CN108017673A - ligand compound, its preparation method and its application - Google Patents

ligand compound, its preparation method and its application Download PDF

Info

Publication number
CN108017673A
CN108017673A CN201610962306.4A CN201610962306A CN108017673A CN 108017673 A CN108017673 A CN 108017673A CN 201610962306 A CN201610962306 A CN 201610962306A CN 108017673 A CN108017673 A CN 108017673A
Authority
CN
China
Prior art keywords
compound
alkyl
substituted
ligand compound
general formula
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.)
Pending
Application number
CN201610962306.4A
Other languages
Chinese (zh)
Inventor
吴红飞
郑明芳
韩春卉
王霄青
栗同林
刘珺
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
Original Assignee
Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Sinopec Beijing Research Institute of Chemical Industry, China Petroleum and Chemical Corp filed Critical Sinopec Beijing Research Institute of Chemical Industry
Priority to CN201610962306.4A priority Critical patent/CN108017673A/en
Publication of CN108017673A publication Critical patent/CN108017673A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
    • C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
    • C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1845—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing phosphorus
    • B01J31/1875—Phosphinites (R2P(OR), their isomeric phosphine oxides (R3P=O) and RO-substitution derivatives thereof)
    • B01J31/188—Amide derivatives thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/19—Catalysts containing parts with different compositions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • 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
    • C07C2/26—Catalytic processes with hydrides or organic compounds
    • C07C2/32—Catalytic processes with hydrides or organic compounds as complexes, e.g. acetyl-acetonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/20—Olefin oligomerisation or telomerisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
    • B01J2531/62—Chromium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
    • B01J31/143—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of aluminium
    • 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)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • General Health & Medical Sciences (AREA)
  • Molecular Biology (AREA)
  • Biochemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

The present invention relates to a kind of ligand compound, as shown in general formula I：Wherein, R is unsubstituted or substituted alkyl radical, cycloalkyl or aryl；R ' is unsubstituted or substituted aryl.The invention further relates to a kind of preparation method and applications of the ligand compound.

