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CN106432336B - PNN ligands, its iron complex based on chinoline backbone and preparation method and application - Google Patents

PNN ligands, its iron complex based on chinoline backbone and preparation method and application Download PDF

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CN106432336B
CN106432336B CN201610820958.4A CN201610820958A CN106432336B CN 106432336 B CN106432336 B CN 106432336B CN 201610820958 A CN201610820958 A CN 201610820958A CN 106432336 B CN106432336 B CN 106432336B
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pnn
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ligand
ethylene
alkyl
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CN106432336A (en
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黄正
张丹
张延路
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Shanghai Institute of Organic Chemistry of CAS
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Shanghai Institute of Organic Chemistry of CAS
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    • 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
    • C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
    • C07F9/576—Six-membered rings
    • C07F9/60—Quinoline or hydrogenated quinoline ring systems
    • 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
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/02—Iron compounds
    • C07F15/025—Iron compounds without a metal-carbon linkage
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F10/00—Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F10/02—Ethene

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Abstract

The invention discloses a kind of PNN ligands, its iron complex and preparation method and application based on chinoline backbone.Ligand structure is shown in formula I, and the definition of each substituent group is as described in specification and claims.Iron complex is obtained by the reaction with iron halide in ligand, complex structure is as shown in Formula II, it can be used for catalyzed ethylene polymerization reaction, ethylene and alhpa olefin or non-conjugated diene copolyreaction and (ethylene non-conjugated diene) copolymer functionalization, have excellent catalytic activity.

Description

PNN ligands, its iron complex based on chinoline backbone and preparation method and application
Technical field
The present invention relates to the PNN ligands based on chinoline backbone, its iron complex, preparation methods and in vinyl polymerization, ethylene With the application in alpha-olefin or non-conjugated diene copolymerization.
Background technology
Ziegler-Natta catalyst (the K.Ziegler et that nineteen fifties find al.Angew.Chem.1995,67,424；K.Ziegler et al.Angew.Chem.1995,67,541；N.Kashiwa et Al.USP3642746,1968), it is widely used in industrially to produce high density polyethylene (HDPE) (HDPE), linear low density polyethylene Alkene (LLDPE), syndiotactic polypropylene (i-PP).Ziegler-Natta catalyst is heterogeneous, dynamics model, at present also not Can the structure and performance of polymer be controlled by adjusting catalyst structure well.The metallocene catalyst that the eighties are found This problem is then preferably resolved, enables people to obtain specific structure as desired by the structure for changing catalyst Polymer (W.Kaminsky et al.Adv.Organomet.Chem.1980,18,99；W.Kaminsky et al.Angew.Chem.Int.Ed.Engl.1980,19,390；H.H.Brintzinger et al.Angew.Chem.Int.Ed.Engl.1995,34,1143).Its active center is single, can generate highly homogeneous point Minor structure and the uniform polymer of component can obtain the advantages that polymer of narrow molecular weight distribution, but electrophilic due to metallocene Property it is strong, central metallic ions easily with polar functional group be coordinated and lose activity, it is difficult to realize the polymerization or copolymerization of polar monomer. Also, metallocene catalyst is larger to the dosage of co-catalyst MAO, and production cost is high.
Nineteen ninety-five, Brookhart etc. report alpha-diimine nickel/palladium complex catalyzed ethylene polymerization and with polar monomer It is copolymerized (M.Brookhart et al.J.Am.Chem.Soc.1995,117,6414；M.Brookhart et Al.J.Am.Chem.Soc.1996,118,267.), which results in people to the numerous studies of late transition metal complex.It crosses afterwards Metal is crossed due to its weaker oxytropism, it is possible to preferably tolerate polar monomer.Transition catalyst can be catalyzed behind part The copolyreaction of alkene and polar monomer, to provide possibility to produce novel polyolefine material.
1998, Brookhart and Gibson et al. reported pyridine diimine iron complex catalysis olefinic polymerization simultaneously Reaction, energy catalyzed ethylene polymerization obtains high polymer or ethylene oligomerization obtains statistical distribution linear terminal olefinic hydrocarbons (M.Brookhart et al.J.Am.Chem.Soc.1998,120,4049；M.Brookhart et al.J.Am.Chem.Soc.1998,120,7143；V.C.Gibson et al.Chem.Commun.1998,849).Ferrous metal Complex compound due to its high catalytic polymerization activity, abundant reserves, cheap price and it is environmentally friendly the advantages that, attract Researchers greatly interest.From this, the iron complex of many new ligands is devised, by an imido grpup on ligand It is substituted by amido (V.C.Gibson et al.Eur.J.Inorg.Chem.2001,2001,431), carbonyl (P.T.Gomes； M.M.Marques et al.Polym.Int.2002,51,1301), hydroxyl (V.C.Gibson；G.A.Solan et Al.Organometallics 2007,26,5119) the iron catalyst of tridentate ligand be devised, but activity is relatively low.And There is presently no the reports that the iron complex of the PNN type tridentate ligands based on chinoline backbone is used for catalysis in olefine polymerization.
Based on pyridine diimine skeleton NNN type tridentate ligand iron complexes catalysis ethylene reacted with alpha-olefin copolymer once by Report.Fr é d é ric Peruch et al. simply report 2,6- (2,6- 3,5-dimethylphenyls) bis-imine pyridine iron network of small steric hindrance Object catalysis ethylene and 1- hervene copolymers are closed, wherein 1- hexenes insertion rate is about 3.5%, and author does not provide the molecular weight of polymer And its distribution, in addition, this complex compound cannot be catalyzed 1- hexene oligomerizations (F.Peruch et al.C.R.Chimie 2002,5, 43.).The polymerization of Kohtaro Osakada group studies pyridine diimine iron (cobalt) complex catalysis 1,6- heptadiene and 1,6- Heptadiene reacts (Kohtaro Osakada et al.J.Am.Chem.Soc.2007,129,7002 with ethylene copolymer； Macromol.Rapid Commun.2008,29,1932；Dalton Transactions 2009,8955.).Wherein, 2,6- Cyclisation polymerisation occurs for (2,6- 3,5-dimethylphenyl) bis-imine pyridine iron complex catalysis 1,6- heptadiene, with high selectivity To containing cis- pentacyclic polymer；In catalysis ethylene and 1, in 6- heptadiene copolyreaction, also cyclisation generates five-membered ring, polymerization There is no hexenyl branch in object.
Therefore, develop efficient olefin polymerization catalysis, realize ethylene and alpha-olefin (such as 1- octenes) adjustable copolymerization, realize second Alkene is copolymerized with non-conjugated diene (such as 1,7- octadienes) non-cyclizing, generates the copolymer of band edge alkene on branch, is rear function dough (such as silicon hydrogenation, hydroboration, epoxidation, hydroxylating) offer is possible, is current urgent need solution so as to improve the property of polymer Certainly the technical issues of.
Invention content
The purpose of the present invention is to provide a kind of PNN ligands and its iron complex based on chinoline backbone.
The first aspect of the present invention, provides a kind of ligand, and structure is shown in formula I：
In formula, R be Ra or
Ra、R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12、R13、R14、R15、R16Be each independently hydrogen atom, Nitro, cyano, formoxyl, benzyl, halogen, C1~C10Alkyl, halogen substitution C1~C10Alkyl, C2~C10Alkenyl, C2~C10Alkynyl, C6~C14Aryl, C1~C10Alkoxy, C6~C14Aryloxy group, C1~C10Alkyl-carbonyl, C1~ C10Alkylthio group,
Wherein, adjacent group is cyclic each other or not cyclic；
Wherein, R17、R18、R19、R20、R21、R22And R23It is each independently hydrogen atom, C1~C10Alkyl or C6~C14's Aryl.
In another preferred example, R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12、R13、R14、R15、R16It is respectively independent Ground is hydrogen atom, nitro, cyano, formoxyl, benzyl, halogen, C1~C6Alkyl, C2~C6Alkenyl, C2~C6Alkynyl, C6 ~C10Aryl, halogen substitution C1~C6Alkyl, C1~C6Alkoxy, C6~C10Aryloxy group, C1~C6Alkyl oxycarbonyl Base, C1~C6Alkylthio group,
Wherein, adjacent group is cyclic each other or not cyclic；
R17、R18、R19、R20、R21、R22And R23It is each independently hydrogen atom, C1~C6Alkyl or C6~C10Aryl.
In another preferred example, R1、R2、R3、R4、R5、R11、R12、R13、R14、R15、R16It is each independently hydrogen atom or C1 ~C6Alkyl.
In another preferred example, R1、R2、R3、R4And R5Preferred hydrogen atom or C each independently1~C4Alkyl, such as first Base, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group or tertiary butyl.
In another preferred example, R11、R12、R13、R14、R15Respectively independent preferred hydrogen atom.
In another preferred example, R16It is preferred that hydrogen atom or methyl.
In another preferred example, R Ra, Ra C1~C6Alkyl.
In another preferred example, Ra C1~C4Alkyl, such as methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl Base or tertiary butyl, preferably, Ra is isopropyl or tertiary butyl.
In another preferred example, R isR6、R7、R8、R9、R10It is each independently hydrogen atom, C1~C4Alkane Oxygroup or the C of halogen substitution1~C4Alkyl.
In another preferred example, R6、R7、R8、R9、R10Hydrogen atom, C each independently1~C4Alkoxy or fluorine, chlorine and The C of one or more of bromine atom substitution1~C4Alkyl.
