CN107417729A - Side arm containing benzamido group mono-metallocene chromium (IV) complex and application thereof - Google Patents
Side arm containing benzamido group mono-metallocene chromium (IV) complex and application thereof Download PDFInfo
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- CN107417729A CN107417729A CN201710700659.1A CN201710700659A CN107417729A CN 107417729 A CN107417729 A CN 107417729A CN 201710700659 A CN201710700659 A CN 201710700659A CN 107417729 A CN107417729 A CN 107417729A
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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
- C07F11/00—Compounds containing elements of Groups 6 or 16 of the Periodic System
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- 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
- C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F110/02—Ethene
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- 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
- C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
Abstract
Side arm containing benzamido group mono-metallocene chromium (IV) complex of the present invention and application thereof belongs to the technical field of olefin polymerization catalysis.Described side arm containing benzamido group mono-metallocene chromium (IV) complex, has following structure expression：
Description
Technical field
The invention belongs to the technical field of olefin polymerization catalysis, more particularly to a kind of mono-metallocene chromium of side arm containing benzamido group
(IV) complex and its application in terms of catalysis ethylene homo and ethylene/alpha-olefin copolymerization.
Background technology
Compared with traditional Ziegler Natta, metallocene olefin polymerization catalysts have many excellent
Performance, catalyst structure can be designed as needed, and then control composition, structure, stereoregularity, the molecular weight of polyolefin products
And the performance indications such as molecular weight distribution.The constrained geometry configuration class cyclopentadienyl titanium of list containing side arm (IV) and Dan Maoge (III) complexs are sent out
Now it is suitable for being catalyzed ethene and alpha-olefin copolymer production of linear low density polyethylene (LDPE), in past more than 20 years, has developed
Go out a variety of monocyclic chromium (III) complexs containing the hetero atom side arm such as N, O, P, and have studied the catalytic property of these complexs.
(bibliography a:Y.Liang,Glenn P.A.Yap,Arnold L.Rheingold,and Klaus
H.Theopold.Organometallics,1996,15,5284-5286.b:A.Dohring,J.Gohre,
P.W.Jolly.Organometallics,2000,19:388-402.c:Emrich R,Heinemann O,Jolly P W,et
al.Organometallics,1997,16(8):1511-1513；A.Hohring,V.R.Jensen,
P.W.Jolly.W.Thiel,J.C.Weber.Macromol.Symp.,2001,173:117-121；A.Hohring,
V.R.Jensen,P.W.Jolly.Organometallics,2001,20:2234-2245.d,e:Enders M,Fernández
P,Ludwig G,et al.Organometallics,2001,20(24):5005-5007.f:Zhang L,Gao W,Tao X,
et al.Organometallics,2010,30(3):433-440.) due to unsuitable chromium (IV) raw material, synthesis is difficult,
Never reported similar to chromium (IV) olefin polymerization catalysis of list containing side arm cyclopentadienyl titanium (IV) catalyst.
The content of the invention
Insufficient in order to overcome existing for background technology, the present invention provides a kind of side arm containing benzamido group, available for being catalyzed ethene
Homopolymerization and mono-metallocene chromium (IV) complex that High molecular weight polyethylene and LLDPE are produced with alpha-olefin copolymer,
And its in the alpha-olefin copolymer reaction such as catalysis ethylene homo, ethene and propylene, 1- butylene, 1- hexenes, 1- octenes, 1- decene
Concrete application.
Concrete technical scheme is as follows：
A kind of side arm containing benzamido group mono-metallocene chromium (IV) complex, has following structure expression：
Wherein Cp ' is cyclopentadienyl group, indenyl, fluorenyl, substituted cyclopentadienyl, substituted indenyl, substitution fluorenyl；R is
Alkyl, substitution alkyl, aryl or substituted aryl less than 30 carbon atoms；X is halogen, alkoxy, amido, alkyl, aryl, alkene
Base, substitution alkyl, substituted aryl or substituted alkenyl.
In structure above, luxuriant ring Cp ' preferably cyclopentadienyl group, indenyl, fluorenyl or above-mentioned group substitute containing 1~4
The derivative of base, wherein substituent are methyl, ethyl, propyl group, isopropyl or phenyl；Cp ' more preferably 1- indenyls, 2- indenyls, fluorenes
Base, dimethylcyclo-pentadienyl or tetramethyl-ring pentadienyl；The preferred phenyl of R, p-methylphenyl, o-methyl-phenyl, 2,6- bis-
Aminomethyl phenyl, 2,6- diethyl phenyls, 2,6- diisopropyl phenyls, 2,4,6- trimethylphenyls, propyl group, isopropyl, normal-butyl,
Isobutyl group, the tert-butyl group, n-pentyl, 2- amyl groups, 3- amyl groups, isopentyl, tertiary pentyl, neopentyl, cyclopenta, n-hexyl, isomery oneself
Base, cyclohexyl, adamantyl, benzyl, aralkyl, two aralkyl or triaryl methyl；R more preferably phenyl, p-methylphenyl, adjacent toluene
Base, propyl group, isopropyl, normal-butyl, isobutyl group, n-pentyl, isopentyl, cyclopenta, n-hexyl, isohesyl, cyclohexyl or benzyl；
The preferred halogens of X, methoxyl group, ethyoxyl, isopropoxy, tert-butoxy, phenoxy group, dimethylamino, diethylin, diisopropylamine
Base, hmds base, methyl, phenyl, benzyl, trimethyl silicane ylmethyl or neopentyl；X more preferably halogens.
