kind of catalytic component and its catalyst for ethylene selectivity oligomerisation, catalytic component is to meet the compound of logical formula (I) or meeting structural unit shown in logical formula (I) containing two or more connects the compound to be formed by group or chemical bond；The structure of logical formula (I) is as follows:Wherein, n is integer, 0≤n≤4；Ph1、Ph2、Ph3、Ph4Selected from phenyl, substituted-phenyl and its derivative；R1, R2, R3Selected from phenyl, chain-like alkyl, cyclic alkyl and its derivative.Catalyst activity of the present invention is high, purpose product 1- hexene+1- octene selectivity is high, 1- butylene and 1-C10+It is few.Catalyst agent synthesizes the features such as simple, at low cost, catalyst life is long, C in product6~C8Mass percentage > 90%, C of linear alpha-alkene8Mass percentage > 60% of linear alpha-alkene.
Description
Technical field
The invention belongs to olefin(e) oligomerization catalytic fields, are related to the catalyst of olefine selective oligomerisation, are that one kind is used for by it
Olefine selective oligomerisation, more particularly to the poly- catalytic component of olefine selective trimerization and four and its catalyst, preparation method,
Using.
Technical background
Linear alpha-alkene is a kind of important Organic Chemicals, in production polyethylene, surfactant, lubricating oil and oil
The fields such as product additive have a wide range of applications.Light component (C therein4-C8Alkene) it can be used as comonomer and ethylene copolymer life
Produce high performance linear low density polyethylene.The 1- hexene and 1- octene of especially high-purity can be obviously improved linea low density
The wear-corrosion resistance of polyethylene and other chemical properties and mechanical performance.It is poly- to high-performance with the continuous development of global economy
The demand of ethylene constantly increases, and continues to increase with average annual 5% or more rate to the demand of 1- hexene and 1- octene.Industrially
The production method of 1- hexene and 1- octene mainly has the methods of wax cracking, ethylene oligomerization and extraction and separation, wherein ethylene oligomerization
Method is to produce the main method of 1- hexene and 1 octene.Such as US6184428 discloses a kind of Raney nickel, using boron compound
For co-catalyst, ethylene oligomerization can be catalyzed and obtain the mixture of linear alpha-alkene, wherein it is pungent to account for 22%, 1- for the content of 1- hexene
The content of alkene accounts for 19%.SHOP technique (US3676523, US3635937) uses similar catalyst system, in oligomerization product 1- oneself
The content that the content of alkene accounts for 21%, 1- octene accounts for 11%.Other typical ethylene oligomerization techniques, such as Gulf Oil Corporation
In Chevron technique (DE1443927), the ethylene oligomerization technique of ethyl corporation (BP/Amoco, US3906053), 1- hexene, 1-
The content of octene is generally 13~25%.The reports such as Brookhart Fe-series catalyst (J.Am.Chem.Soc., 1998,120:
7143；Chem.Commun.1998,849；WO 99/02472) be used for ethylene oligomerization, 1- hexene, 1- octene content also compared with
Low (< 20%).The carbon number of linear alpha-alkene meets Schulz-Flory distribution in these production technologies, and this distribution produces oligomerisation
The content of 1- hexene, 1- octene is it is not possible that too high in object.If the 1- hexene and 1- octene that obtain high-purity are needed by more
Tower rectifying separation realizes that process route is complicated, and equipment investment is huge.Therefore, it finds highly selective preparation 1- hexene and 1- is pungent
The production technology of alkene seems extremely important, and the catalysis highly selective oligomerisation of ethylene is to produce the main method of 1- hexene and 1- octene,
Wherein catalyst is its key technology, and the exploitation and its catalytic mechanism research of novel catalyst are always the research heat in the field
Point and difficulties.In recent years, researchers have carried out a large amount of research to ethylene selectivity oligomerisation technology, also obtain
Many important research achievements.Such as: chromium-based catalysts system prepares 1- hexene for ethylene trimer, also has been carried out industrialization
It produces (US5550305, US5198563), but the content of its principal product 1- hexene is typically greater than the content of 90%, 1- octene very
Few (< 3%).The ethylene tetramerization ternary catalyst systems reported recently can be with high selectivity 1- octene (WO2004/
056478A1, US2006/0229480 and US 2006/0173226), the content of 1- octene reaches 60% in purpose product.Closely
Over a little years, as the highly selective trimerization of ethylene, four gather deepening continuously for research, the highly selective catalyst for oligomerization of ethylene is developed, it is special
It is not that chromium system ethylene tetramerization, five poly- catalyst have become the hot spot studied now.Current research ethylene selectivity trimerization
The central metal of catalyst is mainly based on chromium, titanium, and the central metal of catalyst for ethylene tetramerization is mainly based on chromium.Ligand is in second
It is played an important role in alkene selective oligomerization catalyst system, the structure of ligand directly affects ethylene selectivity oligomerization catalysis system
Selectivity of product, therefore design and synthesize new structural ligand it is very important, and research in the field at present
Hot spot.