In another preferred example, R1And R5It is each independently methyl, ethyl or isopropyl；R2、R3And R4Each independently For hydrogen atom；R6、R8It is each independently methoxyl group or trifluoromethyl；R7、R9、R10It is each independently hydrogen atom；R16For first Base.
In another preferred example, the ligand is in ligand 1 A- ligand 1s H, ligand 2A- ligands 2D prepared by embodiment Any ligand.
The second aspect of the present invention provides a kind of complex compound, and structure is as shown in Formula II：
In formula, R, R1、R2、R3、R4、R5、R11、R12、R13、R14、R15、R16Definition as described in relation to the first aspect；
X, Y is identical or different halogen atom.
In another preferred example, X, Y are identical, are fluorine, chlorine, bromine or iodine, preferably chlorine.
In another preferred example, the complex compound is complex compound 3A- complex compounds 3H, complex compound 4A- prepared by embodiment Any complex compound in complex compound 4D.
The third aspect of the present invention, provides the preparation method of the ligand described in first aspect, including formula III compound with (R)2PH carries out the step of coupling reaction obtains the ligand：
In various, R, R1、R2、R3、R4、R5、R11、R12、R13、R14、R15、R16Definition as described in relation to the first aspect.
The fourth aspect of the present invention provides the preparation method of the complex compound described in second aspect, including ligand shown in Formulas I The step of complex reaction obtains the complex compound is carried out with FeXY：
In various, R, R1、R2、R3、R4、R5、R11、R12、R13、R14、R15、R16Definition as described in relation to the first aspect；
X, Y is identical or different halogen atom.
In another preferred example, X, Y are identical, are fluorine, chlorine, bromine or iodine, preferably chlorine.
The fifth aspect of the present invention provides the purposes of the complex compound described in second aspect, and the complex compound is for being catalyzed alkene Polymerized hydrocarbon or catalysis (ethylene-non-conjugated diene) copolymer functionalization.
In another preferred example, the complex compound is used to be catalyzed the homopolymerization polymerisation of ethylene.
In another preferred example, the complex compound is used to be catalyzed the copolyreaction of ethylene and alpha-olefin.
In another preferred example, alpha-olefin is 1- octenes.
In another preferred example, the complex compound is used to be catalyzed the copolyreaction of ethylene and non-conjugated diene.
In another preferred example, the non-conjugated diene is 1,7- octadienes.
In another preferred example, described (ethylene-non-conjugated diene) the copolymer functionalization be silicon hydrogenation, hydroboration, Epoxidation or hydroxylating.
The sixth aspect of the present invention provides a kind of olefine polymerizing process, is used as and is urged using the complex compound described in second aspect Agent.
In another preferred example, the olefinic polymerization be the homopolymerization polymerization of ethylene, ethylene and alpha-olefin co-polymeric or The co-polymeric of ethylene and non-conjugated diene.
In another preferred example, alpha-olefin is 1- octenes.
In another preferred example, the non-conjugated diene is 1,7- octadienes.
The seventh aspect of the present invention, provides a kind of (ethylene-non-conjugated diene) copolymer functionalization, and the reaction is adopted Use complex compound described in second aspect as catalyst.
In another preferred example, described (ethylene-non-conjugated diene) the copolymer functionalization be silicon hydrogenation, hydroboration, Epoxidation or hydroxylating.
The PNN ligands and its iron complex based on chinoline backbone of the present invention is used for catalysed olefin polymerization, specifically urges Change ethylene polymerization, there is excellent catalytic activity, it is suitable with the highest Qi Geer-Natta catalyst of activity, it produces low The polythene material of molecular weight and narrow molecular weight distribution, this kind of polyethylene product can be applied to high-quality polyethylene wax.In addition should Iron complex catalyst can be catalyzed ethylene and is copolymerized with alpha-olefin (such as 1- octenes), and it is wax-like or oily polyene to produce shape Hydrocarbon product.It can be additionally catalyzed ethylene and non-conjugated diene (such as 1,7- octadienes) copolymerization, generate the copolymerization of band edge alkene on branch Object.End alkene in this analog copolymer can by further function dough (such as silicon hydrogenation, hydroboration, epoxidation, hydroxylating), to The property of polymer can be used for improving.
The PNN ligands of the present invention and its preparation method of iron complex are simple, and raw material is cheap and easy to get, environmentally friendly, after Processing is simple, is suitable for industrialized production.The novel PNN iron catalysts of the present invention can be applied to preparation structure, unique Polyolefine material is especially suitable for preparing high-quality polyethylene wax, high-quality lubricating oil.
In the present invention, ethylene and non-conjugated diene copolyreaction and silicon hydrogen are realized using single PNN sections complex compound Change or hydroboration, generate the copolymer product that branch terminals are active silicon substrate or boryl functional group, and catalyst activity is non- Chang Hao.
It should be understood that within the scope of the present invention, above-mentioned each technical characteristic of the invention and have in below (eg embodiment) It can be combined with each other between each technical characteristic of body description, to form a new or preferred technical solution.As space is limited, exist This no longer tires out one by one states.
Specific implementation mode
Present inventor develops a kind of PNN types based on chinoline backbone for the first time by depth studying extensively The iron complex of tridentate ligand.On this basis, the present invention is completed.
Term
In the present invention, substituent group halogen is preferably fluorine, chlorine, bromine or iodine.
C1~C10Alkyl refer to the linear chain or branched chain alkyl for having 1-10 carbon atom, preferably C1~C6Alkyl, example Such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl group or tertiary butyl.
C2~C10Alkenyl refer to the linear chain or branched chain alkyl for including at least one double bond for having 2-10 carbon atom, it is excellent It is selected as C2~C6Alkenyl, as vinyl,
C2~C10Alkynyl refer to the linear chain or branched chain alkyl for including at least one three key for having 2-10 carbon atom, it is excellent Select C2~C6Alkynyl, as acetenyl,
C6~C14Aryl refer to the alkyl for including one or more aromatic rings for having 6-14 carbon atom, preferably C6~C10 Aryl, preferably phenyl, diphenyl methyl or betanaphthyl.
C1~C10Alkoxy be expressed as-O- (C1-10Alkyl), preferably C1~C6Alkoxy, as methoxyl group, ethyoxyl, Propoxyl group, isopropoxy, butoxy, isobutoxy or tert-butoxy.
C6~C14Aryloxy group be expressed as-O- (C6-14Aryl), preferably C6~C10Aryloxy group, preferably phenoxy group or naphthalene oxygen Base.
C1~C10Alkyl-carbonyl be expressed as-C (O)-(C1~C10Alkyl), preferably C1~C6Alkyl-carbonyl, wherein institute " the C stated1~C6Alkyl " preferably methyl, ethyl, propyl, isopropyl, butyl, isobutyl group or tertiary butyl；" the C1~C6 Alkyl-carbonyl " such as acetyl group.
C1~C10Alkylthio group be expressed as-S- (C1-10Alkyl), preferably C1~C6Alkylthio group, as methyl mercapto, ethylmercapto group, Rosickyite base, isopropyisulfanyl, butylthio, isobutylthio or tertiary butylthio.
The C of halogen substitution1~C10Alkyl in the preferred fluorine of halogen, chlorine or bromine, it is described when there are multiple halogen atoms Halogen atom can be identical or different；" the C of halogen substitution1~C10Alkyl " described in " C1~C10Alkyl " it is excellent Select C1~C6Alkyl, " the C1~C6Alkyl " can be methyl, ethyl, propyl, isopropyl, butyl, isobutyl group or uncle Butyl." the C of halogen substitution1~C10Alkyl " preferably " and one or more of fluorine, chlorine and bromine atom substitution C1~ C6Alkyl ", the described " C of one or more of fluorine, chlorine and bromine atom substitution1~C6Alkyl " preferably " fluorine, chlorine and bromine The methyl of one or more of atom substitution ", " ethyl of one or more of fluorine, chlorine and bromine atom substitution ", " fluorine, chlorine With the propyl of one or more of bromine atom substitution ", " isopropyl of one or more of fluorine, chlorine and bromine atom substitution ", " butyl of one or more of fluorine, chlorine and bromine atom substitution ", " one or more of fluorine, chlorine and bromine atom replace different Butyl " or " tertiary butyl of one or more of fluorine, chlorine and bromine atom substitution "；" methyl of fluorine atom substitution " is preferably Trifluoromethyl, " methyl of bromine atom substitution " are preferred
Ligand
In the present invention, the structure of ligand (also referred to as PNN ligands) is shown in formula I,
Each substituent group is as defined above.
The present invention ligand, be ligand 1 or 2,
Each substituent group is as defined above.
Complex compound
The complex compound of the present invention, also referred to as complex, also referred to as PNN sections complex compound, are a kind of new tridentate ligands 8th subgroup late transition metal complex.
Structure is as shown in Formula II：
Each substituent group is as defined above.
The PNN sections complex compounds of the present invention are iron complex 3 or iron complex 4：
Each substituent group is as defined above.
With preparation
The preparation method of the PNN ligands of the present invention, includes the following steps：Under inert gas shielding, in organic solvent, metal Under the conditions of catalyst is existing, compound 5 and compound 6 or 7 are subjected to coupling reaction, generate PNN ligand 1s or 2；
Wherein, each substituent group is as defined above.
PNN ligand 1s or 2 preparation method can be this field in such coupling reaction conventional method, the present invention in it is excellent Select following reaction methods and condition：
In preparing the method for PNN ligand 1s or 2, in the preferred helium of the inert gas, argon gas, neon and nitrogen It is one or more.