Side arm containing benzamido group mono-metallocene chromium (IV) complex of the present invention can be used to lower section method and prepare：
1) -80 in ether solvent~200 DEG C at a temperature of, with strongly alkaline compound and part in molar ratio 2:1 ratio
Stirring reaction 0~72 hour, removes solvent after reaction, obtain the bimetal salt of part.Described ether solvent is selected from ether, second
Glycol dimethyl ether, tetrahydrofuran or dioxane；Hydride of the described strongly alkaline compound selected from alkali metal or alkaline-earth metal,
Alkylates, amides or alkyl halide, preferably sodium hydride, lithium methide, butyl lithium, Sodamide, benzyl potassium and various lattice
Family name's reagent；Preferably -40~100 DEG C of reaction temperature；Preferably 0~24 hour reaction time；The overall control of ether solvent is being reacted
10~120 times of thing gross mass.
2) -80 in ether solvent~100 DEG C at a temperature of, make the bimetal salt and CrCl of part3(THF)3In molar ratio 1:
After 2 reactions 0~72 hour, solvent is removed, gained crude product is recrystallized to give pure products in a solvent.Described ether solvent
Selected from ether, glycol dimethyl ether or tetrahydrofuran；Preferably -40~60 DEG C of reaction temperature；Preferably 0~24 hour reaction time；
10~120 times in reactant gross mass of the overall control of ether solvent；It can be single solvent or mixing to recrystallize solvent for use
Alkane, halogenated alkane or their mixture of solvent, preferably C1~C10.The Nomenclature Composition and Structure of Complexes of products therefrom is by elementary analysis
It is defined as side arm containing benzamido group mono-metallocene chromium (IV) complex with x-ray crystal structure analysis.
A kind of purposes of side arm containing benzamido group mono-metallocene chromium (IV) complex, it is characterised in that benzylamine is contained with described
Base side arm mono-metallocene chromium (IV) complex is major catalyst, with alkylaluminoxane, or the mixing of alkyl aluminum and organic boron additive
Thing is co-catalyst, is reacted for being catalyzed ethylene homo or ethene with alpha-olefin copolymer；Aluminium and main catalytic wherein in co-catalyst
The mol ratio of metal is 5~10000 in agent:1, preferably 500~5000:1；Boron rubs with metal in major catalyst in co-catalyst
You are than being 0~2:1, preferably 1~2:1；Described alpha-olefin is propylene, 1- butylene, 1- hexenes, 1- octenes or 1- decene；It is described
Alkyl aluminum be trimethyl aluminium, triethyl aluminum or triisobutyl aluminium；Described alkylaluminoxane is MAO (MAO) or changed
Property MAO (MMAO)；Described organic boron additive is Ph3CB(C6F5)4、PhNMe2HB(C6F5)4Or B (C6F5)3, preferably
Ph3CB(C6F5)4。
In the purposes of side arm containing benzamido group mono-metallocene chromium (IV) complex of the present invention, the tool of catalysed olefin polymerization
Body step is：Under at least one olefinic monomer existence condition, major catalyst and co-catalyst are added to polymeric kettle, at -20 DEG C
~200 DEG C, the atmospheric pressure of ethylene pressure scope 0~200, react 0~300 minute under conditions of 0~5mol/L of alpha-olefin concentration；It is poly-
After conjunction reaction terminates, obtained polymer is washed with acid solution, constant weight is dried in 60 DEG C in vacuum drying oven.
In the purposes of side arm containing benzamido group mono-metallocene chromium (IV) complex of the present invention, catalysed olefin polymerization can be with
Carry out, can also be carried out under condition of no solvent in any solvent being had no adverse effect to catalyst system.The pressure of ethene
It can be determined as needed with the concentration of alpha-olefin.Ethylene pressure scope is 0~200 atmospheric pressure, alpha-olefin concentration typically 0~
5mol/L ranges, highest can be alpha-olefin bulk concentration.Polymeric reaction temperature can become in -20 DEG C~200 DEG C scopes
Change, preferable temperature range is 20 DEG C~160 DEG C.
The molecular weight of polyolefin products and molecular weight distribution are determined with high temperature GPC, in copolymerized product co-monomer content according to
High temperature13C H NMR spectroscopies calculate.