Summary of the invention
The purpose of the present invention is to provide a kind of highly selective trimerization of ethylene, four poly- catalyst systems and its catalysis ethylene
Trimerization, four poly- methods, the catalyst system compared with prior art, while keeping higher catalytic activity, improve 1-
The total selectivity of hexene and 1- octene, reduces the selectivity of by-product low molecular weight polyethylene.
Catalyst of the invention is living by heteroatomic ligand (a), transistion metal compound (b), organo-metallic compound
The catalyst of three components of agent (c) composition.Catalyst is used for the selective oligomerization of alkene, especially highly selective preparation 1-
Hexene, 1- octene.Described is to meet general formula (I) compound represented containing heteroatomic ligand (a):
Wherein, n is integer, 0≤n≤4；Ph1、Ph2、Ph3、Ph4Selected from phenyl, substituted-phenyl and its derivative；R1, R2,
R3Selected from phenyl, chain-like alkyl, cyclic alkyl and its derivative.Described contains heteroatomic ligand (a), is also possible to containing two
Or multiple meet structural unit shown in logical formula (I) the noval chemical compound to be formed is connected by group or chemical bond；Described mistake
Cross the compound that metallic compound (b) is chromium, molybdenum, tungsten, titanium, tantalum, vanadium, zirconium, iron, nickel, palladium；Described organo-metallic compound is living
Agent (c) is alkyl aluminum compound, aluminium alkoxide compound, organoboron compound, organic salt, inorganic acid and inorganic salts, can also be with
It is the mixture of one or more of they；In the catalyst, the molar ratio of the component (a), (b) and (c) that include is
(a): (b): (c)=1:0.5~100:0.1~5000；Three components that (a), (b), (c) are formed, are pre-mixed；Or it can be with
It is added directly into reaction system and carries out fabricated in situ；The catalytic component is used for ethylene selectivity oligomerisation, reacts in Sui
It is carried out in property solvent, can be selected from alkane, cycloalkane, aromatic hydrocarbons, alkene, ionic liquid；0 DEG C~200 DEG C of the temperature of reaction, reaction pressure
Ethylene oligomerization product is made in power 0.1MPa~50MPa.
The reaction product that catalyst system contains following components is described in detail:
(1) at least one be selected from shown in logical formula (I) contains heteroatomic ligand (a)
In formula, n is integer, 0≤n≤4；Ph1、Ph2、Ph3、Ph4Can for benzyl, phenyl, tolyl, xylyl,
2,4,6- trimethylphenyl, 3,5- dimethylbenzene methyl, methoxyphenyl, ethylbenzene, sulfur phenenyl, double phenyl, naphthalene, anthryl etc..It is excellent
The Ph of choosing1、Ph2、Ph3、Ph4For phenyl, substituted-phenyl, xylyl, double phenyl, naphthalene and sulfur phenenyl；R1, R2, R3Selected from benzene
Base, chain-like alkyl, cyclic alkyl and its derivative.
(2) a kind of transistion metal compound (b)
Selectable transistion metal compound has the compound of chromium, molybdenum, tungsten, titanium, tantalum, vanadium, zirconium, iron, nickel, palladium.Preferably
It is chromium, zirconium, titanium compound, it is still further preferred that chromium compound.Selectable chromium compound includes general formula CrRn mThose of shown chemical combination
Object, R in formulanFor organic negative ion or neutral molecule, RnIn usually contain 1~10 carbon atom, the integer that n is 0~6, chromium
Valence state is 0~6 valence.Specific RnGroup for example organic matter or its group containing carboxyl, beta-diketon base and alkyl.From easy to dissolve
From the point of view of easily operated, chromium compound preferably include chromic acetate, isooctyl acid chromium, caprylic acid chromium, chromium acetylacetonate,
Diisoamyl diene chromium, dibenzene-chromium, CrCl3(THF)3、CrCl2(THF)2, (phenyl) tricarbonyl chromium, chromium carbonyl one kind and or
A variety of mixtures.Best chromium compound is CrCl3(THF)3, isooctyl acid chromium, chromium acetylacetonate.