In preparing the method for PNN ligand 1s or 2, the organic solvent preferred aromatic hydrocarbons class solvent, the aromatic hydrocarbons are molten The preferred toluene of agent.
In preparing the method for PNN ligand 1s or 2, the volume mass of the organic solvent and the compound 5 is than excellent Select 1mL/g~200mL/g, further preferred 20mL/g~40mL/g.
In preparing the method for PNN ligand 1s or 2, the preferred late transition metal catalyst of the metallic catalyst is described The preferred Pd of late transition metal catalyst (dba)2Or CuI.
In preparing the method for PNN ligand 1s or 2, the metallic catalyst and the molar ratio of the compound 5 are excellent 0.005~0.20 is selected, further preferred 0.01~0.10, still further preferably 0.05~0.06.
In preparing the method for PNN ligand 1s or 2, the molar ratio of the compound 6 or 7 and the compound 5 is excellent 1.0~4.0 are selected, further preferred 1.0~2.0, still further preferably 1.1~1.2.
In preparing the method for PNN ligand 1s or 2, the temperature of the reaction can be such coupling reaction in this field Ordinary temperature, the present invention in preferably 50 DEG C~200 DEG C, further preferred 80 DEG C~150 DEG C, still further preferably 110 DEG C~ 120℃。
In preparing the method for PNN ligand 1s or 2, such coupling reaction in this field may be used in the process of the reaction Routine monitoring method (such as TLC, HPLC or NMR) be monitored, generally existed with compound 6 or 731Phosphorus signal in P NMR It is reaction end when peak disappears, preferably 2 hours~48 hours reaction time, further preferred 10 hours~36 hours, then into one Step preferably 20 hours~24 hours.
PNN ligand 1s or 2 preparation method can also include the following steps：
In organic solvent, under the conditions of acid is existing, compound 8 and compound 9 is subjected to condensation reaction, obtain compound 5 ；
Wherein, the definition of each substituent group is same as above.
The preparation method of compound 5 can be the conventional method of such condensation reaction in this field, under preferred in of the invention State reaction method and condition：
In the method for prepare compound 5, the organic solvent preferred aromatic hydrocarbons class solvent, the aromatic hydrocarbon solvent is excellent Select toluene.
In the method for prepare compound 5, the organic solvent and the volume mass ratio of the compound 8 are preferred 1mL/g~100mL/g, further preferred 10mL/g~20mL/g.
In the method for prepare compound 5, the molar ratio preferably 1~3 of the compound 9 and the compound 8, Further preferred 1~1.5, further preferred 1.1~1.2.
In the method for prepare compound 5, the preferred Bronsted acid of acid, the preferred p-methyl benzenesulfonic acid of the Bronsted acid Or its monohydrate.
In the method for prepare compound 5, the molar ratio preferably 0.005 of the described acid and the compound 8~ 0.20, still further preferably 0.05~0.06.
In the method for prepare compound 5, the temperature of the reaction can be the normal of such condensation reaction in this field Advise temperature, the present invention in preferably 50 DEG C~200 DEG C, further preferred 100 DEG C~180 DEG C, still further preferably 130 DEG C~140 ℃。
In the method for prepare compound 5, such condensation reaction in this field may be used in the process of the reaction Routine monitoring method (such as TLC, HPLC or NMR) is monitored, as reaction end when generally being disappeared using compound 8, when reaction Between preferably 12 hours~96 hours, further preferred 24 hours~60 hours, still further preferably 24 hours~60 hours.
Complex compound preparation method
The present invention also provides the preparation methods of the PNN sections complex compound 3 or 4 comprising following steps：Indifferent gas Under body protection, in organic solvent, PNN ligand 1s or 2 and iron halide FeXY carry out complex reaction, generate PNN sections complex compound 3 Or 4；The PNN ligand 1s or 2 is prepared according to the preparation method of above-mentioned PNN ligand 1s or 2；
Wherein, the definition of each substituent group is same as above.
The preparation method of PNN sections complex compound 3 or 4 can be the conventional method of such complex reaction in this field, this hair Preferred following reaction methods and condition in bright：
In the method for preparing PNN sections complex compound 3 or 4, the preferred helium of the inert gas, argon gas, neon and nitrogen It is one or more in gas.
In the method for preparing PNN sections complex compound 3 or 4, the preferred ether solvent of the organic solvent, the ethers The preferred tetrahydrofuran of solvent.
In the method for preparing PNN sections complex compound 3 or 4, the organic solvent and the PNN ligand 1s or 2 body Product mass ratio preferred 10mL/g~300mL/g, further preferred 30mL/g~150mL/g.
In the method for preparing PNN sections complex compound 3 or 4, the preferred frerrous chlorides of iron halide FeXY.
In the method for preparing PNN sections complex compound 3 or 4, iron halide FeXY and the PNN ligand 1s or 2 mole Ratio preferably 0.5~1, further preferred 0.8~1, still further preferably 0.9~0.95.
In the method for preparing PNN sections complex compound 3 or 4, the temperature of the reaction can be such network in this field Close reaction ordinary temperature, the present invention in preferably 0 DEG C~80 DEG C, further preferred 10 DEG C~35 DEG C.
In the method for preparing PNN sections complex compound 3 or 4, such in this field may be used in the process of the reaction The routine monitoring method (such as TLC, HPLC or NMR) of complex reaction is monitored, and is reaction when generally being disappeared with PNN ligand 1s Terminal, preferably 1 hour~48 hours reaction time, further preferred 5 hours~24 hours, still further preferably 8 hours~10 Hour.
Using
The present invention also provides application of the PNN sections complex compound 3 or 4 in the polymerisation of catalyzed alkene, institutes The alkene stated is ethylene.
In the present invention, the polymerisation of the PNN sections complex compound 3 or 4 catalyzed alkenes includes the following steps：In alkene Under hydrocarbon atmosphere, under specified olefin pressure, under specified polymerization temperature, under the catalysis of PNN sections complex compound 3 or 4, in co-catalysis Under agent activation, in atent solvent, alkene carries out polymerisation, polymerize specified time, produces polyolefine material；
The preferably following reaction methods of polymerisation and condition of the PNN sections complex compound 3 or 4 catalyzed alkenes：
In the polymerisation of PNN sections complex compound 3 or 4 catalyzed alkenes, the alkene is ethylene, alpha-olefin, benzene second (preferably alpha-olefin (alpha-olefin, preferably C such as alkene, methyl methacrylate3-C8Alkene, " the C3-C8Alkene Hydrocarbon " can be propylene, 1- butylene, 1- amylenes, 1- hexenes, 1- octenes, 4-methyl-1-pentene and its mixture)), described is poly- Conjunction includes the homopolymerization and copolymerization of above-mentioned monomer.
In the polymerisation of PNN sections complex compound 3 or 4 catalyzed alkenes, " the specified olefin pressure " preferably 0.1~ 10MPa, further preferred 0.1~5MPa.
In the polymerisation of PNN sections complex compound 3 or 4 catalyzed alkenes, " the specified polymerization temperature " preferably 0~ 120 DEG C, further preferred 10~80 DEG C, much further preferably from 20~60 DEG C.
In the polymerisation of PNN sections complex compound 3 or 4 catalyzed alkenes, the catalyst concn preferably 10-7~10- 3M, further preferred 10-6~10-5M。
In the polymerisation of PNN sections complex compound 3 or 4 catalyzed alkenes, " co-catalyst " preferably MAO (methyl Aikyiaiurnirsoxan beta), MMAO (methylaluminoxane of modification), EAO (ethylaluminoxane), BAO (butyla-luminoxane), LiR ' (R '=C1~ The alkane of C4, " alkane of C1~C4 " is such as methyl, ethyl, isopropyl, tertiary butyl, isobutyl group), AlR '3(R '= The alkane of C1~C4, " alkane of C1~C4 " is such as methyl, ethyl, isopropyl, tertiary butyl, isobutyl group), AlR 'nX’3-n(alkane of R '=C1~C4, described " alkane of C1~C4 " such as methyl, ethyl, isopropyl, tertiary butyl, the isobutyl group Deng；X '=halogen atom, such as fluorine, chlorine, bromine or iodine), borine such as B (C6F5)3Deng or above-mentioned co-catalyst mixture etc..Into One step is preferably MAO (methylaluminoxane), MMAO (methylaluminoxane of modification), AlR '3(alkane of R '=C1~C4, it is described " alkane of C1~C4 " such as methyl, ethyl, isopropyl, tertiary butyl, isobutyl group).
In the polymerisation of PNN sections complex compound 3 or 4 catalyzed alkenes, mole of the catalyst and co-catalyst Than 1:10~1:10000, further preferably 1:200~1:4000.
In the polymerisation of PNN sections complex compound 3 or 4 catalyzed alkenes, the preferred alkanes of the atent solvent or virtue Hydrocarbon solvent；The preferred normal heptane of the alkane solvents or dichloromethane, the preferred toluene of the aromatic hydrocarbon solvent.
In the polymerisation of PNN sections complex compound 3 or 4 catalyzed alkenes, " the polymerization specified time ", preferably 5 points Clock~24 hour, further preferably 10 minutes~4 hours.
On the basis of common knowledge of the art, above-mentioned each optimum condition can be combined arbitrarily to get each preferable reality of the present invention Example.
Gained polyolefine material of the invention has the characteristics that molecular weight is relatively low, is polyethylene wax product, wherein aryl phosphine network Close the polymer molecular weight wider distribution that object 3 is catalyzed, the polymer molecular weight narrow distribution that alkylphosphines complex compound 4 is catalyzed.