The present invention has following beneficial effect：
1st, mono-metallocene chromium (IV) complex structure of the present invention is stable, and heat resistance is good in the course of the polymerization process, the life-span
It is long.
2nd, the complex-catalyzed activity of mono-metallocene chromium (IV) of the present invention is high, and copolymerization performance is moderate, molecular weight of copolymer
Height, it is suitable for being catalyzed ethene and alpha-olefin copolymer production high molecular weight linear low density polyethylene (LDPE).
Embodiment
Example 1 below -15 provides 15 typical mono-metallocene chromium (IV) complex 1-15 of the present invention preparation
Process, part reference literature method synthesis used in each embodiment (Xin Tao, Qiaolin Wu, Hang Huo, Wei Gao,
Ying Mu.Organometallics,2013,32:4185-4191), embodiment 16 and 17 gives Dan Maoge of the present invention
Complex is catalyzed the experimentation and result of ethylene homo and ethene and 1- hervene copolymers as major catalyst.Complex 1-15's
Concrete structure is：1：Cp ' is tetramethyl-ring pentadienyl, and R is isopropyl, and X is chlorine；2：Cp ' is tetramethyl-ring pentadienyl, R
For cyclohexyl, X is chlorine；3：Cp ' is tetramethyl-ring pentadienyl, and R is phenyl, and X is chlorine；4：Cp ' is tetramethyl-ring pentadienyl,
R is p-methylphenyl, and X is chlorine；5：Cp ' is tetramethyl-ring pentadienyl, and R 2,6- 3,5-dimethylphenyls, X is chlorine；6：Cp ' is tetramethyl
Cyclopentadienyl group, R 2,6- diethyl phenyls, X are chlorine；7：Cp ' is tetramethyl-ring pentadienyl, R 2,6- diisopropyls
Phenyl, X are chlorine；8：Cp ' is tetramethyl-ring pentadienyl, and R is benzyl, and X is chlorine；9：Cp ' is 3,4- dimethylcyclo-pentadienyls,
R is isopropyl, and X is chlorine；10：Cp ' is 3,4- dimethylcyclo-pentadienyls, and R is cyclohexyl, and X is chlorine；11：Cp ' is 3,4- diformazans
Cyclopentadienyl group, R are phenyl, and X is chlorine；12：Cp ' is 3,4- hexichol cyclopentadienyl groups, and R is phenyl, and X is chlorine；13：Cp’
For 1- indenyls, R is phenyl, and X is chlorine；14：Cp ' is 2- indenyls, and R is phenyl, and X is chlorine；15：Cp ' is fluorenyl, and R is phenyl, and X is
Chlorine.
Synthesis chromium (IV) complex General reactions formula be：
The preparation of the complex 1 of embodiment 1
Under nitrogen protection, under the conditions of -78 DEG C, to 2- (isopropyl-nitrogen-methyl) phenyl-tetramethyl-ring pentadiene (part
1) in tetrahydrofuran (20mL) solution of (0.700g, 2.60mmol) be added dropwise n-BuLi (2.16mL, 5.20mmol) just oneself
Alkane solution.It is added dropwise, the reactant mixture of gained continues stirring one hour at this temperature, and then this mixture allows to rise to
Room temperature simultaneously continues stirring three hours at this temperature, is slowly added into 2 equivalent CrCl3(THF)3Tetrahydrofuran solution in,
It is stirred overnight, removes solvent, 20mL toluene is added into ampulla, insoluble matter is filtered to remove, the toluene in filtrate is removed in vacuum.Again
20mL hexanes ultrasonic curing is added into ampulla and is filtered, gained solid is washed using cold hexane (5mL × 2), is then utilized
THF/ hexanes recrystallize.Obtain the net product 0.541g of complex 1, yield 53.6%.Its mono-crystalline structures is as follows：
The preparation of the complex 2 of embodiment 2
Under nitrogen protection, under the conditions of -78 DEG C, to 2- (cyclohexyl-nitrogen-methyl) phenyl-tetramethyl-ring pentadiene (part
2) in tetrahydrofuran (20mL) solution of (0.805g, 2.60mmol) be added dropwise n-BuLi (2.16mL, 5.20mmol) just oneself
Alkane solution.It is added dropwise, the reactant mixture of gained continues stirring one hour at this temperature, and then this mixture allows to rise to
Room temperature simultaneously continues stirring three hours at this temperature.Add it to 2 equivalent CrCl3(THF)3Tetrahydrofuran solution, it is stirred
At night, solvent is removed, 20mL toluene is added into ampulla, insoluble matter is filtered to remove, the toluene in filtrate is removed in vacuum.Again to ampulla
Middle addition 20mL hexanes ultrasonic curing is simultaneously filtered, and gained solid is washed using cold hexane (5mL × 2), then using THF/ oneself
Alkane recrystallizes.Obtain the net product 0.653g of complex 2, yield 58.3%.