(3) a kind of organo-metallic compound activating agent (c)
Selectable organo-metallic compound includes alkyl aluminum compound, aluminium alkoxide compound, organoboron compound, organic
Salt, inorganic acid and inorganic salts.It is specifically selected from various trialkylaluminiums and aluminium alkoxide compound, such as triethyl aluminum, triisobutyl
Just base aluminium, tri-n-octylaluminium, methylaluminoxane, ethylaluminoxane, isobutyl aluminium alkoxide and the modification of aluminium, three n-butylaluminums, three
Aikyiaiurnirsoxan beta etc..Also aluminum alkyl halide, alkyl aluminum hydride or alkylaluminium sesquichloride, such as AlEt can be used2Cl and
Al2Et3Cl3, it is also possible to the mixture with the above-mentioned one or more alkyl aluminums referred to or aikyiaiurnirsoxan beta.Organic salt activator
Such as lithium methide, methyl-magnesium-bromide；Inorganic acid and inorganic salts activator such as tetrafluoro boric acid etherate, tetrafluoroborate, hexafluoro
Stibate etc..Organoboron compound includes boroxin, sodium borohydride, boron triethyl, three (pentafluorophenyl group) boron, tri butyl boron
Hydrochlorate etc..
Synthesis containing heteroatomic ligand (a) can carry out by the following method: 1. prepare diphenylphosphino lithium or hexichol
Base phosphino- potassium.It first disperses a certain amount of diphenylphosphine in appropriate n-hexane, n-BuLi is then added dropwise at a certain temperature
Or hydrofining, prepare diphenylphosphino lithium or diphenylphosphino potassium；2. preparing phosphino- chlorosilane.A certain amount of dialkyl is replaced
Dichlorosilane be dissolved in appropriate n-hexane, cool to certain temperature, then by diphenylphosphino lithium or diphenylphosphino potassium
Solid is added in above-mentioned solution in multiple times on a small quantity, is warmed to room temperature naturally, is stirred overnight, the volatilization after filtering in vacuum abstraction filtrate
Property component, yellow oily crude product is obtained, through distilling isolated colourless or faint yellow oil product；3. preparing single phosphine amine intermediate.
A certain amount of primary amino-compound is dissolved in n-hexane, certain temperature is cooled to, by a certain amount of n-BuLi hexane solution
It is slowly added dropwise in above-mentioned solution, is warmed to room temperature naturally, be stirred overnight, filter and take out filter cake after being washed with appropriate n-hexane
It is dry, obtain the lithium salts of primary amino-compound.It disperses the lithium salts of primary amino-compound in appropriate n-hexane, is cooled to certain temperature, it will
A certain amount of dialkyl replaces the hexane solution of chlorination phosphorus compound to be slowly added dropwise in above-mentioned lithium salts, is warmed to room temperature naturally,
It is stirred overnight, after vacuum extracts volatile component, extracts residue with q. s. toluene, the property of will volatilize component vacuum extracts after filtering
Yellow crude is obtained, then obtains white or faint yellow product after the washing of appropriate n-hexane.4. preparing ligand: by a certain amount of single phosphine
Amine intermediate is dissolved in the n-hexane through dehydration, is cooled to certain temperature, by a certain amount of n-BuLi hexane solution
It is slowly added dropwise in above-mentioned solution, is warmed to room temperature naturally after being added dropwise, continues to be stirred overnight, with a certain amount of n-hexane after filtering
Filter cake is washed, single phosphine amine lithium salts is obtained after draining, then lithium salts will be changed and be scattered in n-hexane, it at a certain temperature, will be a certain amount of
Phosphino- chlorosilane is slowly dropped in above-mentioned solution, is warmed to room temperature naturally, is stirred overnight, and vacuum extracts volatile component, with suitable
It measures toluene and extracts residue, the property of will volatilize component vacuum extracts to obtain ligand product after filtering.
Molar ratio containing heteroatomic ligand (a) and transistion metal compound (b) in catalyst is 1:0.5~100.
Molar ratio containing heteroatomic ligand (a) and organo-metallic compound activator (c) in catalyst is 1:0.1~1:
5000, preferably 1:1~1:1000, more preferably 1:1~1:200.
(I) the heteroatomic ligand described in is also possible to one or more units such as (I) formula structures, by group,
Chemical bond or intermolecular force etc. are combined together.Bridging, dendroid and star-shaped compound are such as obtained, is also possible to combine
In the polymer of the producing high-molecular formed on macromolecular chain.
(I) reactive mode of heteroatomic ligand, transistion metal compound and metal organic activator described in, can be with
By liquid phase reactor, such as reacted under the action of the solvent, selectable solvent such as toluene, benzene and its derivative etc.；It can also
To pass through solid phase reaction；Catalyst can also be generated by carrying out reaction in-situ during oligomerisation reaction.Described here is anti-
One kind of above-mentioned heteroatomic ligand, transistion metal compound and metal organic activator, two kinds and three kinds of chemical combination should be can be
Reaction between object.The process of this reaction is also ageing (pre- complexing) process of catalyst.