The present invention also provides the PNN sections complex compounds 3 or 4 in the copolyreaction of catalysis ethylene and alpha-olefin Using the alpha-olefin is 1- octenes.
In the present invention, the PNN sections complex compound 3 or 4 is catalyzed the copolyreaction of ethylene and alpha-olefin, including following step Suddenly：Under alkene atmosphere, in the presence of alpha-olefin, under specified olefin pressure, under specified polymerization temperature, in PNN sections networks It closes under the catalysis of object 3 or 4, under co-catalyst activation, in atent solvent, ethylene carries out copolyreaction with alpha-olefin, and polymerization refers to It fixes time, produces copolymer；
The PNN sections complex compound 3 or 4 is catalyzed the preferably following reaction methods of copolyreaction and item of ethylene and alpha-olefin Part：
In the copolyreaction that PNN sections complex compound 3 or 4 is catalyzed ethylene and alpha-olefin, " alpha-olefin ", preferably C3-C8Alkene, " the C3-C8Alkene " can be propylene, 1- butylene, 1- amylenes, 1- hexenes, 1- octenes, 4- methyl- 1- amylenes and its mixture, further preferably 1- octenes.
In the copolyreaction that PNN sections complex compound 3 or 4 is catalyzed ethylene and alpha-olefin, " the specified olefin pressure " It is preferred that 0.1~10MPa, further preferred 0.1~5MPa.
In the copolyreaction that PNN sections complex compound 3 or 4 is catalyzed ethylene and alpha-olefin, " the specified polymerization temperature " It is preferred that 0~120 DEG C, further preferred 10~80 DEG C, much further preferably from 20~60 DEG C.
In the copolyreaction that PNN sections complex compound 3 or 4 is catalyzed ethylene and alpha-olefin, the catalyst concn is preferred 10-7~10-3M, further preferred 10-6~10-5M。
In the copolyreaction that PNN sections complex compound 3 or 4 is catalyzed ethylene and alpha-olefin, " co-catalyst " is preferred MAO (methylaluminoxane), MMAO (methylaluminoxane of modification), EAO (ethylaluminoxane), BAO (butyla-luminoxane), LiR ' (alkane of R '=C1~C4, " alkane of C1~C4 " is such as methyl, ethyl, isopropyl, tertiary butyl, isobutyl group), AlR’3(alkane of R '=C1~C4, described " alkane of C1~C4 " such as methyl, ethyl, isopropyl, tertiary butyl, the isobutyl group Deng), AlR 'nX’3-n(alkane of R '=C1~C4, " alkane of C1~C4 " such as methyl, ethyl, isopropyl, tertiary fourth Base, isobutyl group etc.；X '=halogen atom, such as fluorine, chlorine, bromine or iodine), borine such as B (C6F5)3Deng or above-mentioned co-catalyst it is mixed Close object etc..Further preferably MAO (methylaluminoxane), MMAO (methylaluminoxane of modification), AlR '3(R '=C1~C4's Alkane, " alkane of C1~C4 " is such as methyl, ethyl, isopropyl, tertiary butyl, isobutyl group).
In the copolyreaction that PNN sections complex compound 3 or 4 is catalyzed ethylene and alpha-olefin, the catalyst and co-catalysis The molar ratio 1 of agent:10~1:10000, further preferably 1:200~1:4000.
In the copolyreaction that PNN sections complex compound 3 or 4 is catalyzed ethylene and alpha-olefin, the preferred alkane of the atent solvent Hydro carbons or aromatic hydrocarbon solvent；The preferred normal heptane of the alkane solvents or dichloromethane, the preferred first of the aromatic hydrocarbon solvent Benzene.
In the copolyreaction that PNN sections complex compound 3 or 4 is catalyzed ethylene and alpha-olefin, " the polymerization specified time ", It is preferred that 5 minutes~24 hours, further preferably 10 minutes~4 hours.
On the basis of common knowledge of the art, above-mentioned each optimum condition can be combined arbitrarily to get each preferable reality of the present invention Example.
Resulting polymers product of the present invention has the characteristics that molecular weight is relatively low and molecular weight distribution is relatively narrow, shape be oily or Wax is especially suitable for preparing high-quality polyethylene wax, high-quality lubricating oil.Branch containing hexyl in structure, additionally by change The electronic property and steric hindrance size of ligand, the insertion rate of controllable 1- octenes.
The present invention also provides the PNN sections complex compounds 3 or 4 in the copolyreaction for being catalyzed ethylene and non-conjugated diene In application, the non-conjugated diene be 1,7- octadienes.
In the present invention, the copolyreaction of the PNN sections complex compound 3 or 4 catalysis ethylene and non-conjugated diene, including with Lower step：Under alkene atmosphere, in the presence of non-conjugated diene, under specified olefin pressure, under specified polymerization temperature, Under PNN sections complex compound 3 or 4 is catalyzed, under co-catalyst activation, in atent solvent, ethylene is total to non-conjugated diene Poly- reaction, polymerize specified time, produces copolymer；
The PNN sections complex compound 3 or 4 is catalyzed the preferably following reaction methods of copolyreaction of ethylene and non-conjugated diene And condition：
In the copolyreaction that PNN sections complex compound 3 or 4 is catalyzed ethylene and non-conjugated diene, described " non-conjugated two Alkene ", preferably C5-C10Alkene, " the C5-C10Alkene " can be 1,4- pentadienes, 1,5- hexadienes, 5,7- diformazans Base -1,6- octadiene, 1,6- heptadiene, 1,7- octadienes and its mixture, further preferably 1,7- octadienes.
In the copolyreaction that PNN sections complex compound 3 or 4 is catalyzed ethylene and non-conjugated diene, " the specified alkene pressure Power " preferably 0.1~10MPa, further preferred 0.1~5MPa.
In the copolyreaction that PNN sections complex compound 3 or 4 is catalyzed ethylene and non-conjugated diene, " the specified polymerization temperature Preferably 0~120 DEG C of degree ", further preferred 10~80 DEG C, much further preferably from 20~60 DEG C.
In the copolyreaction that PNN sections complex compound 3 or 4 is catalyzed ethylene and non-conjugated diene, the catalyst concn It is preferred that 10-7~10-3M, further preferred 10-6~10-5M。
In the copolyreaction that PNN sections complex compound 3 or 4 is catalyzed ethylene and non-conjugated diene, " co-catalyst " It is preferred that MAO (methylaluminoxane), MMAO (methylaluminoxane of modification), EAO (ethylaluminoxane), BAO (butyla-luminoxane), LiR ' (alkane of R '=C1~C4, described " alkane of C1~C4 " such as methyl, ethyl, isopropyl, tertiary butyl, the isobutyl group Deng), AlR '3(alkane of R '=C1~C4, " alkane of C1~C4 " such as methyl, ethyl, isopropyl, tertiary butyl, different Butyl etc.), AlR 'nX’3-n(alkane of R '=C1~C4, " alkane of C1~C4 " for example methyl, ethyl, isopropyl, Tertiary butyl, isobutyl group etc.；X '=halogen atom, such as fluorine, chlorine, bromine or iodine), borine such as B (C6F5)3Deng or above-mentioned co-catalyst Mixture etc..Further preferably MAO (methylaluminoxane), MMAO (methylaluminoxane of modification), AlR '3(R '=C1~ The alkane of C4, " alkane of C1~C4 " is such as methyl, ethyl, isopropyl, tertiary butyl, isobutyl group).
In the copolyreaction that PNN sections complex compound 3 or 4 is catalyzed ethylene and non-conjugated diene, the catalyst and help The molar ratio 1 of catalyst:10~1:10000, further preferably 1:200~1:4000.
In the copolyreaction that PNN sections complex compound 3 or 4 is catalyzed ethylene and non-conjugated diene, the atent solvent is excellent Select alkanes or aromatic hydrocarbon solvent；The preferred normal heptane of the alkane solvents or dichloromethane, the aromatic hydrocarbon solvent are excellent Select toluene.
It is described " when polymerization is specified in the copolyreaction that PNN sections complex compound 3 or 4 is catalyzed ethylene and non-conjugated diene Between ", preferably 5 minutes~24 hours, further preferably 10 minutes~4 hours.
On the basis of common knowledge of the art, above-mentioned each optimum condition can be combined arbitrarily to get each preferable reality of the present invention Example.
Gained copolymer product of the invention has the characteristics that molecular weight is low and narrow molecular weight distribution, and branch is with holding in structure Alkene, end alkene in this analog copolymer can by further function dough (such as silicon hydrogenation, hydroboration, epoxidation, hydroxylating), to It can be used for improving the property of polymer, additionally by the electronic property and steric hindrance size for changing ligand, controllable non-conjugated two The insertion rate of alkene.
The present invention also provides the PNN sections complex compounds 3 or 4 in catalysis (ethylene-non-conjugated diene) copolymer Application in application in the reaction of function dough afterwards, especially silicon hydrogenation or hydroboration.
In the present invention, the PNN sections complex compound 3 or 4 is catalyzed the rear functional group of (ethylene-non-conjugated diene) copolymer Change reaction, includes the following steps：Under inert gas shielding, under the catalysis of PNN sections complex compound 3 or 4, activated in co-catalyst Under, (ethylene-non-conjugated diene) copolymer and borane reagent or silica reagent carry out addition reaction, generate product；
The rear function dough reaction that the PNN sections complex compound 3 or 4 is catalyzed (ethylene-non-conjugated diene) copolymer is excellent Select following reaction methods and condition：
It is described in the rear function dough reaction that PNN sections complex compound 3 or 4 is catalyzed (ethylene-non-conjugated diene) copolymer The preferred helium of inert gas, argon gas, one or more in neon and nitrogen.