The preparation of the complex 3 of embodiment 3
Under nitrogen protection, under the conditions of -78 DEG C, to 2- (phenyl-nitrogen-methyl) phenyl-tetramethyl-ring pentadiene (part 3)
The n-hexane of n-BuLi (2.16mL, 5.20mmol) is added dropwise in tetrahydrofuran (20mL) solution of (0.789g, 2.60mmol)
Solution.It is added dropwise, the reactant mixture of gained continues stirring one hour at this temperature, and then this mixture allows to rise to room
Temperature simultaneously continues stirring three hours at this temperature.Add it to 2 equivalent CrCl3(THF)3Tetrahydrofuran solution, it is stirred
At night, solvent is removed, 20mL toluene is added into ampulla, insoluble matter is filtered to remove, the toluene in filtrate is removed in vacuum.Again to ampulla
Middle addition 20mL hexanes ultrasonic curing is simultaneously filtered, and gained solid is washed using cold hexane (5mL × 2), then using THF/ oneself
Alkane recrystallizes.Obtain the net product 0.612g of complex 3, yield 55.6%.
The preparation of the complex 4 of embodiment 4
Under nitrogen protection, under the conditions of -78 DEG C, to 2- (4- aminomethyl phenyls-nitrogen-methyl) phenyl-tetramethyl-ring pentadiene
N-BuLi (2.16mL, 5.20mmol) is added dropwise in tetrahydrofuran (20mL) solution of (part 4) (0.825g, 2.60mmol)
Hexane solution.It is added dropwise, the reactant mixture of gained continues stirring one hour at this temperature, and then this mixture allows
It is warmed to room temperature and continues stirring three hours at this temperature.Add it to 2 equivalent CrCl3(THF)3Tetrahydrofuran solution, stir
Mix overnight, remove solvent, 20mL toluene is added into ampulla, insoluble matter is filtered to remove, the toluene in filtrate is removed in vacuum.Again to
20mL hexanes ultrasonic curing is added in ampulla and is filtered, gained solid is washed using cold hexane (5mL × 2), is then utilized
THF/ hexanes recrystallize.Obtain the net product 0.594g of complex 4, yield 52.1%.
The preparation of the complex 5 of embodiment 5
Under nitrogen protection, under the conditions of -78 DEG C, to 2- (2,6- 3,5-dimethylphenyls-nitrogen-methyl) phenyl-tetramethyl-ring penta
In tetrahydrofuran (20mL) solution of diene (part 5) (0.862g, 2.60mmol) be added dropwise n-BuLi (2.16mL,
Hexane solution 5.20mmol).It is added dropwise, the reactant mixture of gained continues stirring one hour at this temperature, then
This mixture allows to be warmed to room temperature and continues stirring three hours at this temperature.Add it to 2 equivalent CrCl3(THF)3Four
Hydrogen tetrahydrofuran solution, is stirred overnight, and removes solvent, and 20mL toluene is added into ampulla, insoluble matter is filtered to remove, filtrate is removed in vacuum
In toluene.20mL hexanes ultrasonic curing is added into ampulla again and is filtered, gained solid is washed using cold hexane (5mL × 2)
Wash, then recrystallized using THF/ hexanes.Obtain the net product 0.717g of complex 5, yield 60.8%.Its mono-crystalline structures is
The preparation of the complex 6 of embodiment 6
Under nitrogen protection, under the conditions of -78 DEG C, to 2- (2,6- diethyl phenyls-nitrogen-methyl) phenyl-tetramethyl-ring penta
In tetrahydrofuran (20mL) solution of diene (part 6) (0.935g, 2.60mmol) be added dropwise n-BuLi (2.16mL,
Hexane solution 5.20mmol).It is added dropwise, the reactant mixture of gained continues stirring one hour at this temperature, then
This mixture allows to be warmed to room temperature and continues stirring three hours at this temperature.Add it to 2 equivalent CrCl3(THF)3Four
Hydrogen tetrahydrofuran solution, is stirred overnight, and removes solvent, and 20mL toluene is added into ampulla, insoluble matter is filtered to remove, filtrate is removed in vacuum
In toluene.20mL hexanes ultrasonic curing is added into ampulla again and is filtered, gained solid is washed using cold hexane (5mL × 2)
Wash, then recrystallized using THF/ hexanes.Obtain the net product 0.764g of complex 6, yield 61.1%.
The preparation of the complex 7 of embodiment 7
Under nitrogen protection, under the conditions of -78 DEG C, to 2- (2,6- diisopropyl phenyls-nitrogen-methyl) phenyl-tetramethyl-ring
In tetrahydrofuran (20mL) solution of pentadiene (part 7) (1.008g, 2.60mmol) be added dropwise n-BuLi (2.16mL,
Hexane solution 5.20mmol).It is added dropwise, the reactant mixture of gained continues stirring one hour at this temperature, then
This mixture allows to be warmed to room temperature and continues stirring three hours at this temperature.Add it to 2 equivalent CrCl3(THF)3Four
Hydrogen tetrahydrofuran solution, is stirred overnight, and removes solvent, and 20mL toluene is added into ampulla, insoluble matter is filtered to remove, filtrate is removed in vacuum
In toluene.20mL hexanes ultrasonic curing is added into ampulla again and is filtered, gained solid is washed using cold hexane (5mL × 2)
Wash, then recrystallized using THF/ hexanes.Obtain the net product 0.791g of complex 7, yield 59.8%.