Ethylene selectivity oligomerisation reaction mainly carries out in inert solvent.Selectable solvent includes alkane, cycloalkane, virtue
Hydrocarbon, halogenated hydrocarbons, alkene etc..Typical solvent include, but are not limited to benzene,toluene,xylene, isopropylbenzene, normal heptane, n-hexane,
Hexahydrotoluene, hexamethylene, 1- hexene, 1- octene, ionic liquid etc..
The preparation of catalyst is living containing heteroatomic ligand (a), transistion metal compound (b), organo-metallic compound
Agent (c) is pre-mixed；It can also be living containing heteroatomic ligand (a), transistion metal compound (b), organo-metallic compound
Agent (c), which is added directly into reaction system, carries out fabricated in situ；
The temperature of ethylene selectivity oligomerisation reaction can carry out in 0 DEG C~200 DEG C, and preferably 50 DEG C~150 DEG C.Ethylene tetramerization
The pressure of reaction can carry out under the pressure of 0.1MPa~50MPa, preferably 1.0MPa~10MPa.Catalyst in reaction system
Concentration can be from 0.01 μm of ol metal/L~1000 μm ol metal/L, preferably 0.1 μm of ol metal/L~10 μm ol metal/L.
The trimerization, four poly- of ethylene selectivity oligomerization catalysis system of the invention for ethylene oligomerization, especially ethylene.
The advantages of the present invention:
Catalyst activity of the present invention is high, purpose product 1- hexene+1- octene selectivity is high, 1- butylene and 1-C10+It is few.
Catalyst agent synthesizes the features such as simple, at low cost, catalyst life is long, C in product6~C8The quality percentage of linear alpha-alkene
Content > 90%, C8Mass percentage > 60% of linear alpha-alkene.
Specific embodiment
11 embodiments are set forth below, the present invention is further illustrated, rather than are used to limit the scope of the invention.
Embodiment 1
1, N- diphenylphosphino -2,6- diisopropyl benzene amido (diphenylphosphino) dimethylsilane is prepared
(C38H43NP2Si)
(1) diphenylphosphino lithium is prepared
Through N2The THF (200mL) through dehydration, hexichol is added in the 500mL reactor with stirring being sufficiently displaced from
Base phosphine (18.62g, 0.1mol), is cooled to -80 DEG C with liquid nitrogen after mixing evenly.N-butyl lithium hexane is extracted with 100mL syringe
Solution (41.6mL, 2.4mol/L), is slowly added dropwise while stirring in above-mentioned solution, is warmed to room temperature after keeping -80 DEG C of stirring 1h
It is further continued for stirring 1 hour, then vacuum extracts solvent, is added n-hexane (100mL), filters after dispersion is sufficiently stirred, gained filter
Liquid obtains product 18.82g (0.098mol, 98.6%) after room temperature in vacuo extracts volatile component.
(2) diphenylphosphino dimethylchlorosilane (C is prepared14H16ClPSi)
In N2In the glove box of atmosphere, dimethyldichlorosilane (6.45g, 0.050mol) is dissolved in through dehydration just
Hexane (100mL) is simultaneously added in 250mL reactor, is cooled to -35 DEG C, strong to stir；Take diphenylphosphino lithium (14.31g,
0.049mol), be added in above-mentioned solution in multiple times on a small quantity, after be warmed to room temperature naturally and be further continued for being stirred overnight, it is true after filtering
Empty pump obtains yellow liquid except the volatile component in filtrate, separates through distillation, collects 155 DEG C~160 DEG C fractions, obtains colourless liquid
Body product 11.33g (0.041mol, 83%).
(3) N- diphenylphosphino -2,6- diisopropyl aniline (C is prepared24H28NP)
In N2In the glove box of atmosphere, the 2,6-DIPA (7.09g, 0.040mol) through dehydration is dissolved in
In n-hexane (100mL) through dehydration, be cooled to -35 DEG C, while stirring by n-BuLi hexane solution (17.1mL,
0.041mol, 2.4mol/L) it is slowly added dropwise in above-mentioned solution, continue to be stirred overnight after being added dropwise, after filtering just with 20mL
Hexane washs filter cake twice, drains to obtain 2,6-DIPA lithium salts 6.96g (0.038mol, 95%), among gained
Product is scattered in n-hexane (100mL), is cooled to -35 DEG C, and diphenyl phosphorus chloride (8.38g, 0.038mol) is dissolved in 20mL
It in n-hexane, is slowly added dropwise in above-mentioned solution, is warmed to room temperature naturally, be stirred overnight, vacuum extracts volatile component, uses 50mL
Toluene extracts residue, and vacuum drains volatile component after filtering, is washed 2 times with 20mL n-hexane, drains to obtain 10.8g product
(0.030mol, 78%).