It, can be in the rear function dough reaction that PNN sections complex compound 3 or 4 is catalyzed (ethylene-non-conjugated diene) copolymer Using organic solvent, the preferred alkanes of the organic solvent or ether solvent；The preferred pentane of the alkane solvents or Toluene, the preferred tetrahydrofuran of the ether solvent or ether.
PNN sections complex compound 3 or 4 be catalyzed (ethylene-non-conjugated diene) copolymer rear function dough reaction in, when When being reacted under the conditions of organic solvent is existing, the organic solvent and described (ethylene-non-conjugated diene) copolymer Volume mass ratio can be 1mL/g~100mL/g, further preferred 1mL/g~50mL/g, still further preferably 10mL/g~ 20mL/g。
It is described in the rear function dough reaction that PNN sections complex compound 3 or 4 is catalyzed (ethylene-non-conjugated diene) copolymer PNN ligand metal complexes 3 or 4 with the molar ratio preferably 0.001 of described (ethylene-non-conjugated diene) copolymer~ 0.10, further preferred 0.002~0.02, such as 0.005~0.010.
It is described in the rear function dough reaction that PNN sections complex compound 3 or 4 is catalyzed (ethylene-non-conjugated diene) copolymer Co-catalyst be preferably NaHBEt3(sodium triethylborohydride), MAO (methylaluminoxane), MMAO (the methyl alumina of modification Alkane), LiR ' (alkane of R '=C1~C4, " alkane of C1~C4 " such as methyl, ethyl, isopropyl, tertiary butyl, different Butyl etc.), AlR '3(alkane of R '=C1~C4, " alkane of C1~C4 " such as methyl, ethyl, isopropyl, tertiary fourth Base, isobutyl group etc.), AlR 'nX’3-n(alkane of R '=C1~C4, " alkane of C1~C4 " such as methyl, ethyl, different Propyl, tertiary butyl, isobutyl group etc.；X '=halogen atom, such as fluorine, chlorine, bromine or iodine), borine such as B (C6F5)3Deng or above-mentioned help The mixture etc. of catalyst.Further preferably NaHBEt3(sodium triethylborohydride), MAO (methylaluminoxane), MMAO (is repaiied The methylaluminoxane of decorations), AlR '3(alkane of R '=C1~C4, described " alkane of C1~C4 " such as methyl, ethyl, the isopropyl Base, tertiary butyl, isobutyl group etc.)
It is described in the rear function dough reaction that PNN sections complex compound 3 or 4 is catalyzed (ethylene-non-conjugated diene) copolymer Borane reagent be preferably pinacol borine (HBPin)；The silica reagent is preferably triethoxysilane ((EtO)3SiH) or double Trimethylsiloxy group methyl-monosilane (MD ' M).
It is described in the rear function dough reaction that PNN sections complex compound 3 or 4 is catalyzed (ethylene-non-conjugated diene) copolymer Borane reagent or silica reagent and described (ethylene-non-conjugated diene) copolymer molar ratio preferably 0.5~2, further it is excellent Select 0.75~1.5, still further preferably 1.0~1.2.
It is described in the rear function dough reaction that PNN sections complex compound 3 or 4 is catalyzed (ethylene-non-conjugated diene) copolymer Reaction temperature can be this field in the ordinary temperature of such hydroboration or silicon hydrogenation, the present invention in preferably 0 DEG C~ 60 DEG C, further preferred 10 DEG C~35 DEG C.
It is described in the rear function dough reaction that PNN sections complex compound 3 or 4 is catalyzed (ethylene-non-conjugated diene) copolymer Reaction process may be used such hydroboration in this field or silicon hydrogenation routine monitoring method (such as TLC or NMR it) is monitored, as reaction end when generally being disappeared using (ethylene-non-conjugated diene) copolymer, preferably 1 hour reaction time ~48 hours, further preferred 18 hours~24 hours.
In the rear function dough reaction that PNN sections complex compound 3 or 4 is catalyzed (ethylene-non-conjugated diene) copolymer, preferably Including following post-processing step：After reaction, reaction solution is poured into ethyl alcohol, is filtered, it is dry, obtain product.
On the basis of common knowledge of the art, above-mentioned each optimum condition can be combined arbitrarily to get each preferable reality of the present invention Example.
In the present invention, functional group after the unsaturated carbon-carbon double bond in (ethylene-non-conjugated diene) copolymer on branch occurs Change, i.e. silicon hydrogenation or hydroboration, introduces active silicon substrate or boryl functional group, subsequent coupling reaction etc. can occur.
The feature that the features described above or embodiment that the present invention mentions are mentioned can be in any combination.Disclosed in this case specification All features can be used in combination with any composition form, each feature disclosed in specification, can by it is any provide it is identical, The alternative characteristics of impartial or similar purpose replace.Therefore it is only impartial or similar spy except having special instruction, revealed feature The general example of sign.
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention Rather than it limits the scope of the invention.In the following examples, the experimental methods for specific conditions are not specified, usually according to conventional strip Part or according to the normal condition proposed by manufacturer.Unless otherwise stated, otherwise percentage and number are weight percent and weight Number.
Unless otherwise defined, all professional and scientific terms used in text and meaning known to one skilled in the art Justice is identical.In addition, any method and material similar or impartial to described content can be applied to the method for the present invention.Wen Zhong The preferred implement methods and materials are for illustrative purposes only.
Embodiment 1：The preparation of PNN ligands
Compound 5a:2- acetyl group -8- bromoquinolines (0.50g, 2mmol) are added into the three-necked bottle of 100mL, 2,6- bis- is different Propyl aniline (0.36g, 2mmol), p-methyl benzenesulfonic acid monohydrate (19mg, 0.1mmol) and solvent toluene 35mL, dress Good reflux, heating reaction reflux 48h.It is cooled to room temperature, is concentrated in vacuo, flash column chromatography (ethyl acetate:Petroleum ether =1:200) yellow solid (0.79g, 0.96%), is obtained.1H NMR(400MHz,CD3Cl):δ 8.63 (d, J=8.4Hz, 1H), 8.24 (d, J=8.8Hz, 1H), 8.11 (d, J=7.6Hz, 1H), 7.84 (d, J=8.0Hz, 1H), 7.46 (t, J=7.6Hz, 1H), 7.22 (m, 3H), 2.81 (m, 2H), 2.47 (s, 3H), 1.20 (dd, J=6.4,5.6Hz, 12H)
PhPNNiPr(ligand 1 A):In argon gas glove box, compound 5a (0.3275g, 0.8mmol), Pa (OAc) are weighed2 (0.0090g, 0.04mmol), DPPF (0.0266g, 0.048mmol), NaOtBu (0.0923g, 0.96mmol), is placed in 50mL In tube sealing, toluene (15mL) is added and dissolves.After 1h is stirred at room temperature, HPPh is added2(0.1564g, 0.84mmol).Oil bath heating 120 DEG C, 12h.Column chromatography, ethyl alcohol recrystallization obtain yellow solid 1A (0.3788g, 92%).1H NMR(400MHz,CDCl3)δ 8.47 (d, J=8.8Hz, 1H), 8.24 (d, J=8.4Hz, 1H), 7.86 (d, J=8.0Hz, 1H), 7.47 (t, J=7.6Hz, 1H),7.40(m,4H),7.32(m,6H),7.13(m,3H),7.10(m,1H),2.64(m,CHMe2, 2H), 1.86 (s, N= CMe, 3H), 1.12 (d, J=6.8Hz, CHMe2, 6H), 1.06 (d, J=7.2Hz, CHMe2,6H)；31P{1H}NMR(CDCl3, 162MHz)δ-11.79.Anal.Calcd for C35H35N2P:C,81.68；H,6.85；N,5.44.Found:C,81.19；H, 6.70；N,5.65.
o-MeO-PhPNNiPr(ligand 1 B):The synthesis of the ligand is identical as the synthesis step of 1A, and it is 60% to obtain 1B yields.1H NMR(400MHz,CDCl3) δ 8.45 (d, J=8.8Hz, 1H), 8.22 (d, J=8.8Hz, 1H), 7.83 (d, J=8.0Hz, 1H), 7.47 (t, J=7.6Hz, 1H), 7.32 (m, 2H), 7.25 (m, 1H), 7.15 (m, 2H), 7.11 (m, 1H), 6.93 (m, 2H),6.81(m,4H),3.77(s,PhOMe,6H),2.68(m,CHMe2, 2H), 1.90 (s, N=CMe, 3H), 1.15 (d, J= 6.8Hz,CHMe2, 6H), 1.09 (d, J=6.8Hz, CHMe2,6H)；31P{1H}NMR(CDCl3,162MHz)δ- 34.86.Anal.Calcd for C37H39N2O2P:C,77.33；H,6.84；N,4.87.Found:C,77.13；H,6.79；N, 4.84.