The preparation of the complex 8 of embodiment 8
Under nitrogen protection, under the conditions of -78 DEG C, to 2- (benzyl-nitrogen-methyl) phenyl-tetramethyl-ring pentadiene (part 8)
The n-hexane of n-BuLi (2.16mL, 5.20mmol) is added dropwise in tetrahydrofuran (20mL) solution of (0.825g, 2.60mmol)
Solution.It is added dropwise, the reactant mixture of gained continues stirring one hour at this temperature, and then this mixture allows to rise to room
Temperature simultaneously continues stirring three hours at this temperature.Add it to 2 equivalent CrCl3(THF)3Tetrahydrofuran solution, it is stirred
At night, solvent is removed, 20mL toluene is added into ampulla, insoluble matter is filtered to remove, the toluene in filtrate is removed in vacuum.Again to ampulla
Middle addition 20mL hexanes ultrasonic curing is simultaneously filtered, and gained solid is washed using cold hexane (5mL × 2), then using THF/ oneself
Alkane recrystallizes.Obtain the net product 0.691g of complex 8, yield 60.6%.
The preparation of the complex 9 of embodiment 9
Under nitrogen protection, under the conditions of -78 DEG C, to 2- (isopropyl-nitrogen-methyl) phenyl -3,4- diformazan butylcyclopentadiene
N-BuLi (2.16mL, 5.20mmol) is added dropwise in tetrahydrofuran (20mL) solution of (part 9) (0.628g, 2.60mmol)
Hexane solution.It is added dropwise, the reactant mixture of gained continues stirring one hour at this temperature, and then this mixture allows
It is warmed to room temperature and continues stirring three hours at this temperature.Add it to 2 equivalent CrCl3(THF)3Tetrahydrofuran solution, stir
Mix overnight, remove solvent, 20mL toluene is added into ampulla, insoluble matter is filtered to remove, the toluene in filtrate is removed in vacuum.Again to
20mL hexanes ultrasonic curing is added in ampulla and is filtered, gained solid is washed using cold hexane (5mL × 2), is then utilized
THF/ hexanes recrystallize.Obtain the net product 0.499g of complex 9, yield 53.1%.
The preparation of the complex 10 of embodiment 10
Under nitrogen protection, under the conditions of -78 DEG C, to 2- (cyclohexyl-nitrogen-methyl) phenyl -3,4- diformazan butylcyclopentadiene
N-BuLi (2.16mL, 5.20mmol) is added dropwise in tetrahydrofuran (20mL) solution of (ligand 1 0) (0.732g, 2.60mmol)
Hexane solution.It is added dropwise, the reactant mixture of gained continues stirring one hour at this temperature, and then this mixture is permitted
Permitted to be warmed to room temperature and continue stirring three hours at this temperature.Add it to 2 equivalent CrCl3(THF)3Tetrahydrofuran solution,
It is stirred overnight, removes solvent, 20mL toluene is added into ampulla, insoluble matter is filtered to remove, the toluene in filtrate is removed in vacuum.Again
20mL hexanes ultrasonic curing is added into ampulla and is filtered, gained solid is washed using cold hexane (5mL × 2), is then utilized
THF/ hexanes recrystallize.Obtain the net product 0.575g of complex 10, yield 54.8%.
The preparation of the complex 11 of embodiment 11
Under nitrogen protection, under the conditions of -78 DEG C, (match somebody with somebody to 2- (phenyl-nitrogen-methyl) phenyl -3,4- diformazan butylcyclopentadiene
Body 11) (0.716g, 2.60mmol) tetrahydrofuran (20mL) solution in be added dropwise n-BuLi (2.16mL, 5.20mmol) just
Hexane solution.It is added dropwise, the reactant mixture of gained continues stirring one hour at this temperature, and then this mixture allows to rise
Continue to room temperature and at this temperature stirring three hours.Add it to 2 equivalent CrCl3(THF)3Tetrahydrofuran solution, stirring
Overnight, solvent is removed, 20mL toluene is added into ampulla, insoluble matter is filtered to remove, the toluene in filtrate is removed in vacuum.Again to peace
20mL hexanes ultrasonic curing is added in bottle and is filtered, gained solid is washed using cold hexane (5mL × 2), then utilizes THF/
Hexane recrystallizes.Obtain the net product 0.555g of complex 11, yield 53.9%.