Description

Ligand compound, its preparation method and its application
Technical field
The present invention relates to a kind of ligand compound, and in particular to ethylene oligomerisation catalyst ligand compound, especially ethene Trimerization and four poly- catalyst ligand compounds, the invention further relates to the preparation method of catalyst ligand compound and in ethylene oligomerization Application in technique.
Background technology
Ethylene oligomerization is one of most important reaction in olefinic polymerization industry., can will be cheap small by oligomerisation reaction Molecular olefine is transformed into high value-added product.Ethylene oligomerization product-linear alpha-alkene (LAO) is important organises Work raw material.Such as LAO C4-C8 are mainly used in production high-quality polyethylene as important Organic Ingredients and chemical intermediate (PE) field.PE can be significantly improved by 1- hexenes or 1- octenes and the linear low density polyethylene (LLDPE) of ethylene copolymer production Properties, can particularly significantly improve mechanical performance, optical property and the tear strength and impact strength of polyethylene, Product is very suitable for the fields such as the agricultural mulch films such as packaging film and greenhouse, canopy room.LAO C10-C30 can be used as preparing daily cleaning Agent, flotation agent, emulsifying agent, the emollient component of refrigeration machine and bore liquid emollient component, plasticizer, various additives, low viscosity are closed Into oil, polymer and copolymer, oil and oil product additive, senior alkylamines, advanced organo-aluminum compound, advanced alkane virtue Additive of base hydrocarbon, higher aliphatic and aliphatic acid, epoxides and heat carrier etc..On LAO C20-C30 bases On can also composite adhesives, sealant and coating.In recent years, with the continuous development of polyolefin industry, in world wide to α- The demand rapid development of alkene.Wherein most alpha-olefins is prepared to obtain by ethylene oligomerization.
Since the seventies in last century, the research of transient metal complex catalysis in olefine polymerization and oligomerisation is gradually subject to science The attention of family, people start to make great efforts research raw catelyst and improve existing catalyst, improve the activity and catalysate of catalyst Selectivity.In numerous explorations, research is earliest, with fastest developing speed, compare concentration is nickel cation type catalyst system and catalyzing, such as The United States Patent (USP) reported already has US3686351 and US3676523, and Shell Co. Ltd's SHOP works based on the patented technology Skill.O-P bridging type ligands are arrived involved in Shell Co. Ltd's SHOP techniques, but are containing virose organophosphorous groups in the catalyst, And synthesis step is complicated, stability is poor.The many such as O-O, P-N, P-P and N-N type coordination Raney nickel were developed again later Patent, such as JP11060627, WO9923096, WO991550, CN1401666, CN1769270 etc..However, obtained by above-mentioned patent The shortcomings that catalyst generally existing preparation method obtained is relatively complicated.Other catalyst also have chromium system, zirconium system and aluminium system etc., Brookhart groups (Brookhart, M et al., J.Am.Chem.Soc., 1998,120,7143-7144；WO99/02472, 1999), Gibson groups (Gibson, V.C. et al., Chem.Commun., 1998,849-850；Chem.Eur.J.,2000, Ethylene oligomerization can be catalyzed by 2221-2231) finding the trident pyridinimine complex of some Fe (II) and Co (II) respectively, not only be urged The catalytic activity of agent is very high, and the selectivity of alpha-olefin is also very high.
It is undoubted, remain the demand to the new catalyst of excellent combination property in olefin(e) oligomerization field. Notice is placed on the Novel Ligands compound how obtained for ethylene oligomerisation catalyst, so as to develop with high activity and choosing The ethylene oligomerisation catalyst of selecting property, is worth paying close attention in the industry.
The content of the invention
Present inventor is found that a kind of ethene of brand new is neat when studying ethylene oligomerisation catalyst containing phosphorous Poly- catalyst ligand, the ligand compound contain tri- kinds of hetero atoms of N, P, O, and structure is novel to be prepared simply, and cost is relatively low.Urged by this The composition that agent ligand, transistion metal compound and co-catalyst are formed can effectively be catalyzed ethylene oligomerization reaction, especially Ethylene trimer and four poly- reactions.Catalyst activity is more than 2 × 107G/ (molCrh), reaches as high as 108G/ (molCrh) with On；The overall selectivity of C6 and C8 components can be more than 92%, up to more than 97%；Selectivity of the 1- octenes in C8 99.2% with On.The catalyst containing the new ligand in the present invention has the characteristics that high activity, high selectivity, has preferable commercial Application Prospect and economic value.
The first aspect of the invention is related to a kind of ligand compound, as shown in general formula I：
Wherein, R is unsubstituted or substituted alkyl radical, cycloalkyl or aryl；R ' is unsubstituted or substituted aryl.
In the present invention, the substitution, refers to carbon atom in alkyl, cycloalkyl or aryl and/or hydrogen atom optionally Ground alkyl, cycloalkyl, halogen, aryl or alkoxy etc. substitute.
In a preferred embodiment of the present invention, the R is selected from C1-C6Alkyl, C3-C8Cycloalkyl and C5-C10 Aryl.R ' is selected from phenyl, substituted-phenyl, naphthyl or substituted naphthyl, such as phenyl, alkyl (C1-C6) substitution phenyl, naphthyl or Alkyl (C1-C6) substitution naphthyl.