(ligand 1 C):The synthesis of the ligand is identical as the synthesis step of 1A, and it is 73% to obtain 1C yields.1H NMR(400MHz,CDCl3)δ8.57(d,1H),8.30(d,1H),7.95(d,1H),7.62(d,4H),7.56-7.49(m, 5H),7.17-7.08(m,4H),2.64(m,2H),1.87(s,3H),1.14(d,6H),1.06(d,6H)；31P{1H}NMR (CDCl3,162MHz)δ-53.39；19F NMR(CDCl3,376MHz):δ77.02.Anal.Calcd for C37H33F6N2P:C, 68.30；H,5.11；N,4.31.Found:C,67.98；H,5.12；N,4.28.
p-MeO-PhPNNiPr(ligand 1 D):The synthesis of the ligand is identical as the synthesis step of 1A, and it is 74% to obtain 1D yields.1H NMR(400MHz,CDCl3) δ 8.49 (d, J=8.0Hz, 1H), 8.23 (d, J=8.8Hz, 1H), 7.83 (d, J=8.0Hz, 1H), 7.46 (t, J=8.0Hz, 1H), 7.31 (m, 4H), 7.15-7.06 (m, 4H), 6.86 (d, 4H), 3.78 (s, PhOMe, 6H),2.65(m,CHMe2, 2H), 1.91 (s, N=CMe, 3H), 1.12 (d, J=6.8Hz, CHMe2, 6H), 1.06 (d, J= 6.8Hz,CHMe2,6H)；31P{1H}NMR(CDCl3,162MHz)δ-14.16.Anal.Calcd for C37H39N2O2P:C, 77.33；H,6.84；N,4.87.Found:C,77.05；H,6.88；N,4.84.
(ligand 1 E):The synthesis of the ligand is identical as the synthesis step of 1A, obtains 1E, yield 77% 。1H NMR(400MHz,CDCl3) δ 8.57 (d, J=8.8Hz, 1H), 8.30 (d, J=8.8Hz, 1H), 7.95 (d, J=8.0Hz, 1H), 7.62 (d, J=8.0Hz, 4H), 7.56-7.49 (m, 5H), 7.17-7.08 (m, 4H), 2.64 (m, CHMe2,2H),1.87 (s, N=CMe, 3H), 1.14 (d, J=6.8Hz, CHMe2, 6H), 1.06 (d, J=6.8Hz, CHMe2,6H)；31P{1H}NMR (CDCl3,162MHz)δ-11.39；19F NMR(CDCl3,376MHz):δ77.02.Anal.Calcd for C37H33F6N2P:C, 68.30；H,5.11；N,4.31.Found:C,68.02；H,5.09；4.32.
(ligand 1 F):The synthesis of the ligand is identical as the synthesis step of 1A, and it is 77% to obtain 1F yields.1H NMR(400MHz,CDCl3) δ 8.51 (d, J=8.8Hz, 1H), 8.27 (d, J=8.4Hz, 1H), 7.92 (d, J=8.0Hz, 1H), 7.60 (d, J=8.0Hz, 4H), 7.55-7.46 (m, 5H), 7.12 (ddd, J=6.8,4.0,1.2Hz, 1H), 7.05 (d, J=7.2Hz, 2H), 6.93 (t, J=7.2Hz, 1H), 1.94 (s, 6H), 1.83 (s, 3H)31P{1H}NMR(CDCl3, 162MHz)δ-12.51；19F NMR(CDCl3,376MHz):δ-62.82.Anal.Calcd for C33H25F6N2P:C,66.67； H,4.24；N,4.71.Found:C,66.56；H,4.20；N,4.67.
p-MeO-PhPNNMe(ligand 1 G):The synthesis of the ligand is identical as the synthesis step of 1A, and it is 72% to obtain 1G yields.1H NMR(400MHz,CDCl3) δ 8.46 (d, J=8.8Hz, 1H), 8.21 (d, J=8.8Hz, 1H), 7.82 (d, J=8.0Hz, 1H), 7.46 (t, J=7.6Hz, 1H), 7.33 (t, J=8.0Hz, 4H), 7.14 (dd, J=6.8,4.0Hz, 1H), 7.04 (d, J =7.6Hz, 2H), 6.92 (t, J=7.6Hz, 1H), 6.86 (d, J=8.4Hz, 4H), 3.79 (s, 6H), 1.96 (s, 6H), 1.90(s,3H).31P{1H}NMR(CDCl3,162MHz)δ-15.42.Anal.Calcd for C33H31N2O2P:C,76.43；H, 6.03；N,5.40.Found:C,76.32；H,6.04；N,5.31.
PhPNNMe(ligand 1 H):The synthesis of the ligand is identical as the synthesis step of 1A, and it is 84% to obtain 1H yields.1H NMR (400MHz,CDCl3) δ 8.39 (d, J=8.4Hz, 1H), 8.14 (d, J=8.4Hz, 1H), 7.76 (d, J=8.4Hz, 1H), 7.38 (t, J=7.6Hz, 1H), 7.33-7.28 (m, 4H), 7.24 (m, 6H), 7.04 (ddd, J=6.8,3.6,0.8Hz, 1H), 6.95 (d, J=7.6Hz, 2H), 6.83 (t, J=7.6Hz, 1H), 1.86 (s, 6H), 1.76 (s, 3H)31P{1H}NMR (CDCl3,162MHz)δ-12.02.Anal.Calcd for C31H27N2P:C,81.20；H,6.11；N,5.94.Found:C, 81.13；H,6.09；N,5.95.
tBuPNNiPr(ligand 2A):The synthesis of the ligand is identical as the synthesis step of 1A, and it is 84% to obtain 2A yields.1H NMR (400MHz,CDCl3) δ 8.53 (d, J=8.4Hz, 1H), 8.22 (m, 2H), 7.88 (d, J=8.0Hz, 1H), 7.60 (t, J= 7.6Hz,1H),7.22-7.12(m,3H),2.81(m,CHMe2, 2H), 2.45 (s, N=CMe, 3H), 1.31 (d, J= 11.2Hz,PCMe3, 18H), 1.19 (d, J=6.8Hz, CHMe2,12H)；31P{1H}NMR(CDCl3,162MHz)δ 16.90.Anal.Calcd for C31H43N2P:C,78.44；H,9.13；N,5.90.Found:C,78.71；H,9.36；N, 5.96.
iPrPNNiPr(ligand 2B):The synthesis of the ligand is identical as the synthesis step of 1A, and it is 85% to obtain 2B yields.1H NMR (400MHz,CDCl3) δ 8.55 (d, J=8.4Hz, 1H), 8.25 (d, J=8.8Hz, 1H), 7.87 (m, 2H), 7.59 (t, J= 8.0Hz,1H),7.22-7.12(m,3H),2.81(m,CHMe2,2H),2.54(m,PCHMe2, 2H), 2.43 (s, N=CMe, 3H),1.22(dd,3JP,H=13.2Hz,3JH,H=6.8Hz, PCHMe2, 6H), 1.19 (d, J=6.8Hz, CHMe2,12H), 1.08(dd,3JP,H=13.2Hz,3JH,H=6.8Hz, PCHMe2,6H)；31P{1H}NMR(CDCl3,162MHz)δ 4.94.Anal.Calcd for C29H39N2P:C,77.99；H,8.80；N,6.27.Found:C,77.43；H,8.79；N, 5.73.
iPrPNNEt(ligand 2C):The synthesis of the ligand is identical as the synthesis step of 1A, and it is 80% to obtain 2C yields.1H NMR (400MHz,CDCl3)δ8.57(d,1H),8.24(d,1H),7.89-7.83(m,2H),7.59(t,1H),7.12(d,2H), 6.97(t,1H),2.54(m,2H),2.44(s,3H),2.41(m,4H),1.22(dd,6H),1.17(t,6H),1.07(dd, 6H)；31P{1H}NMR(CDCl3,162MHz)δ5.13.Anal.Calcd for C27H35N2P:C,77.48；H,8.43；N, 6.69.Found:C,77.31；H,8.67；N,6.12.
iPrPNNMe(ligand 2D):The synthesis of the ligand is identical as the synthesis step of 1A, and it is 74% to obtain 2D yields.1H NMR (400MHz,CDCl3) δ 8.57 (d, J=8.8Hz, 1H), 8.30 (d, J=8.8Hz, 1H), 7.95 (d, J=8.0Hz, 1H), (7.62 d, J=8.0Hz, 4H), 7.56-7.49 (m, 5H), 7.17-7.08 (m, 4H), 2.64 (m, CHMe2,2H),1.87(s,N =CMe, 3H), 1.14 (d, J=6.8Hz, CHMe2, 6H), 1.06 (d, J=6.8Hz, CHMe2,6H)；31P{1H}NMR(CDCl3, 162MHz)δ-11.39；19F NMR(CDCl3,376MHz):δ77.02.Anal.Calcd for C37H33F6N2P:C,68.30； H,5.11；N,4.31.Found:C,68.02；H,5.09；4.32.
Embodiment 2：The preparation of PNN sections complex compounds
(PhPNNiPr)FeCl2(complex compound 3A)：In Ar glove boxes, ligand 1 A (0.1544g, 0.3mmol) is slowly added Enter to FeCl2In THF (30mL) clear solution of (0.0380g, 0.3mmol), there is dark green solid precipitation at once.React on room After the lower stirring 10h of temperature, filtering, n-hexane is washed, and is dried in vacuo, is obtained blue-green solid (177mg, 92%).Anal.Calcd for C35H35Cl2FeN2P:C,65.54；H,5.50；N,4.37.Found:C,65.74；H,5.71；N,4.02.μeff(Evan’s method,CD2Cl2, 25 DEG C) and=5.17 μB.
(o-MeO-PhPNNiPr)FeCl2(complex compound 3B)：The synthesis of the complex compound is identical as the synthesis step of 3A, obtains 3B yields It is 96%.Anal.Calcd for C37H39Cl2FeN2O2P:C,63.35；H,5.60；N,3.99.Found:C,63.01；H, 50.71；N,3.96.μeff(Evan’s method,CD2Cl2, 25 DEG C) and=5.06 μB.