The preparation of the complex 12 of embodiment 12
Under nitrogen protection, under the conditions of -78 DEG C, (match somebody with somebody to 2- (phenyl-nitrogen-methyl) phenyl -3,4- hexichol butylcyclopentadiene
Body 12) (1.039g, 2.60mmol) tetrahydrofuran (20mL) solution in be added dropwise n-BuLi (2.16mL, 5.20mmol) just
Hexane solution.It is added dropwise, the reactant mixture of gained continues stirring one hour at this temperature, and then this mixture allows to rise
Continue to room temperature and at this temperature stirring three hours.Add it to 2 equivalent CrCl3(THF)3Tetrahydrofuran solution, stirring
Overnight, solvent is removed, 20mL toluene is added into ampulla, insoluble matter is filtered to remove, the toluene in filtrate is removed in vacuum.Again to peace
20mL hexanes ultrasonic curing is added in bottle and is filtered, gained solid is washed using cold hexane (5mL × 2), then utilizes THF/
Hexane recrystallizes.Obtain the net product 0.760g of complex 12, yield 56.2%.
The preparation of the complex 13 of embodiment 13
Under nitrogen protection, under the conditions of -78 DEG C, to 2- (phenyl-nitrogen-methyl) phenyl -1- indenes (ligand 1 3) (0.773g,
The hexane solution of n-BuLi (2.16mL, 5.20mmol) is added dropwise in tetrahydrofuran (20mL) solution 2.60mmol).It is added dropwise
Finish, the reactant mixture of gained continues stirring one hour at this temperature, and then this mixture allows to be warmed to room temperature and herein
At a temperature of continue stirring three hours.Add it to 2 equivalent CrCl3(THF)3Tetrahydrofuran solution, be stirred overnight, remove it is molten
Agent, 20mL toluene is added into ampulla, insoluble matter is filtered to remove, the toluene in filtrate is removed in vacuum.Added again into ampulla
20mL hexanes ultrasonic curing is simultaneously filtered, and gained solid is washed using cold hexane (5mL × 2), is then tied again using THF/ hexanes
It is brilliant.Obtain the net product 0.644g of complex 13, yield 59.2%.
The preparation of the complex 14 of embodiment 14
Under nitrogen protection, under the conditions of -78 DEG C, to 2- (phenyl-nitrogen-methyl) phenyl -2- indenes (ligand 1 4) (0.773g,
The hexane solution of n-BuLi (2.16mL, 5.20mmol) is added dropwise in tetrahydrofuran (20mL) solution 2.60mmol).It is added dropwise
Finish, the reactant mixture of gained continues stirring one hour at this temperature, and then this mixture allows to be warmed to room temperature and herein
At a temperature of continue stirring three hours.Add it to 2 equivalent CrCl3(THF)3Tetrahydrofuran solution, be stirred overnight, remove it is molten
Agent, 20mL toluene is added into ampulla, insoluble matter is filtered to remove, the toluene in filtrate is removed in vacuum.Added again into ampulla
20mL hexanes ultrasonic curing is simultaneously filtered, and gained solid is washed using cold hexane (5mL × 2), is then tied again using THF/ hexanes
It is brilliant.Obtain the net product 0.618g of complex 14, yield 56.8%.
The preparation of the complex 15 of embodiment 15
Under nitrogen protection, under the conditions of -78 DEG C, to 2- (phenyl-nitrogen-methyl) phenyl-fluorenes (ligand 1 5) (0.903g,
The hexane solution of n-BuLi (2.16mL, 5.20mmol) is added dropwise in tetrahydrofuran (20mL) solution 2.60mmol).It is added dropwise
Finish, the reactant mixture of gained continues stirring one hour at this temperature, and then this mixture allows to be warmed to room temperature and herein
At a temperature of continue stirring three hours.Add it to 2 equivalent CrCl3(THF)3Tetrahydrofuran solution, be stirred overnight, remove it is molten
Agent, 20mL toluene is added into ampulla, insoluble matter is filtered to remove, the toluene in filtrate is removed in vacuum.Added again into ampulla
20mL hexanes ultrasonic curing is simultaneously filtered, and gained solid is washed using cold hexane (5mL × 2), is then tied again using THF/ hexanes
It is brilliant.Obtain the net product 0.686g of complex 15, yield 56.3%.
Embodiment 16 is catalyzed ethylene homo
Polymerization reaction kettle heating in vacuum is carried out to 120 DEG C to remove water process, 50 DEG C is subsequently cooled to, is filled with 1 atmospheric pressure second
Alkene gas.Toluene solutions of the 50mL containing co-catalyst is added into reactor, reaction solution is heated to 50 under agitation
DEG C, then into reactor add 10mL major catalysts containing 1mol toluene solution, ethylene gas pressure is risen into 5 air immediately
Pressure, start timing.After reaction 20 minutes, ethylene gas in reactor is vented, reaction is quenched with 5% hydrochloric acid/methanol solvate, filters out
Polymer, fully washed with water and methanol, 60 DEG C are dried under vacuum to constant weight.Aggregated data is listed in the table below in 1, institute in the present embodiment
It is the complex 1-15 that is prepared in embodiment 1-15 with major catalyst.