In the present invention, term " C1-C6Alkyl " refers to saturated straight chain or branched hydrocarbyl containing 1-6 carbon atom, such as The straight chained alkyl of C1-C6 and the branched alkyl of C3-C6.As C1-C6Alkyl, it can be mentioned that methyl, ethyl, n-propyl, isopropyl Base, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, n-pentyl, isopentyl, sec-amyl, n-hexyl and Sec-Hexyl；Particularly preferred first Base, ethyl, n-propyl and isopropyl.
In the present invention, term " C3-C8Cycloalkyl " refers to the group with cyclic structure containing 3-8 carbon atom. As C3-C8Cycloalkyl, it can be mentioned that cyclopropyl, methylcyclopropyl groups, ethyl cyclopropyl, cyclobutyl, methyl-cyclobutyl, ethyl ring Butyl, cyclopenta, methylcyclopentyl, ethylcyclopentyl, propyl group cyclopenta, cyclohexyl, suberyl and cyclooctyl.
In the present invention, term " C5-C10Aryl " refer to the base with aromatic structure containing 5-10 carbon atom Group.As C5-C10Aryl, it can be mentioned that pyridine radicals, phenyl, naphthyl, tolyl, ethylbenzene, benzyl, phenethyl etc..
In some specific embodiments, the R be selected from methyl, ethyl, isopropyl, cyclopropyl, cyclopenta, cyclohexyl or Phenyl.
The second aspect of the invention provides the preparation method of the ligand compound, including：
A) it is R-NH by general formula2Amine be dissolved in organic solvent, then add R '2PCl, it is II's that general formula is obtained after reaction Compound, wherein, the restriction of R and R ' are same as above,
B) compound as shown in general formula II is dissolved in organic solvent, adds alkyl lithium catalyst, adding general formula is The phosphine chlorine compound of III, obtains ligand compound I after the completion of reaction,
In a preferred embodiment of preparation method of the present invention, R ' in the step a)2PCl and R-NH2Rub You are than being 1:(1-3), preferably 1:2；Mole of compound II described in step b), alkyl lithium catalyst and phosphine chlorine compound III Than for 1:(0.8-1.2):(0.8-1.2).
In a preferred embodiment of preparation method of the present invention, the alkyl lithium catalyst is selected from normal-butyl At least one of lithium, tert-butyl lithium and lithium methide.
In a preferred embodiment of preparation method of the present invention, the organic solvent is selected from arene compounds At least one of with aliphatic hydrocarbon compound, it preferably is selected from toluene, ether, tetrahydrofuran, hexane and dichloromethane at least It is a kind of.
In a preferred embodiment of preparation method of the present invention, the reaction temperature in the step a) is 20- 30 DEG C, when the reaction time is 2-4 small.Reaction temperature in step b) is -10 to 10 DEG C, when the reaction time is 2 to 4 small.
The third aspect of the invention is related to a kind of application of ligand compound in ethylene oligomerization, is such as preparing second Application in alkene oligomerisation carbon monoxide-olefin polymeric.Catalyst ligand of the present invention, with transistion metal compound and co-catalyst Composition is formed, can effectively be catalyzed ethylene oligomerization reaction, particularly ethylene trimer and four poly- reactions.
Carbon monoxide-olefin polymeric provided by the invention, ligand compound are the compound of brand new, it prepares simple, cost Relatively low, the carbon monoxide-olefin polymeric being made of the ligand compound can carry out ethylene trimer and four poly- reactions, and catalyst activity surpasses Cross 2 × 107G/ (molCrh), reaches as high as 108More than g/ (molCrh)；The overall selectivity of C6 and C8 components can exceed 92%, up to more than 97%；Selectivity of the 1- octenes in C8 has the characteristics that high activity, high selectivity more than 99.2%, tool There are preferable prospects for commercial application and economic value.
Embodiment
The following example is only used for that the present invention is described in detail, it will be appreciated that the scope of the present invention is not limited to These embodiments.
In an embodiment of the present invention, nuclear magnetic resonance is detected using Bruker AV400 type Nuclear Magnetic Resonance；Gas phase Chromatography is detected using 5890 chromatograph of Hewlett-Packard.
Wherein, the testing conditions of nuclear magnetic resonance are：Deuterochloroform is solvent, and room temperature is tested.
Wherein, the testing conditions of gas-chromatography are：Chromatographic column SE-54, High Purity Nitrogen carrier gas, fid detector；Column temperature uses two Rank temperature programming.
Embodiment 1
Ligand compound 1 (such as general formula I, R=iPr, R '=Ph) preparation method include：
11mmol isopropylamines are dissolved in 10mL ether solvents, then add 5mol R '2PCl (R '=Ph), is stirred at room temperature Mix reaction 4 it is small when.Filtering, removes solvent with revolving by filtrate and obtains compound II (R=iPr).By compound II (R=iPr it is) molten In 10mL toluene, 5mmol butyl lithiums (1.6M hexane solutions) are added dropwise under ice bath, is added dropwise in half an hour, adds 5mmol Phosphine chlorine compound III, when stirring reaction 3 is small.Revolving removes solvent after the completion of reaction, and column chromatography for separation obtains ligand compound 1. Yield 55.7%.1H NMR(400MHz,CDCl3)：δ=7.43-7.37 (m, 3H), 7.28-7.26 (m, 6H), 7.20-7.22 (m,6H),7.09-7.07(m,3H),3.40-3.25(m,1H),1.03(s,3H),1.01(s,3H)。
Embodiment 2
The preparation method of ligand compound 2 (such as general formula I, R=Cy, R '=Ph) is the same as ligand compound 1.
Yield 61.3%.1H NMR(400MHz,CDCl3)：δ=7.43-7.37 (m, 3H), 7.28-7.26 (m, 6H), 7.20-7.22(m,6H),7.09-7.07(m,3H),2.51(m,1H),1.75-0.71(m,10H)。
Embodiment 3
The preparation method of ligand compound 3 (such as general formula I, R=Cy, R '=2-MePh) is the same as ligand compound 1.