(complex compound 3C)：The synthesis of the complex compound is identical as the synthesis step of 3A, obtains 3C Yield is 94%.Anal.Calcd for C37H33Cl2F6FeN2P:C,57.17；H,4.28；N,3.60.Found:C,57.48； H,4.21；N,3.63.μeff(Evan’s method,CDCl3, 25 DEG C) and=5.41 μB.
(p-MeO-PhPNNiPr)FeCl2(complex compound 3D)：The synthesis of the complex compound is identical as the synthesis step of 3A, obtains 3D yields It is 93%.Anal.Calcd for C37H39Cl2FeN2O2P:C,63.35；H,5.60；N,3.99.Found:C,63.01；H, 5.54；N,3.69.μeff(Evan’s method,CDCl3, 25 DEG C) and=μB.
(complex compound 3E)：The synthesis of the complex compound is identical as the synthesis step of 3A, obtains 3E Yield is 90%.Anal.Calcd for C37H33Cl2F6FeN2P:C,57.17；H,4.28；N,3.60.Found:C,56.73； H,4.21；N,3.45.μeff(Evan’s method,CD2Cl2, 25 DEG C) and=5.36 μB.
(complex compound 3F)：The synthesis of the complex compound is identical as the synthesis step of 3A, obtains 3F Yield is 86%.Anal.Calcd for C37H33Cl2F6FeN2P:C,54.95；H,3.49；N,3.88.Found:C,54.75； H,3.45；N,3.80.
(p-MeO-PhPNNMe)FeCl2(complex compound 3G)：The synthesis of the complex compound is identical as the synthesis step of 3A, obtains 3G yields It is 85%.Anal.Calcd for C33H31Cl2FeN2O2P:C,61.42；H,4.84；N,4.34.Found:C,61.36；H, 4.82；N,4.29.
(PhPNNMe)FeCl2(complex compound 3H)：The synthesis of the complex compound is identical as the synthesis step of 3A, and obtaining 3H yields is 83%.Calcd for C31H27Cl2FeN2P:C,63.62；H,4.65；N,4.79.Found:C,63.47；H,4.62；N, 4.80.
(tBuPNNiPr)FeCl2(complex compound 4A)：The synthesis of the complex compound is identical as the synthesis step of 3A, and obtaining 4A yields is 87%.Anal.Calcd for C31H43Cl2FeN2P:C,61.91；H,7.21；N,4.66.Found:C,61.55；H,7.01； N,4.63.μeff(Evan’s method,CDCl3, 25 DEG C) and=5.11 μB.
(iPrPNNiPr)FeCl2(complex compound 4B)：The synthesis of the complex compound is identical as the synthesis step of 3A, and obtaining 4B yields is 88%.Anal.Calcd for C29H39Cl2FeN2P:C,60.75；H,6.86；N,4.89.Found:C,60.39；H,6.79； N,4.81.μeff(Evan’s method,CDCl3, 25 DEG C) and=5.19 μB.
(iPrPNNEt)FeCl2(complex compound 4C)：The synthesis of the complex compound is identical as the synthesis step of 3A, and obtaining 4C yields is 82%.Anal.Calcd for C27H35Cl2FeN2P:C,59.47；H,6.47；N,5.14.Found:C,59.01；H,6.40； N,5.03.μeff(Evan’s method,CD2Cl2, 25 DEG C) and=5.40 μB.
(iPrPNNMe)FeCl2(complex compound 4D)：The synthesis of the complex compound is identical as the synthesis step of 3A, and obtaining 4D yields is 83%.Anal.Calcd for C25H31Cl2FeN2P:C,58.05；H,6.04；N,5.42.Found:C,57.71；H,6.03； N,5.42.μeff(Evan’s method,CDCl3, 25 DEG C) and=3.89 μB.
Embodiment 3：Complex compound tests the catalytic activity of ethylene polymerization
(Table 1, entry 1) under the ethylene atmosphere of 1atm, Schlenk bottles of the 200mL just dried replaces ethylene Gas is three times.Under ethylene gas stream, 100mL solvent toluenes are added, Schlenk bottles of outer 20 DEG C of constant temperature water baths stir 10 minutes, make molten Liquid reaches predetermined temperature and ethylene is made to be saturated in toluene.Co-catalyst (MMAO, 2000eq) is added, stirs 2 minutes.Network is added The toluene solution for closing object 4B, starts simultaneously at timing.It is rapid to cut off ethylene air-flow after polymerisation 30 minutes, 10% ethyl alcohol is added Polymerisation is quenched in hydrochloric acid solution (5mL).Reaction mixture is poured into a large amount of 10% ethanol solution hydrochlorides, is stirred under room temperature Overnight.Filtering, is washed with 10% ethanol solution hydrochloride and ethyl alcohol, collected polymer successively, and 24 hours are dried in vacuo in 50 DEG C extremely Constant weight obtains polyethylene 4.06g.Catalytic activity is 4.1 × 106g PE(mol Fe)-1h-1.Resulting polymers molecular weight Mw= 1820, molecular weight distribution 2.2.
(Table 1, entry 16) under the ethylene atmosphere of 1atm, Schlenk bottles of the 200mL just dried replaces ethylene Gas is three times.Under ethylene gas stream, 100mL solvent toluenes are added, Schlenk bottles of outer 20 DEG C of constant temperature water baths stir 10 minutes, make molten Liquid reaches predetermined temperature and ethylene is made to be saturated in toluene.Co-catalyst (MMAO, 2000eq) is added, stirs 2 minutes.Network is added The toluene solution for closing object 4B, starts simultaneously at timing.It is rapid to cut off ethylene air-flow after polymerisation 4 hours, 10% ethylate is added Polymerisation is quenched in acid solution (5mL).Reaction mixture is poured into a large amount of 10% ethanol solution hydrochlorides, it is stirred under room temperature Night.Filtering, is washed with 10% ethanol solution hydrochloride and ethyl alcohol, collected polymer successively, and 24 hours are dried in vacuo in 50 DEG C to perseverance Weight, obtains polyethylene 8.90g.Catalytic activity is 1.1 × 106g PE(mol Fe)-1h-1.Resulting polymers molecular weight Mw=12500, Molecular weight distribution is 9.0.
(Table 1, entry 12) under the ethylene atmosphere of 1atm, Schlenk bottles of the 200mL just dried replaces ethylene Gas is three times.Under ethylene gas stream, 100mL solvent toluenes are added, Schlenk bottles of outer 20 DEG C of constant temperature water baths stir 10 minutes, make molten Liquid reaches predetermined temperature and ethylene is made to be saturated in toluene.Co-catalyst (MMAO, 200eq) is added, stirs 2 minutes.Network is added The toluene solution for closing object 4B, starts simultaneously at timing.It is rapid to cut off ethylene air-flow after polymerisation 30 minutes, 10% ethyl alcohol is added Polymerisation is quenched in hydrochloric acid solution (5mL).Reaction mixture is poured into a large amount of 10% ethanol solution hydrochlorides, is stirred under room temperature Overnight.Filtering, is washed with 10% ethanol solution hydrochloride and ethyl alcohol, collected polymer successively, and 24 hours are dried in vacuo in 50 DEG C extremely Constant weight obtains polyethylene 2.13g.Catalytic activity is 2.1 × 106g PE(mol Fe)-1h-1.Resulting polymers molecular weight Mw= 12700, molecular weight distribution 2.9.
(Table 1, entry 11) under the ethylene atmosphere of 500psi, ethylene gas is replaced in the autoclave just dried, assembling Three times.Autoclave is placed in oil bath, 80 DEG C of oil bath temperature is controlled, oil pump vacuum drying 4h is used in combination.Reduce oil bath temperature extremely 20 DEG C, after autoclave body also reaches predetermined temperature, under ethylene gas stream, 100mL solvent toluenes is added, stirs 10 minutes, makes solution Reach predetermined temperature and ethylene is made to be saturated in toluene.A certain amount of co-catalyst (MMAO, 2000eq) is added, stirs 2 minutes. Catalyst complex 4B solution is added, while adjusting ethylene atmospheric pressure to 500psi, starts timing.After polymerization, cut rapidly Disconnected ethylene air-flow opens cock and discharges ethylene atmospheric pressure, 10% ethanol solution hydrochloride (5mL) is added, polymerisation is quenched.It will be anti- It answers mixture to be poured into a large amount of 10% ethanol solution hydrochlorides, is stirred 1 hour under room temperature.Filtering, successively with 10% acidic alcohol Solution and ethyl alcohol washing, collected polymer are dried in vacuo 24 hours in 70 DEG C to constant weight, obtain polyethylene 10.15g.Catalytic activity It is 1.0 × 108g PE(mol Fe)-1h-1.Resulting polymers molecular weight Mw=8600, molecular weight distribution 3.1.
Other experimental procedures are essentially identical, and condition and result are referring to table 1.
1 vinyl polymerization result of table
[a] experiment condition：2 μm of ol catalyst, 100mL toluene, 20 DEG C, yield takes laboratory mean values twice.
[b] pressure unit：Psig. [c] 0.2 μm of ol catalyst 4B.[d] unit：g PE/mol Fe·h.
[e] molecular weight is in bimodal distribution.[f] wider melting transition.[g] basis13C NMR are measured.