The ethylene homo experimental data of table 1[1]
[1] co-catalyst is 90mol AlR3,1.3mol Ph3CB(C6F5)4, 50 DEG C of polymerization temperature and polymerization time 20 divide
Clock；
[2] unit:Kg PE/(mmol Cr×h)；
Measured at [3] 135 DEG C using decahydronaphthalene.
[4]1000eq MAO；
[5]1000eq MMAO；
[6]1.3mol PhNMe2HB(C6F5)4；
[7]1.3mol B(C6F5)3。
The ethene of embodiment 17 and 1- hervene copolymers
Polymerization reaction kettle heating in vacuum is carried out to 120 DEG C to remove water process, 50 DEG C is subsequently cooled to, is filled with 1 atmospheric pressure second
Alkene gas.Toluene solutions of the 50mL containing-alkene and co-catalyst is added into reactor, under agitation adds reaction solution
Heat to 50 DEG C, then into reactor add the 10mL materials of major catalyst containing 1mol toluene solution, immediately by ethylene gas pressure
5 atmospheric pressure are risen to, start timing.After reaction 20 minutes, ethylene gas in reactor is vented, is quenched with 5% hydrochloric acid/methanol solvate
Go out reaction, filter out polymer, fully washed with water and methanol, 60 DEG C are dried under vacuum to constant weight.Aggregated data is listed in the table below in 2,
Major catalyst used is the complex 1-15 prepared in embodiment 1-15 in the present embodiment.
2 ethene of table/1- hervene copolymer experimental datas[1]
[1] co-catalyst is 90 μm of ol Al (Et)3With 1.3 μm of ol Ph3CB(C6F5)4；
[2] unit：Kg polymer/(mmol Cr×h)；
[3] hexene insertion rate data are calculated by high temperature nuclear-magnetism carbon spectrum；
[4] molecular weight data is measured by the type high temperature GPC of PL-GPC 220.
Claims (6)
1. a kind of side arm containing benzamido group mono-metallocene chromium (IV) complex, has following general structure：
Wherein Cp ' is cyclopentadienyl group, indenyl, fluorenyl, substituted cyclopentadienyl, substituted indenyl, substitution fluorenyl；R is less than 30
Alkyl, substitution alkyl, aryl or the substituted aryl of individual carbon atom；X is halogen, alkoxy, amido, alkyl, aryl, alkenyl, taken
Substituted alkyl, substituted aryl or substituted alkenyl.
2. one kind side arm containing benzamido group mono-metallocene chromium (IV) complex according to claim 1, it is characterised in that Cp '
For the derivative containing 1~4 substituent of cyclopentadienyl group, indenyl, fluorenyl or above-mentioned group, wherein substituent is methyl, second
Base, propyl group, isopropyl or phenyl；R is phenyl, p-methylphenyl, o-methyl-phenyl, 2,6- 3,5-dimethylphenyls, 2,6- diethyl
Phenyl, 2,6- diisopropyl phenyls, 2,4,6- trimethylphenyls, propyl group, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, positive penta
Base, 2- amyl groups, 3- amyl groups, isopentyl, tertiary pentyl, neopentyl, cyclopenta, n-hexyl, isomeric hexyls, cyclohexyl, adamantyl,
Benzyl, aralkyl, two aralkyl or triaryl methyl；X is halogen, methoxyl group, ethyoxyl, isopropoxy, tert-butoxy, benzene oxygen
Base, dimethylamino, diethylin, diisopropylamino, hmds base, methyl, phenyl, benzyl, trimethyl silicane ylmethyl
Or neopentyl.
3. one kind side arm containing benzamido group mono-metallocene chromium (IV) complex according to claim 1 or 2, it is characterised in that
Cp ' is 1- indenyls, 2- indenyls, fluorenyl, dimethylcyclo-pentadienyl or tetramethyl-ring pentadienyl；R be phenyl, p-methylphenyl,
O-tolyl, propyl group, isopropyl, normal-butyl, isobutyl group, n-pentyl, isopentyl, cyclopenta, n-hexyl, isohesyl, cyclohexyl
Or benzyl；X is halogen.