(4) N- diphenylphosphino -2,6- diisopropyl benzene amido (diphenylphosphino) dimethylsilane is prepared
(C38H43NP2Si)
In N2In the glove box of atmosphere, N- diphenylphosphino -2,6-DIPA (5.4g, 0.015mol) is dissolved in
In n-hexane through dehydration, -35 DEG C are cooled to, by n-BuLi hexane solution (6.3mL, 0.015mol, 2.4mol/
L it) is slowly added dropwise in above-mentioned solution, continues to be stirred overnight after being added dropwise, wash filter cake twice with 20mL n-hexane after filtering,
It drains to obtain N- diphenylphosphino -2,6-DIPA lithium salts 5.12g (0.014mol, 93%), by gained intermediate product
It is scattered in n-hexane (100mL), is cooled to -35 DEG C, diphenylphosphino dimethylchlorosilane (3.90g, 0.014mol) is molten
In 20mL n-hexane, side stirring is slowly added dropwise in above-mentioned lithium salts dispersion liquid, is warmed to room temperature, is stirred overnight naturally, and vacuum is taken out
After volatile component, residue is extracted with 50mL toluene, the property of will volatilize component vacuum extracts to obtain yellow crude after filtering, then passes through
White product 6.64g (0.011mol, 75%) is obtained after the washing of 20mL n-hexane.
2, the preparation of catalyst
Through N2The hexahydrotoluene through dehydration is added in the 100mL reactor with stirring being sufficiently displaced from
(10mL), DMAO (methylaluminoxane of removal trimethyl aluminium) (0.57g, 9.9mmol), triethyl aluminum (0.38g, 3.3mmol),
N- diphenylphosphino -2,6-DIPA base (diphenylphosphino) dimethylsilane (41mg) (67.8 μm of ol), CrCl3·
(THF)3(12mg, 33 μm of ol), react at room temperature 5min after it is spare.
3, ethylene oligomerization
The autoclave of 500mL is heated to vacuumize 2 hours, is filled with ethylene after nitrogen displacement for several times, cools to predetermined temperature
Hexahydrotoluene (200mL) and above-mentioned catalyst through dehydration is added in degree.Oligomerisation is carried out under 40 DEG C, the pressure of 1MPa
It reacts, with ice bath cooling, release after reaction 30min, is terminated and reacted with the acidic ethanol that mass fraction is 10%.Obtain oligomerisation production
Object 52.0g, catalyst activity are 3.15 × 106G oligomer/mol Crh.The distribution of oligomerization product is shown in Table 1.
Embodiment 2
With embodiment 1.The difference is that Ph1~Ph4It is 3,5-dimethylphenyl.Obtain oligomerization product 50.2g, catalyst
Activity is 3.04 × 106G oligomer/mol Crh.The distribution of oligomerization product is shown in Table 1.
Embodiment 3
With embodiment 1.The difference is that Ph1~Ph4It is naphthalene.Oligomerization product 51.3g is obtained, catalyst activity is
3.11×106G oligomer/mol Crh.The distribution of oligomerization product is shown in Table 1.
Embodiment 4
With embodiment 1.The difference is that R1And R2Respectively methyl and cyclohexyl.Oligomerization product 44.1g is obtained, is catalyzed
Agent activity is 2.67 × 106G oligomer/mol Crh.The distribution of oligomerization product is shown in Table 1.
Embodiment 5
With embodiment 1.The difference is that R1And R2It is respectively phenyl.Obtain oligomerization product 25.6g, catalyst activity
It is 1.55 × 106G oligomer/mol Crh.The distribution of oligomerization product is shown in Table 1.
Embodiment 6
With embodiment 1.The difference is that R3For cyclopenta.Obtaining oligomerization product 29.4g, catalyst activity is 1.78 ×
106G oligomer/mol Crh.The distribution of oligomerization product is shown in Table 1.
Embodiment 7
With embodiment 1.The difference is that R3For isopropyl.Obtaining oligomerization product 37.5g, catalyst activity is 2.27 ×
106G oligomer/mol Crh.The distribution of oligomerization product is shown in Table 1.
Embodiment 8
1, N- diphenylphosphino -2,6- diisopropyl benzene amido (diphenyl-phosphinomethyl) dimethylsilane is prepared
(C39H45NP2Si)
(1) with embodiment 1
(2) diphenyl-phosphinomethyl dimethylchlorosilane (C is prepared14H16ClPSi)
In N2In the glove box of atmosphere, by diphenyl methyl phosphine (10.01g, 0.050mol) and tetramethylethylenediamine
(5.81g, 0.050mol) is dissolved in the n-hexane through dehydration, is cooled to -35 DEG C, n-BuLi is slowly added dropwise while stirring
Hexane solution (20.8mL, 0.05mol, 2.4mol/L), is added dropwise nature and is warmed to room temperature, and stirs 24 hours, uses after filtering
It is drained after 10mL n-hexane washing filter cake, yellow solid 8.66g (0.042mol, 84%) is obtained, by dimethyldichlorosilane
(5.42g, 0.042mol) is dissolved in the n-hexane through dehydration (100mL), is cooled to -35 DEG C, side is stirred above-mentioned yellow
Solid is added in hexane solution in multiple times on a small quantity, is warmed to room temperature, is stirred overnight naturally, volatilizees in vacuum abstraction filtrate after filtering
Property ingredient, obtain yellow oily crude product, through distillation separate, collect 158-165 DEG C of fraction, obtain colourless liquid product 9.96g
(0.034mol, 81%).