The PNN iron complexes based on chinoline backbone of the present invention, catalyzed ethylene polymerization reaction, there is excellent catalysis to live Property, it is suitable with the highest Qi Geer-Natta catalyst of activity, the polythene material of the highly linear of low molecular weight is produced, The polymer molecular weight wider distribution that the iron complex 3 of middle aryl phosphine substitution is catalyzed, the iron complex 4 of alkylphosphines substitution are urged The polymer molecular weight narrow distribution of change, this kind of polyethylene product can be applied to high-quality polyethylene wax.
Embodiment 4：Complex compound tests the catalytic activity of the copolyreaction of ethylene and alpha-olefin
Under the ethylene atmosphere of 1atm, Schlenk bottles of the 200mL just dried, displacement ethylene gas is three times.In ethylene air-flow Under, 60mL 'alpha '-olefin monomers 1- octenes are added, Schlenk bottles of outer 20 DEG C of constant temperature water baths stir 10 minutes, solution is made to reach predetermined Temperature simultaneously makes ethylene be saturated wherein.Co-catalyst (MMAO, 200eq) is added, stirs 2 minutes.The 1- octenes of complex compound are added Solution (table 2, entry 1-3), starts simultaneously at timing.It is rapid to cut off ethylene air-flow after polymerisation 30 minutes, 10% second is added Polymerisation is quenched in alcohol hydrochloric acid solution (5mL).Reaction mixture is poured into a large amount of 10% ethanol solution hydrochlorides, is stirred under room temperature It mixes overnight.Filtering, is washed with 10% ethanol solution hydrochloride and ethyl alcohol, collected polymer successively, is dried in vacuo 24 hours in 50 DEG C To constant weight, copolymerization product is obtained, polymer branch is hexyl.As a result such as table 2, shown in entry 1-3.
The copolyreaction result of 2 ethylene of table and alpha-olefin
[a] experiment condition：2 μm of ol catalyst, 60mL 1- octenes, 20 DEG C, 0.5h, 1atm ethylene pressures.
[b] experiment condition：2 μm of ol catalyst, 30mL 1,7- octadienes, 30mL toluene, 20 DEG C, 0.5h, 1atm ethylene pressures Power.[c] unit：Melting transition wider g polymer/mol Feh. [d].[e] basis13C NMR are measured.
The PNN iron complexes based on chinoline backbone of the present invention are catalyzed ethylene and alpha-olefin (such as 1- octenes) copolyreaction, With excellent catalytic activity, it is wax-like or oily polyolefin products to produce shape, and it is poly- to be especially suitable for preparation high-quality Ethylene waxes, high-quality lubricating oil.The features such as such polymeric articles has molecular weight relatively low, and molecular weight distribution is relatively narrow, structure Upper branch containing hexyl, additionally by the electronic property and steric hindrance size for changing ligand, the insertion rate of controllable 1- octenes.
Embodiment 5：Complex compound tests the catalytic activity of the copolyreaction of ethylene and non-conjugated diene
Under the ethylene atmosphere of 1atm, Schlenk bottles of the 200mL just dried, displacement ethylene gas is three times.In ethylene air-flow Under, 30mL toluene and 30mL non-conjugated dienes 1,7- octadienes is added, Schlenk bottles of outer 20 DEG C of constant temperature water baths stir 10 minutes, So that solution is reached predetermined temperature and ethylene is made to be saturated wherein.Co-catalyst (MMAO, 200eq) is added, stirs 2 minutes.It is added 1, the 7- octadienes solution (table 2, entry 4-6) of complex compound, starts simultaneously at timing.It is rapid to cut off after polymerisation 30 minutes Ethylene air-flow is added 10% alcohol hydrochloric acid solution (5mL) and polymerisation is quenched.Reaction mixture is poured into a large amount of 10% hydrochloric acid In ethanol solution, it is stirred overnight under room temperature.Filtering, is washed with 10% ethanol solution hydrochloride and ethyl alcohol, collected polymer successively, in 50 DEG C are dried in vacuo 24 hours to constant weight, obtain copolymerization product, polymer branch is hexenyl.As a result such as table 2, entry 4-6 institutes Show.
The PNN iron complexes based on chinoline backbone of the present invention are catalyzed ethylene and non-conjugated diene (such as 1,7- octadienes) Copolyreaction has excellent catalytic activity, and it is wax-like or oily polyolefin products to produce shape.Such polymerization produce The features such as product have molecular weight relatively low, and molecular weight distribution is relatively narrow.Branch carries end alkene, the end alkene in this analog copolymer in structure It can be by further function dough (such as silicon hydrogenation, hydroboration, epoxidation, hydroxylating), so as to for improving polymer Property, additionally by the electronic property and steric hindrance size for changing ligand, controllable non-conjugated diene (such as 1,7- octadienes) is inserted Enter rate.
Embodiment 6：Catalytic activity research of the complex compound to the rear function dough reaction of (ethylene-non-conjugated diene) copolymer
By taking hydroboration process as an example：First in argon gas glove box, by complex compound 3F (0.010mmol), toluene (2mL), (ethylene -1,7- octadienes) copolymer (0.28g) and pinacol borine HBpin (0.22mL, 1.5mmol, 1.5equiv) are added After reactions are stirred at room temperature for 24 hours in the reaction bottle of 8mL, it is exposed in air and is quenched.It pours into a large amount of ethyl alcohol, it is stirred Night filters, dry, obtains White waxy polymer.Product is done into high temperature nmr analysis,13On C NMR spectras, former (ethylene -1,7- Octadiene) copolymer carbon carbon unsaturated double-bond disappear i.e. occur hydroboration；11On B NMR spectras, newly occur at 33.8 One is unimodal, is the characteristic peak of boron in hydroboration product.
The PNN iron complexes based on chinoline backbone of the present invention are catalyzed the rear function of (ethylene-non-conjugated diene) copolymer Dough is reacted, and silicon hydrogenation or hydroboration occur for the unsaturated carbon-carbon double bond in copolymer on branch, have excellent catalysis Activity introduces active silicon substrate or boryl functional group, significantly improves polymer property in the polymer, also can be used for occurring follow-up Coupling reaction etc..
All references mentioned in the present invention is incorporated herein by reference, independent just as each document It is incorporated as with reference to such.In addition, it should also be understood that, after reading the above teachings of the present invention, those skilled in the art can To be made various changes or modifications to the present invention, such equivalent forms equally fall within model defined by the application the appended claims It encloses.

Claims (10)

1. a kind of ligand, structure are shown in formula I：
In formula, R be Ra or
Ra、R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12、R13、R14、R15、R16Be each independently hydrogen atom, nitro, Cyano, formoxyl, benzyl, halogen, C1~C10Alkyl, halogen substitution C1~C10Alkyl, C2~C10Alkenyl, C2~C10 Alkynyl, C6~C14Aryl, C1~C10Alkoxy, C6~C14Aryloxy group, C1~C10Alkyl-carbonyl, C1~C10Alkane Sulfenyl,
Wherein, adjacent group is cyclic each other or not cyclic；
Wherein, R17、R18、R19、R20、R21、R22And R23It is each independently hydrogen atom, C1~C10Alkyl or C6~C14Virtue Base.
2. ligand as described in claim 1, which is characterized in that R1、R2、R3、R4、R5、R6、R7、R8、R9、R10、R11、R12、R13、 R14、R15、R16It is each independently hydrogen atom, nitro, cyano, formoxyl, benzyl, halogen, C1~C6Alkyl, C2~C6Alkene Base, C2~C6Alkynyl, C6~C10Aryl, halogen substitution C1~C6Alkyl, C1~C6Alkoxy, C6~C10Fragrant oxygen Base, C1~C6Alkyl-carbonyl, C1~C6Alkylthio group,
Wherein, adjacent group is cyclic each other or not cyclic；
R17、R18、R19、R20、R21、R22And R23It is each independently hydrogen atom, C1~C6Alkyl or C6~C10Aryl.
3. ligand as described in claim 1, which is characterized in that R1、R2、R3、R4、R5、R11、R12、R13、R14、R15、R16Respectively solely It is on the spot hydrogen atom or C1~C6Alkyl.
4. ligand as described in claim 1, which is characterized in that R Ra, Ra C1~C6Alkyl.
5. ligand as described in claim 1, which is characterized in that R isR6、R7、R8、R9、R10It is each independently Hydrogen atom, C1~C4Alkoxy or halogen substitution C1~C4Alkyl.
6. a kind of complex compound, structure is as shown in Formula II：
In formula, R, R1、R2、R3、R4、R5、R11、R12、R13、R14、R15、R16Definition as described in claim any one of 1-5；
X, Y is identical or different halogen atom.
7. the preparation method of ligand as described in any one in claim 1-5, which is characterized in that the preparation method includes formula III compounds and (R)2PH carries out the step of coupling reaction obtains the ligand：
In various, R, R1、R2、R3、R4、R5、R11、R12、R13、R14、R15、R16Definition as described in claim any one of 1-5.
8. the preparation method of complex compound as claimed in claim 6, which is characterized in that the preparation method includes shown in Formulas I Ligand carries out the step of complex reaction obtains the complex compound with FeXY：
In various, R, R1、R2、R3、R4、R5、R11、R12、R13、R14、R15、R16Definition as described in claim any one of 1-5；
X, Y is identical or different halogen atom.
9. the purposes of complex compound as claimed in claim 6, which is characterized in that the complex compound is for catalysis in olefine polymerization or urges Change ethylene-non-conjugated diene copolymer functionalization.
10. a kind of olefine polymerizing process, which is characterized in that the polymerization is using the complex compound conduct described in claim 6 Catalyst.
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