Yield 49.0%.1H NMR(400MHz,CDCl3)：δ=7.61-7.55 (m, 3H), 7.33-7.29 (m, 6H), 7.26-7.23(m,4H),7.09-7.07(m,3H),3.40-3.25(m,1H),2.70(s,6H),1.03(s,3H),1.01(s, 3H)。
Embodiment 4
The preparation method of ligand compound 4 (such as general formula I, R=Ph, R '=Ph) is the same as ligand compound 1.
Yield 57.9%.1H NMR(400MHz,CDCl3)：δ=7.55-7.20 (m, 18H), 7.01-6.68 (m, 5H).It is real Apply example 5 (Polymerization Example)
Ethylene oligomerization reaction uses stainless steel polymeric kettle.Autoclave is heated to 80 DEG C, with nitrogen displacement number after vacuumizing It is secondary, it is then charged with when ethene to ethylene pressure is 3MPa and is down to room temperature.Then hexahydrotoluene is added at 60 DEG C, is added at the same time 2.5 μm of ol tetrahydrofurans chromium chlorides and 5 μm of ol ligand compounds 1 and 500 μm of ol triethyl aluminums, the cumulative volume of mixed liquor are The molar ratio of 100mL, wherein chromium, ligand compound and co-catalyst are 1：2：200, reaction pressure 2MPa is controlled, is passed through ethene, Carry out ethylene oligomerization reaction.
After the completion of reaction, system is cooled to room temperature, and gaseous products are collected in aerometer measuring tank, and liquid-phase product is collected In conical flask, 1mL ethanol is added as terminator, terminates ethylene oligomerization reaction.Gas-chromatography is carried out after liquid phase gauging of products Analysis.It is as follows to measure reaction result：Catalytic activity is 2.3 × 107G/ (molCrh), C6 compositional selectings are 29.8%, C8 Compositional selecting is that the overall selectivity of 63.3%, C6 components and C8 components is that 93.1%, 1- octenes account for 99.6% in C8,
Embodiment 6 (Polymerization Example)
Reaction pressure is changed to 4MPa, the other the same as in Example 5.It is as follows to measure reaction result：Catalytic activity for 6.2 × 107G/ (molCrh), C6 compositional selectings are that 24.8%, C8 compositional selectings are the total of 70.3%, C6 components and C8 components Selectivity accounts for 99.7% for 95.1%, 1- octenes in C8.
Embodiment 7 (Polymerization Example)
Ligand compound 1 is changed to ligand compound 2, other same embodiments 6.It is as follows to measure reaction result：Catalytic activity For 5.8 × 107G/ (molCrh), C6 compositional selectings are that 25.2%, C8 compositional selectings are 72.5%, C6 components and C8 groups The overall selectivity divided accounts for 99.5% for 97.7%, 1- octenes in C8.
Embodiment 8 (Polymerization Example)
Ligand compound 1 is changed to ligand compound 3, other same embodiments 6.It is as follows to measure reaction result：Catalytic activity For 5.5 × 107G/ (molCrh), C6 compositional selectings are that 28.5%, C8 compositional selectings are 68.0%, C6 components and C8 groups The overall selectivity divided accounts for 99.2% for 96.5%, 1- octenes in C8.
Embodiment 9 (Polymerization Example)
Ligand compound 1 is changed to ligand compound 4, other same embodiments 6.It is as follows to measure reaction result：Catalytic activity For 6.1 × 107G/ (molCrh), C6 compositional selectings are that 25.9%, C8 compositional selectings are 70.1%, C6 components and C8 groups The overall selectivity divided accounts for 99.4% for 96%, 1- octenes in C8.
Embodiment 10 (Polymerization Example)
Reaction temperature is changed to 45 DEG C by 60 DEG C, other conditions are the same as embodiment 6.It is as follows to measure reaction result：Catalytic activity For 6.8 × 107G/ (molCrh) (i.e. 1.3 × 106G/ (gCrh)), C6 compositional selectings are 21.5%, C8 compositional selectings It is that 94.6%, 1- octenes account for 99.5%, C10 and above component in C8 for the overall selectivity of 73.1%, C6 and C8 components 3.0%.
Embodiment 11 (Polymerization Example)
Co-catalyst is changed to modified methylaluminoxane (MMAO-3A) by triethyl aluminum, other conditions are the same as embodiment 6.Survey It is as follows to obtain reaction result：Catalytic activity is 11.7 × 107G/ (molCrh), C6 compositional selectings select for 18.8%, C8 components Selecting property is 74.1%, C6 and the overall selectivity of C8 components is that 92.9%, 1- octenes account for 99.5%, C10 and above component in C8 5.0%.
In the present invention：Ph represents phenyl,iPr represents isopropyl, and Cy represents cyclohexyl, and Me represents methyl.In the present invention In the preparation process of ligand compound, the yield being related to refers to the gross production rate of two-step reaction, with raw material R '2Calculated on the basis of PCl. In the present invention, mass percentage of the component in gross product is reacted selectively is referred to.In the present invention, the work of catalyst Property unit be g/ (molCrh), i.e. the gross mass in the generation product of interior every mole of chromic salts catalytic polymerization per hour also may be used G/ (gCrh) is scaled, is calculated according to the atomic weight of chromium, 52g/ (molCrh)=1g/ (gCrh).
It should be noted that embodiment described above is applied to explain the present invention, do not form to any of the present invention Limitation.By referring to above-mentioned exemplary embodiments, invention has been described, it should be appreciated that wherein all words are Descriptive and explanatory vocabulary, rather than limited vocabulary.Can be according to the rules within the scope of the claims to this Modification is made in invention, and the present invention is revised in without departing substantially from scope and spirit of the present invention.Although described in it The present invention relates to specific method, material and embodiment, it is not intended that the present invention is limited to wherein disclosed particular case, phase Instead, the present invention can be extended to other all methods and applications with identical function.