4. the purposes of side arm containing benzamido group mono-metallocene chromium (IV) complex of a kind of claim 1, it is characterised in that with described
Side arm containing benzamido group mono-metallocene chromium (IV) complex be major catalyst, helped with alkylaluminoxane, or alkyl aluminum with organic boron
The mixture of agent is co-catalyst, is reacted for being catalyzed ethylene homo or ethene with alpha-olefin copolymer；Wherein aluminium in co-catalyst
Mol ratio with metal in major catalyst is 5~10000:1, the mol ratio of boron and metal in major catalyst is 0 in co-catalyst
~2:1；Described alpha-olefin is propylene, 1- butylene, 1- hexenes, 1- octenes or 1- decene；Described alkyl aluminum be trimethyl aluminium,
Triethyl aluminum or triisobutyl aluminium；Described alkylaluminoxane is MAO or modified methylaluminoxane；Described is organic
Boron additive is Ph3CB(C6F5)4、PhNMe2HB(C6F5)4Or B (C6F5)3。
5. the purposes of one kind side arm containing benzamido group mono-metallocene chromium (IV) complex according to claim 4, its feature exist
In the molar ratio of alkylaluminoxane and mono-metallocene chromium (IV) complex is 500~5000 in described catalyst system and catalyzing:1, alkane
The molar ratio of base aluminium and mono-metallocene chromium (IV) complex is 50~500:1, organic boron additive is matched somebody with somebody with mono-metallocene chromium (IV)
The molar ratio of compound is 1~2:1；Described organic boron additive is Ph3CB(C6F5)4。
6. the purposes of one kind side arm containing benzamido group mono-metallocene chromium (IV) complex according to claim 4 or 5, its feature
It is, catalysed olefin polymerization concretely comprises the following steps：Under at least one olefinic monomer existence condition, add and lead to polymeric kettle
Catalyst and co-catalyst, -20 DEG C~200 DEG C, the atmospheric pressure of ethylene pressure scope 0~200,0~5mol/L of alpha-olefin concentration
Under conditions of react 0~300 minute；After polymerisation terminates, obtained polymer is washed with acid solution, in vacuum drying oven
In in 60 DEG C be dried to constant weight.
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| CN110655538A (en) * | 2019-10-08 | 2020-01-07 | 吉林大学 | Mono-metallocene trivalent transition metal complex containing neutral benzyl heteroatom ligand and application thereof |
| CN111729688A (en) * | 2020-07-09 | 2020-10-02 | 吉林大学 | Application of single cyclopentadienyl fourth subgroup metal complex containing neutral coordination side group |
| CN113185545A (en) * | 2021-04-28 | 2021-07-30 | 吉林大学 | Benzyl amino side arm-containing half-metallocene fourth subgroup metal complex and application thereof |
| CN113880881A (en) * | 2021-10-20 | 2022-01-04 | 中化泉州石化有限公司 | Synthesis of rigid organic phosphine ligand and application thereof in ethylene oligomerization |
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| JP2004189690A (en) * | 2002-12-13 | 2004-07-08 | Sumitomo Chem Co Ltd | Transition metal complex, olefin-polymerization catalyst and method for producing olefin polymer using the same |
| US20040242410A1 (en) * | 2001-09-14 | 2004-12-02 | Hidenori Hanaoka | Transition metal complex, catalyst for olefin polymerization, and process for producing olefin polymer with the same |
| CN102070732A (en) * | 2010-12-08 | 2011-05-25 | 吉林大学 | Constrained-geometry chromium metallocene catalyst and use thereof |
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| US20040242410A1 (en) * | 2001-09-14 | 2004-12-02 | Hidenori Hanaoka | Transition metal complex, catalyst for olefin polymerization, and process for producing olefin polymer with the same |
| JP2004189690A (en) * | 2002-12-13 | 2004-07-08 | Sumitomo Chem Co Ltd | Transition metal complex, olefin-polymerization catalyst and method for producing olefin polymer using the same |
| CN102070732A (en) * | 2010-12-08 | 2011-05-25 | 吉林大学 | Constrained-geometry chromium metallocene catalyst and use thereof |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110655538A (en) * | 2019-10-08 | 2020-01-07 | 吉林大学 | Mono-metallocene trivalent transition metal complex containing neutral benzyl heteroatom ligand and application thereof |
| CN110655538B (en) * | 2019-10-08 | 2021-08-31 | 吉林大学 | Mono-metallocene trivalent transition metal complex containing neutral benzyl heteroatom ligand and application thereof |
| CN111729688A (en) * | 2020-07-09 | 2020-10-02 | 吉林大学 | Application of single cyclopentadienyl fourth subgroup metal complex containing neutral coordination side group |
| CN111729688B (en) * | 2020-07-09 | 2021-08-17 | 吉林大学 | Application of single cyclopentadienyl fourth subgroup metal complex containing neutral coordination side group |
| CN113185545A (en) * | 2021-04-28 | 2021-07-30 | 吉林大学 | Benzyl amino side arm-containing half-metallocene fourth subgroup metal complex and application thereof |
| CN113880881A (en) * | 2021-10-20 | 2022-01-04 | 中化泉州石化有限公司 | Synthesis of rigid organic phosphine ligand and application thereof in ethylene oligomerization |
| CN113880881B (en) * | 2021-10-20 | 2023-11-17 | 中化泉州石化有限公司 | Synthesis of rigid organic phosphine ligand and application of rigid organic phosphine ligand in ethylene oligomerization |
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