(3) with embodiment 1
(4) N- diphenylphosphino -2,6- diisopropyl benzene amido (diphenyl-phosphinomethyl) dimethylsilane is prepared
(C39H45NP2Si)
The preparation such as embodiment 1 of N- diphenylphosphino -2,6- diisopropyl aniline lithium salts.
N-hexane is dispersed by N- diphenylphosphino -2,6-DIPA lithium salts (5.51g, 0.015mol)
In (100mL), be cooled to -35 DEG C, by diphenyl-phosphinomethyl dimethylchlorosilane (4.39g, 0.015mol) be dissolved in 20mL just oneself
In alkane, side stirring is slowly added dropwise in above-mentioned lithium salts dispersion liquid, is warmed to room temperature, is stirred overnight naturally, and vacuum extracts volatility group
After point, residue is extracted with 50mL toluene, the property of will volatilize component vacuum extracts to obtain yellow crude after filtering, then through 20mL n-hexane
White product 7.17g (0.012mol, 77%) is obtained after washing.
2, the preparation of catalyst
Through N2The hexahydrotoluene through dehydration is added in the 100mL reactor with stirring being sufficiently displaced from
(10mL), DMAO (methylaluminoxane of removal trimethyl aluminium) (0.57g, 9.9mmol), triethyl aluminum (0.38g, 3.3mmol),
N- diphenylphosphino -2,6-DIPA base (diphenyl-phosphinomethyl) dimethylsilane (42mg) (67.8 μm of ol),
CrCl3·(THF)3(12mg, 33 μm of ol), react at room temperature 5min after it is spare.
3, ethylene oligomerization
With embodiment 1.Oligomerization product 57.3g is obtained, catalyst activity is 3.47 × 106G oligomer/mol Cr.h.
The distribution of oligomerization product is shown in Table 1.
Embodiment 9
With embodiment 8.The difference is that reaction temperature is 75 DEG C.Oligomerization product 66.2g is obtained, catalyst activity is
4.01×106G oligomer/mol Crh.The distribution of oligomerization product is shown in Table 1.
Embodiment 10
With embodiment 8.The difference is that reaction pressure is 2MPa.Oligomerization product 65.5g is obtained, catalyst activity is
3.97×106G oligomer/mol Crh.The distribution of oligomerization product is shown in Table 1.
Embodiment 11
With embodiment 8.The difference is that Ph1~Ph4It is o-methoxyphenyl.Oligomerization product 46.4g is obtained, is catalyzed
Agent activity is 2.81 × 106G oligomer/mol Crh.The distribution of oligomerization product is shown in Table 1.
Embodiment 12
With embodiment 8.The difference is that reaction pressure is 20MPa.Oligomerization product 92.1g is obtained, catalyst activity is
5.58×106G oligomer/mol Cr.h.The distribution of oligomerization product is shown in Table 1.
Embodiment 13
With embodiment 8.Difference chromium compound is CrCl2(THF)2.Oligomerization product 22.8g is obtained, catalyst activity is
1.38×106G oligomer/mol Crh.The distribution of oligomerization product is shown in Table 1.
The experiment condition and catalyst activity of embodiment 1~13 are shown in Table 2.
The comparison of 1 oligomerization product carbon number distribution of table
aRefer to C6Middle 1-C6 =Percentage composition.bRefer to C8Middle 1-C8 =Percentage composition.
The experiment condition and catalyst activity of 2 embodiment 1~13 of table.
Claims (9)
1. a kind of catalytic component for ethylene selectivity oligomerisation, for containing heteroatom ligand, it is characterised in that: be to meet general formula
(I) compound or meet structural unit shown in logical formula (I) containing two or more is keyed by group or chemistry
Come the compound formed；The structure of logical formula (I) is as follows:
(I)
Wherein, n is integer, 0≤n≤4；Ph1、Ph2、Ph3、Ph4Selected from phenyl, substituted-phenyl and its derivative；R1, R2, R3It is selected from
Phenyl, chain-like alkyl, cyclic alkyl and its derivative.