Claims (10)

  1. A kind of 1. ligand compound, as shown in general formula I：
    Wherein, R is unsubstituted or substituted alkyl radical, cycloalkyl or aryl；R ' is unsubstituted or substituted aryl.
  2. 2. compound according to claim 1, it is characterised in that the R is selected from C1-C6Alkyl, C3-C8Cycloalkyl and C5-C10Aryl, preferably be selected from methyl, ethyl, isopropyl, cyclopropyl, cyclopenta, cyclohexyl or phenyl.
  3. 3. compound according to claim 1 or 2, it is characterised in that the R ' be selected from phenyl, substituted-phenyl, naphthyl and Substituted naphthyl；It is preferably selected from phenyl, C1-C6Alkyl-substituted phenyl, naphthyl and C1-C6Alkyl-substituted naphthyl.
  4. 4. a kind of preparation method of ligand compound according to any one of claim 1-3, including：
    A) it is R-NH by general formula2Amine be dissolved in organic solvent, then add R '2PCl, obtains the chemical combination that general formula is II after reaction Thing, wherein, R is unsubstituted or substituted alkyl radical, cycloalkyl or aryl；R ' is unsubstituted or substituted aryl,
    B) compound as shown in general formula II is dissolved in organic solvent, it is III's to add alkyl lithium catalyst and add general formula Phosphine chlorine compound, obtains ligand compound I after the completion of reaction,
  5. 5. according to the method described in claim 5, it is characterized in that, R ' described in step a)2PCl and R-NH2Molar ratio be 1: (1-3), preferably 1:(1-2).
  6. 6. according to the method described in claim 5, it is characterized in that, compound II described in step b), alkyl lithium catalyst and The molar ratio of phosphine chlorine compound III is 1:(0.8-1.2):(0.8-1.2).
  7. 7. according to the method any one of claim 4-6, it is characterised in that the alkyl lithium catalyst preferably is selected from positive fourth At least one of base lithium, tert-butyl lithium and lithium methide.
  8. 8. according to the method any one of claim 4-7, it is characterised in that the organic solvent is selected from aromatic hydrocarbons chemical combination At least one of thing and aliphatic hydrocarbon compound, preferably are selected from toluene, ether, tetrahydrofuran, hexane and dichloromethane extremely Few one kind.
  9. 9. according to the method any one of claim 4-8, it is characterised in that the reaction temperature in the step a) is 20-30 DEG C, the reaction time for 2-4 it is small when, and/or reaction temperature in the step b) is -10 to 10 DEG C, the reaction time 2 To 4 it is small when.
  10. 10. in a kind of ligand compound according to any one of claim 1-3 or claim 4-9 described in any one The application of ligand compound prepared by method in ethylene oligomerization, especially in ethylene oligomerization carbon monoxide-olefin polymeric is prepared Using.
CN201610962306.4A 2016-11-04 2016-11-04 ligand compound, its preparation method and its application Pending CN108017673A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610962306.4A CN108017673A (en) 2016-11-04 2016-11-04 ligand compound, its preparation method and its application