2. catalytic component according to claim 1, it is characterised in that: preparation method includes the following steps:
1. preparing diphenylphosphino lithium or diphenylphosphino potassium: first disperse a certain amount of diphenylphosphine in appropriate n-hexane,
Then n-BuLi or hydrofining are added dropwise at a certain temperature, prepares diphenylphosphino lithium or diphenylphosphino potassium；
2. preparing phosphino- chlorosilane；The dichlorosilane that a certain amount of dialkyl replaces is dissolved in appropriate n-hexane, the hydrocarbon
Base is selected from phenyl, chain-like alkyl, cyclic alkyl and its derivative, cools to certain temperature, then by diphenylphosphino lithium or
Diphenylphosphino potassium solid is added in above-mentioned solution in multiple times on a small quantity, is warmed to room temperature, is stirred overnight naturally, and vacuum extracts after filtering
Volatile component in filtrate obtains yellow oily crude product, is distilled isolated colourless or faint yellow oil product；
3. preparing single phosphine amine intermediate: by a certain amount of primary amino-compound R3NH2It is dissolved in n-hexane, wherein R3Selected from phenyl, chain
Shape alkyl, cyclic alkyl and its derivative, are cooled to certain temperature, and a certain amount of n-BuLi hexane solution is slowly added dropwise
Enter in above-mentioned solution, be warmed to room temperature naturally, be stirred overnight, filter and drain filter cake after being washed with appropriate n-hexane, obtains primary amine
The lithium salts of compound disperses the lithium salts of primary amino-compound in appropriate n-hexane, is cooled to certain temperature, by a certain amount of two
Alkyl replaces the hexane solution of chlorination phosphorus compound to be slowly added dropwise in above-mentioned lithium salts, and the alkyl is selected from phenyl, replaces
Phenyl and its derivative, are warmed to room temperature naturally, are stirred overnight, and after vacuum extracts volatile component, are extracted with q. s. toluene remaining
Object, the property of will volatilize component vacuum extracts to obtain yellow crude after filtering, then white or faint yellow is obtained after the washing of appropriate n-hexane
Product；
4. preparing ligand: a certain amount of single phosphine amine intermediate is dissolved in the n-hexane through dehydration, certain temperature is cooled to,
A certain amount of n-BuLi hexane solution is slowly added dropwise in above-mentioned solution, is warmed to room temperature naturally after being added dropwise, is continued
Be stirred overnight, wash filter cake with a certain amount of n-hexane after filtering, after draining single phosphine amine lithium salts, then by the lithium salts be scattered in just oneself
In alkane, at a certain temperature, a certain amount of phosphino- chlorosilane is slowly dropped in above-mentioned solution, is warmed to room temperature naturally, stirred
Overnight, vacuum extracts volatile component, extracts residue with q. s. toluene, the property of will volatilize component vacuum, which extracts, after filtering is matched
Body product.
3. a kind of catalyst for ethylene selectivity oligomerisation, it is characterised in that: described in claim 1 contain comprising at least one
Heteroatomic ligand, a kind of transistion metal compound, a kind of organo-metallic compound activator.
4. catalyst according to claim 3, it is characterised in that: the transistion metal compound be chromium, molybdenum, tungsten, titanium,
Tantalum, vanadium, zirconium, iron, nickel or palladium compound.
5. catalyst according to claim 3, it is characterised in that: the organo-metallic compound activator is alkyl aluminum
Compound, aluminium alkoxide compound, organoboron compound, organic salt, inorganic acid or inorganic salts；It is several mixed either in them
Close object.
6. catalyst according to claim 3, it is characterised in that: in catalyst, contain heteroatomic ligand, transition metal
Close object, the molar ratio of organo-metallic compound activator is 1:0.5 ~ 100:0.1 ~ 5000.
7. catalyst according to claim 3, it is characterised in that: the preparation method comprises the following steps: heteroatomic ligand, transition gold will be contained
Belong to compound, organo-metallic compound activator is pre-mixed；Or it is added directly into reaction system and carries out fabricated in situ.
8. a kind of application of catalyst as claimed in claim 3 in ethylene oligomerization.