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610962306.4A CN108017673A (en) 2016-11-04 2016-11-04 ligand compound, its preparation method and its application

Publications (1)

Publication Number Publication Date
CN108017673A true CN108017673A (en) 2018-05-11

Family

ID=62084051

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610962306.4A Pending CN108017673A (en) 2016-11-04 2016-11-04 ligand compound, its preparation method and its application

Country Status (1)

Country Link
CN (1) CN108017673A (en)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102040624A (en) * 2009-10-19 2011-05-04 中国石油化工股份有限公司 Method for synthesizing ligand for ethylene trimerization or tetramerization catalyst and ligand synthesized thereby and application thereof
CN105263890A (en) * 2013-05-09 2016-01-20 沙索技术有限公司 Tetramerisation of ethylene

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102040624A (en) * 2009-10-19 2011-05-04 中国石油化工股份有限公司 Method for synthesizing ligand for ethylene trimerization or tetramerization catalyst and ligand synthesized thereby and application thereof
CN105263890A (en) * 2013-05-09 2016-01-20 沙索技术有限公司 Tetramerisation of ethylene

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
YUSHENG ZHOU ET AL.: "Highly active chromium-based selective ethylene tri-/tetramerization catalysts supported by PNPO phosphazane ligands", 《DALTON TRANSACTIONS》 *

Similar Documents

Publication Publication Date Title
CN104415790B (en) A kind of catalyst for ethylene tetramerization composition and application
CN106146555A (en) A kind of ligand compound and its preparation method and application
CN103566973B (en) For the carbon monoxide-olefin polymeric of ethylene oligomerization
CN104415787B (en) A kind of olefin Polymerization catalyst compositions and using method thereof
CN108017674A (en) A kind of ligand compound, its preparation method and its application
CN104230908B (en) Heterocyclic ligand compound, catalyst composition containing this compound and application
CN104415788B (en) Olefin Polymerization catalyst compositions and application thereof
CN108017673A (en) ligand compound, its preparation method and its application
CN109701642A (en) A kind of carbon monoxide-olefin polymeric and its application
CN105566038B (en) A kind of ethylene oligomerization continuous reaction method
CN107233919A (en) A kind of catalyst for oligomerization composition and its application
CN105457679B (en) A kind of ethylene oligomerization carbon monoxide-olefin polymeric and its application
CN105498840B (en) A kind of catalyst for ethylene tetramerization composition and ethylene tetramerization method
CN107282127A (en) A kind of ethylene trimer and four poly- carbon monoxide-olefin polymerics and application
CN106140304A (en) A kind of ethylene trimerization and four poly-carbon monoxide-olefin polymeric and preparation and application thereof
CN107282112A (en) A kind of ethylene oligomerisation catalyst composition and application
CN109701648A (en) A kind of carbon monoxide-olefin polymeric and application
CN105562089B (en) A kind of ethylene oligomerisation catalyst composition and ethylene oligomerization method
CN105562085B (en) A kind of ethylene oligomerization carbon monoxide-olefin polymeric and its application
CN105478167B (en) A kind of ethylene oligomerisation catalyst composition and ethylene oligomerization method
CN105562088B (en) A kind of ethylene oligomerisation catalyst composition and ethylene oligomerization method
CN107282128A (en) A kind of catalyst for ethylene tetramerization composition and ethylene tetramerization method
CN105566043B (en) A kind of method of ethylene oligomerization reaction
CN107282133A (en) Catalyst for ethylene tetramerization composition and application
CN105562102B (en) A kind of catalyst for ethylene tetramerization composition and ethylene tetramerization method

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
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20180511