9. application according to claim 8, it is characterised in that: reaction carries out in atent solvent, 0 DEG C of the temperature of reaction ~
200 DEG C, reaction pressure 0.1MPa ~ 50MPa, ethylene selectivity oligomerization product is made.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610902531.9A CN106582851B (en) | 2016-10-17 | 2016-10-17 | Catalytic component and its catalyst for ethylene selectivity oligomerisation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610902531.9A CN106582851B (en) | 2016-10-17 | 2016-10-17 | Catalytic component and its catalyst for ethylene selectivity oligomerisation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106582851A CN106582851A (en) | 2017-04-26 |
| CN106582851B true CN106582851B (en) | 2019-04-30 |
Family
ID=58555893
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610902531.9A Active CN106582851B (en) | 2016-10-17 | 2016-10-17 | Catalytic component and its catalyst for ethylene selectivity oligomerisation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106582851B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108686706B (en) * | 2018-06-22 | 2020-12-01 | 中国石油天然气股份有限公司 | Ethylene selective oligomerization method and catalyst |
| CN109331878B (en) * | 2018-09-17 | 2021-08-13 | 天津科技大学 | Catalyst for ethylene oligomerization |
| CN109174191B (en) * | 2018-09-17 | 2022-01-25 | 天津科技大学 | Catalyst for ethylene selective oligomerization reaction |
| CN110368994B (en) * | 2019-06-28 | 2021-12-24 | 天津科技大学 | Reaction method for selective oligomerization of ethylene, catalyst system and application thereof |
| CN110479381B (en) * | 2019-08-19 | 2022-04-29 | 迈瑞尔实验设备（上海）有限公司 | Catalyst system for selective oligomerization of ethylene and preparation method and application thereof |
| CN112570026B (en) * | 2019-09-29 | 2023-02-24 | 天津科技大学 | Catalyst system for ethylene oligomerization and oligomerization method |
| CN112517080B (en) * | 2020-12-25 | 2023-06-23 | 中化泉州石化有限公司 | Ethylene selective tetramerization catalyst composition and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1741850A (en) * | 2002-12-20 | 2006-03-01 | Sasol技术股份有限公司 | Tetramerization of olefins |
| CN105289742A (en) * | 2015-11-11 | 2016-02-03 | 天津科技大学 | Catalyst for ethylene selectivity oligomerization, novel ligand and preparation method thereof |
-
2016
- 2016-10-17 CN CN201610902531.9A patent/CN106582851B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1741850A (en) * | 2002-12-20 | 2006-03-01 | Sasol技术股份有限公司 | Tetramerization of olefins |
| CN105289742A (en) * | 2015-11-11 | 2016-02-03 | 天津科技大学 | Catalyst for ethylene selectivity oligomerization, novel ligand and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106582851A (en) | 2017-04-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106582851B (en) | Catalytic component and its catalyst for ethylene selectivity oligomerisation | |
| CN108097322B (en) | Catalyst system for selective oligomerization of ethylene and ethylene oligomerization reaction method | |
| CN105289742B (en) | For the catalyst of ethylene selectivity oligomerisation, ligand and preparation method thereof | |
| CN101351269B (en) | Catalytic oligomerization of olefinic monomers | |
| EP2396112B1 (en) | Oligomerisation of olefinic compounds in the presence of an activated oligomerisation catalyst | |
| KR101074202B1 (en) | Ethylene tetramerization catalyst systems and method for preparing 1-octene using the same | |
| CN102282179B (en) | Highly active and highly selective ethylene oligomerization catalyst, and preparation method of hexene or octene using same | |
| NL2023317B1 (en) | Method and catalyst for selective oligomerization of ethylene | |
| CN101450326B (en) | Catalyst composition for ethylene oligomerization and application thereof | |
| CN105228973B (en) | Ethylene oligomerization is into 1 hexene and the oligomerization process of the mixture of 1 octene | |
| JP4273257B2 (en) | Catalyst composition for dimerization, codimerization, oligomerization and polymerization of olefins | |
| CN108031493A (en) | Catalyst system and ethylene oligomerization reaction method for ethylene selectivity oligomerisation | |
| CN104169003A (en) | Catalyst systems for preparing 1-hexene and/or 1-octene from ethylene | |
| CN104245640B (en) | The four of ethene gather | |
| NL2017640B1 (en) | Ligand based chromium catalyst and application in catalyzing ethylene oligomerization | |
| CN105503763A (en) | Novel polyolefin oil catalyst and applications thereof | |
| CN104549510A (en) | Ethylene oligomerization catalyst and use method thereof | |
| WO2019113752A1 (en) | Catalyst system for ethylene selective oligomerization and ethylene oligomerization reaction method | |
| CN109174191A (en) | A kind of catalyst of ethylene selectivity oligomerisation reaction | |
| CN108607612B (en) | Catalyst system for ethylene selective oligomerization, preparation method and ethylene oligomerization reaction method | |
| KR102605188B1 (en) | Ligand, Oligomerization Catalyst And Process For Preparing Ethylene Oligomer Using Thereof | |
| CN105263890A (en) | Tetramerisation of ethylene | |
| Lecocq et al. | Biphasic Ni-catalyzed ethylene oligomerization in ionic liquids | |
| CN110449186B (en) | Reaction method for selective oligomerization of ethylene, catalyst system and application thereof | |
| CN107250170B (en) | Olefin polymerization catalyst and process for producing olefin oligomer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |